CN101709397A - Method for preparing titanium carbide dispersion strengthening copper-based composite material - Google Patents
Method for preparing titanium carbide dispersion strengthening copper-based composite material Download PDFInfo
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- CN101709397A CN101709397A CN200910095170A CN200910095170A CN101709397A CN 101709397 A CN101709397 A CN 101709397A CN 200910095170 A CN200910095170 A CN 200910095170A CN 200910095170 A CN200910095170 A CN 200910095170A CN 101709397 A CN101709397 A CN 101709397A
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- 239000010949 copper Substances 0.000 title claims abstract description 65
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005728 strengthening Methods 0.000 title claims description 12
- 239000006185 dispersion Substances 0.000 title description 6
- 239000000843 powder Substances 0.000 claims abstract description 70
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 17
- 239000011812 mixed powder Substances 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000005245 sintering Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 12
- 238000005275 alloying Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910000881 Cu alloy Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 238000013459 approach Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 229910017945 Cu—Ti Inorganic materials 0.000 description 1
- 229910017985 Cu—Zr Inorganic materials 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910001009 interstitial alloy Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种制备碳化钛弥散强化铜基复合材料的方法：以粒度均小于100目，纯度均大于99％的Cu粉、Ti粉和C粉为原料，先将Ti粉和C粉按1∶1(mole)混合后在室温下高能球磨2～20小时；然后向球磨后的混合粉末中添加一定比例的Cu粉，使Ti+C粉与Cu粉的质量比为1∶99～20∶80；把添加了Cu粉后的新混合粉末在室温下继续进行高能球磨2～10小时；将球磨后的Cu、Ti、C混合粉末冷压成型；最后在800～1000℃温度下的氩气保护气氛电阻炉中烧结1～3小时，得到粒径为5～10μm的TiC弥散强化的铜基复合材料。本发明采用简单的高能球磨化方法合成制备TiC弥散强化铜基复合材料，具有工艺简单、生产成本低、产品产量和质量高等优点。The invention discloses a method for preparing a titanium carbide dispersion-strengthened copper-based composite material: using Cu powder, Ti powder and C powder whose particle size is less than 100 mesh and purity greater than 99% as raw materials, the Ti powder and C powder are first pressed After 1:1 (mole) mixing, high-energy ball milling at room temperature for 2-20 hours; then add a certain proportion of Cu powder to the mixed powder after ball milling, so that the mass ratio of Ti+C powder to Cu powder is 1:99-20 : 80; continue high-energy ball milling for 2 to 10 hours at room temperature with the new mixed powder added with Cu powder; cold press the mixed powder of Cu, Ti and C after ball milling; Sintering in a gas-protected atmosphere resistance furnace for 1-3 hours to obtain a TiC dispersion-strengthened copper-based composite material with a particle size of 5-10 μm. The invention adopts a simple high-energy ball milling method to synthesize and prepare the TiC dispersion-strengthened copper-based composite material, and has the advantages of simple process, low production cost, high product yield and quality, and the like.
Description
Technical field
The invention belongs to the metal-base composites preparing technical field, a kind of method for preparing titanium carbide dispersion strengthening copper-based composite material is provided, has can be used for the production preparation of the high-strength highly-conductive Cu-base composites of field widespread uses such as power industry, national defense industry, unicircuit, welding set.
Background technology
Copper alloy with high strength and high conductivity is the structure function material that a class has good comprehensive physicals and mechanical property, irreplaceable effect is arranged in numerous industrial circles, be widely used in electric power, electrician, the mechanical manufacturing field such as electrode, power asynchronous traction motor of high rotor, electric railway contact wire, thermonuclear reactor experiment (ITER) divertor vertical target radiator element of the lead frame mouth of unicircuit, all kinds of spot welding and roll seam welding machine.But intensity in the copper alloy and electroconductibility are a pair of conflicting characteristics always, and this disappears and other rises, generally can only improve the mechanical property of copper under the prerequisite of sacrificing specific conductivity and thermal conductivity, to obtain high intensity.How to solve this contradiction, be the key subject of copper alloy with high strength and high conductivity research always.
The approach that obtains copper alloy with high strength and high conductivity at present mainly contains two kinds: the one, and the alloying approach is promptly introduced alloying element and is strengthened to form copper alloy in copper; The 2nd, compoundization approach is promptly introduced second strengthening phase and is strengthened to form matrix material in the copper matrix.
Alloying is to add alloying element in copper, and solute atoms can cause the lattice lattice distortion after dissolving in lattice, causes stress field, thereby intensity is improved.Traditional alloying is mainly strengthened the copper matrix by means such as solution strengthening and precipitation strengths.According to the alloy solid solution strengthening principle, solid solution alloy unit commonly used in the copper alloy have Sn, Cd, Ag etc.According to the precipitation strength principle, such copper alloy of having developed at present has Cu-Cr, Cu-Zr, Cu-Ti, Cu-Fe etc.The advantage of alloying is that technology is ripe, technology is simple, cost is lower, suitability for scale production.Its shortcoming is that distored dot matrix has reduced electroconductibility to the corresponding aggravation of the scattering process of moving electron in the crystal.Generally can only under the prerequisite of sacrificing specific conductivity, improve the mechanical property of copper.The copper alloy intensity of alloying preparation is between 350～650MPa, and specific conductivity generally is no more than 90%IACS, is difficult to satisfy electrical part of new generation to performance demands.
According to conductivity theory, a little less than the scattering process that second the scattering process of the electronics that causes in the copper matrix causes in the copper matrix than the solid solution atom many, so complex intensifying can not cause the obvious reduction of copper matrix electroconductibility, and wild phase can also improve the mechanical property of matrix, becomes the main means that obtain high-strength high-conductive copper alloy.Research data shows that the composite material strengths such as Cu-Ta, Cu-Nd that utilize the preparation of compoundization of material are greater than 1400MPa, and electric conductivity reaches more than the 90%IACS, and has obtained the engineering application.The difference that compoundization approach is introduced mode according to strengthening phase can be divided into artificial composite algorithm and in-situ compositing.
Artificial composite algorithm is strengthened the copper matrix by the whisker or the fiber that add second phase artificially in copper, or dependence strengthening phase itself increases the method for the strength of materials, for example oxidation reinforcement, mechanical alloying method and carbon fiber composite algorithm etc.The characteristics of artificial composite algorithm are part method comparative maturities, and its product has obtained engineering and used, but complex process, the production cost height.In-situ compositing is to add a certain amount of alloying element in copper, by certain technology, make the inner original position of copper generate wild phase, rather than strengthen body and two kinds of materials of matrix copper with regard to existing before the processing, comprise viscous deformation composite algorithm, reaction in composite algorithm and growth in situ composite algorithm.Contrast artificial composite algorithm, the matrix and the second phase interface consistency are better in the product that in-situ compositing obtained, and step of preparation process reduces, and production cost reduces.
Titanium carbide (TiC) is a kind of interstitial compound of FCC structure, has plurality of advantages such as high rigidity, high-melting-point, low-resistivity, is widely used in fields such as powder metallurgy.If the TiC disperse is distributed in the fine copper matrix, just can prepare a kind of TiC dispersed and strengthened copper-based composite material of high-strength highly-conductive.Traditional TiC dispersed and strengthened copper-based composite material is earlier separately preparation TiC and Cu powder, obtaining by methods such as mechanical alloyings then.But traditional TiC powder process is comparatively complicated, and cost is higher, thereby causes the production process complexity of TiC dispersed and strengthened copper-based composite material, and cost is higher.
2006; Chinese patent CN1804077A has reported a kind of produced in situ titanium carbide dispersion strengthening copper-based composite material and preparation method thereof: the tin titanium carbide ultrafine powder is mixed with copper powder by predetermined proportion; behind the ball milling 5～15 hours; pack into and cold pressing in the graphite jig; sintering is 0.5～3 hour in the protective atmosphere hot pressing furnace under 800～900 ℃ of temperature, the matrix material that obtains is annealed 2～8 hours at 950～1050 ℃ at last again.This method can successfully be prepared the TiC dispersed and strengthened copper-based composite material, but need prepare ultra-fine high-purity tin titanium carbide powder earlier, has increased preparation section, has improved production cost.
High-energy ball milling (high-energy ball milling) reaction in mechanical alloying method is to utilize mechanical energy to come induced chemical reaction or induced material tissue, structure and changes of properties, has become a kind of important channel of preparation super-fine material and advanced composite material.As a kind of new technology, the high-energy ball-milling alloying method has obvious reduction reaction activity, crystal grain thinning, greatly improves powder activity and improve even particle distribution and strengthen combining of interface between body and the matrix, promote the solid ionic diffusion, bring out the cryochemistry reaction, thereby having improved the performance such as degree of compactness, electricity, calorifics of material, is a kind of energy-conservation, material preparation technology efficiently.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of method for preparing titanium carbide dispersion strengthening copper-based composite material is provided, shorten operational path, reduce production costs, improve the quality of products.
The technical scheme that the present invention prepares titanium carbide dispersion strengthening copper-based composite material is: with granularity all less than 100 orders, purity is raw material greater than 99% Cu powder, Ti powder and C powder all, earlier Ti powder and C powder are carried out the proportioning mixing by the ratio row of 1: 1 (mole), is ratio of grinding media to material that 10: 1～100: 1 steel ball and mixed powder put into ball grinder in being full of the glove box of argon gas, makes the ball material mixture account for 10～50% of ball grinder cavity volume; At room temperature carried out high-energy ball milling 2～20 hours with 1000～2000 rev/mins rotating speed; Then, add a certain proportion of Cu powder in the mixed powder in glove box behind ball milling, the mass ratio that makes Ti+C powder and Cu powder is 1: 99～20: 80; The new mixed powder that has added behind the Cu powder was at room temperature carried out high-energy ball milling 2～10 hours with 1000～2000 rev/mins rotating speed; With the mixed powder coldmoulding behind the ball milling once more; At last, sintering is 1～3 hour in the argon shield atmosphere resistance furnace under 800～1000 ℃ of temperature, and obtaining particle diameter is the Cu-base composites of the TiC dispersion-strengthened of 5～10 μ m.
The present invention is simple high-energy ball-milling alloying method, do not add process control agent in the preparation process, make the Cu-base composites of the synthetic preparation of pure Cu powder, Ti powder and C powder reaction TiC dispersion-strengthened, have that technology is simple, production cost is low, product production and a quality advantages of higher.The present invention is by the control to milling parameters, utilize pure Cu powder, Ti powder and C powder at room temperature to react synthetic preparation TiC dispersed and strengthened copper-based composite material, shorten operational path, reduce production costs, improve the quality of products, to realize the extensive widespread use of TiC dispersed and strengthened copper-based composite material.
Embodiment
Further specify flesh and blood of the present invention with example below, but content of the present invention is not limited to this.
Embodiment 1: be 150 orders with granularity, it is raw material that purity is 99.9% Cu powder, Ti powder and C powder, with Ti powder and the C powder uniform mixing that carries out by 1: 1 mole (mole); Is ratio of grinding media to material that 20: 1 steel ball and mixed powder put into the high energy ball mill ball grinder in being full of the glove box of argon gas, makes the ball material mixture account for 15% of ball grinder cavity volume; At room temperature the ball material mixture is carried out 6 hours high-energy ball millings with 1000 rev/mins rotating speed; In the glove box of argon gas atmosphere, in ball grinder, add a certain amount of Cu powder, make the mass ratio between Ti powder+C powder and the Cu powder reach 5: 95; The mixed powder that has added the Cu powder is continued with 1000 rev/mins rotating speed high-energy ball milling 3 hours; Be cold-pressed into right cylinder after taking out powder; Sintering is 3 hours in the argon gas atmosphere resistance furnace under 800 ℃ of temperature, obtains median size and be the TiC dispersed and strengthened copper-based composite material about 9.5 μ m.
Embodiment 2: be 200 orders with granularity, it is raw material that purity is 99.9% Cu powder, Ti powder and C powder, with Ti powder and the C powder uniform mixing that carries out by 1: 1 (mole); Is ratio of grinding media to material that 40: 1 steel ball and mixed powder put into the high energy ball mill ball grinder in being full of the glove box of argon gas, makes the ball material mixture account for 25% of ball grinder cavity volume; At room temperature the ball material mixture is carried out 12 hours high-energy ball millings with 1500 rev/mins rotating speed; In the glove box of argon gas atmosphere, in ball grinder, add a certain amount of Cu powder, make the mass ratio between Ti powder+C powder and the Cu powder reach 15: 85; The mixed powder that has added the Cu powder is continued with 1500 rev/mins rotating speed high-energy ball milling 6 hours; Be cold-pressed into right cylinder after taking out powder; Sintering is 2 hours in the argon gas atmosphere resistance furnace under 900 ℃ of temperature, obtains median size and be the TiC dispersed and strengthened copper-based composite material about 7 μ m.
Embodiment 3: be 300 orders with granularity, it is raw material that purity is 99.9% Cu powder, Ti powder and C powder, with Ti powder and the C powder uniform mixing that carries out by 1: 1 (mole); Is ratio of grinding media to material that 80: 1 steel ball and mixed powder put into the high energy ball mill ball grinder in being full of the glove box of argon gas, makes the ball material mixture account for 35% of ball grinder cavity volume; At room temperature the ball material mixture is carried out 18 hours high-energy ball millings with 2000 rev/mins rotating speed; In the glove box of argon gas atmosphere, in ball grinder, add a certain amount of Cu powder, make the mass ratio between Ti powder+C powder and the Cu powder reach 20: 80; The mixed powder that has added the Cu powder is continued with 2000 rev/mins rotating speed high-energy ball milling 9 hours; Be cold-pressed into right cylinder after taking out powder; Sintering is 1 hour in the argon gas atmosphere resistance furnace under 1000 ℃ of temperature, obtains median size and be the TiC dispersed and strengthened copper-based composite material about 5.5 μ m.
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| CN200910095170A CN101709397A (en) | 2009-11-11 | 2009-11-11 | Method for preparing titanium carbide dispersion strengthening copper-based composite material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102114543A (en) * | 2011-03-23 | 2011-07-06 | 北京矿冶研究总院 | Preparation and spraying method of aluminum bronze powder containing dispersion strengthening phase |
| RU2458165C1 (en) * | 2011-05-04 | 2012-08-10 | Государственное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)" | Method of manufacturing cuprum-based powdered material |
| RU2458166C1 (en) * | 2011-05-04 | 2012-08-10 | Государственное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)" | Method of manufacturing cuprum-based powdered material |
| CN102836998A (en) * | 2012-09-26 | 2012-12-26 | 河南科技大学 | Preparation method for spot-welding electrode with high abrasion resistance, high strength and high conductivity |
| CN106756177A (en) * | 2017-02-23 | 2017-05-31 | 吉林大学 | A kind of preparation method of titanium carbide ceramic granule reinforced copper base composite material |
| CN108610081A (en) * | 2018-06-27 | 2018-10-02 | 河南泛锐复合材料研究院有限公司 | A kind of preparation method of C/C-Cu composite materials |
| CN113881867A (en) * | 2021-10-13 | 2022-01-04 | 佛山市南海宝碳石墨制品有限公司 | Rapid preparation method of high-thermal-conductivity carbon copper |
| CN113981263A (en) * | 2021-10-26 | 2022-01-28 | 北京科技大学 | A kind of method for preparing copper-based titanium carbide composite material by in-situ reaction |
| CN114427049A (en) * | 2022-01-12 | 2022-05-03 | 中国科学院金属研究所 | A kind of Cu-TiCx composite material and preparation method thereof |
| CN117840437A (en) * | 2024-02-28 | 2024-04-09 | 江西国创院新材料有限公司 | A method for preparing copper-based composite material powder for laser 3D printing |
-
2009
- 2009-11-11 CN CN200910095170A patent/CN101709397A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102114543A (en) * | 2011-03-23 | 2011-07-06 | 北京矿冶研究总院 | Preparation and spraying method of aluminum bronze powder containing dispersion strengthening phase |
| RU2458165C1 (en) * | 2011-05-04 | 2012-08-10 | Государственное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)" | Method of manufacturing cuprum-based powdered material |
| RU2458166C1 (en) * | 2011-05-04 | 2012-08-10 | Государственное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)" | Method of manufacturing cuprum-based powdered material |
| CN102836998A (en) * | 2012-09-26 | 2012-12-26 | 河南科技大学 | Preparation method for spot-welding electrode with high abrasion resistance, high strength and high conductivity |
| CN106756177A (en) * | 2017-02-23 | 2017-05-31 | 吉林大学 | A kind of preparation method of titanium carbide ceramic granule reinforced copper base composite material |
| CN106756177B (en) * | 2017-02-23 | 2018-04-24 | 吉林大学 | A kind of preparation method of titanium carbide ceramic granule reinforced copper base composite material |
| CN108610081A (en) * | 2018-06-27 | 2018-10-02 | 河南泛锐复合材料研究院有限公司 | A kind of preparation method of C/C-Cu composite materials |
| CN108610081B (en) * | 2018-06-27 | 2021-04-09 | 巩义市泛锐熠辉复合材料有限公司 | Preparation method of C/C-Cu composite material |
| CN113881867A (en) * | 2021-10-13 | 2022-01-04 | 佛山市南海宝碳石墨制品有限公司 | Rapid preparation method of high-thermal-conductivity carbon copper |
| CN113881867B (en) * | 2021-10-13 | 2022-05-17 | 佛山市南海宝碳石墨制品有限公司 | Rapid preparation method of high-thermal-conductivity carbon copper |
| CN113981263A (en) * | 2021-10-26 | 2022-01-28 | 北京科技大学 | A kind of method for preparing copper-based titanium carbide composite material by in-situ reaction |
| CN114427049A (en) * | 2022-01-12 | 2022-05-03 | 中国科学院金属研究所 | A kind of Cu-TiCx composite material and preparation method thereof |
| CN117840437A (en) * | 2024-02-28 | 2024-04-09 | 江西国创院新材料有限公司 | A method for preparing copper-based composite material powder for laser 3D printing |
| CN117840437B (en) * | 2024-02-28 | 2024-06-07 | 江西国创院新材料有限公司 | Preparation method of copper-based composite material powder for laser 3D printing |
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