CN113777835B - Electric response dimming device and preparation method and application thereof - Google Patents
Electric response dimming device and preparation method and application thereof Download PDFInfo
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- CN113777835B CN113777835B CN202110955489.8A CN202110955489A CN113777835B CN 113777835 B CN113777835 B CN 113777835B CN 202110955489 A CN202110955489 A CN 202110955489A CN 113777835 B CN113777835 B CN 113777835B
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- 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
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- 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
- G02F1/13306—Circuit arrangements or driving methods for the control of single liquid crystal cells
-
- G—PHYSICS
- G02—OPTICS
- 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
Abstract
The application discloses an electric response dimming device, a preparation method and application thereof. The electric response dimming device provided by the embodiment of the application has at least the following beneficial effects: halloysite nanotubes have a typical large aspect ratio nanotube-like structure, and the outer surface of the halloysite nanotubes are negatively charged, and the inner surface of the halloysite nanotubes are positively charged, so that the halloysite nanotubes have unique internal and external charge anisotropy characteristics, and are easy to drive under an electric field. When the electric field between the transparent conductive substrates of the intelligent window changes, the halloysite nanotubes change the arrangement sequence under the action of the electric field, so that the adjacent small-molecule liquid crystals are induced to rotate rapidly, and the aim of improving the electric response performance of the small-molecule liquid crystals in the electric response dimming device is fulfilled.
Description
Technical Field
The application relates to the technical field of intelligent windows, in particular to an electric response dimming device and a preparation method and application thereof.
Background
The intelligent window is a device which can respond under external stimulus, change optical properties such as transmittance of sunlight and the like, and further regulate lighting and temperature according to indoor sunlight intake. Smart windows can be divided into three main categories according to their specific reaction mechanisms: electrochromic smart windows, thermochromic smart windows, and electrically responsive smart windows. The electrochromic intelligent window generally uses electrochromic materials such as heavy metal oxides and the like, and has the hazard of causing heavy metal pollution; the thermochromic intelligent window is difficult to be actively controlled by a user, so that the actual use experience is not ideal. In contrast, an electrically responsive smart window based on rotation of electrically responsive liquid crystal molecules presents significant advantages due to the fast response behavior of liquid crystal molecules to electric fields. However, current electrically responsive smart windows tend to have long electrical response times and excessive drive voltages.
Disclosure of Invention
The present application aims to solve at least one of the technical problems existing in the prior art. Therefore, the application provides the electric response dimming device with short electric response time and low driving voltage.
The application also aims to provide a preparation method of the electric response dimming device.
The application also aims to provide a dimming method of the electric response dimming device.
The application also aims to provide a display device.
According to a first aspect of the application, an electric response dimming device is provided, the electric response dimming device comprises at least two light-transmitting conductive substrates which are oppositely arranged, a dimming area is formed by packaging the at least two light-transmitting conductive substrates, and small-molecule liquid crystal and halloysite nanotubes are filled in the dimming area.
The electric response dimming device provided by the embodiment of the application has at least the following beneficial effects:
Halloysite nanotubes have a typical large aspect ratio nanotube-like structure, and the outer surface of the halloysite nanotubes are negatively charged, and the inner surface of the halloysite nanotubes are positively charged, so that the halloysite nanotubes have unique internal and external charge anisotropy characteristics, and are easy to drive under an electric field. When the electric field between the transparent conductive substrates of the intelligent window changes, the halloysite nanotubes change the arrangement sequence under the action of the electric field, so that the adjacent small-molecule liquid crystals are induced to rotate rapidly, and the aim of improving the electric response performance of the small-molecule liquid crystals in the electric response dimming device is fulfilled. Under the same condition, the small molecular liquid crystal can generate the same rotation under a weaker electric field due to the induction of the halloysite nanotube, so that the driving voltage of the intelligent window can be effectively reduced. Similarly, the response time of the small molecule liquid crystal to the response of the electric field is also greatly shortened due to the induction of the halloysite nanotubes.
In addition, the saturation voltage, the optical modulation range, and the like of the smart window are also improved, and higher haze and excellent cycle stability can be obtained.
In some embodiments of the application, the halloysite nanotubes are modified halloysite nanotubes. Different hydroxyl groups such as siloxane groups (Si-O-Si), silanol (Si-OH), aluminum hydroxyl groups (Al-OH) and the like are distributed on the inner surface and the outer surface of the halloysite nanotube, so that the performance of the halloysite nanotube can be changed while the structural integrity of the halloysite nanotube is maintained in a physical modification and/or chemical modification mode, and the overall performance of the intelligent window is further improved. Wherein the physical modification includes, but is not limited to, complexing the modifying molecule with the halloysite nanotube by van der Waals forces, hydrogen bonding, electrostatic attraction, etc., and the chemical modification includes, but is not limited to, introducing specific functional groups of the modifying molecule into the halloysite nanotube by covalent bonding.
In some embodiments of the present application, the modifying agent used to modify halloysite nanotubes is selected from at least one of an acid, a base, a coupling agent, and a surfactant. Wherein the acid includes, but is not limited to, strong acids such as hydrochloric acid, sulfuric acid, nitric acid, and weak acids such as acetic acid; bases include, but are not limited to, sodium hydroxide, potassium hydroxide, and the like. The hydroxyl groups on the tube wall of the halloysite nanotube are activated in an acid or alkali modification mode, so that the density of the surface hydroxyl groups is improved. And the compatibility of halloysite nanotubes and small-molecule liquid crystals can be improved by modifying the coupling agent such as a silane coupling agent and a surfactant.
In some embodiments of the application, halloysite nanotubes are surface protonated. The halloysite nanotubes after the protonation treatment have higher surface charge density, so that the smart window can obtain more excellent electric response characteristics. In particular, any surface protonation technique known in the art may be used, such as by low concentration hydrochloric acid.
In some embodiments of the application, halloysite nanotubes are modified with small molecule liquid crystal compatible groups. Wherein the compatible group is a group capable of improving compatibility between the halloysite nanotube and the small molecule liquid crystal. The groups can be stably dispersed and suspended in the small-molecule liquid crystal by modifying the halloysite nanotubes, so that the small-molecule liquid crystal can not be deposited on the edge of a dimming area due to incompatibility of the groups, and the induction effect of the small-molecule liquid crystal steering in the whole dimming area is further affected.
In some embodiments of the application, the compatibilizing group comprises a mesogen of a small molecule liquid crystal. The mesogen refers to a key structural unit in a small-molecule liquid crystal that forms a liquid crystal state. The liquid crystal element structure similar to the small molecular liquid crystal structure is introduced on the halloysite nanotube, so that the compatibility between the halloysite nanotube and the small molecular liquid crystal is greatly improved.
Taking ase:Sub>A small molecule liquid crystal with ase:Sub>A structure of A-B or A-B-A 'as an example, wherein A or A' is ase:Sub>A polar or polarizable flexible group; b is a rigid group comprising one or more moieties directly or bridged to benzene rings, alicyclic rings, heterocyclic rings, polycyclic aromatic hydrocarbons. The liquid crystal element modified on the halloysite nanotube refers to a derivative group which comprises the same rigid group as that of the small molecule liquid crystal or is subjected to substitution modification. It is understood that in order to further enhance the compatibility effect, the compatible group may also be ase:Sub>A group comprising A-B, B-A ', A-B-A', or ase:Sub>A derivative thereof to further enhance the similarity with the small molecule liquid crystal structure.
In some embodiments of the application, the small molecule liquid crystal is at least one of a nematic liquid crystal, a cholesteric liquid crystal. The small molecule liquid crystal used in the electrically responsive dimming device may be nematic liquid crystal, cholesteric liquid crystal or mixed liquid crystal molecular material.
In some embodiments of the present application, the liquid crystal mixture within the dimming region includes a small molecule liquid crystal, halloysite nanotubes, and a chiral dopant, wherein the weight fraction of the halloysite nanotubes is 0.1-1 wt%. Because halloysite nanotubes are inorganic materials, even after surface modification, the compatibility with small-molecule liquid crystals is still limited. If the doping concentration is too high, agglomeration or deposition is easy to cause, electric field regulation is not facilitated, the phenomenon that local irrecoverable is possibly caused is canceled after power is applied, and the repeatable times are affected.
In a second aspect of the present application, there is provided a method for manufacturing the aforementioned electrically responsive dimming device, the method comprising the steps of:
taking a first light-transmitting conductive substrate and a second light-transmitting conductive substrate, preparing a first alignment layer on one surface of the first light-transmitting conductive substrate, and preparing a second alignment layer on the second light-transmitting conductive substrate;
placing a small molecular liquid crystal and halloysite nanotubes on the first alignment layer;
And compounding the second light-transmitting conductive substrate with the first light-transmitting conductive substrate, so that the first alignment layer and the second alignment layer are oppositely arranged, and curing and packaging to form the electric response light modulation device.
According to the mode, the halloysite nanotubes are doped into the electric response dimming device formed by the small-molecule liquid crystals, when the electric field between the light-transmitting conductive substrates of the intelligent window changes, the halloysite nanotubes change the arrangement sequence under the action of the electric field, so that the adjacent small-molecule liquid crystals are induced to rotate rapidly, and the purpose of improving the electric response performance of the small-molecule liquid crystals in the electric response dimming device is achieved. Under the same condition, the small molecular liquid crystal can generate the same rotation under a weaker electric field due to the induction of the halloysite nanotube, so that the driving voltage of the intelligent window can be effectively reduced. Similarly, the response time of the small molecule liquid crystal to the response of the electric field is also greatly shortened due to the induction of the halloysite nanotubes.
In some embodiments of the application, the method of preparation comprises the steps of:
taking a first light-transmitting conductive substrate and a second light-transmitting conductive substrate, preparing a first alignment layer on one surface of the first light-transmitting conductive substrate, and preparing a second alignment layer on the second light-transmitting conductive substrate;
taking a first transparent conductive substrate, wherein the conductive layer is a conductive pixel wall and is used as a lower substrate, and forming a frame on the first alignment layer by using spacers on the periphery to form a dimming area; placing a small molecular liquid crystal and halloysite nanotubes in a dimming region on the first alignment layer;
And compounding the second transparent conductive substrate with the first transparent conductive substrate, arranging the first alignment layer and the second alignment layer oppositely, performing ultraviolet irradiation curing to form a dimming box, and electrically connecting two poles of a power supply with the first transparent conductive substrate and the second transparent conductive substrate respectively to prepare the electric response dimming device.
In some embodiments of the application, halloysite nanotubes are surface protonated.
In some embodiments of the application, halloysite nanotubes are modified with small molecule liquid crystal compatible groups.
In some embodiments of the application, the first alignment layer and the second alignment layer are vertical alignment layers.
In some embodiments of the application, the small molecule liquid crystal and halloysite nanotubes are placed on the alignment layer after being mixed uniformly in proportion.
In some embodiments of the application, the mode of mixing the small molecule liquid crystal and halloysite nanomixing includes ultrasound.
In a third aspect of the present application, there is provided a dimming method of an electrically responsive dimming device, the dimming method comprising: and adjusting an electric field between at least two light-transmitting conductive substrates so as to lead the halloysite nanotubes to induce the turning of the small molecular liquid crystal while turning, and change the transmission and reflection of light.
Wherein, adjusting the electric field between at least two transparent conductive substrates means to include adjusting the presence or absence of the electric field. According to the dimming method, due to the doping of halloysite nanotubes in the intelligent window, a better electric response effect can be obtained in a smaller driving voltage and a shorter driving time.
In a fourth aspect of the application, a display device is provided comprising the electrically responsive dimming device as described above.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
Fig. 1 is a schematic diagram of an electrically responsive dimmer device of the present application in a powered-off state.
Fig. 2 is a schematic diagram of an electrically-responsive dimmer device of the present application in an energized state.
Fig. 3 is a graph showing the transmittance results of light of different wavelength bands in different states of the electrically-responsive dimming device in embodiment 1 of the present application.
Reference numerals: the light-transmitting conductive substrate comprises a first light-transmitting conductive substrate 11, a second light-transmitting conductive substrate 12, an alignment layer 20, a light modulation region 30, a small molecule liquid crystal 31, halloysite nanotubes 32 and a power component 40.
Detailed Description
The conception and the technical effects produced by the present application will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present application. It is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present application based on the embodiments of the present application.
The following detailed description of embodiments of the application is exemplary and is provided merely to illustrate the application and is not to be construed as limiting the application.
In the description of the present application, the meaning of a number is one or more, the meaning of a number is two or more, and greater than, less than, exceeding, etc. are understood to exclude the present number, and the meaning of a number is understood to include the present number. The description of the first and second is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present application, unless explicitly defined otherwise, terms such as arrangement, installation, connection, etc. should be construed broadly and the specific meaning of the terms in the present application can be reasonably determined by a person skilled in the art in combination with the specific contents of the technical scheme.
In the description of the present application, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Referring to fig. 1, there is shown an electrically-responsive dimming device according to an embodiment of the present application, which includes a first light-transmitting conductive substrate 11 and a second light-transmitting conductive substrate 12 disposed opposite to each other, a dimming region 30 is formed by encapsulation between the first light-transmitting conductive substrate 11 and the second light-transmitting conductive substrate 12, and the dimming region 30 is filled with a small-molecular liquid crystal 31 and halloysite nanotubes 32 dispersed between the small-molecular liquid crystals 31. Halloysite nanotubes 32 have a large aspect ratio and unique internal and external charge anisotropy characteristics, making them more easily driven under electric field conditions. In some of these embodiments, the first transparent conductive substrate 11 and the second transparent conductive substrate 12 are further connected to the positive and negative electrodes of the power supply assembly 40, respectively.
In some embodiments, an alignment layer 20 is disposed on a side of the first transparent conductive substrate 11 adjacent to the second transparent conductive substrate 12, and a side of the second transparent conductive substrate 12 adjacent to the first transparent conductive substrate 11, so as to align the small molecule liquid crystal 31 filled therebetween. The material of the alignment layer 20 includes, but is not limited to, self-aligned polyimide, non-aligned polyimide, polyvinyl alcohol, etc., and the alignment layer 20 is formed by a process of preparation well known in the art such as rubbing, scratching, brushing, etc. In some of these embodiments, the alignment layer 20 is a vertical alignment layer.
Referring to fig. 1 and 2, fig. 1 is an electrically responsive dimming device in a powered-off state, and fig. 2 is an electrically responsive dimming device after power is applied. When the power is not applied, the halloysite nanotubes 32 are suspended in the dimming area and are arranged in a disordered manner, and at this time, light irradiates on the halloysite nanotubes 32 and the small-molecule liquid crystal 31, and reflection occurs, so that incident light is difficult to transmit. When an electric field is generated by electrifying the first transparent conductive substrate 11 and the second transparent conductive substrate 12, the small molecule liquid crystal 31 turns under the action of the electric field, meanwhile, the halloysite nanotubes 32 doped in the embodiment of the application also change the arrangement sequence under the action of the electric field, the small molecule liquid crystal 31 at the adjacent position is further induced to rapidly rotate, the alignment is changed into nematic phase alignment perpendicular to potential lines, a large amount of light rays do not irradiate on the halloysite nanotubes 32 any more and directly penetrate through the intelligent window, and the regulation and control of light rays from reflection to transmission are realized. In this case, the response time of the small molecular liquid crystal 31 to the electric field is shortened, and the same rotation can be generated under a weaker electric field due to the induction of the halloysite nanotube 32, thereby effectively reducing the driving voltage of the smart window. In addition, saturation voltage, optical modulation range and the like can be obviously reduced, and higher haze and excellent cycle stability can be obtained.
In some embodiments, halloysite nanotubes 32 are modified to achieve more excellent electrical response properties. Specific modes of modification include, but are not limited to, acid modification (such as strong acid, hydrochloric acid, sulfuric acid, nitric acid, etc.), alkali modification (such as strong alkali, sodium hydroxide, potassium hydroxide, etc.), coupling agent modification (such as silane coupling agent), surfactant modification, etc., so as to achieve the purposes of increasing surface hydroxyl groups, improving dispersion effect and electric response effect.
In some embodiments, halloysite nanotubes 32 are also surface protonated. The protonated halloysite nanotubes 32 have a higher surface charge density and may have more sensitive electrical response characteristics.
In some embodiments, the halloysite nanotubes 32 are modified with a compatible group of the small-molecule liquid crystal, so that the halloysite nanotubes 32 can be stably dispersed and suspended in the small-molecule liquid crystal 31, and cannot be deposited on the edge of the dimming area 30 due to incompatibility of the halloysite nanotubes and further influence the induction effect on the turning of the small-molecule liquid crystal 31 and the response effect on the reflection and transmission. In some of the preferred embodiments, the compatible group comprises a mesogen of a small molecule liquid crystal 31. A mesogen structure similar to the structure of the small-molecule liquid crystal 31 is introduced into the halloysite nanotube 32, so that the compatibility between the mesogen structure and the small-molecule liquid crystal 31 is greatly improved.
In some embodiments, a spacer is further disposed within the dimming region. By using the spacers, the interval between the first light-transmitting conductive substrate 11 and the second light-transmitting conductive substrate 12 is ensured to be fixed.
The embodiment of the application also provides a preparation method of the electric response dimming device, which comprises the following steps: taking a first light-transmitting conductive substrate and a second light-transmitting conductive substrate, preparing a first alignment layer on one surface of the first light-transmitting conductive substrate, and preparing a second alignment layer on the second light-transmitting conductive substrate; placing a small molecular liquid crystal and halloysite nanotubes on the first alignment layer; and compounding the second transparent conductive substrate with the first transparent conductive substrate, wherein the first alignment layer and the second alignment layer are oppositely arranged, and curing and packaging to form the electric response light modulation device. In some specific embodiments, the first transparent conductive substrate after the alignment layer is prepared is first made into a frame by using spacers around, and then the small molecule liquid crystal and halloysite nanotubes are placed on the first alignment layer by injection, coating and other modes. In some specific embodiments, the second transparent conductive substrate and the first transparent conductive substrate are attached to each other, the dimming box is formed by ultraviolet light curing or other modes well known in the art, and two poles of the power supply assembly are respectively connected with the first transparent conductive substrate and the second transparent conductive substrate, so that the electric response dimming device is prepared.
In some specific embodiments, halloysite nanotubes are grafted with a compatibility group after being subjected to surface treatment by a coupling agent, so that the compatibility of the halloysite nanotubes with small-molecule liquid crystals is improved; then, the halloysite nanotubes and the small molecular liquid crystal are mixed in proportion, uniformly dispersed by a mode such as ultrasonic and the like, and then are placed on the alignment layer.
The embodiment of the application also provides a dimming method of the electric response dimming device, which is characterized in that the halloysite nanotube induces the turning of the small-molecule liquid crystal while turning by adjusting the electric field between at least two light-transmitting conductive substrates, so that the transmission and reflection of light are changed. The adjustment of the electric field at least means that whether the electric field is regulated or not is judged, when the electric field is not electrified, halloysite nanotubes in the dimming area are uniformly suspended in the small-molecule liquid crystal, and after the electric field is electrified, the halloysite nanotubes are converted into an arrangement sequence, and the similar small-molecule liquid crystal is induced to rapidly rotate and orient, so that the light ray transreflective effect is regulated and controlled, and a better electric response effect can be obtained in a smaller driving voltage and a shorter driving time.
Example 1
The present embodiment provides an electrically-responsive dimming device, the structure of which is shown in fig. 2, and the electrically-responsive dimming device includes two oppositely disposed first transparent conductive substrates 11 and second transparent conductive substrates 12, an alignment layer 20 is disposed on opposite sides of the first transparent conductive substrates 11 and the second transparent conductive substrates 12, the alignment layer 20 is a vertical alignment layer, the first transparent conductive substrates 11 and the second transparent conductive substrates 12 are sealed around by spacers (not shown in fig. 1), and a dimming area 30 is formed therebetween, and the dimming area 30 is filled with a liquid crystal composite material, wherein the liquid crystal composite material includes small molecule liquid crystals 31, halloysite nanotubes 32 and chiral dopants (not shown in the figure). The two poles of the power supply assembly 40 are connected to the first light-transmitting conductive substrate 11 and the second light-transmitting conductive substrate 12, respectively.
In this embodiment, the small molecule liquid crystal is nematic liquid crystal, and specifically 4-cyano-4' hydroxybiphenyl is selected. Halloysite nanotubes are surface-protonated halloysite nanotubes and have a branched chain of 4-cyanobiphenyl grafted thereto with an amide group. The chiral dopant is cholesterol nonanoate. Wherein, the mass percent of the 4-cyano-4' hydroxyl biphenyl in the liquid crystal composite material is 95.83 percent, the mass percent of the halloysite nanotube is 1.00 percent, and the mass percent of the chiral dopant is 3.17 percent.
The method for forming the liquid crystal composite material from the small molecule liquid crystal, the halloysite nanotube and the chiral dopant comprises the following steps: .
The preparation method of the electric response dimming device provided by the embodiment is as follows:
s1, taking a first light-transmitting conductive substrate and a second light-transmitting conductive substrate, and respectively coating a liquid crystal vertical alignment layer on the non-conductive inner surfaces of the first light-transmitting conductive substrate and the second light-transmitting conductive substrate;
s2, taking the first light-transmitting conductive substrate as a lower substrate, manufacturing a frame by using spacers around the first light-transmitting conductive substrate, and presetting a dimming area inside the frame;
S3, mixing halloysite nanotubes with small molecular liquid crystal and chiral dopants in proportion, performing ultrasonic dispersion and other treatments to form a uniform liquid crystal composite material, and injecting the liquid crystal composite material into a dimming area;
S4, bonding the second transparent conductive substrate serving as an upper substrate and a lower substrate, and curing by ultraviolet irradiation to form a dimming box;
s5, connecting two poles of the alternating current power supply assembly with electrode layers of the upper substrate and the lower substrate respectively to manufacture the electric field regulation intelligent window.
Referring to fig. 1 to 2, when not energized, halloysite nanotubes in a dimming region are uniformly suspended in the dimming region to be arranged in a disordered manner, light irradiates on the halloysite nanotubes and a small-molecule liquid crystal, and light in a visible light band is reflected to show good haze performance; after the halloysite nanotubes are electrified, the arrangement direction of the halloysite nanotubes is changed under the action of an electric field, and meanwhile, adjacent small molecular liquid crystals are driven to be arranged in a vertical orientation mode, under the condition, a large amount of light rays do not irradiate on particles any more and directly penetrate through the intelligent window, and the regulation and control of light rays from reflection to transmission are realized. In this case, the response time of the small molecular liquid crystal to the electric field is shortened, and the same rotation can be generated under a weaker electric field due to the induction of the halloysite nanotubes, so that the driving voltage of the smart window is effectively reduced. In addition, saturation voltage, optical modulation range and the like can be obviously reduced, and higher haze and excellent cycle stability can be obtained. Through up to 1 ten thousand electric field modulation haze experiments, stability and repeatability are still very good.
Referring to fig. 3, the result of detecting the light transmittance of the electrically-responsive dimming device provided in this embodiment can be seen from the graph that the light transmittance of the visible light band is significantly improved after power is applied.
Example 2
The present example provides an electrically responsive dimming device, which differs from example 1 in that small molecule liquid crystals select HTW138200-100 hybrid liquid crystals (available from Jiangsu and display technologies); whereas halloysite nanotubes were surface protonated only with 0.1M hydrochloric acid, without other modifications. In this embodiment, the doped halloysite nanotubes have poor compatibility with small-molecule liquid crystals, are not uniformly distributed in the dimming region, and are mostly deposited on the edge of the dimming region in an agglomeration manner.
Example 3
The present embodiment provides an electrically responsive dimming device, which is different from embodiment 1 in that a small-molecule liquid crystal selects E7 mixed liquid crystal; whereas halloysite nanotubes are surface-protonated and modified with cationic surfactants. In this embodiment, the doped halloysite nanotubes have good compatibility with small molecular liquid crystals, can be uniformly distributed in the dimming area, and finally reduce the driving voltage, saturation voltage, response time and optical modulation range of the electric response dimming device to a certain extent, but the halloysite nanotubes and the surfactant are disintegrated to form agglomeration and deposition after multiple electric field effects, so that the repeatability is poor.
As can be seen from the above embodiments, the electric response dimming device provided by the embodiment of the application has the advantages of low cost, fast response, high haze performance, excellent stability, environment-friendly material and the like. Light rays of various wavelength bands of visible light can be covered, and most of the light rays can be reflected, so that the light rays are expected to become reflective projection display devices.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present application. Furthermore, embodiments of the application and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The electric response dimming device is characterized by comprising two light-transmitting conductive substrates which are oppositely arranged, wherein a dimming area is formed by packaging the two light-transmitting conductive substrates, and small-molecule liquid crystal and halloysite nanotubes are filled in the dimming area.
2. The electrically responsive dimming device of claim 1, wherein the halloysite nanotubes are modified halloysite nanotubes; the modifier used for modifying the halloysite nanotube is at least one selected from acid, alkali, coupling agent and surfactant.
3. The electrically responsive dimming device of claim 1, wherein the halloysite nanotubes are surface protonated.
4. The electrically responsive dimming device of claim 1, wherein the halloysite nanotubes are modified with compatible groups for the small molecule liquid crystals.
5. The electrically responsive dimming device of claim 4, wherein the compatible group comprises a mesogen of the small molecule liquid crystal.
6. An electrically responsive dimming device as claimed in any one of claims 1 to 5, wherein the small molecule liquid crystal is at least one of nematic liquid crystal, cholesteric liquid crystal.
7. A method of manufacturing an electrically responsive dimming device as claimed in any one of claims 1 to 6, comprising the steps of:
Taking a first light-transmitting conductive substrate and a second light-transmitting conductive substrate, preparing a first alignment layer on one surface of the first light-transmitting conductive substrate, and preparing a second alignment layer on the second light-transmitting conductive substrate;
placing a small molecule liquid crystal and halloysite nanotubes on the first alignment layer;
And compounding the second light-transmitting conductive substrate with the first light-transmitting conductive substrate, so that the first alignment layer and the second alignment layer are oppositely arranged, and curing and packaging to form the electric response dimming device.
8. The method of claim 7, wherein the halloysite nanotubes are modified with a compatible group for small molecule liquid crystals.
9. The dimming method of an electrically-responsive dimming device according to any one of claims 1 to 6, wherein an electric field between two light-transmitting conductive substrates is adjusted so that halloysite nanotubes induce small-molecule liquid crystal to turn while turning, changing transmission and reflection of light.
10. A display device comprising an electrically responsive dimming device as claimed in any of claims 1 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102645777A (en) * | 2011-12-13 | 2012-08-22 | 北京京东方光电科技有限公司 | Liquid crystal panel manufacturing method, liquid crystal panel and display |
| KR20180060368A (en) * | 2016-11-29 | 2018-06-07 | 한국화학연구원 | Manufacturing method of modified halloysite nanotube and polymer composite containing it |
| CN108998851A (en) * | 2018-06-28 | 2018-12-14 | 成都新柯力化工科技有限公司 | A kind of low cost halloysite nanotubes coordination plasticizing aramid fiber and preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102645777A (en) * | 2011-12-13 | 2012-08-22 | 北京京东方光电科技有限公司 | Liquid crystal panel manufacturing method, liquid crystal panel and display |
| KR20180060368A (en) * | 2016-11-29 | 2018-06-07 | 한국화학연구원 | Manufacturing method of modified halloysite nanotube and polymer composite containing it |
| CN108998851A (en) * | 2018-06-28 | 2018-12-14 | 成都新柯力化工科技有限公司 | A kind of low cost halloysite nanotubes coordination plasticizing aramid fiber and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 埃洛石纳米管在高分子纳米复合材料中的应用进展;伍 巍 等;《化工进展》;第30卷(第12期);2647-2657 * |
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