CN109251572A - A kind of glass flake/graphene conductive composite material and preparation method thereof - Google Patents
A kind of glass flake/graphene conductive composite material and preparation method thereof Download PDFInfo
- Publication number
- CN109251572A CN109251572A CN201710571819.7A CN201710571819A CN109251572A CN 109251572 A CN109251572 A CN 109251572A CN 201710571819 A CN201710571819 A CN 201710571819A CN 109251572 A CN109251572 A CN 109251572A
- Authority
- CN
- China
- Prior art keywords
- graphene
- glass flake
- present
- composite material
- preparation
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K3/40—Glass
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
The present invention provides a kind of glass flake/graphene composite materials, including glass flake；And it is compounded in the graphite alkenes material on the glass flake surface.The present invention carries out graphite alkenes material (graphene and its derivative) with glass flake compound, it is formed and stablizes composite construction, achievable graphene surface is uniformly distributed, effectively graphene sheet layer is prevented to reunite, the conductivity for substantially increasing glass flake has obtained a kind of glass flake/graphene composite material with superior electrical conductivity energy, has made efficient conductive filler, it is not only able to improve the electric conductivity of post-coatings application, also effectively improves corrosion resistance.Graphene is successfully compounded in glass flake surface by easy method by the present invention, and endangers reducing agent without using hydrazine hydrate is contour, not only avoids environmental pollution, but also technique is more simple, mild condition, safety and environmental protection, is more suitable technology mass production.
Description
Technical field
The invention belongs to conducing composite material technical field, it is related to a kind of glass flake/graphene composite material and its system
Preparation Method more particularly to a kind of glass flake/graphene conductive composite material and preparation method thereof.
Background technique
Glass flake (Glass Flakes) is a kind of very thin, is in flakey with a thickness of the glass fragment of 5 microns
(alkali-containing glass, C glass), it is alkali glass in the melting by 1200 DEG C or more, is frothed, cooled down, crushed, screen and milled
Obtained by processing step.Glass flake, due to being to carry out rapid cooling in the state that melten glass is in drawing force and be made.
Therefore, the internal structure of glass flake and glass fibre is quite similar, is not entirely a kind of stable structure, but one
The structure of kind meta-stable, but it is entirely different on ingredient.The performance of glass flake, not with gradually cooling plate glass
Together, its intensity is more much bigger than simple glass plate.
Anticorrosive paint using glass flake as filler, have very high cohesive force and excellent chemical resistance,
Persistence and anti-aging property have more superior property compared to using packing materials such as mica, calcium silicates and alumina silicate
Energy.It is small more than glass reinforced plastic lining to the permeability of chemical mediator, gas, steam first, it is difficult to cause water vapor diffusion phenomenon, this
It is the glass flake due to overlapping arrangement layer by layer, makes the reason of medium osmosis distance；Secondly solidify when shrink it is low, due to point
It dissipates, bonding plane residual stress is small；Then thermal expansion coefficient is small, and bonding thermal stress is accordingly also small, and heat resisting temperature is high, thermal shock resistance
It can be good；Though mechanical strength is not so good as glass reinforced plastic lining again, wearability, scraping and wiping resistance performance are outstanding, are also only limited to mechanical damage
Part；Furthermore glass-flake coating construction technology performance is also fine.
Just because of glass-flake coating have it is above-mentioned anti-corrosion, permeability resistance is good, and film shrinking percentage is low, thermal expansion coefficient
Small, Googol motion controller is few, wear-resistant, easy construction, is easy to repairing etc. many advantages, thus glass-flake coating is being changed
The industries such as work, metallurgy, chemical fibre, plating, building have extensive application.Especially in various offshore engineering equipments, offshore oil day
Right gas platform, bay harbour and marine vessel applications are more extensive.But due to coating be mostly using the good high polymer of insulating properties as
Main film forming substance, but be easy to generate and accumulate electrostatic.When accumulation of static electricity to a certain extent when, static discharge will be generated and
Cause the malignant events such as explosion, fire.Therefore, it takes measures to assign glass flake anticorrosion paint certain electric conductivity, is to solve
The effective way of the above problem.
Traditional compound-type conducting glass flake is mainly that the addition of graphite substance and its surface of electroless plating method coat one layer
Or composite material obtained from the conductive materials that several layers of chemical stabilities are good, corrosion resistance is strong, conductivity is high.Usual prior art
It is using traditional electroless plating method technique, not only process is cumbersome, but also using the huge sum of money such as plurality of heavy metal nickel salt, mantoquita or chromic salts
Belong to salting liquid and carry out chemical plating, has very big pollution to environment, while the electric conductivity of compound glass scale is also weaker, Wu Faman
The growing requirement of sufficient downstream industry.
Therefore, a kind of compound glass scale with preferable electric conductivity how is found, while preparation method is again simple and easy,
It is pollution-free, it has also become many production firms and downstream application field one of major issue urgently to be resolved.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of glass flake/graphene composite material and
Preparation method, glass flake/graphene provided by the invention has preferable electric conductivity, and preparation method is simply easy
Row is suitable for large-scale industrial production.
The present invention provides a kind of glass flake/graphene composite materials, including glass flake；
And it is compounded in the graphite alkenes material on the glass flake surface.
Preferably, the piece diameter of the glass flake is 50~800 mesh；
The piece diameter of the graphite alkenes material is 10~30 μm.
Preferably, the graphite alkenes material includes graphene, graphene oxide, redox graphene and modified graphite
One of alkene is a variety of.
Preferably, it is 0.01%~05% that the graphite alkenes material, which accounts for the mass ratio of the glass flake,.
The present invention also provides a kind of preparation methods of glass flake/graphene composite material, comprising the following steps:
A after) mixing graphite alkenes material solution and glass flake, mixture is obtained；
B) mixture for obtaining above-mentioned steps is after drying, then is ground, and solid powder is obtained；
C) solid powder for obtaining above-mentioned steps obtains glass flake/graphene composite material after Overheating Treatment.
Preferably, the graphite alkenes material solution is the graphene solution after dispersion；
The mass fraction of the graphite alkenes material solution is 0.5 ‰~5 ‰.
Preferably, described to be separated into ultrasonic disperse；
The time of the dispersion is 10~60min；
The frequency of the ultrasound is 10~40Hz；
The mixed time is 10~60min.
Preferably, the time of the drying is 60~120min；
The temperature of the drying is 50~100 DEG C；
It further include filtering step before the drying.
Preferably, the time of the grinding is 10~180min；
The revolving speed of the grinding is 200~500r/s.
Preferably, the temperature of the heat treatment is 200~380 DEG C；
The soaking time of the heat treatment is 60~180min；
The heating rate of the heat treatment is 5~10 DEG C/min.
The present invention provides a kind of glass flake/graphene composite materials, including glass flake；And it is compounded in the glass
The graphite alkenes material on glass scale surface.The present invention also provides a kind of preparation methods of glass flake/graphene composite material.
Compared with prior art, the present invention is directed to the electroless plating method technique of traditional conductive compound glass scale, and not only process is cumbersome, right
Environment has a very big pollution, and the weaker problem of electric conductivity of compound glass scale；Or in later period coating mixed process, directly
Addition conductive material can make the performance of material change, it is difficult to the defects of adapting to the requirement of conductive coating.The present invention is by graphite
Alkenes material (graphene and its derivative) and glass flake progress are compound, are formed and stablize composite construction, it can be achieved that graphene table
Face is uniformly distributed, and effectively graphene sheet layer is prevented to reunite, is substantially increased the conductivity of glass flake, has been obtained a kind of with excellent
Glass flake/graphene composite material of different electric conductivity, makes efficient conductive filler.The present invention has abandoned traditional
Graphene is successfully compounded in foliated glass scale surface by easy method by preparation method, and without using hydrazine hydrate etc.
Height endangers reducing agent, does not also need any reduction process, not only avoids environmental pollution, but also technique is more simple, using its system
Standby glass flake conductive coating not only has excellent electric conductivity, while also effectively improving corrosion resistance.
The experimental results showed that the effective compound of graphene and glass flake may be implemented in preparation method provided by the invention,
Effectively graphene sheet layer is prevented to reunite, substantially increases the conductivity of glass flake, volume resistivity is up to 152.75 Ω
Cm, meanwhile, the addition of graphene influences its Corrosion Protection, and testing neutral salt-fog resistant time is to reach as high as 1200h.
Detailed description of the invention
Fig. 1 is glass flake/graphene composite material optical imagery figure and Raman image prepared by the embodiment of the present invention 1
Figure；
Fig. 2 is the preparation process flow schematic diagram that the embodiment of the present invention 1 provides；
Fig. 3 is glass flake/graphene composite material stereoscan photograph prepared by the embodiment of the present invention 1.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyzing, pure or graphene is compound
The conventional purity that Material Field uses.
The present invention provides a kind of glass flake/graphene composite materials, including glass flake；
And it is compounded in the graphite alkenes material on the glass flake surface.
The glass flake is not particularly limited in the present invention, is with glass flake well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright glass flake is preferably coating glass flake, more preferably alkali-containing glass glass flake, more preferably C glass glass
Scale.
The design parameter of the glass flake is not particularly limited in the present invention, with glass well known to those skilled in the art
The conventional parameter of scale, those skilled in the art can according to practical condition, product requirement and quality requirement into
Row selection and adjustment, the piece diameter (size) of glass flake of the present invention is preferably 50~800 mesh, more preferably 100~700
Mesh, more preferably 200~600 mesh, most preferably 300~500 mesh.
The definition of the graphite alkenes material is not particularly limited in the present invention, with graphite well known to those skilled in the art
The concept of alkene and its derivative, those skilled in the art can want according to practical situations, product requirement and quality
It asks and is selected and adjusted, the graphene concept of graphite alkenes material, that is, broad sense of the present invention preferably includes graphene, oxidation
One of graphene, redox graphene and modified graphene are a variety of, more preferably single-layer graphene, Multi-layer graphite
Alkene, graphene oxide, redox graphene or modified graphene, most preferably graphene or graphene oxide.
Specifically, graphene of the present invention may include the graphite alkenes material of a variety of types commercially available on the market, specifically
Preferably the high-quality graphene (patent No.: CN 106082198A) of Ou Bo company production, the graphene oxide (patent No.: CN
106115669A) and one of graphene oxide (CN 106430175A) or a variety of.
The design parameter of the graphene is not particularly limited in the present invention, with graphene well known to those skilled in the art
Conventional parameter, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, the size of graphene of the present invention, i.e. piece diameter are preferably 10~30 μm, and more preferably 12~28 μm, more preferably
It is 15~25 μm, most preferably 18~23 μm.
The ratio of the graphite alkenes material and glass flake is not particularly limited in the present invention, with those skilled in the art
Well known conventional ratio, those skilled in the art can according to practical situations, product requirement and quality requirement into
Row selection and adjustment, the mass ratio that graphite alkenes material of the present invention accounts for the glass flake is preferably 0.01%~5%, more
Preferably 0.05%~4%, more preferably 0.1%~3%, most preferably 0.5%~2%.
The present invention also provides a kind of preparation methods of glass flake/graphene composite material, comprising the following steps:
A after) mixing graphite alkenes material solution and glass flake, mixture is obtained；
B) mixture for obtaining above-mentioned steps is after drying, then is ground, and solid powder is obtained；
C) solid powder for obtaining above-mentioned steps obtains glass flake/graphene composite material after Overheating Treatment.
In the preparation method of the above-mentioned glass flake/graphene composite material of the present invention, the optimum principle of material therefor and plus
Optimum principle and the additional amount for entering amount and material in foregoing glass scale/graphene composite material are consistent, herein no longer one by one
It repeats.
After the present invention first mixes graphite alkenes material solution and glass flake, mixture is obtained.
The concentration of the graphite alkenes material solution is not particularly limited in the present invention, with well known to those skilled in the art
The concentration of graphite alkenes material solution, those skilled in the art can be according to practical condition, product requirement and matter
Amount requires to be selected and adjusted, and the mass fraction of graphite alkenes material solution of the present invention is preferably 0.5 ‰~5 ‰, more
Preferably 1 ‰~4 ‰, most preferably 2 ‰~3 ‰.
The solvent of the graphite alkenes material solution is not particularly limited in the present invention, with well known to those skilled in the art
For the Conventional solvents of graphite alkenes material solution, those skilled in the art can want according to practical condition, product
It asks and quality requirement is selected and adjusted, the solvent of graphite alkenes material solution of the present invention is preferably water, ethyl alcohol, third
One of ketone, dimethylbenzene, n-butanol, espeleton, isopropanol and ethyl acetate are a variety of, more preferably water, ethyl alcohol, third
Ketone, dimethylbenzene, n-butanol, espeleton, isopropanol or ethyl acetate, more preferably water, ethyl alcohol, acetone or dimethylbenzene.
The present invention is to improve the dispersion effect of subsequent graphite alkenes material, and the graphite alkenes material solution preferably passes through
Graphite alkenes material solution after dispersion.The dispersing method of the graphite alkenes material solution is not particularly limited in the present invention,
With dispersing method well known to those skilled in the art, those skilled in the art can want according to practical condition, product
It asks and quality requirement is selected and adjusted, dispersion of the present invention is preferably ultrasonic disperse processing, and more preferably ultrasound is stirred
Mix processing.
The time of the dispersion is not particularly limited in the present invention, is with jitter time well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The time of the bright dispersion is preferably 10~60min, more preferably 20~50min, most preferably 30~40min.
The frequency of the ultrasound is not particularly limited in the present invention, is with supersonic frequency well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The frequency of the bright ultrasound is preferably 10~40Hz, more preferably 15~35Hz, most preferably 20~30Hz.
The mixed detailed process is not particularly limited in the present invention, with mixed process well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, with
It is uniformly mixed into preferred embodiment, the present invention is to further increase Compound Degree, guarantees the evenly dispersed of graphite alkenes material, described
Mixed specific steps, i.e. step A) it is particularly preferred as:
Glass flake is slowly added into the graphite alkenes material solution after dispersion, while uniformly mixing, is obtained
Mixture.
The design parameter being slowly added to is not particularly limited in the present invention, with well known to those skilled in the art slow
The addition speed of addition, those skilled in the art can according to practical condition, product requirement and quality requirement into
Row selection and adjustment.
The mixed mode is not particularly limited in the present invention, is with hybrid mode well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright mixing preferably includes to be stirred.
The mixed time is not particularly limited in the present invention, is with incorporation time well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright mixed time is preferably 10~60min, more preferably 20~50min, most preferably 30~40min.
The design parameter being stirred is not particularly limited in the present invention, with mixing well known to those skilled in the art
Parameter, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the revolving speed of the present invention being stirred is preferably 200~1000rpm, more preferably 300~900rpm, more preferably
400~800rpm, more preferably 500~700rpm, most preferably 350~500rpm.
Then mixture that the present invention obtains above-mentioned steps is after drying, then is ground, and solid powder is obtained.
The temperature of the drying is not particularly limited in the present invention, and the temperature with drying well known to those skilled in the art is
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
Bright is preferably graphene and glass flake to be combined closely, and improve the dispersing uniformity of graphene, the temperature of the drying
Preferably 50~100 DEG C, more preferably 60~90 DEG C, most preferably 70~80 DEG C.
The time of the drying is not particularly limited in the present invention, is with drying time well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
Bright is preferably graphene and glass flake to be combined closely, and improve the dispersing uniformity of graphene, the time of the drying
Preferably 60~120min, more preferably 70~110min, most preferably 80~100min.
The present invention is preferably to improve the dispersing uniformity of graphene, complete and selection process process, before the drying
It is also preferable to include filter step.
The specific method and parameter of the suction filtration is not particularly limited in the present invention, with pumping well known to those skilled in the art
Filtering method and parameter, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment.
The specific method of the grinding is not particularly limited in the present invention, with grinding method well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
Invention improves the dispersing uniformity of graphene for preferably graphene and glass flake are combined closely, and the grinding is preferred
For ball milling.
The time of the grinding is not particularly limited in the present invention, is with milling time well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
Bright is preferably graphene and glass flake to be combined closely, and improve the dispersing uniformity of graphene, the time of the grinding
Preferably 10~180min, more preferably 30~160min, more preferably 50~140min, most preferably 70~120min, tool
Body can be 30min.
The revolving speed of the grinding is not particularly limited in the present invention, is with grinding revolving speed well known to those skilled in the art
Can, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
Bright is preferably graphene and glass flake to be combined closely, and improve the dispersing uniformity of graphene, the revolving speed of the grinding
Preferably 200~500r/s, more preferably 250~450r/s, most preferably 300~400r/s.
It is multiple to obtain glass flake/graphene after Overheating Treatment for the solid powder that the present invention finally obtains above-mentioned steps
Condensation material.
The concrete mode of the heat treatment is not particularly limited in the present invention, with heat treatment well known to those skilled in the art
Mode, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, the present invention is preferably graphene and glass flake to be combined closely, and improve the dispersing uniformity of graphene, at the heat
The concrete mode of reason is preferably calcined.
The time of the heat treatment is not particularly limited in the present invention, with heat treatment time well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
Invention improves the dispersing uniformity of graphene for preferably graphene and glass flake are combined closely, the heat treatment
Soaking time, i.e. constant temperature time are preferably 60~180min, more preferably 80~160min, more preferably 100~140min, most
Preferably 110~130min.
The temperature of the heat treatment is not particularly limited in the present invention, with heat treatment temperature well known to those skilled in the art
, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
Invention improves the dispersing uniformity of graphene for preferably graphene and glass flake are combined closely, the heat treatment
Temperature is preferably 200~380 DEG C, more preferably 240~340 DEG C, most preferably 280~300 DEG C.
The heating rate of the heat treatment is not particularly limited in the present invention, with heat treatment well known to those skilled in the art
Heating rate, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the present invention is preferably graphene and glass flake to be combined closely, and improve the dispersing uniformity of graphene, described
The heating rate of heat treatment is preferably 5~10 DEG C/min, more preferably 6~9 DEG C/min, most preferably 7~8 DEG C/min.
The present invention is to improve glass flake/graphene composite material electric conductivity and stability, in numerous influence factors
In, start with from the compound tightness degree of composite material, in all multi-methods, creative selection is dry, grind and heat treatment is forged
The mode burnt etc., and further preferred specific reaction step and parameter, to obtain that there is satisfactory electrical conductivity and stabilization
Glass flake/graphene composite material of property.
Above-mentioned steps of the present invention provide a kind of glass flake/graphene composite material and preparation method thereof.The present invention will
Graphite alkenes material (graphene and its derivative) and glass flake progress are compound, are formed and stablize composite construction, it can be achieved that graphite
Alkene surface is uniformly distributed, and effectively graphene sheet layer is prevented to reunite, is substantially increased the conductivity of glass flake, obtained a kind of tool
There is glass flake/graphene composite material of superior electrical conductivity energy, makes efficient conductive filler, fundamentally solve stone
Black alkene mixes non-uniform disadvantage in solution or later period application, can guarantee the evenly dispersed of graphene, and by graphene
Coated on glass flake surface, it is ensured that the tiled state of graphene reduces fold, preferably plays its performance, thus will place
Particle after reason is added in practical application, can well solve graphene dispersion problem, guarantees the perfection of its excellent performance
It plays, not only there is excellent electric conductivity using its glass flake conductive coating prepared, while also effectively improving corrosion resistant
Corrosion energy.
The present invention has abandoned traditional preparation method, and graphene is successfully compounded in foliated glass squama by easy method
Piece surface, it is creative by the way of dry, grinding and heat treatment calcining, make graphite by controlling process sequence and parameter etc.
Alkene is coated uniformly on glass flake surface, so that graphene and micron-sized glass flake are closely linked, it can not only
Enough effective solution graphene dispersion problem of non-uniform, preferably play its excellent performance, and can also be obtain a uniformly coated stone
The glass flake of black alkene material makes graphene become a reality the evenly dispersed coating of glass flake.And the present invention is being not necessarily to
Under the conditions of protective gas or reducing gas is existing, above-mentioned heat treatment process is carried out, endangers reducing agent without using hydrazine hydrate is contour,
Any reduction process is not needed, environmental pollution is not only avoided, but also simplifies production procedure, production equipment and reduces life yet
Produce consumption.Preparation method simple process provided by the invention, mild condition, safety and environmental protection, are more suitable technology mass production.
The experimental results showed that the effective compound of graphene and glass flake may be implemented in preparation method provided by the invention,
Effectively graphene sheet layer is prevented to reunite, substantially increases the conductivity of glass flake, volume resistivity is up to 152.75 Ω
Cm, meanwhile, the addition of graphene influences its Corrosion Protection, and testing neutral salt-fog resistant time is to reach as high as 1200h.
In order to further illustrate the present invention, with reference to embodiments to a kind of glass flake/graphene provided by the invention
Composite material and preparation method is described in detail, but it is to be understood that these embodiments are with technical solution of the present invention
Premised under implemented, the detailed implementation method and specific operation process are given, only be further illustrate the present invention
Feature and advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following implementation
Example.
Embodiment 1
One, the graphene solution that Shandong Ou Bo new material Co., Ltd produces is dissolved in ethyl alcohol to (mass fraction is
5 ‰), ultrasound and stirs 30min under room temperature and obtains graphene dispersion solution；
Two, 400 mesh glass flakes are added to graphene dispersion solution obtained in step 1 (graphene ratio is
2.5 ‰), persistently stirs 60min, obtains mixed solution；
Three, it filters mixed solution obtained in step 2 to obtain filter cake, is placed in oven drying 60min, drying temperature is
80 DEG C, obtain solid powder 1；
Four, solid powder 1 obtained in step 3 is subjected to low speed ball milling, ball milling speed 300r/s, Ball-milling Time is
30min obtains solid powder 2；
Five, solid powder 2 obtained in step 4 is placed in Muffle furnace, heats up and is kept for a period of time, obtained compound
Electro-conductive glass scale.Wherein, calcination temperature is 300 DEG C, soaking time 120min.
Referring to fig. 2, Fig. 2 is the preparation process flow schematic diagram that the embodiment of the present invention 1 provides.
Glass flake/the graphene composite material prepared to the embodiment of the present invention 1 characterizes.
Referring to Fig. 1, Fig. 1 be glass flake/graphene composite material optical imagery figure prepared by the embodiment of the present invention 1 and
Raman image figure.
In Fig. 1, left side is optical imagery figure, and right side is the Raman image figure of composite material, and shade and graphene are special
It levies peak (peak D and the peak G) to be positively correlated, as shown in Figure 1, glass flake composite graphite alkene material has successfully been prepared in the present embodiment.
It is that glass flake/graphene composite material scanning electron microscope prepared by the embodiment of the present invention 1 is shone referring to Fig. 3, Fig. 3
Piece.
From the figure 3, it may be seen that the surface for being supported on piece type glass flake of graphene uniform.
Glass flake/the graphene composite material prepared to the embodiment of the present invention 1 detects, and prepares expoxy glass squama
Simultaneously appropriate solvent is added in piece coating, is sufficiently stirred, and carbon steel sheet is sprayed after mixing and carries out neutral salt spray resistance experiment test.
Referring to table 1, table 1 is glass flake/graphene composite material electric conductivity data of preparation of the embodiment of the present invention
With apply data.
As shown in Table 1, the powdered product that the embodiment of the present invention 1 obtains, measuring volume resistivity is 152.75 Ω cm, is surveyed
Trying its neutral salt-fog resistant time is 1200h.
Embodiment 2
One, the graphene solution that Shandong Ou Bo new material Co., Ltd produces is dissolved in ethyl alcohol to (mass fraction is
3 ‰), ultrasound and stirs 20min under room temperature and obtains graphene dispersion solution；
Two, 500 mesh glass flakes are added to graphene dispersion solution obtained in step 1 (graphene ratio is
1.5 ‰), persistently stirs 30min, obtains mixed solution；
Three, it filters mixed solution obtained in step 2 to obtain filter cake, is placed in oven drying 40min, drying temperature is
60 DEG C, obtain solid powder 1；
Four, solid powder 1 obtained in step 3 is subjected to low speed ball milling, ball milling speed 400r/s, Ball-milling Time is
120min obtains solid powder 2；
Five, solid powder 2 obtained in step 4 is placed in Muffle furnace, heats up and is kept for a period of time, obtained compound
Electro-conductive glass scale.Wherein, calcination temperature is 350 DEG C, soaking time 60min.
Glass flake/the graphene composite material prepared to the embodiment of the present invention 2 detects, and prepares expoxy glass squama
Simultaneously appropriate solvent is added in piece coating, is sufficiently stirred, and carbon steel sheet is sprayed after mixing and carries out neutral salt spray resistance experiment test.
Referring to table 1, table 1 is glass flake/graphene composite material electric conductivity data of preparation of the embodiment of the present invention
With apply data.
As shown in Table 1, the powdered product that the embodiment of the present invention 2 obtains, measuring volume resistivity is 196.23 Ω cm, is surveyed
Trying its neutral salt-fog resistant time is 860h.
Embodiment 3
One, graphene solution is dissolved in ethyl alcohol (mass fraction is 3 ‰), ultrasound and stirs 20min under room temperature and obtain
Graphene dispersion solution；
Two, 800 mesh glass flakes (graphene ratio is 5%) is added to graphene dispersion solution obtained in step 1,
30min is persistently stirred, mixed solution is obtained；
Three, it filters mixed solution obtained in step 2 to obtain filter cake, is placed in oven drying 120min, drying temperature is
60 DEG C, obtain solid powder 1；
Four, solid powder 1 obtained in step 3 is subjected to low speed ball milling, ball milling speed 500r/s, Ball-milling Time is
32min obtains solid powder 2；
Five, solid powder 2 obtained in step 4 is placed in Muffle furnace, heats up and is kept for a period of time, obtained compound
Electro-conductive glass scale.Wherein, calcination temperature is 250 DEG C, soaking time 120min.
Glass flake/the graphene composite material prepared to the embodiment of the present invention 3 detects, and prepares expoxy glass squama
Simultaneously appropriate solvent is added in piece coating, is sufficiently stirred, and carbon steel sheet is sprayed after mixing and carries out neutral salt spray resistance experiment test.
Referring to table 1, table 1 is glass flake/graphene composite material electric conductivity data of preparation of the embodiment of the present invention
With apply data.
As shown in Table 1, the powdered product that the embodiment of the present invention 3 obtains, measuring volume resistivity is 222.73 Ω cm, is surveyed
Trying its neutral salt-fog resistant time is 940h.
Embodiment 4
One, the graphene solution that Shandong Ou Bo new material Co., Ltd produces is dissolved in the water (mass fraction is 2 ‰),
It ultrasound and stirs 20min under room temperature and obtains graphene dispersion solution；
Two, 200 mesh glass flakes are added to graphene dispersion solution obtained in step 1 (graphene ratio is
0.5 ‰), persistently stirs 10min, obtains mixed solution；
Three, it filters mixed solution obtained in step 2 to obtain filter cake, is placed in oven drying 70min, drying temperature is
40 DEG C, obtain solid powder 1；
Four, solid powder 1 obtained in step 3 is subjected to low speed ball milling, ball milling speed 180r/s, Ball-milling Time is
72min obtains solid powder 2；
Five, solid powder 2 obtained in step 4 is placed in Muffle furnace, heats up and is kept for a period of time, obtained compound
Electro-conductive glass scale.Wherein, calcination temperature is 210 DEG C, soaking time 70min.
Glass flake/the graphene composite material prepared to the embodiment of the present invention 4 detects, and prepares expoxy glass squama
Simultaneously appropriate solvent is added in piece coating, is sufficiently stirred, and carbon steel sheet is sprayed after mixing and carries out neutral salt spray resistance experiment test.
Referring to table 1, table 1 is glass flake/graphene composite material electric conductivity data of preparation of the embodiment of the present invention
With apply data.
As shown in Table 1, the powdered product that the embodiment of the present invention 3 obtains, measuring volume resistivity is 287.66 Ω cm, is surveyed
Trying its neutral salt-fog resistant time is 770h.
Table 1
A kind of glass flake/graphene conductive composite material provided by the invention and preparation method thereof has been carried out in detail above
Thin introduction, used herein a specific example illustrates the principle and implementation of the invention, above embodiments
Illustrate to be merely used to help understand method and its core concept of the invention, including best mode, and but also this field
Any technical staff can practice the present invention, including any device or system of manufacture and use, and implement the side of any combination
Method.It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, may be used also
With several improvements and modifications are made to the present invention, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The range of the invention patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other realities
Apply example.If these other embodiments, which have, is not different from the structural element of claim character express, or if they
Equivalent structural elements including the character express with claim without essence difference, then these other embodiments should also be included in
In the scope of the claims.
Claims (10)
1. a kind of glass flake/graphene composite material, which is characterized in that including glass flake；
And it is compounded in the graphite alkenes material on the glass flake surface.
2. composite material according to claim 1, which is characterized in that the piece diameter of the glass flake is 50~800 mesh；
The piece diameter of the graphite alkenes material is 10~30 μm.
3. composite material according to claim 1, which is characterized in that the graphite alkenes material includes graphene, oxidation
One of graphene, redox graphene and modified graphene are a variety of.
4. composite material according to claim 1, which is characterized in that the graphite alkenes material accounts for the glass flake
Mass ratio is 0.01%~5%.
5. a kind of preparation method of glass flake/graphene composite material, which comprises the following steps:
A after) mixing graphite alkenes material solution and glass flake, mixture is obtained；
B) mixture for obtaining above-mentioned steps is after drying, then is ground, and solid powder is obtained；
C) solid powder for obtaining above-mentioned steps obtains glass flake/graphene composite material after Overheating Treatment.
6. preparation method according to claim 1, which is characterized in that the graphite alkenes material solution is after dispersion
Graphite alkenes material solution；
The mass fraction of the graphite alkenes material solution is 0.5 ‰~5 ‰.
7. preparation method according to claim 6, which is characterized in that described to be separated into ultrasonic disperse；
The time of the dispersion is 10~60min；
The frequency of the ultrasound is 10~40Hz；
The mixed time is 10~60min.
8. preparation method according to claim 1, which is characterized in that the time of the drying is 60~120min；
The temperature of the drying is 50~100 DEG C；
It further include filtering step before the drying.
9. preparation method according to claim 1, which is characterized in that the time of the grinding is 10~180min；
The revolving speed of the grinding is 200~500r/s.
10. preparation method according to claim 1, which is characterized in that the temperature of the heat treatment is 200~380 DEG C；
The soaking time of the heat treatment is 60~180min；
The heating rate of the heat treatment is 5~10 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710571819.7A CN109251572B (en) | 2017-07-13 | 2017-07-13 | Glass flake/graphene conductive composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710571819.7A CN109251572B (en) | 2017-07-13 | 2017-07-13 | Glass flake/graphene conductive composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109251572A true CN109251572A (en) | 2019-01-22 |
| CN109251572B CN109251572B (en) | 2021-05-18 |
Family
ID=65051707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710571819.7A Active CN109251572B (en) | 2017-07-13 | 2017-07-13 | Glass flake/graphene conductive composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109251572B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI690113B (en) * | 2019-05-13 | 2020-04-01 | 國家中山科學研究院 | Method for manufacturing ternary cathode material |
| WO2020245570A1 (en) * | 2019-06-05 | 2020-12-10 | Silberline Limited | New product comprising coated substrate particles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105219219A (en) * | 2015-10-19 | 2016-01-06 | 国网浙江省电力公司湖州供电公司 | A kind of novel wear resistant, protection against corrosion, Antistatic Paint and preparation method thereof |
| CN105623466A (en) * | 2014-11-28 | 2016-06-01 | 中国科学院金属研究所 | High-conductivity heavy anti-corrosion coating and preparation method therefor |
| CN106746688A (en) * | 2017-03-22 | 2017-05-31 | 西北大学 | A kind of lead-free glass powder based on graphene modified and preparation method thereof and electric slurry |
-
2017
- 2017-07-13 CN CN201710571819.7A patent/CN109251572B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623466A (en) * | 2014-11-28 | 2016-06-01 | 中国科学院金属研究所 | High-conductivity heavy anti-corrosion coating and preparation method therefor |
| CN105219219A (en) * | 2015-10-19 | 2016-01-06 | 国网浙江省电力公司湖州供电公司 | A kind of novel wear resistant, protection against corrosion, Antistatic Paint and preparation method thereof |
| CN106746688A (en) * | 2017-03-22 | 2017-05-31 | 西北大学 | A kind of lead-free glass powder based on graphene modified and preparation method thereof and electric slurry |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI690113B (en) * | 2019-05-13 | 2020-04-01 | 國家中山科學研究院 | Method for manufacturing ternary cathode material |
| WO2020245570A1 (en) * | 2019-06-05 | 2020-12-10 | Silberline Limited | New product comprising coated substrate particles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109251572B (en) | 2021-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6933699B2 (en) | Method of surface modification of submicron silicon fine powder | |
| CN105017831B (en) | Water-based electric heating nano paint composition and coating and its preparation method and application | |
| CN104087093B (en) | A kind of for LED lamp heat radiation coating and preparation method thereof | |
| WO2017016079A1 (en) | Method for synthesizing high-purity ultrafine zrc-sic composite powder | |
| CN106634264B (en) | Graphene enhances super-hydrophobic finish and preparation method thereof | |
| CN109251572A (en) | A kind of glass flake/graphene conductive composite material and preparation method thereof | |
| JP6828514B2 (en) | Heat ray shielding fine particles, heat ray shielding fine particle dispersion liquid, coating liquid for heat ray shielding film, and heat ray shielding film using these, heat ray shielding resin film, heat ray shielding fine particle dispersion | |
| CN103193513B (en) | Coating method of silicon carbide ceramic membrane for high-temperature filtration | |
| CN110628264B (en) | Preparation method of graphene far-infrared additive and far-infrared slurry | |
| CN105331207B (en) | A kind of heat insulation extra-high voltage anti-flaming dope and preparation method thereof | |
| CN110256961A (en) | Electric-heating coatings and its preparation method and application, electro-thermal coatings and electrothermal device | |
| CN109280425A (en) | A kind of preparation method of floor heating electric hot plate | |
| CN109181469A (en) | The preparation method of graphene-based-aqueous epoxy resins composite anti-corrosive coating solution | |
| US20230182098A1 (en) | Composition and process for pelletizing carbon-based materials for proppant and industrial applications | |
| CN103922713B (en) | A kind of lightweight dichroite-mullite composite ceramic material and preparation method thereof | |
| CN109251558B (en) | Mica powder/graphene conductive composite material and preparation method thereof | |
| CN111393874A (en) | Method for producing high-temperature-resistant zirconium iron red pigment by electrically melting zirconia | |
| CN208853701U (en) | A kind of preparation facilities of graphene aluminium alloy powder | |
| CN104944454A (en) | Granularity-controllable boehmite preparation method | |
| CN111849275B (en) | Preparation method and application of water-based two-component electric heating coating | |
| CN109233398A (en) | A kind of heavy antisepsis dry powder paint special graphite alkene masterbatch and preparation method | |
| Gubernat et al. | Thermomechanical characterisation of coal tar pitch-based carbon containing SiC nanoparticles | |
| CN103359764B (en) | Preparation method of sheet-shaped alpha-aluminium oxide | |
| CN108574998B (en) | Carbon far infrared radiation electric heating plate and preparation method thereof | |
| CN112980256A (en) | Multi-dimensional composite hydrophobic coating and preparation process thereof |
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 |