CN113292766B - Combined coupling agent, modified carbonaceous aggregate, preparation method of modified carbonaceous aggregate and electric contact material - Google Patents

Combined coupling agent, modified carbonaceous aggregate, preparation method of modified carbonaceous aggregate and electric contact material Download PDF

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CN113292766B
CN113292766B CN202110573394.XA CN202110573394A CN113292766B CN 113292766 B CN113292766 B CN 113292766B CN 202110573394 A CN202110573394 A CN 202110573394A CN 113292766 B CN113292766 B CN 113292766B
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coupling agent
carbonaceous aggregate
powder
contact material
aggregate
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CN113292766A (en
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涂川俊
谭姣
刘平
巩佩
徐宇轩
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Ankang Shunxiang Carbon Co ltd
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Hunan University
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    • 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
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/029—Composite material comprising conducting material dispersed in an elastic support or binding material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • 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
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    • C08K2003/3009—Sulfides

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Abstract

The invention discloses a combined coupling agent for modifying carbonaceous aggregate, which comprises a borate coupling agent and a titanate coupling agent, wherein the ratio of the borate coupling agent to the titanate coupling agent is 1: (1-3). The invention also provides a modified carbonaceous aggregate obtained by modifying the combined coupling agent and a preparation method of the modified carbonaceous aggregate. The invention also provides an electrical contact material containing the modified carbonaceous aggregate. The invention provides a novel combined coupling agent, designs and prepares a modified carbonaceous aggregate and a resin type sliding electric contact material, expands the application range of the coupling agent, and provides theoretical basis and basis of application research for upgrading and updating of the resin type sliding electric contact material.

Description

Combined coupling agent, modified carbonaceous aggregate, preparation method of modified carbonaceous aggregate and electric contact material
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a coupling agent, a modified carbonaceous aggregate, a preparation method of the modified carbonaceous aggregate and an electrical contact material.
Background
The materials from which the elements that conduct current (electrical signals, electrical energy) in contact with each other are made are called electrical contact materials. The electric contact material is a functional carrier for completing the 'on-conduction-off' current and signal generation and transmission of an electric appliance, the electric contact performance of the electric contact material is a key influencing the reliability of electric and electronic engineering, the electric contact material has the name of 'heart of low-voltage electric appliance' in the field of low-voltage electric appliances, and the electric contact material is widely applied to products such as relays, circuit breakers, contactors, sensors, industrial control and the like. The electrical contact material includes fixed, sliding and separable contact elements.
The carbon brush prepared by taking matrix binder resin and reinforcing phase carbonaceous aggregate as main raw materials is a typical sliding electric contact material, and is a core component for maintaining the normal operation of sliding and rotating electromechanical systems and friction systems. However, the materials have the following disadvantages: the surface of carbonaceous aggregate graphite powder only contains a small amount of free hydroxyl, so that the interface bonding property with binder resin is poor; secondly, the adhesive has poor fluidity in the kneading process, so that the adhesive is unevenly dispersed among aggregates, and inevitable random microcracks are easily generated at an aggregate phase/adhesive phase interface. The problems can cause poor breaking strength, unstable current-carrying friction and wear performance, poor abrasion resistance and the like of the carbon brush, and even cause the motor to be burnt.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, and provide a combined coupling agent for modifying carbonaceous aggregate, a modified carbonaceous aggregate, a preparation method thereof and an electric contact material, wherein the combined coupling agent can improve the dispersibility of the carbonaceous aggregate and the interface bonding strength of an aggregate phase and a matrix binder phase. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the combined coupling agent for modifying the carbonaceous aggregate comprises a borate coupling agent and a titanate coupling agent, wherein the ratio of the borate coupling agent to the titanate coupling agent is 1: (1-3).
In the above combination coupling agent, preferably, the combination coupling agent further comprises an aluminate coupling agent, and the ratio of the borate coupling agent to the titanate coupling agent to the aluminate coupling agent is 1: (1-3): (1-2).
In the above combination coupling agent, preferably, the borate coupling agent, the titanate coupling agent and the aluminate coupling agent are mixed in a ratio of 1: 3: 1.
In the above combination type coupling agent, preferably, the borate coupling agent comprises one or more of borate LD-100P, borate ZB-99 and borate PEA; the titanate coupling agent comprises one or more of titanate TTS, titanate KHT-101, titanate KHT-302 and titanate 238S; the aluminate coupling agent comprises one or more of aluminate DL-411, aluminate SG-A1821 and aluminate DL-411 DF.
In the invention, the three coupling agents have different properties and different coupling effects under single action, but research shows that the three coupling agents can exert respective characteristics under the synergistic action and complement each other to realize better coupling effect, and finally measured performances of the electric contact material are superior to those of other ratios under the action of the coupling agents with the ratio, so that the coupling agents with the ratio are the preferable coupling agent ratio in the invention. In addition, the preferable specific types of the borate coupling agent, the titanate coupling agent and the aluminate coupling agent can better ensure the synergistic effect of the three coupling agents. More preferably, further research shows that the titanate coupling agent is titanate TTS, the borate coupling agent is borate LD-100P, the aluminate coupling agent is aluminate DL-411, and the three specific types of coupling agents have better synergistic effect.
The present invention also provides, as a general technical concept, a modified carbonaceous aggregate modified by the above-mentioned combination-type coupling agent.
As a general technical concept, the present invention also provides a method for preparing the modified carbonaceous aggregate, comprising the steps of: preparing carbonaceous aggregate powder by a gas flow mixing method; and then uniformly dispersing the combined coupling agent solution on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the modified carbonaceous aggregate.
In the above preparation method, preferably, the carbonaceous aggregate powder includes one or more of artificial graphite powder, flake graphite powder and isostatic pressing graphite powder.
In the above production method, preferably, the carbonaceous aggregate includes one or more of artificial graphite powder KS5-75TT, artificial graphite powder G800-and artificial graphite powder KS150-600 SP.
As a general technical concept, the present invention also provides an electrical contact material includingThe following components in parts by weight: 70-80 parts of modified carbonaceous aggregate, 20-30 parts of epoxy resin, 1-4 parts of curing agent and WS22-8 parts of powder, wherein the modified carbonaceous aggregate is the modified carbonaceous aggregate.
In the above electrical contact material, preferably, the epoxy resin includes one or more of 656, 662E, 634 and 6101, and the curing agent is dicyandiamide.
The preparation process of the electric contact material comprises the following steps: mixing modified carbonaceous aggregate with WS2And dry-mixing the powder, uniformly mixing, adding a solution in which the epoxy resin and the curing agent are dissolved, wet-mixing, drying, crushing, screening, molding and curing to obtain the resin type sliding electrical contact material.
The idea of the invention is as follows: in order to improve the dispersibility of the carbonaceous aggregate and the interface bonding strength of the aggregate phase and the matrix binder phase, the invention provides a concept of congenital deficiency and acquired complement, and introduces a combined coupling agent to pretreat the carbonaceous aggregate based on the interface theory of the composite material. The method comprises the following specific steps: 1. the carbonaceous aggregate can be effectively wetted and dispersed under the action of the steric effect of the combined coupling agent, so that the agglomeration phenomenon between the aggregate and the aggregate is weakened; 2. by constructing a chain structure, the liquid combined coupling agent around the carbonaceous aggregate is connected into a net shape, and pores are distributed among the liquid combined coupling agent and the carbon aggregate, so that a binder phase can be better filled, and the interface strength is enhanced; 3. through the bridge function of the combined coupling agent, functional groups on the surface of the carbonaceous aggregate powder react with groups carried by the combined coupling agent to form chemical bonding, long chains of the combined coupling agent are wound with epoxy resin molecules, formed physical winding nodes are increased, the carbonaceous aggregate and the resin are combined to form a net-shaped framework structure (the internal pulling effect of the resin type sliding electric contact material is enhanced, the mechanical strength of the material is improved, the integrity, the stability and the consistency of the micro-area structure of the resin type sliding electric contact material are enhanced, the internal defects are reduced), the carbonaceous aggregate and the resin are tightly fused into a whole, through the bridge function of the combined coupling agent, the bonding function between the carbonaceous aggregate and the resin is improved, and the interface compatibility between the carbonaceous aggregate powder and the epoxy resin is enhanced,improving the dispersibility of the carbonaceous aggregate in the resin matrix and reducing the enrichment of the carbonaceous aggregate in the resin matrix. 4. The inventor discovers through research that the WS can be improved by optimizing the components and the proportion of the combined coupling agent of the invention compared with other coupling agents2Dispersibility of powder and carbonaceous aggregate, and, at the same time, WS under the action of a combination-type coupling agent2The powder is firmly adsorbed on the surface of the carbonaceous aggregate, thereby preventing WS2Powder (density about 7.5 g/cm)3) And carbonaceous aggregate (density of about 1.6 to 2.2 g/cm)3) WS caused by large density difference2The powder settled (as shown in figure 3).
For the action mechanism of the invention, the single coupling agent cannot well achieve the action effect, and the function realized by the single coupling agent is inferior to that of the combined coupling agent adopted in the invention.
Compared with the prior art, the invention has the advantages that:
the invention solves the problems of easy agglomeration and difficult dispersion of the carbonaceous aggregate, overcomes the difficult problems of poor interface bonding and poor material matching of the resin type sliding electric contact material, provides a novel combined coupling agent, designs and prepares a modified carbonaceous aggregate and a resin type sliding electric contact material, and provides thought and theoretical basis for preparation and process improvement of other composite materials with the problems of poor raw material powder dispersibility and interface bonding, thereby realizing functionalization, expanding the application range of the coupling agent, and providing the theoretical basis and the basis for application research for upgrading and updating of the resin type sliding electric contact material. The method comprises the following specific steps:
1. the invention provides a thought of congenital deficiency and acquired complement, based on the interface theory of composite materials, the carbonaceous aggregate powder of the invention can be effectively dispersed by itself and uniformly dispersed in a resin matrix after being modified by a combined coupling agent, the interface bonding property of the carbonaceous aggregate and the resin is good, a framework-branched chain structure of a carbon graphite system is constructed, the mechanical strength and the electrical conductivity of the material are improved, and meanwhile, WS (WS) which is added later can be added under the action of the combined coupling agent2The powder is effectively dispersed and overcomeDue to carbonaceous aggregate and WS2WS due to large powder density difference2The powder was allowed to settle.
2. The combined coupling agent used in the invention has the advantages of simple preparation, low price, multiple functions and wide application, and the preparation method of the modified carbonaceous aggregate powder is simple and easy to implement, low in cost, good in modification effect and stable in performance of the obtained product.
3. The resin type sliding electric contact material is prepared by modifying carbonaceous aggregate powder by using the combined coupling agent, has the advantages of favorable matching resistivity and Shore hardness, improved breaking strength and compressive strength, favorable mechanical strength and electric contact performance and prolonged service life. Compared with the resin type sliding electric contact material which is not modified by the coupling agent, the resin type sliding electric contact material prepared by the carbonaceous aggregate modified by the combined coupling agent has the advantages that the flexural strength and the compressive strength are both improved, and the current-carrying wear performance is also obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a graph showing the flexural strength of samples of the electrical contact materials in examples 1 to 3 and comparative example 1.
Fig. 2 is a graph showing the compressive strength of samples of the electric contact materials of examples 1 to 3 and comparative example 1.
FIG. 3 is SEM photographs of resin type sliding electric contact material powders of example 1 and comparative example 1 (a) without adding a coupling agent; (b) the combination coupling agent of example 1 was added.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a combined coupling agent for modifying carbonaceous aggregate comprises a titanate coupling agent in the following ratio: a borate coupling agent: the aluminate coupling agent is 3: 1: 1, the titanate coupling agent is titanate TTS, the borate coupling agent is borate LD-100P, and the aluminate coupling agent is aluminate DL-411.
The modified carbonaceous aggregate is obtained by modifying the combined coupling agent, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the combined coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of modified carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and a curing agent into an acetone solution, adding the mixture into a container containing modified carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, forming and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, keeping the temperature at 205 ℃ for 2h, and then keeping the temperature with the temperature for 2hThe furnace was cooled to room temperature to obtain the final sample.
The samples are subjected to measurement of volume density, resistivity and Shore hardness, then the samples are prepared into standard samples, and the flexural strength (shown in figure 1) and the compressive strength (shown in figure 2) are measured, and the test data are shown in the following table 1:
table 1: performance data for the samples of example 1
Figure BDA0003083489010000051
An SEM image of the powder used for preparing the resin type sliding electrical contact material in this example is shown in fig. 3 (b).
Example 2:
a combined coupling agent for modifying carbonaceous aggregate comprises a titanate coupling agent in the following ratio: a borate coupling agent: the aluminate coupling agent is 2: 1: 2, the titanate coupling agent is titanate TTS, the borate coupling agent is borate LD-100P, and the aluminate coupling agent is aluminate DL-411.
The modified carbonaceous aggregate is obtained by modifying the combined coupling agent, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the combined coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of modified carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and curing agent into acetone solution, adding the mixture into a container containing modified carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, forming,And curing to obtain the resin type sliding electric contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, the temperature is kept at 205 ℃ for 2h, and then the resin type sliding electric contact material is cooled to room temperature along with a furnace to obtain a final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same manner as in example 1, and then the samples were prepared into standards, and the flexural strength (as shown in fig. 1) and the compressive strength (as shown in fig. 2) were measured, and the test data are shown in table 2 below:
table 2: example 2 Performance data of samples
Figure BDA0003083489010000052
Example 3:
a combined coupling agent for modifying carbonaceous aggregate comprises a titanate coupling agent in the following ratio: a borate coupling agent: the aluminate coupling agent is 1: 1: 1, the titanate coupling agent is titanate TTS, the borate coupling agent is borate LD-100P, and the aluminate coupling agent is aluminate DL-411.
The modified carbonaceous aggregate is obtained by modifying the combined coupling agent, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the combined coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of modified carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and curing agent into acetone solution, dissolving, and addingAnd (2) uniformly mixing the modified carbonaceous aggregate in a container, drying, crushing, screening, forming and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, the temperature is kept at 205 ℃ for 2h, and then the mixture is cooled to room temperature along with a furnace to obtain a final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same manner as in example 1, and then the samples were prepared into standards, and the flexural strength (as shown in fig. 1) and the compressive strength (as shown in fig. 2) were measured, and the test data are shown in table 3 below:
table 3: example 3 Performance data of samples
Figure BDA0003083489010000061
Example 4:
a combined coupling agent for modifying carbonaceous aggregate comprises a titanate coupling agent in the following ratio: the borate coupling agent is 3: 1, the titanate coupling agent is titanate TTS, and the borate coupling agent is borate LD-100P.
The modified carbonaceous aggregate is obtained by modifying the combined coupling agent, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the combined coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of modified carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and curing agent to acetoneAnd (2) after dissolving, adding the solution into a container filled with modified carbonaceous aggregate, uniformly mixing, drying, crushing, screening, forming and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, keeping the temperature at 205 ℃ for 2h, and then cooling to room temperature along with a furnace to obtain the final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same measurement manner as in example 1, and then the samples were prepared into standards to measure the flexural strength and compressive strength, and the test data are shown in table 4 below:
table 4: example 4 Performance data of samples
Figure BDA0003083489010000071
Example 5:
a combined coupling agent for modifying carbonaceous aggregate comprises a titanate coupling agent in the following ratio: a borate coupling agent: the aluminate coupling agent is 3: 1: 1, the titanate coupling agent is KHT-101, the borate coupling agent is ZB-99, and the aluminate coupling agent is aluminate DL-411.
The modified carbonaceous aggregate is obtained by modifying the combined coupling agent, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the combined coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of modified carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The above electrical contactThe preparation process of the material is as follows: adding epoxy resin and a curing agent into an acetone solution, adding the epoxy resin and the curing agent into a container containing modified carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, forming and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, keeping the temperature at 205 ℃ for 2h, and then cooling to room temperature along with a furnace to obtain the final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same measurement manner as in example 1, and then the samples were prepared into standards to measure the flexural strength and compressive strength, and the test data are shown in table 5 below:
table 5: performance data for the samples of example 5
Figure BDA0003083489010000081
Example 6:
a combined coupling agent for modifying carbonaceous aggregate comprises a titanate coupling agent in the following ratio: a borate coupling agent: the aluminate coupling agent is 3: 1: 1, the titanate coupling agent is KHT-101, the borate coupling agent is LD-100P, and the aluminate coupling agent is DL-411.
The modified carbonaceous aggregate is obtained by modifying the combined coupling agent, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the combined coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of modified carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, fixThe mass of dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and a curing agent into an acetone solution, adding the epoxy resin and the curing agent into a container containing modified carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, forming and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, keeping the temperature at 205 ℃ for 2h, and then cooling to room temperature along with a furnace to obtain the final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same measurement manner as in example 1, and then the samples were prepared into standards to measure the flexural strength and compressive strength, and the test data are shown in table 6 below:
table 6: performance data for the samples of example 6
Figure BDA0003083489010000082
Comparative example 1:
a resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and a curing agent into an acetone solution, adding the mixture into a container containing carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, forming and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, keeping the temperature at 205 ℃ for 2h, and then cooling to room temperature along with a furnace to obtain the final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same manner as in example 1, and the samples were prepared as standards, and the flexural strength (as shown in fig. 1) and the compressive strength (as shown in fig. 2) were measured, and the test data are shown in table 7 below:
table 7: performance data for comparative example 1 sample
Figure BDA0003083489010000091
An SEM image of the powder used for producing the resin type sliding electric contact material in this comparative example is shown in fig. 3 (a).
Comparative example 2:
a combined coupling agent for modifying carbonaceous aggregate comprises a titanate coupling agent in the following ratio: silane coupling agent: the aluminate coupling agent is 3: 1: 1. the titanate coupling agent is titanate TTS, the silane coupling agent is KH570, and the aluminate coupling agent is aluminate DL-411.
The modified carbonaceous aggregate is obtained by modifying the combined coupling agent, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the combined coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and a curing agent into an acetone solution, adding the mixture into a container containing carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, forming and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, keeping the temperature at 205 ℃ for 2h, and then cooling to room temperature along with a furnace to obtain the final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same measurement manner as in example 1, and then the samples were prepared into standards to measure the flexural strength and compressive strength, and the test data are shown in table 8 below:
table 8: performance data for comparative example 2 sample
Figure BDA0003083489010000092
Figure BDA0003083489010000101
Comparative example 3:
a combined coupling agent for modifying carbonaceous aggregate comprises a titanate coupling agent in the following ratio: silane coupling agent: the borate coupling agent is 3: 1: 1. the titanate coupling agent is titanate TTS, the silane coupling agent is KH570, and the borate coupling agent is borate LD-100P.
The modified carbonaceous aggregate is obtained by modifying the combined coupling agent, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the combined coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and curing agent into acetone solution, adding the mixture into a container containing carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, molding and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature is lowThe temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, the temperature is kept at 205 ℃ for 2h, and then the sample is cooled to room temperature along with the furnace to obtain the final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same measurement manner as in example 1, and then the samples were prepared into standards to measure the flexural strength and compressive strength, and the test data are shown in table 9 below:
table 9: performance data for comparative example 3 sample
Figure BDA0003083489010000102
Comparative example 4:
a combined coupling agent for modifying carbonaceous aggregate comprises the following components in percentage by weight: aluminate coupling agent: the borate coupling agent is 3: 1: 1. the silane coupling agent is KH570, the aluminate coupling agent is aluminate DL-411, and the borate coupling agent is borate LD-100P.
The modified carbonaceous aggregate is obtained by modifying the combined coupling agent, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the combined coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
An electrical resin type sliding electrical contact material comprises the following components in parts by weight: 75 parts of carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and curing agent into acetone solution, adding the mixture into a container containing carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, forming and curing to obtain the epoxy resin-curing agentThe resin type sliding electric contact material has a curing temperature curve of 0-40-205 ℃, a first temperature rise time of 10min and a second temperature rise time of 4h, is subjected to heat preservation at 205 ℃ for 2h, and is cooled to room temperature along with a furnace to obtain a final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same measurement manner as in example 1, and then the samples were prepared into standards to measure the flexural strength and compressive strength, and the test data are shown in table 10 below:
table 10: performance data for comparative example 4 sample
Figure BDA0003083489010000111
Comparative example 5:
the composition of the combined coupling agent is titanate coupling agent: a borate coupling agent: the aluminate coupling agent is 3: 1: 1, the titanate coupling agent is titanate TTS, the borate coupling agent is borate LD-100P, and the aluminate coupling agent is aluminate DL-411.
The preparation process of the resin type sliding electric contact material comprises the following steps:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a combined coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) directly adding the combined coupling agent solution obtained in the step (2) into carbonaceous aggregate powder, and uniformly mixing
(4) And (3) adding epoxy resin and a curing agent into an acetone solution, adding the epoxy resin and the curing agent into the step (3) after dissolution, uniformly mixing, drying, crushing, screening, forming and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, keeping the temperature at 205 ℃ for 2h, and then cooling to room temperature along with a furnace to obtain a final sample.
The resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of carbonaceous aggregate, 22 parts of epoxy resin,WS2the powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same manner as in example 1, and then the samples were prepared into standards, and the flexural strength and compressive strength were measured, and the test data are shown in table 11 below:
table 11: performance data for comparative example 5 sample
Figure BDA0003083489010000121
The aggregate graphite powder is easy to agglomerate, and the aggregate phase can be coated by the combination coupling agent through the pre-modification treatment of the combination coupling agent and the pre-dispersion of the combination coupling agent, so that the good dispersion effect is achieved, and the dispersion of the aggregate phase in the matrix resin can be enhanced after the reinforcing phase binder resin is added at the later stage. With the mode of operation of this comparative example, however, the aggregate dispersion was not ideal, which is why the aggregate graphite powder was previously treated with the combined coupling agent.
Comparative example 6:
a modified carbonaceous aggregate is obtained by modifying a borate coupling agent, wherein the borate coupling agent is borate LD-100P, and the specific process is as follows:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a boric acid ester coupling agent solution with the mass of 3% of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the borate coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of modified carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: will be provided withAdding epoxy resin and a curing agent into an acetone solution, adding the epoxy resin and the curing agent into a container containing modified carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, forming and curing to obtain the resin type sliding electrical contact material, wherein the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, keeping the temperature at 205 ℃ for 2h, and then cooling to room temperature along with a furnace to obtain the final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same measurement manner as in example 1, and then the samples were prepared into standards to measure the flexural strength and compressive strength, and the test data are shown in table 12 below:
table 12: performance data for comparative example 6 sample
Figure BDA0003083489010000122
Comparative example 7:
a modified carbonaceous aggregate is obtained by modifying a titanate coupling agent, wherein the titanate coupling agent is titanate TTS, and the specific process comprises the following steps:
(1) preparing carbonaceous aggregate powder by a gas flow mixing method;
(2) preparing a titanate coupling agent solution with the mass of 3 percent of the mass of the carbonaceous aggregate powder;
(3) and (3) uniformly dispersing the titanate coupling agent solution obtained in the step (2) on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the treated modified carbonaceous aggregate powder.
A resin type sliding electric contact material comprises the following components in parts by weight: 75 parts of modified carbonaceous aggregate, 22 parts of epoxy resin and WS2The powder is 3 parts. On the basis of the above, the mass of the curing agent dicyandiamide accounts for 3.5% of the mass of the epoxy resin. The preparation process of the electric contact material is as follows: adding epoxy resin and curing agent into acetone solution, adding the mixture into a container containing modified carbonaceous aggregate after dissolving, uniformly mixing, drying, crushing, screening, molding and curing to obtain the resinThe sliding electric contact material is characterized in that the curing temperature curve is 0-40-205 ℃, the first temperature rise time is 10min, the second temperature rise time is 4h, the temperature is kept at 205 ℃ for 2h, and then the material is cooled to room temperature along with a furnace to obtain a final sample.
The samples were subjected to the measurement of bulk density, resistivity and shore hardness in the same manner as in example 1, and then the samples were prepared into standards, and the flexural strength and compressive strength were measured, and the test data are shown in table 13 below:
table 13: performance data for comparative example 7 sample
Figure BDA0003083489010000131

Claims (8)

1. The combined coupling agent for modifying the carbonaceous aggregate is characterized by comprising a borate coupling agent, a titanate coupling agent and an aluminate coupling agent, wherein the ratio of the borate coupling agent to the titanate coupling agent to the aluminate coupling agent is 1: 3: 1.
2. the combination coupling agent of claim 1, wherein the borate coupling agent comprises one or more of the borates LD-100P, ZB-99, and PEA; the titanate coupling agent comprises one or more of titanate TTS, titanate KHT-101, titanate KHT-302 and titanate 238S; the aluminate coupling agent comprises one or more of aluminate DL-411, aluminate SG-A1821 and aluminate DL-411 DF.
3. A modified carbonaceous aggregate modified by the combination coupling agent of any one of claims 1-2.
4. A method of preparing a modified carbonaceous aggregate according to claim 3, comprising the steps of: preparing carbonaceous aggregate powder by a gas flow mixing method; and then uniformly dispersing the combined coupling agent solution on the surface of the carbonaceous aggregate powder by an atomization method, and uniformly mixing to obtain the modified carbonaceous aggregate.
5. The method of claim 4, wherein the carbonaceous aggregate powder comprises one or more of artificial graphite powder, flake graphite powder, and isostatic graphite powder.
6. The method according to claim 5, wherein the carbonaceous aggregate comprises one or more of artificial graphite powder KS5-75TT, artificial graphite powder G800 and artificial graphite powder KS150-600 SP.
7. The electric contact material is characterized by comprising the following components in parts by weight: 70-80 parts of modified carbonaceous aggregate, 20-30 parts of epoxy resin, 1-4 parts of curing agent and WS22-8 parts of powder; the modified carbonaceous aggregate is the modified carbonaceous aggregate described in claim 3 or the modified carbonaceous aggregate obtained by the production method described in any one of claims 4 to 6.
8. The electrical contact material of claim 7, wherein the epoxy resin comprises one or more of 656, 662E, 634, and 6101, and the curing agent is dicyandiamide.
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