CN111231439A - Heat-conducting graphene-high polymer material composite film and preparation method thereof - Google Patents

Heat-conducting graphene-high polymer material composite film and preparation method thereof Download PDF

Info

Publication number
CN111231439A
CN111231439A CN202010028061.4A CN202010028061A CN111231439A CN 111231439 A CN111231439 A CN 111231439A CN 202010028061 A CN202010028061 A CN 202010028061A CN 111231439 A CN111231439 A CN 111231439A
Authority
CN
China
Prior art keywords
graphene
polymer material
heat
composite film
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010028061.4A
Other languages
Chinese (zh)
Other versions
CN111231439B (en
Inventor
丁鹏
崔思奇
宋娜
施利毅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Transpacific Technology Development Ltd
University of Shanghai for Science and Technology
Original Assignee
Beijing Transpacific Technology Development Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Transpacific Technology Development Ltd filed Critical Beijing Transpacific Technology Development Ltd
Priority to CN202010028061.4A priority Critical patent/CN111231439B/en
Publication of CN111231439A publication Critical patent/CN111231439A/en
Application granted granted Critical
Publication of CN111231439B publication Critical patent/CN111231439B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a heat-conducting graphene-high polymer material composite film, which is a multilayer composite film and is prepared from the following components in percentage by weight: 20-40% of graphene, 30-40% of nano-cellulose and 30-40% of thermoplastic polymer material. The invention discloses a preparation method of the compound, which comprises the following steps: respectively adding graphene, nano-cellulose and thermoplastic polymer into a dispersing agent, stirring and carrying out ultrasonic treatment to prepare a dispersion liquid; mixing, stirring and ultrasonically treating the raw materials according to a set weight ratio to obtain a mixed solution; drying part of the mixed solution, pouring the dried mixed solution into a mold, and drying to obtain a single-layer heat-conducting graphene-high polymer material composite film; and repeating the steps for multiple times, and stacking the single layers together to obtain the multilayer anisotropic heat conduction graphene-high polymer material composite film with the heat-driven three-level shape memory characteristic, wherein the composite film has flexibility, high transverse heat conductivity, low vertical heat conductivity, high heat conduction anisotropy and heat-driven three-level shape memory performance.

Description

Heat-conducting graphene-high polymer material composite film and preparation method thereof
Technical Field
The invention relates to a functional composite material, belongs to the field of heat-conducting polymer material composite materials and shape memory polymer material composite materials, in particular to a multilayer anisotropic heat-conducting graphene-polymer material composite film with three-level shape memory driven by heat and a preparation method thereof,
background
Shape Memory Material (SMM) is a stimulus-responsive material that has received much attention for its unique shape memory properties. It can sense the stimulus of external environment change (such as temperature, electricity, light, magnetism, solvent, pH, etc.), and respond to the stimulus to return from the temporary shape to the original shape. Compared with other SMMs (such as shape memory alloy, shape memory ceramic and the like), the Shape Memory Polymer (SMP) has the advantages of high shape recovery rate, low response temperature, low cost, excellent processing and forming performance, easiness in modification and the like, and has very wide application prospects in the fields of biomedicine, information electronics, intelligent devices and the like.
Graphene is a two-dimensional carbon nanomaterial with a series of excellent properties including high specific surface area, excellent mechanical properties, excellent conductivity and the like. Notably, graphene possesses the highest thermal conductivity known at present, with theoretical thermal conductivity at room temperature as high as 5300W · m-1·K-1. Therefore, the heat-conducting performance of the high polymer material can be obviously improved by adding the heat-conducting agent into the high polymer material, and other characteristics of the high polymer material can be kept.
The cellulose material is a high molecular material taken from nature. The nano-cellulose fiber has the properties of a transparent high-molecular material, light weight, high strength and the like, and also has the characteristics of good biocompatibility, wide source, reproducibility, degradability and the like, and also has the characteristic of specific surface area. The abundant oxygen-containing functional groups on the surface provide good conditions for the interaction with other high molecular materials and inorganic fillers. Thus, nanocellulose may be used to enhance the mechanical properties of the material.
In the prior art, the shape memory material has the capability of generating shape change under external stimulation and is an intelligent material. The shape memory polymer material has the characteristics of light weight, low price, chemical corrosion resistance and easy processing. Compared with shape memory alloy, the shape memory polymer material has the advantages of high shape recovery rate, wide memory recovery temperature and the like. Therefore, the shape memory polymer material shows a huge application prospect in the fields of sensors, aerospace and the like.
In the prior art, chinese patent application No. 201811061546.2 discloses a multiple-drive type shape memory composite material and a method for preparing the same, wherein the multiple-drive type shape memory composite material uses a thermotropic shape memory polymer as a substrate, and a graphene film is attached to the surface of the substrate; the multiple driving includes thermal driving, electrical driving, and optical driving. The multiple driving type shape memory composite material provided by the invention can realize thermal driving, electric driving and optical driving, and the application field is expanded.
However, the shape memory polymer material provided by the invention only has one permanent shape and one temporary shape, and cannot realize three-level shape memory with one permanent shape and two different temporary shapes, so that the shape memory polymer material has fewer functions and still has great limitation on the application field; meanwhile, the existing preparation method of the shape memory composite material is complex, the adopted components are high in price, the overall cost is high, and the industrial popularization and application are difficult.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a multilayer anisotropic heat conduction graphene-high polymer material composite film material capable of realizing thermally-driven three-level shape memory and a preparation method thereof, so that the prepared composite film material has flexibility, high transverse heat conductivity, low longitudinal heat conductivity, high heat conduction anisotropy and thermally-driven three-level shape memory performance; meanwhile, the preparation method is improved, the process is simplified, and the overall manufacturing cost is reduced, so that the industrial popularization and application are facilitated.
In order to achieve the purpose, the invention provides the following technical scheme:
the heat-conducting graphene-high polymer material composite film is characterized by being a multilayer composite film, having heat-conducting anisotropy and heat-driven three-level shape memory characteristics and being prepared from the following components in percentage by weight:
20 to 40 percent of graphene,
30 to 40 percent of nano-cellulose,
30 to 40 percent of thermoplastic polymer material.
The average horizontal size of the graphene is 10-15 mu m, the average thickness of the graphene is 1-5 nm, and the content of oxygen is less than or equal to 2.0%;
the diameter of the nano-cellulose is 5-100 nm, and the length-diameter ratio is 100-1000.
The thermoplastic polymer materials are two thermoplastic polymer materials (namely A + B) with different components, the using temperatures are A, B respectively, and the difference between A, B and A, B is more than 20 ℃;
the thermoplastic polymer material is a mixture prepared from polyethylene glycol, polyurethane, polycaprolactone, paraffin, thermoplastic polyimide and the like.
The preparation method of the heat-conducting graphene-high polymer material composite film is characterized by comprising the following steps:
(1) adding graphene into a dispersing agent, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a graphene dispersion solution with the concentration of 1-3 mg/mL;
(2) adding the nano-cellulose into a dispersing agent, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a nano-cellulose dispersion solution with the concentration of 1-3 mg/mL;
(3) adding a thermoplastic polymer material into a dispersing agent, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a thermoplastic polymer material dispersion liquid with the concentration of 1-3 mg/mL;
(4) mixing the graphene dispersion liquid obtained in the step (1) and the polymer material dispersion liquid obtained in the step (3) according to a set weight ratio, stirring for 0.5-1 h, and performing ultrasonic treatment for 5-10 min to obtain a graphene-polymer material mixed liquid with the concentration of 5-10 mg/mL;
(5) mixing the nano-cellulose dispersion liquid obtained in the step (2) and the polymer material dispersion liquid obtained in the step (3) according to a set weight ratio, stirring for 0.5-1 h, and performing ultrasonic treatment for 5-10 min to obtain a nano-cellulose-polymer material mixed liquid with the concentration of 5-10 mg/mL;
(6) placing the graphene-polymer material mixed solution and the nano cellulose-polymer material mixed solution in a vacuum drying oven, standing for 0.5-1 h in a vacuum environment at room temperature, and removing gas existing in the mixed solution;
(7) pouring a set amount of graphene-high polymer material mixed solution into a mold, placing the mold in an oven at 40-50 ℃ for drying for 6-10 h, pouring a set amount of nanocellulose-high polymer material mixed solution into the mold, placing the mold in an oven at 40-50 ℃ for drying for 6-10 h, and preparing a single-layer heat-conducting graphene-high polymer material composite membrane;
(8) and (5) repeating the step (7) for multiple times, and stacking the single layers together to obtain the multilayer anisotropic heat-conducting graphene-high polymer material composite membrane with the heat-driven three-level shape memory characteristic.
In the preparation method, the dispersant is one or more of deionized water, cyclohexane, ethanol, N-dimethylformamide and other solvents.
Compared with the prior art, the invention has the following advantages and effects:
(1) the heat-conducting graphene-high polymer material composite film provided by the invention has the characteristics of two thermally-driven three-stage shape memories responding to (triggering) temperature, and the material has a permanent shape and two different temporary shapes; therefore, compared with the traditional shape memory polymer material, the three-level shape memory polymer material can realize more complicated functional actions, thereby further improving the application range of the material.
(2) The heat-conducting graphene-high polymer material composite film has multilayer anisotropy, particularly has high transverse heat conductivity, low vertical heat rate and high heat-conducting anisotropy, has a large transverse and longitudinal heat-conducting anisotropy ratio which can reach 20-35 or higher, and can enable the material to have more unique functions by combining the characteristics of three-level heat-driven shape memory with two response temperatures, and can be applied to the wider and more complicated control field.
(3) According to the invention, the components of the high polymer material and the graphene and the preparation method are synchronously optimized, so that the composite membrane with a multilayer structure can be obtained, and meanwhile, the nano-cellulose is added as a reinforcing phase, so that the composite membrane has good flexibility.
(4) The preparation method of the heat-conducting graphene-high polymer material composite film provided by the invention has the advantages of compact process, easiness in control, low requirement on equipment, simplicity in operation method, high adjustability, easiness in obtaining raw materials, low overall manufacturing cost and easiness in industrial application and popularization.
Drawings
FIG. 1 is an electron microscope image of a cross section of a three-layer composite film in an example of the present invention;
FIG. 2 is a schematic cross-sectional view of a three-layer composite film according to an embodiment of the present invention;
FIG. 3 is a graph showing a relationship between a temperature response and a shape recovery rate of a three-level shape memory property of a graphene-polyethylene glycol/paraffin-nanocellulose composite membrane according to an embodiment of the present invention;
fig. 4 is a graph showing a correspondence relationship between the number of layers of the graphene-polyethylene glycol/paraffin-nanocellulose composite membrane and each anisotropy in the embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Referring to the accompanying drawings 1-4, the heat-conducting graphene-polymer material composite film provided by the invention is a multilayer composite film, has heat-conducting anisotropy and thermal driving three-level shape memory characteristics, and is prepared from the following components in percentage by weight:
20 to 40 percent of graphene,
30 to 40 percent of nano-cellulose,
30 to 40 percent of thermoplastic polymer material.
The average horizontal size of the graphene is 10-15 mu m, the average thickness of the graphene is 1-5 nm, and the content of oxygen is less than or equal to 2.0%;
the diameter of the nano-cellulose is 5-100 nm, and the length-diameter ratio is 100-1000.
The thermoplastic polymer materials are two thermoplastic polymer materials (namely A + B) with different components, the using temperatures are A, B respectively, and the difference between A, B and A, B is more than 20 ℃;
the thermoplastic polymer material is a mixture prepared from polyethylene glycol, polyurethane, polycaprolactone, paraffin, thermoplastic polyimide and the like.
The preparation method of the heat-conducting graphene-high polymer material composite film is characterized by comprising the following steps:
(1) adding graphene into a dispersing agent, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a graphene dispersion solution with the concentration of 1-3 mg/mL;
(2) adding the nano-cellulose into a dispersing agent, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a nano-cellulose dispersion solution with the concentration of 1-3 mg/mL;
(3) adding a thermoplastic polymer material into a dispersing agent, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a thermoplastic polymer material dispersion liquid with the concentration of 1-3 mg/mL;
(4) mixing the graphene dispersion liquid obtained in the step (1) and the thermoplastic polymer material dispersion liquid obtained in the step (3) according to a set weight ratio, stirring for 0.5-1 h, and performing ultrasonic treatment for 5-10 min to obtain a graphene-polymer material mixed liquid with the concentration of 5-10 mg/mL;
(5) mixing the nano-cellulose dispersion liquid obtained in the step (2) and the polymer material dispersion liquid obtained in the step (3) according to a set weight ratio, stirring for 0.5-1 h, and performing ultrasonic treatment for 5-10 min to obtain a nano-cellulose-polymer material mixed liquid with the concentration of 5-10 mg/mL;
(6) placing the graphene-polymer material mixed solution and the nano cellulose-polymer material mixed solution in a vacuum drying oven, standing for 0.5-1 h in a vacuum environment at room temperature, and removing gas existing in the mixed solution;
(7) pouring a set amount of graphene-high polymer material mixed solution into a mold, placing the mold in an oven at 40-50 ℃ for drying for 6-10 h, pouring a set amount of nanocellulose-high polymer material mixed solution into the mold, placing the mold in an oven at 40-50 ℃ for drying for 6-10 h, and preparing a single-layer heat-conducting graphene-high polymer material composite membrane;
(8) and (5) repeating the step (7) for multiple times, and stacking the single layers together to obtain the multilayer anisotropic heat-conducting graphene-high polymer material composite membrane with the heat-driven three-level shape memory characteristic.
In the foregoing preparation method, the dispersant is one or more of deionized water, cyclohexane, ethanol, N-dimethylformamide and other solvents.
Example 1
The multilayer anisotropic heat conduction graphene-polymer material composite film with the heat-driven three-level dynamic shape memory provided by the embodiment comprises graphene, polyethylene glycol, paraffin and nanocellulose, wherein the mass fraction of the graphene in the composite film is 20%, the mass fraction of the nanocellulose is 40%, the mass fraction of the polyethylene glycol is 20%, and the mass fraction of the paraffin is 20%. The average horizontal size of the graphene is 10-15 mu m, the average thickness of the graphene is 1-5 nm, and the content of oxygen is less than or equal to 2.0%; the diameter of the nano-cellulose is 5-100 nm, and the length-diameter ratio is 100-1000; the molecular weight of polyethylene glycol is 10000; paraffin wax having a melting point of 30 ℃.
The preparation method of the multilayer anisotropic heat conduction graphene-high polymer material composite film with thermally driven three-level shape memory comprises the following steps:
(1) adding graphene into deionized water, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a graphene dispersion solution with the concentration of 1-3 mg/mL;
(2) adding the nano-cellulose into cyclohexane, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a nano-cellulose dispersion solution with the concentration of 1-3 mg/mL;
(3) adding polyethylene glycol into deionized water, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a polyethylene glycol dispersion solution with the concentration of 1-3 mg/mL;
(4) adding paraffin into cyclohexane, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing 1-3 mg/mL paraffin dispersion liquid;
(5) mixing the graphene dispersion liquid obtained in the step (1) and the polyethylene glycol dispersion liquid obtained in the step (3) according to a ratio of 1: mixing the components according to the weight ratio of 1, stirring for 1h, and performing ultrasonic treatment for 10min to obtain a graphene-polyethylene glycol mixed solution.
(6) Mixing the nano cellulose dispersion liquid obtained in the step (2) and the paraffin dispersion liquid obtained in the step (4) according to the ratio of 1: mixing at a weight ratio of 1, stirring for 1h, and performing ultrasonic treatment for 10min to obtain a nano cellulose-paraffin mixed solution.
(7) Placing the graphene-polyethylene glycol mixed solution and the nano cellulose-paraffin mixed solution obtained in the steps (5) and (6) in a vacuum drying oven, standing for 1h in a vacuum environment at room temperature, and removing gas in the mixed solution;
(8) pouring 10mL of graphene-polyethylene glycol mixed solution into a mold, placing the mold in a 40 ℃ oven, drying for 10h, pouring 10mL of nano cellulose-paraffin mixed solution into the mold, placing the mold in the 40 ℃ oven, drying for 6h, and repeating for 2 times to obtain the thermally-driven three-level shape memory multilayer anisotropic heat conduction graphene-high polymer material composite membrane.
The thermal conductivity of the multilayer anisotropic thermal conductivity graphene-polymer material composite film with thermally driven three-level shape memory prepared in this example 1 was tested by using an LFA447 type laser thermal conductivity meter of germany Netzsch company, and the test results were: transverse thermal conductivity of 15.80 W.m-1·K-1Longitudinal thermal conductivity of 0.58 W.m-1·K-1The anisotropic ratio reaches 27, the flexibility is good, and the variation range of the thermal conductivity coefficient after the bending at 200 degrees is 0-5%. The testing method of the shape memory performance comprises the steps of bending the composite film at 70 ℃ to form 90-degree bending deformation, then bending the composite film at 30 ℃ to form 90-degree bending deformation, fixing the temporary shape at room temperature, raising the temperature to 30 ℃ again to record the recovery rate, and raising the temperature to 70 ℃ again to record the recovery rate. The test results are: the shape recovery rate is more than 70% in 30s at 30 ℃, and the shape recovery rate is more than 70% in 30s at 70 ℃.
The temperatures used in this example were 30 ℃, room temperature (20 ℃) and 70 ℃, these three temperatures being the temperatures at which the memory effect was produced.
Example 2
The multilayer anisotropic heat conduction graphene-polymer material composite film with the heat-driven three-level motion shape memory provided by the embodiment comprises graphene, polyethylene glycol, paraffin and nanocellulose, wherein the mass fraction of the graphene in the composite film is 40%, the mass fraction of the nanocellulose is 30%, the mass fraction of the polyethylene glycol is 15%, and the mass fraction of the paraffin is 15%. The average horizontal size of the graphene is 10-15 mu m, the average thickness of the graphene is 1-5 nm, and the content of oxygen is less than or equal to 2.0%; the diameter of the nano-cellulose is 5-100 nm, and the length-diameter ratio is 100-1000; the molecular weight of polyethylene glycol is 10000; paraffin wax having a melting point of 30 ℃.
The preparation method of the multilayer anisotropic heat conduction graphene-high polymer material composite film with thermally driven three-level shape memory comprises the following steps:
(1) adding graphene into ethanol, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a graphene dispersion solution with the concentration of 1-3 mg/mL;
(2) adding the nano-cellulose into cyclohexane, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a nano-cellulose dispersion solution with the concentration of 1-3 mg/mL;
(3) adding polyethylene glycol into ethanol, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a polyethylene glycol dispersion solution with the concentration of 1-3 mg/mL;
(4) adding paraffin into cyclohexane, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing 1-3 mg/mL paraffin dispersion liquid;
(5) and (3) mixing the graphene dispersion liquid obtained in the step (1) and the polycaprolactone dispersion liquid obtained in the step (3) according to a ratio of 1: mixing the components according to the weight ratio of 1, stirring for 1h, and performing ultrasonic treatment for 10min to obtain a graphene-polyethylene glycol mixed solution.
(6) Mixing the nano cellulose dispersion liquid obtained in the step (2) and the paraffin dispersion liquid obtained in the step (4) according to the ratio of 1: mixing at a weight ratio of 1, stirring for 1h, and performing ultrasonic treatment for 10min to obtain a nano cellulose-paraffin mixed solution.
(7) And (3) placing the graphene-polyethylene glycol mixed solution and the nano cellulose-paraffin mixed solution obtained in the steps (5) and (6) into a vacuum drying oven, standing for 1h in a vacuum environment at room temperature, and removing gas in the mixed solution.
(8) Pouring 10mL of graphene-polyethylene glycol mixed solution into a mold, placing the mold in a 40 ℃ oven, drying for 10h, pouring 10mL of nano cellulose-paraffin mixed solution into the mold, placing the mold in the 40 ℃ oven, drying for 6h, and repeating for 1 time to obtain the thermally-driven three-level shape memory multilayer anisotropic heat conduction graphene-high polymer material composite membrane.
The thermal conductivity of the multilayer anisotropic thermal conductivity graphene-polymer material composite film with thermally driven three-level shape memory prepared in this example 2 was tested by using an LFA447 type laser thermal conductivity meter of germany Netzsch company, and the test results were: transverse thermal conductivity of 13.46 W.m-1·K-1Longitudinal thermal conductivity of 0.38 W.m-1·K-1The anisotropic ratio reaches 35, the flexibility is good, and the variation range of the thermal conductivity coefficient after the bending at 200 degrees is 0-5%. The shape recovery rate of the composite film at 30 ℃ within 30s is more than 70%, and the shape recovery rate at 70 ℃ within 30s is more than 70%.
Example 3
The multilayer anisotropic heat conduction graphene-high polymer material composite film with the heat-driven three-level driving shape memory provided by the embodiment is composed of graphene, polyurethane, polycaprolactone and nanocellulose, wherein the mass fraction of the graphene in the composite film is 30%, the mass fraction of the nanocellulose is 35%, the mass fraction of the polycaprolactone is 17.5%, and the mass fraction of the polyurethane is 17.5%. The average horizontal size of the graphene is 10-15 mu m, the average thickness of the graphene is 1-5 nm, and the content of oxygen is less than or equal to 2.0%; the diameter of the nano-cellulose is 5-100 nm, and the length-diameter ratio is 100-1000.
The preparation method of the multilayer anisotropic heat conduction graphene-high polymer material composite film with thermally driven three-level shape memory comprises the following steps:
(1) adding graphene into N, N-dimethylformamide, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a graphene dispersion solution with the concentration of 1-3 mg/mL;
(2) adding the nano-cellulose into N, N-dimethylformamide, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a nano-cellulose dispersion solution with the concentration of 1-3 mg/mL;
(3) adding polyurethane into N, N-dimethylformamide, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a polyethylene glycol dispersion solution with the concentration of 1-3 mg/mL;
(4) adding polycaprolactone into N, N-dimethylformamide, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a polycaprolactone dispersion liquid with the concentration of 1-3 mg/mL;
(5) mixing the graphene dispersion liquid obtained in the step (1) and the polyurethane dispersion liquid obtained in the step (3) according to a ratio of 1: mixing the components according to the weight ratio of 1, stirring for 1h, and performing ultrasonic treatment for 10min to obtain a graphene-polyurethane mixed solution.
(6) And (3) mixing the nano cellulose dispersion liquid obtained in the step (2) and the polycaprolactone dispersion liquid obtained in the step (4) according to the ratio of 1: mixing at a weight ratio of 1, stirring for 1h, and performing ultrasonic treatment for 10min to obtain a nano cellulose-polycaprolactone mixed solution.
(7) And (3) placing the graphene-polyurethane mixed liquor and the nano cellulose-polycaprolactone mixed liquor obtained in the steps (5) and (6) into a vacuum drying oven, standing for 1h in a vacuum environment at room temperature, and removing gas in the mixed liquor.
(8) Pouring 10mL of graphene-polyurethane mixed solution into a mold, placing the mold in a 40 ℃ oven, and drying for 10h, pouring 6mL of nanocellulose-polycaprolactone mixed solution into the mold, placing the mold in the 40 ℃ oven, drying for 6h, and repeating for 3 times to obtain the thermally-driven three-level shape memory multilayer anisotropic heat conduction graphene-high polymer material composite membrane.
The thermal conductivity of the multilayer anisotropic thermal conductivity graphene-polymer material composite film with thermally driven three-level shape memory prepared in this example 1 was tested by using an LFA447 type laser thermal conductivity meter of germany Netzsch company, and the test results were: transverse thermal conductivity of 19.25 W.m-1·K-1Longitudinal thermal conductivity of 0.78 W.m-1·K-1The anisotropic ratio reaches 25, the flexibility is good, and the variation range of the thermal conductivity coefficient after the bending of the plate 200 is 0-5%. The testing method of the shape memory performance comprises the steps of bending the composite film at 150 ℃ to form 90-degree bending deformation, then bending the composite film at 70 ℃ to form 90-degree bending deformation, fixing the temporary shape at room temperature, raising the temperature to 70 ℃ again to record the recovery rate, and raising the temperature to 150 ℃ again to record the recovery rate. The test results are: the shape recovery rate is more than 85% in 30s at 70 ℃, and the shape recovery rate is more than 85% in 30s at 150 ℃.
Example 4
The multilayer anisotropic heat conduction graphene-polymer material composite film with the heat-driven three-level driving shape memory provided by the embodiment is composed of graphene, polyurethane, thermoplastic polyimide and nanocellulose, wherein the mass fraction of the graphene in the composite film is 30%, the mass fraction of the nanocellulose is 35%, the mass fraction of the thermoplastic polyimide is 17.5%, and the mass fraction of the polyurethane is 17.5%. The average horizontal size of the graphene is 10-15 mu m, the average thickness of the graphene is 1-5 nm, and the content of oxygen is less than or equal to 2.0%; the diameter of the nano-cellulose is 5-100 nm, and the length-diameter ratio is 100-1000.
The preparation method of the multilayer anisotropic heat conduction graphene-high polymer material composite film with thermally driven three-level shape memory comprises the following steps:
(1) adding graphene into N, N-dimethylformamide, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a graphene dispersion solution with the concentration of 1-3 mg/mL;
(2) adding the nano-cellulose into N, N-dimethylformamide, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a nano-cellulose dispersion solution with the concentration of 1-3 mg/mL;
(3) adding polyurethane into N, N-dimethylformamide, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a polyethylene glycol dispersion solution with the concentration of 1-3 mg/mL;
(4) adding thermoplastic polyimide into N, N-dimethylformamide, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing 1-3 mg/mL paraffin dispersion liquid;
(5) mixing the graphene dispersion liquid obtained in the step (1) and the polyurethane dispersion liquid obtained in the step (3) according to a ratio of 1: mixing the components according to the weight ratio of 1, stirring for 1h, and performing ultrasonic treatment for 10min to obtain a graphene-polyurethane mixed solution.
(6) Mixing the nano-cellulose dispersion liquid obtained in the step (2) and the thermoplastic polyimide dispersion liquid obtained in the step (4) according to the ratio of 1: 1 weight ratio, stirring for 1h, and performing ultrasonic treatment for 10min to obtain a mixed solution of the nano-cellulose and the thermoplastic polyimide.
(7) And (3) placing the graphene-polyurethane mixed solution and the nano cellulose-thermoplastic polyimide mixed solution obtained in the steps (5) and (6) in a vacuum drying box, standing for 1h in a vacuum environment at room temperature, and removing gas in the mixed solution.
(8) Pouring 10mL of graphene-polyurethane mixed solution into a mold, placing the mold in a 40 ℃ oven, drying for 10h, pouring 6mL of nano cellulose-thermoplastic polyimide mixed solution into the mold, placing the mold in the 40 ℃ oven, drying for 6h, and repeating for 3 times to obtain the thermally-driven three-level shape memory multilayer anisotropic heat conduction graphene-high polymer material composite membrane.
The thermal conductivity of the thermally-driven shape-memory thermal conductive graphene-polymer material composite film prepared in the embodiment 1 was tested by using an LFA447 type laser thermal conductivity meter of germany Netzsch, and the test result is as follows: transverse thermal conductivity of 16.55 W.m-1·K-1Longitudinal thermal conductivity of 0.68 W.m-1·K-1The anisotropy ratio reaches 24, the flexibility is good, and the variation range of the thermal conductivity coefficient after the bending of 200 is 0-5%. The composite film is at 150 ℃ within 30sThe shape recovery rate is more than 80%, and the shape recovery rate within 30s at 230 ℃ is more than 80%.
In other embodiments, the polymer thermoplastic material may also be resin paraffin, thermoplastic polyimide, or nylon, which may all achieve the technical effect, and embodiments of the present invention are not listed one by one.
In each embodiment of the invention and other embodiments, the specific component ratios of the components in the composite material can be selected according to specific requirements between 20 wt% to 40 wt% of graphene, 30 wt% to 40 wt% of nanocellulose and 30 wt% to 40 wt% of polymer material, and the dispersant is one or more of deionized water, cyclohexane and other solvents, so that the technical effects can be achieved.
The invention is not limited to the above embodiment, and other multilayer anisotropic heat-conducting graphene-polymer material composite films containing thermally-driven three-level shape memory, which are obtained by using the same or similar components, proportions and methods as those of the invention, are within the scope of the invention.

Claims (7)

1. The heat-conducting graphene-high polymer material composite film is characterized by being a multilayer composite film, having heat-conducting anisotropy and heat-driven three-level shape memory characteristics and being prepared from the following components in percentage by weight:
20 to 40 percent of graphene,
30 to 40 percent of nano-cellulose,
30 to 40 percent of thermoplastic polymer material.
2. The heat-conducting graphene-polymer material composite film according to claim 1, wherein the average horizontal size of the graphene is 10-15 μm, the average thickness is 1-5 nm, and the content of oxygen is less than or equal to 2.0%.
3. The heat-conducting graphene-polymer material composite film according to claim 1, wherein the diameter of the nanocellulose is 5-100 nm, and the length-diameter ratio is 100-1000.
4. The thermally conductive graphene-polymer composite film according to claim 1, wherein the thermoplastic polymer is two thermoplastic polymers with different compositions, and the application temperatures thereof are A, B, and the difference between A, B and the two thermoplastic polymers is greater than 20 ℃.
5. The graphene-polymer composite film according to claim 4, wherein the thermoplastic polymer is a mixture of polyethylene glycol, polyurethane, polycaprolactone, paraffin, and thermoplastic polyimide.
6. The method for preparing the heat-conducting graphene-polymer material composite film according to any one of claims 1 to 5, wherein the method comprises the following steps:
(1) adding graphene into a dispersing agent, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a graphene dispersion solution with the concentration of 1-3 mg/mL;
(2) adding the nano-cellulose into a dispersing agent, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a nano-cellulose dispersion solution with the concentration of 1-3 mg/mL;
(3) adding a thermoplastic polymer material into a dispersing agent, stirring for 0.5-1 h, performing ultrasonic treatment for 5-10 min, and preparing a thermoplastic polymer material dispersion liquid with the concentration of 1-3 mg/mL;
(4) mixing the graphene dispersion liquid obtained in the step (1) and the thermoplastic polymer material dispersion liquid obtained in the step (3) according to a set weight ratio, stirring for 0.5-1 h, and performing ultrasonic treatment for 5-10 min to obtain a graphene-polymer material mixed liquid with the concentration of 5-10 mg/mL;
(5) mixing the nano-cellulose dispersion liquid obtained in the step (2) and the polymer material dispersion liquid obtained in the step (3) according to a set weight ratio, stirring for 0.5-1 h, and performing ultrasonic treatment for 5-10 min to obtain a nano-cellulose-polymer material mixed liquid with the concentration of 5-10 mg/mL;
(6) placing the graphene-polymer material mixed solution and the nano cellulose-polymer material mixed solution in a vacuum drying oven, standing for 0.5-1 h in a vacuum environment at room temperature, and removing gas existing in the mixed solution;
(7) pouring a set amount of graphene-high polymer material mixed solution into a mold, placing the mold in an oven at 40-50 ℃ for drying for 6-10 h, pouring a set amount of nanocellulose-high polymer material mixed solution into the mold, placing the mold in an oven at 40-50 ℃ for drying for 6-10 h, and preparing a single-layer heat-conducting graphene-high polymer material composite membrane;
(8) and (5) repeating the step (7) for multiple times, and stacking the single layers together to obtain the multilayer anisotropic heat-conducting graphene-high polymer material composite membrane with the heat-driven three-level shape memory characteristic.
7. The method of claim 6, wherein the dispersant is one or more of deionized water, cyclohexane, ethanol, and N, N-dimethylformamide.
CN202010028061.4A 2020-01-10 2020-01-10 Heat-conducting graphene-high polymer material composite film and preparation method thereof Active CN111231439B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010028061.4A CN111231439B (en) 2020-01-10 2020-01-10 Heat-conducting graphene-high polymer material composite film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010028061.4A CN111231439B (en) 2020-01-10 2020-01-10 Heat-conducting graphene-high polymer material composite film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111231439A true CN111231439A (en) 2020-06-05
CN111231439B CN111231439B (en) 2021-12-14

Family

ID=70866833

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010028061.4A Active CN111231439B (en) 2020-01-10 2020-01-10 Heat-conducting graphene-high polymer material composite film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111231439B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112874043A (en) * 2021-01-19 2021-06-01 上海大学 High-thermal-conductivity high-polymer material composite membrane with thermal response performance and preparation method thereof
CN112937013A (en) * 2021-01-28 2021-06-11 上海大学 High-thermal-conductivity and three-level shape memory multilayer structure flexible film and preparation method thereof
WO2023060739A1 (en) * 2021-10-12 2023-04-20 中国科学院深圳先进技术研究院 Self-healing electromagnetic shielding material, preparation method therefor and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101637987A (en) * 2008-07-29 2010-02-03 通用汽车环球科技运作公司 Polymer systems with multiple shape memory effect
CN105602213A (en) * 2015-12-29 2016-05-25 哈尔滨工业大学 Preparation of shape memory micro-nano composite material and application of shape memory micro-nano composite material in 4D (four-dimensional) printing
CN106566398A (en) * 2016-10-20 2017-04-19 广东工业大学 Tri-shape shape memory conductive polymeric nanocomposite and preparation method thereof
KR20180027158A (en) * 2016-09-06 2018-03-14 동의대학교 산학협력단 Thermal conductive adhesives having graphite and zinc oxide, and preparation method thereof
WO2018109618A1 (en) * 2016-12-15 2018-06-21 Sabic Global Technologies B.V. Thermally conductive three-dimensional (3-d) graphenepolymer composite materials, methods of making, and uses thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101637987A (en) * 2008-07-29 2010-02-03 通用汽车环球科技运作公司 Polymer systems with multiple shape memory effect
CN105602213A (en) * 2015-12-29 2016-05-25 哈尔滨工业大学 Preparation of shape memory micro-nano composite material and application of shape memory micro-nano composite material in 4D (four-dimensional) printing
KR20180027158A (en) * 2016-09-06 2018-03-14 동의대학교 산학협력단 Thermal conductive adhesives having graphite and zinc oxide, and preparation method thereof
CN106566398A (en) * 2016-10-20 2017-04-19 广东工业大学 Tri-shape shape memory conductive polymeric nanocomposite and preparation method thereof
WO2018109618A1 (en) * 2016-12-15 2018-06-21 Sabic Global Technologies B.V. Thermally conductive three-dimensional (3-d) graphenepolymer composite materials, methods of making, and uses thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112874043A (en) * 2021-01-19 2021-06-01 上海大学 High-thermal-conductivity high-polymer material composite membrane with thermal response performance and preparation method thereof
CN112937013A (en) * 2021-01-28 2021-06-11 上海大学 High-thermal-conductivity and three-level shape memory multilayer structure flexible film and preparation method thereof
WO2023060739A1 (en) * 2021-10-12 2023-04-20 中国科学院深圳先进技术研究院 Self-healing electromagnetic shielding material, preparation method therefor and application thereof

Also Published As

Publication number Publication date
CN111231439B (en) 2021-12-14

Similar Documents

Publication Publication Date Title
CN111231439B (en) Heat-conducting graphene-high polymer material composite film and preparation method thereof
CN104672502B (en) Cyanoethyl cellulose based high-dielectric flexible nano-composite film and preparation method thereof
CN109181301A (en) A kind of doped quantum dot functionalization boron nitride polymer bond composite membrane and preparation method
CN113121887A (en) Nano-cellulose heat-conducting composite film and preparation method thereof
Wu et al. Flexible and transparent polymer/cellulose nanocrystal nanocomposites with high thermal conductivity for thermal management application
CN112937013A (en) High-thermal-conductivity and three-level shape memory multilayer structure flexible film and preparation method thereof
CN105218845B (en) A kind of preparation method of modified graphene polymethyl methacrylate laminated film
Jin et al. Fe3O4-functionalized κ-carrageenan/melanin hybrid aerogel-supported form-stable phase-change composites with excellent solar/magnetic–thermal conversion efficiency and enhanced thermal conductivity
Yue et al. Fabrication of anti-freezing and self-healing nanocomposite hydrogels based on phytic acid and cellulose nanocrystals for high strain sensing applications
Chen et al. Enhanced electrical and thermal properties of semi-conductive PANI-CNCs with surface modified CNCs
Shen et al. Significantly enhancing mechanical and thermal properties of cellulose-based composites by adding small amounts of lysozyme-modified graphene nanoplatelets via forming strong double-cross-linked interface interactions
Xie et al. Thermo-and near infrared light-induced reversible multi-shape memory materials for actuators and sensors
CN110734560A (en) heat-conducting graphene-polymer composite film, and preparation method and application thereof
Zhang et al. Preparation and properties of a chitosan–hyaluronic acid-polypyrrole conductive hydrogel catalyzed by laccase
Wu et al. Heat-and freeze-tolerant organohydrogel with enhanced ionic conductivity over a wide temperature range for highly mechanoresponsive smart paint
Guo et al. Shape memory polyimide aerogel composites with high programming temperatures and exceptional shape recovery capability
Wang et al. Large flakes of Al–Ti3C2Tx MXene constructing highly ordered layered MXene/ANF films with integrated multifunctionalities
CN112874043B (en) High-thermal-conductivity high-polymer material composite membrane with thermal response performance and preparation method thereof
Geng et al. Boron nitride-alginate coordination interactions enabling hydrogels with enhanced mechanical strength and heat resistance
Chen et al. Enlightening thermoelectric mastery: Bio-inspired cellulose gel containing eco-friendly deep eutectic solvents
CN110577700A (en) Polypropylene composite material with high vertical thermal conductivity and excellent mechanical property and preparation method thereof
Zhou et al. In-situ polymerisation of carbon nanotubes/blended polyimide composites for flexible thermal conductive special-shaped structures
CN114456526A (en) Polymer composite material and preparation method and application thereof
CN111205579B (en) High-efficiency high-temperature-resistant aluminum nitride/polymer composite material and preparation method thereof
CN103265701A (en) Preparation method of bismaleimide prepolymer and conductive silver adhesive prepared thereby

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant