CN1900332A - Method for preparing copper base composite material by chemical precipitation method to obtain composite powder - Google Patents
Method for preparing copper base composite material by chemical precipitation method to obtain composite powder Download PDFInfo
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- CN1900332A CN1900332A CN 200610041098 CN200610041098A CN1900332A CN 1900332 A CN1900332 A CN 1900332A CN 200610041098 CN200610041098 CN 200610041098 CN 200610041098 A CN200610041098 A CN 200610041098A CN 1900332 A CN1900332 A CN 1900332A
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- 239000002131 composite material Substances 0.000 title claims abstract description 112
- 239000000843 powder Substances 0.000 title claims abstract description 104
- 239000010949 copper Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 238000009388 chemical precipitation Methods 0.000 title claims abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012452 mother liquor Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 10
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 8
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract 25
- 229910018626 Al(OH) Inorganic materials 0.000 claims abstract 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 229910052593 corundum Inorganic materials 0.000 claims description 28
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 23
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 19
- 238000003825 pressing Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 13
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 13
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- -1 ammonium aluminum sulfate Ammonium Chemical compound 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000012716 precipitator Substances 0.000 description 6
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 5
- 238000000265 homogenisation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910052927 chalcanthite Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000000615 nonconductor Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- FOJJCOHOLNJIHE-UHFFFAOYSA-N aluminum;azane Chemical compound N.[Al+3] FOJJCOHOLNJIHE-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
本发明公开了一种利用化学沉淀法获得复合粉制备铜基复合材料的方法，首先在25～30℃的温度下，硫酸铜和硫酸铝铵组成的母液中滴加碳酸氢铵，沉淀得到NH4Al(OH)2CO3－Cu2(OH)2CO3溶胶，陈化8小时，离心得到NH4Al(OH)2CO3－Cu2(OH)2CO3凝胶，凝胶经无水乙醇洗涤和离心脱醇，50℃烘干研磨得NH4Al(OH)2CO3－Cu2(OH)2CO3前驱体，前驱体经1100～1200℃灼烧得Al2O3－CuO复合粉；然后Al2O3－CuO复合粉在350℃的甲醇或氢气还原性气氛中还原0.5～1小时得Al2O3－Cu复合粉；最后将Al2O3－Cu复合粉在100kN的压力下双面冷压成坯，800～850℃下烧结成型。本发明采用化学共沉淀法可精确控制Al2O3－Cu复合粉中Al2O3的含量，满足耐磨性和导电性不同要求的工况。The invention discloses a method for preparing copper-based composite materials from composite powders obtained by chemical precipitation. First, ammonium bicarbonate is added dropwise to a mother liquor composed of copper sulfate and aluminum ammonium sulfate at a temperature of 25 to 30°C, and NH 4 Al(OH) 2 CO 3 -Cu 2 (OH) 2 CO 3 sol, aged for 8 hours, and centrifuged to obtain NH 4 Al(OH) 2 CO 3 -Cu 2 (OH) 2 CO 3 gel, which was Washing with absolute ethanol and centrifugal dealcoholization, drying and grinding at 50°C to obtain NH 4 Al(OH) 2 CO 3 -Cu 2 (OH) 2 CO 3 precursor, and burning the precursor at 1100-1200°C to obtain Al 2 O 3 -CuO composite powder; then Al 2 O 3 -CuO composite powder is reduced in methanol or hydrogen reducing atmosphere at 350°C for 0.5 to 1 hour to obtain Al 2 O 3 -Cu composite powder; finally, Al 2 O 3 -Cu composite powder Under the pressure of 100kN, both sides are cold-pressed into a billet, and sintered at 800-850°C. The invention adopts the chemical co-precipitation method to accurately control the content of Al 2 O 3 in the Al 2 O 3 -Cu composite powder, and satisfies working conditions with different requirements for wear resistance and electrical conductivity.
Description
Technical Field
The invention relates to a preparation method of a nano composite material, in particular to a method for preparing a copper-based composite material by using composite powder obtained by a chemical precipitation method.
Background
The dispersion strengthening copper-based composite material is characterized in that second phase particles with good thermal stability are formed in a copper matrix in a dispersion distribution manner through a certain process, so that the strength and the high-temperature stability of the material are improved. The copper-based composite material has excellent electrical and thermal conductivity, high-temperature stability and high strength, has great application potential in the high-tech fields of electromechanics, astronavigation, microelectronics and the like, is widely applied to large-scale integrated circuit lead frames, electric welding electrodes, change-over switches, electric contacts and the like, and is a key material for the development of the modern electronic information industry.
At present, tungsten, molybdenum, graphite andsilicon carbide are often selected as reinforcing phases to be sintered into a copper-based composite material together with Cu powder through powder metallurgy, but the proportion of tungsten and molybdenum is high, and the compounding amount of silicon carbide is large. Nano Al2O3Has the characteristics of high strength, excellent thermal conductivity, small thermal expansion coefficient and good high-temperature stability, and can be used for reinforcing the copper-based material, not only can not greatly reduce the electrical conductivity of the matrix, but also can ensure the strength of the matrix due to the reinforcing effectAnd the high temperature performance is significantly improved. Al in the prior art2O3the-Cu composite powder ① adopts a mechanical alloying method, namely Cu and Al2O3Grinding the powder in high-energy ball mill for a long time to obtain composite powder, ② internal oxidation by adding unstable compound powder into alloy powder to make the components in alloy and added compound generate thermal reduction reaction to generate more stable ceramic reinforced particles, ③ nm Al2O3Powder chemical copper plating method. These methods have more or less some problems: such as mechanical alloying, cannot completely open nanoscale Al2O3The oxygen supply amount of the powder and internal oxidation method cannot be accurately controlled, and the proportion of the powder and the internal oxidation method cannot be accurately controlled by the powder chemical copper plating method.
Disclosure of Invention
The invention provides a method for preparing a copper-based composite material by using composite powder obtained by a chemical precipitation method, and nanoscale Al is obtained by using the chemical precipitation method2O3-Cu composite powder with precise control of Al2O3Al in-Cu composite powder2O3The content of the copper-based composite material is convenient for preparing copper-based composite materials with different properties, and the requirements of various working conditions are met.
The technical solution of the invention is as follows: firstly, at the temperature of 25-30 ℃, adding precipitator ammonium bicarbonate dropwise into mother liquor consisting of copper sulfate and ammonium aluminum sulfate, and coprecipitating to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Sol, NH4Al(OH)2CO3-Cu2(OH)2CO3Aging the sol at room temperature for 8 hours, removing supernatant, and centrifugally dewatering to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Soaking gel in anhydrous ethanol for 4 hr, centrifuging to remove alcohol to obtain gel, washing with alcohol for more than 3 times, oven drying the gel slowly at 50 deg.C, grinding, and sieving with 100 mesh and 200 mesh sieve to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Firing the precursor powder at 1100-1200 DEG CGrinding the precursor powder for 0.5-1 hour, and sieving with a 200-mesh sieve and a 400-mesh sieve to obtain the nano Al2O3-CuO composite powder; then, adding Al2O3reducing-CuO composite powder at 350 ℃ in methanol or hydrogen reducing atmosphere to obtain Al2O3-a Cu composite powder; finally, Al2O3And (4) cold-pressing the-Cu composite powder into a blank, and sintering and forming at 800-850 ℃ to obtain the copper-based composite material.
The invention relates to a method for preparing a copper-based composite material by using composite powder obtained by a chemical precipitation method, wherein the raw materials comprise copper sulfate, aluminum ammonium sulfate, ammonium bicarbonate and sulfurThe acid copper and the aluminum ammonium sulfate form mother liquor, and the ammonium bicarbonate is used as a precipitator; according to Al2O3Al in-Cu composite2O3To determine NH4Al(SO4)2And CuSO4According to NH4Al(SO4)2And NH4HCO3In a molar ratio of 1: 4 and CuSO4And NH4HCO3Is 1: 2 to determine NH4HCO3Amount of Al2O3Al in-Cu2O3Less than 5% by mass; NH (NH)4Al(OH)2CO3-Cu2(OH)2CO3The precursor powder is burnt at the high temperature of 1100-1200 ℃ for 0.5-1 hour to obtain Al2O3-a Cu composite powder; al (Al)2O3Reducing the-CuO composite powder in a reducing atmosphere of methanol or hydrogen at 350 ℃ for 0.5 to 1 hour to obtain Al2O3-a Cu composite powder; al (Al)2O3And (4) carrying out cold pressing on the-Cu composite powder under the pressure of 100kN to form a blank, and sintering at the temperature of 800-850 ℃ to obtain the copper-based composite material.
The invention relates to a method for preparing a copper-based composite material by using composite powder obtained by a chemical precipitation method, which comprises the following specific steps:
(1) firstly, preparing nano Al by a chemical precipitation method2O3-CuO composite powder;
the operating conditions are as follows: the temperature of the constant temperature water bath is set to be 25-30 ℃;
mother liquor and precipitant: according to Al2O3Al in-Cu2O3Ratiometric determination of NH4Al(SO4)2And CuSO4In accordance with NH4Al(SO4)2And NH4HCO3In a molar ratio of 1: 4 and CuSO4And NH4HCO3Is 1: 2 to determine NH4HCO3Amount of (1), Al2O3Al in-Cu2O3Less than 5% by mass;
surfactant (b): the weight of the sodium hexametaphosphate with the concentration of 0.5mg/L is two ten-thousandth of the weight of the raw material;
the method comprises the following operation steps: A. NH to be configured according to the above requirements4Al(SO4)2And CuSO4Adding the mother liquor into a reaction kettle, simultaneously adding sodium hexametaphosphate, and mechanically stirring until the mother liquor is dissolved;
B. dripping the precipitant into the mother liquid at a speed of 10ml/min, and continuously stirring for 0.5 hour after all the precipitant is dripped out to ensure the homogenization of the system and finally generate NH4Al(OH)2CO3And Cu2(OH)2CO3Sol;
C. aging the sol for 8 hours at room temperature, removing supernatant, and centrifugally dewatering to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Soaking the gel in absolute ethyl alcohol for 4 hours, centrifuging and dealcoholizing to obtain gel, and repeating the alcohol washing process for more than 3 times;
D. slowly drying the dealcoholized gel at 50 ℃, grinding, and sieving with 100-mesh and 200-mesh sieves to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Precursor powder;
E. calcining the precursor powder for 0.5-1 hour at 1100-1200 ℃, grinding, and sieving with a 200-mesh sieve and a 400-mesh sieve to obtain the nano Al2O3-CuO composite powder;
(2) then, reducing Al2O3Al from CuO2O3-Cu composite powder:
reducing the mixture in a reducing atmosphere of methanol or hydrogen at 350 ℃ for 0.5 to 1 hour to obtain Al2O3-a Cu composite powder.
(3) And finally, cold pressing to form a blank, and sintering at normal pressure:
mixing Al2O3Carrying out cold pressing on the Cu composite powder on a press to form a blank, and selecting the double-sided cold pressing for more than 6 times under the pressure of 100 kN; and then sintering and molding in a sintering furnace at 800-850 ℃ to obtain the copper-based composite material.
It is known to use aluminum ammonium sulfate (NH)4AlSO4·12H2O) is mother liquid, ammonium hydrogen carbonate (NH)4HCO3) As a precipitant, alumina (Al) can be obtained2O3) Powder:
copper sulfate (CuSO) is known4·5H2O) is mother liquor, ammonium hydrogen carbonate (NH)4HCO3) As a precipitant, copper oxide powder can be produced:
thus, ammonium bicarbonate (NH) is employed4HCO3) As co-precipitating agent, depending on the Al content of the composite2O3To determine NH4Al(SO4)2、CuSO4And NH4HCO3The quality of the reactant is controlled, and the agglomeration of the powder is controlled by controlling the technical parameters in the preparation process, so that the nano-grade composite powder is obtained.
Due to Al2O3The non-conductor is added, although the strength and the wear resistance can be improved, the electrical conductivity of the product is influenced to a certain extent, and the more the content of the non-conductor is, the poorer the electrical conductivity is. Therefore, according to different requirements, different Al contents can be obtained by adjusting the relative amount of the mother liquor2O3The copper-based composite material has high strength, high conductivity, good thermal property, high hardness and good wear resistance, and can be used for contact materials, spot welding electrodes, integrated circuit lead frames, aviation and other occasions requiring high strength and high wear resistance in the field of microelectronic packaging.
Detailed Description
Method for preparing copper-based composite material by using composite powder obtained by chemical precipitation methodThe method comprises the following steps: firstly, at the temperature of 25-30 ℃, in the group of copper sulfate and aluminum ammonium sulfateThe mother liquid is added with ammonium bicarbonate as precipitant and then coprecipitated to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Aging the solat room temperature for 8 hours, removing supernatant, centrifugally dewatering to obtain gel, soaking the gel in absolute ethyl alcohol for 4 hours, centrifugally dealcoholizing, repeating the alcohol washing process for more than 3 times, slowly drying the dealcoholized gel at 50 ℃, grinding, sieving by a 100-mesh sieve and a 200-mesh sieve to obtain precursor powder, calcining the precursor powder for 0.5-1 hour at 1100-1200 ℃, grinding, sieving by a 200-mesh sieve and a 400-mesh sieve to obtain the nano Al2O3-CuO composite powder; then, adding Al2O3reducing-CuO composite powder at 350 ℃ in methanol or hydrogen reducing atmosphere to obtain Al2O3-a Cu composite powder; finally, Al2O3And (4) carrying out cold pressing on Cu to form a blank, and sintering and forming at 800-850 ℃ to obtain the copper-based composite material.
The method comprises the following specific steps:
(1) firstly, preparing nano Al by a chemical precipitation method2O3-CuO composite powder:
the operating conditions are as follows: the temperature of the constant temperature water bath is set to be 25-30 ℃;
mother liquor and precipitant: according to Al2O3Al in-Cu2O3Ratiometric determination of NH4Al(SO4)2And CuSO4In accordance with NH4Al(SO4)2And NH4HCO3In a molar ratio of 1: 4 and CuSO4And NH4HCO3Is 1: 2 to determine NH4HCO3Amount of (1), Al2O3Al in-Cu2O3Less than 5% by mass;
surfactant (b): the weight of the sodium hexametaphosphate with the concentration of 0.5mg/L is two ten-thousandth of the weight of the rawmaterial;
the method comprises the following operation steps: A. NH to be configured according to the above requirements4Al(SO4)2And CuSO4Adding the mother liquor into a reaction kettle, simultaneously adding sodium hexametaphosphate, and mechanically stirring until the mother liquor is dissolved;
B. adding a precipitator NH4HCO3Dropping into the mother liquor at a speed of 10ml/minAfter the partial dripping is finished, stirring is continued for 0.5 hour to ensure the homogenization of the system and finally generate NH4Al(OH)2CO3And Cu2(OH)2CO3Sol;
C. aging the sol for 8 hours at room temperature, removing supernatant, and centrifugally dewatering to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Soaking the gel in absolute ethyl alcohol for 4 hours, centrifuging and dealcoholizing to obtain gel, and performing alcohol washing for more than 3 times;
D. slowly drying the gel after dealcoholization at 50 ℃, grinding and sieving with 100-mesh and 200-mesh sieves to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Precursor powder;
E. calcining the precursor powder for 0.5-1 hour at 1100-1200 ℃, grinding and sieving with 200-mesh and 400-mesh sieves to obtain the nano Al2O3-CuO composite powder;
(2) then, reducing Al2O3Al from CuO2O3-Cu composite powder:
reducing the mixture in a reducing atmosphere of methanol or hydrogen at 350 ℃ for 0.5 to 1 hour to obtain Al2O3-a Cu composite powder.
(3) And finally, cold pressing to form a blank, and sintering at normal pressure:
mixing Al2O3Carrying out cold pressing on the Cu composite powder on a press to form a blank, and selecting the double-sided cold pressing for more than 6 times under the pressure of 100 kN; and sintering and molding in a sintering furnace at 800-850 ℃ to obtain the copper-based composite material.
Example 1:
(1) firstly, preparing nano Al by adopting a chemical precipitation method2O3-CuO composite powder:
the operating conditions are as follows: the temperature of the constant temperature water bath is set at 25 ℃;
mother liquor and precipitant: by Al in copper-based composites2O3For an example of a content of 5% (mass fraction), 0.75g of NH was weighed4Al(SO4)2And 6.25g of CuSO4Adding water to prepare 200mlSolution according to NH4Al(SO4)2And NH4HCO3In a molar ratio of 1 to4 and CuSO4And NH4HCO3In a molar ratio of 1: 2, 4.47g of NH are determined4HCO3Adding water to prepare 200ml of solution; to make CuSO4·5H2O and NH4Al(SO4)2·12H2Complete reaction of O and make up for the waste, NH, during the addition4HCO3An appropriate excess was made, so 4.5g of NH were weighed4HCO3Adding water to prepare 205ml of solution;
surfactant (b): 0.2mg of sodium hexametaphosphate;
the method comprises the following operation steps: A. NH to be configured according to the above requirements4Al(SO4)2And CuSO4Adding the mother liquor into a reaction kettle, simultaneously adding sodium hexametaphosphate, and mechanically stirring until the mother liquor is dissolved;
B. adding a precipitator NH4HCO3Dripping into the mother liquor at a speed of 10ml/min, and continuing stirring for 0.5 hour after all dripping to ensure the homogenization of the system and finally generate NH4Al(OH)2CO3And Cu2(OH)2CO3Sol;
C. aging the sol for 8 hours at room temperature, removing supernatant, and centrifugally dewatering to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Soaking the gel in absolute ethyl alcohol for 4 hours, centrifuging and dealcoholizing to obtain gel, and performing alcohol washing for more than 3 times;
D. slowly drying the dealcoholized gel at 50 ℃, grinding, and sieving with a 100-mesh sieve to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Precursor powder;
E. calcining the precursor powder for 0.5 hour at 1100 ℃, grinding, and sieving with a 200-mesh sieve to obtain the nano Al2O3-CuO composite powder;
(2) then, reducing Al2O3Al from CuO2O3-Cu composite powder:
methanol at 350 ℃Reducing for 0.5 hour in reducing atmosphere to obtain Al2O3-a Cu composite powder.
(3) And finally, cold pressing to form a blank, and sintering at normal pressure:
mixing Al2O3Carrying out cold pressing on-Cu composite powder on a press to form a blank, wherein the pressure is selected to be100kN, cold pressing the two surfaces for more than 6 times; and then sintering and molding in a sintering furnace at 800 ℃ to obtain the high-strength medium-conductivity copper-based composite material.
Example 2:
(1) firstly, preparing nano Al by adopting a chemical precipitation method2O3-CuO composite powder:
the operating conditions are as follows: the temperature of the constant temperature water bath is set at 28 ℃;
mother liquor and precipitant: by Al in copper-based composites2O3For example, the content was 3% (mass fraction), and 0.44g of NH was weighed4Al(SO4)2And 6.25g of CuSO4Adding water to prepare 200ml of solution according to NH4Al(SO4)2And NH4HCO3In a molar ratio of 1: 4 and CuSO4And NH4HCO3In a molar ratio of 1: 2, 4.26g of NH are determined4HCO3Adding water to prepare 200ml of solution; to make CuSO4·5H2O and NH4Al(SO4)2·12H2Complete reaction of O and make up for the waste, NH, during the addition4HCO3An appropriate excess was made, so 4.3g of NH were weighed4HCO3Adding water to prepare 205ml of solution;
surfactant (b): 0.2mg of sodium hexametaphosphate;
the method comprises the following operation steps: A. NH to be configured according to the above requirements4Al(SO4)2And CuSO4Adding the mother liquor into a reaction kettle, simultaneously adding sodium hexametaphosphate, and mechanically stirring until the mother liquor is dissolved;
B. adding a precipitator NH4HCO3Dripping into the mother liquor at a speed of 10ml/min, and continuing stirring for 0.5 hour after all dripping to ensure the homogenization of the system and finally generate NH4Al(OH)2CO3And Cu2(OH)2CO3Sol;
C. aging the sol for 8 hours at room temperature, removing supernatant, and centrifugally dewatering to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Soaking the gel in absolute ethyl alcohol for 4 hours, centrifuging and dealcoholizing to obtain gel, and performing alcohol washing for more than 3 times;
D. slowly drying the dealcoholized precursor gel at 50 ℃, grinding,sieving with 200 mesh sieve to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Precursor powder;
E. calcining the precursor powder for 0.8 hour at 1150 ℃, grinding and sieving with a 400-mesh sieve to obtain the nano Al2O3-CuO composite powder;
(2) then, reducing Al2O3Al from CuO2O3-Cu composite powder:
reducing for 0.8 hours in hydrogen reducing atmosphere at 350 ℃ to obtain Al2O3-a Cu composite powder.
(3) And finally, cold pressing to form a blank, and sintering at normal pressure:
mixing Al2O3Carrying out cold pressing on the Cu composite powder on a press to form a blank, and selecting the double-sided cold pressing for more than 6 times under the pressure of 100 kN; and then sintering and molding in a 830 ℃ sintering furnace to obtain the high-strength high-conductivity copper-based composite material.
Example 3:
(1) firstly, preparing nano Al by adopting a chemical precipitation method2O3-CuO composite powder:
the operating conditions are as follows: the temperature of the constant temperature water bath is set at 30 ℃;
mother liquor and precipitant: by Al in copper-based composites2O3For an example of a content of 1% (mass fraction), 0.144g of NH was weighed4Al(SO4)2And 6.25g of CuSO4Adding water to prepare 200ml of solution according to NH4Al(SO4)2And NH4HCO3In a molar ratio of 1: 4 and CuSO4And NH4HCO3Is determined to be 4.1 when the molar ratio of (1: 2)g NH of4HCO3Adding water to prepare 200ml of solution; to make CuSO4·5H2O and NH4Al(SO4)2·12H2Complete reaction of O and make up for the waste, NH, during the addition4HCO3An appropriate excess was made, so 4.2g of NH were weighed4HCO3Adding water to prepare 205ml of solution;
surfactant (b): 0.2mg of sodium hexametaphosphate;
the method comprises the following operation steps: A. NH to be configured according to the above requirements4Al(SO4)2And CuSO4FemaleAdding the solution into a reaction kettle, simultaneously adding sodium hexametaphosphate, and mechanically stirring until the solution is dissolved;
B. adding a precipitator NH4HCO3Dripping into the mother liquor at a speed of 10ml/min, and continuing stirring for 0.5 hour after all dripping to ensure the homogenization of the system and finally generate NH4Al(OH)2CO3And Cu2(OH)2CO3Sol;
C. aging the sol for 8 hours at room temperature, removing supernatant, and centrifugally dewatering to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3Soaking the gel in absolute ethyl alcohol for 4 hours, centrifuging and dealcoholizing to obtain gel, wherein the alcohol washing process needs more than 3 times;
D. slowly drying the dealcoholized precursor gel at 50 ℃, grinding and sieving by a 100-mesh sieve to obtain precursor powder;
E. calcining the precursor powder for 1 hour at 1200 ℃, grinding and sieving with a 400-mesh sieve to obtain the nano Al2O3-CuO composite powder;
(2) then, reducing Al2O3Al from CuO2O3-Cu composite powder:
reducing for 1 hour in a methanol reducing atmosphere at 350 ℃ to obtain Al2O3-a Cu composite powder.
(3) And finally, cold pressing to form a blank, and sintering at normal pressure:
mixing Al2O3Cold pressing the-Cu composite powder on a press to form a blank, and selecting pressureThe steel is 100kN, and the double faces are cold-pressed for more than 6 times; and then sintering and molding in a sintering furnace at 850 ℃ to obtain the medium-strength high-conductivity copper-based composite material.
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