CN109251558B - Mica powder/graphene conductive composite material and preparation method thereof - Google Patents
Mica powder/graphene conductive composite material and preparation method thereof Download PDFInfo
- Publication number
- CN109251558B CN109251558B CN201710571831.8A CN201710571831A CN109251558B CN 109251558 B CN109251558 B CN 109251558B CN 201710571831 A CN201710571831 A CN 201710571831A CN 109251558 B CN109251558 B CN 109251558B
- Authority
- CN
- China
- Prior art keywords
- graphene
- mica powder
- composite material
- powder
- heat treatment
- 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.)
- Active
Links
Images
Classifications
-
- 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
- C09C1/40—Compounds of aluminium
-
- 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
- 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
- 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
Abstract
The invention provides a mica powder/graphene composite material, which comprises mica powder; and graphene materials compounded on the surface of the mica powder. According to the invention, the graphene material (graphene and derivatives thereof) and the mica powder are compounded to form a stable composite structure, so that the graphene surface can be uniformly distributed, the graphene lamellar agglomeration is effectively prevented, the conductivity of the mica powder is greatly improved, and the mica powder/graphene composite material with excellent conductivity is obtained, so that the mica powder/graphene composite material becomes an efficient conductive filler, the conductivity of subsequent coating application can be improved, and the corrosion resistance is effectively improved. According to the invention, the graphene is successfully compounded on the surface of the mica powder by a simple method, and a high-hazard reducing agent such as hydrazine hydrate is not used, so that the environmental pollution is avoided, the process is simpler, the condition is mild, the method is safe and environment-friendly, and the method is more suitable for industrialized mass production.
Description
Technical Field
The invention belongs to the technical field of conductive composite materials, relates to a mica powder/graphene composite material and a preparation method thereof, and particularly relates to a mica powder/graphene conductive composite material and a preparation method thereof.
Background
The mica powder is a non-metallic mineral, belonging to monoclinic crystal, and its crystal is scaly and has silk luster (white mica powder isGlass luster), pure blocks are gray, purple rose, white and the like, and the ratio of diameter to thickness>80, specific gravity of 2.6-2.7, hardness of 2-3, contains multiple components, wherein SiO is mainly contained2The content is about 49% in general, and Al2O3The content is about 30 percent. The mica powder has the characteristics of good elasticity, toughness, sliding property, insulativity, high temperature resistance, acid and alkali resistance, corrosion resistance, strong adhesive force, heat resistance, sound insulation, small thermal expansion coefficient and the like, is one of important functional fillers in modern industry, and can improve the mechanical strength, enhance the toughness, the adhesive force, the ageing resistance, the corrosion resistance and the like. In addition, the mica powder has chemical composition, structure and structure similar to those of kaolin, and has certain characteristics of clay minerals, namely good dispersion and suspension properties in aqueous medium and organic solvent, white color, fine particles, viscosity and the like. Therefore, the mica powder has the characteristics of both mica minerals and clay minerals, and is widely applied to industries such as electric appliances, welding electrodes, rubber, plastics, papermaking, paint, coating, pigment, ceramics, cosmetics, novel building materials and the like.
Most of the polymer materials are widely used as housings of electronic instruments and meters and surface coating materials of space shuttles and missiles nowadays due to their excellent processability and insulation properties. However, a polymer material having high insulation property is likely to generate and accumulate static electricity when its surface is rubbed or impacted. The static electricity accumulated on the surface of the product is hard to purify due to serious dust absorption, so that the appearance of the product is influenced and the product is applied to an ultra-clean environment (such as an operating room, a computer room, a precision instrument and the like), and particularly, when the static electricity is accumulated to a certain degree, the static electricity can be generated to discharge, various precision instruments and precision electronic components can be broken down to be scrapped, and even inflammable and explosive substances can be ignited or exploded, so that huge malignant accidents can be caused. Therefore, the preparation of conductive coatings from conductive fillers and the brush application on the surface of electronic devices are effective ways to solve the above problems.
Just because the mica powder has such many characteristics, with the continuous development of science and technology, new application fields are continuously developed, and the field of the conductive filler is one of the fields. Although mica powder has insulation property, the conductive property can be realized by compounding the conductive material. The composite conductive mica is a cheap and light material, i.e. mica is used as a substrate or a core material, and one or more layers of conductive substances (such as metal and the like) with good chemical stability, strong corrosion resistance and high conductivity are coated on the surface of the mica to obtain the conductive composite material. The composite conductive mica has the advantages of small specific gravity, good conductivity, adjustable color, rich raw materials, low price and the like, and has partial characteristics of mica, so the composite conductive mica is generally regarded as important in related application fields.
The traditional composite conductive mica powder is mainly a composite material obtained by adding a conductive carbon material and coating one or more layers of conductive substances with good chemical stability, strong corrosion resistance and high conductivity on the surface by a chemical plating method. The prior art adopts the traditional chemical plating method, which not only has complicated process, but also has great pollution to the environment because of adopting a great deal of heavy metal salt solution such as heavy metal nickel salt, copper salt or chromium salt to carry out chemical plating. Although it has been reported in recent years that graphene materials or carbon nanotubes are used for compounding, chemical reduction and complex post-treatment steps are still required, so that the process is complex, the cost is high, the industrial mass production is not facilitated, and meanwhile, the conductivity of the composite mica powder is weak, and the increasing requirements of downstream industries cannot be met.
Therefore, how to find the composite mica powder with better conductivity, and the preparation method is simple and easy to implement and free of pollution, which becomes one of the important problems to be solved urgently in a plurality of manufacturers and downstream application fields.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a mica powder/graphene composite material and a preparation method thereof, wherein the mica powder/graphene provided by the present invention has good electrical conductivity, and the preparation method is simple and easy, and is suitable for large-scale industrial production.
The invention provides a preparation method of a mica powder/graphene composite material, which comprises the following steps:
A) mixing the graphene material solution and mica powder to obtain a mixture;
B) drying the mixture obtained in the step, and then grinding to obtain solid powder;
C) and (3) carrying out heat treatment on the solid powder obtained in the step to obtain the mica powder/graphene composite material.
Preferably, the graphene-based material solution is a dispersed graphene-based material solution.
Preferably, the mass fraction of the graphene material solution is 0.5-5 per mill;
the dispersion is ultrasonic stirring dispersion.
Preferably, the dispersing time is 10-60 min;
the frequency of the ultrasonic wave is 20-60 Hz.
Preferably, the particle size of the mica powder is 50-800 meshes;
the sheet diameter of the graphene material is 10-30 mu m.
Preferably, the graphene-based material comprises one or more of graphene, graphene oxide, reduced graphene oxide and modified graphene;
the mixing time is 10-60 min.
Preferably, the graphene material accounts for 0.01-5% of the mica powder by mass.
Preferably, the drying time is 60-120 min;
the drying temperature is 50-100 ℃;
and a suction filtration step is also included before the drying.
Preferably, the grinding time is 10-180 min;
the rotation speed of the grinding is 200-500 r/s.
Preferably, the temperature of the heat treatment is 200-380 ℃;
the heat preservation time of the heat treatment is 60-180 min;
the heating rate of the heat treatment is 1-10 ℃/min.
The invention provides a preparation method of a mica powder/graphene composite material, which comprises the following steps of firstly, mixing a graphene material solution with mica powder to obtain a mixture; then drying the mixture obtained in the step, and then grinding to obtain solid powder; and finally, carrying out heat treatment on the solid powder obtained in the step to obtain the mica powder/graphene composite material. Compared with the prior art, the invention aims at the problems that the traditional chemical plating process of the conductive composite mica powder has complicated process, causes great pollution to the environment and has weaker conductivity; or in the later paint mixing process, the direct addition of the conductive material can change the performance of the material, and the conductive paint is difficult to adapt to the requirements of the conductive paint and the like. According to the invention, the graphene material (graphene and derivatives thereof) and the mica powder are compounded to form a stable composite structure, so that the graphene surface can be uniformly distributed, the graphene lamellar layer agglomeration is effectively prevented, the conductivity of the mica powder is greatly improved, and the mica powder/graphene composite material with excellent conductivity is obtained and becomes an efficient conductive filler. The method abandons the traditional preparation method, successfully compounds the graphene on the surface of the flake mica powder by a simple method, does not use a high-hazard reducing agent such as hydrazine hydrate and the like, does not need any reduction process, avoids environmental pollution, has simpler process, and has excellent electrical conductivity and effectively improved corrosion resistance.
Experimental results show that the preparation method provided by the invention can realize effective compounding of graphene and mica powder, effectively prevent graphene sheets from agglomerating, greatly improve the conductivity of the mica powder and enable the volume resistivity to reach 87.66 omega cm.
Drawings
Fig. 1 is an optical image and a raman image of the mica powder/graphene oxide composite prepared in example 1 of the present invention;
FIG. 2 is a simplified flow chart of a preparation process provided in example 1 of the present invention;
fig. 3 is a scanning electron microscope photograph of the mica powder/graphene oxide composite material prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably adopts a conventional purity used in the field of analytical purification or graphene composite materials.
The invention provides a preparation method of a mica powder/graphene composite material, which comprises the following steps:
A) mixing the graphene material solution and mica powder to obtain a mixture;
B) drying the mixture obtained in the step, and then grinding to obtain solid powder;
C) and (3) carrying out heat treatment on the solid powder obtained in the step to obtain the mica powder/graphene composite material.
The method comprises the steps of firstly mixing a graphene material solution with mica powder to obtain a mixture.
The mica powder is not particularly limited in the invention, and can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and is preferably mica powder for a filler, and more preferably mica powder for a core of a conductive filler.
The specific parameters of the mica powder are not particularly limited, and the conventional parameters of the mica powder known by the technical personnel in the field can be used, and the technical personnel in the field can select and adjust the specific parameters according to the actual production condition, the product requirement and the quality requirement, and the sheet diameter (size) of the mica powder is preferably 50-800 meshes, more preferably 100-700 meshes, more preferably 200-600 meshes, and most preferably 300-500 meshes.
The definition of the graphene-based material is not particularly limited in the present invention, and may be based on the concept of graphene and its derivatives well known to those skilled in the art, and those skilled in the art can select and adjust the concept according to the actual application, product requirements and quality requirements, and the graphene-based material in the present invention, i.e. the concept of graphene in a broad sense, preferably includes one or more of graphene, graphene oxide, reduced graphene oxide and modified graphene, more preferably single-layer graphene, multi-layer graphene, graphene oxide, reduced graphene oxide or modified graphene, and most preferably graphene or graphene oxide.
Specifically, the graphene of the present invention may include a plurality of commercially available types of graphene-based materials, and is preferably one or more of high-quality graphene (patent number: CN 106082198A), graphene oxide (patent number: CN 106115669a) and graphene oxide (CN 106430175a) produced by platinum corporation.
The specific parameters of the graphene are not particularly limited, and may be conventional parameters of graphene known to those skilled in the art, and those skilled in the art may select and adjust the parameters according to actual production conditions, product requirements and quality requirements, and the sheet diameter (size) of the graphene in the present invention is preferably 10 to 30 μm, more preferably 12 to 28 μm, more preferably 15 to 25 μm, and most preferably 18 to 23 μm.
The concentration of the graphene-based material solution is not particularly limited in the present invention, and may be a concentration of the graphene-based material solution known to those skilled in the art, and those skilled in the art may select and adjust the concentration according to actual production conditions, product requirements, and quality requirements, and the mass fraction of the graphene-based material solution in the present invention is preferably 0.5 to 5%, more preferably 1 to 4%, and most preferably 2 to 3%.
The solvent of the graphene-based material solution of the present invention is not particularly limited, and may be a conventional solvent for graphene-based material solutions well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements, and quality requirements, and the solvent of the graphene-based material solution of the present invention is preferably one or more of water, ethanol, acetone, xylene, methyl butanone, isopropanol, and ethyl acetate, more preferably water, ethanol, acetone, xylene, n-butanol, methyl butanone, isopropanol, or ethyl acetate, and even more preferably water, ethanol, acetone, or xylene.
In order to improve the dispersion effect of the subsequent graphene material, the graphene material solution is preferably a dispersed graphene material solution. The dispersion method of the graphene-based material solution is not particularly limited in the present invention, and may be a dispersion method known to those skilled in the art, and those skilled in the art may select and adjust the dispersion method according to actual production conditions, product requirements, and quality requirements, and the dispersion in the present invention is preferably ultrasonic dispersion treatment, and more preferably ultrasonic agitation treatment.
The dispersing time is not particularly limited in the invention, and can be selected and adjusted by a person skilled in the art according to the actual production situation, the product requirements and the quality requirements, and the dispersing time is preferably 10-60 min, more preferably 20-50 min, and most preferably 30-40 min.
The frequency of the ultrasound is not particularly limited, and can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and the frequency of the ultrasound is preferably 20 to 60Hz, more preferably 25 to 55Hz, more preferably 30 to 50Hz, and most preferably 35 to 45 Hz.
According to the invention, preferably through the special dispersing method, steps and conditions, under the condition that no dispersing agent is needed, the graphene material solution, namely the graphene material dispersion liquid, is obtained, has good dispersing performance, overcomes the technical bias that the graphene dispersion liquid in the prior art is poor in performance and cannot be directly applied, and further overcomes the defects that chemical reduction and high-temperature reduction are carried out in the middle and later stages in the prior art, and the reducing agent pollution, high-temperature conditions and the like are not suitable for large-scale industrial popularization.
The specific mixing process is not particularly limited by the present invention, and may be a mixing process known to those skilled in the art, and those skilled in the art may select and adjust the mixing process according to the actual production situation, the product requirement and the quality requirement, and use uniform mixing as a preferred scheme, and in order to further improve the degree of compounding and ensure uniform dispersion of the graphene-based material, the specific mixing step, i.e., step a), is specifically preferably:
and slowly adding the mica powder into the dispersed graphene material solution, and uniformly mixing to obtain a mixture.
The specific parameters of the slow addition are not particularly limited in the present invention, and the slow addition rate known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production situation, product requirements and quality requirements.
The mixing method is not particularly limited by the present invention, and can be a mixing method known to those skilled in the art, and those skilled in the art can select and adjust the mixing method according to the actual production situation, the product requirement and the quality requirement, and the mixing method of the present invention preferably includes stirring mixing.
The mixing time is not particularly limited in the present invention, and the mixing time known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production situation, product requirements and quality requirements, and the mixing time in the present invention is preferably 10 to 60min, more preferably 20 to 50min, and most preferably 30 to 40 min.
The specific parameters of the stirring and mixing are not particularly limited, and the mixing parameters known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production situation, the product requirements and the quality requirements, and the rotation speed of the stirring and mixing in the invention is preferably 200-1000 rpm, more preferably 300-900 rpm, more preferably 400-800 rpm, more preferably 500-700 rpm, and most preferably 350-500 rpm.
According to the invention, the mixture obtained in the step is dried and then ground to obtain solid powder.
The drying temperature is not particularly limited, and can be selected and adjusted according to the actual production situation, the product requirements and the quality requirements, and is preferably 50-100 ℃, more preferably 60-90 ℃, and most preferably 70-80 ℃.
The drying time is not particularly limited, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, the graphene and mica powder are better and tightly combined, the dispersion uniformity of the graphene is improved, and the drying time is preferably 60-120 min, more preferably 70-110 min, and most preferably 80-100 min.
In order to better improve the dispersion uniformity of the graphene, complete and optimal process flow, the method preferably further comprises a suction filtration step before drying.
The invention has no special limitation on the specific method and parameters of the suction filtration, and the suction filtration method and parameters known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production condition, product requirements and quality requirements.
The specific method of the grinding is not particularly limited, and the grinding method known to those skilled in the art can be used, and those skilled in the art can select and adjust the method according to the actual production situation, the product requirements and the quality requirements.
The grinding time is not particularly limited, and the grinding time known by a person skilled in the art can be selected and adjusted by the person skilled in the art according to actual production conditions, product requirements and quality requirements, the method is used for better closely combining graphene and mica powder and improving the dispersion uniformity of the graphene, and the grinding time is preferably 10-180 min, more preferably 30-160 min, more preferably 50-140 min, most preferably 70-120 min, and particularly 30 min.
The grinding rotating speed is not particularly limited, and can be selected and adjusted according to actual production conditions, product requirements and quality requirements, and is preferably 200-500 r/s, more preferably 250-450 r/s, and most preferably 300-400 r/s.
Finally, carrying out heat treatment on the solid powder obtained in the step to obtain the mica powder/graphene composite material.
The specific manner of the heat treatment is not particularly limited, and may be a heat treatment manner known to those skilled in the art, and those skilled in the art may select and adjust the heat treatment manner according to actual production conditions, product requirements, and quality requirements.
The heat treatment time is not particularly limited, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, the heat treatment time is preferably selected to closely combine graphene and mica powder, the dispersion uniformity of the graphene is improved, and the heat preservation time, namely the constant temperature time, of the heat treatment is preferably 60-180 min, more preferably 80-160 min, more preferably 100-140 min, and most preferably 110-130 min.
The temperature of the heat treatment is not particularly limited, and can be selected and adjusted according to the actual production condition, the product requirement and the quality requirement, and the temperature of the heat treatment is preferably 200-380 ℃, more preferably 240-340 ℃, and most preferably 280-300 ℃.
The temperature rise rate of the heat treatment is not particularly limited, and can be selected and adjusted by a person skilled in the art according to the actual production condition, the product requirement and the quality requirement, the graphene and the mica powder are better and tightly combined, the dispersion uniformity of the graphene is improved, and the temperature rise rate of the heat treatment is preferably 1-10 ℃/min, more preferably 2-9 ℃/min, more preferably 4-7 ℃/min, and most preferably 5-6 ℃/min.
The proportion of the graphene material and the mica powder is not particularly limited in the present invention, and may be a conventional proportion known to those skilled in the art, and those skilled in the art can select and adjust the proportion according to the actual application situation, the product requirement and the quality requirement, and the mass ratio of the graphene material in the mica powder in the present invention is preferably 0.01% to 5%, more preferably 0.05% to 4%, more preferably 0.1% to 3%, and most preferably 0.5% to 2%.
In order to improve the conductivity and stability of the mica powder/graphene composite material, starting from the composite compactness of the composite material among a plurality of influencing factors, modes such as drying, grinding, heat treatment and calcination and the like are creatively selected in a plurality of methods, and specific reaction steps and parameters are further optimized, so that the mica powder/graphene composite material with good conductivity and stability is obtained.
The invention provides a mica powder/graphene composite material and a preparation method thereof. The invention compounds the graphene material (graphene and derivatives thereof) and the mica powder to form a stable composite structure, can realize the uniform distribution of the surface of the graphene, effectively prevents graphene sheet layers from agglomerating, greatly improves the conductivity of the mica powder, obtains the mica powder/graphene composite material with excellent conductivity, enables the mica powder/graphene composite material to become efficient conductive filler, fundamentally solves the problem of uneven mixing of the graphene in solution or later application, can ensure the uniform dispersion of the graphene, and coats the graphene on the surface of the mica powder, can ensure the flat laying state of the graphene to reduce folds, better exerts the performance of the graphene, thereby adding the treated particles into practical application, well solving the problem of graphene dispersion, ensuring the perfect exertion of the excellent performance of the graphene, and the mica powder conductive coating prepared by the method has excellent conductivity, meanwhile, the corrosion resistance is effectively improved.
According to the invention, the traditional preparation method is abandoned, graphene is successfully compounded on the surface of flake mica powder by a simple method, the drying, grinding and heat treatment calcining modes are creatively adopted, and the graphene is uniformly coated on the surface of the mica powder by controlling the process sequence, parameters and the like, so that the graphene and micron-sized mica powder are tightly combined together, the problem of non-uniform dispersion of the graphene can be effectively solved, the excellent performance of the graphene can be better exerted, the mica powder uniformly coated with the graphene material can be obtained, and the uniform dispersion coating of the graphene on the mica powder can be realized; particularly, the invention can obtain better conductivity only by using a smaller adding amount; in addition, the invention carries out the heat treatment process without protective gas or reducing gas, does not use high-harm reducing agent such as hydrazine hydrate, high-temperature reducing condition and any reducing process, not only avoids environmental pollution, but also simplifies production flow and production equipment and reduces production consumption. The preparation method provided by the invention has the advantages of simple process, mild conditions, safety and environmental protection, and is more suitable for industrialized production.
Experimental results show that the preparation method provided by the invention can realize effective compounding of graphene and mica powder, effectively prevent graphene sheets from agglomerating, greatly improve the conductivity of the mica powder and enable the volume resistivity to reach 74.55 omega cm.
For further illustration of the present invention, the following will describe in detail a mica powder/graphene composite material and a preparation method thereof with reference to examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific procedures are given, which are only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Firstly, dispersing a graphene oxide solution produced by Shandong Europe platinum New Material Co., Ltd in ethanol (mass fraction is 3 per thousand), performing ultrasound at normal temperature, and stirring for 30min to obtain a graphene oxide dispersion solution;
secondly, adding mica powder (the proportion of the graphene oxide is 2.5 per mill) into the graphene oxide dispersion solution obtained in the step one, and continuously stirring for 60min to obtain a mixed solution;
thirdly, filtering the mixed solution obtained in the second step to obtain a filter cake, and placing the filter cake in an oven for drying for 60min at the drying temperature of 80 ℃ to obtain solid powder 1;
fourthly, performing low-speed ball milling on the solid powder 1 obtained in the third step, wherein the ball milling speed is 280r/s, and the ball milling time is 20min to obtain solid powder 2;
fifthly, placing the solid powder 2 obtained in the fourth step into a muffle furnace, heating and keeping for a period of time to obtain the composite conductive mica powder. Wherein the calcining temperature is 250 ℃, and the heat preservation time is 120 min.
Referring to fig. 2, fig. 2 is a simplified flow chart of the preparation process provided in example 1 of the present invention.
The mica powder/graphene oxide composite material prepared in the embodiment 1 of the invention is characterized.
Referring to fig. 1, fig. 1 is an optical imaging graph and a raman imaging graph of the mica powder/graphene oxide composite material prepared in example 1 of the present invention.
In fig. 1, the left side is an optical imaging graph, the right side is a raman imaging graph of the composite material, and the color depth is positively correlated with the characteristic peaks (D peak and G peak) of graphene, as can be seen from fig. 1, the mica powder composite graphene oxide material is successfully prepared in this embodiment.
Referring to fig. 3, fig. 3 is a scanning electron micrograph of the mica powder/graphene oxide composite material prepared in example 1 of the present invention.
As can be seen from fig. 3, the graphene oxide is uniformly supported on the surface of the sheet-shaped mica powder.
The electrical properties of the mica powder/graphene oxide composite material prepared in the embodiment 1 of the invention are detected.
Referring to table 1, table 1 shows conductivity data of the mica powder/graphene composite material prepared in the embodiment of the present invention.
As can be seen from table 1, the volume resistivity of the mica powder/graphene oxide powder product prepared in this example 1 was 87.66 Ω · cm.
TABLE 1
Example 2
Firstly, dispersing a graphene oxide solution produced by Shandong Europe platinum New Material Co., Ltd in ethanol (mass fraction is 3 per thousand), and performing ultrasonic treatment and stirring at normal temperature for 20min to obtain a graphene oxide dispersion solution;
secondly, adding mica powder (the proportion of the graphene oxide is 1 per mill) into the graphene oxide dispersion solution obtained in the step one, and continuously stirring for 30min to obtain a mixed solution;
thirdly, filtering the mixed solution obtained in the second step to obtain a filter cake, and drying the filter cake in an oven for 40min at the drying temperature of 60 ℃ to obtain solid powder 1;
fourthly, performing low-speed ball milling on the solid powder 1 obtained in the third step, wherein the ball milling speed is 300r/s, and the ball milling time is 120min to obtain solid powder 2;
fifthly, placing the solid powder 2 obtained in the fourth step into a muffle furnace, heating and keeping for a period of time to obtain the composite conductive mica powder. Wherein the calcining temperature is 350 ℃, and the heat preservation time is 90 min.
The electrical properties of the mica powder/graphene oxide composite material prepared in embodiment 2 of the invention are detected.
Referring to table 1, table 1 shows conductivity data of the mica powder/graphene composite material prepared in the embodiment of the present invention.
As can be seen from table 1, the volume resistivity of the mica powder/graphene oxide powder product prepared in this example 1 is 178.53 Ω · cm.
Example 3
Firstly, dispersing a graphene oxide solution in ethanol (the mass fraction is 3 per thousand), and performing ultrasonic treatment and stirring at normal temperature for 20min to obtain a graphene oxide dispersion solution;
secondly, adding mica powder (the proportion of the graphene oxide is 5%) into the graphene oxide dispersion solution obtained in the step one, and continuously stirring for 30min to obtain a mixed solution;
thirdly, filtering the mixed solution obtained in the second step to obtain a filter cake, and placing the filter cake in an oven for drying for 120min at the drying temperature of 60 ℃ to obtain solid powder 1;
fourthly, performing low-speed ball milling on the solid powder 1 obtained in the third step, wherein the ball milling speed is 560r/s, and the ball milling time is 40min, so as to obtain solid powder 2;
fifthly, placing the solid powder 2 obtained in the fourth step into a muffle furnace, heating and keeping for a period of time to obtain the composite conductive mica powder. Wherein the calcining temperature is 250 ℃, and the heat preservation time is 120 min.
And (3) detecting the electrical properties of the mica powder/graphene oxide composite material prepared in the embodiment 3 of the invention.
Referring to table 1, table 1 shows conductivity data of the mica powder/graphene composite material prepared in the embodiment of the present invention.
As can be seen from table 1, the volume resistivity of the mica powder/graphene oxide powder product prepared in this example 1 is 112.73 Ω · cm.
Example 4
Firstly, dispersing graphene slurry graphene powder produced by Shandong Europe platinum New Material Co., Ltd in water (mass fraction is 2 per mill), and performing ultrasonic treatment and stirring at normal temperature for 20min to obtain a graphene dispersion solution;
secondly, adding mica powder (the proportion of the graphene is 6 per mill) into the graphene dispersion solution obtained in the step one, and continuously stirring for 10min to obtain a mixed solution;
thirdly, filtering the mixed solution obtained in the second step to obtain a filter cake, and placing the filter cake in an oven for drying for 70min at the drying temperature of 40 ℃ to obtain solid powder 1;
fourthly, performing low-speed ball milling on the solid powder 1 obtained in the third step, wherein the ball milling speed is 180r/s, and the ball milling time is 12min to obtain solid powder 2;
fifthly, placing the solid powder 2 obtained in the fourth step into a muffle furnace, heating and keeping for a period of time to obtain the composite conductive mica powder. Wherein the calcining temperature is 210 ℃, and the heat preservation time is 70 min.
And (3) detecting the electrical properties of the mica powder/graphene composite material prepared in the embodiment 4 of the invention.
Referring to table 1, table 1 shows conductivity data of the mica powder/graphene composite material prepared in the embodiment of the present invention.
As can be seen from table 1, the volume resistivity of the mica powder/graphene powder product prepared in this example 4 was 74.45 Ω · cm.
The above detailed description of the present invention provides a mica powder/graphene conductive composite material and a method for preparing the same, and the principle and embodiments of the present invention are described herein by using specific examples, which are provided only to help understand the method of the present invention and the core idea thereof, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any method in combination. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (7)
1. A preparation method of a mica powder/graphene composite material is characterized by comprising the following steps:
A) mixing the graphene material solution and mica powder to obtain a mixture;
the mass fraction of the graphene material solution is 0.5-5 per mill;
the graphene material solution is dispersed graphene material solution;
the graphene material solution does not contain a dispersing agent;
the mass ratio of the graphene material to the mica powder is 0.01-5%;
the mixing time is 10-60 min;
B) drying the mixture obtained in the step, and then grinding to obtain solid powder;
C) carrying out heat treatment on the solid powder obtained in the step to obtain a mica powder/graphene composite material;
the temperature of the heat treatment is 200-380 ℃;
the heat preservation time of the heat treatment is 60-180 min;
the heating rate of the heat treatment is 1-10 ℃/min.
2. The production method according to claim 1, wherein the dispersion is ultrasonic agitation dispersion.
3. The method according to claim 2, wherein the dispersion time is 10 to 60 min;
the frequency of the ultrasonic wave is 20-60 Hz.
4. The preparation method according to claim 1, wherein the particle size of the mica powder is 50-800 meshes;
the sheet diameter of the graphene material is 10-30 mu m.
5. The production method according to claim 1, wherein the graphene-based material includes graphene and/or modified graphene.
6. The method according to claim 1, wherein the drying time is 60 to 120 min;
the drying temperature is 50-100 ℃;
and a suction filtration step is also included before the drying.
7. The method according to claim 1, wherein the grinding time is 10 to 180 min;
the rotation speed of the grinding is 200-500 r/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710571831.8A CN109251558B (en) | 2017-07-13 | 2017-07-13 | Mica powder/graphene conductive composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710571831.8A CN109251558B (en) | 2017-07-13 | 2017-07-13 | Mica powder/graphene conductive composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109251558A CN109251558A (en) | 2019-01-22 |
| CN109251558B true CN109251558B (en) | 2021-03-23 |
Family
ID=65050580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710571831.8A Active CN109251558B (en) | 2017-07-13 | 2017-07-13 | Mica powder/graphene conductive composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109251558B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201908011D0 (en) * | 2019-06-05 | 2019-07-17 | Silberline Ltd | New product |
| CN114316762A (en) * | 2021-06-30 | 2022-04-12 | 英德市西洲气体有限公司 | Antistatic polyurea material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183353A (en) * | 2011-12-29 | 2013-07-03 | 中国科学院成都有机化学有限公司 | Conductive mica powder and preparation method thereof |
| CN104167258A (en) * | 2014-06-05 | 2014-11-26 | 哈尔滨工程大学 | Method for preparing graphene and diatomite conductive composite material |
| CN104392767A (en) * | 2014-09-30 | 2015-03-04 | 中国科学院上海硅酸盐研究所 | Graphene-based conductive pearlescent pigment and preparation method thereof |
| WO2016091354A1 (en) * | 2014-12-12 | 2016-06-16 | Merck Patent Gmbh | Electrically conductive, colored interference pigments |
| CN105838115A (en) * | 2016-04-27 | 2016-08-10 | 中国科学院上海硅酸盐研究所 | Method for preparing graphene-based conductive pearlescent pigment |
| WO2016162885A1 (en) * | 2015-04-09 | 2016-10-13 | Indian Institute Of Technology Bombay | Process for transferring graphene oxide monolayer sheets on substrates |
| CN106146886A (en) * | 2016-06-30 | 2016-11-23 | 常州第六元素材料科技股份有限公司 | A kind of composite of Graphene intercalation silicate 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 |
| CN106854389A (en) * | 2017-01-11 | 2017-06-16 | 山东欧铂新材料有限公司 | A kind of micaceous iron oxide/graphene oxide composite material and preparation method thereof |
-
2017
- 2017-07-13 CN CN201710571831.8A patent/CN109251558B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183353A (en) * | 2011-12-29 | 2013-07-03 | 中国科学院成都有机化学有限公司 | Conductive mica powder and preparation method thereof |
| CN104167258A (en) * | 2014-06-05 | 2014-11-26 | 哈尔滨工程大学 | Method for preparing graphene and diatomite conductive composite material |
| CN104392767A (en) * | 2014-09-30 | 2015-03-04 | 中国科学院上海硅酸盐研究所 | Graphene-based conductive pearlescent pigment and preparation method thereof |
| WO2016091354A1 (en) * | 2014-12-12 | 2016-06-16 | Merck Patent Gmbh | Electrically conductive, colored interference pigments |
| WO2016162885A1 (en) * | 2015-04-09 | 2016-10-13 | Indian Institute Of Technology Bombay | Process for transferring graphene oxide monolayer sheets on substrates |
| CN105838115A (en) * | 2016-04-27 | 2016-08-10 | 中国科学院上海硅酸盐研究所 | Method for preparing graphene-based conductive pearlescent pigment |
| CN106146886A (en) * | 2016-06-30 | 2016-11-23 | 常州第六元素材料科技股份有限公司 | A kind of composite of Graphene intercalation silicate and preparation method thereof |
| CN106854389A (en) * | 2017-01-11 | 2017-06-16 | 山东欧铂新材料有限公司 | A kind of micaceous iron oxide/graphene oxide composite material 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 |
Non-Patent Citations (3)
| Title |
|---|
| A novel mica-titania@graphene core-shell structured antistatic composite pearlescent pigment;Yan Wang et al.;《Dyes and Pigments》;20160822;197-204 * |
| Tuning Electrical Conductivity of Inorganic Minerals with Carbon Nanomaterials;Anton A. Kovalchuk et al.;《ACS Applied Materials & Interfaces》;20151106;26079-26084 * |
| 云母-石墨烯界面纳米尺度受限水层的湿润-去湿润研究;杨硕等;《核技术》;20160710;第39卷(第07期);1-5 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109251558A (en) | 2019-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105017831B (en) | Water-based electric heating nano paint composition and coating and its preparation method and application | |
| CN108003701B (en) | Far infrared heat conduction slurry and preparation method and application thereof | |
| Fan et al. | Graphene/poly (vinylidene fluoride) composites with high dielectric constant and low percolation threshold | |
| Wang et al. | A novel core-shell silica@ graphene straticulate structured antistatic anticorrosion composite coating | |
| CN104392767A (en) | Graphene-based conductive pearlescent pigment and preparation method thereof | |
| CN109251558B (en) | Mica powder/graphene conductive composite material and preparation method thereof | |
| WO2013099818A1 (en) | Silver fine particles, production process therefor, and conductive paste, conductive membrane and electronic device, containing said silver fine particles | |
| CN109207029A (en) | Conductive coating with strong attachment fastness | |
| Du et al. | Synthesis and characterization of nano-TiO 2/SiO 2-acrylic composite resin | |
| CN110256961A (en) | Electric-heating coatings and its preparation method and application, electro-thermal coatings and electrothermal device | |
| Hu et al. | Preparation and study of hydrophobic silica@ ZSM-5 nanocomposites for multi-functional coating | |
| CN104036875B (en) | Copper composite conductive powder of carbon-coating cladding of graphene-structured and preparation method thereof | |
| Tang et al. | High-temperature-resistant barium strontium titanate@ Ag/poly (arylene ether nitrile) composites with enhanced dielectric performance and high mechanical strength | |
| CN109021620B (en) | High-performance graphene-based conductive pearlescent pigment composite material and preparation method thereof | |
| Zhao et al. | ZrO2 functionalized graphene Oxide/SEBS‐Based nanocomposites for efficient electromagnetic interference shielding applications | |
| CN111849275B (en) | Preparation method and application of water-based two-component electric heating coating | |
| CN109251572B (en) | Glass flake/graphene conductive composite material and preparation method thereof | |
| JP2015160759A (en) | Transparent electroconductive compound oxide fine powder, production method thereof, and transparent electroconductive film | |
| Zhou et al. | Preparation of SiO2 particles with silicone-methoxy groups on surface and its co-curing hydroxyl silicone oil | |
| TWI568781B (en) | Sulfonated polymer/graphene nano-composite material and its preparation method and application | |
| Xu et al. | Surface analysis of stearic acid modification for improving thermal resistant of calcium phosphate coated iron oxide yellow pigments | |
| Qian et al. | Modification of graphene with organic/inorganic silicon‐based materials and its reinforcement on the UV‐curing polyurethane composite coatings | |
| Qian | Functionalized graphene with DOPO based organic/inorganic flame retardants: Preparation and its reinforcements on the flame retardancy of polyurea composites | |
| JP5289077B2 (en) | Acicular tin oxide fine powder and method for producing the same | |
| KR101450380B1 (en) | Enhanced thermal conductivity of nanofluid using reduced graphene oxide by mechanical mixing |
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 |