CN109136606B - Enhanced self-lubricating copper-based composite material and preparation method and application thereof - Google Patents
Enhanced self-lubricating copper-based composite material and preparation method and application thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
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- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0068—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only nitrides
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Abstract
The invention relates to a reinforced self-lubricating copper-based composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: titanium powder, boron nitride powder, copper powder or/and copper-based alloy powder are/is used as raw materials, and precursor powder is prepared by adopting self-propagating sintering after uniform mixing; and carrying out pressureless sintering or hot-pressing sintering on the precursor powder to obtain the enhanced self-lubricating copper-based composite material. Compared with the prior art, the TiB provided by the invention2Enhanced self-lubricating copper-based composite material with/TiN as binary enhanced phase and BN as self-lubricating medium and TiB2High hardness and high wear resistance of TiN, and high thermal conductivity of pure copper or copper-based alloy.
Description
Technical Field
The invention relates to a reinforced self-lubricating copper-based composite material and a preparation method and application thereof, in particular to a composite material prepared from TiB2The enhanced copper-based composite material takes BN as a self-lubricating medium and the preparation method and the application thereof.
Background
Copper and its alloy material have excellent electric conduction, heat-conducting property, generally as friction part, heat dissipation part, conductive part widely apply to various machinery, electric power, etc. system. However, their low hardness, high density, poor wear resistance at high temperature and high speed conditions, and the like, have limited their use in high performance automobiles, airplanes, high speed trains, and advanced weaponry systems. Ceramic phase reinforced copper-based composite materials (CMMCs) are prepared by taking ceramic (particles, short fibers and continuous long fibers) as a reinforcing phase and taking copper and copper alloy as a matrix, and have comprehensive properties of metal and nonmetal. The composite material generally keeps good heat conduction and electric conduction performance of the copper alloy material, has higher hardness and strength, better corrosion resistance, more excellent wear resistance and relatively lower density and thermal expansion coefficient compared with the traditional copper alloy, and is an ideal choice for replacing the traditional copper alloy material.
Titanium diboride (TiB)2) The copper-based composite material is a ceramic material with high strength, high hardness and high Young modulus, has good electrical conductivity, is an ideal reinforcing phase of the copper-based composite material, and can keep the material to have higher electrical conductivity on the basis of improving the mechanical property and the wear-resisting property of the material. In addition, since TiB2Has a lower density and can contribute to weight reduction of parts. Titanium nitride (TiN) is a ceramic material with excellent mechanical and wear-resisting properties, has good electric conductivity, heat conductivity, high temperature resistance and chemical stability, has good interface bonding performance with metal materials, and is widely applied to a reinforcing phase of a hard alloy material.
Currently, TiB2And TiN have been gradually developed as reinforcing phases for copper-based composites. The patent number CN102828060B discloses a titanium nitride ceramic reinforced copper-based composite material and a preparation method thereof, wherein the raw materials comprise titanium nitride, titanium oxide, a sintering aid and carbon black according to the weight ratio, wherein a copper alloy is added into a preform, and the preparation method comprises the steps of heating, heat preservation, sintering and flowing nitrogen gas introduction, so that a porous titanium nitride preform with the porosity of 45-75% is obtained; preheating a die casting machine, and simultaneously heating the copper alloy to a molten state; pouring the molten copper alloy liquid into a die cavity for placing the prefabricated body, pressing the molten copper alloy liquid into the porous titanium nitride prefabricated body through a press, separating the cast ingot from the die after the cast ingot is cooled, and carrying out heat treatment to obtain the titanium nitride reinforced copper-based composite material. The patent number CN105220000A discloses a high-strength titanium diboride particle reinforced copper-based composite material and a preparation method thereof, wherein the high-strength titanium diboride particle reinforced copper-based composite material consists of the following components in percentage by volume: high-purity diboride with a purity of > 98%6-9% of titanium and copper alloy ZCuSn5Zn5Pb5And the content of the titanium diboride particles is 91-94%, and the high-strength titanium diboride particle reinforced copper-based composite material is obtained through the steps of smelting, stirring, heat preservation, casting and the like.
All the above works are with TiB2Or TiN particles are used as raw materials, and the density of the material is uneven and the performance of the composite material is influenced due to the difference of the particle density and the agglomeration of ceramic particles in the material mixing process. Although the method adopting the ceramic prefabricated block can avoid the influence of agglomeration of ceramic particles, the method needs to prepare the ceramic prefabricated block, and has more complex process and equipment and higher cost, thereby having greater limitation on large-scale production.
Disclosure of Invention
In view of the above problems in the prior art, it is an object of the present invention to provide a TiB2Enhanced self-lubricating copper-based composite material with/TiN as binary enhanced phase and BN as self-lubricating medium, wherein TiB is not directly added into raw materials2the/TiN ceramic particles are synthesized in situ through the self-propagating reaction of Ti and BN, and the reaction residual BN serves as a self-lubricating medium in a system. The material can meet the application requirements of brake pads, gears, worm gears or motor brushes and the like.
In one aspect, the invention provides a preparation method of a reinforced self-lubricating copper-based composite material, which comprises the following steps:
titanium powder, boron nitride powder, copper powder or/and copper-based alloy powder are/is used as raw materials, and precursor powder is prepared by adopting self-propagating sintering after uniform mixing;
and carrying out pressureless sintering or hot-pressing sintering on the precursor powder to obtain the enhanced self-lubricating copper-based composite material.
The invention is synthesized in situ through the self-propagating reaction of Ti and BN, namely 3Ti +2BN → 2TiN + TiB2So that the BN powder and the Ti powder generate a ceramic reinforced phase TiN + TiB through self-propagating2And then the reinforced self-lubricating copper-based composite material is prepared by pressureless sintering or hot-pressing sintering. The method of the invention not only avoids directly adopting TiB2Or TiN particles are used as ceramic reinforcing phase, and the process and equipment are simple, thereby saving the manufacturing costAnd (4) preparation cost. Furthermore, 3Ti +2BN → 2TiN + TiB according to the above reaction2: if the Ti powder is excessive in the self-propagating reaction process, BN basically completely reacts, and the excessive Ti powder and Cu or Cu-based alloy can form a Cu/Ti alloy phase; if the BN is excessive, the titanium powder is completely reacted and the BN phase remains, and the remaining BN can also be used as a self-lubricating medium to exist in the enhanced self-lubricating copper-based composite material, so that the friction coefficient and the wear rate of the enhanced self-lubricating copper-based composite material are reduced. And then pressureless sintering or hot-pressing sintering is carried out to obtain the required copper-based composite material with good mechanical and wear-resisting properties.
Preferably, after copper powder or/and copper-based alloy powder is added into precursor powder, the reinforced self-lubricating copper-based composite material is obtained after pressureless sintering or hot-pressing sintering. In the process, the metal powder is added for the second time, so that the heat-conducting property, the mechanical property and the frictional wear property of the material can be controllably adjusted. Still preferably, the mass fraction of the precursor powder in all raw materials is 10% to 80%.
Preferably, the pressureless sintering comprises: prepressing the precursor into blocks, and sintering at 750-1000 ℃ for 0.5-2 hours in vacuum or inert atmosphere.
Preferably, the pre-pressing and blocking mode is dry pressing forming or/and cold isostatic pressing forming.
Preferably, the pressure of the dry-pressing is 15-30MPa, and the pressure of the cold isostatic pressing is 100-300 MPa.
Preferably, the hot-pressing sintering process comprises the following steps: the sintering temperature is 750-1000 ℃, the sintering pressure is 10-40 MPa, the sintering time is 0.5-2 hours, and the sintering atmosphere is vacuum or inert atmosphere.
On the other hand, the invention also provides a preparation method of the enhanced self-lubricating copper-based composite material, which comprises the following steps:
titanium powder, boron nitride powder, copper powder or/and copper-based alloy powder are/is used as raw materials, and a blank is prepared by dry pressing forming or/and cold isostatic pressing forming after uniform mixing;
the obtained blank is prepared into the enhanced self-lubricating copper-based composite material by self-propagating sintering.
The invention takes titanium powder, boron nitride powder, copper powder or/and copper base alloy powder as raw materials, firstly prepares into a blank, and then carries out in-situ synthesis through the self-propagating reaction of Ti and BN, namely 3Ti +2BN → 2TiN + TiB2So that the BN powder and the Ti powder generate a ceramic reinforced phase TiN + TiB through self-propagating2And directly preparing the reinforced self-lubricating copper-based composite material. The method of the invention not only avoids directly adopting TiB2Or TiN particles are used as a ceramic reinforcing phase, and the reinforced self-lubricating copper-based composite material is directly prepared without pressureless sintering or hot-pressing sintering, so that the process and equipment are simple, and the preparation cost is saved. Furthermore, 3Ti +2BN → 2TiN + TiB according to the above reaction2: if the Ti powder is excessive in the self-propagating reaction process, the BN completely reacts, the obtained composite material does not contain a BN phase, and the excessive Ti phase and the Cu or Cu alloy matrix form a Cu/Ti alloy phase; if the BN is excessive, the titanium powder is completely reacted and the BN phase remains, and the remaining BN can also be used as a self-lubricating medium to exist in the enhanced self-lubricating copper-based composite material, so that the friction coefficient and the wear rate of the enhanced self-lubricating copper-based composite material are reduced.
Preferably, the pressure of the dry pressing is 15-30 MPa.
Preferably, the pressure of the cold isostatic pressing is 100-300 MPa.
In the method of the present invention (if not specifically stated, the method is at least one of the two methods), the raw material preferably contains 7.5 to 50% by mass of titanium powder, 2.5 to 20% by mass of boron nitride powder, and 90 to 30% by mass of copper powder or/and copper-based alloy powder, based on 100% by mass of the total raw material.
Preferably, the alloy element in the copper-based alloy powder is at least one of lead, tin, aluminum, manganese, titanium, lead, zinc, beryllium, tellurium and antimony. For example, the copper-based alloy powder is at least one of tin copper, aluminum copper, antimony copper, beryllium copper, titanium copper, and the like.
Preferably, the average particle size of the titanium powder is 1-50 microns, the average particle size of the boron nitride powder is 0.05-20 microns, and the average particle size of the copper powder or/and the copper-based alloy powder is 10-100 microns.
Preferably, the atmosphere of the self-propagating sintering is vacuum or inert atmosphere, and is preferably vacuum or Ar gas atmosphere.
In a third aspect, the invention also provides a reinforced self-lubricating copper-based composite material prepared by the method. The phase composition of the reinforced self-lubricating copper-based composite material can comprise at least one of Cu and copper-based alloy and TiB2And TiN. Preferably, BN or/and Ti phases are also included. Is a lubricating medium. Wherein TiB2the/TiN is a binary enhanced phase, the pure Cu or Cu-based alloy is a matrix phase, and the BN is a lubricating medium.
In a fourth aspect, the invention also provides an application of the reinforced self-lubricating copper-based composite material prepared by the method in preparation of brake pads, gears, worm gears or motor brushes.
Compared with the prior art, the TiB provided by the invention2Enhanced self-lubricating copper-based composite material with/TiN as binary enhanced phase and BN as self-lubricating medium and TiB2High hardness and high wear resistance of TiN, and high thermal conductivity of pure copper or copper-based alloy. The introduction of the BN lubricating medium is beneficial to obtaining a lower and more stable friction coefficient of the material and reducing the wear rate of the material. Brake pads, gears, worm gears, motor brush materials and the like prepared by the material have the characteristics of low abrasion, long service life and high stability; in addition, the introduction of the ceramic phase can obviously improve the high-temperature mechanical and tribological properties of the material, improve the reliability of the device in a high-temperature environment and have stronger practical value.
Drawings
FIG. 1 is a topographical view of a composite precursor powder prepared in example 1;
FIG. 2 is the phase composition of the composite precursor powder prepared in example 1;
FIG. 3 is a topographical view of a composite precursor powder prepared in example 2;
FIG. 4 is the phase composition of the composite precursor powder prepared in example 2;
FIG. 5 is a surface topography map of the reinforced self-lubricating copper-based composite prepared in example 3;
FIG. 6 is a surface topography map of the reinforced self-lubricating copper-based composite material prepared in example 4.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The invention takes pure titanium powder, boron nitride powder, copper powder or/and copper base alloy powder as raw materials, the raw materials are ball-milled and mixed evenly, self-propagating sintering is carried out to prepare precursor powder, and then hot pressing or pressureless sintering is carried out to prepare the enhanced self-lubricating copper base composite material. Or directly carrying out self-propagating sintering on the titanium/boron nitride/copper (alloy) mixture blank obtained by cold pressing to obtain the enhanced self-lubricating copper-based composite material. In the prepared enhanced self-lubricating copper-based composite material, TiB2the/TiN is a binary enhanced phase, and the pure Cu or Cu-based alloy is a matrix phase. The reinforced self-lubricating copper-based composite material can also comprise BN serving as a lubricating medium.
The following exemplarily illustrates a method for preparing the reinforced self-lubricating copper-based composite material provided by the present invention. The invention takes titanium powder, boron nitride powder, copper or copper alloy powder as raw materials, the raw materials are ball-milled and mixed to obtain a uniform raw material mixture, the raw material mixture is sintered by self-propagating to obtain a compound precursor, and the compound precursor is sintered by hot pressing or pressureless sintering to obtain the composite material.
Titanium powder, boron nitride powder and copper or copper-based alloy powder are used as raw materials, and after being uniformly mixed, self-propagating sintering is adopted to prepare composite material precursor powder. The alloy element in the copper-based alloy powder can be at least one of lead, tin, aluminum, manganese, titanium, lead, zinc, beryllium, tellurium and antimony. The copper-based alloy powder can be at least one of tin copper, aluminum copper, antimony copper, beryllium copper, titanium copper and the like. The manner of uniform mixing includes, but is not limited to, milling, ball milling, etc. And drying, sieving and the like can be carried out after grinding or ball milling to obtain precursor powder. Wherein the drying can be ball milling and drying at 50-80 ℃ for 2-6 hours. The sieve can be generally 100 meshes. The precursor powder is prepared by self-propagating sintering of raw material powder. The precursor powder prepared is made of TiB2TiN, Cu, BN, etcAnd (4) forming. The raw materials comprise 15-50% by mass of titanium powder, 5-20% by mass of boron nitride powder and 40-80% by mass of copper powder. Preferably 15-40% of titanium powder, 5-20% of boron nitride powder and 40-80% of copper powder. In the raw material powder, the average particle size of titanium powder can be 1-50 mu m, the average particle size of boron nitride powder can be 0.05-20 mu m, and the average particle size of copper or/and copper-based alloy powder can be 10-100 mu m. The atmosphere adopted by the self-propagating sintering process is vacuum, Ar gas or other inert atmosphere. The method for self-propagating synthesis of precursor powder provided by the invention takes titanium powder, boron nitride powder, copper powder or/and copper-based alloy powder as raw materials, the raw materials are uniformly mixed and then prepared by self-propagating sintering, ceramic prefabricated blocks do not need to be prepared, the process is simple, and TiB can be avoided2Or TiN particles as raw materials, due to the difference of particle density and the agglomeration problem of ceramic particles in the mixing process. The prepared precursor powder phase composition comprises Cu (and/or copper-based alloy) and TiB2And TiN. Preferably, the main constituent phase of the material is TiB2TiN, BN, Cu (and/or copper-based alloys). More preferably, the precursor powder comprises 30-90% of Cu (and/or copper-based alloy) and 10-68% of TiB by mass2And TiN, 0 to 15% BN (or/and Ti phase).
And then adding copper powder or/and copper-based alloy powder into the precursor powder, and then carrying out pressureless sintering or hot-pressing sintering to obtain the enhanced self-lubricating copper-based composite material. The mass fraction of the precursor powder in all raw materials (precursor powder and copper powder or/and copper-based alloy powder) is 10-80%. In the process, copper powder or/and copper-based alloy powder is added for the second time, so that the heat-conducting property, the mechanical property and the frictional wear property of the material can be controllably adjusted. The hot-pressing sintering process can comprise the following steps: the sintering temperature is 750-1000 ℃, the sintering pressure is 10-40 MPa, the sintering time is 0.5-2 hours, and the sintering atmosphere is vacuum or inert atmosphere. The pressureless sintering may include: prepressing the precursor into blocks, and sintering at 750-1000 ℃ for 0.5-2 hours in vacuum or inert atmosphere. The pre-pressing and blocking mode can be dry pressing forming or/and cold isostatic pressing forming. The pressure of the dry pressing molding can be 15-30 MPa. The pressure of the cold isostatic pressing can be 100-300 MPa. Preferably, the dry-pressing molding is carried out under 15-30MPa, and then the cold isostatic pressing molding is carried out under 100-300 MPa.
As an example, a) titanium powder, boron nitride powder, copper or copper-based alloy powder are weighed according to the proportion, and are subjected to ball milling to be uniformly mixed to prepare raw material powder; b) carrying out self-propagating sintering on the raw material powder obtained in the previous step to obtain composite precursor powder; c) and carrying out hot-pressing sintering or pressureless sintering on the composite precursor to obtain the required composite material. The hot-pressing sintering process in step c) is as follows: the sintering temperature is 750-1000 ℃, the sintering pressure is 10-40 MPa, the heat preservation time is 0.5-2 hours, and the sintering atmosphere is vacuum, Ar gas or other inert atmosphere. The pressureless sintering process described in step c) is as follows: prepressing the precursor prepared in the step a) into blocks under the pressure of 15-30MPa, then carrying out cold isostatic pressing treatment under the pressure of 100-300MPa, and then carrying out heat preservation for 0.5-2 hours at 750-1000 ℃ under vacuum, Ar gas or other inert atmosphere.
The invention is prepared by using titanium powder, boron nitride powder, copper powder or/and copper-based alloy powder as raw materials, cold pressing the raw materials to obtain a mixture blank, and then carrying out self-propagating sintering on the mixture blank. The enhanced self-lubricating copper-based composite material prepared by the method can avoid TiB2Or TiN particles as raw materials, due to the difference of particle density and the agglomeration problem of ceramic particles in the mixing process. The phase composition of the prepared reinforced self-lubricating copper-based composite material comprises Cu (and/or copper-based alloy) and TiB2And TiN. The main composition phase of the material is TiB2TiN, BN, Cu (and/or copper-based alloys). More preferably, the reinforced self-lubricating metal matrix composite material comprises 30-90% of Cu (and/or copper-based alloy) and 10-68% of TiB by mass2And TiN, 0 to 15% BN (or/and Ti phase). In addition, the composite material can also be used as a reinforcement to prepare other metal matrix composite materials such as Al, Ti, Mg, Ni and the like. The following exemplary description of the enhancements provided by the present inventionA preparation method of a self-lubricating copper-based composite material.
Titanium powder, boron nitride powder, copper powder or/and copper-based alloy powder are/is used as raw materials, and the raw materials are uniformly mixed and then cold-pressed to prepare a blank. The copper-based alloy powder can be at least one of tin copper, aluminum copper, antimony copper, beryllium copper, titanium copper and the like. The manner of uniform mixing includes, but is not limited to, milling, ball milling, etc. After grinding or ball milling, drying, sieving and the like can be carried out. Wherein the drying can be ball milling and drying at 50-80 ℃ for 2-6 hours. The sieve can be generally 100 meshes. The composite material blank can be pressed by a cold pressing process, wherein the cold pressing preparation mode can be dry pressing or/and cold isostatic pressing. The pressure of the dry pressing molding can be 15-30 MPa. The pressure of the cold isostatic pressing can be 100-300 MPa. Preferably, the dry-pressing molding is carried out under 15-30MPa, and then the cold isostatic pressing molding is carried out under 100-300 MPa. The raw materials comprise 15-50% by mass of titanium powder, 5-20% by mass of boron nitride powder and 40-80% by mass of copper powder. Preferably 15-40% of titanium powder, 5-20% of boron nitride powder and 40-80% of copper powder. In the raw material powder, the average particle size of titanium powder can be 1-50 mu m, the average particle size of boron nitride powder can be 0.05-20 mu m, and the average particle size of copper or/and copper-based alloy powder can be 10-100 mu m.
The obtained blank is prepared into the enhanced self-lubricating copper-based composite material by self-propagating sintering. The enhanced self-lubricating copper-based composite material is directly prepared by a self-propagating sintering process, further sintering is not needed, and the obtained material has high-temperature mechanical and tribological properties. The self-propagating sintering is sintering in vacuum or inert atmosphere. The atmosphere adopted by the self-propagating sintering process is vacuum, Ar gas or other inert atmosphere. In the self-propagating sintering process, the temperature is achieved spontaneously through reaction, and no specific temperature requirement exists.
As an example, a) titanium powder, boron nitride powder, copper or copper-based alloy powder are weighed according to the proportion, and are mixed uniformly by ball milling to prepare mixed powder; b) performing cold pressing on the raw material powder obtained in the previous step to obtain a mixture blank; c) and carrying out self-propagating sintering on the mixture blank to obtain the required composite material. The ball milling is rolling ball milling.
One application of the reinforced copper-based composite material is to manufacture brake pads, worm gears, motor brushes and the like.
The reinforcing phase of the copper-based composite material prepared by the invention is TiB2The matrix of the/TiN binary reinforced phase is pure Cu or Cu-based alloy, the self-lubricating medium is BN, and the composite material has TiB2The TiN ceramic phase has high wear resistance and high heat conductivity of pure Cu or Cu-based alloy, and due to the introduction of BN lubricating medium, the material has lower and more stable friction coefficient, and the wear resistance of the material is further improved. One application of the reinforced copper-based composite material is that the reinforced copper-based composite material can be applied to manufacturing brake pads, worm gears, motor brushes and the like.
The bending strength of the reinforced copper-based composite material is not lower than 150MPa measured by an Instron5566 type material universal tester. The Rockwell Hardness (HRF) of the enhanced copper-based composite material obtained by the invention is not less than 70. The friction coefficient of the obtained enhanced copper-based composite material is measured to be 0.4-0.8 by adopting a vertical universal material friction wear tester. And measuring the abrasion of the obtained reinforced copper-based composite material by adopting a weighing method.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Firstly, weighing 5g of boron nitride powder with the median particle size of 0.5 mu m, 14g of pure titanium powder with the median particle size of 40 mu m and 14g of pure copper powder with the median particle size of 40 mu m, adding 40g of absolute ethyl alcohol, and performing rolling ball milling for 3 hours to prepare uniform and stable slurry; then drying for 2 hours at 50-80 ℃, and sieving to obtain mixture powder; placing the mixture powder into a graphite crucible, and placing the graphite crucible into a self-propagating sintering furnace for sintering to obtain composite precursor powder; and then pouring the compound precursor powder into a hot-pressing die, and carrying out hot-pressing sintering at the sintering temperature of 900 ℃ for 1 hour under the hot-pressing pressure of 25MPa to obtain the required self-lubricating copper-based composite material.
The morphology of the composite precursor powder prepared in this example is shown in FIG. 1, and the phase composition is shown in FIG. 2. From fig. 1, it can be seen that the powder surface has no bare fine particles, indicating no BN residue. From FIG. 2, it can be seen that the phase composition of the composite powder includes TiB2TiN and Cu, no BN phase. The flexural strength and Rockwell hardness of the composite are shown in Table 1.
Example 2
Firstly, weighing 6g of boron nitride powder with the median particle size of 0.5 mu m, 14g of pure titanium powder with the median particle size of 40 mu m and 24g of pure copper powder with the median particle size of 40 mu m, adding 40g of absolute ethyl alcohol, and performing rolling ball milling for 3 hours to prepare uniform and stable slurry; then drying for 2 hours at 50-80 ℃, and sieving to obtain mixture powder; placing the mixture powder into a graphite crucible, and placing the graphite crucible into a self-propagating sintering furnace for sintering to obtain composite precursor powder; and then pouring the compound precursor powder into a hot-pressing die, and carrying out hot-pressing sintering at the sintering temperature of 900 ℃ for 1 hour under the hot-pressing pressure of 25MPa to obtain the required self-lubricating copper-based composite material.
The morphology of the composite precursor powder prepared in this example is shown in FIG. 3, and the phase composition is shown in FIG. 4. From FIG. 3, it can be seen that a certain amount of fine nanoscale particles are present on the surface of the powder, and are residual BN particles, and from FIG. 4, it can be seen that the phase composition of the composite powder comprises TiB2TiN, Cu and BN. The flexural strength and Rockwell hardness of the composite are shown in Table 1.
Example 3
Firstly, weighing 5g of boron nitride powder with the median particle size of 0.5 mu m, 14g of pure titanium powder with the median particle size of 40 mu m and 14g of pure copper powder with the median particle size of 40 mu m, adding 40g of absolute ethyl alcohol, and performing rolling ball milling for 3 hours to prepare uniform and stable slurry; then drying for 2 hours at 50-80 ℃, and sieving to obtain mixture powder; then dry-pressing the prepared mixture powder to form, wherein the dry-pressing pressure is 20 MPa; carrying out cold isostatic pressing treatment on the blank formed by dry pressing, wherein the pressure is 200 MPa; and (3) carrying out self-propagating sintering on the blank subjected to the cold isostatic pressing treatment to obtain the enhanced self-lubricating copper-based composite material.
The surface topography of the composite material prepared in this example is shown in fig. 5, and it can be seen from fig. 5 that the composite material has high density, and shows a surface topography in which the Cu phase is continuous, but a small amount of pores are discretely distributed. The flexural strength and Rockwell hardness of the resulting composite are shown in Table 1.
Example 4
Firstly, weighing 6g of boron nitride powder with the median particle size of 0.5 mu m, 14g of pure titanium powder with the median particle size of 40 mu m and 24g of pure copper powder with the median particle size of 40 mu m, adding 40g of absolute ethyl alcohol, and performing rolling ball milling for 3 hours to prepare uniform and stable slurry; then drying for 2 hours at 50-80 ℃, and sieving to obtain mixture powder; then dry-pressing the prepared mixture powder to form, wherein the dry-pressing pressure is 20 MPa; carrying out cold isostatic pressing treatment on the blank formed by dry pressing, wherein the pressure is 200 MPa; and (3) carrying out self-propagating sintering on the blank subjected to the cold isostatic pressing treatment to obtain the enhanced self-lubricating copper-based composite material.
The surface topography of the composite material prepared in this example is shown in fig. 6, and it can be seen from fig. 6 that the obtained composite material is relatively dense, but a certain amount of discontinuous pores are formed inside the composite material, and the diameter of the pores is about 20 micrometers. The flexural strength and Rockwell hardness of the composite are shown in Table 1.
Example 5
Firstly, weighing 5g of boron nitride powder with the median particle size of 0.5 mu m, 14g of pure titanium powder with the median particle size of 40 mu m and 14g of pure copper powder with the median particle size of 40 mu m, adding 40g of absolute ethyl alcohol, and performing rolling ball milling for 3 hours to prepare uniform and stable slurry; then drying for 2 hours at 50-80 ℃, and sieving to obtain mixture powder A; placing the mixture powder A into a graphite crucible, and placing the graphite crucible into a self-propagating sintering furnace for sintering to obtain composite precursor powder B; and then sieving the compound precursor powder B, mixing the sieved compound precursor powder B with 647g of pure copper powder with the median particle size of 40 mu m, carrying out ball milling for 3 hours, then drying for 2 hours at 50-80 ℃, sieving to obtain mixture powder C, then pouring the compound precursor powder C into a hot-pressing mold, carrying out hot-pressing sintering at the sintering temperature of 900 ℃ for 1 hour under the hot-pressing pressure of 25MPa, and thus obtaining the required self-lubricating copper-based composite material.
The flexural strength and Rockwell hardness of the composite material obtained in this example are shown in Table 1.
Example 6
Firstly, weighing 6g of boron nitride powder with the median particle size of 0.5 mu m, 14g of pure titanium powder with the median particle size of 40 mu m and 14g of pure copper powder with the median particle size of 40 mu m, adding 40g of absolute ethyl alcohol, and performing rolling ball milling for 3 hours to prepare uniform and stable slurry; then drying for 2 hours at 50-80 ℃, and sieving to obtain mixture powder A; placing the mixture powder A into a graphite crucible, and placing the graphite crucible into a self-propagating sintering furnace for sintering to obtain composite precursor powder B; and then sieving the compound precursor powder B, mixing the sieved compound precursor powder B with 647g of pure copper powder with the median particle size of 40 mu m, carrying out ball milling for 3 hours, then drying for 2 hours at 50-80 ℃, sieving to obtain mixture powder C, then pouring the compound precursor powder C into a hot-pressing mold, carrying out hot-pressing sintering at the sintering temperature of 900 ℃ for 1 hour under the hot-pressing pressure of 25MPa, and thus obtaining the required self-lubricating copper-based composite material.
The flexural strength and Rockwell hardness of the composite material obtained in this example are shown in Table 1.
Table 1 shows the composition and mechanical and tribological properties of the composite prepared in the examples:
Claims (7)
1. the preparation method of the enhanced self-lubricating copper-based composite material is characterized by comprising the following steps of:
titanium powder, boron nitride powder, copper powder or/and copper-based alloy powder are/is used as raw materials, precursor powder is prepared by adopting self-propagating sintering after uniform mixing, and the self-propagating sintering is sintering in vacuum or inert atmosphere;
carrying out pressureless sintering or hot-pressing sintering on precursor powder to obtain the enhanced self-lubricating copper-based composite material; the pressureless sintering comprises: prepressing the obtained precursor into blocks, and sintering at 750-1000 ℃ for 0.5-2 hours in vacuum or inert atmosphere; the hot-pressing sintering process comprises the following steps: the sintering temperature is 750-1000 ℃, the sintering pressure is 10-40 MPa, the sintering time is 0.5-2 hours, and the sintering atmosphere is vacuum or inert atmosphere;
the mass fraction of titanium powder in the raw materials is 7.5-50%, the mass fraction of boron nitride powder is 2.5-20%, and the mass fraction of copper powder or/and copper-based alloy powder is 90-30% by taking the total mass of the raw materials as 100%; the average particle size of the titanium powder is 1-50 microns, the average particle size of the boron nitride powder is 0.05-20 microns, and the average particle size of the copper powder or/and copper-based alloy powder is 10-100 microns.
2. The preparation method according to claim 1, wherein the reinforced self-lubricating copper-based composite material is obtained by pressureless sintering or hot-pressing sintering after adding copper powder or/and copper-based alloy powder into precursor powder.
3. The preparation method according to claim 2, wherein the precursor powder accounts for 10-80% of the total mass of the precursor powder and the copper powder or/and the copper-based alloy powder.
4. The preparation method of the enhanced self-lubricating copper-based composite material is characterized by comprising the following steps of:
titanium powder, boron nitride powder, copper powder or/and copper-based alloy powder are/is used as raw materials, and a blank is prepared by dry pressing or/and cold isostatic pressing after uniform mixing;
the obtained blank is prepared into the enhanced self-lubricating copper-based composite material by adopting self-propagating sintering, and the self-propagating sintering is sintering in vacuum or inert atmosphere;
the mass fraction of titanium powder in the raw materials is 7.5-50%, the mass fraction of boron nitride powder is 2.5-20%, and the mass fraction of copper powder or/and copper-based alloy powder is 90-30% by taking the total mass of the raw materials as 100%; the average particle size of the titanium powder is 1-50 microns, the average particle size of the boron nitride powder is 0.05-20 microns, and the average particle size of the copper powder or/and copper-based alloy powder is 10-100 microns.
5. The method according to claim 1 or 4, wherein the alloying element in the copper-based alloy powder is at least one of lead, tin, aluminum, manganese, titanium, lead, zinc, beryllium, tellurium and antimony.
6. A reinforced self-lubricating copper-based composite material prepared according to the method of any one of claims 1 to 5.
7. Use of a reinforced self-lubricating copper-based composite material prepared according to the method of any one of claims 1 to 5 for the preparation of brake pads, gears, worm gears or brushes for electric machines.
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