CN114438367B - Elastic electric contact composite material and preparation method thereof - Google Patents

Elastic electric contact composite material and preparation method thereof Download PDF

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CN114438367B
CN114438367B CN202210070213.6A CN202210070213A CN114438367B CN 114438367 B CN114438367 B CN 114438367B CN 202210070213 A CN202210070213 A CN 202210070213A CN 114438367 B CN114438367 B CN 114438367B
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graphene
composite material
copper
material belt
stainless steel
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CN114438367A (en
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郑鹏
施赞纳
李明学
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Shanghai Yinfei Alloy Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

The application relates to the field of elastic electric contact materials, and particularly discloses an elastic electric contact composite material and a preparation method thereof. The elastic electric contact composite material consists of a graphene reinforced copper material belt and stainless steel material belts fixed on one side or two sides of the graphene reinforced copper material belt; the preparation method of the graphene reinforced copper strip comprises the following steps: a, placing graphene in SnCl 2 Sensitizing in hydrochloric acid solution, cleaning, filtering, and placing in PdCl 2 Activating in a hydrochloric acid solution, and then carrying out surface copper plating to obtain graphene subjected to surface treatment; b, mixing the graphene subjected to surface treatment with copper powder, prepressing, and carrying out vacuum hot-pressing sintering in an inert gas atmosphere to obtain the graphene/copper composite material; the copper powder in the graphene reinforced copper material belt is 99.5-99.9%, and the graphene after surface treatment is 0.1-0.5%. The composite material can replace beryllium copper alloy to be used in an environment with the temperature of more than 200 ℃, and has the advantages of high strength, good elasticity and good conductivity.

Description

Elastic electric contact composite material and preparation method thereof
Technical Field
The application relates to the technical field of elastic electric contact materials, in particular to an elastic electric contact composite material and a preparation method thereof.
Background
Beryllium copper, also known as beryllium bronze, is the "elastic king" of copper alloy, and has mechanical properties such as high strength, hardness, wear resistance, fatigue resistance and the like, and also has properties such as electric conduction, heat conduction, no magnetism, spark resistance and the like. The beryllium copper alloy has wide application in the fields of electricity, electricians, electronics, machinery and the like, and is suitable for manufacturing switch parts, strong contact and similar current-carrying elements, resistance welding clamps, electrode materials, plastic dies, inner sleeves of crystallizers of hydroelectric continuous casting machines and the like.
However, beryllium copper, when used in an environment exceeding 200 ℃, is fatigued with an increase in temperature or an increase in service time, and is significantly reduced in strength and reduced in elasticity. Therefore, there is a need to develop a resilient electrical contact material that can be used at temperatures in excess of 200 ℃ and has comparable performance to beryllium copper.
Disclosure of Invention
In order to research an elastic electric contact material capable of replacing beryllium copper in an environment with the temperature of more than 200 ℃, the application provides an elastic electric contact composite material and a preparation method thereof.
Stainless steel is a metal material which is widely used at present, has good plasticity, toughness, tensile strength, corrosion resistance and other properties, and compared with beryllium copper alloy, the tensile strength of the stainless steel can be improved by about 10 percent, the hardness can be improved by about 18 percent, the melting point can be improved by about 35 percent, the elongation can be doubled, and the price of the stainless steel is low and is far lower than the prices of pure copper and beryllium copper alloy. Therefore, it is very important to develop a composite material which has the properties of stainless steel and copper and can be used in the environment of more than 200 ℃. On the basis, the stainless steel strip and the copper strip are subjected to composite rolling to obtain the stainless steel/copper composite material, the copper strip is further subjected to reinforcement treatment, and the application range of copper is expanded by taking graphene as a reinforcement, so that the strength of the stainless steel/copper composite material is improved. However, the wettability, the interface bonding property and the dispersibility in a copper matrix of graphene are poor, so that in the research process, the inventor also performs surface treatment and modification on graphene, improves the dispersibility of graphene and the compatibility with copper powder, and further improves the comprehensive performance of the stainless steel/copper composite material. Finally, the technical scheme obtained by the inventor is as follows:
in a first aspect, the present application provides an elastic electrical contact composite material, which adopts the following technical scheme:
an elastic electric contact composite material is composed of a graphene reinforced copper material belt and stainless steel material belts fixed on one side or two sides of the graphene reinforced copper material belt;
the preparation method of the graphene reinforced copper material belt comprises the following steps:
a, placing graphene in SnCl 2 Sensitizing in hydrochloric acid solution, cleaning, filtering, and placing in PdCl 2 Activating in hydrochloric acid solution, and then carrying out surface copper plating on the treated graphene to obtain the surface-treated grapheneGraphene;
b, mixing the graphene with the surface treated in the step a with copper powder, prepressing, and then carrying out vacuum hot-pressing sintering under the protection of inert gas atmosphere to obtain a graphene reinforced copper material belt;
in the graphene reinforced copper material belt, the weight percentage of copper powder is 99.5-99.9%, and the weight percentage of graphene after surface treatment is 0.1-0.5%.
Through adopting above-mentioned technical scheme, this application uses graphite alkene as the reinforcement, has improved the intensity of copper material area. In the preparation process of the graphene reinforced copper material belt, the graphene is subjected to surface treatment firstly, the compatibility of the graphene and copper powder is improved, then a prepressing body of the graphene and copper powder is obtained through mixing and prepressing, the uniformity of the material in the hot-pressing sintering process is ensured, the density of the material is improved, and finally gas in the material is reduced through vacuum hot-pressing sintering, so that the graphene reinforced copper material belt with high strength and good elasticity is obtained. Through the selection of the percentage content of the graphene, the strength of the copper material belt is improved on the premise of ensuring the conductivity of the graphene reinforced copper material belt. When the content of the graphene is less than 0.1%, the enhanced effect is not obvious, and when the content of the graphene is more than 0.5%, the conductivity is obviously reduced compared with that of pure copper, and the reason for analyzing the enhanced effect is probably that when the content of the graphene is more, part of the graphene is agglomerated at an interface, the compactness of the material is reduced, and the conductivity is reduced. Further, the stainless steel material belt and the graphene reinforced copper material belt are compositely rolled to obtain the composite material which can be used in the environment with the temperature of more than 200 ℃ and has high strength, high elasticity and high conductivity.
Preferably, in the graphene reinforced copper material belt, the weight percentage of copper powder is 99.7-99.8%, and the weight percentage of graphene after surface treatment is 0.2-0.3%.
By adopting the technical scheme, when the content of the graphene in the graphene reinforced copper material belt is 0.2-0.3%, the obtained elastic electric contact composite material has better electric conductivity and higher tensile strength.
Preferably, the graphene after surface treatment in step b is wet-milled and mixed with copper powder.
Preferably, the wet grinding solvent is ethanol, the grinding ball is a stainless steel grinding ball, the ball-material ratio is 8:1, the rotating speed is 220r/min, and the wet grinding time is 6h.
By adopting the technical scheme, the graphene subjected to surface treatment can be better bonded with the copper powder interface by wet grinding, so that the mixing degree of the graphene and the copper powder is improved, and the heating phenomenon in the wet grinding process can be improved and the heating oxidation of the copper powder is reduced by adopting ethanol as a solvent.
Preferably, in the wet grinding process, grinding is stopped for 10-20 min after each 30-60 min of grinding.
Through adopting above-mentioned technical scheme, along with wet grinding's going on, material temperature constantly risees, when the high temperature, easily makes the copper powder oxidation that generates heat, as above setting, stops grinding after every grinds a period, can make the material temperature reduce, has effectively reduced the probability that the copper powder oxidation that generates heat takes place.
Preferably, in the prepressing process of the step b, the pressure is controlled to be 8-12 MPa, and the prepressing time is 5-10 min.
By adopting the technical scheme, the dispersed powder can be pre-pressed into the block material with a certain shape through pre-pressing, the uniformity of the material in the subsequent hot-pressing sintering process is ensured, the occurrence of overflow of the powder raw material in the hot-pressing process is effectively reduced, and the density of the material is improved.
Preferably, in the vacuum hot-pressing sintering process of the step b, the vacuum degree is controlled to be 30-40 Pa, the temperature is 800-1050 ℃, the pressure is 40-58 MPa, and the sintering is carried out for 20-30 min.
By adopting the technical scheme, in the vacuum hot-pressing sintering process, the pre-pressed block material expands along with the rise of temperature, and gas in the block material is discharged due to the existence of pressure, so that the block material is integrally contracted, the bonding strength between graphene and copper powder is improved, and the compactness and strength of the graphene reinforced copper material belt are further improved.
Preferably, in the vacuum hot pressing sintering process of the step b, the sintering temperature is controlled to be 850-900 ℃.
By adopting the technical scheme, when the sintering temperature is in the range, the obtained elastic electric contact composite material has better mechanical strength. The reason for this analysis may be that when the temperature is below 850 ℃, the diffusion of atoms is slow, and the bond between graphene and copper powder is merely a mechanical bond, resulting in an insignificant increase in mechanical strength. When the temperature is higher than 950 ℃, the crystal grains grow abnormally, and a continuous network structure generated by the copper matrix deforms, so that the relation between copper and graphene is weakened, and the strength of the product is reduced.
Preferably, in the vacuum hot-pressing sintering process of the step b, the heating rate is 80-100 ℃/min.
By adopting the technical scheme, when the heating rate is in the range, the obtained graphene reinforced copper strip has better compactness and higher strength, so that the mechanical properties such as the strength of the elastic electric contact composite material are improved.
Preferably, the elastic electric contact composite material consists of a graphene reinforced copper material belt and a stainless steel material belt fixed on one side of the graphene reinforced copper material belt, wherein the thickness of the stainless steel material belt accounts for 20-90% of the total thickness of the elastic electric contact composite material.
Preferably, the elastic electric contact composite material consists of a graphene reinforced copper material belt and stainless steel material belts fixed on two sides of the graphene reinforced copper material belt, wherein the thickness of the stainless steel material belt on one side accounts for 10-45% of the total thickness of the elastic electric contact composite material.
In a second aspect, the present application provides a method for preparing an elastic electrical contact composite material, which adopts the following technical scheme:
a preparation method of an elastic electric contact composite material comprises the following steps:
s1, rolling a graphene reinforced copper material belt and a stainless steel material belt in a compounding manner to obtain a composite material belt;
s2, performing diffusion heat treatment and softening heat treatment on the composite material belt to obtain a heat-treated composite material belt;
s3, performing straightening, cleaning and drying on the heat-treated composite material belt to obtain the elastic electric contact composite material.
By adopting the technical scheme, the preparation method is simple in preparation process, easy in realization of process conditions, capable of realizing large-scale mechanical production, and capable of stably preparing the elastic electric contact composite material with high strength, good elasticity, good conductivity and uniform size.
In summary, the present application has the following beneficial effects:
1. the elastic electric contact composite material is prepared by compositely rolling the stainless steel material belt and the copper material belt, and the obtained composite material has high strength, high elasticity and high conductivity, still has various high performances when being applied in an environment of more than 200 ℃, and is wide in application range;
2. in the application, the graphene is used as a reinforcement to reinforce the copper material belt, so that the mechanical strength of the copper material belt is further improved, and the performances of the elastic electric contact composite material are improved;
3. according to the application, the mechanical strength and the conductivity of the elastic electric contact composite material are further improved by optimizing the dosage ratio of the graphene subjected to surface treatment to the copper powder.
Drawings
FIG. 1 is a schematic structural view of an elastic electric contact composite material in examples 1 to 16 of the present application;
fig. 2 is a schematic structural view of an elastic electrical contact composite material in example 17 of the present application.
Reference numerals: 1. a stainless steel strip; 2. graphite alkene reinforcing copper material area.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the examples of the present application are commercially available, except for the following specific descriptions:
the graphene is collected from Guangzhou Eimei graphene investment management Limited company, and the purity is more than 97 percent;
the copper powder is obtained from Shanghai Chaowei nanometer science and technology Limited company, model CW-Cu-001;
the stainless steel material belt is 304 stainless steel material belt which is obtained from tin-free Tairaz steel industry Co., ltd;
the pure copper material belt is prepared from nonferrous metal materials of Qianlong in Dongguan city, the purity is more than or equal to 99.9 percent, and the model is ztd053.
Preparation examples
Preparation example 1
A graphene reinforced copper material belt is prepared by the following steps:
a, placing graphene in SnCl with the mass concentration of 20% 2 Hydrochloric acid solution (solute is SnCl) 2 Hydrochloric acid with the solvent concentration of 10 percent by mass), controlling the frequency to be 25KHz, carrying out ultrasonic treatment for 20min, taking out, cleaning with deionized water, filtering, and placing in PdCl with the mass concentration of 20 percent 2 Hydrochloric acid solution (solute PdCl) 2 Hydrochloric acid with the solvent concentration of 10 percent by mass), controlling the frequency to be 20KHz, carrying out ultrasonic treatment for 15min, taking out, cleaning with deionized water, filtering, and adding 25g/L of CuSO 4 、20g/L HCHO、25g/L EDTA-2Na、10g/L NaKC 4 H 4 O 6 Preparing a plating solution according to the proportion of 10g/L NaOH, immersing the treated graphene into the plating solution for surface copper plating, controlling the frequency to be 20KHz, carrying out ultrasonic treatment for 80min, taking out, washing with deionized water, and carrying out vacuum drying to obtain the surface-treated graphene;
b, controlling the rotating speed to be 200r/min, stirring and mixing 0.1kg of the graphene subjected to surface treatment in the step a with 99.9kg of copper powder for 5h, prepressing for 10min at the normal temperature (25 ℃) and under the pressure of 5MPa, controlling the vacuum degree to be 25Pa under the protection of inert gas (nitrogen) atmosphere, heating to 800 ℃ from the normal temperature (25 ℃) at the heating rate of 50 ℃/min, controlling the pressure to be 30MPa, carrying out vacuum hot-pressing sintering for 40min, and cooling to obtain the graphene reinforced copper material belt.
Preparation examples 2 to 5
A graphite alkene reinforcing copper material area, difference with preparation example 1 lies in: the mixing amount of the graphene and the copper powder after the surface treatment in the step b is different, and is specifically shown in the following table.
In preparation examples 1 to 5, the mixing amount of graphene and copper powder after surface treatment:
Figure BDA0003481789580000051
preparation example 6
A graphite alkene reinforcing copper material area, difference with preparation example 3 lies in: and d, wet grinding and mixing the graphene subjected to surface treatment and the copper powder in the step b. In the wet grinding process, the solvent is ethanol, the grinding balls are stainless steel grinding balls, the ball-material ratio is 8:1, the rotating speed is 220r/min, and the continuous wet grinding is carried out for 6 hours.
The inventor discovers that: compared with continuous wet grinding, the intermittent sectional wet grinding can obviously improve the mechanical strength of the finally prepared elastic electric contact composite material. In particular, the wet milling method of stopping milling for 10 to 20min after 30 to 60min of milling is adopted for mixing, so that the performance of the obtained composite material is the best, and the performance difference of the composite material is not obvious within the range, therefore, the preparation example 7 is only used as an example for illustration.
Preparation example 7
A graphite alkene reinforcing copper material area, difference with preparation example 6 lies in: in wet grinding, mixing is carried out by wet grinding for 10min after each 40min of grinding.
The inventor discovers that: in the preparation process of the graphene reinforced copper material belt, the pressure and time of the pre-pressing process and the vacuum degree, temperature, pressure, time and heating rate of the vacuum hot-pressing sintering process can all influence the mechanical strength of the obtained elastic electric contact composite material. Wherein, during prepressing, the pressure is controlled to be 8-12 MPa, and the mechanical strength of the composite material obtained by prepressing for 5-10 min is better; when in vacuum hot-pressing sintering, the vacuum degree is controlled to be 30-40 Pa, the pressure is controlled to be 40-58 MPa, the mechanical strength of the composite material obtained by sintering for 20-30 min is better, and the performance difference of the composite material is not obvious in the range. However, in the vacuum hot press sintering process, the sintering temperature or the temperature rise rate is different, and the difference in mechanical strength of the obtained composite material is significant, as will be described in the following preparation examples 8 to 16.
Preparation example 8
The graphene reinforced copper material belt is different from the preparation example 7 in that: and c, the prepressing condition of the step b is different from the vacuum hot-pressing sintering condition.
In the preparation example, the prepressing process is performed for 8min under the pressure of 10 MPa;
the vacuum hot-pressing sintering process is that under the vacuum degree of 35Pa, the temperature is increased to 800 ℃ from normal temperature (25 ℃) at the heating rate of 50 ℃/min, the pressure is 45MPa, and the vacuum hot-pressing sintering is carried out for 25min.
Preparation examples 9 to 12
A graphite alkene reinforcing copper material area, difference with preparation example 8 lies in: the temperature of the vacuum hot pressing sintering process in the step b is different, and is shown in the following table.
In preparation examples 8 to 12, the temperature during the vacuum hot press sintering was:
Figure BDA0003481789580000061
preparation examples 13 to 16
The graphene reinforced copper material belt is different from the preparation example 10 in that: the heating rates in the vacuum hot pressing sintering process of step b are different, and are shown in the following table.
In preparation examples 10 and 13 to 16, the temperature during the vacuum hot-press sintering process:
Figure BDA0003481789580000062
examples
Example 1
An elastic electric contact composite material comprises a graphene reinforced copper material belt 2 and stainless steel material belts 1 fixed on two sides of the graphene reinforced copper material belt 2, wherein the total thickness is 3mm, and the width is 200mm. During actual production, the thickness of the single-side stainless steel strip 1 can be selected from 10 to 45% of the total thickness, and the thickness of the single-side stainless steel strip 1 in this embodiment accounts for 30% of the total thickness, that is, 0.9mm.
The preparation method of the elastic electric contact composite material comprises the following steps:
s1, rolling the graphene reinforced copper material belt and the stainless steel material belt obtained in the preparation example 1 in a composite mode, wherein the rolling deformation is 50%, and the composite speed is 1.5m/min, so that a composite material belt is obtained;
s2, controlling the gas flow to be 3m in the hydrogen atmosphere 3 H, the temperature is 860 ℃, the speed is 1m/min, the composite material belt is subjected to diffusion heat treatment, and then the gas flow is controlled to be 3m in the hydrogen atmosphere 3 Performing softening heat treatment on the composite material belt at the temperature of 930 ℃ and the speed of 0.6m/min to obtain the heat-treated composite material belt;
s3, performing withdrawal and straightening on the composite material belt subjected to heat treatment, controlling the withdrawal and straightening elongation rate to be 0.3%, and then cleaning and drying to obtain the elastic electric contact composite material.
Examples 2 to 16
An elastic electric contact composite material comprises a graphene reinforced copper material belt 2 and stainless steel material belts 1 fixed on two sides of the graphene reinforced copper material belt 2, wherein the total thickness is 3mm, and the width is 200mm. Wherein, the thickness of the one-side stainless steel material belt 1 accounts for 30 percent of the total thickness, namely 0.9mm.
The preparation method of the elastic electric contact composite material is different from the preparation method of the embodiment 1 in that: the graphene reinforced copper material belt is prepared from preparation examples 2 to 16 respectively.
Example 17
The utility model provides an elasticity electrical contact combined material, by graphite alkene reinforcing copper strip 2 and fix the stainless steel strip 1 of 2 one sides in graphite alkene reinforcing copper strip and constitute, the gross thickness is 3mm, the width is 200mm. During actual production, the thickness of the single-side stainless steel strip 1 can be selected from the total thickness of 20 to 90%, and the thickness of the single-side stainless steel strip 1 in this embodiment accounts for 60% of the total thickness, that is, 1.8mm.
The above elastic electric contact composite was prepared in the same manner as in example 1.
Comparative example
Comparative example 1
An elastic electric contact material is beryllium copper alloy QBee 1.7, the thickness is 3mm, and the width is 200mm.
Comparative examples 2 to 3
An elastic electric contact material differing from embodiment 1 in that: the mixing amount of the graphene and the copper powder after the surface treatment in the graphene reinforced copper strip is different, and is specifically shown in the following table.
In example 1 and comparative example 2, the mixing amount of graphene and copper powder after surface treatment:
Figure BDA0003481789580000081
comparative example 4
An elastic electric contact material, which is different from embodiment 1 in that: in the preparation process, the graphene reinforced copper material belt is replaced by the pure copper material belt with the same specification.
Performance test
The tensile strength and elongation after fracture of the product were measured by the method of GB/T11251-2020 with the products of examples 1-17 and comparative examples 1-4 as test objects; measuring the resistivity of the product by referring to the method in GB/T19289-2019; the vickers hardness of the product at 25 ℃ and 400 ℃ was measured with reference to the method in GB/T4340.1-2009 and the test results are reported in the table below.
The results of testing the products obtained in examples 1 to 17 and comparative examples 1 to 4:
Figure BDA0003481789580000082
Figure BDA0003481789580000091
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as can be seen from the data in the table above, the tensile strength of the elastic electric contact composite material obtained in the examples of the present application is not less than 1266MPa, the elongation after fracture is not more than 6%, the electrical conductivity is not more than 7.7 mu omega cm, the Vickers hardness at 25 ℃ is not less than 435HV, the Vickers hardness at 400 ℃ is not less than 430HV, and one or more values in the comparative examples 1 to 4 are significantly reduced. Therefore, the elastic electric contact composite material has good mechanical strength and conductivity, can meet the application in the environment with the temperature of more than 200 ℃, and has wide application prospect.
Compared with beryllium copper alloy, the elastic electric contact composite material has higher mechanical strength and better conductivity, does not obviously reduce the mechanical strength at 400 ℃, and can be used in a high-temperature environment.
It can be seen from the data of comparative examples 1-5 and comparative examples 2-3 that when the content of graphene in the graphene reinforced copper tape is 0.1-0.5%, the obtained composite material has better tensile strength on the basis of better conductivity, and especially when the content of graphene is 0.2% or 0.3%, the obtained product has the best combination of properties. In contrast, in comparative example 2, the content of graphene is 0.05%, the tensile strength of the obtained product is significantly reduced compared to example 1, and in comparative example 3, the content of graphene is 0.6%, and the guiding performance of the obtained product is significantly reduced compared to example 1.
As can be seen from the data of the comparative example 1 and the comparative example 4, the graphene is adopted as the reinforcement to reinforce the copper material belt, so that various performances of the copper material belt are obviously improved, and the obtained product has better tensile strength and better conductivity.
As can be seen from the data of comparative examples 8-12, the tensile strength and Vickers hardness of the composite materials obtained in examples 8 and 12 are significantly reduced compared to those of examples 9-11, thus showing that the properties of the composite materials obtained are superior when the temperature is 850-900 ℃ during sintering.
As is clear from the data of comparative example 10 and examples 13 to 16, the tensile strength and Vickers hardness of the composite materials obtained in examples 10 and 16 were significantly reduced as compared with those of examples 13 to 15, and it was thus demonstrated that the properties of the composite materials obtained were superior when the temperature increase rate was 80 to 100 ℃/min during sintering.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.

Claims (5)

1. An elastic electric contact composite material is characterized by comprising a graphene reinforced copper material belt and stainless steel material belts fixed on one side or two sides of the graphene reinforced copper material belt;
the preparation method of the graphene reinforced copper material belt comprises the following steps:
a, placing graphene in SnCl 2 Sensitizing in hydrochloric acid solution, cleaning, filtering, and placing in PdCl 2 Activating in a hydrochloric acid solution, and then carrying out surface copper plating on the treated graphene to obtain surface-treated graphene;
b, mixing the graphene with the surface treated in the step a with copper powder, prepressing, and then carrying out vacuum hot-pressing sintering under the protection of inert gas atmosphere to obtain a graphene reinforced copper material belt;
in the graphene reinforced copper material belt, the weight percentage of copper powder is 99.5-99.9%, and the weight percentage of graphene after surface treatment is 0.1-0.5%;
wet grinding and mixing the graphene subjected to surface treatment and copper powder in the step b;
in the wet grinding process, grinding is stopped for 10-20 min after each grinding for 30-60 min;
in the vacuum hot pressing sintering process of the step b, the sintering temperature is controlled to be 850-900 ℃;
and c, in the vacuum hot-pressing sintering process of the step b, the heating rate is 80-100 ℃/min.
2. The elastic electrical contact composite material according to claim 1, wherein in the graphene reinforced copper tape, the weight percentage of copper powder is 99.7-99.8%, and the weight percentage of graphene after surface treatment is 0.2-0.3%.
3. The elastic electrical contact composite material as claimed in claim 1, wherein the composite material is composed of a graphene reinforced copper strip and a stainless steel strip fixed on one side of the graphene reinforced copper strip, and the thickness of the stainless steel strip is 20-90% of the total thickness of the elastic electrical contact composite material.
4. The elastic electrical contact composite material as claimed in claim 1, wherein the composite material is composed of a graphene reinforced copper strip and stainless steel strips fixed on both sides of the graphene reinforced copper strip, and the thickness of the single stainless steel strip accounts for 10-45% of the total thickness of the elastic electrical contact composite material.
5. A process for preparing an elastic electrical contact composite according to any one of claims 1 to 4, characterized in that it comprises the following steps:
s1, carrying out composite rolling on a graphene reinforced copper material belt and a stainless steel material belt to obtain a composite material belt;
s2, performing diffusion heat treatment and softening heat treatment on the composite material belt to obtain a heat-treated composite material belt;
s3, performing straightening, cleaning and drying on the heat-treated composite material belt to obtain the elastic electric contact composite material.
CN202210070213.6A 2022-01-21 2022-01-21 Elastic electric contact composite material and preparation method thereof Active CN114438367B (en)

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US9379368B2 (en) * 2011-07-11 2016-06-28 California Institute Of Technology Electrochemical systems with electronically conductive layers
JP2016062651A (en) * 2014-09-12 2016-04-25 国立大学法人東京工業大学 Method for producing conductive composite, and conductive composite
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