POLYMER-BASED PORTION, ADHESIVE, FOLDABLE APPARATUS, AND METHODS OF MAKING
20210108077 · 2021-04-15
Inventors
- TARA MARIE BERLEUE (HORNELL, NY, US)
- Charles Brandenburg (Wellsboro, PA, US)
- Justin Bernard Bult (Geneseo, NY, US)
- Matthew John Dejneka (Corning, NY)
- Sushmit Sunil Kumar Goyal (Painted Post, NY)
- Timothy Michael Gross (Corning, NY)
- Yungfeng Gu (Painted Post, NY, US)
- Yuhui Jin (Painted Post, NY)
- Jenny Kim (Horseheads, NY, US)
- Xinghua Li (Horseheads, NY)
- Jian Luo (Painted Post, NY)
- Kevin Robert McCarthy (Horseheads, NY, US)
- Weijun Niu (Painted Post, NY)
- TERRI LEE SINES-MELOCK (CORNING, NY, US)
- Michael Lesley Sorensen (Waverly, NY)
- Jonathan Earl Walter (Woodhull, NY, US)
- Arline Lee Weikel (Mansfield, PA, US)
- Lei Yuan (Painted Post, NY, US)
Cpc classification
C08K5/205
CHEMISTRY; METALLURGY
C08K5/5406
CHEMISTRY; METALLURGY
C08F287/00
CHEMISTRY; METALLURGY
C08L51/08
CHEMISTRY; METALLURGY
C08G18/672
CHEMISTRY; METALLURGY
C09J151/08
CHEMISTRY; METALLURGY
C08L83/16
CHEMISTRY; METALLURGY
C08K5/0025
CHEMISTRY; METALLURGY
C08G18/673
CHEMISTRY; METALLURGY
C08L75/16
CHEMISTRY; METALLURGY
C08F287/00
CHEMISTRY; METALLURGY
C08K5/09
CHEMISTRY; METALLURGY
International classification
C08L75/16
CHEMISTRY; METALLURGY
C08G18/67
CHEMISTRY; METALLURGY
C08K5/09
CHEMISTRY; METALLURGY
C08K5/205
CHEMISTRY; METALLURGY
Abstract
Polymer-based portions comprise an index of refraction ranging from about 1.49 to about 1.55. In some embodiments, the polymer-based portion comprises the product of curing 45-75 wt % of a difunctional urethane-acrylate oligomer with 25-55 wt % of a difunctional cross-linking agent and optionally a reactive diluent. In some embodiments, the polymer-based portion comprises the product of curing 75-100 wt % of a reactive diluent and optionally one or more a difunctional urethane-acrylate oligomer and/or a difunctional cross-linking agent. Adhesives comprise an index of refraction ranging from about 1.49 to about 1.55. In some embodiments, the adhesive comprises the product of heating 10-35 wt % of a silane-hydride-terminated siloxane and 65-90 wt % of a vinyl-terminated siloxane. In some embodiments, the adhesive comprises the product of irradiating a thiol-containing siloxane and a photo-initiator with at least one wavelength of light that the photo-initiator is sensitive to. Foldable apparatus can comprise the polymer-based portion and/or adhesive.
Claims
1-336. (canceled)
337. A polymer-based portion comprising an index of refraction in a range from about 1.49 to about 1.55, wherein the polymer-based portion comprises the product of curing a composition, the composition comprising the following in weight % (wt %): 0-25 wt % of a difunctional urethane-acrylate oligomer; 0-5 wt % of a difunctional cross-linking agent; and 75-100 wt % of a reactive diluent.
338. The polymer-based portion of claim 337, wherein the reactive diluent comprises one or more of biphenylmethyl acrylate, nonyl phenol acrylate, or isooctyl acrylate.
339. The polymer-based portion of claim 337, wherein the reactive diluent comprises a vinyl-terminated mono-acrylate monomer.
340. The polymer-based portion of claim 337, wherein the difunctional cross-linking agent comprises a urethane diacrylate monomer.
341. The polymer-based portion of claim 337, wherein the difunctional cross-linking agent comprises 2-[[(butylamino)carbonyl]oxy]ethyl acrylate.
342. The polymer-based portion of claim 337, wherein the polymer-based portion comprises a glass transition temperature of about 0° C. or less.
343. The polymer-based portion of claim 342, wherein the glass transition temperature is in a range from about −60° C. to about −20° C.
344. The polymer-based portion of claim 337, wherein the composition further comprises 0.1-3 wt % of a photo-initiator, and curing the composition comprises irradiating the composition with at least one wavelength of light that the photo-initiator is sensitive to.
345. The polymer-based portion of claim 337, wherein curing the composition comprises heating the composition at a temperature in a range from about 100° C. to about 200° C. for a time in a range from about 15 minutes to about 6 hours.
346. The polymer-based portion of claim 337, wherein the composition further comprises 1-4.9 wt % of a silane coupling agent.
347. The polymer-based portion of claim 346, wherein the silane coupling agent comprises a mercapto-silane.
348. The polymer-based portion of claim 337, further comprising a thermoplastic elastomer.
349. The polymer-based portion of claim 337, wherein the polymer-based portion comprises an average transmittance of about 90% or more measured over optical wavelengths in a range from 400 nanometers to 760 nanometers.
350. The polymer-based portion of claim 337, wherein the polymer-based portion comprises a haze of about 0.2% or less.
351. The polymer-based portion of claim 337, wherein the polymer-based portion comprises an ultimate elongation of about 50% or more.
352. The polymer-based portion of claim 337, wherein the polymer-based portion comprises a tensile strength of about 1 MegaPascal or more.
353. The polymer-based portion of claim 337, wherein the polymer-based portion comprises an elastic modulus in a range from about 1 MegaPascal to about 100 MegaPascals.
354. The polymer-based portion of claim 337, wherein a storage modulus of the polymer-based portion at 23° C. is in a range from about 0.3 MegaPascals to about 3 MegaPascals.
355. The polymer-based portion of claim 337, wherein the polymer-based portion at 23° C. can fully recover after being extended to a strain of 40% at a strain rate of 10% strain per minute.
356. The polymer-based portion of claim 337, wherein the polymer-based portion can withstand 2,000 bending cycles at a parallel plate distance of 3 millimeters.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0362] The above and other features and advantages of embodiments of the present disclosure are better understood when the following detailed description is read with reference to the accompanying drawings, in which:
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[0392] Throughout the disclosure, the drawings are used to emphasize certain aspects. As such, it should not be assumed that the relative size of different regions, portions, and substrates shown in the drawings are proportional to its actual relative size, unless explicitly indicated otherwise.
DETAILED DESCRIPTION
[0393] Embodiments will now be described more fully hereinafter with reference to the accompanying drawings in which example embodiments are shown. Whenever possible, the same reference numerals are used throughout the drawings to refer to the same or like parts. However, claims may encompass many different aspects of various embodiments and should not be construed as limited to the embodiments set forth herein.
[0394] The polymer-based portions and/or adhesives of embodiments of the disclosure can be used, for example, in a foldable apparatus 101, 301, 401, 501, 601, 701, 801, 901, 1001, 1701, and 1801 (e.g., see
[0395] Embodiments of the disclosure can comprise polymer-based portions. Throughout the disclosure, an index of refraction may be a function of a wavelength of light passing through a material. Throughout the disclosure, for light of a first wavelength, an index of refraction of a material is defined as the ratio between the speed of light in a vacuum and the speed of light in the corresponding material. Without wishing to be bound by theory, an index of refraction of a material can be determined using a ratio of a sine of a first angle to a sine of a second angle, where light of the first wavelength is incident from air on a surface of the material at the first angle and refracts at the surface of the material to propagate light within the material at a second angle. The first angle and the second angle are both measured relative to a normal of a surface of the material. As used herein, the refractive index is measured in accordance with ASTM E1967-19, where the first wavelength comprises 589 nm. In some embodiments, an index of refraction of the polymer-based portion may be about 1.4 or more, about 1.45 or more, about 1.49 or more, about 1.50 or more, about 1.53 or more, about 1.6 or less, about 1.55 or less, about 1.54 or less, or about 1.52 or less. In some embodiments, the index of refraction of the polymer-based portion can be in a range from about 1.4 to about 1.6, from about 1.45 to about 1.6, from about 1.45 to about 1.55, from about 1.49 to about 1.55, from about 1.50 to about 1.55, from about 1.53 to about 1.55, from about 1.49 to about 1.54, from about 1.49 to about 1.52, or any range or subrange therebetween.
[0396] As used herein, “optically transparent” or “optically clear” means an average transmittance of 70% or more in the wavelength range of 400 nm to 700 nm through a 1.0 mm thick piece of material. As used herein, an average transmittance of a material is measured by averaging over optical wavelengths in a range from 400 nm to 700 nm through a 1.0 mm thick piece of the material, which comprises measuring the transmittance of whole number wavelengths from about 400 nm to about 700 nm and averaging the measurements. Unless specified otherwise, “transmittance” of a material refers to the average transmittance of the material. In some embodiments, an “optically transparent material” or an “optically clear material” may have an average transmittance of 75% or more, 80% or more, 85% or more, or 90% or more, 92% or more, 94% or more, 96% or more in the wavelength range of 400 nm to 700 nm through a 1.0 mm thick piece of the material. In some embodiments, the polymer-based portion can be optically transparent. In further embodiments, the polymer-based portion can comprise an average transmittance measured over optical wavelengths in a range from 400 nm to 700 nm of about 90% or more, about 91% or more, about 92% or more, about 93% or more, 100% or less, about 96% or less, about 95% or less, or about 94% or less. In further embodiments, the polymer-based portion can comprise an average transmittance measured over optical wavelengths in a range from 400 nm to 700 nm in a range from about 90% to 100%, from about 90% to about 96%, from about 91% to about 96%, from about 91% to about 95%, from about 92% to about 95%, from about 92% to about 94%, from about 93% to about 94%, or any range or subrange therebetween.
[0397] The polymer-based portion can comprise a haze as a function of an angle of illumination relative to a direction normal to a surface of the polymer-based portion. As used herein, haze refers to transmission haze that is measured in accordance with ASTM E430. Haze can be measured using a haze meter supplied by BYK Gardner under the trademark HAZE-GUARD PLUS, using an aperture over the source port. The aperture has a diameter of 8 mm. A CIE C illuminant is used as the light source for illuminating the foldable apparatus. Unless indicated otherwise, haze is measured at about 10° relative to an angle of incidence normal to a surface of the polymer-based portion. In some embodiments, the haze at about 0° and/or 10° relative to an angle of incidence normal to the surface of the polymer-based portion measured through a 1.0 millimeter (mm) thick piece of the polymer-based portion can be about 1% or less, about 0.5% or less, about 0.2% or less, about 0.1% or less, or about 0.01% or more, or about 0.05% or more. In some embodiments, the haze at about 0° and/or 10° relative to an angle of incidence normal to the surface of the polymer-based portion measured through a 1.0 mm thick piece of the polymer-based portion can be in a range from 0% to about 1%, from 0% to 0.5%, from 0% to 0.2%, from about 0.01% to about 0.2%, from about 0.05% to about 0.2%, from about 0.05% to about 0.1%, or any range or subrange therebetween. In some embodiments, the haze at about 20° relative to an angle of incidence normal to the surface of the polymer-based portion can be within one or more of the ranges specified above for 0° and/or 10°. Providing a polymer-based portion comprising low haze can enable good visibility through the polymer-based portion.
[0398] The polymer-based portion can comprise a glass transition (Tg) temperature. As used herein, the glass transition temperature, a storage modulus at a range of temperatures, a storage modulus (e.g., at a glassy plateau), and a loss modulus (e.g., at a glass plateau) are measured using Dynamic Mechanical Analysis (DMA) with an instrument, for example, the DMA 850 from TA Instruments. The samples for the DMA analysis comprise a film secured by a tension clamp. As used herein, the storage modulus refers to the in-phase component of a response of the polymer-based material to the dynamic testing. Throughout the disclosure, the modulus of elasticity of a polymer-based material refers to the storage modulus of the polymer-based material because, without wishing to be bound by theory, the in-phase component of the response is attributed to the elastic portion of a viscoelastic material. As used herein, the loss modulus refers to the out-of-phase component of a response to the polymer-based material during the dynamic testing. Without wishing to be bound by theory, the loss modulus can correspond to the viscous component of a viscoelastic material. As used herein, the glass transition temperature corresponds to a maximum value of a tan delta, which is a ratio of the loss modulus to the storage modulus. In some embodiments, the glass transition temperature of the polymer-based portion can be about 40° C. or less, about 20° C. or less, about 0° C. or less, about −5° C. or less, about −15° C. or less, about −20° C. or less, or about −30° C. or less, about −40° C. or less, about −80° C. or more, about −60° C. or more, or about −50° C. or more. In further embodiments, the glass transition temperature of the polymer-based portion can be 0° C. or less. In some embodiments, the glass transition temperature of the polymer-based portion can in a range from about −80° C. to about 40° C., from about −80° C. to about 20° C., from about −80° C. to about 0° C., from about −60° C. to about 0° C., from about −60° C. to about −5° C., from about −60° C. to about −15° C., from about −60° C. to about −20° C., from about −50° C. to about −20° C., from about −50° C. to about −30° C., from about −50° C. to about −40° C., or any range or subrange therebetween. Providing a polymer-based portion with a glass transition temperature outside of an operating range (e.g., from about 0° C. to about 40° C., from about −20° C. to about 60° C.) can enable consistent properties across the operating range.
[0399] Throughout the disclosure, a storage modulus (i.e., modulus of elasticity) is measured for a polymeric material (e.g., polymer-based portion, adhesive) at 23° C. unless indicated otherwise. In some embodiments, the polymer-based portion can comprise a storage modulus of about 0.1 MegaPascals (MPa) or more, about 0.3 MPa or more, about 0.5 MPa or more, about 1 MPa or more, about 5 MPa or less, about 3 MPa or less, about 2 MPa or less, or about 1 MPa or less. In some embodiments, the polymer-based portion can comprise a storage modulus in a range from about 0.1 MPa to about 5 MPa, from about 0.3 MPa to about 5 MPa, from about 0.3 MPa to about 3 MPa, from about 0.3 MPa to about 2 MPa, from about 0.3 MPa to about 1 MPa, from about 0.5 MPa to about 1 MPa, from about 0.5 MPa to about 3 MPa, from about 1 MPa to about 3 MPa, or any range or subrange therebetween.
[0400] Throughout the disclosure, a loss modulus is measured for a material (e.g., polymer-based portion, adhesive) at 23° C. unless indicated otherwise. In some embodiments, the polymer-based portion can comprise a loss modulus of about 10 kiloPascals (kPa) or more, about 20 kPa or more, about 50 kPa or more, about 100 kPa or more, about 5 MPa or less, about 3 MPa or less, or about 1 MPa or less, or about 500 kPa or less. In some embodiments, the polymer-based portion can comprise a loss modulus in a range from about 10 kPa to about 5 MPa, from about 10 kPa to about 3 MPa, from about 20 kPa to about 3 MPa, from about 20 kPa to about 1 MPa, from about 50 kPa to about 1 MPa, from about 100 kPa to about 1 MPa, from about 100 kPa to about 500 kPa, or any range or subrange therebetween.
[0401] Throughout the disclosure, a tensile strength, ultimate elongation (e.g., strain at failure), and yield point of the polymer-based portion and elastomers is determined using ASTM D412A using a tensile testing machine, for example, an Instron 3400 or Instron 6800, at 23° C. and 50% relative humidity with a type I dogbone shaped sample. In some embodiments, a tensile strength of the polymer-based portion can be about 0.4 MPa or more, 0.5 MPa or more, about 1 MPa, about 2 MPa or more, about 5 MPa or more, about 20 MPa or less, about 15 MPa or less, about 10 MPa or less, or about 2.5 MPa or less. In some embodiments, a tensile strength of the polymer-based portion can be in a range from about 0.4 MPa to about 20 MPa, from about 0.5 MPa to about 20 MPa, from about 1 MPa to about 20 MPa, from about 1 MPa to about 15 MPa, from about 2 MPa to about 15 MPa, from about 5 MPa to about 15 MPa, from about 5 MPa to about 10 MPa, or any range or subrange therebetween. In some embodiments, a tensile strength of the polymer-based portion can be from about 0.4 MPa to about 20 MPa, 0.4 MPa to about 15 MPa, from about 0.5 MPa to about 15 MPa, from about 0.5 MPa to about 10 MPa, from about 0.5 MPa to about 2.5 MPa, or any range or subrange therebetween.
[0402] In some embodiments, an ultimate elongation of the polymer-based portion can be about 40% or more, about 50% or more, about 65% or more, about 80% or more, about 95% or more, about 150% or more, about 300% or less, about 200% or less, about 125% or less, about 110% or less, or about 80% or less. In some embodiments, an ultimate elongation of the polymer-based portion can be in a range from about 40% to about 300%, from about 50% to about 300%, from about 65% to about 300%, from about 80% to about 300%, from about 95% to about 300, from about 150% to about 300%, from about 150% to about 200%, or any range or subrange therebetween. In some embodiments, an ultimate elongation of the polymer-based portion can be in a range from about 40% to about 300%, from about 40% to about 200%, from about 50% to about 200%, from about 50% to about 125%, from about 65% to about 125%, from about 80% to about 125%, from about 95% to about 125%, from about 40% to about 80%, from about 50% to about 80%, from about 65% to about 80%, or any range or subrange therebetween.
[0403] Throughout the disclosure, an elastic modulus of the polymer-based portion and elastomers is measured using ISO 527-1:2019. In some embodiments, an elastic modulus of the polymer-based portion can be about 0.5 MPa or more, about 1 MPa or more, about 2 MPa or more, about 5 MPa or more, about 10 MPa or more, about 20 MPa or more, about 100 MPa or less, about 50 MPa or less, about 30 MPa or less, about 10 MPa or less, or about 5 MPa or less. In some embodiments, an elastic modulus of the polymer-based portion can be in a range from about 0.5 MPa to about 100 MPa, from about 1 MPa to about 100 MPa, from about 1 MPa to about 50 MPa, from about 2 MPa to about 50 MPa, from about 5 MPa to about 50 MPa, from about 10 MPa to about 50 MPa, from about 20 MPa to about 50 MPa, from about 20 MPa to about 30 MPa, or any range or subrange therebetween. In some embodiments, an elastic modulus of the polymer-based portion can be in a range from about 0.5 MPa to about 50 MPa, from about 0.5 MPa to about 30 MPa, from about 0.5 MPa to about 10 MPa, from about 1 MPa to about 10 MPa, from about 1 MPa to about 5 MPa, from about 2 MPa to about 5 MPa, or any range or subrange therebetween.
[0404] Throughout the disclosure, tension set of a sample is measured using ASTM D-412 as the strain at zero stress after the sample is stretched to a specified strain. In some embodiments, the polymer-based portion can comprise a tension set after being extended to a strain of 40% at a strain rate of 10% strain per minute at 23° C. In further embodiments, the tension set can be about 2% or less, about 1% or less, about 0.5% or less, or 0% or more. In further embodiments, the tension set can be in a range from 0% to about 2%, from 0% to about 1%, from 0% to about 0.5%, or any range or subrange therebetween. In further embodiments, the polymer-based portion can fully recover after being extended to a strain of 40% at a strain rate of 10% strain per minute at 23° C. In some embodiments, the polymer-based portion can fully recover after being extended to a strain of 40% at a strain rate of 10% strain per minute at 0° C. In some embodiments, the polymer-based portion can comprise a tension set after 200 cycles extending the polymer-based portion to a strain of 40% at a strain rate of 10% strain per minute at 23° C. In further embodiments, the tension set can be about 2% or less, about 1% or less, about 0.5% or less, or 0% or more. In further embodiments, the tension set can be in a range from 0% to about 2%, from 0% to about 1%, from 0% to about 0.5%, or any range or subrange therebetween.
[0405] The polymer-based portion described above can be formed as the product of curing a composition. Methods of forming the polymer-based portion described above will now be described.
[0406] Methods of forming the polymer-based portion can comprise creating a composition. The composition can comprise a difunctional urethane-acrylate oligomer. In some embodiments, the difunctional urethane-acrylate oligomer can comprise one or more of the following products in the Miramer product line available from Miwon: PU210, PU256, PU2050, PU2100, PU2300C, PU2560, PU320, PU340, PU3000, PU3200, PU340, PU5000, PU610, PU6510, PU9500, PU9800, PUA2516, SC2100, SC2404, SC2565, and/or SC9211. In some embodiments, the difunctional urethane-acrylate oligomer can comprise one or more of the following products in the Photomer product line available from IGM Resins: 6009, 6210, 6230, 6620, 6630, 6638, 6643, 6645, 6891, 6582, and/or 6581. In some embodiments, the difunctional urethane-acrylate oligomer can comprise the following products available from Arkema (Sartomer): PRO13944, PRO14213, CN8881, CN90004, CN9009, CN9030, CN9031, CN964, CN966J75, CN981, CN991, and/or CN 96. In some embodiments, the difunctional urethane-acrylate oligomer can comprise the following products from Dymax (Bomar): BR-374, BR-3042, BR-3641AA, BR-3641AJ, BR-3741AJ, BR-3747AE, BR-541S, BR-543, BR-543TF, BR-571, BR-582E8, BR-641E, BR-744BT, BR-744SD, and/or BR-771F. Exemplary embodiments of difunctional urethane-acrylate oligomers include Miramer SC9211 (Miwon), Photomer 6230 (IGM Resin), RX0057 (Allinex), and BR-543 (Dymax/Bomar).
[0407] In some embodiments, the composition can comprise a difunctional urethane-acrylate oligomer in a weight % (wt %) of about 45 wt % or more, about 47% or more, about 50 wt % or more, about 55 wt % or more, about 75 wt % or less, about 70 wt % or less, about 65 wt % or less, or about 60 wt % or less. In some embodiments, the composition can comprise a difunctional urethane-acrylate oligomer in a weight % (wt %) ranging from about 45 wt % to about 75 wt %, from about 45 wt % to about 70 wt %, from about 45 wt % to about 65 wt %, from about 47 wt % to about 65 wt %, from about 50 wt % to about 65 wt %, from about 50 wt % to about 60 wt %, from about 55 wt % to about 60 wt %, or any range or subrange therebetween.
[0408] In some embodiments, the composition can comprise a difunctional urethane-acrylate oligomer in a weight % (wt %) of 0 wt % or more, 1 wt % or more, about 5 wt % or more, about 10 wt % or more, about 25 wt % or less, about 20 wt % or less, or about 15 wt % or less. In some embodiments, the composition can comprise a difunctional urethane-acrylate oligomer in a weight % (wt %) ranging from 0 wt % to about 25 wt %, from 1 wt % to about 25 wt %, from about 1 wt % to about 20 wt %, from about 5 wt % to about 20 wt %, from about 10 wt % to about 20 wt %, from about 10 wt % to about 15 wt %, or any range or subrange therebetween. In some embodiments, the composition can be substantially free of comprise a difunctional urethane-acrylate oligomer.
[0409] In some embodiments, the composition can comprise a difunctional cross-linking agent. In some embodiments, the difunctional cross-linking agent can comprise a difunctional methacrylate monomer, for example, propylene-glycol dimethacrylate (e.g., SR-644 (Sartomer)). In some embodiments, the difunctional cross-linking agent can comprise a difunctional acrylate monomer. Exemplary embodiments of difunctional acrylate monomers include without limitation dipropylene-glycol diacrylate (DPGDA) (e.g., SR-508 (Sartomer), Photomer 4226 (IGM Resins)), 1,6-hexanediol diacrylate (e.g., Miramer M200 (Miwon)), bisphenol A diacrylate (e.g., Miramer M210 (Miwon)), bisphenol-A [4 EO] diacrylate (e.g., Photomer 4028 (IGM Resins)), tripropylene-glycol diacrylate (TPGDA) (e.g.,
[0410] Photomer 4061 (IGM Resins)), 3-methyl-1,5,-pentanediol diacrylate (MPDDA) (e.g., Photomer 4071 (IGM Resins)), neopentyl-glycol diacrylate (e.g., Photomer 4127 (IGM Resins)), Miramer HR 3700 (Miwon), and 1,6-hexanediol ethoxylate diacrylate (e.g., Photomer 4369 (IGM Resins)). In even further embodiments, the difunctional cross-linking agent can comprise dipropylene-glycol diacrylate and/or 2-[[(butylamino)carbonyl]oxy]ethyl acrylate (e.g., Photomer 4184 (IGM Resins)). In even further embodiments, the difunctional cross-linking agent comprising a difunctional acrylate monomer can comprise a urethane diacrylate monomer. An exemplary embodiment of a difunctional cross-linking agent comprises 2-[[(butylamino)carbonyl]oxy]ethyl acrylate (e.g., Photomer 4184 (IGM Resins)).
[0411] In some embodiments, the composition can comprise a difunctional cross-linking agent in a weight % (wt %) of about 25 wt % or more, about 30 wt % or more, about 35 wt % or more, about 40 wt % or more, about 55 wt % or less, about 50 wt % or less, or about 45 wt % or less. In some embodiments, the composition can comprise a difunctional cross-linking agent in a weight % (wt %) ranging from about 25 wt % to about 55 wt %, from about 30 wt % to about 55 wt %, from about 35 wt % to about 55 wt %, from about 35 wt % to about 50 wt %, from about 40 wt % to about 50 wt %, from about 40 wt % to about 45 wt % or any range or subrange therebetween.
[0412] In some embodiments, the composition can comprise a difunctional cross-linking agent in a weight % (wt %) of 0 wt % or more, about 0.1 wt % or more, about 0.2 wt % or more, about 1 wt % or less, or about 0.5 wt % or less. In some embodiments, the composition can comprise a difunctional cross-linking agent in a weight % (wt %) ranging from 0 wt % to about 1 wt %, from about 0.1 wt % to about 1 wt %, from about 0.1 wt % to about 0.5 wt %, from about 0.2 wt % to about 0.5 wt %, or any range or subrange therebetween. In some embodiments, the composition can be substantially free of a difunctional cross-linking agent.
[0413] In some embodiments, the composition can comprise a reactive diluent. As used herein, a reactive diluent is a monofunctional compound that can decrease the viscosity of composition and decrease a cross-linking density of the polymer-based portion. Without wishing to be bound by theory, decreasing the cross-linking density of the polymer-based portion can decrease the glass transition temperature of the polymer-based portion. In some embodiments, the reactive diluent can comprise a monofunctional acrylate. In further embodiments, the reactive diluent comprising a monofunctional acrylate include isobornyl acrylate (e.g., Miramer 1140 (Miwon), Photomer 4012 (IGM Resins)), biphenyl-methyl acrylate (e.g., Miramer 1192 (Miwon)), 2-propyl-heptyl acrylate, butyl acrylate, biphenyl methyl acrylate, nonyl phenol acrylates (e.g., Miramer 166 (Miwon)), ethoxy ethoxy ethyl acrylate (e.g., Miramer 170 (Miwon)), and/or isooctyl acrylate (e.g., Miramer 1084 (Miwon)). In further embodiments, the reactive diluent can comprise a vinyl-terminated mono-acrylate monomer. Exemplary embodiments of the reactive diluent include biphenylmethyl acrylate, nonyl phenol acrylate, and/or isooctyl acrylate.
[0414] In some embodiments, the composition can comprise a reactive diluent in combination with a difunctional urethane-acrylate oligomer and a difunctional cross-linking agent. In further embodiments, the composition can comprise the reactive diluent in a weight % (wt %) of 0 wt % or more, about 1 wt % or more, about 8 wt % or more, about 18 wt % or more, about 25 wt % or less, about 22 wt % or less, or about 20 wt % or less. In further embodiments, the composition can comprise the reactive diluent in a weight % (wt %) ranging from 0 wt % to about 25 wt %, from about 1 wt % to about 25 wt %, from about 5 wt % to about 25 wt %, from about 8 wt % to about 25 wt %, from about 8 wt % to about 22 wt %, from about 18 wt % about 22 wt %, from about 18 wt % to about 20 wt %, or any range or subrange therebetween. In some embodiments, the composition can be substantially free of a reactive diluent.
[0415] In some embodiments, the composition can comprise a reactive diluent, which can optionally be in combination with a difunctional urethane-acrylate oligomer and/or a difunctional cross-linking agent. In further embodiments, the composition can comprise the reactive diluent in a weight % (wt %) of 75 wt % or more, about 77 wt % or more, about 80 wt % or more, about 85 wt % or more, about 87 wt % or more, 100 wt % or less, about 99 wt % or less, about 95 wt % or less, or about 90 wt % or less. In further embodiments, the composition can comprise the reactive diluent ranging from about 75 wt % to 100 wt %, from about 77 wt % to 100 wt %, from 80 wt % to 100 wt %, from about 85 wt % to 100 wt %, from about 87 wt % to about 99 wt %, from about 87 wt % to about 95 wt %, from about 87 wt % to about 90 wt %, or any range or subrange therebetween. In further embodiments, the composition can comprise the reactive diluent ranging from about 75 wt % to 100 wt %, from about 75 wt % to about 99 wt %, from about 75 wt % to about 95 wt %, from about 75 wt % to about 90 wt %, from about 77 wt % to about 90 wt %, from about 80 wt % to about 90 wt %, from about 85 wt % to about 90 wt %, from about 87 wt % to about 90 wt %, or any range or subrange therebetween
[0416] In some embodiments, the composition can comprise a silane coupling agent. In further embodiments, the silane coupling agent can comprise a mercapto silane. In even further embodiments, silane coupling agent can comprise 3-mercaptopropyltrimethoxysilane (e.g., SIM6476.0 (Gelest)), 3-mercaptopropyltriethoxysilane (e.g., SIM6475. (Gelest)), 11-mercaptoundecyltrimethoxysilane (e.g., SIM6480.0 (Gelest)), (mercaptomethyl)methyldiethoxysilane (e.g., SIM6473.0 (Gelest)), and/or 3-mercaptopropylmethyldimethoxysilane (e.g., SIM6474.0 (Gelest)). An exemplary embodiment of the silane coupling agent comprises 3-mercaptopropyltrimethoxysilane. In some embodiments, the composition can comprise the silane coupling agent in a weight % (wt %) of about 0.1 wt % or more, about 0.2 wt % or more, about 0.5 wt % or more, about 5 wt % or less, about 2 wt % or less, or about 1 wt % or less. In some embodiments, the composition can comprise the silane coupling agent in a weight % (wt %) ranging from about 0.1 wt % to about 5 wt %, from about 0.1 wt % to about 2 wt %, from about 0.2 wt % to about 2 wt %, from about 0.2 wt % to about 1 wt %, from about 0.5 wt % to about 1 wt %, or any range or subrange therebetween.
[0417] In some embodiments, the composition can comprise a photo-initiator. As used herein a photo-initiator is a compound sensitive to one or more wavelengths that upon absorbing light comprising the one or more wavelengths undergoes a reaction to produce one or more radicals or ionic species that can initiate a polymerization reaction. In further embodiments, the photo-initiator may be sensitive to one or more wavelengths of ultraviolet (UV) light. Example embodiments of photo-initiators sensitive to UV light include without limitation benzoin ethers, benzil ketals, dialkoxyacetophenones, hydroxyalkylphenones, aminoalkylphenones, acylphosphine oxides, thioxanthones, hydroxyalkylketones, and thoxanthanamines. In further embodiments, the photo-initiator may be sensitive to one or more wavelengths of visible light. Example embodiments of photo-initiators sensitive to visible light include without limitation 5,7-diiodo-3-butoxy-6-fluorone, bis (4-methoxybenzoyl) diethylgermanium, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 3-methyl-4-aza-6-helicene, and thiocyanide borates. In further embodiments, the photo-initiator may be sensitive to a wavelength that the other components of the composition are substantially transparent at. As used herein, a compound (e.g., component of the composition) is substantially transparent at a predetermined wavelength if it comprises an average transmittance of 75% or more (e.g., 80% or more, 85% or more, or 90% or more, 92% or more, 94% or more, 96% or more) through a 1.0 mm thick piece of the compound at the predetermined wavelength. Providing a photo-initiator can enable controlled activation of curing of the composition. Providing a photo-initiator can enable uniform curing of the composition. In further embodiments, the photo-initiator may produce one or more radicals (e.g., free radicals). Example embodiments of photo-initiators producing one or more radicals include acetophenone, anisoin, anthraquinone, benzene, benzil, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin methyl ether, benzophenone, hydroxycyclohexyl phenyl ketone, 4-benzoylbiphernyl, camphorquinone, 2-chlorothioxanthen-9-one, bibezosuberenone, 2-,2-diethyoxyacetophenone, dimethylbenzil, ferrocene, ethylanthraquinone, hydroxyacetophenone, hydroxybenzophenone, thioxanthene-9-one, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and phophineoxide. Example embodiments of photo-initiators producing one or more ions include without limitation triarylsulfonium hexfluoroantimonate and bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate. Commercially available photo-initiators include without limitation the Irgacure product line from Ciba Specialty Chemical. Exemplary embodiments of photo-initiators include acetophenone-based compounds, for example, dimethoxyphenyl acetophenone. In some embodiments, the composition can comprise the photo-initiator in a weight % (wt %) of about 0.1 wt % or more, about 0.2 wt % or more, about 0.5 wt % or more, about 3 wt % or less, about 2 wt % or less, or about 1 wt % or less. In some embodiments, the composition can comprise the silane coupling agent in a weight % (wt %) ranging from about 0.1 wt % to about 3 wt %, from about 0.1 wt % to about 2 wt %, from about 0.2 wt % to about 2 wt %, from about 0.2 wt % to about 1 wt %, from about 0.5 wt % to about 1 wt %, or any range or subrange therebetween.
[0418] In some embodiments, the composition can comprise a catalyst. Without wishing to be bound by theory, a catalyst can increase a rate of the curing (e.g., polymerization, reaction), and the catalyst may avoid permanent chemical change as a result of the curing. In some embodiments, the catalyst can comprise one or more platinum group metals, for example, ruthenium, rhodium, palladium, osmium, iridium, and/or platinum. In some embodiments, the catalyst can comprise a platinum-based Karstedt' s catalyst solution. Exemplary embodiments of platinum-based catalysts include chloroplatinic acid, platinum-fumarate, colloidal platinum, metallic platinum, and/or platinum-nickel nanoparticles.
[0419] In some embodiments, the composition can comprise an elastomer. In some embodiments, the composition can comprise a thermoplastic elastomer, for example, a thermoplastic polyurethane, a thermoplastic polyamide, poly(dichlorophosphazene), a silicone-based rubber, and/or block copolymers. In some embodiments, the composition can comprise a block copolymer. Exemplary embodiments of block-copolymers include high-impact polystyrene, styrene-butadiene block copolymer, and styrene-ethylene-butylene-styrene block copolymer (e.g., Kraton G1650 (Kraton)). In some embodiments, the composition can comprise an elastomer in a weight % (wt %) of about 0.1 wt % or more, about 0.2 wt %, about 0.5 wt % or more, about 5 wt % or less, about 2 wt % or less, or about 1 wt % or less. In some embodiments, the composition can comprise the elastomer in a weight % (wt %) ranging from about 0.1 wt % to about 5 wt %, from about 0.1 wt % to about 2 wt %, from about 0.2 wt % to about 2 wt %, from about 0.2 wt % to about 1 wt %, from about 0.5 wt % to about 1 wt %, or any range or subrange therebetween.
[0420] In some embodiments, the composition can be substantially solvent-free. In further embodiments, the composition can be solvent-free. In even further embodiments, the composition can be entirely solvent-free. As used herein, a composition is entirely solvent-free if it only contains components that participate in the curing reaction and/or are considered a photo-initiator, or a catalyst based on the above discussion. As used herein, a composition is solvent-free if it contains 99.5 wt % or more components that participate in the curing reaction and/or are considered a photo-initiator, or a catalyst based on the above discussion. As used herein a composition is substantially solvent-free if it contains 98 wt % or more components that participate in the curing reaction and/or are considered a photo-initiator, or a catalyst based on the above discussion. For example, water and octanol are considered solvents. Solvents can comprise one or more of a polar solvent (e.g., water, an alcohol, an acetate, acetone, formic acid, dimethylformamide, acetonitrile, dimethyl sulfoxone, nitromethane, propylene carbonate, poly(ether ether ketone)) or a non-polar solvent (e.g., pentane, 1,4-dioxane, chloroform, dichloromethane, diethyl ether, hexane, heptane, benzene, toluene, xylene). For example, a composition comprising up to 0.5 wt % solvent is considered to be both substantially solvent-free and solvent-free. Likewise, a composition containing no solvent is considered to be substantially solvent-free, solvent-free, and entirely solvent-free. Providing a composition that is substantially solvent-free (e.g., entirely solvent-free) can increase the curing rate of the composition, which can decrease processing time. Providing a composition that is substantially solvent-free (e.g., entirely solvent-free) can reduce (e.g. decrease, eliminate) the use of additives, for example, rheology modifiers, and increase composition homogeneity, which can improve the quality of the resulting polymer-based portion (e.g., increased transmittance, decreased haze, increased mechanical properties). In some embodiments, the composition can comprise the photo-initiator in a weight % (wt %) of about 0.1 wt % or more, about 0.2 wt % or more, about 0.5 wt % or more, about 3 wt % or less, about 2 wt % or less, or about 1 wt % or less. In some embodiments, the composition can comprise the silane coupling agent in a weight % (wt %) ranging from about 0.1 wt % to about 3 wt %, from about 0.1 wt % to about 2 wt %, from about 0.2 wt % to about 2 wt %, from about 0.2 wt % to about 1 wt %, from about 0.5 wt % to about 1 wt %, or any range or subrange therebetween.
[0421] Methods of forming the polymer-based portion can comprise curing the composition to form the polymer-based portion. In some embodiments, curing the composition to form the polymer-based portion can comprise heating, ultraviolet (UV) irradiation, and/or waiting for a predetermined period of time. In some embodiments where the composition comprises a photo-initiator, curing can comprise irradiating the composition with at least one wavelength of light that the photo-initiator is sensitive to. In some embodiments, the irradiating can comprise impinging the composition with a light beam emitted from a light source. In further embodiments, the light source can be configured to emit a light beam comprising an ultra-violet (UV) wavelength or a visible wavelength. In even further embodiments, the wavelength of the light beam can be in a range from about 10 nm to about 400 nm, from about 100 nm to about 400 nm, from about 200 nm to about 400 nm, from about 10 nm to about 300 nm, from about 100 nm to about 300 nm, from about 200 nm to about 300 nm, from about 10 nm to about 200 nm, from about 100 nm to about 200 nm, or any range or subrange therebetween. In even further embodiments, an operating wavelength range of the light source may be over a range of optical wavelengths from about 315 nm to about 400 nm, from about 280 nm to about 315 nm, from about 100 nm to about 280 nm, or from 122 nm to about 200 nm. In even further embodiments, the wavelength of the light beam can be in a range from about 300 nm to about 1,000 nm, from about 350 nm to about 900 nm, from about 400 to about 800 nm, from about 500 nm to about 700 nm, or any range or subrange therebetween. In still further embodiments, the wavelength of the light beam can be about 365 nm, about 415 nm, or about 590 nm.
[0422] In some embodiments, curing can comprise heating the composition at a temperature for a time. As used herein, heating a composition “at a temperature” means that the composition is exposed to the temperature, for example, by being placed in an oven. In further embodiments, the temperature can be about 80° C. or more, about 100° C. or more, about 120° C. or more, about 140° C. or more, about 250° C. or less, about 200° C. or less, about 180° C. or less, or about 160° C. or less. In further embodiments, the temperature can be in a range from about 80° C. to about 250° C., from about 80° C. to about 200° C., from about 100° C. to about 200° C., from about 100° C. to about 180° C., from about 120° C. to about 180° C., from about 120° C. to about 160° C., from about 140° C. to about 160° C., or any range or subrange therebetween. In further embodiments, the time can be about 15 minutes or more, about 30 minutes or more, 1 hour or more about 12 hours or less, about 6 hours or less, about 3 hours or less, or about 2 hours or less. In further embodiments, the time can be in a range from about 15 minutes to about 12 hours, from about 15 minutes to about 6 hours, from about 15 minutes to about 3 hours, from about 30 minutes to about 3 hours, from about 1 hour to about 3 hours, from about 1 hour to about 2 hours, or any range or subrange therebetween.
[0423] In some embodiments, curing the composition to form the polymer-based material can result in a volume change of the polymer-based portion relative to a volume of the composition. In further embodiments, a magnitude of a difference of the volume the polymer-based portion relative to the volume of the composition as a percentage of the volume of the composition can be about 5% or less, about 2% or less, about 1% or less, about 0.5% or less, about 0.1% or less, about 0.01% or more, about 0.1% or more, about 0.5% or more, about 1% or more. In further embodiments, a magnitude of a difference of the volume the polymer-based portion relative to the volume of the composition as a percentage of the volume of the composition can be in a range from 0% to about 5%, from 0% to about 2%, from 0% to about 1%, from 0.01% to about 1%, from about 0.1% to about 1%, from about 0.5% to about 1%, from about 0.01% to about 5%, from about 0.01% to about 2%, from about 0.1% to about 2%, from about 0.5% to about 2%, or any range or subrange therebetween.
[0424] It is to be understood that any of the above ranges for the above-mentioned components can be combined in embodiments of the disclosure. Example ranges of some embodiments of the disclosure are presented in Table 1. R1 and R5 are the broadest of the ranges in Table 1 while R3-R4 and R8 are the narrowest ranges of the ranges in Table 1. R2 and R6-R7 represent intermediate ranges. R1-R4 comprise a difunctional cross-linking agent, R3 and R5-R8 comprise a reactive diluent, and R1-R2 can optionally include a reactive diluent. Again, it is to be understood that other ranges or subranges discussed above for these components can be used in combination with any of the ranges presented in Table 1.
TABLE-US-00001 TABLE 1 Composition ranges (wt %) of embodiments of polymer-based portions Range R1 R2 R3 R4 R5 R6 R7 R8 Difunctional 45-75 47-65 47-55 55-65 0-25 0 1-25 1-25 Urethane-Acrylate Oligomer Difunctional 25-55 25-45 25-45 35-45 0-1 0 0.1-1.sup. 0-1 Cross-linking Agent Reactive Diluent 0-25 0-20 17-25 0 75-100 87-100 75-100 77-99 Photo-initiator 0-3 0.1-3.sup. 0-3 0.1-3.sup. 0-3 0-3 0-3 0.1-3.sup. Silane Coupling 0-5 1.5-3.sup. 0-5 0-5 0-5 0-5 0-5 1.5-3.sup. Agent Elastomer 0-5 0-5 0-5 0-5 0-5 0-5 0-5 0-5
[0425] Embodiments of the disclosure can comprise adhesives. In some embodiments, an index of refraction of the adhesive may be about 1.4 or more, about 1.45 or more, about 1.49 or more, about 1.50 or more, about 1.53 or more, about 1.6 or less, about 1.55 or less, about 1.54 or less, or about 1.52 or less. In some embodiments, the index of refraction of the adhesive can be in a range from about 1.4 to about 1.6, from about 1.45 to about 1.6, from about 1.45 to about 1.55, from about 1.49 to about 1.55, from about 1.50 to about 1.55, from about 1.53 to about 1.55, from about 1.49 to about 1.54, from about 1.49 to about 1.52, or any range or subrange therebetween.
[0426] In some embodiments, the adhesive can be optically transparent. In further embodiments, the adhesive can comprise an average transmittance (i.e., measured over optical wavelengths in a range from 400 nm to 700 nm by measuring the transmittance of whole number wavelengths from about 400 nm to about 700 nm and averaging the measurements) of about 90% or more, about 94% or more, about 95% or more, about 96% or more, 100% or less, about 99% or less, about 98% or less, or about 97% or less. In further embodiments, the adhesive can comprise an average transmittance measured over optical wavelengths in a range from 400 nm to 700 nm in a range from about 90% to 100%, from about 94% to 100%, from about 95% to 100%, from about 95% to about 99%, from about 95% to about 98%, from about 96% to about 98%, from about 96% to about 97%, or any range or subrange therebetween.
[0427] The adhesive can comprise a haze as a function of an angle of illumination relative to a direction normal to a surface of the adhesive. In some embodiments, the haze at about 0° and/or 10° relative to an angle of incidence normal to the surface of the adhesive measured through a 1.0 mm thick piece of the adhesive can be about 1% or less, about 0.5% or less, about 0.2% or less, about 0.1% or less, or about 0.01% or more, or about 0.05% or more. In some embodiments, the haze at about 0° and/or 10° relative to an angle of incidence normal to the surface of the adhesive measured through a 1.0 mm thick piece of the adhesive can be in a range from 0% to about 1%, from 0% to 0.5%, from 0% to 0.2%, from about 0.01% to about 0.2%, from about 0.05% to about 0.2%, from about 0.05% to about 0.1%, or any range or subrange therebetween. In some embodiments, the haze at about 20° relative to an angle of incidence normal to the surface of the adhesive can be within one or more of the ranges specified above for 0° and/or 10°. Providing an adhesive comprising low haze can enable good visibility through adhesive.
[0428] The adhesive can comprise a glass transition (Tg) temperature. In some embodiments, the glass transition temperature of the adhesive can be about −40° C. or less, about −60° C. or less, about −70° C. or less, about −130° C. or more, or about −120° C. or more, about −100° C. or more, or about −80° C. or more, or about −75° C. or more. In some embodiments, the glass transition temperature of the adhesive can in a range from about −130° C. to about −40° C., from about −130° C. to about −60° C., from about −120° C. to about −60° C., from about −100° C. to about −60° C., from about −100° C. to about −70° C., from about −80° C. to about −70° C., from about −75° C. to about −70° C., or any range or subrange therebetween. Providing an adhesive with a glass transition temperature outside of an operating range (e.g., outside of an operating range from about 0° C. to about 40° C., or outside of an operating range from about −20° C. to about 60° C.) can enable consistent properties across the operating range.
[0429] In some embodiments, the adhesive can comprise a storage modulus (i.e., modulus of elasticity) of about 1 MPa or more, about 2 MPa or more, about 5 MPa or more, about 5 MPa or more, about 25 MPa or less, about 20 MPa or less, about 15 MPa or less, or about 11 MPa or less. In some embodiments, the adhesive can comprise a storage modulus in a range from about 1 MPa to about 25 MPa, from about 1 MPa to about 20 MPa, from about 2 MPa to about 20 MPa, from about 2 MPa to about 15 MPa, from about 2 MPa to about 11 MPa, from about 3 MPa to about 11 MPa, from about 5 MPa to about 11 MPa, or any range or subrange therebetween.
[0430] In some embodiments, the adhesive can comprise a loss modulus of about 0.1 kPa or more, about 0.2 kPa or more, about 0.5 kPa or more, about 3 kPa or less, about 2 kPa or less, or about 1 kPa or less. In some embodiments, the adhesive can comprise a loss modulus in a range from about 0.1 kPa to about 3 kPa, from about 0.2 kPa to about 3 kPa, from about 0.2 kPa to about 2 kPa, from about 0.2 kPa to about 1 kPa, from about 0.5 kPa to about 1 kPa, or any range or subrange therebetween.
[0431] Throughout the disclosure, a tensile strength, ultimate elongation (e.g., strain at failure), and yield point of the adhesive and other materials is determined using ASTM D638 using a tensile testing machine, for example, an Instron 3400 or Instron 6800, at 23° C. and 50% relative humidity with a type I dogbone shaped sample. In some embodiments, a tensile strength of the adhesive can be about 1 MPa, about 3 MPa or more, about 10 MPa or more, about 50 MPa or less, about 35 MPa or less, about 25 MPa or less, or about 10 MPa or less. In some embodiments, a tensile strength of the adhesive can be in a range from about 1 MPa to about 50 MPa, from about 3 MPa to about 50 MPa, from about 3 MPa to about 35 MPa, from about 5 MPa to about 35 MPa, from about 10 MPa to about 35 MPa, from about 10 MPa to about 25 MPa, from about 1 MPa to about 10 MPa, or any range or subrange therebetween.
[0432] In some embodiments, an ultimate elongation of the adhesive can be about 50% or more, about 75% or more, about 100% or more, about 300% or more, about 1,000% or less, about 700% or less, or about 400% or less. In some embodiments, an ultimate elongation of the adhesive can be in a range from about 50% to about 1,000%, from about 50% to about 750%, from about 75% to about 700%, from about 100% to about 700%, from about 300% to about 700%, from about 300% to about 400%, or any range or subrange therebetween.
[0433] In some embodiments, an elastic modulus of the adhesive can be about 1 MPa or more, about 10 MPa or more, about 25 MPa or more, about 40 MPa or more, about 100 MPa or less, about 75 MPa or less, or about 60 MPa or less. In some embodiments, an elastic modulus of the adhesive can be in a range from about 1 MPa to about 100 MPa, from about 1 MPa to about 75 MPa, from about 10 MPa to about 75 MPa, from about 25 MPa to about 75 MPa, from about 25 MPa to about 60 MPa, from about 40 MPa to about 60 MPa, or any range or subrange therebetween.
[0434] Haze and transmittance of the adhesives can be evaluated as included in a shattered pane. The shattered pane (described below) can comprise the adhesive positioned between at least an adjacent pair of the plurality of shattered pieces comprising the shattered pane. As used herein, the transmittance and haze of the adhesive included in an apparatus comprising the shattered pane comprises the shattered pane comprising a 1 mm thick glass-based substrate comprising Composition 1 (see below) and a second material comprising a thickness of 75 μm comprising the material listed in parenthesis. Unless indicated otherwise, the second material comprises KrystalFlex PESOS available from Huntsman for measuring the transmittance and haze of the adhesive included in an apparatus comprising the shattered pane. In some embodiments, the average transmittance of the adhesive included in an apparatus comprising the shattered pane can be about 80% or more, about 85% or more, about 90% or more, about 99% or less, about 95% or less, or about 93% or less. In some embodiments, the average transmittance of the adhesive included in an apparatus comprising the shattered pane can be in a range from about 80% to about 99%, from about 85% to about 99%, from about 85% to about 95%, from about 90% to about 95%, from about 90% to about 93%, or any range or subrange therebetween. In some embodiments, the haze of the adhesive included in an apparatus comprising the shattered pane can be about 40% or less, about 35% or less, about 30% or less, about 25% or less, about 0.1% or more, about 1% or more, about 5% or more, about 10% or more or about 20% or more. In some embodiments, the haze of the adhesive included in an apparatus comprising the shattered pane can be in a range from about 0.1% to about 40%, from about 1% to about 40%, from about 1% to about 35%, from about 5% to about 35%, from about 5% to about 30%, from about 10% to about 30%, from about 10% to about 25%, from about 20% to about 25%, or any range or subrange therebetween.
[0435] The adhesive described above can be formed as the product of curing a composition. Methods of forming the adhesive described above will now be described.
[0436] Methods of forming the adhesive can comprise creating a composition. In some embodiments, the composition can comprise a silane-hydride-terminated siloxane. Exemplary embodiments of silane-hydride-terminated siloxanes include phenylmethylsiloxane (e.g., HPM-502 (Gelest)) and poly(phenylmethylsiloxane) (e.g., PMS-H11 (Gelest)). In some embodiments, the composition can comprise the silane-hydride terminated siloxane in a weight % (wt %) of about 10% or more, about 20% or more, about 25 wt % or more, about 27 wt %, about 29 wt % or more, about 35 wt % or less, about 33 wt % or less, or about 31 wt % or less. In some embodiments, the composition can comprise the silane-hydride terminated siloxane in a weight % (wt %) ranging from about 10 wt % to about 35 wt %, from about 20 wt % to about 35 wt %, from about 25 wt % to about 35 wt %, from about 25 wt % to about 33 wt %, from about 27 wt % to about 33 wt %, from about 27 wt % to about 31 wt %, from about 29 wt % to about 31 wt %, or any range or subrange therebetween.
[0437] In some embodiments, the composition can comprise a vinyl-terminated siloxane. In some embodiments, the vinyl-terminated siloxane can comprise three or more vinyl-terminated ends, for example, a vinyl T-structure siloxane polymer (e.g., MTV-112 (Gelest)). In some embodiments, the vinyl-terminated siloxane can comprise a short (e.g., 10 carbons or less), vinyl-terminated alkyl chain, for example, vinyltrimethoxysilane. In some embodiments, the vinyl-terminated siloxane can comprise a copolymer, including terpolymers. In further embodiments, the vinyl-terminated siloxane copolymer can comprise a copolymer comprising diphenyl siloxane and/or a copolymer comprising dimethyl siloxane. Exemplary embodiments of vinyl-terminated siloxane copolymers include vinyl-terminated dimethylsiloxane copolymer (e.g., PDV-2331 (Gelest)) and a vinyl-methylsiloxane-phenylmethylsiloxane-dimethylsiloxane terpolymer (e.g., VPT-1323 (Gelest). In some embodiments, the composition can comprise the vinyl-terminated siloxane in a weight % (wt %) of about 65 wt % or more, about 67 wt % or more, about 69 wt % or more, about 90 wt % or less, about 80 wt % or less, about 75% or less, about 73% or less, or about 71% of less. In some embodiments, the composition can comprise the vinyl-terminated siloxane in a weight % (wt %) ranging from about 65 wt % to about 90 wt %, from about 65 wt % to about 80 wt %, from about 65 wt % to about 75 wt %, from about 67 wt % to about 75 wt %, from about 67 wt % to about 73 wt %, from about 69 wt % to about 73 wt %, from about 69 wt % to about 71 wt %, or any range or subrange therebetween.
[0438] In some embodiments, the composition can comprise a thiol-containing siloxane. An exemplary embodiment of a thiol-containing siloxane includes (mercaptopropyl)methylsiloxane (e.g., SMS 922 (Gelest)). In some embodiments, the composition can comprise the thiol-containing siloxane in a weight % (wt %) of about 10 wt % or more, about 20 wt % or more, about 25 wt % or more, about 27 wt %, about 29 wt % or more, about 35 wt % or less, about 33 wt % or less, or about 31 wt % or less. In some embodiments, the composition can comprise the thiol-containing siloxane in a weight % (wt %) ranging from about 10 wt % to about 35 wt %, from about 20 wt % to about 35 wt %, from about 25 wt % to about 35 wt %, from about 25 wt % to about 33 wt %, from about 27 wt % to about 33 wt %, from about 27 wt % to about 31 wt %, from about 29 wt % to about 31 wt %, or any range or subrange therebetween. In some embodiments, the composition can comprise the thiol-containing siloxane in a weight % (wt %) of about 90 wt % or more, about 95 wt % or more, 98 wt % or more, or 100 wt % or less. In some embodiments, the composition can comprise the thiol-containing siloxane in a weight % (wt %) in a range from about 10 wt % to 100 wt %, from about 25 wt % to 100 wt %, from about 90 wt % to 100 wt %, from about 95 wt % to 100 wt %, from about 98 wt % to 100 wt %, or any range or subrange therebetween.
[0439] In some embodiments, the composition can comprise a silane coupling agent. In further embodiments, the silane coupling agent can comprise 3-mercaptopropyltrimethoxysilane, (3-mercaptopropyl)methyldimethoxysilane, tertaethylorthosilicate, tetraethylmethoxysilane, 3-mercaptopropyltriethoxysilane, (3-mercaptopropyl)methyldiethoxysilane, tertaethylorthosilicate, and/or tetraethylethoxysilane. An exemplary embodiment of the silane coupling agent comprises 3-mercaptopropyltrimethoxysilane. In some embodiments, the composition can comprise the silane coupling agent in a weight % (wt %) of about 0.1 wt % or more, about 0.2 wt % or more, about 0.5 wt % or more, about 5 wt % or less, about 2 wt % or less, or about 1 wt % or less. In some embodiments, the composition can comprise the silane coupling agent in a weight % (wt %) ranging from about 0.1 wt % to about 5 wt %, from about 0.1 wt % to about 2 wt %, from about 0.2 wt % to about 2 wt %, from about 0.2 wt % to about 1 wt %, from about 0.5 wt % to about 1 wt %, or any range or subrange therebetween.
[0440] In some embodiments, the composition can comprise a photo-initiator. The photo-initiator can comprise one or more of the photo-initiators discussed above with regards to the composition for the polymer-based portion. Exemplary embodiments of photo-initiators include acetophenone-based compounds, for example, dimethoxyphenyl acetophenone. In some embodiments, the composition can comprise the photo-initiator in a weight % (wt %) of about 0.1 wt % or more, about 0.2 wt % or more, about 0.5 wt % or more, about 3 wt % or less, about 2 wt % or less, or about 1 wt % or less. In some embodiments, the composition can comprise the silane coupling agent in a weight % (wt %) ranging from about 0.1 wt % to about 3 wt %, from about 0.1 wt % to about 2 wt %, from about 0.2 wt % to about 2 wt %, from about 0.2 wt % to about 1 wt %, from about 0.5 wt % to about 1 wt %, or any range or subrange therebetween.
[0441] In some embodiments, the composition can comprise a catalyst. In some embodiments, the catalyst can comprise one or more platinum group metals, for example, ruthenium, rhodium, palladium, osmium, iridium, and/or platinum. In some embodiments, the catalyst can comprise a platinum-based Karstedt's catalyst solution. Exemplary embodiments of platinum-based catalysts include chloroplatinic acid, platinum-fumarate, colloidal platinum, metallic platinum, and/or platinum-nickel nanoparticles. In some embodiments, the composition can comprise the photo-initiator in a weight % (wt %) of about 0.1 wt % or more, about 0.2 wt % or more, about 0.5 wt % or more, about 3 wt % or less, about 2 wt % or less, or about 1 wt % or less. In some embodiments, the composition can comprise the silane coupling agent in a weight % (wt %) ranging from about 0.1 wt % to about 3 wt %, from about 0.1 wt % to about 2 wt %, from about 0.2 wt % to about 2 wt %, from about 0.2 wt % to about 1 wt %, from about 0.5 wt % to about 1 wt %, or any range or subrange therebetween.
[0442] In some embodiments, the composition can be substantially solvent-free. In further embodiments, the composition can be solvent-free. In even further embodiments, the composition can be entirely solvent-free. Providing a composition that is substantially solvent-free (e.g., entirely solvent-free) can reduce (e.g. decrease, eliminate) the use of additives, for example, rheology modifiers, and increase composition homogeneity, which can improve the quality of the resulting adhesive (e.g., increased transmittance, decreased haze, increased mechanical properties).
[0443] Methods of forming the adhesive can comprise curing the composition to form the adhesive. In some embodiments, curing the composition to form the adhesive can comprise heating, ultraviolet (UV) irradiation, and/or waiting for a predetermined period of time. In some embodiments where the composition comprises a photo-initiator, curing can comprise irradiating the composition with at least one wavelength of light that the photo-initiator is sensitive to. In some embodiments, the irradiating can comprise impinging the composition with a light beam emitted from a light source. In further embodiments, the light source can be configured to emit a light beam comprising an ultra-violet (UV) wavelength or a visible wavelength. In even further embodiments, the wavelength of the light beam can be in a range from about 10 nm to about 400 nm, from about 100 nm to about 400 nm, from about 200 nm to about 400 nm, from about 10 nm to about 300 nm, from about 100 nm to about 300 nm, from about 200 nm to about 300 nm, from about 10 nm to about 200 nm, from about 100 nm to about 200 nm, or any range or subrange therebetween. In even further embodiments, an operating wavelength range of the light source may be over a range of optical wavelengths from about 315 nm to about 400 nm, from about 280 nm to about 315 nm, from about 100 nm to about 280 nm, or from 122 nm to about 200 nm. In even further embodiments, the wavelength of the light beam can be in a range from about 300 nm to about 1,000 nm, from about 350 nm to about 900 nm, from about 400 to about 800 nm, from about 500 nm to about 700 nm, or any range or subrange therebetween. In still further embodiments, the wavelength of the light beam can be about 365 nm, about 415 nm, or about 590 nm.
[0444] In some embodiments, curing can comprise heating the composition at a temperature for a time. In further embodiments, the temperature can be about 80° C. or more, about 100° C. or more, about 120° C. or more, about 140° C. or more, about 250° C. or less, about 200° C. or less, about 180° C. or less, or about 160° C. or less. In further embodiments, the temperature can be in a range from about 80° C. to about 250° C., from about 80° C. to about 200° C., from about 100° C. to about 200° C., from about 100° C. to about 180° C., from about 120° C. to about 180° C., from about 120° C. to about 160° C., from about 140° C. to about 160° C., or any range or subrange therebetween. In further embodiments, the time can be about 15 minutes or more, about 30 minutes or more, 1 hour or more about 12 hours or less, about 6 hours or less, about 3 hours or less, or about 2 hours or less. In further embodiments, the time can be in a range from about 15 minutes to about 12 hours, from about 15 minutes to about 6 hours, from about 15 minutes to about 3 hours, from about 30 minutes to about 3 hours, from about 1 hour to about 3 hours, from about 1 hour to about 2 hours, or any range or subrange therebetween.
[0445] In some embodiments, curing the composition to form the adhesive can result in a volume change of the adhesive relative the composition. In further embodiments, a magnitude of a difference of the volume the adhesive relative the composition as a percentage of the volume of the composition can be about 5% or less, about 2% or less, about 1% or less, about 0.5% or less, about 0.1% or less, about 0.01% or more, about 0.1% or more, about 0.5% or more, about 1% or more. In further embodiments, a magnitude of a difference of the volume the adhesive relative the composition as a percentage of the volume of the composition can be in a range from 0% to about 5%, from 0% to about 2%, from 0% to about 1%, from 0.01% to about 1%, from about 0.1% to about 1%, from about 0.5% to about 1%, from about 0.01% to about 5%, from about 0.01% to about 2%, from about 0.1% to about 2%, from about 0.5% to about 2%, or any range or subrange therebetween.
[0446] It is to be understood that any of the above ranges for the above-mentioned components can be combined in embodiments of the disclosure. Example ranges of some embodiments of the disclosure are presented in Table 2. R10 and R13 are the broadest of the ranges in Table 2 while R12, R14, and R16 are the narrowest ranges of the ranges in Table 2. R11 and R15 represent intermediate ranges. R10-R13 comprise a silane-hydride-terminated siloxane, R10-12 and R15-R16 comprise a vinyl-terminated siloxane, R13-R16 comprise a thiol-containing siloxane, and R13 can optionally include a vinyl-terminated siloxane. Again, it is to be understood that other ranges or subranges discussed above for these components can be used in combination with any of the ranges presented in Table 2.
TABLE-US-00002 TABLE 2 Composition ranges (wt %) of embodiments of polymer-based portions Range R10 R11 R12 R13 R14 R15 R16 Silane- 10-35 25-35 10-25 0 0 0 0 hydride- terminated Siloxane Vinyl- 65-90 65-75 75-90 0-90 0 65-90 65-75 terminated Siloxane Thiol- 0 0 0 10-100 90-100 10-35 25-35 containing Siloxane Photo- 0-3 0-3 0-3 0-3 0-3 0-3 0-3 initiator Catalyst 0-3 0-3 0-3 0-3 0-3 0-3 0-3 Silane 0-5 0-5 0-5 0-5 0-5 0-5 0-5 Coupling Agent
[0447]
[0448] In some embodiments, as shown in
[0449] In some embodiments, as shown in
[0450] In some embodiments, as shown in
[0451] Throughout the disclosure, with reference to
[0452] Foldable apparatus 101, 301, 401, 501, 601, 701, 801, 901, 1001, 1402, 1501, 1701, and 1801 the disclosure can comprise a foldable substrate 201 or 803. In some embodiments, the foldable substrate 201 or 803 can comprise a glass-based substrate and/or a ceramic-based substrate having a pencil hardness of 8H or more, for example, 9H or more.
[0453] In some embodiments, the foldable substrate 201 or 803 can comprise a glass-based substrate. As used herein, “glass-based” includes both glasses and glass-ceramics, wherein glass-ceramics have one or more crystalline phases and an amorphous, residual glass phase. A glass-based material (e.g., glass-based substrate) may comprise an amorphous material (e.g., glass) and optionally one or more crystalline materials (e.g., ceramic). Amorphous materials and glass-based materials may be strengthened. As used herein, the term “strengthened” may refer to a material that has been chemically strengthened, for example, through ion-exchange of larger ions for smaller ions in the surface of the substrate, as discussed below. However, other strengthening methods known in the art, for example, thermal tempering, or utilizing a mismatch of the coefficient of thermal expansion between portions of the substrate to create compressive stress and central tension regions, may be utilized to form strengthened substrates. Exemplary glass-based materials, which may be free of lithia or not, comprise soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, alkali-containing aluminoborosilicate glass, alkali-containing phosphosilicate glass, and alkali-containing aluminophosphosilicate glass. In one or more embodiments, a glass-based material may comprise, in mole percent (mol %): SiO.sub.2 in a range from about 40 mol % to about 80%, Al.sub.2O.sub.3 in a range from about 5 mol % to about 30 mol %, B.sub.2O.sub.3 in a range from 0 mol % to about 10 mol %, ZrO.sub.2 in a range from 0 mol % to about 5 mol %, P.sub.2O.sub.5 in a range from 0 mol % to about 15 mol %, TiO.sub.2 in a range from 0 mol % to about 2 mol %, R.sub.2O in a range from 0 mol % to about 20 mol %, and RO in a range from 0 mol % to about 15 mol %. As used herein, R.sub.2O can refer to an alkali metal oxide, for example, Li.sub.2O, Na.sub.2O, K.sub.2O, Rb.sub.2O, and Cs.sub.2O. As used herein, RO can refer to MgO, CaO, SrO, BaO, and ZnO. In some embodiments, a glass-based substrate may optionally further comprise in a range from 0 mol % to about 2 mol % of each of Na.sub.2SO.sub.4, NaCl, NaF, NaBr, K.sub.2SO.sub.4, KCl, KF, KBr, As.sub.2O.sub.3, Sb.sub.2O.sub.3, SnO.sub.2, Fe.sub.2O.sub.3, MnO, MnO.sub.2, MnO.sub.3, Mn.sub.2O.sub.3, Mn.sub.3O.sub.4, Mn.sub.2O.sub.7. “Glass-ceramics” include materials produced through controlled crystallization of glass. In some embodiments, glass-ceramics have about 1% to about 99% crystallinity. Examples of suitable glass-ceramics may include Li.sub.2O—Al.sub.2O.sub.3—SiO.sub.2 system (i.e. LAS-System) glass-ceramics, MgO—Al.sub.2O.sub.3—SiO.sub.2 system (i.e. MAS-System) glass-ceramics, ZnO×Al.sub.2O.sub.3×nSiO.sub.2 (i.e. ZAS system), and/or glass-ceramics that include a predominant crystal phase including β-quartz solid solution, β-spodumene, cordierite, petalite, and/or lithium disilicate. The glass-ceramic substrates may be strengthened using the chemical strengthening processes. In one or more embodiments, MAS-System glass-ceramic substrates may be strengthened in Li.sub.2SO.sub.4 molten salt, whereby an exchange of 2Li.sup.+ for Mg.sup.2+ can occur.
[0454] In some embodiments, the foldable substrate 201 or 803 can comprise a ceramic-based substrate. As used herein, “ceramic-based” includes both ceramics and glass-ceramics, wherein glass-ceramics have one or more crystalline phases and an amorphous, residual glass phase. Ceramic-based materials may be strengthened (e.g., chemically strengthened). In some embodiments, a ceramic-based material can be formed by heating a glass-based material to form ceramic (e.g., crystalline) portions. In further embodiments, ceramic-based materials may comprise one or more nucleating agents that can facilitate the formation of crystalline phase(s). In some embodiments, the ceramic-based materials can comprise one or more oxide, nitride, oxynitride, carbide, boride, and/or silicide. Example embodiments of ceramic oxides include zirconia (ZrO.sub.2), zircon zirconia (ZrSiO.sub.4), an alkali metal oxide (e.g., sodium oxide (Na.sub.2O)), an alkali earth metal oxide (e.g., magnesium oxide (MgO)), titania (TiO.sub.2), hafnium oxide (Hf.sub.2O), yttrium oxide (Y.sub.2O.sub.3), iron oxide, beryllium oxide, vanadium oxide (VO.sub.2), fused quartz, mullite (a mineral comprising a combination of aluminum oxide and silicon dioxide), and spinel (MgAl.sub.2O.sub.4). Example embodiments of ceramic nitrides include silicon nitride (Si.sub.3N.sub.4), aluminum nitride (AlN), gallium nitride (GaN), beryllium nitride (Be.sub.3N.sub.2), boron nitride (BN), tungsten nitride (WN), vanadium nitride, alkali earth metal nitrides (e.g., magnesium nitride (Mg.sub.3N.sub.2)), nickel nitride, and tantalum nitride. Example embodiments of oxynitride ceramics include silicon oxynitride, aluminum oxynitride, and a SiAlON (a combination of alumina and silicon nitride and can have a chemical formula, for example, Si.sub.12°m°nAl.sub.m+nO.sub.nN.sub.16−n, Si.sub.6−nAl.sub.nO.sub.nN.sub.8−n, or Si.sub.2−nAl.sub.nO.sub.1+nN.sub.2−n, where m, n, and the resulting subscripts are all non-negative integers). Example embodiments of carbides and carbon-containing ceramics include silicon carbide (SiC), tungsten carbide (WC), an iron carbide, boron carbide (B.sub.4C), alkali metal carbides (e.g., lithium carbide (Li.sub.4C.sub.3)), alkali earth metal carbides (e.g., magnesium carbide (Mg.sub.2C.sub.3)), and graphite. Example embodiments of borides include chromium boride (CrB.sub.2), molybdenum boride (Mo.sub.2B.sub.5), tungsten boride (W.sub.2B.sub.5), iron boride, titanium boride, zirconium boride (ZrB.sub.2), hafnium boride (HfB.sub.2), vanadium boride (VB.sub.2), Niobium boride (NbB.sub.2), and lanthanum boride (LaB.sub.6). Example embodiments of silicides include molybdenum disilicide (MoSi.sub.2), tungsten disilicide (WSi.sub.2), titanium disilicide (TiSi.sub.2), nickel silicide (NiSi), alkali earth silicide (e.g., sodium silicide (NaSi)), alkali metal silicide (e.g., magnesium silicide (Mg.sub.2Si)), hafnium disilicide (HfSi.sub.2), and platinum silicide (PtSi).
[0455]
[0456] As shown in
[0457] As further shown in
[0458] As shown in
[0459] As also shown in
[0460] As discussed previously, as shown in
[0461] In some embodiments, as shown in
[0462] As shown in
[0463] As shown in
[0464] A width 230a of the first transition portion 227 can be defined between the shattered pane 231 or the plurality of panes 950 and the first portion 221 in the direction 106 of the length 105 of the foldable apparatus. A width 230b of the second transition portion 229 can be defined between the shattered pane 231 or the plurality of panes 950 and the second portion 223 in the direction 106 of the length 105 of the foldable apparatus. In some embodiments, the width 230a of the first transition portion 227 and/or the width 230b of the second transition portion 229 can be sufficiently large (e.g., 1 mm or more) to avoid optical distortions that may otherwise occur at a step transition or small transition width (e.g., less than 1 mm) between the first and central thickness. In some embodiments, the width 230a of the first transition portion 227 and/or the width 230b of the second transition portion 229 can be reduced (e.g., 5 millimeters (mm) or less) to minimize the extent that the transition portions that have a thickness in the vicinity of 65 μm (e.g., in a range from about 50 μm to about 80 μm), thereby enhancing the puncture resistance of a larger area of the foldable substrate. In some embodiments, to enhance puncture resistance of the foldable substrate while also avoiding optical distortions, the width 230a of the first transition portion 227 and/or the width 230b of the second transition portion 229 can be about 1 mm or more, about 2 mm or more, about 3 mm or more, about 5 mm or less, about 4 mm or less, or about 3 mm or less. In some embodiments, the width 230a of the first transition portion 227 and/or the width 230b of the second transition portion 229 can be in a range from about 1 mm to about 5 mm, from about 1 mm to about 4 mm, from about 1 mm to about 3 mm, from about 2 mm to about 5 mm, from about 2 mm to about 4 mm, from about 2 mm to about 3 mm, or any range or subrange therebetween.
[0465] As mentioned previously, as shown in
[0466] In some embodiments, a density of the plurality of shattered pieces 1305 in the shattered pane 231 can be about 5 pieces per square centimeter (pc/cm.sup.2) or more. As used herein, a density of shattered pieces is measured over a surface area (e.g., first central surface area, second central surface area) of the shattered pane comprising one of the first major surface, the second major surface, or the first central surface area of the foldable substrate, where the surface area is in a range from about 1 cm.sup.2 to about 5 cm.sup.2. As used herein, any portion of a shattered piece within the surface area measured counts as a whole shattered piece for the purposes of calculating the density of shattered pieces. In further embodiments, the shattered pane 231 can comprise at least a portion of the central portion 225 and the surface area can be at least a portion of the second central surface area 245.
[0467] In some embodiments, as shown in
[0468] In some embodiments, as shown in
[0469] In some embodiments, a shattered piece of the plurality of shattered pieces 1305 of the foldable substrate 201 or 803 can comprise a glass-based material and/or a ceramic-based material. In some embodiments, an elastic modulus of a shattered piece of the plurality of shattered pieces 1305 of the foldable substrate 201 or 803 can be about 1 GigaPascal (GPa) or more, about 3 GPa or more, about 5 GPa or more, about 10 GPa or more, about 100 GPa or less, about 90 GPa or less, about 80 GPa or less, about 70 GPa or less, about 60 GPa or less, or about 20 GPa or less. In some embodiments, an elastic modulus of a shattered piece of the plurality of shattered pieces 1305 of the foldable substrate 201 or 803 can be in a range from about 1 GPa to about 100 GPa, from about 1 GPa to about 90 GPa, from about 1 GPa to about 80 GPa, from about 3 GPa to about 80 GPa, from about 3 GPa to about 70 GPa, from about 3 GPa to about 60 GPa, from about 5 GPa to about 60 GPa, from about 5 GPa to about 20 GPa, from about 10 GPa to about 20 GPa, or any range or subrange therebetween. In further embodiments, the shattered piece can comprise a glass-based portion or a ceramic-based portion comprising an elastic modulus in a range from about 10 GPa to about 100 GPa, from about 40 GPa to about 100 GPa, from about 60 GPa to about 100 GPa, from about 60 GPa to about 80 GPa, from about 60 GPa to about 70 GPa, from about 70 GPa to about 100 GPa, from about 80 GPa to about 100 GPa, from about 80 GPa to about 90 GPa, or any range or subrange therebetween.
[0470] The shattered pane 231 will now be described with reference to the foldable apparatus 101 of
[0471] In some embodiments, a total mass of the first material 254 as a percentage of a total mass of the plurality of shattered pieces 1305 can be about 20% or less, about 15% or less, about 10% or less, about 8% or less, about 6% or less, about 5% or less, about 4% or less, about 2% or less, about 0.1% or more, about 0.5% or more, about 1% or more, about 2% or more, about 3% or more, or about 4% or more. In some embodiments, a total mass of the first material 254 as a percentage of a total mass of the plurality of shattered pieces 1305 can be in a range from about 0.1% to about 20%, from about 0.1% to about 15%, from about 0.5% to about 15%, from about 0.5% to about 10%, from about 1% to about 10%, from about 1% to about 8%, from about 2% to about 8%, from about 2% to about 6%, from about 3% to about 6%, from about 3% to about 5%, from about 4% to about 5%, or any range or subrange therebetween. In further embodiments, the total mass of the first material 254 as a percentage of the total mass of the plurality of shattered pieces 1305 can be in a range from about 0.1% to about 5%, from about 0.5% to about 5%, from about 1% to about 5%, from about 2% to about 5%, from about 3% to about 5%, from about 0.1% to about 4%, from about 0.1% to about 3%, from about 0.1% to about 2%, from about 0.1% to about 1%, from about 0.5% to about 1%, or any range or subrange therebetween. By minimizing a total mass of first material (e.g., about 10% or less of a total weight of the plurality of shattered pieces), scratch resistance, impact resistance, and/or puncture resistance of the foldable apparatus can be further improved. In some embodiments, the first material 254 can be substantially devoid of air pockets. In further embodiments, a total volume of air pockets within the total volume of the first material can be about 5% or less, about 2% or less, or about 1% or less.
[0472] In some embodiments, as shown in
[0473] As shown in
[0474] As shown in
[0475] Referring to
[0476] In some embodiments, a shattered piece of the plurality of panes 950 of the foldable substrate 201 can comprise a glass-based material and/or a ceramic-based material. In some embodiments, an elastic modulus of a shattered piece of the plurality of panes 950 of the foldable substrate 201 can be about 1 GigaPascal (GPa) or more, about 3 GPa or more, about 5 GPa or more, about 10 GPa or more, about 100 GPa or less, about 90 GPa or less, about 80 GPa or less, about 70 GPa or less, about 60 GPa or less, or about 20 GPa or less. In some embodiments, an elastic modulus of a shattered piece of the plurality of panes 950 of the foldable substrate 201 can be in a range from about 1 GPa to about 100 GPa, from about 1 GPa to about 90 GPa, from about 1 GPa to about 80 GPa, from about 3 GPa to about 80 GPa, from about 3 GPa to about 70 GPa, from about 3 GPa to about 60 GPa, from about 5 GPa to about 60 GPa, from about 5 GPa to about 20 GPa, from about 10 GPa to about 20 GPa, or any range or subrange therebetween. In further embodiments, the shattered pane of the plurality of panes 950 can comprise a glass-based portion or a ceramic-based portion comprising an elastic modulus in a range from about 10 GPa to about 100 GPa, from about 40 GPa to about 100 GPa, from about 60 GPa to about 100 GPa, from about 60 GPa to about 80 GPa, from about 60 GPa to about 70 GPa, from about 70 GPa to about 100 GPa, from about 80 GPa to about 100 GPa, from about 80 GPa to about 90 GPa, or any range or subrange therebetween.
[0477] In some embodiments, a total mass of the first material 254 as a percentage of a total mass of the plurality of panes 950 can be about 20% or less, about 15% or less, about 10% or less, about 8% or less, about 6% or less, about 5% or less, about 4% or less, about 2% or less, about 0.1% or more, about 0.5% or more, about 1% or more, about 2% or more, about 3% or more, or about 4% or more. In some embodiments, a total mass of the first material 254 as a percentage of a total mass of the plurality of panes 950 can be in a range from about 0.1% to about 20%, from about 0.1% to about 15%, from about 0.5% to about 15%, from about 0.5% to about 10%, from about 1% to about 10%, from about 1% to about 8%, from about 2% to about 8%, from about 2% to about 6%, from about 3% to about 6%, from about 3% to about 5%, from about 4% to about 5%, or any range or subrange therebetween. In further embodiments, the total mass of the first material 254 as a percentage of the total mass of the plurality of panes 950 can be in a range from about 0.1% to about 5%, from about 0.5% to about 5%, from about 1% to about 5%, from about 2% to about 5%, from about 3% to about 5%, from about 0.1% to about 4%, from about 0.1% to about 3%, from about 0.1% to about 2%, from about 0.1% to about 1%, from about 0.5% to about 1%, or any range or subrange therebetween. By minimizing a total mass of first material (e.g., about 10% or less of a total weight of the plurality of shattered pieces), scratch resistance, impact resistance, and/or puncture resistance of the foldable apparatus can be further improved. In some embodiments, the first material 254 can be substantially devoid of air pockets. In further embodiments, a total volume of air pockets within the total volume of the first material can be about 5% or less, about 2% or less, or about 1% or less.
[0478] In some embodiments, as shown in
[0479] Providing the thickness of the shattered pieces 1305 with the central thickness 226 within the ranges discussed above can help reduce stress concentrations of a first material 254 positioned between adjacent pairs of shattered pieces. In further embodiments, a reduced thickness of the shattered pieces 1305 can reduce the strain on the first material 254 positioned between corresponding outer edges 251 of pairs of adjacent shattered pieces 1305 to accommodate folding of the foldable apparatus about the fold axis 102. The reduced strain of the first material 254 can reduce the tensile force on the first material 254 positioned between the outer edges 251 that can reduce the probability of rupturing of the first material 254. Additionally, reducing the tensile force can reduce the stress at the bonding interface between the first material 254 and the shattered pieces 1305, thereby reducing the probability of delamination of the first material 254 from the shattered pieces 1305. Furthermore, due to the reduced tensile force and/or reduced stress at the bonding interface provided by the reduced thickness of the shattered pieces 1305, the types of materials suitable for use as the first material 254 can be broader than otherwise permitted because of the lower tensile force and/or lower stress provided by the reduced thickness of the shattered pieces 1305. These additional types of materials may have more desirable characteristics for use as a filler material between the shattered pieces 1305 that may not be available due to the higher tensile force and/or higher stress at the bonding interface that may result from using shattered pieces 1305 with a greater thickness (e.g., a thickness equal to the thickness of the first portion 221 and/or the thickness of the second portion 223).
[0480] Providing the thickness of the panes 950 with the central thickness 226 within the ranges discussed above can help reduce stress concentrations of material positioned between adjacent pairs of panes. Indeed, a reduced thickness of the panes 950 can reduce the strain on the first material 254 positioned between corresponding outer edges (e.g., side walls 5701 or 5801 shown in
[0481] In some embodiments, the elastic modulus of the first material 254 can be about 18 GigaPascals (GPa) or less at 23° C. For example, in some embodiments, the elastic modulus of the first material 254 at 23° C. can be about 0.01 MPa or more, about 0.1 MPa or more, about 1 MegaPascal (MPa) or more, about 30 MPa or more, about 100 MPa or more, 300 MPa or more, about 500 MPa or more, about 1,000 MPa or more, about 3,000 MPa or less, about 18,000 MPa or less, about 10,000 MPa or less, about 5,000 MPa or less, about 3,000 MPa or less, about 2,000 MPa or less, or about 1,000 MPa or less. In some embodiments, the elastic modulus of the first material 254 at 23° C. can be in a range from about 0.01 MPa to about 18,000 MPa, from about 0.01 MPa to about 10,000 MPa, from about 0.1 MPa to about 10,000 MPa, from about 0.1 MPa to about 5,000 MPa, from about 1 MPa to about 5,000 MPa, from about 1 MPa to about 3,000 MPa, from about 30 MPa to about 3,000 MPa, from about 30 MPa to about 1,000 MPa, from about 100 MPa to about 1,000 MPa, from about 300 MPa to about 1,000 MPa, from about 500 MPa to about 1,000 MPa, or any range or subrange therebetween. In some embodiments, the elastic modulus of the first material 254 can comprise a elastic modulus in a range from about 1,000 MPa to about 18,000 MPa, from about 1,000 MPa to about 10,000 MPa, from about 3,000 MPa to about 10,000 MPa, from about 3,000 MPa to about 5,000 MPa, from about 5,000 MPa to about 10,000 MPa, or any range or subrange therebetween. In some embodiments, the elastic modulus of the first material 254 at 23° C. can be in a range from about 1 MPa to about 500 MPa, from about 10 MPa to about 500 MPa, from about 10 MPa to about 400 MPa, from about 30 MPa to about 400 MPa, from about 30 MPa to about 300 MPa, from about 50 MPa to about 300 MPa, from about 100 MPa to about 300 MPa, from about 100 MPa to about 300 MPa, or any range or subrange therebetween.
[0482] In some embodiments, the first material 254 can comprise a polymeric material (e.g., optically transparent polymer, adhesive). In further embodiments, the first material 254 can comprise the adhesive described above. In further embodiments, the first material 254 can comprise one or more of a silicone-based polymer, an acrylate-based polymer, an epoxy-based polymer, a thiol-containing polymer, or a polyurethane. In even further embodiments, the silicone-based polymer can comprise a silicone elastomer. Exemplary embodiments of a silicone elastomer include PP2-0E50 available from Gelest and LS 8941 available from NuSil. In even further embodiments, the first material 254 can comprise one or more of an optically transparent: an acrylic (e.g., polymethylmethacrylate (PMMA)), an epoxy, a silicone, and/or a polyurethane. Examples of epoxies include bisphenol-based epoxy resins, novolac-based epoxies, cycloaliphatic-based epoxies, and glycidylamine-based epoxies. In further embodiments, the first material can comprise one or more of a polyolefin, a polyamide, a halide-containing polymer (e.g., polyvinylchloride or a fluorine-containing polymer), an elastomer, a urethane, phenolic resin, parylene, polyethylene terephthalate (PET), and polyether ether ketone (PEEK). Example embodiments of polyolefins include low molecular weight polyethylene (LDPE), high molecular weight polyethylene (HDPE), ultrahigh molecular weight polyethylene (UHMWPE), and polypropylene (PP). Example embodiments of fluorine-containing polymers include polytetrafluoroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), perfluoropolyether (PFPE), perfluorosulfonic acid (PFSA), a perfluoroalkoxy (PFA), fluorinated ethylene propylene (FEP) polymers, and ethylene tetrafluoro ethylene (ETFE) polymers. Example embodiments of elastomers include rubbers (e.g., polybutadiene, polyisoprene, chloroprene rubber, butyl rubber, nitrile rubber) and block copolymers (e.g., styrene-butadiene, high-impact polystyrene, poly(dichlorophosphazene)). In some embodiments, the first material 254 can comprise a sol-gel material.
[0483] In some embodiments, the first material 254 can comprise a polymer-based material comprising a glass-transition (Tg) temperature. Throughout the disclosure, a storage modulus (i.e., modulus of elasticity) and/or a loss modulus is measured for a polymeric material (e.g., polymer-based portion, adhesive) at 23° C. unless indicated otherwise. In further embodiments, the glass transition temperature of the first material 254 can be about 0° C. or less, about −20° C. or less, or about −40° C. or less. In further embodiments, the glass transition temperature of the first material 254 can be in a range from about −200° C. to about 0° C., from about −160° C. to about 0° C., from about −100° C. to about 0° C., from about −100° C. to about −20° C., from about −80° C. to about −20° C., from about −80° C. to about −40° C., or any range or subrange therebetween. In further embodiments, the glass transition temperature of the first material 254 can be about 40° C. or more, about 50° C. or more, about 60° C. or more, or about 70° C. or more. In further embodiments, the glass transition temperature of the first material 254 can be in a range from about 40° C. to about 250° C., from about 50° C. to about 220° C., from about 60° C. to about 200° C., from about 60° C. to about 180° C., from about 60° C. to about 150° C., from about 60° C. to about 120° C., from about 70° C. to about 100° C., or any range or subrange therebetween. Providing a first material with a glass transition temperature outside of an operating range (e.g., from about 0° C. to about 40° C., from about −20° C. to about 60° C.) of a foldable apparatus can enable the foldable apparatus to have consistent properties across the operating range.
[0484] Without wishing to be bound by theory, the elastic modulus can be substantially equal to or greater than the storage modulus (i.e., modulus of elasticity of a polymeric material). In some embodiments, a storage modulus of the first material 254 can change by a multiple of about 200 or less, about 100 or less, about 50 or less, about 20 or less, about 10 or less, or about 5 or less when a temperature of the first material 254 is changed from about 100° C. to about −20° C. In some embodiments, a storage modulus of the first material 254 can change when a temperature of the first material 254 is changed from about 100° C. to about −20° C. by a multiple in a range from about 1 to about 200, from about 5 to about 200, from about 10 to about 100, from about 20 to about 100, from about 50 to about 100, from about 1 to about 100, from about 1 to about 50, from about 1 to about 20, from about 1 to about 10, or any range or subrange therebetween.
[0485] In some embodiments, the first material 254 can comprise a polymer-based material comprising a glassy plateau. In further embodiment, the storage modulus (i.e., modulus of elasticity) of the first material 254 in the glassy plateau can be about 0.1 MPa or more, about 1 MPa or more, about 30 MPa or more, about 100 MPa or more, 300 MPa or more, about 500 MPa or more, about 1,000 MPa or more, about 3,000 MPa or less, about 18,000 MPa or less, about 10,000 MPa or less, about 5,000 MPa or less, about 3,000 MPa or less, about 2,000 MPa or less, or about 1,000 MPa or less. In some embodiments, the storage modulus of the first material 254 in the glassy plateau can be in a range from about 0.01 MPa to about 18,000 MPa, from about 0.01 MPa to about 10,000 MPa, from about 0.1 MPa to about 10,000 MPa, from about 0.1 MPa to about 5,000 MPa, from about 1 MPa to about 5,000 MPa, from about 1 MPa to about 3,000 MPa, from about 30 MPa to about 3,000 MPa, from about 30 MPa to about 1,000 MPa, from about 100 MPa to about 1,000 MPa, from about 300 MPa to about 1,000 MPa, from about 500 MPa to about 1,000 MPa, or any range or subrange therebetween. In some embodiments, the storage modulus of the first material 254 in the glassy plateau can be in a range from about 1,000 MPa to about 18,000 MPa, from about 1,000 MPa to about 10,000 MPa, from about 3,000 MPa to about 10,000 MPa, from about 3,000 MPa to about 5,000 MPa, from about 5,000 MPa to about 10,000 MPa, or any range or subrange therebetween. In some embodiments, the storage modulus of the first material 254 in the glassy plateau can be can be in a range from about 1 MPa to about 500 MPa, from about 10 MPa to about 500 MPa, from about 10 MPa to about 400 MPa, from about 30 MPa to about 400 MPa, from about 30 MPa to about 300 MPa, from about 50 MPa to about 300 MPa, from about 100 MPa to about 300 MPa, from about 100 MPa to about 300 MPa, or any range or subrange therebetween.
[0486] In some embodiments, the first material 254 and/or the second material 256 can remain within an elastic deformation regime. As used herein, an elastic deformation regime includes the range of the deformations that a material can recover 99% or its original dimension after being deformed to that deformation. Without wishing to be bound by theory, a first material may remain within its elastic deformation regime when the tensile strength of the first material is less than the product of the first material's elastic modulus and the first material's thickness divided by the product of twice the first material's volume fraction and the effective minimum bend radius of the foldable apparatus when the thickness of the first material divided by the effective minimum bend radius of the foldable apparatus is less than the first material's yield strain. As used herein, a yield strain is a material's strain at yield. As used herein, the first material's volume fraction means the ratio of a combined volume of the first material in a region between the first central surface area and the second material surface circumscribed by an outer periphery of the shattered pane to the total volume of the region between the first central surface area and the second material surface circumscribed by an outer periphery of the shattered pane. For example, a first material would be within its elastic deformation regime if it is in a foldable apparatus comprising an effective minimum bend radius of 1 mm as the thickness of the first material is 100 μm as long as the yield strain of the first material is 0.1 and the tensile strength of the first material is more than 10 times the elastic modulus of the first material. In some embodiments, the first material 254 and/or the second material 256 can comprise a strain at yield of about 5% or more, about 8% or more, about 10% or more, about 12% or more, or about 20% or more. In some embodiments, the first material 254 and/or the second material 256 can comprise a strain at yield in a range from about 5% to about 10,000%, from about 5% to about 5,000%, from about 8% to about 1,000%, from about 8% to about 500%, from about 10% to about 300%, from about 10% to about 100%, from about 12% to about 100%, from about 20% to about 100%, from about 20% to about 50%, or any range or subrange therebetween. In some embodiments, the first material can comprise one or more of a polyamide, LDPE, HDPE, PTFE, perfluoroalkoxyethylene, PVF, ETFE, polybutadiene rubber, nitrile rubber, and styrene-butadiene rubber. In some embodiments, the second material can comprise the polymer-based portion described above. In some embodiments, as described below, the first material 254 may be cured in a bent configuration (e.g., when a bending force is applied to the foldable substrate), although it is to be understood that the second material 256 may be cured in a bent configuration in addition to or alternatively to curing the first material 254 in a bent configuration. Curing the first material in a bent configuration can reduce the effective maximum strain on the first material as the foldable apparatus is bent between unfolded and folded configurations, which can allow more materials to be used as first materials while still keeping the first material within its elastic deformation regime.
[0487] In some embodiments, the first material 254 and/or the second material 256 can comprise a negative coefficient of thermal expansion (CTE). As used herein, a coefficient of thermal expansion is measured in accordance with ASTM E289-17 using a Picoscale Michelson Interferometer between -20° C. and 40° C. In some embodiments, the first material 254 and/or the second material 256 can comprise particles of one or more of copper oxide, beta-quartz, a tungstate, a vanadate, a pyrophosphate, and/or a nickel-titanium alloy. In some embodiments, the first material 254 and/or the second material 256 can comprise a CTE of about −20×10.sup.−7° C..sup.−1 or more, about −10×10.sup.−7° C..sup.−1 or more, about −5×10.sup.−7° C..sup.−1 or more, about −2×10.sup.−7° C..sup.−1 or more, about 10×10.sup.−7° C..sup.−1 or less, about 5×10.sup.−7° C..sup.−1 or less, about 2×10.sup.−7° C..sup.−1 or less, about 1×10.sup.−7° C..sup.−1 or less, or 0° C..sup.−1 or less. In some embodiments, the first material 254 and/or the second material 256 can comprise a CTE in a range from about −20×10.sup.−7° C..sup.−1 to about 10×10.sup.−7° C..sup.−1, from about −20×10.sup.−7° C..sup.−1 to about 5×10.sup.−7° C..sup.−1, from about −10×10.sup.−7° C..sup.−1, to about 5×10.sup.−7° C..sup.−1, from about −10×10.sup.−7° C..sup.−1 to about 2×10.sup.−7° C..sup.−1, from about −10×10.sup.−7° C..sup.−1 to 0° C..sup.−1, from about −5×10.sup.−7° C..sup.−1 to 0° C..sup.−1 from about −2×10.sup.−7° C..sup.−1 to about 0° C..sup.−1, or any range or subrange therebetween. By providing a polymer-based portion comprising a low (e.g., negative) coefficient of thermal expansion, warp caused by volume changes during curing of the polymer-based portion can be mitigated.
[0488] In some embodiments, as shown in
[0489] In some embodiments, as shown in
[0490] The second major surface 205 of the foldable substrate 201 or 803 can comprise the coating 281. In some embodiments, the coating, 281 if provided, may comprise one or more of an easy-to-clean coating, a low-friction coating, an oleophobic coating, a diamond-like coating, a scratch-resistant coating, or an abrasion resistant coating. A scratch-resistant coating may comprise an oxynitride, for example, aluminum oxynitride or silicon oxynitride with a thickness of about 500 micrometers or more. In such embodiments, the abrasion resistant layer may comprise the same material as the scratch resistant layer. In some embodiments, a low friction coating may comprise a highly fluorinated silane coupling agent, for example, an alkyl fluorosilane with oxymethyl groups pendant on the silicon atom. In such embodiments, an easy-to-clean coating may comprise the same material as the low friction coating. In other embodiments, the easy-to-clean coating may comprise a protonatable group, for example, an amine, for example, an alkyl aminosilane with oxymethyl groups pendant on the silicon atom. In such embodiments, the oleophobic coating may comprise the same material as the easy-to-clean coating. In some embodiments, a diamond-like coating comprises carbon and may be created by applying a high voltage potential in the presence of a hydrocarbon plasma.
[0491] In some embodiments, the coating 281 may be an optically transparent polymeric hard-coat layer that can be disposed over and/or bonded to the foldable substrate. Suitable materials for an optically transparent polymeric hard-coat layer include, but are not limited to: a cured acrylate resin material, an inorganic-organic hybrid polymeric material, an aliphatic or aromatic hexafunctional urethane acrylate, a siloxane based hybrid material, and a nanocomposite material, for example, an epoxy and urethane material with nanosilicate. In some embodiments, an optically transparent polymeric hard-coat layer may consist essentially of one or more of these materials. In some embodiments, an optically transparent polymeric hard-coat layer may consist of one or more of these materials. As used herein, “inorganic-organic hybrid polymeric material” means a polymeric material comprising monomers with inorganic and organic components. An inorganic-organic hybrid polymer is obtained by a polymerization reaction between monomers having an inorganic group and an organic group. An inorganic-organic hybrid polymer is not a nanocomposite material comprising separate inorganic and organic constituents or phases, for example, inorganic particulates dispersed within an organic matrix. More specifically, suitable materials for an optically transparent polymeric (OTP) hard-coat layer include, but are not limited to, a polyimide, a polyethylene terephthalate (PET), a polycarbonate (PC), a poly methyl methacrylate (PMMA), organic polymer materials, inorganic-organic hybrid polymeric materials, and aliphatic or aromatic hexafunctional urethane acrylates. In some embodiments, an OTP hard-coat layer may consist essentially of an organic polymer material, an inorganic-organic hybrid polymeric material, or aliphatic or aromatic hexafunctional urethane acrylate. In some embodiments, an OTP hard-coat layer may consist of a polyimide, an organic polymer material, an inorganic-organic hybrid polymeric material, or aliphatic or aromatic hexafunctional urethane acrylate. In some embodiments, an OTP hard-coat layer may include a nanocomposite material. In some embodiments, an OTP hard-coat layer may include a nano-silicate at least one of epoxy and urethane materials. Suitable compositions for such an OTP hard-coat layer are described in U.S. Pat. Pub. No. 2015/0110990, which is hereby incorporated by reference in its entirety by reference thereto. As used herein, “organic polymer material” means a polymeric material comprising monomers with only organic components. In some embodiments, an OTP hard-coat layer may comprise an organic polymer material manufactured by Gunze Limited and having a hardness of 9H, for example, Gunze's “Highly Durable Transparent Film.” As used herein, “inorganic-organic hybrid polymeric material” means a polymeric material comprising monomers with inorganic and organic components. An inorganic-organic hybrid polymer is obtained by a polymerization reaction between monomers having an inorganic group and an organic group. An inorganic-organic hybrid polymer is not a nanocomposite material comprising separate inorganic and organic constituents or phases, for example, inorganic particulates dispersed within an organic matrix. In some embodiments, the inorganic-organic hybrid polymeric material may include polymerized monomers comprising an inorganic silicon-based group, for example, a silsesquioxane polymer. A silsesquioxane polymer may be, for example, an alky-silsesquioxane, an aryl-silsesquioxane, or an aryl alkyl-silsesquioxane having the following chemical structure: (RSiO.sub.1.5).sub.n, where R is an organic group for example, but not limited to, methyl or phenyl. In some embodiments, an OTP hard-coat layer may comprise a silsesquioxane polymer combined with an organic matrix, for example, SILPLUS manufactured by Nippon Steel Chemical Co., Ltd. In some embodiments, an OTP hard-coat layer may comprise 90 wt % to 95 wt % aromatic hexafunctional urethane acrylate (e.g., PU662NT (Aromatic hexafunctional urethane acrylate) manufactured by Miwon Specialty Chemical Co.) and 10 wt % to 5 wt % photo-initiator (e.g., Darocur 1173 manufactured by Ciba Specialty Chemicals Corporation) with a hardness of 8H or more. In some embodiments, an OTP hard-coat layer composed of an aliphatic or aromatic hexafunctional urethane acrylate may be formed as a stand-alone layer by spin-coating the layer on a polyethylene terephthalate (PET) substrate, curing the urethane acrylate, and removing the urethane acrylate layer from the PET substrate. An OTP hard-coat layer may have a thickness in the range of 1 μm to 150 μm, for example, from 10 μm to 140 μm, from 20 μm to 130 μm, 30 μm to 120 μm, from 40 μm to 110 pm, from 50 μm to 100 μm, from 60 μm to 90 μm, 70 μm, 80 μm, 2μm to 140 μm, from 4μm to 130 μm, 6μm to 120 μm, from 8μm to 110 μm, from 10 μm to 100 μm, from 10 μm to 90 μm, 10 μm, 80 μm, 10 μm, 70 μm, 10 μm, 60 μm, 10 μm, 50 μm, or within a range having any two of these values as endpoints. In some embodiments, an OTP hard-coat layer may be a single monolithic layer.
[0492] In some embodiments, an OTP hard-coat layer may be an inorganic-organic hybrid polymeric material layer or an organic polymer material layer having a thickness in the range of 80 μm to 120 μm, including subranges. For example, an OTP hard-coat layer comprising an inorganic-organic hybrid polymeric material or an organic polymer material may have a thickness of from 80 μm to 110 μm, 90 μm to 100 μm, or within a range having any two of these values as end points. In some embodiments, an OTP hard-coat layer may be an aliphatic or aromatic hexafunctional urethane acrylate material layer having a thickness in the range of 10 μm to 60 μm, including subranges. For example, an OTP hard-coat layer comprising an aliphatic or aromatic hexafunctional urethane acrylate material may have a thickness of 10 μm to 55 μm, 10 μm to 50 μm, 10 μm to 40 μm, 10 μm to 45 μm, 10 μm to 40 μm, 10 μm to 35 μm, 10 μm to 30 μm, 10 μm to 25 μm, 10 μm to 20 μm, or within a range having any two of these values as end points.
[0493] In some embodiments, the foldable substrate (e.g., first portion 221, second portion 223, shattered pane 231, and/or plurality of panes 950) may comprise a foldable glass-based substrate and/or foldable ceramic-based substrate where one or more portions of the foldable substrate may comprise a compressive stress region. In some embodiments, the compressive stress region may be created by chemically strengthening the foldable substrate. Chemically strengthening may comprise an ion exchange process, where ions in a surface layer are replaced by—or exchanged with—larger ions having the same valence or oxidation state. Methods of chemically strengthening will be discussed later. Without wishing to be bound by theory, chemically strengthening the foldable substrate can enable small (e.g., smaller than about 10 mm or less) bend radii because the compressive stress from the chemical strengthening can counteract the bend-induced tensile stress on the outermost surface of the foldable substrate (e.g., first major surface 203 in
[0494] In some embodiments, the first portion 221 may be chemically strengthened to form a first compressive stress region extending to a first depth of compression from the first surface area 237 of the first major surface 203. In some embodiments, the second portion 223 may be chemically strengthened to form a third compressive stress region extending to a third depth of compression from the third surface area 239 of the first major surface 203. In even further embodiments, the first depth of compression (e.g., from the first surface area 237 of the first major surface 203) and/or third depth of compression (e.g., from the third surface area 239 of the first major surface 203) as a percentage of the first thickness 222 can be about 1% or more, about 5% or more, about 10% or more, about 30% or less, about 25% or less, or about 20% or less. In even further embodiments, the first depth of compression and/or the third depth of compression as a percentage of the first thickness 222 can be in a range from about 1% to about 30%, from about 1% to about 25%, from about 5% to about 25%, from about 5% to about 20%, from about 10% to about 20%, or any range or subrange therebetween.
[0495] In some embodiments, the central portion 225 may be chemically strengthened to form a first central compressive stress region extending to a first central depth of compression from the first central surface area 233 of the central portion 225. For example, in some embodiments, the shattered pane 231 of the central portion 225 may be chemically strengthened to a first central depth of compression from the first central surface area 233 of the central portion 225. For example, in some embodiments, the plurality of panes 950 of the central portion 225 may be chemically strengthened to a first central depth of compression from the first central surface area 233 of the central portion 225. In even further embodiments, the first central depth of compression (e.g., from the first central surface area 233 (e.g., central major surface 235) of the central portion 225) as a percentage of the central thickness 226 can be about 1% or more, about 5% or more, about 10% or more, about 20% or more, about 25% or more, about 40% or less, about 35% or less, or about 30% or less, or about 28% or less. In even further embodiments, the first central depth (e.g., depth of compression from the first central surface area 233 (e.g., central major surface 235) of the central portion 225) as a percentage of the central thickness 226 can be in a range from about 1% to about 40%, from about 5% to about 40%, from about 10% to about 40%, from about 15% to about 40%, from about 15% to about 35%, from about 20% to about 35%, from about 25% to about 30%, from about 25% to about 28%, or any range or subrange therebetween.
[0496] In even further embodiments, the first depth (e.g., depth of compression from the first surface area 237 of the first major surface 203) can be greater than the first central depth (e.g., depth of compression from the first central surface area 233 (e.g., central major surface 235) of the central portion 225). In even further embodiments, the third depth of compression (e.g., from the third surface area 239 of the first major surface 203) can be greater than the first central depth of compression (e.g., from the first central surface area 233 (e.g., central major surface 235) of the central portion 225). In even further embodiments, the first depth of compression (e.g., from the first surface area 237 of the first major surface 203) may be substantially equal to the third depth of compression (e.g., from the third surface area 239 of the first major surface 203). In some embodiments, the first depth of compression, the third depth of compression, and/or the first central depth of compression can be about 1 μm or more, about 10 μm or more, about 50 μm or more, about 200 μm or less, about 150 μm or less, or about 100 μm or less. In some embodiments, the first depth of compression, the third depth of compression, and/or the first central depth of compression can be in a range from about 1 μm to about 200 μm, from about 1 μm to about 150 μm, from about 10 μm to about 150 μm, from about 50 μm to about 150 μm, from about 50 μm to about 100 μm, or any range or subrange therebetween. By providing a first portion, second portion, and/or central portion comprising a glass-based and/or ceramic-based portion comprising a first depth of compression, a third depth of compression, and/or a first central depth of compression, respectively, in a range from about 1% to about 30% of the first thickness, good impact and/or puncture resistance can be enabled.
[0497] In some embodiments, the first portion 221 may be chemically strengthened to form a second compressive stress region extending to a second depth of compression from the second surface area 247 of the second major surface 205. In some embodiments, the second portion 223 may be chemically strengthened to form a fourth compressive stress region extending to a fourth depth of compression from the fourth surface area 249 of the second major surface 205. In even further embodiments, the second depth of compression (e.g., from the second surface area 247 of the second major surface 205) and/or fourth depth of compression (e.g., from the fourth surface area 249 of the second major surface 205) as a percentage of the first thickness 222 can be about 1% or more, about 5% or more, about 10% or more, about 30% or less, about 25% or less, or about 20% or less. In even further embodiments, the second depth of compression and/or the fourth depth of compression as a percentage of the first thickness 222 can be in a range from about 1% to about 30%, from about 1% to about 25%, from about 5% to about 25%, from about 5% to about 20%, from about 10% to about 20%, or any range or subrange therebetween.
[0498] In some embodiments, the central portion 225 may be chemically strengthened to form a second central compressive stress region extending to a second central depth of compression from a second central surface area 245 of the second major surface 205 opposite the first central surface area 233 of the central portion 225. For example, in some embodiments, the shattered pane 231 of the central portion 225 may be chemically strengthened to a second central depth from the second central surface area 245 of the second major surface 205 opposite the first central surface area 233 of the central portion 225. In even further embodiments, the second central depth of compression (e.g., from the second central surface area 245 of the second major surface 205) as a percentage of the central thickness 226 can be about 1% or more, about 5% or more, about 10% or more, about 20% or more, about 25% or more, about 40% or less, about 35% or less, or about 30% or less, or about 28% or less. In even further embodiments, the second central depth as a percentage of the central thickness 226 can be in a range from about 1% to about 40%, from about 5% to about 40%, from about 10% to about 40%, from about 15% to about 40%, from about 15% to about 35%, from about 20% to about 35%, from about 25% to about 30%, from about 25% to about 28%, or any range or subrange therebetween.
[0499] In even further embodiments, the second depth of compression (e.g., from the second surface area 247 of the second major surface 205) can be greater than the second central depth of compression (e.g., from the second central surface area 245 of the second major surface 205). In even further embodiments, the fourth depth of compression (e.g., from the fourth surface area 249 of the second major surface 205) can be greater than the second central depth of compression (e.g., from the second central surface area 245 of the second major surface 205). In even further embodiments, the second depth of compression (e.g., from the second surface area 247 of the second major surface 205) may be substantially equal to the fourth depth of compression (e.g., from the fourth surface area 249 of the second major surface 205). In some embodiments, the first depth of compression (e.g., from the first surface area 237 of the first major surface 203) may be substantially equal to the second depth of compression (e.g., depth of compression from the second surface area 247 of the second major surface 205). In some embodiments, the third depth of compression (e.g., from the third surface area 239 of the first major surface 203) may be substantially equal to the fourth depth of compression (e.g., from the fourth surface area 249 of the second major surface 205). In some embodiments, the first central depth of compression (e.g., from the first central surface area 233 (e.g., central major surface 235) of the central portion 225) may be substantially equal to the second central depth of compression (e.g., depth of compression from the second central surface area 245 of the second major surface 205). In some embodiments, the second depth of compression, the fourth depth of compression, and/or the second central depth of compression can be about 1 μm or more, about 10 μm or more, about 50 μm or more, about 200 μm or less, about 150 μm or less, or about 100 μm or less. In some embodiments, the second depth of compression, the fourth depth of compression, and/or the second central depth of compression can be in a range from about 1 μm to about 200 μm, from about 1 μm to about 150 μm, from about 10 μm to about 150 μm, from about 50 μm to about 150 μm, from about 50 μm to about 100 μm, or any range or subrange therebetween. By providing a first portion, second portion, and/or central portion comprising a glass-based and/or ceramic-based portion comprising a second depth of compression, a fourth depth of compression, and/or a second central depth of compression, respectively, in a range from about 1% to about 30% of the first thickness, good impact and/or puncture resistance can be enabled.
[0500] In some embodiments, the first portion 221 can comprise a first depth of layer of one or more alkali metal ions associated with the first compressive stress region and/or a second depth of layer of one or more alkali metal ions associated with the second compressive stress region. In some embodiments, the second portion 223 can comprise a third depth of layer of one or more alkali metal ions associated with the third compressive stress region and/or a fourth depth of layer of one or more alkali metal ions associated with the fourth compressive stress region. In some embodiments, the first depth of layer, second depth of layer, third depth of layer, and/or fourth depth of layer as a percentage of the corresponding thickness (e.g., substrate thickness, first thickness 222, second thickness) can be about 1% or more, about 5% or more, about 10% or more, about 15% or more, about 20% or more, about 35% or less, about 30% or less, about 25% or less, or about 22% or less. In some embodiments, the first depth of layer, second depth of layer, third depth of layer, and/or fourth depth of layer as a percentage of the corresponding thickness (e.g., substrate thickness, first thickness 222, second thickness) can be in a range from about 1% to about 35%, from about 5% to about 35%, from about 5% to about 30%, from about 10% to about 30%, from about 10% to about 25%, from about 15% to about 25%, from about 15% to about 22%, from about 20% to about 22%, or any range or subrange therebetween. In some embodiments, the first depth of layer, second depth of layer, third depth of layer, and/or fourth depth of layer can be about 1 μm or more, about 10 μm or more, about 50 μm or more, about 200 μm or less, about 150 μm or less, or about 100 μm or less. In some embodiments, the first depth of layer, second depth of layer, third depth of layer, and/or fourth depth of layer can be in a range from about 1 μm to about 200 μm, from about 1 μm to about 150 μm, from about 10 μm to about 150 μm, from about 50 μm to about 150 μm, from about 50 μm to about 100 μm, or any range or subrange therebetween.
[0501] In some embodiments, the central portion 225 (e.g., shattered pane 231) can comprise a first central depth of layer of one or more alkali metal ions associated with the first central compressive stress region and/or a second central depth of layer of one or more alkali metal ions associated with the second central compressive stress region. In some embodiments, the first central depth of layer and/or the second central depth of layer as a percentage of the central thickness 226 can be about 10% or more, about 20% or more, about 25% or more, about 30% or more, about 35% or more, about 38% or more, about 50% or less, about 45% or less, about 42% or less, or about 40% or less. In some embodiments, the first central depth of layer and/or the second central depth of layer as a percentage of the central thickness 226 can be in a range from about 10% to about 50%, from about 20% to about 50%, from about 25% to about 50%, from about 30% to about 50%, from about 35% to about 50%, from about 35% to about 45%, from about 38% to about 45%, from about 38% to about 42%, from about 38% to about 40%, or any range or subrange therebetween. In some embodiments, the first central depth of layer and/or second central depth of layer can be about 5μm or more, about 50 μm or more, about 100 μm or more, about 150 μm or more, about 500 μm or less, about 300 μm or less, about 250 μm or less, or about 200 μm or less. In some embodiments, the first central depth of layer and/or second central depth of layer can be in a range from about 5μm to about 500 μm, from about 50 μm to about 500 μm, from about 50 μm to about 300 μm, from about 100 μm to about 300 μm, from about 100 μm to about 250 μm, from about 150 μm to about 250 μm, from about 150 μm to about 200 μm, or any range or subrange therebetween.
[0502] In some embodiments, the first compressive stress region can comprise a maximum first compressive stress. In some embodiments, the second compressive stress region can comprise a maximum second compressive stress. In further embodiments, the maximum first compressive stress and/or the maximum second compressive stress can be about 100 MegaPascals (MPa) or more, about 300 MPa or more, about 500 MPa or more, about 700 MPa or more, about 1,500 MPa or less, about 1,200 MPa or less, about 1,000 MPa or less, or about 900 MPa or less. In further embodiments, the maximum first compressive stress and/or the maximum second compressive stress can be in a range from about 100 MPa to about 1,500 MPa, from about 100 MPa to about 1,200 MPa, from about 300 MPa to about 1,200 MPa, from about 300 MPa to about 1,000 MPa, from about 500 MPa to about 1,000 MPa, from about 700 MPa to about 1,000 MPa, from about 700 MPa to about 900 MPa, or any range or subrange therebetween. Providing a maximum first compressive stress and/or a maximum second compressive stress in a range from about 100 MPa to about 1,500 MPa can enable good impact and/or puncture resistance. In some embodiments, the third compressive stress region can comprise a maximum third compressive stress within one or more of the ranges discussed above in this paragraph. In some embodiments, the fourth compressive stress region can comprise a maximum fourth compressive stress within one or more of the ranges discussed above in this paragraph.
[0503] In some embodiments, the first central compressive stress region can comprise a maximum first central compressive stress. In some embodiments, the second central compressive stress region can comprise a maximum second central compressive stress. In some embodiments, the maximum first central compressive stress and/or the maximum second central compressive stress can be about 50 MPa or more, about 100 MPa or more, about 200 MPa or more, about 250 MPa or more, about 750 MPa or less, about 600 MPa or less, about 500 MPa or less, about 450 MPa or less, about 400 MPa or less, about 350 MPa or less, or about 300 MPa or less. In some embodiments, the maximum first central compressive stress and/or the maximum second central compressive stress can be in a range from about 50 MPa to about 750 MPa, from about 50 MPa to about 600 MPa, from about 100 MPa to about 600 MPa, from about 100 MPa to about 500 MPa, from about 200 MPa to about 500 MPa, from about 200 MPa to about 450 MPa, from about 250 MPa to about 450 MPa, from about 250 MPa to about 350 MPa, from about 250 MPa to about 300 MPa, or any range or subrange therebetween.
[0504] Throughout the disclosure, if a first layer, material and/or component is described as “disposed over” a second layer, material and/or component, other layers, materials and/or components may or may not be present between the first layer, material and/or component and the second layer, material and/or component. As used herein, if a first layer, material and/or component described as “bonded to” a second layer, material and/or component means that the layers, materials and/or components are bonded to each other, either by direct contact and/or bonding between the two layers, materials and/or components or via an adhesive layer. In some embodiments, although not shown, the recess may not be totally filled, for example, to leave room for electronic devices and/or mechanical devices.
[0505] In some embodiments, as shown in
[0506] The second material 256 can comprise a first contact surface 209. In some embodiments, as shown in
[0507] The second material 256 can comprise a second contact surface 257 opposite the first contact surface 209. As shown in
[0508] In some embodiments, the elastic modulus of the second material 256 can be about 5 GigaPascals (GPa) or less at 23° C. For example, in some embodiments, the elastic modulus of the second material 256 at 23° C. can be about 0.01 MegaPascal (MPa) or more, about 0.1 MPa or more, about 1 MPa or more, about 30 MPa or more, about 100 MPa or more, 300 MPa or more, about 500 MPa or more, about 1,000 MPa or more, about 5,000 MPa or less, about 3,000 MPa or less, about 2,000 MPa or less, or about 1,000 MPa or less. In some embodiments, the elastic modulus of the second material 256 at 23° C. can be in a range from about 0.01 MPa to about 5,000 MPa, from about 0.1 MPa to about 5,000 MPa, from about 0.1 MPa to about 3,000 MPa, from about 1 MPa to about 3,000 MPa, from about 1 MPa to about 1,000 MPa, from about 30 MPa to about 1,000 MPa, from about 100 MPa to about 1,000 MPa, from about 300 MPa to about 1,000 MPa, from about 500 MPa to about 1,000 MPa, or any range or subrange therebetween. In some embodiments, the elastic modulus of the second material can comprise an elastic modulus in a range from about 1,000 MPa to about 5,000 MPa, from about 3,000 MPa to about 5,000 MPa, from about 1 MPa to about 500 MPa, from about 10 MPa to about 500 MPa, from about 10 MPa to about 400 MPa, from about 30 MPa to about 400 MPa, from about 30 MPa to about 300 MPa, from about 50 MPa to about 300 MPa, from about 100 MPa to about 300 MPa, from about 100 MPa to about 300 MPa, or any range or subrange therebetween.
[0509] In some embodiments, the second material 256 can comprise a greater elastic modulus than the first material 254. By providing a second material comprising a higher modulus than the first material, bend-induced stresses on the substrate can be reduced, for example, by shifting a neutral axis of the substrate closer to the second material than a mid-plane of the substrate. Further, providing a second material disposed over substantially an entire second major surface of a foldable substrate can present a contact surface with consistent properties across its length and/or width for coupling components to (e.g., substrates, coatings, release liners, display devices). In some embodiments, a first portion and a second portion can be positioned opposite a first major surface of the substrate. Providing a first portion and a second portion with the second material positioned therebetween can provide good bending performance as well as minimize a region of the foldable apparatus with a lower impact resistance (e.g., the portion including the second material compared to the portions comprising the first portion or the second portion).
[0510] In some embodiments, the second material 256 can comprise a lesser elastic modulus than the first material 254. By providing a second material comprising a lesser elastic modulus than that of a first material 254 and that of a shattered piece, flexibility of the foldable apparatus can be increased by reducing bending-induced stresses. In some embodiments, the elastic modulus of the first material 254 can be substantially equal to the elastic modulus of the second material 256.
[0511] In some embodiments, the second material 256 can comprise a polymer-based material. In further embodiments, the second material 256 can comprise the polymer-based portion described above. In further embodiments, the second material 256 can comprise a silicone-based polymer, an acrylate-based polymer, an epoxy-based polymer, a polyimide-based material, or a polyurethane. In even further embodiments, the second material 256 can comprise an ethylene acid copolymer. An exemplary embodiment of an ethylene acid copolymer includes SURLYN available from Dow (e.g., Surlyn PC-2000, Surlyn 8940, Surlyn 8150). Examples of epoxies include bisphenol-based epoxy resins, novolac-based epoxies, cycloaliphatic-based epoxies, and glycidylamine-based epoxies. In further embodiments, the second material can comprise one or more of a polyolefin, a polyamide, a halide-containing polymer (e.g., polyvinylchloride or a fluorine-containing polymer), an elastomer, a urethane, phenolic resin, parylene, polyethylene terephthalate (PET), and polyether ether ketone (PEEK). Example embodiments of polyolefins include low molecular weight polyethylene (LDPE), high molecular weight polyethylene (HDPE), ultrahigh molecular weight polyethylene (UHMWPE), and polypropylene (PP). Example embodiments of fluorine-containing polymers include polytetrafluoroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), perfluoropolyether (PFPE), perfluorosulfonic acid (PFSA), a perfluoroalkoxy (PFA), fluorinated ethylene propylene (FEP) polymers, and ethylene tetrafluoro ethylene (ETFE) polymers. Example embodiments of elastomers include rubbers (e.g., polybutadiene, polyisoprene, chloroprene rubber, butyl rubber, nitrile rubber) and block copolymers (e.g., styrene-butadiene, high-impact polystyrene, polydichlorophosphazene) comprising one or more of polystyrene, polydichlorophosphazene, and poly(5-ethylidene-2-norbornene). Example of embodiments of polyurethanes comprise thermoset polyurethanes, for example, Dispurez 102 available from Incorez and thermoplastic polyurethanes, for example, KrystalFlex PE505 available from Huntsman. In some embodiments, the second material 256 can comprise one or more of a polyimide, a polyethylene terephthalate (PET), a polycarbonate (PC), or a poly methyl methacrylate (PMMA). An additional exemplary embodiment for the second material 256 comprises Eleglass w802-GL044 available from Axalta with from 1 wt % to 2 wt % cross-linker. In some embodiments, the second material 256 can comprise the same material(s) as the first material 254. In further embodiments, the second material 256 can comprise the same material composition (e.g., mixture, proportions) as the first material 254. For example, the first material 254 and the second material 256 can both comprise the adhesive described above or the polymer-based portion described above.
[0512] In some embodiments, the second material 256 can comprise a polymer-based material comprising a glass-transition (Tg) temperature. In further embodiments, the glass transition temperature of the second material 256 can be within one or more of the ranges discussed above for the glass transition temperature of the first material 254. Providing a second material with a glass transition temperature outside of an operating range (e.g., from about 0° C. to about 40° C., from about −20° C. to about 60° C.) of a foldable apparatus can enable the foldable apparatus to have consistent properties across the operating range.
[0513] In some embodiments, a storage modulus (i.e., modulus of elasticity) of the second material 256 can change by a multiple of about 200 or less, about 100 or less, about 50 or less, about 20 or less, about 10 or less, or about 5 or less when a temperature of the second material 256 is changed from about 100° C. to about −20° C. In some embodiments, a storage modulus of the second material 256 can change when a temperature of the second material 256 is changed from about 100° C. to about −20° C. by a multiple in a range from about 1 to about 200, from about 5 to about 200, from about 10 to about 100, from about 20 to about 100, from about 50 to about 100, from about 1 to about 100, from about 1 to about 50, from about 1 to about 20, from about 1 to about 10, or any range or subrange therebetween. In some embodiments, the storage modulus of the second material 256 may change by a greater multiple than the storage modulus of the first material 254. In some embodiments, the storage modulus of the second material 256 may change by a lesser multiple than the storage modulus of the first material 254. In some embodiments, the storage modulus of the second material 256 may change by a substantially the same multiple as the storage modulus of the first material 254.
[0514] In some embodiments, the second material 256 can comprise a polymer-based material comprising a glassy plateau. In further embodiment, the storage modulus (e.g., modulus of elasticity) of the second material 256 in the glassy plateau can within one or more of the ranges discussed above for the storage modulus of the first material 254 in the glassy plateau. In further embodiments, the storage modulus of the second material 256 in the glassy plateau can be greater than the storage modulus of the first material 254 in the glass plateau. In further embodiments, the storage modulus of the second material 256 in the glassy plateau can be less than the storage modulus of the first material 254 in the glass plateau. In further embodiments, the storage modulus of the second material 256 in the glassy plateau can be substantially equal to the storage modulus of the first material 254 in the glass plateau.
[0515] In some embodiments, the second material 256 can remain within an elastic deformation regime. In some embodiments, the second material 256 can comprise a strain at yield of about 10% or more, about 50% or more, about 100% or more, about 150% or more, or about 200% or more. In some embodiments, the second material 256 can comprise a strain at yield in a range from about 10% to about 10,000%, from about 50% to about 5,000%, from about 100% to about 1,000%, from about 100% to about 500%, from about 100% to about 300%, from about 100% to about 200%, from about 150% to about 1,000%, from about 150% to about 500%, from about 200% to about 500%, or any range or subrange therebetween. In some embodiments, the second material can comprise one or more of a polyamide, LDPE, HDPE, PTFE, perfluoroalkoxyethylene, PVF, ETFE, polybutadiene rubber, nitrile rubber, and styrene-butadiene rubber. In some embodiments, as described below, the second material 256 may be cured in a bent configuration (e.g., when a bending force is applied to the foldable substrate). Curing the second material in a bent configuration can reduce the effective maximum strain on the second material as the foldable apparatus is bent between unfolded and folded configurations, which can allow more materials to be used as second materials while still keeping the first material within its elastic deformation regime.
[0516] As shown in
[0517] As shown, the adhesive layer 207 can comprise a second contact surface 211 that can be opposite the first contact surface 208 and spaced from the first contact surface 208. In some embodiments, as shown in
[0518] In some embodiments, the adhesive layer 207 can comprise an elastic modulus within one or more ranges discussed above with reference to elastic modulus of the first material 254. In some embodiments, the adhesive layer 207 can comprise an elastic modulus within one or more ranges discussed above with reference to the elastic modulus of the second material 256. In some embodiments, the adhesive layer 207 can comprise an elastic modulus of about 0.01 MegaPascals (MPa) or more, about 1 MPa or more, about 10 MPa or more, about 100 MPa or more, about 3,000 MPa or less, about 1,000 MPa or less, or about 300 MPa or less. In some embodiments, the adhesive layer 207 can comprise an elastic modulus in a range from about 0.01 MPa to about 3,000 MPa, from about 0.01 MPa to about 1 ,000 MPa, from about 0.01 MPa to about 300 MPa, from about 1 MPa to about 3,000 MPa, from about 1 MPa to about 1,000 MPa, from about 1 MPa to about 1,000 MPa, from about 1 MPa to about 500 MPa, from about 1 MPa to about 300 MPa, from about 10 MPa to about 3,000 MPa, from about 10 MPa to about 1,000 MPa, from about 10 MPa to about 300 MPa, from about 100 MPa to about 3,000 MPa, from about 100 MPa to about 1,000 MPa, from about 100 MPa to about 300 MPa, or any range or subrange therebetween. In further embodiments, the elastic modulus of adhesive layer 207 can be substantially identical to the elastic modulus of the first material 254 and/or the second material 256. In further embodiments, the elastic modulus of the adhesive layer 207 can be less than the elastic modulus of the first material 254 and/or the elastic modulus of the second material 256. In even further embodiments, the elastic modulus of the adhesive layer 207 may be less than the elastic modulus of the first material 254 by a multiple of 10 or more.
[0519] As shown in
[0520] A first substrate thickness can be defined between the sixth surface area 725 of the first substrate 721 and the seventh surface area 723 of the first substrate 721. In some embodiments, the first substrate thickness can be about 10 μm or more, about 25 μm or more, about 30 μm or more, about 50 μm or more, 80 μm or more, about 100 μm or more, about 125 μm or more, about 2 mm or less, about 500 μm or less, about 400 μm or less, about 200 μm or less, or about 125 μm or less. In some embodiments, the first substrate thickness can be in a range from about 10 μm to about 2 mm, from about 30 μm to about 2 mm, from about 50 μm to about 2 mm, from about 80 μm to about 2 mm, from about 80 μm to about 500 μm, from about 80 μm to about 400 μm, from about 80 μm to about 200 μm, from about 125 μm to about 200 μm, or any range or subrange therebetween. In some embodiments, the first substrate thickness can be in a range from about 10 μm to about 200 μm, from about 10 μm to about 125 μm, from about 10 μm to about 60 μm, from about 25 μm to about 60 μm, from about 30 μm to about 60 μm, from about 50 μm to about 60 μm, or any range or subrange therebetween. In some embodiments, the thickness of the first substrate 721 may be substantially uniform between the seventh surface area 723 and the sixth surface area 725 across its corresponding length (i.e., in the direction of the length 105 of the foldable apparatus) and/or its corresponding width (i.e., in the direction of the width 103 of the foldable apparatus).
[0521] The first substrate 721 can comprise a first edge surface 729 defined between the sixth surface area 725 and the seventh surface area 723. The first edge surface 729 comprises an outer peripheral portion 745. In some embodiments, as shown, the first edge surface 729 can comprise a substantially right angle with the seventh surface area 723. In some embodiments, as shown in
[0522] As shown in
[0523] A second substrate thickness can be defined between the eighth surface area 735 of the second substrate 731 and the ninth surface area 733 of the second substrate 731. In some embodiments, the second substrate thickness can be within one or more of the ranges discussed above for the first substrate thickness. In further embodiments, the first substrate thickness can be substantially equal to the second substrate thickness. In some embodiments, the thickness of the second substrate 731 may be substantially uniform between the ninth surface area 733 and the eighth surface area 735 across its corresponding length (i.e., in the direction of the length 105 of the foldable apparatus) and/or its corresponding width (i.e., in the direction of the width 103 of the foldable apparatus).
[0524] In some embodiments, the first substrate 721 can comprise a glass-based substrate. For example, the first substrate 721 can comprise a glass-based substrate while the second substrate 731 can be a glass-based substrate and/or a ceramic-based substrate. In some embodiments, the first substrate 721 can comprise a ceramic-based substrate. For example, the first substrate 721 can comprise a ceramic-based substrate while the second substrate 731 can be a glass-based substrate and/or a ceramic-based substrate. In some embodiments, the first substrate 721 and/or the second substrate 731 can comprise an elastic modulus at 23° C. that can be within one or more of the ranges discussed for the elastic modulus of the foldable substrate 201 (e.g., first portion 221, shattered pieces). In some embodiments, the elastic modulus of the first substrate 721 can be substantially equal to the elastic modulus of the second substrate 731. In some embodiments, the elastic modulus of the first substrate 721 can be greater than the elastic modulus of the second material 256. In further embodiments, the elastic modulus of the second substrate 731 can be greater than the elastic modulus of the second material 256. Providing a first substrate and/or a second substrate comprising an elastic modulus greater than the elastic modulus of the second material can facilitate good bending performance and increase impact resistance.
[0525] In some embodiments, the first substrate 721 may be chemically strengthened. In further embodiments, the first substrate 721 may be chemically strengthened to form a seventh compressive stress region extending to a seventh depth from the sixth surface area 725. In further embodiments, the first substrate 721 may be chemically strengthened to form an eighth compressive stress region extending to an eighth depth from the seventh surface area 723. In some embodiments, the second substrate 731 may be chemically strengthened. In further embodiments, the second substrate 731 may be chemically strengthened to form a ninth compressive stress region extending to a ninth depth from the eighth surface area 735. In further embodiments, the second substrate 731 may be chemically strengthened to form a tenth compressive stress region extending to a tenth depth from the ninth surface area 733. The seventh depth, eighth depth, ninth depth, and/or tenth depth may comprise depths of compression in a range from about 10% to about 30% of the corresponding substrate thickness (e.g., first substrate thickness, second substrate thickness). The seventh compressive stress region can comprise a seventh maximum compressive stress that can be within one or more of the ranges discussed for the first maximum compressive stress. The eighth compressive stress region can comprise an eighth maximum compressive stress that can be within one or more of the ranges discussed for the first maximum compressive stress. The ninth compressive stress region can comprise a ninth maximum compressive stress that can be within one or more of the ranges discussed for the first maximum compressive stress. The tenth compressive stress region can comprise a tenth maximum compressive stress that can be within one or more of the ranges discussed for the first maximum compressive stress.
[0526] The second substrate 731 can comprise a second edge surface 739 defined between the eighth surface area 735 and the ninth surface area 733. The second edge surface 739 comprises an outer peripheral portion 749. In some embodiments, as shown, the second edge surface 739 can comprise a substantially right angle with the ninth surface area 733. In some embodiments, as shown in
[0527] As shown in
[0528] In further embodiments, as shown, the first adhesive portion 703a can comprise a sixth contact surface 709a opposite the fifth contact surface 707a. In some embodiments, as shown, the sixth contact surface 709a can face the first surface area 237 of the first portion 221. In further embodiments, the sixth contact surface 709a can contact the first surface area 237 of the first portion 221. A thickness 705 of the first adhesive portion 703a can be defined between the first surface area 237 of the first portion 221 and the seventh surface area 723 of the first substrate 721. The thickness 705 of the first adhesive portion 703a can be within one or more of the ranges discussed above for the thickness of the adhesive layer 207 (e.g., from about 1 μm to about 30 μm). In some embodiments, the first adhesive portion 703a can attach the first surface area 237 to the seventh surface area 723.
[0529] In further embodiments, as shown, the second adhesive portion 703b can comprise an eighth contact surface 709b opposite the seventh contact surface 707b. In some embodiments, as shown, the eighth contact surface 709b can face the third surface area 239 of the second portion 223. In further embodiments, the eighth contact surface 709b can contact the third surface area 239 of the second portion 223. A thickness of the second adhesive portion 703b can be defined between the third surface area 239 of the second portion 223 and the ninth surface area 733 of the second substrate 731.The thickness of the second adhesive portion 703b can within one or more of the ranges discussed above for the thickness of the adhesive layer 207 (e.g., from about 1 μm to about 30 μm). In some embodiments, the second adhesive portion 703b can attach the third surface area 239 to the ninth surface area 733.
[0530] In some embodiments, the adhesive layer 207, the first adhesive portion 703a, and/or the second adhesive portion 703b can comprise an optically clear adhesive comprising a polymeric material (e.g., optically transparent polymer). Exemplary embodiments of optically clear adhesives can comprise, but are not limited to acrylic adhesives (e.g., 3M 8212 adhesive), an optically transparent liquid adhesive (e.g., a LOCTITE optically transparent liquid adhesive), and transparent acrylics, epoxies, silicones, and polyurethanes. For example, the optically transparent liquid adhesive could comprise one or more of LOCTITE AD 8650, LOCTITE AA 3922, LOCTITE EA E-05MR, LOCTITE UK U-09LV, which are all available from Henkel. In some embodiments, the adhesive layer can comprise the adhesive described above. In some embodiments, the adhesive layer 207, the first adhesive portion 703a, and/or the second adhesive portion 703b may not be optically transparent. In some embodiments, the adhesive layer 207, the first adhesive portion 703a, and/or the second adhesive portion 703b may comprise one or more of the materials discussed above for the first material 254 or the second material 256.
[0531] In some embodiments, the foldable substrate 201 or 803 can be optically transparent. In further embodiments, the first material 254 can be optically transparent. In further embodiments, the second material 256 can be optically transparent. In further embodiments, the adhesive layer 207 can be optically transparent (e.g., comprise an optically clear adhesive (OCA)). In still further embodiments, all of the foldable substrate 201 or 803, the first material 254, the second material 256, and the adhesive layer 207 can be optically transparent. In further embodiments, the first adhesive portion 703a can be optically transparent (e.g., comprise an optically clear adhesive (OCA)). In further embodiments, the second adhesive portion 703b can be optically transparent (e.g., comprise an optically clear adhesive (OCA)). In further embodiments, the first substrate 721 can be optically transparent. In further embodiments, the second substrate 731 can be optically transparent. In still further embodiments, all of the first adhesive portion 703a, the second adhesive portion 703b, the first substrate 721, and the second substrate 731 can be optically transparent.
[0532] The foldable substrate 201 or 803 can be optically transparent. One or more (e.g., all) pieces of the plurality of pieces comprising the shattered pane 231 can be optically transparent. In some embodiments, an index of refraction of the foldable substrate 201 or 803 (e.g., piece of the plurality of shattered pieces 1305 comprising the shattered pane 231) may be about 1 or more, about 1.3 or more, about 1.4 or more, about 1.45 or more, about 1.49 or more, about 3 or less, about 2 or less, about 1.7 or less, about 1.6 or less, or about 1.55 or less. In some embodiments, the index of refraction of the foldable substrate 201 or 803 (e.g., piece of the plurality of shattered pieces 1305 comprising the shattered pane 231, pane of the plurality of panes 950) can be in a range from about 1 to about 3, from about 1 to about 2 from about 1 to about 1.7, from about 1.3 to about 3, from about 1.3 to about 2, from about 1.3 to about 1.7, from about 1.4 to about 2, from about 1.4 to about 1.7, from about 1.45 to about 1.7, from about 1.45 to about 1.6, from about 1.49 to about 1.6, from about 1.49 to about 1.55, or any range or subrange therebetween.
[0533] As used herein, a first surface refractive index is measured at the first major surface comprising a shattered piece of the plurality of shattered pieces comprising the shattered pane or a pane of the plurality of panes. As used herein, a second surface refractive index is measured at the second major surface comprising a shattered piece of the plurality of shattered pieces comprising the shattered pane or a pane of the plurality of panes. As used herein, a central refractive index is measured at a midpoint of the substrate thickness comprising a shattered piece of the plurality of shattered pieces comprising the shattered pane or a pane of the plurality of panes. Unlike the other refractive indices discussed herein, the first surface refractive index, the second surface refractive index, and the central refractive index are measured through a portion of the shattered pane or plurality of panes substantially perpendicular to a direction of the thickness of the shattered pane or plurality of panes (e.g., central thickness 226). In some embodiments, the first surface refractive index can be substantially equal to the second surface refractive index. In some embodiments, the second surface refractive index can be greater than the first surface refractive index.
[0534] Throughout the disclosure, a magnitude of a difference between two values or an absolute difference between two values is the absolute value of the difference between the two values. In some embodiments, an absolute difference between the first surface refractive index and the central refractive index is about 0.006 or less, about 0.005 or less, about 0.004 or less, about 0.001 or more, about 0.001 or more, or about 0.003. In some embodiments, an absolute difference between the first surface refractive index and the central refractive index can be in a range from about 0.001 to about 0.006, form about 0.001 to about 0.005, from about 0.002 to about 0.005, from about 0.002 to about 0.004, from about 0.003 to about 0.004, or any range or subrange therebetween. In some embodiments, the first surface refractive index can be greater than the central refractive index.
[0535] In some embodiments, an absolute difference between the second surface refractive index and the central refractive index is about 0.006 or less, about 0.005 or less, about 0.004 or less, about 0.001 or more, about 0.001 or more, or about 0.003. In some embodiments, an absolute difference between the second surface refractive index and the central refractive index can be in a range from about 0.001 to about 0.006, form about 0.001 to about 0.005, from about 0.002 to about 0.005, from about 0.002 to about 0.004, from about 0.003 to about 0.004, or any range or subrange therebetween. In some embodiments, the second surface refractive index can be greater than the central refractive index.
[0536] In some embodiments, the first material 254 can be optically transparent. In some embodiments, the first material 254 can comprise an index of refraction that can be within any of the ranges for the index of refraction of the foldable substrate 201 or 803 discussed above. The first material 254 can further be selected to have an index of refraction that substantially matches an index of refraction of the shattered piece of the plurality of shattered pieces 1305 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the shattered piece of the plurality of shattered pieces 1305 and the index of refraction of the first material 254 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In some embodiments, the index of refraction of the shattered piece of the plurality of shattered pieces 1305 may be greater than or less than the index of refraction of first material 254. In further embodiments, the magnitude of the difference between the index of refraction of the first material 254 and the index of refraction of the shattered piece of the plurality of shattered pieces 1305 can be at least 0.02 in order achieve angular-dependent haze properties, as discussed below. In further embodiments, the magnitude of the difference can be about 0.02 or more, about 0.03 or more, about 0.05 or more, about 0.07 or more, about 0.10 or less, about 0.08 or less, or about 0.06 or less. In further embodiments, the magnitude of the difference can be in a range from about 0.02 to about 0.10, from about 0.02 to about 0.08, from about 0.02 to about 0.06, from about 0.03 to about 0.06, from about 0.03 to about 0.05, from about 0.03 to about 0.10, from about 0.05 to about 0.10, from about 0.05 to about 0.08, from about 0.05 to about 0.06, from about 0.07 to about 0.10, from about 0.07 to about 0.08, or any range or subrange therebetween. In some embodiments, an absolute difference between the first surface refractive index and the refractive index of the first material 254 can be within one or more of the ranges discussed above in this paragraph. In some embodiments, an absolute difference between the central refractive index and the refractive index of the first material 254 can be within one or more of the ranges discussed above in this paragraph. In some embodiments, an absolute difference between the second surface refractive index and the refractive index of the first material 254 can be within one or more of the ranges discussed above in this paragraph.
[0537] In some embodiments, the second material 256 can comprise an index of refraction in a range of the index of refraction of the first material 254 discussed above. In some embodiments, the second material 256 can further be selected to have an index of refraction that substantially matches an index of refraction of the shattered piece of the plurality of shattered pieces 1305 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the shattered piece of the plurality of shattered pieces 1305 and the index of refraction of the second material 256 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the shattered piece of the plurality of shattered pieces 1305 may be greater than or less than the index of refraction of the second material 256.
[0538] In some embodiments, the adhesive layer 207 can comprise an optically clear adhesive comprising an index of refraction in a range of the index of refraction of the first material 254 discussed above. In some embodiments, the adhesive layer 207 can further be selected to have an index of refraction that substantially matches an index of refraction of the shattered piece of the plurality of shattered pieces 1305 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the shattered piece of the plurality of shattered pieces 1305 and the index of refraction of the adhesive layer 207 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In some embodiments, the index of refraction of the shattered piece of the plurality of shattered pieces 1305 may be greater than or less than the index of refraction of the adhesive layer 207.
[0539] In some embodiments, the first substrate 721 can comprise an index of refraction in a range of the index of refraction of the first material 254 discussed above. In some embodiments, the first substrate 721 can further be selected to have an index of refraction that substantially matches an index of refraction of the shattered piece of the plurality of shattered pieces 1305 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the shattered piece of the plurality of shattered pieces 1305 and the index of refraction of the first substrate 721 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the shattered piece of the plurality of shattered pieces 1305 may be greater than or less than the index of refraction of the first substrate 721.
[0540] In some embodiments, the second substrate 731 can comprise an index of refraction in a range of the index of refraction of the first material 254 discussed above. In some embodiments, the second substrate 731 can further be selected to have an index of refraction that substantially matches an index of refraction of the shattered piece of the plurality of shattered pieces 1305 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the shattered piece of the plurality of shattered pieces 1305 and the index of refraction of the second substrate 731 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the shattered piece of the plurality of shattered pieces 1305 may be greater than or less than the index of refraction of the second substrate 731.
[0541] In some embodiments, the coating 281 can comprise an index of refraction in a range of the index of refraction of the first material 254 discussed above. In some embodiments, the coating 281 can further be selected to have an index of refraction that substantially matches an index of refraction of the shattered piece of the plurality of shattered pieces 1305 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the shattered piece of the plurality of shattered pieces 1305 and the index of refraction of the coating 281 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the shattered piece of the plurality of shattered pieces 1305 may be greater than or less than the index of refraction of the coating 281.
[0542] In some embodiments, the first material 254 can further be selected to have an index of refraction that substantially matches an index of refraction of the pane of the plurality of panes 950 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the pane of the plurality of panes 950 and the index of refraction of the first material 254 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In some embodiments, the index of refraction of the pane of the plurality of panes 950 may be greater than or less than the index of refraction of first material 254. In further embodiments, the magnitude of the difference between the index of refraction of the first material 254 and the index of refraction of the pane of the plurality of panes 950 can be at least 0.02 in order achieve angular-dependent haze properties, as discussed below. In further embodiments, the magnitude of the difference can be about 0.02 or more, about 0.03 or more, about 0.05 or more, about 0.07 or more, about 0.10 or less, about 0.08 or less, or about 0.06 or less. In further embodiments, the magnitude of the difference can be in a range from about 0.02 to about 0.10, from about 0.02 to about 0.08, from about 0.02 to about 0.06, from about 0.03 to about 0.06, from about 0.03 to about 0.05, from about 0.03 to about 0.10, from about 0.05 to about 0.10, from about 0.05 to about 0.08, from about 0.05 to about 0.06, from about 0.07 to about 0.10, from about 0.07 to about 0.08, or any range or subrange therebetween. In some embodiments, an absolute difference between the first surface refractive index and the refractive index of the first material 254 can be within one or more of the ranges discussed above in this paragraph. In some embodiments, an absolute difference between the central refractive index and the refractive index of the first material 254 can be within one or more of the ranges discussed above in this paragraph. In some embodiments, an absolute difference between the second surface refractive index and the refractive index of the first material 254 can be within one or more of the ranges discussed above in this paragraph.
[0543] In some embodiments, the second material 256 can further be selected to have an index of refraction that substantially matches an index of refraction of the pane of the plurality of panes 950 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the pane of the plurality of panes 950 and the index of refraction of the second material 256 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the pane of the plurality of panes 950 may be greater than or less than the index of refraction of the second material 256.
[0544] In some embodiments, the adhesive layer 207 can further be selected to have an index of refraction that substantially matches an index of refraction of the pane of the plurality of panes 950 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the pane of the plurality of panes 950 and the index of refraction of the adhesive layer 207 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In some embodiments, the index of refraction of the pane of the plurality of panes 950 may be greater than or less than the index of refraction of the adhesive layer 207.
[0545] In some embodiments, the first substrate 721 and/or the second substrate 731 can further be selected to have an index of refraction that substantially matches an index of refraction of the pane of the plurality of panes 950 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the shattered piece of the pane of the plurality of panes 950 and the index of refraction of the first substrate 721 and/or the second substrate 731 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the pane of the plurality of panes 950 may be greater than or less than the index of refraction of the first substrate 721 and/or the second substrate 731.
[0546] In some embodiments, the coating 281 can comprise an index of refraction in a range of the index of refraction of the first material 254 discussed above. In some embodiments, the coating 281 can further be selected to have an index of refraction that substantially matches an index of refraction of the shattered piece of the pane of the plurality of panes 950 to avoid optical distortions that may otherwise occur with a mismatched index of refraction. For example, to avoid optical distortions, a differential equal to the absolute value of the difference between the index of refraction of the pane of the plurality of panes 950 and the index of refraction of the coating 281 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the pane of the plurality of panes 950 may be greater than or less than the index of refraction of the coating 281.
[0547] In some embodiments, a differential equal to the absolute value of the difference between the index of refraction of the first material 254 and the index of refraction of the second material 256 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the first material 254 may be greater than or less than the index of refraction of the second material 256.
[0548] In some embodiments, a differential equal to the absolute value of the difference between the index of refraction of the first material 254 and the index of refraction of the adhesive layer 207 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the first material 254 may be greater than or less than the index of refraction of the adhesive layer 207.
[0549] In some embodiments, a differential equal to the absolute value of the difference between the index of refraction of the adhesive layer 207 and the index of refraction of the second material 256 can be about 0.1 or less, about 0.07 or less, about 0.05 or less, about 0.001 or more, about 0.01 or more, or about 0.02 or more. In some embodiments, the differential is in a range from about 0.001 to about 0.1, from about 0.001 to about 0.07, from about 0.001 to about 0.05, from about 0.01 to about 0.1, from about 0.01 to about 0.07, from about 0.01 to about 0.05, from about 0.02 to about 0.1, from about 0.02 to about 0.07, from about 0.02 to about 0.05, or any range or subrange therebetween. In further embodiments, the differential can be in a range from about 0.0001 to about 0.02, from about 0.005 to about 0.02, from about 0.01 to about 0.02, from about 0.0001 to about 0.01, from about 0.005 to about 0.01, or any range or subrange therebetween. In some embodiments, the index of refraction of the adhesive layer 207 may be greater than or less than the index of refraction of the second material 256.
[0550] The foldable apparatus can comprise a haze as a function of an angle of illumination relative to a direction normal to the second major surface of the foldable apparatus. In some embodiments, the haze at about 0° relative to an angle of incidence normal to the second major surface 205 of the foldable substrate 201 or 803 of the foldable apparatus can be about 10% or less, about 8% or less, about 5% or less, about 2% or less, or about 1% or less. In some embodiments, the haze at about 0° relative to an angle of incidence normal to the second major surface 205 of the foldable substrate 201 or 803 of the foldable apparatus can be in a range from 0% to about 20%, from 0% to 15%, from 0% to 10%, from about 1% to about 10%, from about 2% to about 10%, from about 5% to about 10%, from about 8% to about 10%, from about 1% to about 8%, from about 1% to about 5%, from about 2% to about 5%, or any range or subrange therebetween. In some embodiments, the haze at about 10° relative to an angle of incidence normal to the second major surface 205 of the foldable apparatus can be within one or more of the ranges specified above for 0°. In some embodiments, the haze at about 20° relative to an angle of incidence normal to the second major surface 205 of the foldable apparatus can be within one or more of the ranges specified above for 0°. Providing a substrate comprising low haze can enable good visibility through the substrate.
[0551] In some embodiments, the haze at about 20° relative to an angle of incidence normal to the second major surface 205 of the foldable substrate 201 or 803 of the foldable apparatus can be about 50% or less, about 30% or less, about 20% or less, about 15% or less, about 10% or less, 0% or more, about 1% or more, about 2% or more, about 5% or more, about 8% or more. In some embodiments, the haze at about 20° relative to an angle of incidence normal to the second major surface 205 of the foldable substrate 201 or 803 of the foldable apparatus can be in a range from 0% to about 50%, from 0% to about 30%, from about 1% to about 30%, from about 1% to about 20%, from about 2% to about 20%, from about 5% to about 20%, from about 5% to about 15%, from about 5% to about 10%, from about 8% to about 10%, or any range or subrange therebetween. In some embodiments, the haze at about 20° can be greater than the haze at 0° by about 1% or more, about 2% or more, 5% or more, about 15% or less, about 10% or less, or about 8% or less. Providing a first material comprising a similar (e.g., a magnitude of a difference of about 0.02 or less) refractive index than a refractive index of a shattered piece can reduce an angle-dependent visibility (e.g., haze, color shift) through the foldable apparatus.
[0552] In some embodiments, the haze at about 20° relative to an angle of incidence normal to the second major surface 205 of the foldable substrate 201 or 803 of the foldable apparatus can be about 10% or more, about 15% or more, about 20% or more, about 25% or more, about 30% or more, or about 50% or more. In some embodiments, the haze at about 20° relative to an angle of incidence normal to the second major surface 205 of the foldable substrate 201 or 803 of the foldable apparatus can be in a range from 10% to about 200%, from 10% to 150%, from 10% to 100%, from about 10% to about 80%, from about 10% to about 50%, from about 15% to about 50%, from about 20% to about 50%, from about 25% to about 50%, from about 30% to about 50%, from about 25% to about 200%, from about 25% to about 150%, from about 25% to about 100%, from about 25% to about 50%, or any range or subrange therebetween. In some embodiments, the haze at about 20° can be greater than the haze at 0° by about 5% or more, about 10% or more, about 25% or more, about 50% or more, or about 100% or more. Providing a first material comprising a different (e.g., a magnitude of a difference of about 0.02 or more) refractive index than a refractive index of a shattered piece can produce an angle-dependent visibility (e.g., haze, color shift) through the foldable apparatus. In further embodiments, providing the different refractive indices can be useful as a privacy screen. For example, visibility may be at a maxima (e.g., maximum) when viewed at a direction normal to the surface (e.g., first major surface) of the foldable apparatus, and that visibility may decrease (e.g., increasing haze) as an angle relative to a direction normal to the surface is increased. In some embodiments, the haze at about 20° can be greater than the haze at about 10° by an amount that is within one or more of the ranges discussed above in this paragraph for the amount that the haze at about 20° can be greater than the haze at 0°.
[0553] Providing a foldable apparatus comprising a shattered pane or a plurality of panes with a low difference (e.g., about 0.008 or less) between a refractive index at a major surface of the foldable apparatus and a central location of the foldable apparatus can minimize optical distortions from the plurality of shattered pieces comprising the shattered pane or the plurality of panes. Also, Providing a foldable apparatus comprising a shattered pane or a plurality of panes with a low difference (e.g., about 0.008 or less) between a refractive index at a major surface of the foldable apparatus and a central location of the foldable apparatus can minimize optical distortions between an adjacent pair of shattered pieces of the plurality of shattered pieces or an adjacent pair of panes of the plurality panes and a first material positioned therebetween, if provided. Also, providing a shattered pane with a plurality of shattered pieces attached together by a first material can provide a smooth (e.g., regular, planar) surface (e.g., first major surface), especially when the shattered pane was generated from a substrate deposed on a backer when it was shattered. Providing a smooth surface of the foldable apparatus can reduce optical distortions. Likewise, providing a second material disposed over substantially an entire second major surface of a foldable substrate can reduce optical distortions. In some embodiments, the first material can substantially match (e.g., a magnitude of a difference of about 0.1 or less) a refractive index of a shattered piece or a pane, which can minimize the visibility of the shattered pane or the plurality of panes to a user. In some embodiments, providing the first material between a pair of shattered pieces or a pair of shattered panes can produce an anti-glare and/or anti-reflective property in the foldable apparatus that can improve visibility of an electronic device that the foldable apparatus may be disposed over. In some embodiments, providing a first material comprising a different (e.g., a magnitude of a difference of about 0.02 or more) refractive index than a refractive index of a shattered piece or a pane can produce an angle-dependent visibility (e.g., haze, color shift) through the foldable apparatus. In further embodiments, providing the different refractive indices can be useful as a privacy screen. For example, visibility may be at a maxima (e.g., maximum) when viewed at a direction normal to the surface (e.g., first major surface) of the foldable apparatus, and that visibility may decrease (e.g., increasing haze) as an angle relative to a direction normal to the surface is increased.
[0554] In some embodiments, as shown in
[0555] In some embodiments, as shown in
[0556] In some embodiments, the foldable apparatus 101, 301, 401, 501, 601, 701, 801, 901, and 1001 may be substantially symmetric about a plane (e.g., see plane 109 in
[0557]
[0558]
[0559] As used herein, “foldable” includes complete folding, partial folding, bending, flexing, or multiple capabilities. As used herein, the terms “fail,” “failure” and the like refer to breakage, destruction, delamination, or crack propagation. A foldable substrate achieves an effective bend radius of “X,” or has an effective bend radius of “X,” or comprises an effective bend radius of “X” if it resists failure when the substrate is held at an effective bend radius of “X” for 24 hours at about 60° C. and about 90% relative humidity.
[0560] As used herein, the “effective minimum bend radius” and the “parallel plate distance” of a foldable substrate (e.g., foldable substrate 201 or 803) or a foldable substrate is measured with the following test configuration and process using a parallel plate apparatus 1401 (see
[0561] In some embodiments, the foldable substrate 201 or 803 of the foldable apparatus can achieve an effective minimum bend radius of 100 mm or less, 50 mm or less, 20 mm or less, or 10 mm or less. In further embodiments, the foldable substrate 201 or 803 of the foldable apparatus can achieve an effective bend radius of 10 millimeters (mm), or 7 mm, or 5 mm, or of 1 mm. In some embodiments, the foldable substrate 201 or 803 of the foldable apparatus can comprise an effective minimum bend radius of about 10 mm or less, about 7 mm or less, about 5 mm or less, about 1 mm or more, about 2 mm or more, or about 5 mm or more. In some embodiments, the foldable substrate 201 or 803 of the foldable apparatus can comprise an effective minimum bend radius in a range from about 1 mm to about 10 mm, from about 1 mm to about 7 mm, from about 1 mm to about 5 mm, from about 2 mm to about 10 mm, from about 2 mm to about 7 mm, from about 2 mm to about 5 mm, from about 5 mm to about 10 mm, from about 5 mm to about 7 mm, from about 7 mm to about 10 mm or any range or subrange therebetween.
[0562] In some embodiments, the foldable apparatus 101, 301, 401, 501, 601, 701, 801, 901, 1001, 1402, 1501, 1701, or 1801 can achieve an effective minimum bend radius of 100 mm or less, 50 mm or less, 20 mm or less, or 10 mm or less. In further embodiments, the foldable apparatus 101, 301, 401, 501, 601, 701, 801, 901, 1001, 1402, 1501, 1701, or 1801 can achieve an effective bend radius of 10 millimeters (mm), or 7 mm, or 5 mm, or of 1 mm. In some embodiments, the foldable apparatus 101, 301, 401, 501, 601, 701, 801, 901, 1001, 1402, 1501, 1701, or 1801 can comprise an effective minimum bend radius of about 10 mm or less, about 7 mm or less, about 5 mm or less, about 1 mm or more, about 2 mm or more, or about 5 mm or more. In some embodiments, the foldable apparatus 101, 301, 401, 501, 601, 701, 801, 901, 1001, 1402, 1501, 1701, or 1801 can comprise an effective minimum bend radius in a range from about 1 mm to about 10 mm, from about 1 mm to about 7 mm, from about 1 mm to about 5 mm, from about 2 mm to about 10 mm, from about 2 mm to about 7 mm, from about 2 mm to about 5 mm, from about 5 mm to about 10 mm, from about 5 mm to about 7 mm, from about 7 mm to about 10 mm or any range or subrange therebetween.
[0563] In some embodiments, the first material 254, second material 256, and/or foldable apparatus 101, 301, 401, 501, 601, 701, 801, 901, or 1001 can withstand a cyclic bending test. As used herein, the cyclic bending test comprises placing a testing apparatus comprising the material to be tested in the parallel plate apparatus 1401 (see
[0564] Furthermore, in some embodiments, the central thickness 226 of the shattered pieces 1305 can be less than the first thickness 222 of the first portion 221 and/or the second portion 223 to help prevent failure of the bond interface between the first material 254 and the shattered piece 1305 or pane 950. For example, decreasing the central thickness 226 can reduce the tensile stress of the first material 254 between the corresponding outer edges 251 of the adjacent pair of shattered pieces 1305 or adjacent pair of shattered panes 950 and can thereby reduce the stress at the interface between the first material 254 and the corresponding outer edges (e.g., outer edge 251) compared to embodiments including a larger central thickness 226 of the shattered pieces 1305 or the plurality of panes 950 (e.g., a thickness equal to the first thickness 222 of the first portion 221 and/or the second portion 223). The reduced stress at the interface between the first material 254 and the corresponding outer edges (e.g., outer edge 251) can reduce failure that may otherwise occur by the first material 254 ripping away from the outer edges (e.g., outer edge 251) and/or can allow use of alternative materials that may have better scratch resistance and/or better puncture resistance that may not be an option with the shattered pieces 1305 or the plurality panes 950 including a larger central thickness 226 due to unacceptable stress at the interface.
[0565] Referring to
[0566] In some embodiments, the width 1303 of the shattered pane 231 can be about 4.4 times the effective minimum bend radius or more. Without wishing to be bound by theory, the length of a bent portion in an elliptical configuration between parallel plates can be about 2.2 times the parallel plate distance 1411 (e.g., about 4.4 times the effective minimum bend radius). In some embodiments, the width 1303 of the shattered pane 231 can be substantially equal to or greater than the bend length of the foldable substrate at its effective minimum bend radius. In some embodiments, the width 1303 of the shattered pane 231 can extend from the first transition portion 227 to the second transition portion 229. In some embodiments, the width 1303 of the shattered pane 231 can be about 4 mm or more, about 10 mm or more, about 20 mm or more, about 45 mm or less, about 40 mm or less, or about 30 mm or less. In some embodiments, the width 1303 of the shattered pane 231 can be in a range from about 4 mm to about 45 mm, from about 4 mm to about 40 mm, from about 4 mm to about 30 mm, from about 4 mm to about 20 mm, from about 4 mm to about 10 mm, from about 10 mm to about 45 mm, from about 10 mm to about 40 mm, from about 10 mm to about 30 mm, from about 10 mm to about 20 mm, from about 20 mm to about 45 mm, from about 20 mm to about 40 mm, from about 20 mm to about 30 mm, from about 30 mm to about 45 mm, from about 30 mm to about 40 mm, from about 40 mm to about 45 mm, or any range of subrange therebetween. It is to be understood that, in some embodiments, the central major surface 235 of the shattered pane 231 extending along a third plane 204c parallel to the second plane 204b can comprise a width within the ranges specified above in this paragraph.
[0567] Dividing the central portion 225 into the plurality of panes 950 illustrated in
[0568] The width 903 of the plurality of panes 950 of the foldable substrate 201 is defined as the maximum distance in a direction 106 perpendicular to the fold axis 102 between (i) a first separation between the first portion 221 or first transition portion 227, if present, and a first pane of the plurality of panes 950 and (ii) a portion of a second separation between the second portion 223 or the second transition portion 229, if present, and a second pane of the plurality of panes 950, where the first separation and the second separation as far apart as possible in the direction 106. In some embodiments, as shown in
[0569] The foldable apparatus may have an impact resistance defined by the capability of the first portion 221 and/or second portion 223 of the foldable substrate 201 or 803 of the foldable apparatus to avoid failure at a pen drop height (e.g., 5 centimeters (cm) or more, 8 cm or more, 10 cm or more, 12 cm or more, 15 cm or more), when measured according to the “Pen Drop Test.” As used herein, the “Pen Drop Test” is conducted such that samples of foldable apparatus are tested with the load (i.e., from a pen dropped from a certain height) imparted to an outer surface (e.g., second major surface 205 of foldable substrate 201 or 803 shown in
[0570] As shown in
[0571] A tube is used for the Pen Drop Test to guide a pen to the outer surface (e.g., second major surface 205 of foldable substrate 201 or 803, fourth major surface 285 of the coating 281) of the foldable apparatus (e.g., comprising foldable substrate 201 or 803), and the tube is placed in contact with the outer surface of the foldable apparatus so that the longitudinal axis of the tube is substantially perpendicular to the outer surface with the longitudinal axis of the tube extending in the direction of gravity. The tube has an outside diameter of 1 inch (2.54 cm), an inside diameter of nine-sixteenths of an inch (1.4 cm) and a length of 90 cm. An acrylonitrile butadiene (ABS) shim is employed to hold the pen at a predetermined height for each test. After each drop, the tube is relocated relative to the sample to guide the pen to a different impact location on the sample (e.g., foldable apparatus). The pen employed in Pen Drop Test is a BIC Easy Glide Pen, Fine, having a tungsten carbide ballpoint tip of 0.7 mm (0.68 mm) diameter, and a weight of 5.73 grams (g) including the cap (4.68 g without the cap).
[0572] For the Pen Drop Test, the ballpoint pen 5903 is dropped with the cap attached to the top end (i.e., the end opposite the tip) so that the ballpoint tip 5905 can interact with the outer surface (e.g., second major surface 205 of foldable substrate 201 or 803, fourth major surface 285 of the coating 281) of the foldable apparatus. In a drop sequence according to the Pen Drop Test, one pen drop is conducted at an initial height of 1 cm, followed by successive drops in 0.5 cm increments up to 20 cm, and then after 20 cm, 2 cm increments until failure of the foldable apparatus. After each drop is conducted, the presence of any observable fracture, failure, or other evidence of damage to the foldable apparatus is recorded along with the particular predetermined height 5909 for the pen drop. Using the Pen Drop Test, multiple foldable apparatus (e.g., samples) can be tested according to the same drop sequence to generate a population with improved statistical accuracy. For the Pen Drop Test, the ballpoint pen 5903 is to be changed to a new pen after every 5 drops, and for each new foldable apparatus tested. In addition, all pen drops are conducted at random locations on the foldable apparatus at or near the center of the foldable apparatus unless indicated otherwise, with no pen drops near or on the edge of the foldable apparatus.
[0573] For purposes of the Pen Drop Test, “failure” means the formation of a visible mechanical defect in a laminate. The mechanical defect may be a crack or plastic deformation (e.g., surface indentation). The crack may be a surface crack or a through crack. The crack may be formed on an interior or exterior surface of a laminate. The crack may extend through all or a portion of the foldable substrate 201 or 803 and/or the coating 281. A visible mechanical defect has a minimum dimension of 0.2 millimeters or more.
[0574]
[0575] The foldable apparatus 101, 301, 401, 501, 601, 701, 801, 901, 1001, 1402, and 1501 can comprise a neutral stress configuration. Throughout the disclosure, the “neutral stress configuration” is measured with the following test configuration and process. When measuring the “neutral stress configuration”, the foldable test apparatus 6001 as shown in
[0576] In some embodiments, the deviation of the neutral stress configuration from the flat configuration can be quantified using a maximum magnitude of a deviatoric strain. As used herein, “deviatoric strain” means the shape changing component of the strain tensor (e.g., the strain tensor minus the as the hydrostatic strain—average of the on-diagonal components of the strain tensor). The strain tensor can be measured using digital image recognition and/or topography of a portion (e.g., second material) of the folded apparatus to compare the shape and dimensions between the flat configuration and the neutral stress configuration. For example, as shown in
[0577] In some embodiments, the deviation of the neutral stress configuration from the flat configuration can be quantified using an angle “B” measured between a first line extending in the direction of the length from the first portion and a second line extending in the direction of the length from the second portion. For example, with reference to
[0578] By providing a neutral stress configuration when the foldable apparatus is in a bent configuration, the force to bend the foldable apparatus to a predetermined parallel plate distance can be reduced. Further, providing a neutral stress configuration when the foldable apparatus is in a bent state can reduce the maximum stress and/or strain experienced by the second material during normal use conditions, which can, for example, enable increased durability and/or reduced fatigue of the foldable apparatus. In some embodiments, the neutral stress configuration can be generated by providing a second material that expands as a result of curing. In some embodiments, the neutral stress configuration can be generated by curing the second material in a bent configuration. In some embodiments, the neutral stress configuration can be generated by bending a ribbon at an elevated temperature (e.g., when the ribbon comprises a viscosity in a range from about 10.sup.4 Pascal-seconds and about 10.sup.7 Pascal-seconds).
[0579] As shown in
[0580] As discussed above, the foldable substrate 201 can comprise a glass-based material and/or a ceramic-based material. In some embodiments, the foldable substrate 201 can comprise alkali-containing aluminosilicate, borosilicate, boroaluminosilicate, and/or silicate glass compositions. In certain aspects, alkaline earth modifiers can be added to any of the foregoing compositions for the foldable substrate 201. In some embodiments, the foldable substrate 201 can comprise: SiO.sub.2 at 50 to 75% (by mol %); Al.sub.2O.sub.3 at 5 to 20%; B.sub.2O.sub.3 at 8 to 23%; MgO at 0.5 to 9%; CaO at 1 to 9%; SrO at 0 to 5%; BaO at 0 to 5%; SnO.sub.2 at 0.1 to 0.4%; ZrO.sub.2 at 0 to 0.1%; Na.sub.2O at 0 to 10%; K.sub.2O at 0 to 5%; and Li.sub.2O at 0 to 10%. In some embodiments, the foldable substrate 201 can comprise: SiO.sub.2 at 64 to 69% (by mol %); Al.sub.2O.sub.3 at 5 to 12%; B.sub.2O.sub.3 at 8 to 23%; MgO at 0.5 to 2.5%; CaO at 1 to 9%; SrO at 0 to 5%; BaO at 0 to 5%; SnO.sub.2 at 0.1 to 0.4%; ZrO.sub.2 at 0 to 0.1%; and Na.sub.2O at 0 to 1%. In some embodiments, the foldable substrate 201 can comprise: SiO.sub.2 at ˜67.4% (by mol %); Al.sub.2O.sub.3 at ˜12.7%; B.sub.2O.sub.3 at ˜3.7%; MgO at ˜2.4%; CaO at 0%; SrO at 0%; SnO.sub.2 at ˜0.1%; and Na.sub.2O at ˜13.7%. In further embodiments, the foldable substrate 201 can comprise: SiO.sub.2 at 68.9% (by mol %); Al.sub.2O.sub.3 at 10.3%; Na.sub.2O at 15.2%; MgO at 5.4%; and SnO.sub.2 at 0.2%. In some embodiments, the foldable substrate 201 can comprise the following glass composition (“Glass 1”): SiO.sub.2 at ˜64% (by mol %); Al.sub.2O.sub.3 at ˜16%; Na.sub.2O at ˜11 mol %; Li.sub.2O at ˜6 mol %; ZnO at ˜1 mol %; and P.sub.2O.sub.5 at ˜2%. In further embodiments, the foldable substrate 201 can comprise: SiO.sub.2 at 68.9% (by mol %); Al.sub.2O.sub.3 at 10.3%; Na.sub.2O at 15.2%; MgO at 5.4%; and SnO2 at 0.2%. Exemplary embodiments of glass compositions for the foldable substrate 201 denoted Glasses A-E are listed in Table 3.
TABLE-US-00003 TABLE 3 Properties of Glasses A-E Glass ID oxide (mol %) A B C D E SiO.sub.2 66.4 69.2 69.11 67.37 64.48 B.sub.2O.sub.3 0.6 3.67 7.00 Al.sub.2O.sub.3 10.3 8.5 10.19 12.73 13.92 Na.sub.2O 13.8 13.9 15.09 13.75 14.04 K.sub.2O 2.4 1.2 0.01 0.01 0.49 MgO 5.7 6.5 5.48 2.36 CaO 0.6 0.5 Fe.sub.2O.sub.3 0.01 0.01 0.03 ZrO.sub.2 0.01 0.01 SnO.sub.2 0.2 0.2 0.1 0.09 0.04 Annealing Temp (° C.) 600 609 650 632 600 Softening Temp (° C.) 843 844 892 899 862
[0581] Foldable apparatus 1701 and/or 1801 can be characterized by about zero residual stress in an as-bent configuration, for example, in the configuration shown in
[0582] Referring to foldable apparatus 1701 and 1801 shown in
[0583] In some embodiments, as shown in
[0584] In some embodiments, as shown in
[0585] In some embodiments, as shown in
[0586] In some embodiments, as shown in
[0587] In further embodiments, the micro-cracks of the plurality of micro-cracks 1821 in the central shattered region 1836 can be oriented substantially normal to the first major surface 203 and/or the second major surface 205 of the foldable substrate 201. In further embodiments, the first shattered region 1832 can comprise a first plurality of micro-cracks 1831 extending from the second surface area 247, and the micro-cracks of the first plurality of micro-cracks 1831 can be oriented in a substantially random fashion within the first portion 221 of the foldable substrate 201 while remaining substantially normal to the first major surface 203 and/or the second major surface 205. In further embodiments, the second shattered region 1834 can comprise a second plurality of micro-cracks 1833 extending from a fourth surface area 249, and the micro-cracks of the second plurality of micro-cracks 1833 can be oriented in a substantially random fashion within the second portion 223 of the foldable substrate 201 while remaining substantially normal to the first major surface 203 and/or the second major surface 205.
[0588] In some embodiments, the foldable substrate 201 of the foldable apparatus 1701 and/or 1801 can comprise one or more of the compressive stress regions discussed above for the foldable substrate 201 or 803. For example, the foldable substrate 201 can comprise one or more compressive stress regions extending from the second major surface 205, a first major surface 203, and/or a first central surface area 233. The foldable substrate can comprise a second compressive stress region extending to a second depth of compression from the second surface area 247 of the first portion 221 comprising the second major surface 205 and/or a second depth of layer of one or more alkali metal ions associated with the second compressive stress region. The foldable substrate 201 can comprise a fourth compressive stress region extending to a fourth depth of compression from the fourth surface area 249 of the second portion 223 comprising the second major surface 205 and/or a fourth depth of layer of one or more alkali metal ions associated with the fourth compressive stress region. The foldable substrate can comprise a second central compressive stress region extending to a second central depth of compression from the second central surface area 245 of the central portion 225 and/or a second central depth of layer of one or more alkali metal ions associated with the second central compressive stress region. For example, the foldable substrate 201 can comprise one or more compressive stress regions extending from the first major surface 203 and/or the first central surface area 233. The foldable substrate can comprise a first compressive stress region extending to a first depth of compression from the first surface area 237 of the first portion 221 comprising the first major surface 203 and/or a first depth of layer of one or more alkali metal ions associated with the first compressive stress region. The foldable substrate 201 can comprise a third compressive stress region extending to a third depth of compression from the third surface area 239 of the second portion 223 comprising the first major surface 203 and/or a third depth of layer of one or more alkali metal ions associated with the third compressive stress region. The foldable substrate can comprise a first central compressive stress region extending to a first central depth of compression from the first central surface area 233 of the central portion 225 and/or a first central depth of layer of one or more alkali metal ions associated with the first central compressive stress region. The compressive stress regions discussed above can comprise a corresponding maximum compressive stress that can be within one or more of the ranges discussed above for the corresponding compressive stress region. In some embodiments, the corresponding maximum compressive stress can be in a range from about 500 MPa to about 1,500MPa, from about 600 MPa to about 1,500 MPa, from about 800 MPa to about 1,500 MPa, or any range or subrange therebetween. In some embodiments, the corresponding maximum compressive stress can exceed 1,000 MPa at the corresponding surface, up to 2,000 MPa. Providing one or more compressive stress regions can offset tensile stresses generated in the substrate upon folding of the foldable apparatus 1701 and 1801, particularly tensile stresses that reach a maximum on the first major surface 203 or the second major surface 205, depending on the direction of the fold.
[0589] In some embodiments, the shattered region 1804 can include one or more polymeric material having a refractive index that substantially matches a refractive index of the foldable substrate 201 or a refractive index intended to differ from the refractive index of the foldable substrate 201, as detailed in U.S. Provisional Patent Application No. 62/958117, filed on Jan. 7, 2020, the salient portions of which are hereby incorporated by reference in this disclosure.
[0590] In some embodiments, as shown in
[0591] In some embodiments, as discussed below with reference to step 1903 and/or 1905 and
[0592] In some embodiments, foldable apparatus can be further characterized by bend fatigue resistance, for example, using the Clamshell Cyclic Fatigue Test. As used herein, the “Clamshell Cyclic Fatigue Test” is conducted by situating a foldable apparatus between two plates of a test fixture. In particular, the ends of the foldable apparatus are held in contact and normal to these plates, and each bend cycle involves moving the plates toward each other to a spacing of a specified, predetermined value (e.g., 10 mm) to bend the foldable apparatus and then returning the plates to a spacing such that the foldable apparatus is substantially planar. Unless otherwise noted, the Clamshell Cyclic Fatigue Test is conducted according to the following test conditions: an auto speed of 30%, a jog speed of 20%, a delay of 0.3 seconds, and a test rate of ˜31 cycles per minute. Further, the Clamshell Cyclic Fatigue Test can be conducted on a number of samples within a particular configuration (N) and the cycles-to-failure values are tabulated for each such sample. The data for each sample configuration can then be reported according to standard statistical measures over the given sample size (N), e.g., a mean, an average, a standard deviation, no failures over a specified number of cycles (e.g., 25,000 cycles), etc., as would be understood by those of ordinary skill in the field of the disclosure. In some embodiments, the foldable apparatus and/or foldable substrate can be characterized with no failures upon being subjected to at least 25,000 bend cycles in a Clamshell Cyclic Fatigue Test with a 10 mm plate separation. In some embodiments, the foldable apparatus and/or foldable substrate can be characterized with no failures upon being subject to at least 25,000 bend cycles in a Clamshell Cyclic Fatigue Test with a 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 12 mm, 14 mm, 16 mm, 18 mm, or 20 mm plate separation, including plate separations therebetween. In some embodiments, the foldable apparatus and/or the foldable substrate can be characterized with no failures upon being subjected to at least 5,000, 10,000, 15,000, 20,000, 25,000, 30,000, 40,000, or 50,000 bend cycles in a Clamshell Cyclic Fatigue Test with a 10 mm plate separation, including values therebetween.
[0593] Embodiments of the disclosure can comprise a consumer electronic product. The consumer electronic product can comprise a front surface, a back surface and side surfaces. The consumer electronic product can further comprise electrical components at least partially within the housing. The electrical components can comprise a controller, a memory, and a display. The display can be at or adjacent the front surface of the housing. The consumer electronic product can comprise a cover substrate disposed over the display. In some embodiments, at least one of a portion of the housing or the cover substrate comprises the foldable apparatus discussed throughout the disclosure.
[0594] The foldable apparatus disclosed herein may be incorporated into another article, for example, an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches) and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance articles, or any article that may benefit from some transparency, scratch-resistance, abrasion resistance or a combination thereof. An exemplary article incorporating any of the foldable apparatus disclosed herein is shown in
[0595] Embodiments of methods of making the foldable apparatus in accordance with embodiments of the disclosure will be discussed with reference to the flow charts in
[0596] Embodiments of methods of making the foldable apparatus 1701 and 1801 in accordance with embodiments of the disclosure will be discussed with reference to the flow chart in
[0597] With reference to the flow chart of
[0598] After step 1901, as shown in
[0599] In some embodiments, in step 1903, the sol-gel coating can be disposed over the central portion 225 of the second major surface 205 (e.g., existing second central surface area 2035). In further embodiments, the sol-gel coating can comprise a width in the direction (e.g., direction 106) of the width of the foldable substrate 201 that can be within one or more of the ranges discussed above for the width 2009 of the oxide coating 2007 (e.g., from about 1 mm to about 200 mm or from about 5% to about 70% of the longest dimension (e.g., length) of the foldable substrate). In further embodiments, a thickness of the sol-gel coating can be about 0.1 μm or more, about 0.5 μm or more, about 1 μm or more, about 2μm or more, about 5μm or more, about 20 μm or less, about 15 μm or less, about 12 μm or less, about 10 μm or less, or about 8 μm or less. In further embodiments, a thickness of the sol-gel coating can be in a range from about 0.1 μm to about 20 μm, from about 0.1 μm to about 15 μm, from about 0.5 μm to about 15 μm, from about 0.5 μm to about 12 μm, from about 1 μm to about 12 μm, from about 1 μm to about 10 μm, from about 2 μm to about 10 μm, from about 2 μm to about 8 μm, from about 5 μm to about 8 μm, or any range or subrange therebetween. For example, the thickness of the sol-gel coating can be 0.1 μm, 0.5 μm, 1 μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, or any value therebetween.
[0600] After step 1903, as shown in
[0601] In some embodiments, in step 1905, the heating can be conducted to define the foldable substrate 201 and oxide coating 2007 thereon in a bent configuration (e.g., as-bent configuration, neutral stress configuration). In further embodiments, the bent configuration (e.g., as-bent configuration, neutral stress configuration) can be achieved as the natural product of the heating, for example, as the organic components in the sol-gel coating are burned off (e.g., oxidized, removed) and the oxide coating is formed (e.g., consolidates). For example, the bent configuration (e.g., as-bent configuration, neutral stress configuration) can be within any of the ranges discussed above for the angle (e.g., from greater than 0° to about)90° and/or diameter of curvature (e.g., from 2 mm to about 20 mm). In some embodiments, as shown in
[0602] After step 1905 or 1909, methods can proceed to step 1907 comprising chemically strengthening the foldable substrate 201. In some embodiments, step 1907 can comprise contacting (e.g., immersing) the foldable substrate with an ion-exchange bath (e.g., salt solution 3003 contained in a salt bath 3001) as discussed below with reference to step 2703 and
[0603] In further embodiments, the chemically strengthening in step 1907 can be conducted while the foldable substrate comprising the oxide coating 2007 disposed over the existing second central surface area 2035, for example, resembling one of the configurations shown in
[0604] After step 1905 or 1907, as shown in
[0605] In some embodiments, step 1909 can comprise etching a recess (e.g., recess 1709 in the first major surface 203 shown in
[0606] After step 1907 or 1909, as shown in
[0607] After step 1907, 1909, or 1911, as shown in
[0608] In some embodiments, as shown in
[0609] After step 1913, methods can be complete at step 1915. In some embodiments, as shown in
[0610] In some embodiments, the foldable apparatus 1701 and/or 1801 formed by the methods discussed above can be characterized by fatigue resistance, for example, by no failures upon being subjected to at least 25,000 bend cycles in a Clamshell Cyclic Fatigue Test with a 10 mm plate separation. In further embodiments, the foldable substrate 201 of the foldable apparatus 1701 and/or 1801 can be characterized with no failures upon being subjected to at least 25,000 bend cycles in a Clamshell Cyclic Fatigue Test with a 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, 12 mm, 14 mm, 16 mm, 18 mm, or 20 mm plate separation, including all values therebetween. In further embodiments, the foldable substrate 201 of the foldable apparatus 1701 and/or 1801 can be characterized with no failures upon being subjected to at least 5,000, 10,000, 15,000, 20,000, 25,000, 30,000, 40,000, or 50,000 bend cycles in a Clamshell Cyclic Fatigue Test with a 10 mm plate separation, including all other bend cycles therebetween.
[0611] In some embodiments, as discussed above with reference to the flow chart in
[0612] Embodiments of methods of making the foldable apparatus 101, 301, 401, 501, 601, 701, and 801 in accordance with embodiments of the disclosure will be discussed with reference to the flow chart in
[0613] In some embodiments where there is a recess defined between (i) a first plane comprising the first surface area and the third surface area and (ii) a first central surface area, the recess may be formed by etching, laser ablation or mechanically working the first major surface. For example, the first major surface may be mechanically worked by diamond engraving (e.g., using computer numeric control (CNC)) to produce very precise patterns in foldable substrates. Materials other than diamond can be used for engraving with a CNC machine. Furthermore, other methods of forming the recess include lithography, etching, and laser ablation. In some embodiments, the substrate can be etched by placing it in an etching bath comprising one or more mineral acids (e.g., HCl, HF, H.sub.2SO.sub.4, HNO.sub.3). Etching can comprise reducing a thickness of the substrate and/or removing surface flaws (e.g., surface imperfections generated during formation of the recess, surface imperfections generated during chemically strengthening). In further embodiments, etching can be designed to remove less than 5-10 nanometers (nm) of a compressive stress layer generated by chemical strengthening. In some embodiments, methods of forming a recess can follow the flow chart in
[0614] After step 2701, as shown in
[0615] In some embodiments, chemically strengthening the substrate can create a stored strain energy within at least a portion of the substrate. As used herein, stored strain energy refers to the product of a prefactor and an area integral of the square of tensile portions (e.g., central tension) of a stress profile between a midplane of the substrate and a surface of the substrate. The prefactor is the (1−v)/E, where v is Poisson's ratio of the substrate and E is the elastic modulus of the substrate. In some embodiments, the stored strain energy within at least a portion of the substrate can be about 10 Joules per meter squared (J/m.sup.2) or more, about 20 J/m.sup.2 or more, about 25 J/m.sup.2 or more, about 30 J/m.sup.2 or more, about 100 J/m.sup.2 or less, about 60 J/m.sup.2 or less, about 40 J/m.sup.2 or less. In some embodiments, the stored strain energy within at least a portion of the substrate can be in a range from about 10 J/m.sup.2 to about 100 J/m.sup.2, from about 10 J/m.sup.2 to about 60 J/m.sup.2, from about 20 J/m.sup.2 to about 60 J/m.sup.2, from about 25 J/m.sup.2 to about 60 J/m.sup.2, from about 25 J/m.sup.2, to about 40 J/m.sup.2, from about 30 J/m.sup.2 to about 40 J/m.sup.2, from about 25 J/m.sup.2 to about 100 J/m.sup.2, from about 30 J/m.sup.2 to about 100 J/m.sup.2, from about 30 J/m.sup.2 to about 60 J/m.sup.2, or any range or subrange therebetween. In further embodiments, the central portion can comprise the stored strain energy. In further embodiments, the first portion and/or the second portion can comprise the stored strain energy. In even further embodiments, at least a portion of the first portion, the second portion, and the central portion can comprise the stored strain energy. Providing a stored strain energy within one or more of the above-mentioned ranges can facilitate the formation of a shattered pane.
[0616] In some embodiments, as shown in
[0617] The backer layer 3101 can comprise a flexible layer (e.g., a flexible film) and, in some embodiments, may be able to stretch to increase the length of the backer layer 3101. In some embodiments, the backer layer 3101 can comprise the second material 256, as discussed above. In some embodiments, the backer layer 3101 can comprise a removable layer that may be removed by a wide range of techniques, for example, peeling off the layer, heating the layer, exposing the layer to light or other techniques. In some embodiments, the backer layer 3101 can comprise a polymeric material although the backer layer 3101 may be formed from other materials in further embodiments. In further embodiments, a liquid or other material may be sprayed, printed or otherwise applied to the second major surface 205 and cured into the backer layer 3101. In even further embodiments, the backer layer 3101 may comprise applying a previously formed layer to the second major surface 205. In further embodiments, the previously formed layer can comprise a tape that is adhered to the second major surface 205 of the foldable substrate 201. In even further embodiments, the backer layer 3101 can comprise a polymeric pressure sensitive adhesive, for example, a block copolymer (e.g., a styrene-rubber block copolymer). In still further embodiments, the pressure sensitivity adhesive can comprise a high-temperature release film, meaning that the adhesion of the polymeric adhesive to the foldable substrate 201 decreases above a predetermined temperature (e.g., 100° C., 150° C., 200° C., 300° C., 400° C.), which can comprise, for example, polypropylene, PVF, ETFE, FEP, polyimide, and/or polymethylpentene. In still further embodiments, the pressure sensitivity adhesive can comprise a low-temperature release film, meaning that the adhesion of the polymeric adhesive to the foldable substrate 201 decreases below a predetermined temperature (e.g., 100° C., 50° C., 30° C.). Providing a pressure sensitive adhesive that comprises a temperature sensitive release film (e.g., high-temperature release film, low-temperature release film) can reduce processing costs and potential damage to the foldable substrate associated with removing the layer.
[0618] In some embodiments, as shown in
[0619] As shown in
[0620] In some embodiments, as shown in
[0621] In some embodiments, as shown in
[0622] In some embodiments, as shown in
[0623] Without wishing to be bound by theory, heating the shattered pane (e.g., a portion of the shattered pane) after it has been chemically strengthened and then shattered can redistribute an ion-concentration gradient introduced by the chemically strengthening and, thereby reduce the compressive stress in the shattered pane. Also, redistributing the ion-concentration gradient can change a refractive index of the shattered pane and, thereby reduce a difference in refractive index from a surface of the shattered pane (e.g., first major surface, first central surface area, second major surface) and a refractive index at the midpoint of the substrate thickness, which can reduce optical distortions. Additionally, redistributing the ion-concentration gradient can reduce the maximum compressive stress of the corresponding compressive stress region at the heated surface. Without wishing to be bound by theory, heating the shattered pane (e.g., a portion of the shattered pane) after it has been chemically strengthened and then shattered can increase a depth of layer of the one or more alkali metal ions associated with the corresponding compressive stress region at the heated surface, for example, by increasing diffusion of the ions. Without wishing to be bound by theory, the period of time that the shattered pane is heated can be decreased as the temperature that the shattered pane is heated to and/or heated at is increased, for example, following an Arrhenius relationship to obtain a predetermined change in refractive index, maximum compressive stress, and/or depth of layer. Also, heating the shattered pane may reduce the compressive stress by causing stress relaxation in the composition matrix of the material of the shattered pieces.
[0624] In some embodiments, the heating of step 2717 or step 2719 can increase an existing depth of layer, increase an existing depth of compression, and/or reduce an existing maximum compressive stress. As used here, “existing” refers to prior to step 2717 or step 2719. An existing compressive stress region comprising an existing depth of compression and existing maximum compressive stress as well as an associated existing depth of layer can be provided, as a result of step 2703 comprising chemically strengthening the foldable substrate 201 or providing a foldable substrate 201 in step 2701 that has been chemically strengthened. In some embodiments, step 2717 or step 2719 can produce a first central depth of layer as a percent of the thickness (e.g., central thickness 226) of the shattered pane 231 that can be greater than an existing first central depth of layer as a percent of the thickness (e.g., central thickness 226) of the shattered pane 231 by about 1% or more, by about 2% or more, by about 5% or more, by about 8% or more, by about 10% or more, by about 12% or more, by about 30% or less, by about 25% or less, by about 20% or less, by about 18% or less, or about 15% or less. In some embodiments, step 2717 or step 2719 can produce a first central depth of layer as a percent of the thickness (e.g., central thickness 226) of the shattered pane 231 that can be greater than an existing first central depth of layer as a percent of the thickness (e.g., central thickness 226) of the shattered pane 231 in a range from about 1% to about 30%, from about 1% to about 25%, from about 2% to about 25%, from about 2% to about 20%, from about 5% to about 20%, from about 5% to about 18%, from about 8% to about 18%, from about 8% to about 15%, from about 10% to about 15%, from about 12% to about 15%, or any range or subrange therebetween. In some embodiments, step 2717 or step 2719 can produce a first maximum compressive stress of the first compressive stress region as a percentage of an existing first maximum compressive stress of the existing first compressive stress region of about 10% or more, about 20% or more, about 30% or more, about 40% or more, about 45% or more, about 90% or less, about 80% or less, about 70% or less, about 60% or less, about 55% or less, or about 50% or less. In some embodiments, step 2717 or step 2719 can produce a first maximum compressive stress of the first compressive stress region as a percentage of an existing first maximum compressive stress of the existing first compressive stress region in a range from about 10% to about 90%, from about 20% to about 90%, from about 20% to about 80%, from about 30% to about 80%, from about 30% to about 70%, from about 40% to about 70%, from about 40% to about 60%, from about 45% to about 60%, from about 45% to about 55%, from about 45% to about 50%, or any range subrange therebetween. In some embodiments, step 2717 or step 2719 can produce a first central depth of compression of the first compressive stress region that can be greater than an existing first central depth of compression of an existing first compressive stress region.
[0625] In some embodiments, the heating of step 2717 or step 2719 can decrease an existing surface refractive index. In further embodiments, the heating step 2717 or step 2719 can decrease an existing first surface refractive index to a first surface refractive index by about 0.001 or more, about 0.002 or more, about 0.003 or more, about 0.004 or more, about 0.02 or less, about 0.015 or less, about 0.01 or less, about 0.008 or less, about 0.006 or less, or about 0.005 or less. In further embodiments, the heating step 2717 or step 2719 can decrease an existing first surface refractive index to a first surface refractive index in a range from about 0.001 to about 0.02, from about 0.001 to about 0.015, from about 0.002 to about 0.015, from about 0.002 to about 0.01, from about 0.003 to about 0.01, from about 0.003 to about 0.008, from about 0.004 to about 0.008, from about 0.004 to about 0.006, from about 0.004 to about 0.005, or any range or subrange therebetween. In further embodiments, an absolute difference between the first surface refractive index and the central refractive index can be greater than an absolute difference between the existing first surface refractive index and the existing central refractive index can be within one or more of the ranges discussed above in this paragraph for the decreased in the existing first surface refractive index. In some embodiments, the heating step 2717 or step 2719 can decreases an existing second surface refractive index to a second surface refractive index within one or more of the ranges discussed above in this paragraph for the decreased in the existing first surface refractive index. In further embodiments, an absolute difference between the second surface refractive index and the central refractive index can be greater than an absolute difference between the existing second surface refractive index and the existing central refractive index can be within one or more of the ranges discussed above in this paragraph for the decreased in the existing first surface refractive index.
[0626] In some embodiments, as shown in
[0627] As further shown in
[0628] In some embodiments, the first liquid 3505 can comprise any of the materials or precursors of the first material 254 and can optionally comprise a solvent. Precursors can comprise, without limitation, one or more of a monomer, an accelerator, a curing agent, an epoxy, and/or inorganic particles. Example embodiments of solvents include polar solvents (e.g., water, an alcohol, an acetate, acetone, formic acid, dimethylformamide, acetonitrile, dimethyl sulfoxone, nitromethane, propylene carbonate, polyether ether ketone) and non-polar solvents (e.g., pentane, 1,4-dioxane, chloroform, dichloromethane, diethyl ether, hexane, heptane, benzene, toluene, xylene). In some embodiments, the first liquid 3505 can be substantially solvent free. In some embodiments, the first liquid 3505 can comprise the composition that can be cured to form the adhesive described above. In some embodiments, the first liquid 3505 can comprise a viscosity. As used herein, a viscosity of a liquid is measured at 23° C. using a rotational rheometer (e.g., RheolabQC from Anton Par or a Discovery Hybrid Rheometer (DHR-3) from TA Instruments) at a shear rates of about 0.01 1/second (s). In further embodiments, the first liquid 3505 can comprise a viscosity of about 10 milliPascal-seconds (mPa-s) or more, about 50 mPa-s or more, about 100 mPa-s or more, about 300 mPa-s or more, about 500 mPa-s or more, about 1,000 mPa-s or more, about 3,000 mPa-s or more, about 10,000 mPa-s or less, about 7,000 mPa-s or less, about 6,000 mPa-s or less, about 5,000 mPa-s or less, about 2,000 mPa-s or less, or about 1,000 mPa-s or less. In some embodiments, the first liquid 3505 can comprise a viscosity in a range from about 10 mPa-s to about 10,000 mPa-s, from about 10 mPa-s, to about 7,000 mPa-s, from about 10 mPa-s to about 6,000 mPa-s, from about 50 mPa-s to about 6,000 mPa-s, from about 100 mPa-s to about 6,000 mPa-s, from about 100 mPa-s to about 5,000 mPa-s, from about 300 mPa-s to about 5,000 mPa-s, from about 500 mPa-s to about 5,000 mPa-s, from about 1,000 mPa-s to about 5,000 mPa-s, from about 3,000 mPa-s to about 5,000 mPa-s, from about 100 mPa-s to about 3,000 mPa-s, from about 5,000 mPa-s to about 7,000 mPa-s, or any range or subrange therebetween. In some embodiments, the first material 254 can comprise the adhesive and/or the polymer-based portion discussed above, and the first liquid 3505 can comprise precursors of (e.g., the compositions described above to form) the corresponding material. In some embodiments, the first liquid 3505 can be substantially solvent free.
[0629] In some embodiments, step 2709 can further comprise curing the first liquid 3505 to form the first material 254. In further embodiments, as shown in
[0630] The first material 254 can comprise an elastic modulus within one or more of the ranges discussed above for the elastic modulus of the first material 254 (e.g., in a range from about 10 kPa to about 18 GPa). In some embodiments, as discussed above, the elastic modulus of the first material 254 can be less than the elastic modulus of a shattered piece of the plurality of shattered pieces 1305. In some embodiments, the elastic modulus of the first material 254 can change as the temperature of the first material 254 goes from about 100° C. to about −20° C. by a multiple within one or more of the ranges discussed above (e.g., about 100 or less). In some embodiments, the first material 254 can comprise one or more of the materials discussed above for the first material 254. In further embodiments, the first material 254 can comprise one or more of a silicone-based polymer, an acrylate-based polymer, an epoxy-based polymer, a thiol-containing polymer, and/or a polyurethane. In further embodiments, the first material 254 can comprise a silicone elastomer. In some embodiments, the first material 254 can comprise a glass transition temperature within at least one of the ranges discussed above for the glass transition temperature of the first material 254 (e.g., about 0° C. or less, about −20° C. or less, about 60° C. or more). In some embodiments, the first material 254 can comprise a glassy plateau, and an elastic modulus of the first material 254 in the glassy plateau can be within one or more of the ranges discussed above for the first material 254 (e.g., in a range from about 100 kPa to about 18 GPa). In some embodiments, a total mass of the first material 254 as a percentage of the total mass of the plurality of shattered pieces can be within one or more of the ranges discussed above (e.g., about 10% or less).
[0631] After step 2709, as shown in
[0632] In some embodiments, after step 2711 methods can proceed to step 2743 comprising assembling the foldable apparatus by deposing one or more items over the adhesive layer. In further embodiments, a release liner (e.g., see release liner 213 in
[0633] Further embodiments of the disclosure will now be discussed with reference to the flow chart of
[0634] After step 2721, methods can proceed to step 2723 comprising removing the backer layer 3101. In some embodiments, as shown in
[0635] Curing the second liquid 4003 to form the second material 256 can integrate and permanently attach the shattered pane 231 with respect to the first and second portions 221, 223 (e.g., by contacting the first and second transition portions 227, 229 or the first and second portions 221, 223). In some embodiments, as discussed above, the first material 254 and the second material 256 may comprise the same material although different materials may be provided in further embodiments.
[0636] The second material 256 can comprise an elastic modulus within one or more of the ranges discussed above for the elastic modulus of the second material 256 (e.g., in a range from about 100 kPa to about 5 GPa). In some embodiments, the storage modulus (i.e., modulus of elasticity) of the second material 256 can change as the temperature of the second material 256 goes from about 100° C. to about −20° C. by a multiple within one or more of the ranges discussed above (e.g., about 100 or less). In some embodiments, the second material 256 can comprise one or more of the materials discussed above for the first material 254 and/or the second material 256. In further embodiments, the second material 256 can comprise one or more of a silicone-based polymer, an acrylate-based polymer, an epoxy-based polymer, a polyimide-based material, and/or a polyurethane. In further embodiments, the second material 256 can comprise an ethylene acid copolymer. In some embodiments, the second material 256 can comprise a glass transition temperature within at least one of the ranges discussed above for the glass transition temperature of the second material 256 (e.g., about 0° C. or less, about −20° C. or less, about 60° C. or more). In some embodiments, the second material 256 can comprise a glassy plateau, and a storage modulus of the second material 256 in the glassy plateau can be within one or more of the ranges discussed above for the second material 256 (e.g., in a range from about 100 kPa to about 10 GPa). In some embodiments, a strain at yield of the second material 256 as a can be within one or more of the ranges discussed above (e.g., about 100% or more).
[0637] Further embodiments of the disclosure will now be discussed with reference to the flow chart of
[0638] After step 2727, as shown in
[0639] In some embodiments, as discussed above with reference to the flow chart in
[0640] In some embodiments, the foldable apparatus after step 2743 can comprise a neutral stress configuration when the foldable apparatus is in a bent configuration. In further embodiments, the foldable apparatus can comprise a maximum magnitude of the deviatoric strain of the polymer-based portion in one or more of the ranges discussed above (e.g., in a range from about 1% to about 8%, from about 2% to about 6%) in the neutral stress configuration. In further embodiments, the foldable apparatus can comprise an angle within one or more of the ranges discussed above in the neutral stress configuration. In some embodiments, the neutral stress configuration can correspond to a bent configuration as a result of curing the liquid (e.g., first liquid 3505, second liquid 4003) to form the second material 256 (or the first material 254) while the foldable substrate 201 was in a bent configuration. In some embodiments, the neutral stress configuration can correspond to a bent configuration as a result of an increase in volume in curing the liquid (e.g., first liquid 3505, second liquid 4003) to form the second material 256 (or the first material 254). In some embodiments, the neutral stress configuration can correspond to a bent configuration as a result of the second material 256 (or first material 254) comprising a negative coefficient of thermal expansion.
[0641] Embodiments of methods of making the foldable apparatus 901 and 1001 in accordance with embodiments of the disclosure will be discussed with reference to the flow chart in
[0642] Example embodiments of making the foldable apparatus 901 and 1001 can include providing the foldable substrate 201 as indicated at 4311 in
[0643] Referring to the flow chart in
[0644] After step 4301, as shown in
[0645] After step 4303, as further shown in
[0646] In some embodiments, the thickness of the foldable substrate 2801 can be reduced by removing a layer from the first major surface 2803 of the foldable substrate 2801 to expose a new first major surface that can comprise the first major surface 203. In addition, or alternatively, the thickness of the foldable substrate 2801 can be reduced by removing a layer from the second major surface 2805 of the foldable substrate 2801 to expose a new second major surface that can comprise the second major surface 205.
[0647] In some embodiments, removing the layer from the first major surface 2803 can be beneficial to remove surface imperfections generated during formation of the recess 2809. For example, mechanically working the first major surface 2803 (e.g., with a diamond tip probe) to generate the recess 2809 may generate cracks or other imperfections that can present points of weakness where catastrophic failure of the foldable substrate 2801 may occur upon bending. Thus, by removing the layer from the first major surface 2803, surface imperfections generated in the layer during formation of the recess 2809 may be removed where a new first major surface 203 with less surface imperfections can be presented. As fewer surface imperfections are present, a smaller bend radius may be achieved without failure of the foldable substrate. Furthermore, some processing of foldable substrates comprising glass-based substrate may present differences in glass-based material properties at the first and second major surfaces of the glass-based substrate than central portions of the glass-based substrate. For example, during a down-draw process, properties of the glass-based substrate at the major surfaces of the glass-based substrate may be different than central portions of the glass-based substrate. Thus, by removing the layer from the first major surface 2803 at the first portion 2821 and the second portion 2823, the new first major surface 203 of these portions can have the same properties as the material forming the first central surface area 2807 to provide consistent optical properties across the length of the foldable substrate.
[0648] In some embodiments, the second major surface 2805 (e.g., the entire second major surface 2805) may be covered with the optional mask 2905 such that the second major surface 2805 is not etched and may provide the second major surface 2805 as the second major surface 205 discussed above. Preventing etching of the second major surface 2805 may be beneficial to preserve a pristine nature of the second major surface 2805 that may exist with some processing techniques (e.g., up draw or down draw). Maintaining the pristine surface may present a particularly smooth surface for the second major surface 2805 that may form the outermost surface of the foldable apparatus that may be observed and/or touched by a user of the foldable apparatus. Alternatively, the thickness of the foldable substrate 2801 can be reduced by removing the layer from the second major surface 2805, for example, to remove the skin layer to expose a central layer with more consistent optical properties across the length of the foldable substrate at discussed above. Thus, in some embodiments, a layer can be removed from the second major surface 2805 to expose a new second major surface that can comprise the second major surface 205.
[0649] In some embodiments, the layer can be removed from the first major surface 2803 to expose the new first major surface that can comprise the first major surface 203, and the layer can be removed from the second major surface 2805 to expose the new second major surface that can comprise the second major surface 205. Removing the layers from both the first and second major surfaces can remove that outer skin layers of the foldable substrate comprising a glass-based substrate that may have more inconsistent optical properties than the underlying interior portions of the foldable substrate. Consequently, the entire thickness throughout the length and the width of the foldable substrate may have more consistent optical properties to provide consistent optical performance with little or no distortions across the entire foldable substrate.
[0650] As shown in
[0651] After step 4305, as further shown in
[0652] Chemically strengthening the foldable substrate 201 comprising a glass-based substrate can comprise chemically strengthening the first central surface area 233 of the central portion 225, chemically strengthening the first surface area 237 of the first portion 221 of the first major surface 203, chemically strengthening the third surface area 239 of the second portion 223 of the first major surface 203, and the second major surface 205 of the foldable substrate 201 comprising a glass-based substrate and/or a ceramic-based substrate. In some embodiments, chemically strengthening comprises chemically strengthening the first portion 221 to a first depth of compression from the first surface area 237 of the first major surface 203, chemically strengthening the second portion 223 to a third depth of compression from the third surface area 239 of the first major surface 203, and chemically strengthening the central portion 225 to a first central depth of compression from the first central surface area 233 of the central portion 225. In further embodiments, the first central depth of compression (e.g., of the central portion 225 from the first central surface area 233) can be less than the first depth of compression (e.g., of the first portion 221 from the first major surface 203). In further embodiments, the first central depth of compression (e.g., of the central portion 225 from the first central surface area 233) can be less than the third depth of compression (e.g., of the second portion 223 from the first major surface 203).
[0653] In some embodiments, chemically strengthening the second major surface 205 of the foldable substrate 201 comprising a glass-based substrate and/or a ceramic-based substrate can comprise chemically strengthening the second surface area 247 of the first portion 221 of the second major surface 205, chemically strengthening the fourth surface area 249 of the second portion 223 of the second major surface 205, and chemically strengthening the second central surface area 245 of the central portion 225 of second major surface 205. In some embodiments, chemically strengthening the second major surface 205 can comprise chemically strengthening the first portion 221 to a second depth of compression from the second surface area 247 of the second major surface 205, chemically strengthening the second portion 223 to a fourth depth of compression from fourth surface area 249 of the second major surface 205, and chemically strengthening the central portion 225 to a second central depth of compression from the second central surface area 245 of the second major surface 205.
[0654] In further embodiments, the second central depth of compression (e.g., of the central portion 225 from the second central surface area 245 of the second major surface 805) can be less than the second depth of compression (e.g., of the first portion 221 from the second surface area 247 of the second major surface 205). In further embodiments, the second central depth of compression (e.g., of the central portion 225 from the second central surface area 245 of the second major surface 805) can be less than the fourth depth of compression (e.g., of the second portion 223 from the fourth surface area 249 of the second major surface 205).
[0655] After step 4307, as further shown in
[0656] In some embodiments, methods of making the foldable substrate 201 appearing at step 4311 in
[0657] Methods of making the foldable apparatus 901 and 1001 from the provided foldable substrate 201 from
[0658] Methods of making the foldable apparatus 901 and 1001 can modify the foldable substrate 201 provided at step 4311 by dividing the central portion into the plurality of panes 950 as represented by step 4403 in
[0659] Other embodiments of the step 4403 of dividing is illustrated in
[0660] Other embodiments of the step 4403 of dividing is illustrated in
[0661] The holes 5001 (e.g., through holes) can be provided in a wide range of ways, for example, mechanical drilling, chemical etching, ablating with a laser or other techniques. By way of example, as shown in
[0662] As shown in
[0663] In any of the embodiments of the disclosure can including applying the backer layer 3101 (e.g., tape) to the central portion 225 prior to the step 4403 of dividing the central portion 225 into the plurality of panes 950 in any of the embodiments discussed above. The backer layer 3101 can act to help maintain the position of the first portion 221, the central portion 225 (including the plurality of panes 950) and the second portion 223 relative to one another despite the fact that the panes 950 may separate and independent from one another with the first portion 221 separated from a first outer pane 950, the second portion 223 separated from a second outer pane 950 opposite the first outer pane 950 and adjacent pairs of panes 950 separated from one another and positioned between and including the first and second outer panes 950.
[0664]
[0665] As further shown in
[0666]
[0667] As indicated by arrow 4402 in
[0668]
[0669] As shown by arrow 4406, the method may end at 4413 after the step 4407 of flowing and curing the first material 254. Alternatively, in some embodiments, the method may proceed to step 4415 of removing the backer layer 3101 from the foldable substrate 201. The backer layer 3101 can be removed in a wide range of ways, for example, by heating, exposing to UV light, peeling, or other techniques.
[0670] After step 4415, as shown in
[0671] As shown in
[0672] In some embodiments, during step 4421 of
[0673] In some embodiments, the foldable apparatus after step 4413 can comprise a neutral stress configuration when the foldable apparatus is in a bent configuration. In further embodiments, the foldable apparatus can comprise a maximum magnitude of the deviatoric strain of the polymer-based portion in one or more of the ranges discussed above (e.g., in a range from about 1% to about 8%, from about 2% to about 6%) in the neutral stress configuration. In further embodiments, the foldable apparatus can comprise an angle within one or more of the ranges discussed above in the neutral stress configuration. In some embodiments, the neutral stress configuration can correspond to a bent configuration as a result of curing the liquid (e.g., first liquid 3505, second liquid 4003) to form the first material 254 (or the second material 256) while the foldable substrate 201 was in a bent configuration. In some embodiments, the neutral stress configuration can correspond to a bent configuration as a result of an increase in volume in curing the liquid (e.g., first liquid 3505, second liquid 4003) to form the first material 254 (or the second material 256). In some embodiments, the neutral stress configuration can correspond to a bent configuration as a result of the first material 254 (or second material 256) comprising a negative coefficient of thermal expansion.
EXAMPLES
[0674] Various embodiments will be further clarified by the following examples. Tables 4-7 present information about embodiments of polymer-based portions, which may be used as the first material 254 and/or the second material 256. Tables 8-10 present information about embodiments of adhesives. Tables 11-12 present calculated times to halve a maximum initial compressive stress for a glass-based substrate (having a Composition 1 of, nominally, in mol % of: 69.1 SiO.sub.2; 10.2 Al.sub.2O.sub.3; 15.1 Na.sub.2O; 0.01 K.sub.2O; 5.5 MgO; 0.09 SnO.sub.2) having a substrate thickness of 100 μm. Examples 1-10 demonstrate exemplary methods of making a glass-based substrate. As used herein, a liquid refractive index refers to the refractive index of the composition before it is cured while the cured refractive index refers to the refractive index of the composition after it is cured. Haze values were measured with a CIE D65 illuminant. Haze values were measured at an angle of 10° relative to an angle of incidence normal to the surface.
[0675] Compositions of Examples A-O are presented in Table 4. RX0057 (Allinex), Photomer 6320 (IGM Resins), and Miramer SC2565 (Miwon) are difunctional urethane-acrylate oligomers. Photomer 4184 (IGM Resins) is a difunctional cross-linking agent, Miramer M166 (Miwon), Miramer M170 (Miwon), Miramer M1084 (Miwon), Miramer M1539 (Miwon), Miramer M1192 (Miwon), and Miramer M1140 (Miwon) are reactive diluents. Kraton G1650 (Kraton) is an elastomer. These examples can be combined with a mercapto-silane and/or a photo-initiator. Examples A-N are embodiments of the polymer-based portion of the disclosure. Specifically, Examples C-N fall within one or more of the ranges R1-R4 in Table 1. Example O is a comparative example.
TABLE-US-00004 TABLE 4 Composition ranges (wt %) of embodiments of polymer-based portions Example A B C D E F G H I J K L M N O RX0057 20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Photomer 6230 40 40 64 50 50 60 50 50 50 50 0 0 0 0 0 Dymax BR-543 0 0 0 0 0 0 0 0 0 0 50 50 50 50 0 Miramer SC2565 0 0 0 0 0 0 0 0 0 0 0 0 0 0 50 Photomer 4184 20 24 32 30 30 40 0 0 0 0 0 0 0 0 0 Miramer M166 0 0 0 0 0 0 40 0 0 0 40 0 0 25 0 Miramer M170 0 0 0 0 0 0 0 40 0 0 0 0 0 0 0 Miramer M1084 0 0 0 0 0 0 0 0 40 0 0 40 20 25 0 Miramer M1539 0 0 0 0 0 0 0 0 0 40 0 0 0 0 0 Miramer M1192 0 16 0 20 10 10 10 10 10 10 10 10 0 0 0 Miramer M1140 0 0 0 0 0 0 0 0 0 0 0 0 0 0 50 Miramer HR3700 0 0 0 0 0 0 0 0 0 0 0 0 30 0 0 Kraton G1650 20 20 0 0 0 0 0 0 0 0 0 0 0 0 0
TABLE-US-00005 TABLE 5 Properties of embodiments of polymer-based portions Example A B C D E F Tg (° C.) n/a n/a 34 12 16 13 Tensile Strength (MPa) 2.30 0.75 12.3 1.32 1.74 2.15 Ultimate Elongation (%) 37 67 65 100 107 107 Elastic Modulus (MPa) 7.0 0.1 23.4 2.9 2.7 3.4 Transmittance (%) 87.2 87.4 91.4 91.8 87.6 87.4 Haze (%) 0.79 3.06 0.15 0.07 0.51 0.10 Liquid Refractive Index 1.466 1.503 1.495 1.481 1.482 1.494 Cured Refractive Index 1.465 1.498 1.500 1.513 1.499 1.499 Example G H I J K L N O Tg (° C.) −29 −24 −13 −17 −32 −39 −35 45 Tensile Strength 0.55 0.66 0.62 0.47 0.71 0.51 0.53 24.4 (MPa) Ultimate 59 42 76 44 172 181 150 297 Elongation (%) Elastic Modulus 1.5 2.1 1.6 1.5 1.2 0.9 0.9 27.0 (MPa) Transmittance 87.3 87.6 87.4 87.8 87.4 87.5 87.5 87.6 (%) Haze (%) 0.92 0.33 0.81 0.49 0.58 0.14 0.03 0.10 Liquid 1.493 1.471 1.469 1.478 1.493 1.471 1.481 1.485 Refractive Index Cured Refractive 1.503 1.491 1.491 1.492 1.500 1.489 1.493 1.499 Index
[0676] Table 5 presents properties of Examples A-N and Example 0. Examples C-F comprise glass transition temperatures from about 10° C. to about 35° C. while Examples G-N comprise glass transition temperatures less than −10° C., and Examples G-H and Examples K-N comprise glass transition temperatures less than −20° C. Example C comprises a tensile strength of 12.3 MPa. Example A and Examples D-F comprise tensile strengths from about 1 MPa to about 3 MPa while Example B, Examples G-L, and Example N comprise tensile strengths from about 0.3 MPa to about 0.7 MPa. Examples D-F, Examples K-L, and Example K comprise ultimate elongations of 100% or more while Examples B-C and Example I comprise ultimate elongations from about 60% to about 80%, and Examples G-H and Example J comprise ultimate elongations from about 40% to about 60%. Example C comprises an elastic modulus of 23.4 MPa while Example A comprises an elastic modulus of 7.0 MPa. Examples D-L and Example N comprise elastic moduli from about 0.9 MPa to about 3.4 MPa. Examples C-D comprise transmittances of more than 90% and hazes from about 0.05% to about 0.20%. Examples A-O comprise transmittances of more than 87%. Example A an Examples C-O comprise hazes less than 1%. Examples B-O comprise cured refractive indices from about 1.49 to about 1.52. The refractive index can be increased by increasing the content of Miramer M1192 with refractive indices between 1.49 and 1.53 observed when the content of Miramer M1192 in Example E was adjusted from 0% wt to about 30% wt. The liquid refractive index for Examples B-G, Example K, and Examples N-O are from 1.48 and 1.505 while the liquid refractive index for Example A, Examples H-J, and Example L is from 1.46 to 1.48. In Examples C-O, the cured refractive index is greater than the liquid refractive index. Examples C-N all withstood 2,000 bending cycles at a parallel plate distance of 3 millimeters. In contrast, Example O failed to withstand 2,000 cycles at a parallel plate distance of 4 millimeters. Example C 23° C. fully recovered after being extended to a strain of 40% at a strain rate of 10% strain per minute at 23° C. In contrast, Example N comprised a strain set of 3% after being extended to a strain of 40% at a strain rate of 10% strain per minute at 23° C.
TABLE-US-00006 TABLE 6 Composition ranges (wt %) of embodiments of polymer-based portions Example P Q R S T U V W X Dymax BR-543 0 0 0 0 0 0 9 23 1 Miramer M200 0.1 0.5 1 0.1 0.5 1 0 0 0 2-Propylheptyl 0 0 0 60 59.8 59.5 55 46 59 acrylate Butyl Acrylate 55 54.8 54.5 0 0 0 0 0 0 Miramer 1192 44.9 44.7 44.5 39.9 39.7 39.5 36 31 40
TABLE-US-00007 TABLE 7 Properties of embodiments of polymer-based portions Example P Q R S T U V W X Tg (° C.) −5 −4 −3 n/a −19 −19 −27 −28 n/a Transmittance (%) 86.7 86.7 86.7 87.1 87.0 87.1 87.1 n/a 87.3 Haze (%) 0.07 0.03 0.04 0.11 0.08 0.06 0.12 n/a 0.06 Liquid 1.495 1.495 1.494 1.497 1.498 1.497 1.495 1.492 1.497 Refractive Index Cured 1.616 1.621 1.609 1.528 1.528 1.528 1.549 n/a 1.532 Refractive Index
[0677] Table 6 presents the compositions of Examples P-X. Examples P-X are embodiments of the polymer-based portion of the disclosure. Specifically, Examples P-X fall within one or more of the ranges R1-R4 in Table 1. Properties of Examples P-X are presented in Table 7. Examples P-R and Examples T-W comprised a glass transition temperature less than 0° C. Further, Examples T-U comprised a glass transition temperature of -19° C. while Examples V-W comprised a glass transition temperature less than −20° C. The liquid refractive index for Examples P-X were between 1.49 and 1.50. The cured refractive indices for Examples S-U were 1.528, the cured refractive index for Example X was 1.532, and the cured refractive index for Example V was 1.549. Also, Example U comprised a tensile strength of 0.07 MPa, an ultimate elongation of 161%, and an elastic modulus of 0.13 MPa. Example V comprises a tensile strength of 0.12 MPa, an ultimate elongation of 205%, and an elastic modulus of 0.17 MPa. Additionally, Example W comprised a tensile strength of 0.4 MPa, an ultimate elongation of 99%, and an elastic modulus of 0.6 MPa.
TABLE-US-00008 TABLE 8 Composition ranges (wt %) of embodiments of adhesive materials Range AA BB CC DD EE FF GG SMS-992 98 19.5 16.2 25 20 11.3 0 Miramer 2 0.5 0.3 0 0 0 0 M1192 PDV-2331 0 20 22 25 40 87.5 45.7 MTV-112 0 0 8.8 0 0 1.2 0 VPT-1323 0 60 52.7 50 40 0 22.8
TABLE-US-00009 TABLE 9 Properties of embodiments of adhesive materials Property BB DD EE FF Tg (° C.) −73 −74 −73 −73 Storage Modulus 9.6 3.0 3.2 6.6 (MPa), 23° C. Loss Modulus 1.20 0.50 0.31 0.82 (MPa), 23° C.
[0678] Compositions of Examples AA-GG are presented in Table 8. SMS-992 (Gelest) is a silane-hydride-terminated siloxane. PDV-2331 (Gelest), MTV-112 (Gelest), and VPT-1323 are vinyl-terminated siloxanes. SMS-992 (Gelest) is a thiol-containing siloxane. These examples can be combined with a silane coupling agent, catalyst, and/or photo-initiator. Examples AA-GG are embodiments of the polymer-based portion of the disclosure. Specifically, Examples AA-GG fall within one or more of the ranges R10-R12 in Table 2.
[0679] Table 9 presents properties of Examples BB and DD-FF. Examples BB and DD-FF comprise glass transition temperatures from about −75° C. to about −70° C. At 23° C., Example BB comprises a storage modulus of 9.6 MPa and a loss modulus of 1.20 MPa while Examples DD-FF comprise storage moduli from about 3 MPa to about 7 MPa and loss moduli from about 0.30 MPa to about 0.90 MPa.
TABLE-US-00010 TABLE 10 Properties of embodiments of adhesive materials Property BB Control Transmittance (%) 85.9 85.7 (KrystalFlex) Haze (%) 20 20 (KrystalFlex) Transmittance (%) 92.2 85.7 (Sylgard 184) Haze (%) 15 30 (Sylgard 184) Steel Wool Ripped after Ripped after Abrasion 1,700 cycles 5 cycles (Sylgard 184)
[0680] Haze and transmittance of the adhesives (e.g., Example BB) can be evaluated as included in a shattered pane. The shattered pane with the adhesive positioned between at least an adjacent pair of the plurality of shattered pieces comprising the shattered pane was prepared following Example 2 or Example 3 (see below). The shattered pane comprised a 1 mm thick glass-based substrate comprising Composition 1 (see below). The control example comprised a shattered pane without a first material positioned between the shattered pieces comprising the shattered pane. For the data presented in Table 10, the shattered pane was attached to a second material comprising a thickness of 75 μm comprising the material listed in parenthesis. KrystalFlex refers to KrystalFlex PE505 available from Huntsman. Sylgard 184 is available from Dow Chemical. The transmittance and/or haze are then measured for the combined apparatus as described above. Further, a steel wool abrasion test can be conducted using type #0000 steel wool rubbed at a rate of 40 cycles per minute until failure.
[0681] As shown in Table 10, Example BB comprises a higher transmittance than the control for both KrystalFlex (0.2% higher) and Sylgard 184 (6.5% higher). For KrystalFlex, both Example BB and the control comprise the same haze. For Sylgard 184, the control comprises a haze of 30% while Example BB comprises a haze of 15% (15% less). For the steel wool test, the control failed after 5 cycles while Example BB failed after 1,700 cycles.
[0682] Tables 11-12 were calculated based on the diffusion of alkali metal ions introduced in a prior chemically strengthening step and assumed an Arrhenius relationship for the time at different temperatures. Table 11 presents the time needed to halve a maximum initial compressive stress at temperatures from 250° C. to 400° C. Without wishing to be bound by theory, these temperatures correspond to temperatures easily achievable with commercial ovens. While the time at 250° C. is 505 hours, it drops as temperature is increased. For example at 300° C., the time is 68 hours, and at 400° C. it is less than 3 hours. While these times are for 100 μm thick glass-based substrates, the times are expected to be less for thinner glass-based substrates and greater for thicker glass-based substrates.
TABLE-US-00011 TABLE 11 Time to halve maximum initial compressive stress Temperature (° C.) Time (hours) 250 505 275 176 300 68 325 28 350 12.5 375 5.93 400 2.97
[0683] Example AAA having Composition 1, a substrate thickness of 100 μm, and an initial DOL of 43.5 μm (43.5% of the substrate thickness) was heated at 300° C. for 68 hours. Example AAA comprised a final DOL of 51.6 μm (51.6% of the substrate thickness). As suggested by Table 11, the final maximum compressive stress was half of the maximum initial compressive stress. A final difference between a first refractive index and a central refractive index was reduced by more than half of an initial difference between an initial first surface area refractive index and an initial central refractive index as a result of the heating.
[0684] Table 12 presents the time needed to halve a maximum initial compressive stress at temperatures from 575° C. to 1100° C. Without wishing to be bound by theory, these temperatures correspond to temperatures easily achievable with laser heating. While the time at 575° C. is 4.44 minutes, it drops as temperature is increased. For example at 600° C., the time is 2.96 minutes, and at 675° C. it is less than 1 minute. Further increasing the temperature, for example to 900° C., the time is 0.09 minutes (e.g., 5.5 seconds), and at 1100° C., the time is 0.02 minutes (e.g., 1.2 seconds). While these times are for 100 μm thick glass-based substrates, the times are expected to be less for thinner glass-based substrates and greater for thicker glass-based substrates.
TABLE-US-00012 TABLE 12 Time to halve maximum initial compressive stress Temperature (° C.) Time (min) 575 4.44 600 2.96 650 1.40 675 0.99 700 0.72 750 0.39 800 0.23 850 0.14 900 0.09 1000 0.04 1100 0.02
[0685] Examples 1-8 all comprise a foldable substrate comprising a glass-based substrate (having a Composition 1 of, nominally, in mol % of: 69.1 SiO.sub.2; 10.2 Al.sub.2O.sub.3; 15.1 Na.sub.2O; 0.01 K.sub.2O; 5.5 MgO; 0.09 SnO.sub.2) and a first thickness of 100 μm.
[0686] Example 1 comprised a glass-based substrate (Composition 1) with dimensions of 160 mm by 100 mm by 100 μm that was chemically strengthened in a bath comprising 100% molten KNO.sub.3 at 420° C. for 7 hours. Example 1 comprised compressive stress regions extending for a depth of compression of 18 μm (18% of the first thickness) from the first major surface and the second major surface, a maximum central tension of about 380 MPa, and a stored strain energy of about 38.6 J/m.sup.2.
[0687] Example 2 comprised chemically strengthened glass-based substrate of Example 1. A second material comprising a sheet of cured polyimide comprising a thickness of 50 μm was disposed over the second major surface of the substrate with a 25 μm OCA (3M 8146) positioned between the polyimide sheet and the substrate. Next, the substrate was shattered by cutting with scissors for a length of about 3 mm or less. The substrate curled, which increased the space between the shattered pieces at the first major surface. Then, a first liquid comprising a thermally curable sol-gel material comprising a viscosity of about 4,000 mPa-s infiltrated the spaces between the shattered pieces. The first liquid was cured at 150° C. for 1 hour to form the first material comprising a sol gel with an elastic modulus of about 15 GPa.
[0688] Example 3 comprised chemically strengthened glass-based substrate of Example 1 that was treated with gamma-aminopropyltrimethoxysilane on the second major surface. A 25 μm coating of a second liquid comprising a solution of polyimide precursors was slot die coated on to the second major surface and cured at 150° C. for 1 hour to form a polyimide layer as the second material. Next, the substrate was shattered using a silicon carbide scribe. Then, a first liquid comprising precursors of a thiol-ene-based UV curable silicone infiltrated the spaces between the shattered pieces. The first liquid was cured using a mercury lamp emitting UV light to form the first material. A 50 μm PET layer was disposed over the PI layer using an OCA (3M 8146) comprising a thickness of 25 μm.
[0689] Example 4 comprised chemically strengthened glass-based substrate of Example 1. A second liquid comprising a 150 μm coating of Eleglass W802-GL044 with only 2 wt % cross-linker was applied using a down-draw method. The second liquid was cured at 120° C. for 1 hour to form a 75 μm layer of the second material. Next, the substrate was shattered using a silicon carbide scribe. Then, a first liquid comprising precursors of a silicone elastomer (PP2-OE50 available from Gelest) infiltrated the spaces between the shattered pieces. The first liquid was cured at 100° C. for 1 hour to form the first material.
[0690] Example 5 was the same as Example 4 except that the second material comprising the Eleglass material was replaced with a polyurethane layer resulting from curing a 150 μm coating of an aqueous polyurethane dispersion (Dispurez 102) at 100° C. for 1 hour resulting in a 75 μm layer of the second material.
[0691] Example 6 was the same as Example 4 except that the second material comprising the Eleglass material was replaced with a silicone layer resulting from curing a 25 μm coating of Nu-Sil LS 8941 at 150° C. for 1 hour.
[0692] Example 7 was the same as Example 4 except that the second material comprising a 200 μm layer of mounting wax applied to the first major surface. After the first material was cured, a 50 μm PET layer was disposed over the second major surface using an OCA (3M 8146) comprising a thickness of 25 μm. Then, the mounting wax was removed by heating the substrate to 100° C. followed by using an acetone solution.
[0693] Example 8 comprised chemically strengthened glass-based substrate of Example 1. A first material comprising a 50 μm layer of thermoplastic polyurethane (TPU) (KrystalFlex PESOS) was disposed on the second major surface of the substrate. The TPU layer was adhered to the substrate using a vacuum-assisted autoclave process with a maximum temperature of 110° C. Next, the substrate was shattered using a silicon carbide scribe. Then, a substrate was placed in a Carver press that was heated to 150° C. and 300 pounds per square inch (psi) (e.g., about 2 GPa) of pressure was applied to force the TPU into the space between the shattered pieces.
[0694] Examples 9-10 relate to the foldable apparatus 1701, 1801, and 2401 shown in
[0695] In Example 9, glass substrates comprising Composition 1 and dimensions of 53 mm×90 mm×0.2 mm were spin coated with the final sol-gel coating solution. All spin coating was conducted by ramping for 5 seconds to 1,000 revolutions per minute (rpm) and holding this speed for 30 seconds followed by an immediate stop. Samples were removed from the spin coater and placed on a 150° C. hotplate for 30 minutes to drive off residual solvents and to begin curing the sol gel. Various bendable glass article samples were prepared by applying a narrow strip of the sol-gel coating to the center of the part with widths of 20 mm, 10 mm and 20 mm for Samples 9B, 9C, and 9D, respectively. Sample 9A is a control and was not subjected to spin coating with the sol-gel coating solution. During the spin coating, an adhesive mask was applied to mask off the uncoated area. The masked substrate was placed on the spin coater chuck and a disposable pipette was used to apply the sol-gel solution. The masked and coated substrate was then spun at 1,000 rpm for 30 seconds after which time the mask material was removed and the now unmasked substrate was placed on a hotplate that was preheated to 150° C. It was left on the hotplate for 30 minutes to drive off residual solvent and to begin the condensation of the sol-gel material. Once removed from the hotplate, each sample was placed on an alumina setter in a room temperature furnace and heated at 5° C./min to 700° C. The furnace was held at this temperature for 20 minutes and then the furnace was allowed to cool naturally to room temperature.
[0696] Further, in Example 9, the parts were removed from the furnace and examined for bend properties. Samples 9B, 9C, and 9D naturally developed into as-bent configurations with bend angles of 90° (“hamburger” configuration), 45° (“taco” configuration), 90° (“hot dog” configuration), respectively. These bend angles refer to the amount of movement of each end of the sample relative to a flat configuration. That is, the left end moved about 45° in a clockwise direction and the right end moved about 45° in a counterclockwise direction. For example, in Sample 9C each end of the sample moved about 45° from a flat configuration, leading to the “taco” configuration. As for Samples 9A and 9C, each of the right end and the left end of the sample moved about 90° in a counter-clockwise and clockwise direction, respectively, from a flat configuration, leading to the “hamburger” and “hot dog” configurations, respectively. Also, the as-bent Samples 9B-9D can be characterized with the following diameters of curvature: 4.75 mm, 3 mm, and 4.75 mm, respectively. At this stage of the process, the samples could be etched to remove the oxide layer derived from the sol-gel coating and manually adjusted to a substantially non-bent configuration. Once in the non-bent configuration, the samples will retain residual compressive stress at the primary surface opposite the bends discussed above. In contrast, the samples are characterized by about zero residual stress as bent configurations (Samples 9B and 9C). That is, the as-bent configuration is the new neutral stress state of the glass and, therefore, it will return to the as-bent configuration when unconstrained after being flattened. The goal is to provide a glass article that contains minimal residual, tensile stress when flexed to either an open (flat) or closed (fully bent) state. As such, these samples are resistant to bend fatigue-related failures when being subjected to the as-bent configurations of Samples 9B-9C and back to a substantially non-bent configuration.
[0697] In Example 10, a secondary ion mass spectrometry (SIMS) of sodium ions (Na.sup.+) diffusing through a glass substrate with an oxide coating formed from a sol-gel coating, according to embodiments of the disclosure, was measured. In order to provide flat samples for SIMS analysis, a glass substrate (50 mm×50 mm×0.7 mm) was dip coated in a sol gel solution (so as to coat both sides of the substrate, whereby after drying the sol gel solution the effects of drying it on each side cause the substrate to maintain a flat configuration as opposed to the bent configurations described above) that was made according to the principles of this disclosure by diluting the sol-gel with n-propyl acetate. The sample was dried, to remove residual solvents in a 150° C. oven for 30 minutes. The sample was then placed in a furnace and heated per the previously described schedule set forth in Example 1 to consolidate the oxide layer. After the SIMS analysis was conducted: a 3 kV Cs.sup.+ primary ion beam was used to sputter and a quadrupole mass spectrometer was used to analyze positive and negative secondary ions. For reference, a depth of 0.0 μm refers to the surface of the oxide coating and the SIMS is conducted through the coating and to a depth within the substrate of about 0.9 μm (as measured through the coating). A mole fraction of Na.sup.+ ions of about 0.02 to about 0.07 Na was observed within the coating while a mole fraction of Na.sup.+ ions of about 0.09 was observed beyond the coating (within the glass sample). As is evident from the SIMS analysis, Na.sup.+ ions are able to travel through the oxide coating. As such, without being bound by theory, it is believed that the oxide coating has sufficient alkali ion diffusivity to allow for ion-exchange processes to impart an ion-exchange compressive stress region in an underlying glass substrate through an oxide coating, as formed in a manner consistent with the principles of the disclosure.
[0698] The above observations can be combined to provide polymer-based portions, adhesives, foldable apparatus comprising a polymer-based portion and/or an adhesive, foldable apparatus comprising a shattered pane, foldable apparatus comprising a plurality of planes, and methods of making the same. The polymer-based portions of embodiments of the disclosure can provide several technical benefits. For example, the polymer-based portion can comprise a urethane acrylate material that is elastomeric. By providing an elastomeric polymer-based portion, the polymer-based portion can recover (e.g., fully recover) from folding-induced strains and/or impact-induced strains, which can decrease fatigue of the polymer-based portion from repeated folding, enable a low force to achieve a given parallel plate distance, and enable good impact and/or good puncture resistance. Further, the polymer-based portion can be cross-linked, for example, using a difunctional cross-linking agent, which can further increase the elastomeric character of the polymer-based portion. Also, the polymer-based portion can further comprise a block copolymer or silicone-based rubber, which can further increase the elastomeric character of the polymer-based portion. In some embodiments, the polymer-based portion can be made using a reactive diluent, which can decrease the glass transition temperature of the polymer-based portion. Providing a low glass transition temperature (e.g., about 0° C. or less, about −20° C. or less) can enable consistent mechanical properties of the polymer-based portion across a temperature range in which it is used (e.g., from about 0° C. to about 60° C., from about 10° C. to about 30° C.). Also, the polymer-based portion can withstand high strains (e.g., about 50% or more, from about 65% to about 110%), which can improve folding performance and durability. Providing a silane-coupling agent can increase adhesion of the polymer-based portion to substrates (e.g., glass-based substrates, polymer-based substrates) and/or adhesives. Additionally, the polymer-based portion can comprise high transmittance (e.g., about 90% or more) and low haze (e.g., about 0.2% or less).
[0699] The adhesives of embodiments of the disclosures can provide several technical benefits. The adhesive can comprise a silicone-based polymer with a low glass-transition temperature (e.g., about −60° C. or less). Providing a low glass transition temperature (e.g., about −60° C. or less) can enable consistent mechanical properties of the polymer-based portion across a temperature range in which it is used (e.g., from about −20° C. to about 60° C., from about 10° C. to about 30° C.). The adhesive can withstand high strains (e.g., about 75% or more), comprise a low storage modulus (e.g., from about 0.2 kiloPascals to about 2 kiloPascals), and/or comprise a low Young's modulus (e.g., elastic modulus about 75 MegaPascals or less). Providing an adhesive with a low storage modulus and/or low Young's modulus can improve folding performance of a foldable apparatus, for example, by decoupling the stresses of different components in the foldable apparatus. Providing a low modulus (e.g., storage, Young's) and high strain adhesive can improve folding performance and durability. The adhesive can be formed by curing a substantially solvent-free composition. Providing a composition that is substantially solvent-free can increase its curing rate, which can decrease processing time. Providing a composition that is substantially solvent-free can reduce (e.g. decrease, eliminate) the use of rheology modifiers and increase composition homogeneity, which can increase the optical transparency (e.g., transmittance) of the resulting adhesive. Providing a silane-coupling agent can increase adhesion of the polymer-based portion to substrates (e.g., glass-based substrates, polymer-based substrates), polymer-based portions, and/or adhesives.
[0700] Foldable apparatus can exhibit good optical performance, for example, low optical distortions across the thickness of the foldable apparatus. Providing a foldable apparatus comprising a shattered pane and/or a plurality of panes with a low difference (e.g., about 0.008 or less) between a refractive index at a major surface of the foldable apparatus and a central location of the foldable apparatus can minimize optical distortions from the plurality of shattered pieces comprising the shattered pane and/or the plurality of panes. Also, providing a foldable apparatus comprising a shattered pane and/or a plurality of panes with a low difference (e.g., about 0.008 or less) between a refractive index at a major surface of the foldable apparatus and a central location of the foldable apparatus can minimize optical distortions between an adjacent pair of shattered pieces of the plurality of shattered pieces and/or the plurality of panes and a first material positioned therebetween, if provided.
[0701] Providing a smooth surface of the foldable apparatus can reduce optical distortions and provide a perceived continuous surface for a user touching the foldable apparatus. Likewise, providing a second material disposed over substantially an entire second major surface of a foldable substrate can reduce optical distortions. In some embodiments, the first material can substantially match (e.g., a magnitude of a difference of about 0.1 or less) a refractive index of a shattered piece and/or a pane, which can minimize the visibility of the shattered pane and/or plurality of panes to a user. In some embodiments, providing the first material between a pair of shattered pieces and/or a pair of panes can produce an anti-glare and/or anti-reflective property in the foldable apparatus that can improve visibility of an electronic device that the foldable apparatus may be disposed over. In some embodiments, providing a first material comprising a different (e.g., a magnitude of a difference of about 0.02 or more) refractive index than a refractive index of a shattered piece and/or a pane can produce an angle-dependent visibility (e.g., haze, color shift) through the foldable apparatus. For example, visibility may be at a maxima (e.g., maximum) when viewed at a direction normal to the surface (e.g., first major surface) of the foldable apparatus, and that visibility may decrease (e.g., increasing haze) as an angle relative to a direction normal to the surface is increased.
[0702] Providing a foldable apparatus comprising a central portion comprising a central thickness that is less than a first thickness of the first portion and/or second portion can enable small effective minimum bend radii (e.g., about 10 millimeters or less) based on the reduced thickness in the central portion. As indicated by surprising results of the Pen Drop Test presented in
[0703] A foldable apparatus according to embodiments of the disclosure can comprise the adhesive and/or the polymer-based portion. For example, the foldable apparatus can provide small effective minimum bend radii while simultaneously providing good impact and puncture resistance. By providing a shattered pane with a plurality of shattered pieces attached together by a first material having an elastic modulus that is less than an elastic modulus of a shattered piece of the plurality of shattered pieces, a foldable apparatus can enable good flexibility and folding performance (e.g., achieve an effective bend radius of about 10 millimeters or less). By providing a plurality of panes attached together by a first material having an elastic modulus that is less than an elastic modulus of a pane of the plurality of panes, a foldable apparatus can enable good flexibility and folding performance (e.g., achieve an effective bend radius of about 10 millimeters or less). The foldable apparatus can comprise glass-based and/or ceramic-based materials comprising one or more compressive stress regions, which can further provide increased impact resistance and/or increased puncture resistance while simultaneously facilitating good folding performance.
[0704] Also, by providing a shattered pane with a plurality of shattered pieces and/or a plurality of panes attached together by a first material, a smooth (e.g., regular, planar) surface (e.g., first major surface) can be enabled, for example, when the shattered pane and/or plurality of panes was generated from a substrate deposed on a backer when it was shattered. Providing a smooth surface of the foldable apparatus can reduce optical distortions and provide a perceived continuous surface for a user touching the foldable apparatus. Likewise, providing a second material disposed over substantially an entire second major surface of a foldable substrate can reduce optical distortions. In some embodiments, the first material can substantially match (e.g., a magnitude of a difference of about 0.1 or less) a refractive index of a shattered piece, which can minimize the visibility of the shattered pane to a user.
[0705] In some embodiments, providing the first material between a pair of shattered pieces and produce an anti-glare and/or anti-reflective property in the foldable apparatus that can improve visibility of an electronic device that the foldable apparatus may be disposed over. In some embodiments, providing a first material comprising a different (e.g., a magnitude of a difference of about 0.02 or more) refractive index than a refractive index of a shattered piece can produce an angle-dependent visibility (e.g., haze, color shift) through the foldable apparatus. In further embodiments, providing the different refractive indices can be useful as a privacy screen. For example, visibility may be at a maxima (e.g., maximum) when viewed at a direction normal to the surface (e.g., first major surface) of the foldable apparatus, and that visibility may decrease (e.g., increasing haze) as an angle relative to a direction normal to the surface is increased.
[0706] Providing a central portion with a shattered pane and/or a plurality of panes with the first material can help further reduce the effective minimum bend radius compared to a monolithic pane entirely fabricated from a glass-based material or a ceramic-based material. Also, providing the plurality of shattered pieces of the shattered pane and/or a plurality of panes can provide good scratch resistance, good impact resistance, and/or good puncture resistance to the foldable apparatus, which may be difficult to achieve if fabricating the foldable substrate entirely of the first material. The foldable apparatus can comprise glass-based and/or ceramic-based materials comprising one or more compressive stress regions, which can further provide increased impact resistance and/or puncture resistance while simultaneously facilitating good bending performance.
[0707] By providing a shattered pane with a plurality of shattered pieces and/or plurality of panes attached together by a first material having an elastic modulus that is less than an elastic modulus of a shattered piece of the plurality of shattered pieces and/or a pane of the plurality of panes, a foldable substrate can enable good folding performance (e.g., achieve an effective bend radius of about 10 millimeters or less) as well as limiting the extent of potential damages to the foldable apparatus. For example, the damage resistance of the foldable apparatus may increase because damage to the foldable apparatus may be limited to a shattered piece and/or pane impacted rather than the entire foldable substrate. Additionally, the first material between pairs of shattered pieces and/or pairs of panes can improve the ability of the foldable apparatus to absorb impacts without failure. Furthermore, providing a central portion with a shattered pane with the first material can help further reduce the effective minimum bend radius compared to an unshattered pane entirely fabricated from a glass-based or ceramic-based material. Also, providing the plurality of shattered pieces of the shattered pane can provide good scratch resistance, good impact resistance, and/or good puncture resistance to the foldable apparatus, which may be difficult to achieve if fabricating the shattered pane entirely of the first material.
[0708] Minimizing a total mass of first material (e.g., about 10% or less of a total weight of the plurality of shattered pieces) can further improve scratch resistance, impact resistance, and/or puncture resistance of the foldable apparatus. The foldable apparatus can comprise glass-based and/or ceramic-based materials comprising one or more compressive stress regions, which can further provide increased impact resistance and/or puncture resistance while simultaneously facilitating good bending performance.
[0709] Providing a second material comprising a higher modulus than the first material can reduce bend-induced stresses on the foldable substrate, for example, by shifting a neutral axis of the substrate closer to the second material than a mid-plane of the substrate. Further, providing a second material disposed over substantially an entire second major surface of a foldable substrate can present a contact surface with consistent properties across its length and/or width for coupling components to (e.g., substrates, coatings, release liners, display devices). In some embodiments, a first portion and a second portion can be positioned opposite a first major surface of the substrate. Providing a first portion and a second portion with the second material positioned therebetween can provide good bending performance as well as minimize a region of the foldable apparatus with a lower impact resistance (e.g., the portion including the second material compared to the portions comprising the first portion or the second portion).
[0710] Further, the net mechanical properties of the foldable apparatus can be adjusted by changing the relationship between the elastic modulus of the first material relative to the elastic modulus of a piece of the shattered pieces and/or a pane of the plurality of panes. Providing a first material and/or a second material with a glass transition temperature outside of an operating range (e.g., from about −20° C. to about 60°) of a foldable apparatus can enable the foldable apparatus to have consistent properties across the operating range. Similarly, by providing a first material and/or a second material comprising a storage modulus that changes by a multiple of 100 or less when changing a temperature of the corresponding material from 100° C. to about −20° C. there can be achieved consistent properties across a wide range of temperatures. As discussed above, the adhesives can comprise the first material.
[0711] Providing a foldable apparatus and/or a foldable substrate comprising a neutral stress configuration when the foldable apparatus and/or a foldable substrate is in a bent configuration, the force to bend the foldable apparatus to a predetermined parallel plate distance can be decreased. Further, providing a neutral stress configuration when the foldable apparatus is in a bent state can reduce the maximum stress and/or maximum strain experienced by a polymer-based portion and/or an adhesive, if provided, during normal use conditions, which can, for example, enable increased durability and/or reduced fatigue of the foldable apparatus. In some embodiments, the neutral stress configuration can be generated by heating the foldable substrate and a sol-gel coating disposed on the foldable substrate to form the foldable substrate into a bent configuration (e.g., neutral stress configuration). Providing a width of the sol-gel coating from about 5% to about 30% or a longest dimension of the foldable substrate can minimize the amount of material and/or cost associated with making the foldable substrate and/or foldable apparatus.
[0712] Providing a neutral stress configuration when the foldable apparatus is in a bent configuration can decrease the force to fold the foldable apparatus to a predetermined parallel plate distance. Further, providing a neutral stress configuration when the foldable apparatus is in a bent state can reduce the maximum stress and/or the maximum strain experienced by the polymer-based portion during normal use conditions, which can, for example, enable increased durability and/or reduced fatigue of the foldable apparatus. In some embodiments, the polymer-based portion can comprise a low (e.g., substantially zero and/or negative) coefficient of thermal expansion, which can mitigate warp caused by volume changes during curing of the polymer-based portion. In some embodiments, the neutral stress configuration can be generated by providing a polymer-based portion that expands as a result of curing. In some embodiments, the neutral stress configuration can be generated by curing the polymer-based portion in a bent configuration.
[0713] Methods are disclosed that shift the neutral stress configuration of a foldable apparatus that, as used in its intended application, may experience large compressive and tensile stresses when folded to tight bend radii. These methods can reduce the incidence of fatigue failure in the foldable apparatus. In some embodiments, the neutral stress configuration can correspond to a bent (e.g., as-bent) configuration through the deposition and annealing of a sol-gel oxide coating, leading to a neutral stress state in the as-bent configuration and a beneficial stress state in a substantially non-bent configuration. Foldable apparatus of embodiments of the disclosure, for example, can be shaped in a desired as-bent configuration (e.g., neutral stress configuration) without the use of a mold and at lower temperatures than employed in thermal sagging processes. The methods also have flexibility in terms of developing the two-dimensional and three-dimensional as-bent configurations of the intended bendable glass articles by virtue of the ease in which the sol-gel coatings can be patterned on the glass substrate.
[0714] Directional terms as used herein—for example, up, down, right, left, front, back, top, bottom—are made only with reference to the figures as drawn and are not intended to imply absolute orientation.
[0715] It will be appreciated that the various disclosed embodiments may involve features, elements, or steps that are described in connection with that embodiment. It will also be appreciated that a feature, element, or step, although described in relation to one embodiment, may be interchanged or combined with alternate embodiments in various non-illustrated combinations or permutations.
[0716] It is also to be understood that, as used herein the terms “the,” “a,” or “an,” mean “at least one,” and should not be limited to “only one” unless explicitly indicated to the contrary. For example, reference to “a component” comprises embodiments having two or more such components unless the context clearly indicates otherwise. Likewise, a “plurality” is intended to denote “more than one.”
[0717] As used herein, the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, embodiments include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. Whether or not a numerical value or endpoint of a range in the specification recites “about,” the numerical value or endpoint of a range is intended to include two embodiments: one modified by “about,” and one not modified by “about.” It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint and independently of the other endpoint.
[0718] The terms “substantial,” “substantially,” and variations thereof as used herein are intended to note that a described feature is equal or approximately equal to a value or description. For example, a “substantially planar” surface is intended to denote a surface that is planar or approximately planar. Moreover, as defined above, “substantially similar” is intended to denote that two values are equal or approximately equal. In some embodiments, “substantially similar” may denote values within about 10% of each other, for example, within about 5% of each other, or within about 2% of each other.
[0719] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that any particular order be inferred.
[0720] While various features, elements or steps of particular embodiments may be disclosed using the transitional phrase “comprising,” it is to be understood that alternative embodiments, including those that may be described using the transitional phrases “consisting” or “consisting essentially of,” are implied. Thus, for example, implied alternative embodiments to an apparatus that comprises A+B+C include embodiments where an apparatus consists of A+B+C and embodiments where an apparatus consists essentially of A+B+C. As used herein, the terms “comprising” and “including”, and variations thereof shall be construed as synonymous and open-ended unless otherwise indicated.
[0721] The above embodiments, and the features of those embodiments, are exemplary and can be provided alone or in any combination with any one or more features of other embodiments provided herein without departing from the scope of the disclosure.
[0722] It will be apparent to those skilled in the art that various modifications and variations can be made to the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present disclosure cover the modifications and variations of the embodiments herein provided they come within the scope of the appended claims and their equivalents.