BAND-GAP TUNABLE ELASTIC OPTICAL MULTILAYER FIBERS
20190227224 ยท 2019-07-25
Assignee
Inventors
- Joanna Aizenberg (Boston, MA)
- Mathias Kolle (Hull, MA, US)
- Peter Vukusic (Exeter, GB)
- Robert D. HOWE (Cambridge, MA, US)
Cpc classification
G02B6/0285
PHYSICS
G02B6/03611
PHYSICS
G02B6/023
PHYSICS
G02B6/0239
PHYSICS
G02B6/02309
PHYSICS
G02B6/02304
PHYSICS
International classification
G02B1/00
PHYSICS
Abstract
The rolled photonic fibers presents two codependent, technologically exploitable features for light and color manipulation: regularity on the nanoscale that is superposed with microscale cylindrical symmetry, resulting in wavelength selective scattering of light in a wide range of directions. The bio-inspired photonic fibers combine the spectral filtering capabilities and color brilliance of a planar Bragg stack compounded with a large angular scattering range introduced by the microscale curvature, which also decreases the strong directional chromaticity variation usually associated with flat multilayer reflectors. Transparent and elastic synthetic materials equip the multilayer interference fibers with high reflectance that is dynamically tuned by longitudinal mechanical strain. A two-fold elongation of the elastic fibers results in a shift of reflection peak center wavelength of over 200 nm.
Claims
1-39. (canceled)
40. A suture filament comprising: a central core extending along the length of the filament, wherein the central core has a diameter in the range of 10 m to 500 m; a first polymer layer having a first refractive index; and a second layer having a second refractive index, wherein the first and second polymer layers are positioned adjacent to one another to form a bilayer and wherein the first and second refractive indices are selected to provide interference of light reflected from the optical interfaces between the first and second layers; wherein the bilayer is concentrically wound around the central core to provide a multilayer cladding having a jelly roll structure and form a tunable band-gap multilayer fiber having a first color at zero axial strain, wherein the suture filament changes to a second color in response to an axial extension of the filament.
41. The suture filament of claim 40, wherein the tunable band-gap multilayer fiber is spliced into the filament.
42. The suture filament of claim 40, wherein the change in color is related to the amount of applied axial strain and the fiber's Poisson ratio.
43. The suture filament of claim 40, wherein the axial extension produces a color change from higher to lower wavelengths.
44. The suture filament of claim 40, wherein the second layer comprises a polymer.
45. The suture filament of claim 40, wherein the second layer comprises a metal.
46. The suture filament of claim 40, wherein the central core comprises a glass fiber.
47. The suture filament of claim 40, wherein the central core comprises a polymer fiber.
48. The suture filament of claim 47, wherein the central core comprises an elastomer fiber.
49. The suture filament of claim 47, wherein the polymer fiber is capable of being reversibly stretched and/or laterally compressed.
50. The suture filament of claim 40, wherein the central core is hollow.
51. The suture filament of claim 40, wherein the central core is a space defining an open central axis.
52. The suture filament of claim 40, wherein the first and second layers comprise an elastomer, or the first and second layers are capable of being reversibly stretched and/or laterally compressed.
53. The suture filament of claim 40, wherein the first and second layer have a layer thickness in the range of 50-300 nm.
54. The suture filament of claim 40, wherein the multilayer cladding comprises 10-200 bilayer windings.
55. The suture filament of claim 40, wherein the periodicity of the wound bilayers is the same.
56. The suture filament of claim 40, wherein the fiber comprises regions of wound bilayers having different periodicities.
57. The suture filament of claim 40, wherein the fiber comprises regions of wound bilayers having a controlled gradient in periodicity.
58. The suture filament of claim 40, further comprising a third layer positioned adjacent to the bilayer to form a trilayer.
59. The suture filament of claim 58, wherein the third layer is a metal layer.
60. The suture filament of claim 40, further comprising a patterning, or axial variation or axial symmetry breaking imposed by a one or several micron-sized objects or patterns on the initial bilayer or trilayer incorporated in the cladding during rolling.
61. The suture filament of claim 40, wherein the fiber is expandable to up to 200% of its length.
62. The suture filament of claim 40, wherein at least one of the first layer and the second layer comprises an elastomer and the tunable band-gap multilayer fiber is reversibly expandable to 200% of its length.
63. A method for monitoring a suture operation, comprising: providing a suture filament comprising: a central core extending along the length of the filament, wherein the central core has a diameter in the range of 10 m to 500 m; a first polymer layer having a first refractive index; and a second layer having a second refractive index, wherein the first and second polymer layers are positioned adjacent to one another to form a bilayer and wherein the first and second refractive indices are selected to provide interference of light reflected from the optical interfaces between the first and second layers; wherein the bilayer is concentrically wound around the central core to provide a multilayer cladding having a jelly roll structure and form a tunable band-gap multilayer fiber having a first color at zero axial strain, wherein the suture filament changes to a second color in response to an axial extension of the filament; and monitoring the axial extension of the filament based on color changes of the suture filament.
64. The method of claim 63 wherein the suturing operation occurs during robotic surgery.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0048] The invention is described with reference to the following figures, which are presented for the purpose of illustration only and are not intended to be limiting.
[0049] In the Drawings:
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DETAILED DESCRIPTION
[0059] In one aspect, a room temperature fiber rolling technique is described that allows fabrication of multilayer fibers with hundreds of layers from a wide range of polymeric material combinations that would not be realizable by conventional thermal fiber drawing. The fibers' band-gap center frequency can be tuned by adjusting the individual film thicknesses of the two constituent layers prior to the rolling process, which allows shifting of the fibers' tuning range within the visible range and into the near UV or near IR. The optical properties of the rolled photonic fiber can be further modified during the rolling process to allow changes in the periodicity of the windings. Chirped multilayer fibers can be realized by applying an appropriate force on the elastic bilayer during rolling of the multilayer cladding. Internal structures that break axial symmetry are created by incorporating microscopic objects or micro- to nano-scale patterns in or on the bilayer prior to rolling of the fibers.
[0060] In one aspect, micron-scale multilayer-wrapped fibers are fabricated at room temperature from a wide range of soft organic and also inorganic materials with varying optical and mechanical properties that are not restricted to a translational symmetry along the fiber axis as in thermally drawn fibers. In exemplary embodiments, the fibers comprise two elastomeric dielectrics, polydimethylsiloxane (PDMS) and polyisoprene-polystyrene triblock copolymer (PSPI), two inexpensive materials that are commercially available in industrial quantities and provide a sufficiently high refractive index contrast (n.sub.PDMS=1.410.02, n.sub.PSPI=1.540.02, determined by ellipsometry). Multilayer fibers are produced by initially forming a bilayer of the two constituent materials, which is subsequently rolled up onto a thin glass fiber, polymer fiber or elastomer diameters ranging from 10 m to 500 m) to form the multilayer cladding. Refractive index differences as small as 0.01 between the fiber materials can induce the multilayer interference necessary for the photonic effect described herein to occur, provided the number of layers in the cladding is scaled accordingly. The smaller the refractive index contrast, the higher the number of layers required to induce a pronounced effect. Larger refractive index contrasts of the constituent materials provide fibers with wider band-gaps. In exemplary embodiments, the difference in the refractive index is greater than 0.01, or greater than 0.05, or greater than 0.1, or greater than 0.15, or greater than 0.2, or greater than 0.25. In other embodiments, the difference in the refractive index is between 0.01 and 1.0, or between 0.05 and 0.5 or between 0.1 and 0.25. Any combination of these ranges is contemplated as suitable ranges for the generation of appropriate interference effects resulting from light reflection of the optical interfaces between the layers. Effective refractive index differences can in general result from a difference in the real part of the refractive index or alternatively a different in the imaginary part, which describes the absorption strength of a material. In some embodiments, the refractive interference difference can be higher than 1.0, for example combinations of Teflon components (for instance Teflon AF) and metal oxides (for instance titanium oxide).
[0061] Fabrication of a photonic multilayer-wrapped fiber is shown in
[0062] Any organic material with a desirable dielectric or mechanical property that can be processed with the techniques outlined above is suitable for use in the rolled photonic fibers described herein. Non-limiting examples include polystyrene, poly(methyl methacrylate), polyisoprene, polystyrene-polyisoprene block co-polymers, polydimethylsiloxane, polybutadiene and various photoresists.
[0063] In one or more embodiments, the soft organic material is an elastomer, for instance polyisoprene-polystyrene block co-polymers, polyisoprene, or polydimethylsiloxane. Other dielectric materials can be used in the fiber manufacture including thermoplastics, for instance polystyrene and poly(methyl methacrylate).
[0064] In one or more embodiments, thin metal films can be incorporated into the bilayer. Such metal layers can be included as an additional layer, e.g., forming a trilayer structure for winding, or can be used as one of the two layers that form the photonic structure.
[0065] In one exemplary system, polydimethylsiloxane (PDMS) is dissolved in heptane and spun onto a silicon substrate. A sacrificial water soluble layer can be first deposited on the silicon substrate to assist release of the layer during the rolling step. Annealing in an oven at 120 C. for one hour leads to crosslinking of the PDMS which makes it resistant to toluene, the solvent used for the polyisoprene-polystyrene triblock (PSPI) copolymer. Annealing can happen at a variety of temperatures under varying conditions. PSPI copolymer is subsequently spun onto the PDMS layer. The resulting layer thicknesses can be optimized to maximize the distributed Bragg reflector (DBR) reflectivity in any desired part of the visible spectrum. This is done following the Bragg relation for ideal multilayers (at normal light incidence) d.sub.i=.sub.c/(4n.sub.i) that provides the optimum thickness of layer i for a given material with refractive index n.sub.i for a desired reflection band center wavelength .sub.c. In this particular example, the micro-phase separation of the polystyrene component in the PSPI copolymer leads to nanoscopic glassy minority domains in a polyisoprene matrix, which act as cross-links, rendering the curing of the polyisoprene rubber unnecessary. The optical properties of this material system provide for the controlled reversible tuning of the fiber's optical performance, which is demonstrated below.
[0066] The fiber rolling technique can produce concentric multilayers on core fibers of only 10 m diameter using elastic materials. Fibers have been rolled on cores with diameters as small as 10 m up to 500 m. Such multilayer fibers with curvature on the microscale display optical properties that are distinctly different from materials produced on macroscopic rolls, whose radius of curvature more closely mimics planar structures. It has been determined that rolled fibers having a fiber core greater than 1 mm tend to have properties that are consistent with planar photonic devices. To form the rolled photonic fiber, strips of the bilayer are released from the substrate and positioned floating on the surface of a water bath. This can be accomplished by slow lowering the supported bilayer into a water bath, as shown in
[0067] The individual thicknesses of the two films in the initial bilayer can be tuned during the film deposition. Consequently, the spectral position of the reflection band of the fibers can be freely adjusted. In addition, while a bilayer is described, it is contemplated that three or more layers of different dielectric properties may be used to provide a more complex photonic response. Three fibers with high reflectivity in different color ranges of blue, green and red, respectively, and the corresponding complementary color in transmission are shown in
[0068] In addition, small modifications in the process of rolling the multilayer cladding onto the core fiber permit the realization of different internal geometries in the fiber. Attachment of the core fiber at the end of a free floating bilayer results in a fiber with one periodicity throughout the whole cladding.
[0069] In another embodiment, claddings with two distinct multilayer periodicities can be realized.
[0070] In another embodiment, the periodicity of the rolled photonic fiber can vary across the diameter. Chirped multilayer claddings with a gradient in periodicity are realized by fixing the distance between the core fiber and the far edge of the bilayer during rolling leading to a successive stretching of the bilayer and a corresponding thinning of the rolled-up layers. As expected, such chirped multilayer fibers have a silvery appearance due to a wide reflection band.
[0071] In another embodiment, the internal structure of the photonic fiber can be modified by incorporating micro-scale elements, such as fibers or colloidal particles, or patterns obtained by nano-embossing or photolithography onto the initial bilayer (or multilayer) film that is rolled onto the core fiber. For example, patterns can be introduced into the fiber by inclusion of a fiber element while assembling the photonic fiber, which breaks the axial symmetry of the rolled fibers.
[0072] In one or more embodiments, the glass fiber that can act as the substrate for the multilayers in the rolling process can be removed from the fiber, for example, by dissolution in hydrofluoric acid or by simply pulling it out of the multilayer cladding. Once the glass core is removed, the fiber, remaining multilayered being composed of two elastomers, can be elastically deformed by stretching it along its axis. In one or more embodiments, the fiber that acts as the substrate for the multilayers in the rolling process can be made of a stretchable polymer, such as PDMS. In this way, the resulting rolled photonic fiber can be elastically deformed by stretching it along its axis. An elongation along the fiber axis leads to a compression perpendicular to it, causing a decrease of its overall diameter and a reduction of the thickness of each individual layer. Due to the comparable Poisson's ratio of the constituent elastic materials the thickness ratio and the reflection intensity remain constant while the reflection band blue-shifts. This way, the reflected and transmitted color can be reversibly tuned by axial extension of the fibers.
[0073] The core fiber can be produced from elastomeric, absorbing materials (such as PDMS-carbon nanoparticle composites) to provide strong absorption in the fiber core, which suppresses transmitted colors and thereby purifies the reflected colors. This gives the fibers a superior color brilliance especially in environments with multiple light sources and light reflecting surfaces that result in complex illumination environments.
[0074] The incorporation of gold or silver layers into the concentric multilayer offers potential for the development of novel micron-scale fiber-based meta-materials. Asymmetric structures or chirality could be incorporated into the fibers by patterning of the initial bilayer prior to the rolling, promising additional interesting optical properties. Removal of glass fiber core from inside the multilayer cladding or rolling of the cladding on elastic core fiber permits mechanical deformation of fibers to more than twice their original length, which causes a tuning of the band-gap and a spectral blue-shift of over 200 nm. I one or more embodiments, the rolled photonic fiber incorporates a flexible core fibers. The flexibility in the choice of constituent materials for the multilayer fibers and their unique combination of mechanical and optical properties holds great potential for applications in mechanically tunable light guides or optical strain sensing. The fibers' mechanical flexibility and elasticity, in addition to the demonstrated color brilliance and tunability, can make them a versatile novel material for smart, color-dynamic textiles. The reported multilayer fiber manufacturing process can in principle be applied to a wide range of synthetic materials with varying optical and mechanical properties. Large area deposition of the initial bilayer can be achieved by spraying or blade coating in a roll-to-roll process before final rolling of the multilayer fibers. Hollow photonic fibers providing good thermal insulation can be produced by employing hollow polymeric micro-tubing as the inner fiber core. Exposure of the fibers to different solvents in the vapor or liquid phase would result in varying degrees of swelling and a corresponding reflection peak red-shift endowing the fibers or textiles made thereof with optical solvent sensing capacities. The final formation of the multilayer rolls could in principle also be achieved by self-induced rolling of the bilayer caused by directional stresses, which can be induced by gradually swelling one of the bilayer phases selectively.
[0075] Fibers prepared according to one or more embodiments show a pronounced reflection in a finite wavelength range imposed by the multilayer periodicity of the multilayer windings and a corresponding drop in transmission.
[0076] In one or more embodiments, the optical performance of the photonic fibers can be tuned by mechanical deformation. Due to the comparable Poisson's ratio of the constituent elastic materials used in the rolled photonic fibers, the thickness ratio and the reflection intensity remain constant while the reflection band blue-shifts. This way, the reflected and transmitted color can be reversibly tuned by axial extension of the fibers
[0077] From Poisson's ratio and the proportionality between the thickness of individual layers in the cladding and the spectral band-gap position, the reflection peak center wavelength .sub.Peak is predicted to follow the relation .sub.peak=.sub.peak.sup.0(1+).sup., where .sub.peak.sup.0 represents the reflection peak centre wavelength at zero axial strain, the applied axial strain and the fibre's Poisson's ratio. Fitting the experimental data with this relation yields a Poisson's ratio of =0.460.02 for the stretchable multilayer fibers matching the Poisson's ratios of the constituent rubber materials (
[0078] In one or more embodiments, stress/strain sensors based on photonic fibers are contemplated. The tunable photonic fibers can be used in applications where it is desirable to have information regarding stress, strain and/or compression, or sensing of compressive or tensional compressive strains in a device for compressive stress/strain sensing the fibers are oriented perpendicularly to the direction of acting stresses and resulting strains, which leads to a compression of the layers in the fiber cladding resulting in a variation of color to shorter wavelengths (blue-shift). In tensile stress and strain sensing applications the fibers are aligned with the direction of stress and strain. A longitudinal expansion will result in a lateral compression of the layers in the cladding, leading to a color variation from higher to lower wavelengths. Light levels necessary for obtaining visual information about mechanical forces from such mechano-responsive optical fiber sensors can originate from environmental light (in well and homogeneously lit environments) but also can be imposed by an internal light source (for instance LEDs). Qualitative read-out can be based on a visual assessment with the human eye or suitable imaging devices, while quantitative read-outs are achieved with appropriately calibrated photodiodes or CCD arrays.
[0079] In one aspect, the photonic fibers can be incorporated into threads used as sutures. Small sections of photonic fibers can be spliced into conventional suturing filaments. Fibers can be co-wound around suturing filaments. Alternatively, the fibers can be the suturing filaments. The resultant stress/strain-sensitive sutures can provide information regarding the strain applied to the suture, for example, during suturing operations. This information can be useful, for example, for suturing operations in robotic surgery, providing information about the amount of stress and strain exerted on the filament by the robotic tool that performs the suture and also providing information about the forces exerted by the suture on the bonded biological tissue.
[0080] In other embodiments, the stress/strain sensors based on photonic fibers can be used for the structural health monitoring of buildings, bridges or other infrastructure.
[0081] In other aspects, the photonic fibers can be incorporated into devices that provide a visual indicator of compressive forces. Pressure sensors can incorporate photonic fibers that are capable of registering a pressure/compression via a color change resulting from lateral compression of the layers. In one embodiment, the photonic fibers can be incorporated into compression bandages. Application of the fibers in compression bandages can give medical staff a direct visual read-out for the force and amount of compression employed by the bandage. In other embodiments, the photonic fibers can function as solvent sensors. The photonic fibers can be made of polymers that swell in the presence of specific solvents. The swelling of fibers in solvent vapor atmosphere will generate compressive forces on the fiber that lead to a predictable change in color.
[0082] The invention is illustrated in the following examples, which are presented for the purpose of illustration only and are not intended to be limiting of the invention.
Experimental Section
Fiber Manufacture
[0083] A thin polydimethylsiloxane (PDMS, Sylgard 184, Dow Corning) film was spun from a 4% wt solution in heptane onto a sacrificial water-soluble polystyrene-sulfonic acid layer on a silicon wafer. The PDMS film was cross-linked by curing it on a hotplate for 2 h at 70 C. Subsequently, a bilayer was formed by spin-coating a polystyrene-polyisoprene-polystyrene triblock copolymer (PSPI, Sigma Aldrich, 14% wt content polystyrene) film on top of the cross-linked PDMS layer from a 4% wt solution in toluene. The bilayer was then released from the wafer onto the surface of a water bath. This was achieved by immersing the sample slowly into the water at an angle varying between 30-45 allowing the water to dissolve the sacrificial water-soluble film between the elastomer bilayer and the substrate, thereby detaching the bilayer from the substrate. A thin glass, polymer or elastomer fiber was then lowered onto the end of the floating bilayer, where it adhered to the PSPI film, the top layer in the bilayer. Once the core glass fiber had attached it was rotated at a speed of 10-20 turns per minute rolling up the bilayer to form the multilayer cladding.
Structural and Optical Analysis
[0084] Images were obtained by scanning electron microscopy (Hitachi S-3200N SEM). For imaging, the samples were coated with a 3 nm thick film of a gold/palladium alloy. Cross-sections of the fibers were obtained by cryo-fracture. Fractured fibers were coated with a 3-5 nm thick platinum film to avoid charging artifacts during imaging and visualized using a field emission scanning electron microscope (Zeiss Supra55VP).
[0085] Simultaneous imaging and micro-spectroscopic spatial reflection/transmission intensity mapping of the fibers was performed in a modified optical microscope. The samples were illuminated in the area of interest with a halogen lamp in reflection or transmission. Via an additional microscope port, a fraction of the reflected light was collected confocally and guided by a fiber to a spectrometer. The detection spot size depends on the diameter of the fiber and the magnification of the objective lens. Measurements with a 50 objective (NA=0.55) and a fiber with 50 m core diameter resulted in a spatial resolution of 1 m. All spectra are referenced against a flat silver mirror of 95% reflectance in the wavelength range of 400-800 nm. In order to acquire spatially and spectrally resolved intensity distributions of a specific area on a sample, the sample was translated step-wise in the focal plane of the microscope with a minimum step size of 1 m using an automated, remote-controlled stage. Individual spectra were acquired after each scanning step resulting in a complete map of the spectrally-resolved intensity distribution of the samples in reflection or transmission.
[0086] It will be appreciated that while a particular sequence of steps has been shown and described for purposes of explanation, the sequence may be varied in certain respects, or the steps may be combined, while still obtaining the desired configuration. Additionally, modifications to the disclosed embodiment and the invention as claimed are possible and within the scope of this disclosed invention.