CN115220267B - Construction method of liquid crystal injection porous smooth surface and microfluidic application thereof - Google Patents
Construction method of liquid crystal injection porous smooth surface and microfluidic application thereof Download PDFInfo
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- CN115220267B CN115220267B CN202210914902.0A CN202210914902A CN115220267B CN 115220267 B CN115220267 B CN 115220267B CN 202210914902 A CN202210914902 A CN 202210914902A CN 115220267 B CN115220267 B CN 115220267B
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133784—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by rubbing
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1341—Filling or closing of cells
- G02F1/13415—Drop filling process
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13775—Polymer-stabilized liquid crystal layers
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Abstract
The invention provides a construction method of a liquid crystal injection porous smooth surface and microfluidic application thereof, wherein a liquid crystal box with orientation control is prepared through selection of a substrate, control of box thickness, selection of an orientation material and orientation design; the liquid crystal injection porous system is controlled in advance by changing the types and the proportions of liquid crystal and liquid crystal polymer monomers; filling the mixed liquid crystal material into a liquid crystal box, controlling the temperature, forming a polymer network through exposure wavelength and dosage control under a specific phase state, and naturally forming a liquid crystal injection porous polymer network film by using small molecule liquid crystal without being influenced by an exposure step, so as to finish the preparation of the liquid crystal injection porous material; and then opening the box, and scraping and coating small molecule liquid crystal to obtain the liquid crystal functional surface with liquid injection holes. The liquid crystal injection porous smooth surface provided by the invention has smooth characteristics, adjustability and self-repairing property, can be used for micro-flow control, pollution resistance, ultra-smooth surface, biological sensing, biological engineering and other aspects, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a construction method of a smooth surface of a liquid injection porous material based on liquid crystal and microfluidic application of the construction method.
Background
The surface (SLIPS Slippery Liquid Infused Porous Surfaces) of the liquid injection smooth porous material can realize comprehensive transfusion performance on liquids with different surface tension, has good compression resistance and self-repairing function, and is a smooth and chemically homogeneous lubricating layer formed on the surface of a rough porous substrate by respectively taking epoxy resin with a silanized nano array structure and a poly tetra krypton ethylene film as substrates, injecting low-surface energy and chemically inert liquid perfluoro tri-n-pentylamine FC-70 and perfluoropolyether Krytox 100. The SLIPS surface has the following advantages: 1. repel various simple and complex liquids (water, hydrocarbons, crude oil and blood), 2 maintain good hydrophobicity and low contact angle, 3 have rapid self-healing after physical damage. The lubricating liquid is locked in the material by utilizing the micro-nano level intercommunication network structure, and the lubricating liquid can slowly overflow from the material due to low surface tension, so that a layer of liquid film is formed on the surface of the material, the effect of repelling other liquid can be achieved, and compared with the surface of the traditional ultra-lyophobic material, the SLIPS has better pressure stability due to the fact that the lubricating liquid is filled in the pores, and air in the pores is replaced. The bionic smooth surface has become a hot spot for research of academic researchers in recent years, and has wide application in the fields of lyophobia, anti-icing, dust prevention, drag reduction, biological adhesion resistance, micro-flow control and the like.
At present, common methods for preparing the surface of the liquid injection smooth porous material comprise a chemical deposition method, a coating method, femtosecond laser etching, ion etching and the like, and most of the methods have complicated processes, high cost, poor flexibility and no universality.
The design of the open-surface microfluid can realize independent control of various characteristics of liquid, is important for designing a next-generation microfluidic platform, and can be widely applied to the fields of chemistry, environment, biology, medicine and the like. In order to realize a controllable functional microfluidic system, scientists have conducted a great deal of research to drive droplets with stimulus responses on the surface of an open fluid based on topology morphology on the micro/nano scale. However, the method of manipulating the chemical composition of the droplets often relies on chemisorption directly from the underlying surface, which has been demonstrated to anchor the droplets to the surface and to cause them to lose mobility. This inherent coupling of droplet chemistry and mobility greatly weakens the robustness of conventional open surface microfluidic systems and can hamper their practical use. If this can be overcome, the potential of open surface microfluidic systems will be exerted to a greater extent.
Liquid Crystals (LCs) are a unique class of anisotropic fluid materials that have exhibited a number of odd colloid/interface phenomena with complexity and functionality. Due to its inherent excellent properties, including alignment and position order of various mesophases, cured liquid crystals have been developed for use in the fields of chemical sensing and active substance release, etc. At present, people realize a super-hydrophobic bionic structure on the hard surface of metal and the like by simulating the hydrophobicity of lotus leaves, so as to control the movement of liquid drops, but the fine design and preparation of the hard structure need to depend on complex processing means and higher instrument precision; the group Yanlei of the complex denier university devised a solution for controlling the fixed-point directional flow of liquid droplets in a liquid crystal polymer tube, but it was not realized by an open droplet transport control, and was not well suited for such specific applications as sensing/detection.
People also orient and control microorganisms, such as bacteria, through liquid crystal orientation structuring based on a liquid crystal system in which a liquid crystal polymer network and small molecular liquid crystals coexist, and move and proliferate along the liquid crystal orientation direction without applying additional control conditions, but the structure mainly aims at realizing movement direction assistance of active cells and fails to realize control of orientation movement of objects without vital signals. Due to the inherent anisotropism of the liquid crystal, the micro-fluidic system for designing and regulating the liquid crystal-based liquid drop fluidity and chemical composition according to the requirement has bright research prospect. However, at present, since liquid crystal films coated on conventional hydrophobically modified substrates such as silane, azlactone and porous polystyrene coating functionalized surfaces undergo liquid droplet-induced dehumidification, open-surface microfluidic systems based on liquid crystals have not been truly realized.
In summary, how to stabilize the liquid crystal, how to find a solution to the problem of water-induced liquid crystal surface dehumidification, how to manufacture the surface of the liquid injection smooth porous material by using a simple preparation process, and how to programmably design the surface of the liquid injection smooth porous material to obtain a microfluidic platform with a special function can be known, and the solution of the problems can be helpful for the wide application of the surface of the liquid injection smooth porous material. The preparation method for finding an excellent programmable porous material is particularly important, and the specific proposal is expected to provide an effective thought for designing and developing a functional surface liquid crystal micro-fluidic platform capable of realizing dynamic control and chemical composition control of liquid drops in the future, and hopefully excite more surface micro-fluidic systems based on liquid crystals.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for constructing a porous smooth surface of a liquid crystal injection, which has the advantages of simple preparation process, low cost, simple operation and programmable design; based on the porous smooth surface of the liquid crystal injection with programmable design, a microfluidic technology of directional transportation of liquid drops is developed, and a technical means is provided for the application of the microfluidic technology in the fields of chemical reaction, detection sensing, biological medicine and the like.
The specific technical scheme of the invention is as follows: the construction method of the smooth surface of the liquid injection porous material based on the liquid crystal specifically comprises the following steps:
s1, mixing liquid crystal material
Mixing a liquid crystal polymer monomer, smectic phase liquid crystal and a photoinitiator, heating and melting under a dark condition, and then vibrating and stirring uniformly;
s2, preparing a liquid crystal box:
1) Cleaning two glass substrates coated with the conductive films;
2) Spin-coating an orientation agent on the conductive film surfaces of the two glass substrates, and drying; when the used orientation agent is a friction orientation agent, continuing the steps 3) -5); when the used orientation agent is a light-operated orientation agent, the steps 4) -6) are continued;
3) Unidirectional rubbing with flannelette to form uniform orientation on the surface of the film coated with the friction orientation agent;
4) The spacer strip is clamped between two glass substrates, the conductive film of the glass substrates faces inwards, and the glass substrates are fixed;
5) Glue is coated and fixed on the side edge of the glass substrate, a filling opening and an exhaust opening are reserved during glue sealing, and the manufacturing of the liquid crystal box is completed;
6) The liquid crystal box is irradiated by linear polarized structure light with the wavelength of 350 nm-410 nm to carry out specific photo-alignment;
s3, preparation of porous smooth surface of liquid crystal injection
Heating the liquid crystal compound prepared in the step S1 to a temperature above the clearing point, and filling the liquid crystal compound into a liquid crystal box; slowly reducing to different temperatures to enable the liquid crystal to be in a smectic phase state or a nematic phase state; polymerizing under ultraviolet light, opening a liquid crystal box after polymerization, attaching a liquid crystal polymer layer on a glass substrate, and attaching small-molecule liquid crystal in a polymer network to form a liquid crystal polymer porous network structure and a composite layer of the small-molecule liquid crystal; then spreading small molecule liquid crystal on the liquid crystal injection porous smooth surface film by using a capillary tube, and standing.
Further, in the step S1, the mass ratio of the liquid crystal polymer monomer, the smectic phase liquid crystal and the photoinitiator is 10.5-20.5:78-88:0.5-2.
Further, the liquid crystal polymer monomer used in step S1 is selected from the Reactivemonomer (RM) series of liquid crystal monomers which can undergo polymerization reaction, preferably RM257 (2-methyl-1, 4-phenyl 4- (3-acryloxypropoxy) benzoate), RM82 (1, 4-bis- [4- (6-acryloxyhexyloxy) benzoyl oxy ] -2-methylphenyl), RM006 (4- [ [6- [ (1-oxo-2-propenyl) oxy ] hexyl ] oxy ] benzoic acid 4-methoxyphenyl ester) or RM23 (4-cyanophenyl 4- ((6- (acryloxyhexyl) oxy) hexyl) oxy) benzoate).
Further, the smectic phase liquid crystal used in step S1 is preferably 8CB (octylbiphenyl nitrile) or 8OCB (octyloxybiphenyl nitrile).
Further, the photoinitiator used in step S1 may be any photoinitiator conventionally used to induce polymerization of RM-series liquid crystal polymer monomers, and preferably Irgaucure 651 photoinitiator or Irgacure 819 photoinitiator.
Further, in step S2, the photo-alignment agent used is an alignment agent SD1, and the rubbing alignment agent is polyimide.
Further, in step S2, the structured light is linearly polarizedThe total exposure dose of the irradiation is not less than 5J/cm 2 。
Further, in step S2, the cell thickness of the liquid crystal cell is 100 to 160. Mu.m.
Further, in step S3, the small molecular liquid crystal laid by the capillary may be smectic phase liquid crystal or nematic phase liquid crystal, if it is smectic phase liquid crystal material (which can change phase from isotropic to nematic phase and then from nematic phase to smectic phase through temperature control, temperature reduction process), such material is most suitable, and is suitable for both nematic phase polymerization and smectic phase polymerization, and after polymerization film formation, the liquid crystal phase state can be switched to realize two state switching for droplet transport and stagnation; however, some smectic phase liquid crystals have a phase change process of directly changing from isotropic phase to smectic phase, and skip nematic phase, such as semi-fluorinated rod-shaped smectic phase liquid crystals, so that the material can only polymerize at the smectic phase temperature, and after the material is polymerized to form a film, only smectic phase exists, so that liquid drops are difficult to slide, and therefore, the material is not suitable; however, common nematic materials such as E7 (mixed crystal, common nematic liquid crystal), SLC1717 (mixed crystal, common nematic liquid crystal), 5CB (pentylbiphenyl), TEB300 (mixed crystal, common nematic liquid crystal) and the like are all possible, but the nematic liquid crystal does not have a smectic phase, so that it is impossible to polymerize in the smectic phase, and after polymerization into a film, it exists in the nematic phase itself, and although it is also possible to realize droplet transport, the small molecular liquid crystal used in this step is preferably smectic liquid crystal 8CB or 8OCB, comprehensively considered.
Further, in the step S3, the ultraviolet light intensity is 2-5 mW/cm during ultraviolet polymerization 2 The irradiation duration is 20-30 min.
The preparation method comprises the steps of selecting to construct a liquid injection porous smooth surface by utilizing photo-control orientation, carrying out exposure orientation by utilizing a DMD dynamic mask miniature projection exposure system during construction, and accurately controlling the flow speed and direction of liquid drops by utilizing the structured liquid injection porous smooth surface with programmable design through patterning orientation structural design, so that the micro-fluidic technology based on liquid crystals can be realized.
Compared with the prior art, the invention has the following advantages:
1. the anisotropy of the liquid crystal material is utilized, so that a good directional transport effect on liquid drops is realized;
2. the application provides a method for preparing a functional liquid crystal injection porous smooth surface by utilizing a photo-control orientation technology in a programmable manner to accurately control the flow speed and direction of liquid drops, so that a micro-fluidic technology based on liquid crystals can be realized;
3. in the application, when a smooth surface is constructed, small molecular liquid crystals are paved on a liquid crystal injection porous smooth surface film by using capillaries, so that on one hand, the smooth performance of the surface of a porous structure is improved, and on the other hand, the small molecular liquid crystals play a certain role in protecting the porous structure;
4. the liquid crystal injection porous smooth surface has smooth characteristics, adjustability and self-repairing property, can be used for microfluidic, dust-proof, pollution-proof, ultra-smooth surfaces, chemical reactions, biological sensing, biological engineering and other aspects, and has the advantages of simple and convenient whole preparation process, readily available raw materials and low cost.
Drawings
FIG. 1 is a schematic view of a porous smooth surface of a liquid crystal injection prepared in example one; wherein, the glass substrate of 1-ITO, 2-orientation layer, 3-liquid crystal polymer/micromolecular liquid crystal composite layer, 4-micromolecular liquid crystal layer;
FIG. 2 is a schematic view of a droplet instilled on a porous smooth surface of a liquid crystal injection, wherein the left view is a state diagram of a droplet immediately before a liquid crystal is not formed into a coating layer after the droplet is instilled on the porous smooth surface of the liquid crystal injection, and the right view is a state diagram of a liquid crystal coating layer formed, wherein a-substrate, b-liquid crystal coating layer and c-droplet;
FIG. 3 is a schematic illustration of a liquid crystal injected porous smooth surface with droplets "immobilized" when the small molecule liquid crystal is in a smectic phase;
FIG. 4 is a schematic illustration of a droplet sliding in an alignment direction and a vertical alignment direction on a glass substrate having an inclination of about 7℃when a small molecule liquid crystal is in a nematic phase, wherein the three panels of the first row are schematic illustrations of sliding in the alignment direction and the three panels of the second row are schematic illustrations of sliding in the vertical alignment direction;
FIG. 5 is a schematic illustration of a droplet sliding in an alignment direction on a glass substrate having an inclination of about 1℃when a small molecule liquid crystal is in a nematic phase;
FIG. 6 is a schematic illustration of a droplet sliding in an alignment direction on a glass substrate having an inclination of about 1℃when a small molecule liquid crystal is in a smectic phase;
FIG. 7 is a schematic view showing that droplets slide in the alignment direction on a glass substrate having an inclination of about 6℃when a small-molecule liquid crystal is in a smectic state, the upper panel showing a position before sliding, and the lower panel showing a position after sliding;
fig. 8 is a schematic diagram of an alignment structure designed by a maskless exposure system based on a digital micromirror array, wherein the alignment structure is designed in a Y shape, and n is an alignment direction, namely a unidirectional arrow direction.
Detailed Description
The following description of the present invention is provided with reference to the accompanying drawings, but is not limited to the following description, and any modifications or equivalent substitutions of the present invention should be included in the scope of the present invention without departing from the spirit and scope of the present invention.
Embodiment one, construction of a porous smooth surface for liquid Crystal injection
1) Mixing liquid crystal materials:
mixing 10% of liquid crystal polymer monomer RM257, 88% of smectic phase liquid crystal 8CB and 2% of photoinitiator 651 according to mass ratio, heating, melting, and vibrating and stirring uniformly;
2) Preparation of a liquid crystal box:
firstly, UVO cleaning two cleaned conductive ITO glass substrates for 30min;
the ITO surfaces of the two glass substrates are coated with liquid crystal aligning agents in a spin mode, the liquid crystal aligning agents can be photo-control aligning agents SD1 or friction aligning agents polyimide, if photo-alignment is needed to be carried out later by using the photo-control aligning agents SD1, if photo-alignment is needed to be carried out later by using friction aligning agents, compared with friction alignment, the photo-alignment has the advantages that structured alignment can be achieved, and a manufactured finished product has better application prospect;
the preparation process of the photo-orientation agent comprises the following steps:
spin-coating photo-alignment agent: dissolving SD1 in DMF (dimethyl formamide) with the mass fraction of 0.3%; SD1 was spin coated onto the substrate in two steps: the spin coating speed in the first step is 800rpm, the duration time is 10s, and the acceleration is 800rpm/s; the spin coating speed in the second step is 3000rpm, the duration time is 30s, and the acceleration is 1000rpm/s;
baking on a hot table at 100 ℃ for 10min after spin coating is finished;
a 125 μm thick spacer bar was sandwiched between two glass substrates (glass substrates ITO facing inward), and the two glass plates were sandwiched by the clips;
mixing the adhesive A and the adhesive B of the adhesive AB, coating the adhesive A and the adhesive B on the side surface of a glass substrate, leaving at least two air gap openings with the width of about 2mm when sealing edges, wherein one opening is used for filling liquid crystal material, the other opening is used for exhausting air, taking the prepared liquid crystal box with the required specific box thickness off a clamp after five minutes, and irradiating the prepared liquid crystal box for specific orientation under linearly polarized light with the wavelength of 405nm for 8 minutes to prepare the liquid crystal box with the specific orientation.
If rubbing orientation is selected, photo-orientation is not used, and after polyimide is spin-coated on a glass substrate, spin-coating parameters are: firstly, 500-550 rpm is turned for 9s, and then 3000-3200 rpm is turned for 30s; baking at 200deg.C for 2 hr, fixing the glass substrate with polyimide coating on the friction table, making the length of the flannel equal to the circumference of the section of the cylinder, wrapping the flannel on the cylinder, holding the two ends of the cylinder, rubbing the polyimide film surface with the flannel to form uniform orientation, making the glass substrate into liquid crystal box, and pouring liquid crystal material according to the same procedure to obtain the final product.
The following steps are mainly performed on the basis of a liquid crystal cell produced by photo-alignment;
3) Preparation of liquid crystal injection porous smooth surface
Heating the liquid crystal compound prepared in the step 1) to a temperature above the clearing point, heating to 50 ℃ in the embodiment, and filling the heated liquid crystal compound into a liquid crystal box. Slowly cooling from clear point temperature to smectic phase or nematic phase, the smectic phase temperature being different from the nematic phase (cooling to 35 ℃ in the control heat stage)The intensity of the ultraviolet light is about 2mW/cm 2 The irradiation duration was 20min; after polymerization, the liquid crystal box is pried from the edge of the liquid crystal box by using a clean blade, a liquid crystal polymer layer is attached to one of the glass substrates (considering that in the polymerization process, one of the substrates is closer to the light source, the other substrate is far away from the light source, and under the condition of slight exposure dose difference, the polymerization degree on the substrate close to the light source is slightly high, so that most of the liquid crystal is left on one glass substrate after the box is opened, and some unpolymerized small molecule liquid crystal possibly remains on the other side), and small molecule liquid crystal is attached to a polymer network to form a composite layer of a liquid crystal polymer porous structure and the small molecule liquid crystal; then, a certain amount of small molecule liquid crystal 8CB is paved on the liquid crystal injection porous smooth surface film by a capillary tube, and the liquid crystal injection porous smooth surface film is stood for a period of time.
Fig. 1 is a schematic view of a porous smooth surface of a liquid crystal injection prepared according to the above method, which sequentially includes an ITO glass substrate 1, an alignment layer 2, a liquid crystal polymer/small molecule liquid crystal composite layer 3, and a small molecule liquid crystal layer 4.
After the liquid drops drop on the porous smooth surface of the prepared liquid crystal injection liquid, a liquid crystal coating layer b (shown in fig. 2) is gradually formed on the liquid drops c on the substrate a, and the coating layer can effectively prevent the liquid drops from evaporating.
The high flatness and hydrophobicity of the porous smooth surface of the polymerized liquid crystal injection liquid under the nematic phase temperature condition enable the liquid crystal injection liquid to have a good liquid drop transport function. At the temperature below the smectic phase-nematic phase transition temperature (e.g. 30 ℃), the small molecular liquid crystal in the liquid crystal liquid injection functional film is in a smectic phase state, and at this time, the liquid drops on the liquid crystal liquid injection functional surface of the liquid crystal polymer film cannot slide, and even if the liquid crystal substrate is vertically placed, the liquid drops can be fixed on the liquid crystal liquid injection functional surface, and cannot be effectively transported (fig. 3).
When the polymerization temperature is higher than the smectic phase-nematic phase transition temperature (the temperature selected in the test example is 35 ℃), namely the small molecular liquid crystal is in the nematic phase, the transport characteristic of the liquid drops on the surface of the liquid crystal liquid injection function is changed essentially, and the liquid drops can slide at a higher speed. If the substrate inclination angle is about 7 degrees, the liquid drops have good conveying function on the smooth surface of the liquid crystal polymer film, and the uniform speed of the liquid drops moving along the orientation direction and the vertical orientation direction is 23-30 mm/min (figure 4); when the inclination angle of the substrate was about 1 °, the average speed of the liquid droplet sliding along the liquid crystal alignment direction was 2.0mm/min, and fig. 5 is a graph showing the initial (left) end (right) position of the liquid droplet after sliding on the porous smooth surface of the liquid crystal injected when the inclination angle of the substrate was about 1 °. Therefore, the micro-fluidic switch capable of realizing temperature control on the liquid crystal liquid injection functional surface prepared based on nematic phase temperature polymerization can be known.
The anisotropy of the porous smooth surface of the polymerized liquid crystal injection liquid under the condition of the smectic phase temperature is more remarkable, so that the liquid crystal injection liquid has a good oriented liquid drop transport function. With this structure, after uniform orientation in the horizontal direction, when the inclination angle is smaller than a certain threshold value, the droplet slides along the orientation direction and cannot move perpendicular to the orientation direction. The liquid crystal injected porous smooth surface slides parallel to the alignment direction when a very small tilt angle (less than about 1 deg.) exists under the microscope (fig. 6). When the tilt angle of the glass substrate was 6 °, the average velocity of the droplet sliding along the orientation direction was 1.5mm/min (fig. 7).
Based on the above results, further using a maskless exposure system based on a digital micromirror array, a structured liquid crystal injection porous smooth surface with programmable design is prepared by patterning the design of an orientation structure, for example, the orientation structure can be designed into a special shape such as a Y-shape (fig. 8) or an S-shape, and taking the Y-shape orientation structure as an example: the prepared liquid crystal box is subjected to exposure orientation by using a DMD (Digital Micro-Mirror Device) dynamic mask miniature projection exposure system, three steps of exposure are respectively carried out, namely an orientation direction shown by a unidirectional arrow is obtained by matching a polarization direction of a region (1) with a long side (shown by a double-headed arrow) of the region, then an orientation direction shown by the unidirectional arrow is obtained by matching a polarization direction of a region (2) with a long side (shown by a double-headed arrow) of the region, finally an orientation direction shown by the unidirectional arrow is obtained by matching a polarization direction of a region (3) with a long side (shown by a double-headed arrow) of the region, and the total exposure dose irradiated under linear polarized light is not less than 5J/cm 2 . The definition of theta and alpha angles is shown in the figure, the values of the theta and alpha angles can be 100-180 degrees, and the alpha angles are obtained according to the preparation methodThe structured liquid crystal injection porous smooth surface is provided with a liquid crystal porous structure with a specific orbit, liquid drops can be controlled to realize the transportation of complex paths on the liquid crystal injection porous smooth surface, and the functions of mixing reaction, chemical analysis, biological detection and the like are further realized, so that the method has important significance in the application fields of biomedicine, synthesis and screening of new medicines, food and commodity inspection, environmental monitoring, military science, aerospace science and the like.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The construction method of the smooth surface of the liquid injection porous material based on the liquid crystal is characterized by comprising the following steps:
s1, mixing liquid crystal material
Mixing a liquid crystal polymer monomer, smectic phase liquid crystal and a photoinitiator, heating and melting under a dark condition, and then vibrating and stirring uniformly;
s2, preparing a liquid crystal box:
1) Cleaning two glass substrates coated with the conductive films;
2) Spin-coating an orientation agent on the conductive film surfaces of the two glass substrates, and drying; when the used orientation agent is a friction orientation agent, continuing the steps 3) -5); when the used orientation agent is a light-operated orientation agent, the steps 4) -6) are continued;
3) Unidirectional rubbing with flannelette to form uniform orientation on the surface of the film coated with the friction orientation agent;
4) The spacer strip is clamped between two glass substrates, the conductive film of the glass substrates faces inwards, and the glass substrates are fixed;
5) Glue is coated and fixed on the side edge of the glass substrate, a filling opening and an exhaust opening are reserved during glue sealing, and the manufacturing of the liquid crystal box is completed;
6) The liquid crystal box is irradiated by linear polarized structure light with the wavelength of 350 nm-410 nm to carry out specific photo-alignment;
s3, preparation of porous smooth surface of liquid crystal injection
Heating the liquid crystal compound prepared in the step S1 to a temperature above the clearing point, and filling the liquid crystal compound into a liquid crystal box; slowly reducing to different temperatures to enable the liquid crystal to be in a smectic phase state or a nematic phase state; polymerizing under ultraviolet light, opening a liquid crystal box after polymerization, attaching a liquid crystal polymer layer on a glass substrate, and attaching small-molecule liquid crystal in a polymer network to form a liquid crystal polymer porous network structure and a composite layer of the small-molecule liquid crystal; then spreading small molecule liquid crystal on the liquid crystal injection porous smooth surface film by using a capillary tube, and standing.
2. The method for constructing a smooth surface of a liquid crystal-based liquid injection porous material according to claim 1, wherein in the step S1, a mass ratio of the liquid crystal polymer monomer, the smectic phase liquid crystal and the photoinitiator is 10.5-20.5:78-88:0.5-2.
3. The method for constructing a smooth surface of a liquid crystal-based liquid injection porous material according to claim 1, wherein the liquid crystal polymer monomer used in the step S1 is RM257, RM82, RM006 or RM23.
4. The method for constructing a smooth surface of a liquid crystal-based liquid-injected porous material according to claim 1, wherein the smectic liquid crystal used in step S1 is 8CB or 8OCB.
5. The method for constructing a smooth surface of a liquid crystal-based liquid crystal injected porous material according to claim 1, wherein the photoinitiator used in the step S1 is Irgaucure 651 photoinitiator or Irgacure 819 photoinitiator.
6. The method for constructing a smooth surface of a liquid crystal-based liquid injection porous material according to claim 1, wherein in the step S2, the photo-alignment agent is an alignment agent SD1, the rubbing alignment agent is polyimide, and the total exposure dose of irradiation under linear polarization structured light is not less5J/cm 2 。
7. The method for constructing a smooth surface of a liquid crystal-based liquid-injected porous material according to claim 1, wherein in the step S2, the thickness of the liquid crystal cell is 100 to 160 μm.
8. The method for constructing a smooth surface of a liquid crystal-based porous material according to claim 1, wherein in the step S3, the small molecular liquid crystal laid on the capillary is 8CB or 8OCB.
9. The method for constructing a smooth surface of a liquid crystal-based porous material according to claim 1, wherein in the step S3, the intensity of ultraviolet light is 2-5 mW/cm during ultraviolet polymerization 2 The irradiation duration is 20-30 min.
10. The application of the liquid crystal-based injection porous material smooth surface in the field of microfluidics is characterized in that the liquid crystal-based injection porous material smooth surface is prepared based on the method of any one of claims 1-9, the injection porous smooth surface is constructed by light control orientation during preparation, the DMD dynamic mask miniature projection exposure system is utilized for exposure orientation during construction, and the flow rate and direction of liquid drops can be accurately controlled by the prepared structured liquid crystal injection porous smooth surface with programmable design through patterning orientation structural design.
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