CN108610501A - A method of realizing super heated rubber conduction using vapor deposition graphene - Google Patents
A method of realizing super heated rubber conduction using vapor deposition graphene Download PDFInfo
- Publication number
- CN108610501A CN108610501A CN201810297033.5A CN201810297033A CN108610501A CN 108610501 A CN108610501 A CN 108610501A CN 201810297033 A CN201810297033 A CN 201810297033A CN 108610501 A CN108610501 A CN 108610501A
- Authority
- CN
- China
- Prior art keywords
- graphene
- pieces
- vapor deposition
- rubber
- nanometer
- 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
Links
Classifications
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08K3/08—Metals
-
- 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
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C08K3/08—Metals
- C08K2003/085—Copper
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of using vapor deposition graphene come the method for realizing super heated rubber conduction, belongs to graphene composite conductive material application field.The technology utilizes plasma enhanced vapor deposition(PECVD)Method deposits graphene film in super heated rubber top layer, utilize the conductive capability of graphene, flexibility and ductility, pass through combining closely for graphene and super heated rubber, realize that super heated rubber generates synchronous strain with graphene when stretching or twisting, so that rubber all has conductive capability under different shape, to change various functional characteristics such as electricity, stability.And the presence that this conductive capability can be stablized under different shapes or temperature condition, with obvious effects, method is simple.
Description
Technical field
The present invention relates to a kind of methods for realizing super heated rubber conduction using vapor deposition graphene, and it is multiple to belong to graphene
Close conductive material application field.
Background technology
The unique structure of graphene and excellent performance make it in hot property, mechanical property and the electrical property for improving material
Energy etc. has prodigious potentiality, it has also become the hot spot of field of compound material research.Since graphene has excellent electricity
Performance makes it ideally suited for use in the preparation of conducing composite material, carrys out other compound functional materials using graphene as one of component
Material, can obtain multi-functional conducing composite material.The research of graphene conductive composite material is the weight of graphene research field
Component part is wanted, electrode of super capacitor, conductive film material, fuel cell, lithium ion cell electrode etc. are can be widely applied to
Field.
In order to realize the conductive capability of rubber material, the methods of people's generally use metal-coated membrane, doping, but these methods
Difficulty is prepared mostly, it is with high costs, it is difficult to control and the service life that rubber can be substantially reduced.
Invention content
It, will using PECVD methods in order to overcome drawbacks described above, the present invention to utilize the flexibility and conductive capability of graphene for the first time
Graphene is combined closely with super heated rubber, changes the electric conductivity of super heated rubber, is provided a kind of using vapor deposition graphene
The method for realizing super heated rubber conduction, the new opplication as graphene composite conductive material.
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of super heated rubber is realized using vapor deposition graphene
Conductive method, including dopen Nano Cu/Ni pieces and the preparation process and gas phase of the acrylic rubber of nanometer GaIn particles are sunk
The preparation process of long-pending graphene surface film;The graphene surface film of vapor deposition is coated on dopen Nano Cu/Ni pieces and nanometer
The acrylic rubber surface of GaIn particles;
In the preparation process of super heated rubber substrate, using butyl acrylate, ethyl acrylate or methyl acrylate as main monomer, main list
It is mixed that body, cure site monomer glycidyl methacrylate, nanometer Cu/Ni pieces, nanometer GaIn particles and solvent are mixed to form monomer
Solution is closed, constant temperature is heated to monomer mixture solution and initiator is added, samples, samples taken is dehydrated and is dried, is mixed
The acrylic rubber of miscellaneous nanometer Cu/Ni pieces and nanometer GaIn particles;
In the preparation process of the graphene surface film of vapor deposition, pass through plasma enhanced vapor deposition(PECVD)Method will
Graphene film is deposited on the acrylic rubber surface of dopen Nano Cu/Ni pieces and nanometer GaIn particles.
Dopen Nano Cu/Ni pieces and the preparation process of the acrylic rubber of nanometer GaIn particles include the following steps:
(1)Butyl acrylate, methyl acrylate or ethyl acrylate are purified, polymerization inhibitor and other impurity are removed, refrigeration is standby
With;
(2)By step(1)Main monomer butyl acrylate, ethyl acrylate or the methyl acrylate and cure site monomer of middle gained
Glycidyl methacrylate, nanometer Cu/Ni pieces and nanometer GaIn particles, monomer mixture solution is mixed to form with solvent;Wherein
Ga is 1 with In atomic ratios:10-10:1;
(3)To step(2)The monomer mixture solution of middle gained is stirred, and the air in stirred autoclave is emptied;
(4)To step(3)The monomer mixture solution of middle gained carries out oil bath heating, is being set when the temperature of monomer mixture solution is constant
Initiator is added when setting temperature-resistant, and starts to sample, it is primary every sampling in 3-10 minutes;
(5)It is more than hour to be maintained at 2 for reaction process, is dehydrated to samples taken after experiment, by sample vacuum drying to perseverance
Weight, obtains the acrylic rubber of dopen Nano Cu/Ni pieces and nanometer GaIn particles.
The preparation process of the graphene surface film of vapor deposition includes the following steps:
By acrylic rubber surface deionized water, the second of the dopen Nano Cu/Ni pieces prepared in advance and nanometer GaIn particles
Alcohol, acetone one or more be cleaned multiple times, be put into tube furnace;
Tube furnace is evacuated to vacuum state, keeps vacuum pump opening state, is passed through protective gas, is kept for 3-10 minutes;It holds later
Vacuum pump opening state is held in continuation of insurance, according to H2:Protective gas=20:(200~300)Gas flow ratio, be passed through in tube furnace;Institute
The protective gas stated can be the mixed gas of pure argon, nitrogen or argon gas and nitrogen;
So that tubular type in-furnace temperature is warming up to 100 ~ 250 DEG C with the rate of 5 ~ 10 DEG C/min, then keeps the temperature 10 ~ 20 minutes;Starting
After five minutes, open plasma transmitter is pre-processing for heat preservation(Refer to cleaning)Dopen Nano Cu/Ni pieces afterwards and nanometer GaIn
Graphene is deposited in the acrylic rubber of particle, continues 3 ~ 10 minutes, closes plasma emitters;
It is cooled to room temperature later, closes vacuum pump, takes out the dopen Nano Cu/Ni pieces and nanometer GaIn particles that deposited graphene
Acrylic rubber.
Realize that the graphene of conductive capability is polyatom layer graphene.
Step(1)It is middle to purify butyl acrylate, methyl acrylate, ethyl acrylate in Rotary Evaporators;Step(2)
In, the solvent is toluene or ethyl acetate;Step(3)In, by step(2)The monomer mixture solution of middle gained is added to glass
Glass reaction kettle magnetic agitation opens agitating paddle and sets rotating speed to 200r/min, and being passed through protective gas will be in reaction kettle
Air empties;Step(4)Middle oil bath heating about 2 hours.The protective gas can be pure argon, nitrogen or argon gas and nitrogen
The mixed gas of gas.
The acrylic rubber of the dopen Nano Cu/Ni pieces that deposited graphene and nanometer GaIn particles is heated to 60
DEG C, 120 DEG C or 180 DEG C, the conductive capability of test sample;The dopen Nano Cu/Ni pieces and nanometer of graphene will then be deposited
The acrylic rubber of GaIn particles stretches 1% ~ 10%(Or 2% ~ 10%), realize graphene film and acrylic rubber substrate
Cooperate with elongation strain, the conductive capability of test sample;The dopen Nano Cu/Ni pieces and nanometer GaIn particles of graphene will be deposited
Acrylic rubber be put into strong acid or highly basic and impregnate, take out after rinsing, the conductive capability of test sample.
Specifically, super heated rubber substrate(That is the acrylic rubber of dopen Nano Cu/Ni pieces and nanometer GaIn particles)'s
Preparation includes the following steps:
(1)Butyl acrylate, methyl acrylate, ethyl acrylate are purified in Rotary Evaporators, polymerization inhibitor therein and
Other impurity removals, are put into refrigerator and refrigerate, spare;
(2)It will(1)The main monomer butyl acrylate of middle gained(Or ethyl acrylate or methyl acrylate), cure site monomer methyl
Glycidyl Acrylate, nanometer Cu/Ni pieces, nanometer GaIn particles, solvent is toluene(Or ethyl acetate)It is mixed to be mixed to form monomer
Close solution;
(3)It will(2)The monomer mixture solution of middle gained is added to 2L glass reaction kettle magnetic agitations, opens rotating speed of agitator setting
200r/min, and be passed through nitrogen and empty the air in reaction kettle;
(4)Open oil bath pump pair(3)The monomer mixed solution of middle gained carries out or so about 2 hours of oil bath heating, when temperature perseverance
Be scheduled on setting it is temperature-resistant when initiator is added, and start to sample, it is primary every sampling in five minutes;
(5)It is more than hour to be maintained at 2 for reaction process, is dehydrated to samples taken after experiment, and sample, which is positioned over vacuum, to be dried
Vacuum drying obtained acrylic rubber to constant weight about 24 hours in case.
The deposition method includes the following steps:
By acrylic rubber surface deionized water, the second of the dopen Nano Cu/Ni pieces prepared in advance and nanometer GaIn particles
Alcohol, acetone etc. are cleaned multiple times, and are put into tube furnace;
Tube furnace is evacuated to vacuum state, keeps vacuum pump opening state, is passed through pure Ar, is kept for 3 minutes;It is lasting later to keep true
Sky pump opening state, according to H2:Ar=20:(200~300)Gas flow ratio, be passed through in tube furnace;
Program is set, tubular type in-furnace temperature is made to be warming up to 100 ~ 250 DEG C with 5 ~ 10 DEG C/min, then keeps the temperature 10 ~ 20 minutes.It is opening
Heat preservation begin after five minutes, open plasma transmitter deposits graphene in acrylic rubber after the pre-treatment, continue 3 ~
10 minutes, close plasma emitters;
It is cooled to room temperature later, closes vacuum pump, takes out the acrylate rubber for the dopen Nano Cu/Ni pieces that deposited graphene
Glue.
Compared with prior art, the invention has the advantages that:
(1)In order to realize the conductive capability of rubber material, the methods of people's generally use metal-coated membrane, doping, but these methods
Difficulty is prepared mostly, it is with high costs, it is difficult to control and the service life that rubber can be substantially reduced, and the design method is sharp for the first time
It is with the flexibility and conductive capability of graphene, graphene is compound with super heated rubber, do not changing super heated rubber ontology chemical composition
Under conditions of machine capability, the electric conductivity of super heated rubber is promoted 100 times or more;
(2)General super heated rubber surface exposure, the environment such as reply strong acid and strong base will produce the counter productives such as be corroded, the design side
Graphene coated to rubber surface is equivalent to and has coated layer protecting film in rubber surface by case, and rubber is exhausted with ambient enviroment
Edge greatly improves the anti-corrosion capability of super heated rubber;
(3)The present invention it is a kind of using be vapor-deposited graphene come the method for realizing super heated rubber conduction, existed using PECVD methods
Graphene is combined closely with super heated rubber with Van der Waals force, overcomes previous transfer by growth in situ graphene in super heated rubber
Graphene contacts defect loosely with substrate when method such as spin coating.A small amount of dopen Nano Cu/Ni pieces are added in preparation process,
It is also the reinforced phase in rubber while as catalyst, the mechanical property of this super heated rubber is substantially improved;
(4)The present invention prepare rubber during add a small amount of GaIn alloy nanoparticles, this is in previous research
Never it reporting, GaIn is low-melting-point metal, if surface graphene layer has rupture during super heated rubber use, GaIn
Alloy can melt in crack position and carry out selfreparing, be obviously improved the high-temperature electric conduction performance of this rubber.In addition GaIn alloys are same
Cu/Ni nanometer sheets are the same, are all nanometer reinforcing phase particle, can be obviously improved its mechanical property.
Description of the drawings
Fig. 1 is the Raman test result for the graphene being prepared in embodiment 1;
Fig. 2 is the test result of the scanning electron microscope of graphene coated super heated rubber made from embodiment 1;
Fig. 3 is the stretching electricity aptitude tests result of graphene coated super heated rubber made from embodiment 1;
Fig. 4 is the structure chart of the dopen Nano Cu pieces and the acrylic rubber of nanometer GaIn particles that deposited graphene.
Specific implementation mode
It is attached referring now to specification in order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood
Figure technical scheme of the present invention is carried out it is described further below, but should not be understood as to the present invention can practical range restriction.
Embodiment 1 is vapor-deposited graphene to realize butyl acrylate main monomer dopen Nano Cu pieces and nanometer GaIn
The method of the acrylic rubber conduction of grain
1, the preparation of butyl acrylate main monomer dopen Nano Cu pieces and the acrylic rubber substrate of GaIn alloy nanoparticles
Include the following steps:
(1)Butyl acrylate is purified in Rotary Evaporators, polymerization inhibitor therein and other impurity are removed, are put into refrigerator
Refrigeration, it is spare;
(2)It will(1)The main monomer butyl acrylate of middle gained, cure site monomer glycidyl methacrylate, nanometer Cu pieces,
GaIn alloy nanoparticles(Ga is 1 with In atomic ratios:10), solvent is that ethyl acetate is mixed to form monomer mixture solution;
(3)It will(2)The monomer mixture solution of middle gained is added to 2L glass reaction kettle magnetic agitations, opens rotating speed of agitator setting
200r/min, and be passed through nitrogen and empty the air in reaction kettle;
(4)Open oil bath pump pair(3)The monomer mixed solution of middle gained carries out or so about 2 hours of oil bath heating, when temperature perseverance
Be scheduled on setting it is temperature-resistant when initiator is added, and start to sample, it is primary every sampling in five minutes;
(5)It is more than hour to be maintained at 2 for reaction process, is dehydrated to samples taken after experiment, and sample, which is positioned over vacuum, to be dried
Vacuum drying obtained the acrylic rubber of dopen Nano Cu pieces and nanometer GaIn particles to constant weight about 24 hours in case;
2, graphene film deposition in surface includes the following steps:
By the acrylic rubber surface deionized water of the dopen Nano Cu pieces prepared in advance and nanometer GaIn particles, ethyl alcohol,
Acetone etc. is cleaned multiple times, and is put into tube furnace;
Tube furnace is evacuated to vacuum state, keeps vacuum pump opening state, is passed through pure Ar, is kept for 3 minutes;It is lasting later to keep true
Sky pump opening state, according to H2:Ar=20:200 gas flow ratio, is passed through in tube furnace;
Program is set, tubular type in-furnace temperature is made to be warming up to 250 DEG C with 10 DEG C/min, then heat preservation 20 minutes.Starting 5 points of heat preservation
Zhong Hou, open plasma transmitter deposit graphene in acrylic rubber after the pre-treatment, continue 10 minutes, close
Plasma emitters;
It is cooled to room temperature later, closes vacuum pump, takes out the dopen Nano Cu pieces and nanometer GaIn particles that deposited graphene
Acrylic rubber, such as Fig. 4;
The graphene of deposition is subjected to Raman test, result such as Fig. 1 of gained(The stress-strain diagram of NiTi films)It is shown.With
The acrylic rubber of the compound GaIn alloy nanoparticles of dopen Nano Cu pieces to deposited graphene carries out Scanning Electron afterwards
Microscope is tested, and the results are shown in Figure 2 for gained, and nano particle is evenly distributed, without apparent agglomeration.To deposited graphene
The acrylic rubber of dopen Nano Cu pieces and GaIn alloy nanoparticles carry out sheet resistance test, obtain sample side at normal temperatures
Resistance is 264 Ω/sq, and the sheet resistance of doped graphene is 2000 Ω/sq or more in the market, and the two differs nearly ten times.Stone will be deposited
The acrylic rubber of the compound GaIn alloy nanoparticles of dopen Nano Cu pieces of black alkene is heated to 60 DEG C, 120 DEG C, 180 DEG C, surveys
The sheet resistance of test agent, respectively 268,274, test obtains the result of 264 Ω/sq almost without difference under 277 Ω/sq, with room temperature
Away from.To then deposited the compound GaIn alloy nanoparticles of dopen Nano Cu pieces of graphene acrylic rubber stretch 1% ~
10%, realize cooperate with elongation strain of the graphene film with acrylic rubber substrate, the sheet resistance variation of test sample, such as Fig. 3
Shown, sheet resistance is only about 325 Ω/sq when sample is stretched to 10%.Sheet resistance variation is little after sample is stretched to 10%, shows again
Excellent practical performance.
Embodiment 2 is vapor-deposited graphene to realize the compound GaIn alloys of butyl acrylate main monomer dopen Nano Ni pieces
The method of the acrylic rubber conduction of nano particle
1, butyl acrylate main monomer dopen Nano Ni pieces and the preparation of the acrylic rubber substrate of nanometer GaIn particles include
Following steps:
(1)Butyl acrylate is purified in Rotary Evaporators, polymerization inhibitor therein and other impurity are removed, are put into refrigerator
Refrigeration, it is spare;
(2)It will(1)The main monomer butyl acrylate of middle gained, cure site monomer glycidyl methacrylate, Ni nanoparticle piece with
GaIn alloy nanoparticles(Ga is 10 with In atomic ratios:1), solvent is that toluene is mixed to form monomer mixture solution;
(3)It will(2)The monomer mixture solution of middle gained is added to 2L glass reaction kettle magnetic agitations, opens rotating speed of agitator setting
200r/min, and be passed through nitrogen and empty the air in reaction kettle;
(4)Open oil bath pump pair(3)The monomer mixed solution of middle gained carries out or so about 2 hours of oil bath heating, when temperature perseverance
Be scheduled on setting it is temperature-resistant when initiator is added, and start to sample, it is primary every sampling in five minutes;
(5)It is more than hour to be maintained at 2 for reaction process, is dehydrated to samples taken after experiment, and sample, which is positioned over vacuum, to be dried
Vacuum drying obtained the acrylic rubber of dopen Nano Ni pieces and nanometer GaIn particles to constant weight about 24 hours in case;
2, graphene film deposition in surface includes the following steps:
By the acrylic rubber surface deionized water of the compound GaIn alloy nanoparticles of dopen Nano Ni pieces prepared in advance,
Ethyl alcohol, acetone etc. are cleaned multiple times, and are put into tube furnace;
Tube furnace is evacuated to vacuum state, keeps vacuum pump opening state, is passed through pure Ar, is kept for 3 minutes;It is lasting later to keep true
Sky pump opening state, according to H2:Ar=20:300 gas flow ratio, is passed through in tube furnace;
Program is set, tubular type in-furnace temperature is made to be warming up to 100 DEG C with 5 DEG C/min, then heat preservation 10 minutes.Starting 5 points of heat preservation
Zhong Hou, open plasma transmitter deposit graphene in acrylic rubber after the pre-treatment, continue 3 minutes, close etc.
Gas ions transmitter;
It is cooled to room temperature later, closes vacuum pump, takes out the compound GaIn alloy nanos of dopen Nano Ni pieces that deposited graphene
The acrylic rubber of particle.
Nano particle is evenly distributed, without apparent agglomeration.Dopen Nano Ni pieces to deposited graphene are closed with GaIn
The acrylic rubber of gold nano grain carries out sheet resistance test, and obtaining sample, sheet resistance is 204 Ω/sq at normal temperatures, is mixed in the market
The sheet resistance of miscellaneous graphene is 2000 Ω/sq or more, and the two differs nearly ten times.The dopen Nano Cu pieces that deposited graphene is compound
The acrylic rubber of GaIn alloy nanoparticles is heated to 50 DEG C, 100 DEG C, 150 DEG C, the sheet resistance of test sample, respectively
210,214, test obtains the result of 204 Ω/sq almost without gap under 218 Ω/sq, with room temperature.Graphite will then be deposited
The acrylic rubber of the compound GaIn alloy nanoparticles of dopen Nano Ni pieces of alkene stretches 1% ~ 10%, realizes graphene film
Change with the sheet resistance of the elongation strain that cooperates with of acrylic rubber substrate, test sample, sheet resistance is only about when sample is stretched to 15%
225 Ω/sq illustrate excellent practical performance again.
Embodiment 3 is vapor-deposited graphene to realize the compound GaIn alloys of ethyl acrylate main monomer dopen Nano Ni pieces
The method of the acrylic rubber conduction of nano particle
1, ethyl acrylate main monomer dopen Nano Ni pieces and the preparation of the acrylic rubber substrate of nanometer GaIn particles include
Following steps:
(1)Ethyl acrylate is purified in Rotary Evaporators, polymerization inhibitor therein and other impurity are removed, are put into refrigerator
Refrigeration, it is spare;
(2)It will(1)The main monomer ethyl acrylate of middle gained, cure site monomer glycidyl methacrylate, Ni nanoparticle piece with
GaIn alloy nanoparticles(Ga is 1 with In atomic ratios:1), solvent is that ethyl acetate is mixed to form monomer mixture solution;
(3)It will(2)The monomer mixture solution of middle gained is added to 2L glass reaction kettle magnetic agitations, opens rotating speed of agitator setting
200r/min, and be passed through nitrogen and empty the air in reaction kettle;
(4)Open oil bath pump pair(3)The monomer mixed solution of middle gained carries out or so about 2 hours of oil bath heating, when temperature perseverance
Be scheduled on setting it is temperature-resistant when initiator is added, and start to sample, it is primary every sampling in five minutes;
(5)It is more than hour to be maintained at 2 for reaction process, is dehydrated to samples taken after experiment, and sample, which is positioned over vacuum, to be dried
Vacuum drying obtained the acrylic rubber of dopen Nano Ni pieces and nanometer GaIn particles to constant weight about 24 hours in case;
2, graphene film deposition in surface includes the following steps:
By the acrylic rubber surface deionized water of the compound GaIn alloy nanoparticles of dopen Nano Ni pieces prepared in advance,
Ethyl alcohol, acetone etc. are cleaned multiple times, and are put into tube furnace;
Tube furnace is evacuated to vacuum state, keeps vacuum pump opening state, is passed through pure Ar, is kept for 3 minutes;It is lasting later to keep true
Sky pump opening state, according to H2:Ar=20:300 gas flow ratio, is passed through in tube furnace;
Program is set, tubular type in-furnace temperature is made to be warming up to 100 DEG C with 5 DEG C/min, then heat preservation 10 minutes.Starting 5 points of heat preservation
Zhong Hou, open plasma transmitter deposit graphene in acrylic rubber after the pre-treatment, continue 3 minutes, close etc.
Gas ions transmitter;
It is cooled to room temperature later, closes vacuum pump, takes out the compound GaIn alloy nanos of dopen Nano Ni pieces that deposited graphene
The acrylic rubber of particle.
Nano particle is evenly distributed, without apparent agglomeration.Dopen Nano Ni pieces to deposited graphene are closed with GaIn
The acrylic rubber of gold nano grain carries out sheet resistance test, and obtaining sample, sheet resistance is 196 Ω/sq at normal temperatures, is mixed in the market
The sheet resistance of miscellaneous graphene is 2000 Ω/sq or more, and the two differs nearly ten times.The dopen Nano Cu pieces that deposited graphene is compound
The acrylic rubber of the compound GaIn alloy nanoparticles of GaIn alloy nanoparticles be heated to 50 DEG C, 100 DEG C, 150 DEG C, 200
DEG C, the sheet resistance of test sample, respectively 200,214,227, test obtains the result phase of 196 Ω/sq under 235 Ω/sq, with room temperature
When.The acrylic rubber that the compound GaIn alloy nanoparticles of dopen Nano Ni pieces of graphene will then be deposited stretches 15%,
Sheet resistance is only about 225 Ω/sq, illustrates excellent practical performance again.
Embodiment 4 is vapor-deposited graphene to realize the compound GaIn alloys of methyl acrylate main monomer dopen Nano Ni pieces
The method of the acrylic rubber conduction of nano particle
1, the system of the acrylic rubber substrate of the compound GaIn alloy nanoparticles of methyl acrylate main monomer dopen Nano Ni pieces
It is standby to include the following steps:
(1)Methyl acrylate is purified in Rotary Evaporators, polymerization inhibitor therein and other impurity are removed, are put into refrigerator
Refrigeration, it is spare;
(2)It will(1)The main monomer methyl acrylate of middle gained, cure site monomer glycidyl methacrylate, Ni nanoparticle piece with
GaIn alloy nanoparticles(Ga is 2 with In atomic ratios:1), solvent is that ethyl acetate is mixed to form monomer mixture solution;
(3)It will(2)The monomer mixture solution of middle gained is added to 2L glass reaction kettle magnetic agitations, opens rotating speed of agitator setting
200r/min, and be passed through nitrogen and empty the air in reaction kettle;
(4)Open oil bath pump pair(3)The monomer mixed solution of middle gained carries out or so about 2 hours of oil bath heating, when temperature perseverance
Be scheduled on setting it is temperature-resistant when initiator is added, and start to sample, it is primary every sampling in five minutes;
(5)It is more than hour to be maintained at 2 for reaction process, is dehydrated to samples taken after experiment, and sample, which is positioned over vacuum, to be dried
Vacuum drying obtained the acrylic rubber of dopen Nano Ni pieces and nanometer GaIn particles to constant weight about 24 hours in case;
2, graphene film deposition in surface includes the following steps:
By the acrylic rubber surface deionized water of the compound GaIn alloy nanoparticles of dopen Nano Ni pieces prepared in advance,
Ethyl alcohol, acetone etc. are cleaned multiple times, and are put into tube furnace;
Tube furnace is evacuated to vacuum state, keeps vacuum pump opening state, is passed through pure Ar, is kept for 3 minutes;It is lasting later to keep true
Sky pump opening state, according to H2:Ar=20:200 gas flow ratio, is passed through in tube furnace;
Program is set, tubular type in-furnace temperature is made to be warming up to 150 DEG C with 5 DEG C/min, then heat preservation 10 minutes.Starting 5 points of heat preservation
Zhong Hou, open plasma transmitter deposit graphene in acrylic rubber after the pre-treatment, continue 5 minutes, close etc.
Gas ions transmitter;
It is cooled to room temperature later, closes vacuum pump, takes out the compound GaIn alloy nanos of dopen Nano Ni pieces that deposited graphene
The acrylic rubber of particle.
Nano particle is evenly distributed, without apparent agglomeration.Dopen Nano Ni pieces to deposited graphene are closed with GaIn
The acrylic rubber of gold nano grain carries out sheet resistance test, and obtaining sample, sheet resistance is 226 Ω/sq at normal temperatures, is mixed in the market
The sheet resistance of miscellaneous graphene is 2000 Ω/sq or more, and the two differs nearly ten times.The dopen Nano Cu pieces that deposited graphene is compound
The acrylic rubber of the compound GaIn alloy nanoparticles of GaIn alloy nanoparticles be heated to 50 DEG C, 100 DEG C, 150 DEG C, 200
DEG C, the sheet resistance of test sample, respectively 228,230,237,235 Ω/sq, to obtain result suitable with test under room temperature.Then will
The acrylic rubber that deposited the compound GaIn alloy nanoparticles of dopen Nano Ni pieces of graphene stretches 15%, and sheet resistance is only
About 250 Ω/sq illustrate excellent practical performance again.
Embodiment 5 is vapor-deposited graphene to realize the compound GaIn alloys of methyl acrylate main monomer dopen Nano Cu pieces
The method of the acrylic rubber conduction of nano particle
1, the system of the acrylic rubber substrate of the compound GaIn alloy nanoparticles of methyl acrylate main monomer dopen Nano Cu pieces
It is standby to include the following steps:
(1)Methyl acrylate is purified in Rotary Evaporators, polymerization inhibitor therein and other impurity are removed, are put into refrigerator
Refrigeration, it is spare;
(2)It will(1)Main monomer methyl acrylate, cure site monomer glycidyl methacrylate, the nanometer Cu pieces of middle gained, it is molten
Agent is that ethyl acetate is mixed to form monomer mixture solution;
(3)It will(2)The monomer mixture solution of middle gained is added to 2L glass reaction kettle magnetic agitations, opens rotating speed of agitator setting
200r/min, and be passed through nitrogen and empty the air in reaction kettle;
(4)Open oil bath pump pair(3)The monomer mixed solution of middle gained carries out or so about 2 hours of oil bath heating, when temperature perseverance
Be scheduled on setting it is temperature-resistant when initiator is added, and start to sample, it is primary every sampling in five minutes;
(5)It is more than hour to be maintained at 2 for reaction process, is dehydrated to samples taken after experiment, and sample, which is positioned over vacuum, to be dried
Vacuum drying obtained the acrylate rubber of the compound GaIn alloy nanoparticles of dopen Nano Cu pieces to constant weight about 24 hours in case
Glue;
2, graphene film deposition in surface includes the following steps:
By the acrylic rubber surface deionized water of the compound GaIn alloy nanoparticles of dopen Nano Cu pieces prepared in advance,
Ethyl alcohol, acetone etc. are cleaned multiple times, and are put into tube furnace;
Tube furnace is evacuated to vacuum state, keeps vacuum pump opening state, is passed through pure Ar, is kept for 3 minutes;It is lasting later to keep true
Sky pump opening state, according to H2:Ar=20:200 gas flow ratio, is passed through in tube furnace;
Program is set, tubular type in-furnace temperature is made to be warming up to 150 DEG C with 5 DEG C/min, then heat preservation 10 minutes.Starting 5 points of heat preservation
Zhong Hou, open plasma transmitter deposit graphene in acrylic rubber after the pre-treatment, continue 5 minutes, close etc.
Gas ions transmitter;
It is cooled to room temperature later, closes vacuum pump, takes out the compound GaIn alloy nanos of dopen Nano Cu pieces that deposited graphene
The acrylic rubber of particle.
Nano particle is evenly distributed, without apparent agglomeration.Dopen Nano Cu pieces to deposited graphene are closed with GaIn
The acrylic rubber of gold nano grain carries out sheet resistance test, and obtaining sample, sheet resistance is 186 Ω/sq at normal temperatures, is mixed in the market
The sheet resistance of miscellaneous graphene is 2000 Ω/sq or more, and the two differs nearly ten times.The dopen Nano Cu pieces that deposited graphene is compound
The acrylic rubber of the compound GaIn alloy nanoparticles of GaIn alloy nanoparticles be heated to 50 DEG C, 100 DEG C, 150 DEG C, 200
DEG C, the sheet resistance of test sample, respectively 202,212,228, test obtains the result phase of 186 Ω/sq under 238 Ω/sq, with room temperature
When.The acrylic rubber that the compound GaIn alloy nanoparticles of dopen Nano Cu pieces of graphene will then be deposited stretches 15%,
Sheet resistance is only about 215 Ω/sq, illustrates excellent practical performance again.
The above display describes the basic principles and main features and advantage of the present invention.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, what is described in the above embodiment and the description is only saying the principle of the present invention,
Without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes and improvements are all
It drops into the claimed scope of the invention.The scope of the present invention is defined by the appended claims and its equivalents.
Claims (8)
1. a kind of method for realizing super heated rubber conduction using vapor deposition graphene, which is characterized in that including dopen Nano
Cu/Ni pieces and the preparation of the preparation process of the acrylic rubber of nanometer GaIn particles and the graphene surface film of vapor deposition walk
Suddenly;The graphene surface film of vapor deposition is coated on the acrylic rubber table of dopen Nano Cu/Ni pieces and nanometer GaIn particles
Face;
In the preparation process of super heated rubber substrate, using butyl acrylate, ethyl acrylate or methyl acrylate as main monomer, main list
It is mixed that body, cure site monomer glycidyl methacrylate, nanometer Cu/Ni pieces, nanometer GaIn particles and solvent are mixed to form monomer
Solution is closed, constant temperature is heated to monomer mixture solution and initiator is added, samples, samples taken is dehydrated and is dried, is mixed
The acrylic rubber of miscellaneous nanometer Cu/Ni pieces and nanometer GaIn particles;
In the preparation process of the graphene surface film of vapor deposition, pass through plasma enhanced vapor deposition(PECVD)Method will
Graphene film is deposited on the acrylic rubber surface of dopen Nano Cu/Ni pieces and nanometer GaIn particles.
2. a kind of method for realizing super heated rubber conduction using vapor deposition graphene according to claim 1, special
Sign is,
Dopen Nano Cu/Ni pieces and the preparation process of the acrylic rubber of nanometer GaIn particles include the following steps:
(1)Butyl acrylate, methyl acrylate or ethyl acrylate are purified, polymerization inhibitor and other impurity are removed, refrigeration is standby
With;
(2)By step(1)Main monomer butyl acrylate, ethyl acrylate or the methyl acrylate and cure site monomer of middle gained
Glycidyl methacrylate, nanometer Cu/Ni pieces, nanometer GaIn particles and solvent are mixed to form monomer mixture solution, wherein Ga
It is 1 with In atomic ratios:10-10:1;
(3)To step(2)The monomer mixture solution of middle gained is stirred, and the air in stirred autoclave is emptied;
(4)To step(3)The monomer mixture solution of middle gained carries out oil bath heating, is being set when the temperature of monomer mixture solution is constant
Initiator is added when setting temperature-resistant, and starts to sample, it is primary every sampling in 3-10 minutes;
(5)It is more than hour to be maintained at 2 for reaction process, is dehydrated to samples taken after experiment, by sample vacuum drying to perseverance
Weight, obtains the acrylic rubber of dopen Nano Cu/Ni pieces and nanometer GaIn particles.
3. a kind of method for realizing super heated rubber conduction using vapor deposition graphene according to claim 1, special
Sign is that the preparation process of the graphene surface film of vapor deposition includes the following steps:
By acrylic rubber surface deionized water, the second of the dopen Nano Cu/Ni pieces prepared in advance and nanometer GaIn particles
Alcohol, acetone one or more be cleaned multiple times, be put into tube furnace;
Tube furnace is evacuated to vacuum state, keeps vacuum pump opening state, is passed through protective gas, is kept for 3-10 minutes;It holds later
Vacuum pump opening state is held in continuation of insurance, according to H2:Protective gas=20:(200~300)Gas flow ratio, be passed through in tube furnace;
So that tubular type in-furnace temperature is warming up to 100 ~ 250 DEG C with the rate of 5 ~ 10 DEG C/min, then keeps the temperature 10 ~ 20 minutes;Starting
It keeps the temperature after five minutes, open plasma transmitter, dopen Nano Cu/Ni pieces and the third of nanometer GaIn particles after the pre-treatment
Graphene is deposited on olefin(e) acid ester rubber, continues 3 ~ 10 minutes, closes plasma emitters;
It is cooled to room temperature later, closes vacuum pump, takes out the dopen Nano Cu/Ni pieces and nanometer GaIn particles that deposited graphene
Acrylic rubber.
4. a kind of according to claim 1-3 any one realizing that super heated rubber is conductive using vapor deposition graphene
Method, which is characterized in that realize that the graphene of conductive capability is polyatom layer graphene.
5. a kind of method for realizing super heated rubber conduction using vapor deposition graphene according to claim 3, special
Sign is that the protective gas is the mixed gas of pure argon, nitrogen or argon gas and nitrogen.
6. a kind of method for realizing super heated rubber conduction using vapor deposition graphene according to claim 2, special
Sign is, step(1)It is middle to purify butyl acrylate, methyl acrylate, ethyl acrylate in Rotary Evaporators;Step(2)
In, the solvent is toluene or ethyl acetate;Step(3)In, by step(2)The monomer mixture solution of middle gained is added to glass
Glass reaction kettle magnetic agitation, opens agitating paddle and rotating speed is set as 100-1000r/min, and being passed through protective gas will be in reaction kettle
Air emptying;Step(4)Middle oil bath heating about 1-5 hours.
7. a kind of method for realizing super heated rubber conduction using vapor deposition graphene according to claim 6, special
Sign is that the protective gas is the mixed gas of pure argon, nitrogen or argon gas and nitrogen.
8. a kind of according to claim 1-3 any one realizing that super heated rubber is conductive using vapor deposition graphene
Method, which is characterized in that add the acrylic rubber of the dopen Nano Cu/Ni pieces that deposited graphene and nanometer GaIn particles
Heat is to 60 DEG C, 120 DEG C or 180 DEG C, the conductive capability of test sample;The dopen Nano Cu/Ni pieces of graphene will then be deposited
1% ~ 10% is stretched with the acrylic rubber of nanometer GaIn particles, realization graphene film is cooperateed with acrylic rubber substrate
Elongation strain, the conductive capability of test sample;The dopen Nano Cu/Ni pieces and the third of nanometer GaIn particles of graphene will be deposited
Olefin(e) acid ester rubber, which is put into strong acid or highly basic, to be impregnated, and is taken out after rinsing, the conductive capability of test sample.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810297033.5A CN108610501B (en) | 2018-03-30 | 2018-03-30 | Method for realizing high-temperature rubber conduction by using vapor deposition graphene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810297033.5A CN108610501B (en) | 2018-03-30 | 2018-03-30 | Method for realizing high-temperature rubber conduction by using vapor deposition graphene |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108610501A true CN108610501A (en) | 2018-10-02 |
CN108610501B CN108610501B (en) | 2021-01-29 |
Family
ID=63659484
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810297033.5A Active CN108610501B (en) | 2018-03-30 | 2018-03-30 | Method for realizing high-temperature rubber conduction by using vapor deposition graphene |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108610501B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009172806A (en) * | 2008-01-22 | 2009-08-06 | Fujikura Rubber Ltd | Laminated body, method of manufacturing the same, and seal member |
KR20130129588A (en) * | 2012-05-21 | 2013-11-29 | (주)고딘테크 | Method for producing graphene-copolymer nanocomposite |
CN104039696A (en) * | 2011-12-22 | 2014-09-10 | 韩国生产技术研究院 | Method for manufacturing large-scale three-dimensional transparent graphene electrodes by electrospraying, and large-scale three-dimensional transparent graphene electrode manufactured by using the method |
CN104498892A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Method for preparing graphene film through low-temperature fixed-point nucleating |
CN105603393A (en) * | 2016-02-22 | 2016-05-25 | 中国石油大学(北京) | Magnesium alloy provided with graphene protection film and preparation method thereof |
-
2018
- 2018-03-30 CN CN201810297033.5A patent/CN108610501B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009172806A (en) * | 2008-01-22 | 2009-08-06 | Fujikura Rubber Ltd | Laminated body, method of manufacturing the same, and seal member |
CN104039696A (en) * | 2011-12-22 | 2014-09-10 | 韩国生产技术研究院 | Method for manufacturing large-scale three-dimensional transparent graphene electrodes by electrospraying, and large-scale three-dimensional transparent graphene electrode manufactured by using the method |
KR20130129588A (en) * | 2012-05-21 | 2013-11-29 | (주)고딘테크 | Method for producing graphene-copolymer nanocomposite |
CN104498892A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Method for preparing graphene film through low-temperature fixed-point nucleating |
CN105603393A (en) * | 2016-02-22 | 2016-05-25 | 中国石油大学(北京) | Magnesium alloy provided with graphene protection film and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
LIQIANG ZHANG ET AL.: ""Graphene enhanced anti-corrosion and biocompatibility of NiTi alloy"", 《NANOIMPACT》 * |
Also Published As
Publication number | Publication date |
---|---|
CN108610501B (en) | 2021-01-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wang et al. | Effect of rare-earth on friction and wear properties of laser cladding Ni-based coatings on 6063Al | |
Zhang et al. | Magnetron sputtering amorphous carbon coatings on metallic lithium: Towards promising anodes for lithium secondary batteries | |
Majumdar | Formation of MoSi2 and Al doped MoSi2 coatings on molybdenum base TZM (Mo–0.5 Ti–0.1 Zr–0.02 C) alloy | |
CN106995914B (en) | A method of preparing self-supporting porous metal film | |
CN107697906B (en) | Preparation method of copper/graphene composite material | |
CN106835260B (en) | The preparation method of oversize multilayer single crystal graphene and large size single crystal corronil | |
Susantyoko et al. | Influences of annealing on lithium-ion storage performance of thick germanium film anodes | |
Sisan et al. | Carbon coating for corrosion protection of SS-316L and AA-6061 as bipolar plates of PEM fuel cells | |
CN106283052B (en) | A kind of two-dimensional material regulation silicon-carbon composite construction hydrogen resistance coating and preparation method thereof | |
WO2024000802A1 (en) | Composite current collector and preparation method therefor, electrode plate, battery, and electronic device | |
CN109326784A (en) | Phosphorus doping MoS2Load the preparation method and application of graphene nanometer sheet | |
EP3620435B1 (en) | Independent free-standing graphene film and preparation method therefor | |
WO2018120601A1 (en) | Preparation method for self-supporting thin film of graphene-enhanced three-dimensional porous carbon | |
CN106803570B (en) | A kind of lithium battery SiCO- carbon nano-tube coextruded film electrode | |
Arie et al. | Surface-coated silicon anodes with amorphous carbon film prepared by fullerene C60 sputtering | |
CN108314019A (en) | A kind of preparation method of the uniform large-area high-quality graphene film of the number of plies | |
CN108610501A (en) | A method of realizing super heated rubber conduction using vapor deposition graphene | |
US8367162B2 (en) | Pretreatment method for improving antioxidation of steel T91/P91 in high temperature water vapor | |
CN107381558B (en) | A kind of preparation method and high-electroconductivity graphene film of high-electroconductivity graphene film | |
CN113684460A (en) | Preparation method of accident-resistant cladding Cr/CrN composite coating | |
Wang et al. | Black rhenium coating prepared on graphite substrate by electrodeposition in NaCl-KCl-CsCl-K2ReCl6 molten salts | |
Sanchette et al. | Nanostructured aluminium based coatings deposited by electron-beam evaporative PVD | |
CN102019168A (en) | Method for manufacturing carbon nanotube solid phase micro-extraction head | |
CN104099661B (en) | A kind of low temperature, the preparation method of self-organizing growth amorphous carbon heterozygosis nanometer monocrystalline graphite | |
Shao et al. | Spontaneous escape behavior of silver from graphite-like carbon coating and its inhibition mechanism |
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 |