CN108610501B - Method for realizing high-temperature rubber conduction by using vapor deposition graphene - Google Patents
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Abstract
The invention relates to a method for realizing high-temperature rubber conduction by using vapor deposition graphene, belonging to the field of application of graphene composite conductive materials. According to the technology, a graphene film is deposited on the uppermost layer of high-temperature rubber by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, and the high-temperature rubber and the graphene generate synchronous strain during stretching or twisting by tightly combining the graphene and the high-temperature rubber by utilizing the conductive capacity, flexibility and ductility of the graphene, so that the rubber has conductive capacity in different forms, and thus, the functional characteristics of electricity, stability and the like are changed. And the conductive capability can exist stably under different shapes or temperature conditions, the effect is obvious, and the method is simple.
Description
Technical Field
The invention relates to a method for realizing high-temperature rubber conduction by using vapor deposition graphene, belonging to the field of application of graphene composite conductive materials.
Background
Due to the unique structure and excellent performance of graphene, graphene has great potential in improving the thermal property, mechanical property, electrical property and the like of materials, and has become a hotspot of research in the field of composite materials. The graphene has excellent electrical properties, so that the graphene is very suitable for preparing the conductive composite material, and the graphene is used as one of the components to compound other functional materials, so that the multifunctional conductive composite material can be obtained. The research on the graphene conductive composite material is an important component in the field of graphene research, and can be widely applied to the fields of super capacitor electrodes, conductive film materials, fuel cells, lithium ion battery electrodes and the like.
In order to realize the conductive capability of the rubber material, metal coating, doping and other methods are generally adopted, but most of the methods are difficult to prepare, high in cost, difficult to control and capable of obviously reducing the service life of the rubber.
Disclosure of Invention
In order to overcome the defects, the flexibility and the conductive capability of the graphene are utilized for the first time, the graphene is tightly combined with the high-temperature rubber by adopting a PECVD method, the conductivity of the high-temperature rubber is changed, and a method for realizing the conductivity of the high-temperature rubber by using vapor deposition of the graphene is provided and is used as a new application of the graphene composite conductive material.
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
In order to achieve the above object, the present invention provides a method for realizing high temperature rubber conductivity using vapor deposition graphene, comprising a preparation step of acrylate rubber doped with a nano Cu composite Ni sheet and nano GaIn particles and a preparation step of a vapor deposition graphene surface film; the surface film of the graphene subjected to vapor deposition is coated on the surface of the acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles;
in the preparation step of the high-temperature rubber substrate, butyl acrylate, ethyl acrylate or methyl acrylate is used as a main monomer, the main monomer, a vulcanization point monomer, glycidyl methacrylate, a nano Cu composite Ni sheet, nano GaIn particles and a solvent are mixed to form a monomer mixed solution, the monomer mixed solution is heated to a constant temperature, an initiator is added, a sample is taken, and the sample is dehydrated and dried to obtain the acrylic rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles;
in the preparation step of the graphene surface film by vapor deposition, the graphene film is deposited on the surface of the acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles by a plasma enhanced vapor deposition (PECVD) method.
The preparation process of the acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles comprises the following steps:
(1) purifying butyl acrylate, methyl acrylate or ethyl acrylate, removing polymerization inhibitor and other impurities, and refrigerating for later use;
(2) mixing the main monomer butyl acrylate, ethyl acrylate or methyl acrylate obtained in the step (1), the vulcanization point monomer epoxypropyl methacrylate, the nano Cu composite Ni sheet and the nano GaIn particles with a solvent to form a monomer mixed solution; wherein the atomic ratio of Ga to In is 1:10-10: 1;
(3) stirring the monomer mixed solution obtained in the step (2), and emptying air in the stirring reaction kettle;
(4) carrying out oil bath heating on the monomer mixed solution obtained in the step (3), adding an initiator when the temperature of the monomer mixed solution is constant and is not changed at the set temperature, starting sampling, and sampling once every 3-10 minutes;
(5) the reaction process is kept for more than 2 hours, the sample is dehydrated after the experiment is finished, and the sample is dried in vacuum to constant weight, so that the acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles is obtained.
The preparation process of the graphene surface film by vapor deposition comprises the following steps:
cleaning the surface of acrylic rubber doped with nano Cu composite Ni sheets and nano GaIn particles prepared in advance for multiple times by using one or more of deionized water, ethanol and acetone, and putting the acrylic rubber into a tubular furnace;
pumping the tube furnace to a vacuum state, keeping the vacuum pump in an opening state, introducing protective gas, and keeping for 3-10 minutes; then continuously keeping the vacuum pump in the open state according to H220 parts of protective gas: (200-300) introducing the gas into the tubular furnace at a gas flow ratio; the protective gas can be pure argon, nitrogen or a mixed gas of argon and nitrogenA body;
raising the temperature in the tubular furnace to 100-250 ℃ at the speed of 5-10 ℃/min, and then preserving the temperature for 10-20 minutes; after the heat preservation is started for 5 minutes, opening a plasma emitter, depositing graphene on the pretreated (cleaned) acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles for 3-10 minutes, and closing the plasma emitter;
and cooling to room temperature, closing the vacuum pump, and taking out the nano Cu-doped composite Ni sheet deposited with the graphene and the acrylic rubber of the nano GaIn particles.
The graphene for realizing the conductivity is multi-atomic-layer graphene.
Purifying butyl acrylate, methyl acrylate and ethyl acrylate in a rotary evaporator in the step (1); in the step (2), the solvent is toluene or ethyl acetate; in the step (3), adding the monomer mixed solution obtained in the step (2) into a glass reaction kettle for magnetic stirring, opening a stirring paddle, setting the rotating speed to be 200r/min, and introducing protective gas to empty air in the reaction kettle; the oil bath in step (4) is heated for about 2 hours. The protective gas can be pure argon, nitrogen or a mixed gas of argon and nitrogen.
Heating the doped nano Cu composite Ni sheet deposited with the graphene and the acrylate rubber of the nano GaIn particles to 60 ℃, 120 ℃ or 180 ℃, and testing the conductive capacity of the sample; then stretching the doped nano Cu composite Ni sheet deposited with the graphene and the acrylate rubber of the nano GaIn particles by 1-10% (or 2-10%), realizing the cooperative stretching strain of the graphene film and the acrylate rubber substrate, and testing the conductive capability of the sample; and (3) soaking the doped nano Cu composite Ni sheet deposited with the graphene and the acrylate rubber of the nano GaIn particles in strong acid or strong base, taking out and washing, and testing the conductivity of the sample.
Specifically, the preparation of the high-temperature rubber substrate (namely, the acrylate rubber doped with the nano-Cu composite Ni sheet and the nano-GaIn particles) comprises the following steps:
(1) purifying butyl acrylate, methyl acrylate and ethyl acrylate in a rotary evaporator, removing a polymerization inhibitor and other impurities, and refrigerating in a refrigerator for later use;
(2) mixing the main monomer butyl acrylate (or ethyl acrylate or methyl acrylate) obtained in the step (1), the vulcanization point monomer epoxypropyl methacrylate, the nano Cu composite Ni sheet and the nano GaIn particles with a solvent of toluene (or ethyl acetate) to form a monomer mixed solution;
(3) adding the monomer mixed solution obtained in the step (2) into a 2L glass reaction kettle for magnetic stirring, opening a stirring paddle, setting the rotating speed at 200r/min, and introducing nitrogen to empty the air in the reaction kettle;
(4) turning on an oil bath pump to carry out oil bath heating on the monomer mixed solution obtained in the step (3) for about 2 hours, adding an initiator when the temperature is constant and the set temperature is not changed, starting sampling, and sampling once every five minutes;
(5) the reaction process is kept for more than 2 hours, the sample is dehydrated after the experiment is finished, and the sample is placed in a vacuum oven to be dried in vacuum until the constant weight is about 24 hours, so that the acrylate rubber is obtained.
The deposition method comprises the following steps:
cleaning the surface of acrylic rubber doped with nano Cu composite Ni sheets and nano GaIn particles prepared in advance for multiple times by using deionized water, ethanol, acetone and the like, and putting the acrylic rubber into a tubular furnace;
pumping the tube furnace to a vacuum state, keeping the vacuum pump in an opening state, introducing pure Ar, and keeping for 3 minutes; then continuously keeping the vacuum pump in the open state according to H2Ar is 20: (200-300) introducing the gas into the tubular furnace at a gas flow ratio;
setting a program, raising the temperature in the tube furnace to 100-250 ℃ at a speed of 5-10 ℃/min, and then preserving the heat for 10-20 minutes. After the heat preservation is started for 5 minutes, opening a plasma emitter, depositing graphene on the pretreated acrylate rubber for 3-10 minutes, and closing the plasma emitter;
and cooling to room temperature, closing the vacuum pump, and taking out the acrylate rubber of the doped nano Cu composite Ni sheet deposited with the graphene.
Compared with the prior art, the invention has the following beneficial effects:
(1) in order to realize the conductive capability of the rubber material, people usually adopt methods such as metal film plating, doping and the like, but most of the methods are difficult to prepare, high in cost and difficult to control and can obviously reduce the service life of the rubber, and the design method is characterized in that the flexibility and the conductive capability of graphene are firstly utilized to compound the graphene and the high-temperature rubber, so that the conductivity of the high-temperature rubber is improved by more than 100 times under the condition of not changing the chemical components and the mechanical capability of a high-temperature rubber body;
(2) the surface of the general high-temperature rubber is exposed, and the negative effects of being corroded and the like can be generated in response to environments such as strong acid, strong alkali and the like;
(3) according to the method for realizing high-temperature rubber conduction by using vapor deposition graphene, disclosed by the invention, the graphene is grown in situ on the high-temperature rubber by using a PECVD (plasma enhanced chemical vapor deposition) method, and the graphene and the high-temperature rubber are tightly combined by Van der Waals force, so that the defect that the graphene is not firmly contacted with a substrate in the conventional transfer method such as spin coating is overcome. A small amount of doped nano Cu composite Ni sheets are added in the preparation process, and are used as a catalyst and a reinforcing phase in rubber, so that the mechanical property of the high-temperature rubber is greatly improved;
(4) a small amount of GaIn alloy nanoparticles are added in the process of preparing the rubber, which has never been reported in previous researches, GaIn is a low-melting-point metal, and when a graphene layer on the surface of the GaIn alloy is cracked in the use process of the high-temperature rubber, the GaIn alloy can be melted at the crack position and can be subjected to self-repairing, so that the high-temperature conductivity of the rubber is remarkably improved. In addition, the GaIn alloy is the same as the Cu composite Ni nano-sheet and is a nano enhanced phase particle, so that the mechanical property of the GaIn alloy can be obviously improved.
Drawings
Fig. 1 is a raman test result of graphene prepared in example 1;
FIG. 2 is a scanning electron microscope test result of the graphene-coated high-temperature rubber prepared in example 1;
FIG. 3 is a result of a tensile electrical capability test of the graphene-coated high-temperature rubber prepared in example 1;
fig. 4 is a structural diagram of an acrylate rubber in which nano Cu flakes and nano GaIn particles are doped, on which graphene is deposited.
Detailed Description
In order to clearly understand the technical features, objects and advantages of the present invention, the technical solutions of the present invention will be described in detail below with reference to the accompanying drawings, but the present invention is not limited to the practical scope of the present invention.
Example 1 method for realizing conduction of butyl acrylate main monomer doped with nano Cu sheet and nano GaIn particle acrylate rubber by vapor deposition of graphene
1. The preparation of the acrylate rubber substrate with butyl acrylate main monomer doped with the nano Cu sheet and the GaIn alloy nano particles comprises the following steps:
(1) purifying butyl acrylate in a rotary evaporator, removing polymerization inhibitor and other impurities, and refrigerating in a refrigerator for later use;
(2) mixing the main monomer butyl acrylate obtained In the step (1), the vulcanization point monomer epoxypropyl methacrylate, the nano Cu sheet and the GaIn alloy nano particles (the atomic ratio of Ga to In is 1:10) and the solvent is ethyl acetate to form a monomer mixed solution;
(3) adding the monomer mixed solution obtained in the step (2) into a 2L glass reaction kettle for magnetic stirring, opening a stirring paddle, setting the rotating speed at 200r/min, and introducing nitrogen to empty the air in the reaction kettle;
(4) turning on an oil bath pump to carry out oil bath heating on the monomer mixed solution obtained in the step (3) for about 2 hours, adding an initiator when the temperature is constant and the set temperature is not changed, starting sampling, and sampling once every five minutes;
(5) the reaction process is kept for more than 2 hours, the sample is dehydrated after the experiment is finished, and the sample is placed in a vacuum oven to be dried in vacuum until the constant weight is about 24 hours, so that the acrylate rubber doped with the nano Cu sheet and the nano GaIn particles is obtained;
2. the surface graphene film deposition comprises the following steps:
cleaning the surface of acrylic ester rubber doped with nano Cu sheets and nano GaIn particles prepared in advance for multiple times by using deionized water, ethanol, acetone and the like, and putting the acrylic ester rubber into a tubular furnace;
pumping the tube furnace to a vacuum state, keeping the vacuum pump in an opening state, introducing pure Ar, and keeping for 3 minutes; then continuously keeping the vacuum pump in the open state according to H2Ar is 20: the gas flow rate is 200, and the gas is introduced into the tube furnace;
the procedure was set to bring the temperature in the tube furnace to 250 ℃ at 10 ℃/min, followed by 20 minutes of incubation. After the heat preservation is started for 5 minutes, a plasma emitter is turned on, graphene is deposited on the pretreated acrylate rubber for 10 minutes, and the plasma emitter is turned off;
then cooling to room temperature, closing the vacuum pump, and taking out the acrylate rubber with the deposited graphene doped with the nano Cu sheets and the nano GaIn particles, as shown in FIG. 4;
the deposited graphene was subjected to raman test, and the obtained result is shown in fig. 1 (stress strain curve of NiTi thin film). Then, scanning electron microscope tests were performed on the acrylate rubber on which the graphene-deposited doped nano Cu sheet-compounded GaIn alloy nanoparticles were deposited, and the obtained results are shown in fig. 2, in which the nanoparticles were uniformly distributed and no significant agglomeration was observed. The sheet resistance of the sample at normal temperature is 264 omega/sq, and the sheet resistance of the doped graphene in the market is more than 2000 omega/sq, which is nearly ten times different from that of the sample obtained by carrying out sheet resistance test on the acrylate rubber of the doped nano Cu sheet deposited with the graphene and the GaIn alloy nanoparticles. The acrylate rubber of the doped nano Cu sheet composite GaIn alloy nano-particles deposited with the graphene is heated to 60 ℃, 120 ℃ and 180 ℃, the sheet resistance of a test sample is 268, 274 and 277 omega/sq respectively, and almost no difference exists between the sheet resistance and the 264 omega/sq result obtained by testing at normal temperature. And then stretching the acrylate rubber of the doped nano Cu sheet composite GaIn alloy nanoparticles deposited with the graphene by 1-10%, so as to realize the cooperative tensile strain of the graphene film and the acrylate rubber substrate, and testing the change of the sheet resistance of the sample, wherein the sheet resistance is only about 325 omega/sq when the sample is stretched to 10%, as shown in FIG. 3. The sheet resistance of the sample does not change much after being stretched to 10%, and the sample shows excellent practical properties again.
Example 2 method for realizing acrylate rubber conduction of butyl acrylate main monomer doped nano Ni sheet composite GaIn alloy nanoparticles by vapor deposition of graphene
1. The preparation method of the butyl acrylate main monomer doped with the nano Ni sheet and the nano GaIn particle acrylate rubber substrate comprises the following steps:
(1) purifying butyl acrylate in a rotary evaporator, removing polymerization inhibitor and other impurities, and refrigerating in a refrigerator for later use;
(2) mixing the main monomer butyl acrylate obtained In the step (1), the vulcanization point monomer epoxypropyl methacrylate, the nano Ni sheet and the GaIn alloy nano particles (the atomic ratio of Ga to In is 10:1) and the solvent is toluene to form a monomer mixed solution;
(3) adding the monomer mixed solution obtained in the step (2) into a 2L glass reaction kettle for magnetic stirring, opening a stirring paddle, setting the rotating speed at 200r/min, and introducing nitrogen to empty the air in the reaction kettle;
(4) turning on an oil bath pump to carry out oil bath heating on the monomer mixed solution obtained in the step (3) for about 2 hours, adding an initiator when the temperature is constant and the set temperature is not changed, starting sampling, and sampling once every five minutes;
(5) the reaction process is kept for more than 2 hours, the sample is dehydrated after the experiment is finished, and the sample is placed in a vacuum oven to be dried in vacuum until the constant weight is about 24 hours, so that the acrylate rubber doped with the nano Ni sheets and the nano GaIn particles is obtained;
2. the surface graphene film deposition comprises the following steps:
cleaning the surface of acrylate rubber doped with nano Ni sheets and compounded with GaIn alloy nano particles prepared in advance for multiple times by using deionized water, ethanol, acetone and the like, and putting the acrylate rubber into a tubular furnace;
pumping the tube furnace to a vacuum state, keeping the vacuum pump in an opening state, introducing pure Ar, and keeping for 3 minutes; then continuously keeping the vacuum pump in the open state according to H2Ar is 20: 300 gas flow ratio, into the tube furnacePerforming the following steps;
the procedure was set to bring the temperature in the tube furnace to 100 ℃ at 5 ℃/min, followed by 10 minutes of incubation. After the heat preservation is started for 5 minutes, a plasma emitter is turned on, graphene is deposited on the pretreated acrylate rubber, the duration is 3 minutes, and the plasma emitter is turned off;
and cooling to room temperature, closing the vacuum pump, and taking out the acrylic rubber of the doped nano Ni sheet composite GaIn alloy nano particles deposited with the graphene.
The nano particles are uniformly distributed and have no obvious agglomeration phenomenon. The sheet resistance of the sample at normal temperature is 204 omega/sq, and the sheet resistance of the doped graphene in the market is more than 2000 omega/sq, which is nearly ten times different from that of the sample obtained by carrying out sheet resistance test on the acrylate rubber of the doped nano Ni sheet deposited with the graphene and the GaIn alloy nanoparticles. The acrylate rubber of the doped nano Cu sheet composite GaIn alloy nano-particles deposited with the graphene is heated to 50 ℃, 100 ℃ and 150 ℃, the sheet resistance of a test sample is 210, 214 and 218 omega/sq respectively, and almost no difference exists between the sheet resistance and the sheet resistance of the test sample obtained by testing at normal temperature to obtain 204 omega/sq. And then, the acrylate rubber of the doped nano Ni sheet composite GaIn alloy nano-particles deposited with the graphene is stretched by 1-10%, so that the cooperative tensile strain of the graphene film and the acrylate rubber substrate is realized, the sheet resistance change of the sample is tested, the sheet resistance is only about 225 omega/sq when the sample is stretched to 15%, and the excellent practical performance is shown again.
Example 3 method for realizing acrylic ester rubber conduction of ethyl acrylate main monomer doped nano Ni sheet composite GaIn alloy nanoparticles by vapor deposition of graphene
1. The preparation method of the acrylate rubber substrate with the ethyl acrylate main monomer doped with the nano Ni sheets and the nano GaIn particles comprises the following steps:
(1) purifying ethyl acrylate in a rotary evaporator, removing a polymerization inhibitor and other impurities, and refrigerating in a refrigerator for later use;
(2) mixing the main monomer ethyl acrylate, the vulcanization point monomer epoxypropyl methacrylate, the nano Ni sheet and the GaIn alloy nano particles (the atomic ratio of Ga to In is 1:1) obtained In the step (1) with ethyl acetate as a solvent to form a monomer mixed solution;
(3) adding the monomer mixed solution obtained in the step (2) into a 2L glass reaction kettle for magnetic stirring, opening a stirring paddle, setting the rotating speed at 200r/min, and introducing nitrogen to empty the air in the reaction kettle;
(4) turning on an oil bath pump to carry out oil bath heating on the monomer mixed solution obtained in the step (3) for about 2 hours, adding an initiator when the temperature is constant and the set temperature is not changed, starting sampling, and sampling once every five minutes;
(5) the reaction process is kept for more than 2 hours, the sample is dehydrated after the experiment is finished, and the sample is placed in a vacuum oven to be dried in vacuum until the constant weight is about 24 hours, so that the acrylate rubber doped with the nano Ni sheets and the nano GaIn particles is obtained;
2. the surface graphene film deposition comprises the following steps:
cleaning the surface of acrylate rubber doped with nano Ni sheets and compounded with GaIn alloy nano particles prepared in advance for multiple times by using deionized water, ethanol, acetone and the like, and putting the acrylate rubber into a tubular furnace;
pumping the tube furnace to a vacuum state, keeping the vacuum pump in an opening state, introducing pure Ar, and keeping for 3 minutes; then continuously keeping the vacuum pump in the open state according to H2Ar is 20: 300 gas flow ratio, and introducing into the tube furnace;
the procedure was set to bring the temperature in the tube furnace to 100 ℃ at 5 ℃/min, followed by 10 minutes of incubation. After the heat preservation is started for 5 minutes, a plasma emitter is turned on, graphene is deposited on the pretreated acrylate rubber, the duration is 3 minutes, and the plasma emitter is turned off;
and cooling to room temperature, closing the vacuum pump, and taking out the acrylic rubber of the doped nano Ni sheet composite GaIn alloy nano particles deposited with the graphene.
The nano particles are uniformly distributed and have no obvious agglomeration phenomenon. The sheet resistance of the sample at normal temperature is 196 omega/sq, and the sheet resistance of the doped graphene in the market is more than 2000 omega/sq, which is nearly ten times different from that of the sample obtained by carrying out sheet resistance test on the acrylate rubber of the doped nano Ni sheet deposited with the graphene and the GaIn alloy nanoparticles. The acrylate rubber of the doped nano Cu sheet compounded with the GaIn alloy nano particles and deposited with the graphene is heated to 50 ℃, 100 ℃, 150 ℃ and 200 ℃, the sheet resistance of a test sample is respectively 200, 214, 227 and 235 omega/sq, and the sheet resistance is equivalent to the result of 196 omega/sq obtained by testing at normal temperature. The acrylate rubber of the doped nano Ni sheet composite GaIn alloy nano-particles deposited with the graphene is stretched by 15 percent, the sheet resistance is only about 225 omega/sq, and the excellent practical performance is shown again.
Example 4 method for realizing acrylate rubber conduction of methyl acrylate main monomer doped nano Ni sheet composite GaIn alloy nanoparticles by vapor deposition of graphene
1. The preparation method of the acrylate rubber substrate with the methyl acrylate main monomer doped with the nano Ni sheet and the GaIn alloy nano particles comprises the following steps:
(1) purifying methyl acrylate in a rotary evaporator, removing a polymerization inhibitor and other impurities, and refrigerating in a refrigerator for later use;
(2) mixing the main monomer methyl acrylate, the vulcanization point monomer epoxypropyl methacrylate, the nano Ni sheet and the GaIn alloy nano particles (the atomic ratio of Ga to In is 2:1) obtained In the step (1) with ethyl acetate to form a monomer mixed solution;
(3) adding the monomer mixed solution obtained in the step (2) into a 2L glass reaction kettle for magnetic stirring, opening a stirring paddle, setting the rotating speed at 200r/min, and introducing nitrogen to empty the air in the reaction kettle;
(4) turning on an oil bath pump to carry out oil bath heating on the monomer mixed solution obtained in the step (3) for about 2 hours, adding an initiator when the temperature is constant and the set temperature is not changed, starting sampling, and sampling once every five minutes;
(5) the reaction process is kept for more than 2 hours, the sample is dehydrated after the experiment is finished, and the sample is placed in a vacuum oven to be dried in vacuum until the constant weight is about 24 hours, so that the acrylate rubber doped with the nano Ni sheets and the nano GaIn particles is obtained;
2. the surface graphene film deposition comprises the following steps:
cleaning the surface of acrylate rubber doped with nano Ni sheets and compounded with GaIn alloy nano particles prepared in advance for multiple times by using deionized water, ethanol, acetone and the like, and putting the acrylate rubber into a tubular furnace;
pumping the tube furnace to a vacuum state, keeping the vacuum pump in an opening state, introducing pure Ar, and keeping for 3 minutes; then continuously keeping the vacuum pump in the open state according to H2Ar is 20: the gas flow rate is 200, and the gas is introduced into the tube furnace;
the procedure was set to raise the temperature in the tube furnace to 150 ℃ at 5 ℃/min, followed by 10 minutes of incubation. After the heat preservation is started for 5 minutes, a plasma emitter is turned on, graphene is deposited on the pretreated acrylate rubber for 5 minutes, and the plasma emitter is turned off;
and cooling to room temperature, closing the vacuum pump, and taking out the acrylic rubber of the doped nano Ni sheet composite GaIn alloy nano particles deposited with the graphene.
The nano particles are uniformly distributed and have no obvious agglomeration phenomenon. The sheet resistance of the sample at normal temperature is 226 omega/sq, and the sheet resistance of the doped graphene in the market is more than 2000 omega/sq, which is nearly ten times different from that of the sample obtained by carrying out sheet resistance test on the acrylate rubber of the doped nano Ni sheet deposited with the graphene and the GaIn alloy nanoparticles. The acrylate rubber of the doped nano Cu sheet compounded with the GaIn alloy nano particles and deposited with the graphene is heated to 50 ℃, 100 ℃, 150 ℃ and 200 ℃, the sheet resistance of a test sample is respectively 228, 230, 237 and 235 omega/sq, and the test result is equivalent to the test result at normal temperature. And then, the acrylic rubber of the doped nano Ni sheet composite GaIn alloy nano-particles deposited with the graphene is stretched by 15 percent, the sheet resistance is only about 250 omega/sq, and the excellent practical performance is shown again.
Example 5 method for realizing acrylate rubber conduction of methyl acrylate main monomer doped nano Cu sheet composite GaIn alloy nanoparticles by vapor deposition of graphene
1. The preparation method of the acrylate rubber substrate with the methyl acrylate main monomer doped with the nano Cu sheet and the GaIn alloy nanoparticles comprises the following steps:
(1) purifying methyl acrylate in a rotary evaporator, removing a polymerization inhibitor and other impurities, and refrigerating in a refrigerator for later use;
(2) mixing the main monomer methyl acrylate obtained in the step (1), the vulcanization point monomer epoxypropyl methacrylate and the nano Cu sheet with ethyl acetate as a solvent to form a monomer mixed solution;
(3) adding the monomer mixed solution obtained in the step (2) into a 2L glass reaction kettle for magnetic stirring, opening a stirring paddle, setting the rotating speed at 200r/min, and introducing nitrogen to empty the air in the reaction kettle;
(4) turning on an oil bath pump to carry out oil bath heating on the monomer mixed solution obtained in the step (3) for about 2 hours, adding an initiator when the temperature is constant and the set temperature is not changed, starting sampling, and sampling once every five minutes;
(5) the reaction process is kept for more than 2 hours, the sample is dehydrated after the experiment is finished, and the sample is placed in a vacuum oven to be dried in vacuum until the constant weight is about 24 hours, so that the acrylic rubber doped with the nano Cu sheet and the GaIn alloy nanoparticles is obtained;
2. the surface graphene film deposition comprises the following steps:
cleaning the surface of acrylate rubber doped with nano Cu sheet composite GaIn alloy nano particles prepared in advance for multiple times by using deionized water, ethanol, acetone and the like, and putting the acrylate rubber into a tubular furnace;
pumping the tube furnace to a vacuum state, keeping the vacuum pump in an opening state, introducing pure Ar, and keeping for 3 minutes; then continuously keeping the vacuum pump in the open state according to H2Ar is 20: the gas flow rate is 200, and the gas is introduced into the tube furnace;
the procedure was set to raise the temperature in the tube furnace to 150 ℃ at 5 ℃/min, followed by 10 minutes of incubation. After the heat preservation is started for 5 minutes, a plasma emitter is turned on, graphene is deposited on the pretreated acrylate rubber for 5 minutes, and the plasma emitter is turned off;
and cooling to room temperature, closing the vacuum pump, and taking out the acrylic rubber of the doped nano Cu sheet composite GaIn alloy nano particles deposited with the graphene.
The nano particles are uniformly distributed and have no obvious agglomeration phenomenon. The sheet resistance of the sample at normal temperature is 186 omega/sq, and the sheet resistance of the doped graphene in the market is more than 2000 omega/sq, which is nearly ten times different from that of the sample obtained by carrying out sheet resistance test on the acrylate rubber of the doped nano Cu sheet deposited with the graphene and the GaIn alloy nanoparticles. The acrylate rubber of the doped nano Cu sheet compounded with the GaIn alloy nano particles and deposited with the graphene is heated to 50 ℃, 100 ℃, 150 ℃ and 200 ℃, the sheet resistance of a test sample is respectively 202, 212, 228 and 238 omega/sq, and the sheet resistance is equivalent to the result of 186 omega/sq obtained by testing at normal temperature. The acrylate rubber with the doped nano Cu sheet and the GaIn alloy nanoparticles deposited thereon is stretched by 15% and the sheet resistance is only about 215 Ω/sq, and the excellent practical performance is shown again.
The foregoing description has described the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is intended to be covered by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A method for realizing high-temperature rubber conduction by using vapor deposition graphene is characterized by comprising a preparation step of acrylate rubber doped with nano Cu composite Ni sheets and nano GaIn particles and a preparation step of a graphene surface film deposited by vapor phase; the surface film of the graphene subjected to vapor deposition is coated on the surface of the acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles;
in the preparation step of the high-temperature rubber substrate, butyl acrylate, ethyl acrylate or methyl acrylate is used as a main monomer, the main monomer, a vulcanization point monomer, glycidyl methacrylate, a nano Cu composite Ni sheet, nano GaIn particles and a solvent are mixed to form a monomer mixed solution, the monomer mixed solution is heated to a constant temperature, an initiator is added, a sample is taken, and the sample is dehydrated and dried to obtain the acrylic rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles;
in the preparation step of the graphene surface film by vapor deposition, the graphene film is deposited on the surface of the acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles by a plasma enhanced vapor deposition (PECVD) method.
2. The method for realizing high-temperature rubber conductivity by using vapor deposition graphene according to claim 1,
the preparation process of the acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles comprises the following steps:
(1) purifying butyl acrylate, methyl acrylate or ethyl acrylate, removing polymerization inhibitor and other impurities, and refrigerating for later use;
(2) mixing the main monomer butyl acrylate, ethyl acrylate or methyl acrylate obtained In the step (1), the vulcanization point monomer epoxypropyl methacrylate, the nano Cu composite Ni sheet, the nano GaIn particles and a solvent to form a monomer mixed solution, wherein the atomic ratio of Ga to In is 1:10-10: 1;
(3) stirring the monomer mixed solution obtained in the step (2), and emptying air in the stirring reaction kettle;
(4) carrying out oil bath heating on the monomer mixed solution obtained in the step (3), adding an initiator when the temperature of the monomer mixed solution is constant and is not changed at the set temperature, starting sampling, and sampling once every 3-10 minutes;
(5) the reaction process is kept for more than 2 hours, the sample is dehydrated after the experiment is finished, and the sample is dried in vacuum to constant weight, so that the acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles is obtained.
3. The method for realizing high-temperature rubber conductivity by using vapor-deposited graphene according to claim 1, wherein the preparation process of the vapor-deposited graphene surface film comprises the following steps:
cleaning the surface of acrylic rubber doped with nano Cu composite Ni sheets and nano GaIn particles prepared in advance for multiple times by using one or more of deionized water, ethanol and acetone, and putting the acrylic rubber into a tubular furnace;
pumping the tube furnace to a vacuum state, keeping the vacuum pump in an opening state, introducing protective gas, and keeping for 3-10 minutes; then continuously keeping the vacuum pump in the open state according to H220 parts of protective gas: (200-300) introducing the gas into the tubular furnace at a gas flow ratio;
raising the temperature in the tubular furnace to 100-250 ℃ at the speed of 5-10 ℃/min, and then preserving the temperature for 10-20 minutes; after the heat preservation is started for 5 minutes, opening a plasma emitter, depositing graphene on the pretreated acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles for 3-10 minutes, and closing the plasma emitter;
and cooling to room temperature, closing the vacuum pump, and taking out the nano Cu-doped composite Ni sheet deposited with the graphene and the acrylic rubber of the nano GaIn particles.
4. The method for realizing high-temperature rubber conductivity by using vapor deposition graphene according to any one of claims 1 to 3, wherein the graphene for realizing conductivity is multi-atomic layer graphene.
5. The method for realizing high-temperature rubber conductivity by using vapor deposition graphene as claimed in claim 3, wherein the protective gas is pure argon, nitrogen or a mixed gas of argon and nitrogen.
6. The method for realizing high-temperature rubber conductivity by using vapor deposition graphene as claimed in claim 2, wherein in the step (1), butyl acrylate, methyl acrylate and ethyl acrylate are purified in a rotary evaporator; in the step (2), the solvent is toluene or ethyl acetate; in the step (3), the monomer mixed solution obtained in the step (2) is added into a glass reaction kettle for magnetic stirring, a stirring paddle is opened, the rotating speed is set to be 100-year 1000r/min, and protective gas is introduced to empty the air in the reaction kettle; and (4) heating the oil bath for 1-5 hours.
7. The method for realizing high-temperature rubber conductivity by using vapor deposition graphene as claimed in claim 6, wherein the protective gas is pure argon, nitrogen or a mixed gas of argon and nitrogen.
8. The method for realizing high-temperature rubber conductivity by using vapor deposition of graphene according to any one of claims 1 to 3, wherein the acrylate rubber doped with the nano Cu composite Ni sheet and the nano GaIn particles deposited with graphene is heated to 60 ℃, 120 ℃ or 180 ℃, and the conductivity of the sample is tested; then stretching the doped nano Cu composite Ni sheet deposited with the graphene and the acrylate rubber of the nano GaIn particles by 1-10%, realizing the cooperative stretching strain of the graphene film and the acrylate rubber substrate, and testing the conductive capability of the sample; and (3) soaking the doped nano Cu composite Ni sheet deposited with the graphene and the acrylate rubber of the nano GaIn particles in strong acid or strong base, taking out and washing, and testing the conductivity of the sample.
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