HIGHLY TUNABLE MAGNETIC LIQUID CRYSTALS
20190377215 ยท 2019-12-12
Inventors
Cpc classification
G02F1/133531
PHYSICS
H01F1/0302
ELECTRICITY
H01F1/0081
ELECTRICITY
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
H01F1/0018
ELECTRICITY
C09K19/54
CHEMISTRY; METALLURGY
International classification
G02F1/137
PHYSICS
C09K19/54
CHEMISTRY; METALLURGY
G02F1/00
PHYSICS
G02F1/1335
PHYSICS
Abstract
In various embodiments magnetically actuated liquid crystals are provided as well as method of manufacturing such, methods of using the liquid crystals and devices incorporating the liquid crystals. In one non-limiting embodiment the liquid crystals comprise Fe.sub.3O.sub.4 nanorods where the nanorods are coated with a silica coating.
Claims
1-91 (canceled)
92. A method of making a thin film patterned with one or more optical polarizations, said method comprising: providing a substrate having deposited thereon a resin containing magnetic nanorods, where said magnetic nanorods are coated with a silica and/or polymer layer and form a stable colloidal dispersion, where said magnetic nanorods function as a liquid crystal that performs optical switching in response to a magnetic field; applying a magnetic field to said resin to align said magnetic nanorods in all or in one or more regions of said substrate coated with said resin; and curing/crosslinking said resin in all or in one or more regions of said substrate coated with said resin to fix said magnetic nanorods in a first alignment thereby providing a first optical polarization.
93. The method of claim 92, further comprising: applying a magnetic field to a second region of said substrate to align magnetic nanorods in said second region in an orientation different than said first alignment; and curing/crosslinking said resin in said second region to fix the magnetic nanorods aligned in the second region in a second alignment to provide a second optical polarization.
94. The method of claim 92, further comprising: applying a magnetic field to a third region of said substrate to align said magnetic nanorods in said third region in an orientation different than said first alignment and/or said second alignment; and curing/crosslinking said resin in third second region to fix the magnetic nanorods aligned in the third region in a third alignment to provide a third optical polarization.
95. The method of claim 92, wherein said method comprises leaving the resin in one or more regions uncured/uncrosslinked so that the magnetic nanorods in said regions reorient when a magnetic field is applied to said film.
96. The method of claim 92, wherein said resin is a UV cured resin and said curing/crosslinking by application of UV light to the region that is to be cured/cross-linked.
97. The method of claim 96, wherein said resin is selected from the group consisting of bisphenol-A-diglycidyl-ether-diacrylate (B GEDA), polyethylene-glycoldiacrylate (PEGDA), and poly(diethylene-glycol-carbonate):diacrylate (PGCDA).
98. The method of claim 92, wherein said resin is a chemically cured resin and said curing/crosslinking by application of the curing catalyst to the region that is to be cured/cross-linked.
99. The method of claim 98, wherein said catalyst is inkjet nanoprinted on the region(s) to be cured.
100. A thin film patterned with one or more optical polarizations, said thin film comprising: magnetic nanorods, where said magnetic nanorods are coated with a silica and/or polymer layer and form a stable colloidal dispersion, where said magnetic nanorods function as a liquid crystal that performs optical switching in response to a magnetic field, and where the magnetic nanorods are disposed in one or more predetermined orientations at different locations in said thin film.
101. The thin film of claim 100, wherein said film comprises one or more first regions comprising magnetic nanorods aligned in a first alignment providing a first polarization.
102. The thin film of claim 101, wherein said film comprises one or more second regions comprising magnetic nanorods aligned in a second alignment different from said first alignment providing a second polarization different from said first polarization.
103. The thin film of claim 102, wherein said film comprises one or more third regions comprising magnetic nanorods aligned in a third alignment different from said first and/or said second alignment providing a third polarization different from said first and/or said second polarization.
104. The thin film of claim 100, wherein said film comprises one or more regions wherein the magnetic nanorods in said regions are free to reorient when a magnetic field is applied to said film.
105. The thin film of claim 100, wherein said film is made according to the method of claim 92.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0113]
[0114]
[0115]
[0116]
[0117]
DEFINITIONS
[0118] The terms suspension and dispersion are used interchangeably herein to refer to nanostructures present in a fluid (or polymerized) medium. In certain embodiments the nanostructures are homogenously dispersed in the medium, while in other embodiments, the nanostructures are not homogenously dispersed. In certain embodiments the nanoparticle provide one or a plurality of phases in the medium.
DETAILED DESCRIPTION
[0119] In various embodiments magnetically actuated liquid crystals are provided as well as method of making the magnetically actuated liquid crystals, methods of using the liquid crystals (e.g., in optical switching applications, displays, and the like), and devices comprising the liquid crystals. In certain embodiments the liquid crystals comprise magnetic anisotropic nanostructures (e.g., nanorods and nanoplates). If necessary, the surfaces of these magnetic anisotropic nanostructures are modified with additional coating for enhanced dispersion in solvents, e.g., coated with a layer of capping ligands, or polymer, or inorganic oxides such as silica. In certain embodiments the nanostructures are coated with a silica layer.
[0120] In one illustrative, but non-limiting embodiment for the fabrication of liquid crystals, superparamagnetic iron oxide nanorods or nanoplates are synthesized, and their surfaces are modified with capping ligands, or oxide such as silica, or polymer for enhanced dispersion (if necessary). The nanorods or nanoplates can be dispersed in a suitable solvent at a certain volume fraction to form magnetically actuated liquid crystals. These liquid crystals show an outstanding magnetic response and magnetic-field-controlled instant and reversible orientation.
[0121] In one illustrative, but non-liming embodiment, for the fabrication of liquid crystals, ferrimagnetic iron oxide nanorods or nanoplates are synthesized, and their surfaces modified with capping ligands, or oxide such as silica, or polymer for enhanced dispersion (if necessary). Then they were dispersed in suitable solvent at a certain volume fraction to form magnetically actuated liquid crystals. These liquid crystals show an outstanding magnetic response and magnetic-field-controlled instant and reversible orientation.
[0122] In one illustrative but non-limiting embodiment, nonmagnetic FeOOH nanorods ARE first synthesized, followed by a coating of silica on their surfaces, and are finally reduced to superparamagnetic or ferrimagnetic iron oxide nanorods encapsulated in a silica layer by diethylene glycol at elevated temperature. The as-reduced nanorods can be dispersed in water or polar solvent at a certain volume fraction, e.g., 10%, and magnetically to provide actuated liquid crystals. Dependent on the volume fraction, this liquid crystal can form nematic or smectic phases. These liquid crystals show an outstanding magnetic response and magnetic-field-controlled instant and reversible orientation tuning is demonstrated.
[0123] In one illustrative, but non-liming embodiment, for the fabrication of liquid crystals,nonmagnetic Ni(OH).sub.2 nanoplates are first synthesized, followed by a coating of SiO.sub.2 on their surfaces, and finally reduced to Fe.sub.3O.sub.4@SiO.sub.2 nanorods by hydrogen. The as-reduced nanoplates were dispersed in water or polar solvent at a certain volume fraction, and magnetically actuated liquid crystals were achieved. Dependent on the volume fraction, this liquid crystal can form nematic or columnar or hexagonal phases. These liquid crystals show an outstanding magnetic response and magnetic-field-controlled instant and reversible orientation.
[0124] In one illustrative, but non-liming embodiment, for the fabrication of liquid crystals, nonmagnetic nanorods or nanoplates were first synthesized, followed by a coating of polymer on their surfaces, and were finally reduced to ferromagnetic core@polymer nanostructures. The as-reduced nanostructures were dispersed in water or polar solvent at a certain volume fraction to form magnetically actuated liquid crystals. These liquid crystals show an outstanding magnetic response and magnetic-field-controlled instant and reversible orientation.
[0125] In one illustrative, but non-liming embodiment, for the application of magnetically actuated liquid crystals in displays, but non-limiting embodiment, magnetically actuated liquid crystals were sandwiched between cross polarizers to form a device. As the field direction changes, this device can tune the transmittance of light. An alternating magnetic field was applied to the device (e.g., 5 mT), the liquid crystal exhibited an optical switching frequency of above 100 Hz, which is comparable to commercial liquid crystals and thus can be a promising substitute for them in device applications. Color filters are attached to this device to create a proto-type of magnetically responsive liquid crystal color display.
[0126] In one illustrative, but non-liming embodiment, for the application of magnetically actuated liquid crystals in polarization pattern printing, but non-limiting embodiment, magnetically actuated liquid crystals were mixed with photocurable polymer precursors, and sandwiched between glasses. A mask was applied to the sample; liquid crystals in selected areas were cured by ultraviolet light and their orientations were fixed with the aid of magnetic fields. The mask was then removed to allow the curing of liquid crystals in the rest areas and the fixing of their orientation in a different direction with the aid of magnetic fields. This process can be repeated for multiple times for the creation of complex patterns.
EXAMPLES
[0127] The following examples are offered to illustrate, but not to limit the claimed invention.
Example 1
Magnetically Actuated Liquid Crystals
[0128] The liquid-like behavior and optical anisotropy of liquid crystals have catalyzed many important applications in modern technology. Their molecular order can be manipulated through external stimuli such as temperature change and electric and magnetic fields, therefore enabling many technological advances, with a particularly successful example being the liquid crystal displays driven by electric fields. Although conventional liquid crystals may be sensitive to magnetic fields, the low magnetic susceptibility of molecular species makes practical applications difficult as extremely strong magnetic fields are required to enable effective switching of the molecular order (Kneppe et al. (1982) Chem. Phys. Lett. 87: 59; Lemaire et al. (2004) Phys. Rev. Lett. 93: 267801; van den Pol et al. (2009) Phys. Rev. Lett. 103: 160952).
[0129] Herein we demonstrate that ferrimagnetic inorganic nanorods can be used as building blocks to construct liquid crystals with optical properties that can be instantly and reversibly controlled by manipulating the nanorod orientation using considerably weak external magnetic fields. Under an alternating magnetic field (5 mT), they exhibit an optical switching frequency above 100 Hz, which is comparable to the performance of commercial liquid crystals based on electrical switching. Developing such magnetically actuated liquid crystals opens the door towards various applications, which may benefit from the instantaneous and contactless nature of magnetic manipulation (Yang and Wu, Fundamentals of liquid crystal devices. Wiley SID series in display technology (John Wiley, Chichester ; Hoboken, N.J., 2006), pp. xvi, 378 p; Boamfa et al. (2005) Adv. Mater. 17: 610).
[0130] Effective switching of the optical properties of liquid crystals using external magnetic fields has remained a great challenge. While direct incorporation of ferro- or ferrimagnetic materials into liquid crystals has been attempted (. Fabre et al. (1990) Phys. Rev. Lett. 64: 539, Vallooran et al. (2011) Adv. Mater. 23: 3932; Cordoyiannis et al. (2009) Phys. Rev. E 79), a long interaction time is usually required to induce uniform molecular alignment. A more straightforward strategy is to enhance the intrinsic magnetic property of the constituents of liquid crystals, for example, by doping rare earth metal ions into liquid crystal molecules (Binnemans et al. (2000) J. Am. Chem. Soc. 122: 4335) or by developing alternative inorganic building blocks with a higher magnetic susceptibility (Hijnen, and Clegg (2012) Chem. Mater. 24: 3449). However, most such studies have been limited to paramagnetic materials, which can only be aligned in extremely strong external magnetic fields(>1 T). In this regard, the direct use of ferro- or ferrimagnetic inorganic materials represents the best solution to design magnetically responsive liquid crystals because they have higher magnetic susceptibility and can rapidly respond to a relatively weak magnetic field. In such systems, the magnetic interaction energy, instead of the nematic potential in the cases involving diamagnetic/paramagnetic materials, dominates the orientation behavior of liquid crystals, so that the orientational control and the optical switching can be effectively carried out with orders of magnitude reduction in the required field strength but with high magnetic ordering efficiency. Onsager theoretically predicted in his pioneering work the spontaneous nematic ordering of long hard rods in the purely entropic regime (Onsager (1949) Ann. N. Y. Acad. Sci. 51: 627), leaving the remaining challenges of developing a controlled synthesis for anisotropically shaped magnetic nanostructures, and more importantly, their effective stabilization as a liquid dispersion because particles with net magnetic dipole moments usually aggregate due to magnetic dipole-dipole interactions.
[0131] Studies on inorganic liquid crystals have been limited to molecular species or highly polydisperse disk- and rod shaped inorganic colloids such as gibbsite (Al(OH).sub.3) and boehmite (AlO(OH)) platelets (van der Beek and Lekkerkerker (2004) Langmuir 20: 8582), platelike smectite clays (Gabriel et al. (1996) J. Phys. Chem. 100: 11139), graphene sheets (Behabtu et al. (2010) Nat. Nano. 5: 406), geothite nanorods (Lemaire et al. (2004) The Europ. Phy. J. E 13: 291), GdPO.sub.4 and LaPO.sub.4 nanorods (Kim et al. (2012) Adv. Funct. Mater. 22: 4949), or semiconductor nanorods of CdSe (Li et al. (2002) Nano. Lett. 2: 557). Magnetic anisotropic nanostructures with a uniform size, well defined shape, and good solution dispersity can be synthesized using various solution phase and gas phase deposition methods. We can also design indirect strategies that involve the preparation of nonmagnetic anisotropic nanostructures as precursors, surface passivation to enhance the colloidal stability, and then conversion of the precursors into magnetic anisotropic nanostructures. As one example, we chose FeOOH nanorods as the starting material, which can be easily prepared through a hydrolysis reaction. A representative transmission electron microscopy (TEM) image of the nanorods is shown in
[0132] Upon the application of an external magnetic field, the magnetic nanorods align themselves along the field direction, producing the orientational order needed for the formation of liquid crystals. Since the average size of the nanorods is much larger than the detection limit of small angle X-ray scattering measurement, resolving the crystal structure of the sample in the magnetic field is difficult to achieve. An alternative method which allows us to directly observe the alignment of the nanorods is to fix the nanorods in a polymer matrix. In this case, Fe.sub.3O.sub.4@SiO.sub.2 nanorods were dispersed in a UV curable poly(ethylene glycol) diacrylate (PEGDA) resin at a volume fraction () of 10%. Under an external magnetic field, the dispersion was exposed to UV light to initiate polymerization. Afterwards, the polymerized solid was cut and its cross section was examined using scanning electron microscopy (SEM). As shown in
[0133] We then demonstrated the optical tuning of such liquid crystal by a magnetic field. The orientation of the nanorods was found to vary with the direction of the magnetic field, resulting in visual changes under POM. Note that the strength of the magnetic fields used in this work is fixed at 10 G, unless otherwise specified. The intensity of light transmitted through a liquid crystal sandwiched between cross polarizers can be typically described as:
I=I.sub.0 sin.sup.2(2)sin.sup.2(nL/) (1)
where I.sub.0 is the intensity of light passing through the first polarizer; is the angle between the transmission axes of the polarizer and the long axis of the liquid crystal; n is the difference in the refractive indices along the long axis and short axis for liquid crystals aligned at a specific angle; L is the sample thickness; and is the wavelength of incident light. The birefringence of the sample dispersion was measured to be 0.15 and did not show significant change as the field strength increased, indicating good alignment of the nanorods. When the field direction is parallel or perpendicular to the polarizer, a is equal to zero or 90, leading to dark optical views (
[0134] The magnetic liquid crystals can rapidly respond to changes in the direction of external magnetic fields. A video demonstrates the continuous optical switching of a liquid crystal in a rotating magnetic field. In order to obtain a quantitative understanding of its switching frequency, we studied the optical properties of the liquid crystal under a high-frequency alternating magnetic field. Upon application of the magnetic field, the nanorods oscillate as a result of the quick switching of field polarity from one direction to the opposite (Zorba et al. (2010) J. Phys. Chem. C 114: 17868). As the orientation of the nanorods is temporarily displaced from the equilibrium position, which is parallel to the transmission axis of the polarizer, a laser beam passes through the cross polarizer and gives a detectable signal. The black curve in
[0135] One of the advantages of inorganic-nanostructure-based liquid crystals is the possibility for convenient fixation of the orientational order. Here we further demonstrate that thin films patterned with various optical polarizations can be conveniently produced by combining the magnetic liquid crystals with lithography processes. As schematically shown in
[0136] Changing the orientation of the nanorods relative to the transmission axis of the polarizer allows convenient modulation of the transmittance intensity. As depicted in the extreme cases in
[0137] Depending on the direction of the applied external field, the liquid crystals alter the polarization of light and are thus able to control the intensity of the light transmitted through them. Optical switching tests indicate that this liquid crystal is extremely sensitive to the directional change of external magnetic fields and exhibits an instant response within 0.01 s. The magnetic nanorods can also be dispersed in a UV curable resin to produce thin film liquid crystals, the orientation of which can be fixed completely or in selected areas by combining magnetic alignment and lithography processes, allowing the creation of patterns of different polarizations and control over the transmittance of light in particular areas.
[0138] The magnetically actuated liquid crystal is expected to provide a new platform for fabricating novel optical devices that can be widely applied in many fields, such as displays, waveguides, actuators, optical modulators, and anti-counterfeiting features.
Experimental
[0139] Synthesis of FeOOH Nanorods:
[0140] The synthesis of FeOOH nanorods is based on a previous report with small modifications. Typically, 7.776 g of anhydrous FeCl.sub.3 were dissolved in 80 mL water. The solution was added into 450 L of 37% HC1 and then centrifuged at 11000 rpm for 3 min for the removal of unsolvable precipitates. The purified solution was heated to 98 C. in a 100 mL three-neck flask with refluxing and was then maintained for 16 hrs. The solid product was collected by centrifugation after the reaction and washed by water for several times.
[0141] Silica Coating of FeOOH Nanorods:
[0142] 30 mg of as-prepared FeOOH nanorods was dispersed in 20 ml of water, and 1 mL 0.1M PAA solution was added for the surface modification of nanorods. After overnight stirring, the nanorods were recovered by centrifugation and were redispersed in 3 mL H.sub.2O. 1 mL of ammonia solution was then added, followed by the addition of 20 mL ethanol and 100 L of TEOS. After 1 hr, the silica-coated nanorods were collected by centrifugation, washed by water for several times and redispersed in 2 mL of water.
[0143] Conversion of FeOOH@SiO.sub.2 Nanorods to Fe.sub.2O.sub.4SiO.sub.2 Nanorods:
[0144] With the protection of nitrogen, 60 mL of diethylene glycol was heated to 220 C., to which 2 mL of FeOOH@SiO.sub.2 dispersion was added. The color of the mixture changes from yellow to brownish, and finally black. The conversion usually takes 24 hrs, after which magnetic nanorods were collected by centrifugation, washed by ethanol for several times and dispersed in 5 mL of water.
[0145] Assembling Fe.sub.3O.sub.4SiO.sub.2 Nanorods into Liquid Crystal:
[0146] As-reduced Fe.sub.3O.sub.4@SiO.sub.2 nanorods were further purified by magnetic separation for three times. Then they were concentrated to a volumetric fraction of 10% to allow the formation of liquid crystal. Dispersions with different volumetric fractions were also prepared by the same procedure.
[0147] Photopolymerization of Liquid Crystal:
[0148] A mixture solution of 7:3 polyethylene glycol diacrylate (PEGDA, Mn: 700) to water was prepared. As-reduced Fe.sub.3O.sub.4@SiO.sub.2 nanorods were dispersed in the mixture solution and purified by magnetic separation for three times. The solution was then concentrated to a volumetric fraction of 10%. Photoinitiator was added into the solution at a mass fraction of 5%. For the photopolymerization, each time 5 L of solution was used, sandwiched between one cover glass and one glass slide, and then exposed under uv-light for 20 seconds.
[0149] It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes.