CN100395360C - 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 PDF

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CN100395360C
CN100395360C CNB2006100410980A CN200610041098A CN100395360C CN 100395360 C CN100395360 C CN 100395360C CN B2006100410980 A CNB2006100410980 A CN B2006100410980A CN 200610041098 A CN200610041098 A CN 200610041098A CN 100395360 C CN100395360 C CN 100395360C
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composite powder
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powder
chemical precipitation
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CN1900332A (en
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丁红燕
周广宏
章跃
符学龙
韩晓萍
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Huaiyin Institute of Technology
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Abstract

The process of preparing copper base composite material with composite powder prepared through chemical precipitation includes the following steps: dropping ammonium bicarbonate into mother liquid comprising copper sulfate and aluminum ammonium sulfate at 25-30 deg.c to obtain settled NH4Al(OH)2CO3-Cu2(OH)2CO3 sol, ageing for 8 hr and centrifuging to obtain NH4Al(OH)2CO3 -Cu2(OH)2CO3 gel, washing the gel with anhydrous alcohol, centrifuging to eliminate alcohol and stoving and grinding at 50deg.c to obtain NH4Al(OH)2CO3-Cu2(OH)2CO3 precursor, igniting the precursor at 1100-1200 deg.c to obtain composite Al2O3-CuO powder, reducing the composite Al2O3-CuO powder in reducing methanol or hydrogen atmosphere at 350 deg.c for 0.5-1 hr to obtain composite Al2O3-Cu powder; cold pressing the composite Al2O3-Cu powder at 100 kN pressure to form blank, and final at 800-850 deg.c. The present invention has precisely controlled Al2O3 content for required wear resistance and conductivity.

Description

A kind of chemical precipitation method of utilizing obtains the method that composite powder prepares Cu-base composites
Technical field
The present invention relates to a kind of preparation method of nano composite material, be specifically related to a kind of chemical precipitation method of utilizing and obtain the method that composite powder prepares Cu-base composites.
Background technology
Dispersed and strengthened copper-based composite material is meant by certain technology to form the second phase particle with good thermal stability that disperse distributes in the copper matrix, thereby improves the intensity and the high-temperature stability of material.Because Cu-base composites has good electrical and thermal conductivity, high-temperature stability and higher intensity, huge at high-tech sector application potentials such as electromechanics, aerospace, microelectronics, being widely used in large-scale integrated circuit lead frame, welding electrode, transfer lever, electrical contact etc., is the critical material of the hyundai electronics information industry development.
At present, tungsten, molybdenum, graphite, silicon carbide often are chosen as wild phase and carry out powder metallurgy sintered one-tenth Cu-base composites with the Cu powder, but tungsten, molybdenum is than great, and the compounding quantity of silicon carbide is many.Nanometer Al 2O 3Have intensity height, thermal conductivity is good, thermal expansivity is little and high-temperature stability is good characteristics, be used for strengthening the electroconductibility of the not only not too large reduction matrix of copper-based material, and because its strengthening effect can make the intensity of matrix and high-temperature behavior be able to obvious improvement.Al in the existing achievement 2O 31.-Cu composite powder adopts mechanical alloying method, is about to Cu and Al 2O 3Powder long-time ground and mixed in high energy ball mill obtains composite powder; 2. internal oxidation promptly utilizes thermal reduction reaction principle chemically, and the unstable compounds powder is joined in the powdered alloy, makes the constituent element in the alloy and the compound generation thermal reduction reaction of adding, generates required more stable ceramic enhanced granule; 3. nanometer Al 2O 3The powder chemistry copper-plating method.More or less there are some problems in these methods: can not open nano level Al fully as mechanical alloying method 2O 3Powder, the oxygen-supplying amount of internal oxidation can't accurately be controlled, and the powder chemistry copper-plating method can't accurately be controlled the ratio of the two.
Summary of the invention
The invention provides a kind of chemical precipitation method of utilizing and obtain the method that composite powder prepares Cu-base composites, utilize chemical precipitation method to obtain nano level Al 2O 3-Cu composite powder, and accurately control Al 2O 3Al in the-Cu composite powder 2O 3Content so that make the Cu-base composites of different performance, satisfy the needs of various operating modes.
Technical solution of the present invention is: at first, under 25~30 ℃ of conditions of temperature, drip precipitation agent bicarbonate of ammonia in the mother liquor of copper sulfate and exsiccated ammonium alum composition, co-precipitation gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Colloidal sol, NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Ageing is 8 hours under the colloidal sol room temperature, removes supernatant liquid, and centrifuge dehydration gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Gel, soaked in absolute ethyl alcohol gel 4 hours, centrifugal dealcoholysis gets gel, and the alcohol process of washing repeats under 50 ℃, gel slowly to be dried more than 3 times, grinds, and crosses 100 orders, 200 mesh sieves, gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Precursor powder 1100~1200 ℃ of following calcination precursor powders 0.5~1 hour, grinds, and crosses 200 orders, 400 mesh sieves, nanometer Al 2O 3-CuO composite powder; Then, with Al 2O 3-CuO composite powder under 350 ℃ methyl alcohol or hydrogen reducing atmosphere, reduce Al 2O 3-Cu composite powder; At last, Al 2O 3-Cu composite powder is cold-pressed into base, and 800~850 ℃ of sinter moldings get Cu-base composites.
A kind of chemical precipitation method acquisition composite powder that utilizes of the present invention prepares in the method for Cu-base composites, and raw material is copper sulfate, exsiccated ammonium alum and bicarbonate of ammonia, and copper sulfate and exsiccated ammonium alum are formed mother liquor, and bicarbonate of ammonia is precipitation agent; According to Al 2O 3Al in the-Cu matrix material 2O 3Content determine NH 4Al (SO 4) 2And CuSO 4Quality, again according to NH 4Al (SO 4) 2And NH 4HCO 3Mol ratio be 1: 4 and CuSO 4With NH 4HCO 3Mol ratio be to determine NH at 1: 2 4HCO 3Amount Al 2O 3Al among the-Cu 2O 3Massfraction less than 5%; NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Precursor powder got Al in 0.5~1 hour at 1100~1200 ℃ of high temperature sinterings 2O 3-Cu composite powder; Al 2O 3-CuO composite powder got Al in 0.5~1 hour 350 ℃ methyl alcohol or the reduction of hydrogen reducing atmosphere 2O 3-Cu composite powder; Al 2O 3-Cu composite powder is cold-pressed into base under 100kN pressure, 800~850 ℃ of sinter moldings get Cu-base composites.
A kind of chemical precipitation method acquisition composite powder that utilizes of the present invention prepares in the method for Cu-base composites, and concrete steps are:
(1) at first, chemical precipitation method prepares nanometer Al 2O 3-CuO composite powder;
Operational condition: the constant temperature water bath temperature is set in 25 ℃~30 ℃;
Mother liquor and precipitation agent: according to Al 2O 3Al among the-Cu 2O 3Ratio is determined NH 4Al (SO 4) 2And CuSO 4Amount, according to NH 4Al (SO 4) 2And NH 4HCO 3Mol ratio be 1: 4 and CuSO 4With NH 4HCO 3Mol ratio be to determine NH at 1: 2 4HCO 3Amount, Al 2O 3Al among the-Cu 2O 3Massfraction less than 5%;
Tensio-active agent: Sodium hexametaphosphate 99, concentration are that the weight of 0.5mg/L Sodium hexametaphosphate 99 is 2/10000ths of reactant copper sulfate, exsiccated ammonium alum and bicarbonate of ammonia weight;
Operation steps: A, will be by the NH of above-mentioned requirements configuration 4Al (SO 4) 2And CuSO 4Mother liquor adds in the reactor, adds Sodium hexametaphosphate 99 simultaneously, till mechanical stirring is extremely dissolved;
B, the speed of precipitation agent with 10ml/min is splashed in the mother liquor, after treating all to drip off, continue to stir 0.5 hour,, and finally generate NH with the guarantee system homogenizing 4Al (OH) 2CO 3And Cu 2(OH) 2CO 3Colloidal sol;
With colloidal sol ageing 8 hours, remove supernatant liquid under C, the room temperature, centrifuge dehydration gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Gel gets gel with the centrifugal dealcoholysis in 4 hours of soaked in absolute ethyl alcohol gel, repeats alcohol and washes process more than 3 times;
D, under 50 ℃, the gel after the dealcoholysis is slowly dried, grind, cross 100 orders or 200 mesh sieves, NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Precursor powder;
E, under 1100~1200 ℃, calcining precursor powder 0.5~1 hour grinds, and crosses 200 orders or 400 mesh sieves, nanometer Al 2O 3-CuO composite powder;
(2) then, reduction Al 2O 3-CuO gets Al 2O 3-Cu composite powder:
In 350 ℃ methyl alcohol or hydrogen reducing atmosphere, reduce and got Al in 0.5~1 hour 2O 3-Cu composite powder.
(3) last, be cold-pressed into base, normal pressure-sintered:
With Al 2O 3-Cu composite powder is cold-pressed into base on pressing machine, selecting pressure for use is 100kN, two-sided colding pressing more than 6 times; Sinter molding in 800~850 ℃ of sintering ovens gets Cu-base composites immediately; The sintering time fibrous root of blank in sintering oven decides according to its thickness, the per 1 millimeter sintering of equivalent depth 10 minutes.
Known to exsiccated ammonium alum (NH 4AlSO 412H 2O) be mother liquor, bicarbonate of ammonia (NH 4HCO 3) be precipitation agent, can make aluminum oxide (Al 2O 3) powder:
NH 4Al(SO 4) 2+4NH 4HCO 3→NH 4Al(OH) 2CO 3+2(NH 4) 2SO 4+3CO 2↑+H 2O
2NH 4Al(OH) 2CO 3→Al 2O 3+2CO 2↑+3H 2O+2NH 3
Known to copper sulfate (CuSO 45H 2O) be mother liquor, bicarbonate of ammonia (NH 4HCO 3) be precipitation agent, can make cupric oxide powder:
2CuSO 4+4NH 4HCO 3→Cu 2(OH) 2CO 3+2(NH 4) 2SO 4+3CO 2↑+H 2O
Cu 2(OH) 2CO 3→2CuO+H 2O+CO 2
Therefore, adopt bicarbonate of ammonia (NH 4HCO 3) be coprecipitator, according to Al in the matrix material 2O 3Content determine NH 4Al (SO 4) 2, CuSO 4And NH 4HCO 3The quality of reactant, and control the reunion of powder by the technical parameter of control in the preparation process, thus obtain the composite powder of Nano grade.
Because Al 2O 3Be non-conductor, though its adding can improve intensity and wear resistance, the electroconductibility of product still had certain influence, its content is many more, and electroconductibility will be poor more.Therefore, according to different needs, obtain different content Al by the relative quantity of adjusting mother liquor 2O 3The composite powder of-Cu, then obtain high-strength highly-conductive, lead in high-strength, in the strong height Cu-base composites of different purposes such as leading, have both high strength, high conductivity and good thermal property, and hardness height, wear resistance are good, can be used for some other occasions that need high-strength, high-anti-friction such as contact material, spot-wedling electrode, circuit lead frame and aviation in microelectronics Packaging field.
Embodiment
A kind of chemical precipitation method of utilizing obtains the method that composite powder prepares Cu-base composites: at first, under 25~30 ℃ of conditions of temperature, drip precipitation agent bicarbonate of ammonia in the mother liquor of copper sulfate and exsiccated ammonium alum composition, co-precipitation gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Supernatant liquid is removed in the ageing 8 hours under room temperature of colloidal sol, colloidal sol, centrifuge dehydration gets gel, and with soaked in absolute ethyl alcohol centrifugal dealcoholysis in 4 hours, alcohol is washed process and repeated more than 3 times, under 50 ℃,, grind the slow oven dry of gel after the dealcoholysis, cross 100 orders or 200 mesh sieves, get precursor powder, under 1100~1200 ℃, calcining precursor powder 0.5~1 hour, grind, cross 200 orders or 400 mesh sieves, get nanometer Al 2O 3-CuO composite powder; Then, with Al 2O 3-CuO composite powder under 350 ℃ methyl alcohol or hydrogen reducing atmosphere, reduce Al 2O 3-Cu composite powder; At last, Al 2O 3-Cu is cold-pressed into base, and 800~850 ℃ of sinter moldings get Cu-base composites.
Concrete steps are:
(1) at first, chemical precipitation method prepares nanometer Al 2O 3-CuO composite powder:
Operational condition: the constant temperature water bath temperature is set in 25 ℃~30 ℃;
Mother liquor and precipitation agent: according to Al 2O 3Al among the-Cu 2O 3Ratio is determined NH 4Al (SO 4) 2And CuSO 4Amount, according to NH 4Al (SO 4) 2And NH 4HCO 3Mol ratio be 1: 4 and CuSO 4With NH 4HCO 3Mol ratio be to determine NH at 1: 2 4HCO 3Amount, Al 2O 3Al among the-Cu 2O 3Massfraction less than 5%;
Tensio-active agent: Sodium hexametaphosphate 99, concentration are that the weight of 0.5mg/L Sodium hexametaphosphate 99 is 2/10000ths of reactant copper sulfate, exsiccated ammonium alum and bicarbonate of ammonia weight;
Operation steps: A, will be by the NH of above-mentioned requirements configuration 4Al (SO 4) 2And CuSO 4Mother liquor adds in the reactor, adds Sodium hexametaphosphate 99 simultaneously, till mechanical stirring is extremely dissolved;
B, with precipitation agent NH 4HCO 3Speed with 10ml/min splashes in the mother liquor, after treating all to drip off, continues to stir 0.5 hour, with the guarantee system homogenizing, and finally generates NH 4Al (OH) 2CO 3And Cu 2(OH) 2CO 3Colloidal sol;
With colloidal sol ageing 8 hours, remove supernatant liquid under C, the room temperature, centrifuge dehydration gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Gel gets gel with the centrifugal dealcoholysis in 4 hours of soaked in absolute ethyl alcohol gel, and alcohol is washed process more than 3 times;
D, under 50 ℃, the gel after the dealcoholysis is slowly dried, ground 100 orders or 200 mesh sieves, NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Precursor powder;
E, under 1100~1200 ℃, calcining precursor powder 0.5~1 hour ground 200 orders or 400 mesh sieves, nanometer Al 2O 3-CuO composite powder;
(2) then, reduction Al 2O 3-CuO gets Al 2O 3-Cu composite powder:
In 350 ℃ methyl alcohol or hydrogen reducing atmosphere, reduce and got Al in 0.5~1 hour 2O 3-Cu composite powder.
(3) last, be cold-pressed into base, normal pressure-sintered:
With Al 2O 3-Cu composite powder is cold-pressed into base on pressing machine, selecting pressure for use is 100kN, two-sided colding pressing more than 6 times; Sinter molding in 800~850 ℃ of sintering ovens obtains Cu-base composites immediately.
Embodiment 1:
(1) at first, adopt chemical precipitation method to prepare nanometer Al 2O 3-CuO composite powder:
Operational condition: the constant temperature water bath temperature is set in 25 ℃;
Mother liquor and precipitation agent: with the Al in the Cu-base composites 2O 3Content is that 5% (massfraction) is example, the NH of weighing 0.75g 4Al (SO 4) 2CuSO with 6.25g 4, add the solution that water is made into 200ml, according to NH 4Al (SO 4) 2And NH 4HCO 3Mol ratio be 1: 4 and CuSO 4With NH 4HCO 3Mol ratio be to determine the NH of 4.47g at 1: 2 4HCO 3, add the solution that water is made into 200ml; In order to make CuSO 45H 2O and NH 4Al (SO 4) 212H 2The O complete reaction, and remedy waste in the dropping process, NH 4HCO 3Should be suitably excessive, so, take by weighing the NH of 4.5g 4HCO 3, add the solution that water is made into 205ml;
Tensio-active agent: Sodium hexametaphosphate 99 0.2mg;
Operation steps: A, will be by the NH of above-mentioned requirements configuration 4Al (SO 4) 2And CuSO 4Mother liquor adds in the reactor, adds Sodium hexametaphosphate 99 simultaneously, till mechanical stirring is extremely dissolved;
B, with precipitation agent NH 4HCO 3Speed with 10ml/min splashes in the mother liquor, after treating all to drip off, continues to stir 0.5 hour, with the guarantee system homogenizing, and finally generates NH 4Al (OH) 2CO 3And Cu 2(OH) 2CO 3Colloidal sol;
With colloidal sol ageing 8 hours, remove supernatant liquid under C, the room temperature, centrifuge dehydration gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Gel gets gel with the centrifugal dealcoholysis in 4 hours of soaked in absolute ethyl alcohol gel, and alcohol is washed process more than 3 times;
D, under 50 ℃, the gel after the dealcoholysis is slowly dried, grind, cross 100 mesh sieves, NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Precursor powder;
E, under 1100 ℃, calcining precursor powder 0.5 hour grinds, and crosses 200 mesh sieves, nanometer Al 2O 3-CuO composite powder;
(2) then, reduction Al 2O 3-CuO gets Al 2O 3-Cu composite powder:
Reduction got Al in 0.5 hour in 350 ℃ methyl alcohol reducing atmosphere 2O 3-Cu composite powder.
(3) last, be cold-pressed into base, normal pressure-sintered:
With Al 2O 3-Cu composite powder is cold-pressed into base on pressing machine, selecting pressure for use is 100kN, two-sided colding pressing more than 6 times; Sinter molding in 800 ℃ of sintering ovens immediately obtains leading the type Cu-base composites in high-strength.
Embodiment 2:
(1) at first, adopt chemical precipitation method to prepare nanometer Al 2O 3-CuO composite powder:
Operational condition: the constant temperature water bath temperature is set in 28 ℃;
Mother liquor and precipitation agent: with the Al in the Cu-base composites 2O 3Content is that 3% (massfraction) is example, the NH of weighing 0.44g 4Al (SO 4) 2CuSO with 6.25g 4, add the solution that water is made into 200ml, according to NH 4Al (SO 4) 2And NH 4HCO 3Mol ratio be 1: 4 and CuSO 4With NH 4HCO 3Mol ratio be to determine the NH of 4.26g at 1: 2 4HCO 3, add the solution that water is made into 200ml; In order to make CuSO 45H 2O and NH 4Al (SO 4) 212H 2The O complete reaction, and remedy waste in the dropping process, NH 4HCO 3Should be suitably excessive, so, take by weighing the NH of 4.3g 4HCO 3, add the solution that water is made into 205ml;
Tensio-active agent: Sodium hexametaphosphate 99 0.2mg;
Operation steps: A, will be by the NH of above-mentioned requirements configuration 4Al (SO 4) 2And CuSO 4Mother liquor adds in the reactor, adds Sodium hexametaphosphate 99 simultaneously, till mechanical stirring is extremely dissolved;
B, with precipitation agent NH 4HCO 3Speed with 10ml/min splashes in the mother liquor, after treating all to drip off, continues to stir 0.5 hour, with the guarantee system homogenizing, and finally generates NH 4Al (OH) 2CO 3And Cu 2(OH) 2CO 3Colloidal sol;
With colloidal sol ageing 8 hours, remove supernatant liquid under C, the room temperature, centrifuge dehydration gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Gel gets gel with the centrifugal dealcoholysis in 4 hours of soaked in absolute ethyl alcohol gel, and alcohol is washed process more than 3 times;
D, under 50 ℃, the aqueous precursor gel after the dealcoholysis is slowly dried, grind, cross 200 mesh sieves, NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Precursor powder;
E, under 1150 ℃, calcining precursor powder 0.8 hour ground 400 mesh sieves, nanometer Al 2O 3-CuO composite powder;
(2) then, reduction Al 2O 3-CuO gets Al 2O 3-Cu composite powder:
Reduction got Al in 0.8 hour in 350 ℃ hydrogen reducing atmosphere 2O 3-Cu composite powder.
(3) last, be cold-pressed into base, normal pressure-sintered:
With Al 2O 3-Cu composite powder is cold-pressed into base on pressing machine, selecting pressure for use is 100kN, two-sided colding pressing more than 6 times; Sinter molding in 830 ℃ of sintering ovens obtains high-strength highly-conductive type Cu-base composites immediately.
Embodiment 3:
(1) at first, adopt chemical precipitation method to prepare nanometer Al 2O 3-CuO composite powder:
Operational condition: the constant temperature water bath temperature is set in 30 ℃;
Mother liquor and precipitation agent: with the Al in the Cu-base composites 2O 3Content is that 1% (massfraction) is example, the NH of weighing 0.144g 4Al (SO 4) 2CuSO with 6.25g 4, add the solution that water is made into 200ml, according to NH 4Al (SO 4) 2And NH 4HCO 3Mol ratio be 1: 4 and CuSO 4With NH 4HCO 3Mol ratio be to determine the NH of 4.1g at 1: 2 4HCO 3, add the solution that water is made into 200ml; In order to make CuSO 45H 2O and NH 4Al (SO 4) 212H 2The O complete reaction, and remedy waste in the dropping process, NH 4HCO 3Should be suitably excessive, so, take by weighing the NH of 4.2g 4HCO 3, add the solution that water is made into 205ml;
Tensio-active agent: Sodium hexametaphosphate 99 0.2mg;
Operation steps: A, will be by the NH of above-mentioned requirements configuration 4Al (SO 4) 2And CuSO 4Mother liquor adds in the reactor, adds Sodium hexametaphosphate 99 simultaneously, till mechanical stirring is extremely dissolved;
B, with precipitation agent NH 4HCO 3Speed with 10ml/min splashes in the mother liquor, after treating all to drip off, continues to stir 0.5 hour, with the guarantee system homogenizing, and finally generates NH 4Al (OH) 2CO 3And Cu 2(OH) 2CO 3Colloidal sol;
With colloidal sol ageing 8 hours, remove supernatant liquid under C, the room temperature, centrifuge dehydration gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Gel gets gel with the centrifugal dealcoholysis in 4 hours of soaked in absolute ethyl alcohol gel, and alcohol is washed process must be more than 3 times;
D, under 50 ℃, the aqueous precursor gel after the dealcoholysis is slowly dried, ground 100 mesh sieves, precursor powder;
E, under 1200 ℃, calcining precursor powder 1 hour ground 400 mesh sieves, nanometer Al 2O 3-CuO composite powder;
(2) then, reduction Al 2O 3-CuO gets Al 2O 3-Cu composite powder:
Reduction got Al in 1 hour in 350 ℃ methyl alcohol reducing atmosphere 2O 3-Cu composite powder.
(3) last, be cold-pressed into base, normal pressure-sintered:
With Al 2O 3-Cu composite powder is cold-pressed into base on pressing machine, selecting pressure for use is 100kN, two-sided colding pressing more than 6 times; Sinter molding in 850 ℃ of sintering ovens immediately, strong height is led the type Cu-base composites in obtaining.

Claims (9)

1. one kind is utilized chemical precipitation method to obtain the method that composite powder prepares Cu-base composites, it is characterized in that: at first, under 25~30 ℃ of conditions of temperature, drip precipitation agent bicarbonate of ammonia in the mother liquor of copper sulfate and exsiccated ammonium alum composition, co-precipitation gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Colloidal sol, colloidal sol was through ageing in 8 hours, and centrifuge dehydration gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Gel, gel be through absolute ethanol washing and centrifugal dealcoholysis, 50 ℃ of oven dry grind NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Precursor powder, precursor powder gets Al through 1100~1200 ℃ of high temperature sinterings 2O 3-CuO composite powder; Then, Al 2O 3-CuO composite powder under 350 ℃ reducing atmosphere, reduce Al 2O 3-Cu composite powder; At last, Al 2O 3-Cu is cold-pressed into base, 800~850 ℃ of following sinter moldings.
2. a kind of chemical precipitation method of utilizing according to claim 1 obtains the method that composite powder prepares Cu-base composites, it is characterized in that: raw material is copper sulfate, exsiccated ammonium alum and bicarbonate of ammonia, copper sulfate and exsiccated ammonium alum are formed mother liquor, and bicarbonate of ammonia is precipitation agent, according to Al 2O 3Al among the-Cu 2O 3Ratio is determined NH 4Al (SO 4) 2And CuSO 4Amount, according to NH 4Al (SO 4) 2And NH 4HCO 3Mol ratio be 1: 4 and CuSO 4With NH 4HCO 3Mol ratio be to determine NH at 1: 2 4HCO 3Amount, Al 2O 3Al among the-Cu 2O 3Massfraction less than 5%.
3. a kind of chemical precipitation method of utilizing according to claim 1 obtains the method that composite powder prepares Cu-base composites, it is characterized in that: NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Precursor powder was 1100~1200 ℃ of high temperature sinterings 0.5~1 hour.
4. a kind of chemical precipitation method of utilizing according to claim 1 obtains the method that composite powder prepares Cu-base composites, it is characterized in that: Al 2O 3-CuO composite powder in 350 ℃ methyl alcohol or hydrogen reducing atmosphere, reduced 0.5~1 hour Al 2O 3-Cu composite powder.
5. a kind of chemical precipitation method of utilizing according to claim 1 obtains the method that composite powder prepares Cu-base composites, it is characterized in that: Al 2O 3-Cu composite powder is cold-pressed into base under the pressure of 100kN, in the moulding in 1 hour of 800~850 ℃ of sintering temperatures, obtain final Cu-base composites subsequently.
6. a kind of chemical precipitation method of utilizing according to claim 1 obtains the method that composite powder prepares Cu-base composites, it is characterized in that the concrete steps of this method are:
(1) at first, chemical precipitation method prepares nanometer Al 2O 3-CuO composite powder:
Operational condition: the constant temperature water bath temperature is set in 25 ℃~30 ℃;
Mother liquor and precipitation agent: according to Al 2O 3Al among the-Cu 2O 3Ratio is determined NH 4Al (SO 4) 2And CuSO 4Amount, according to NH 4Al (SO 4) 2And NH 4HCO 3Mol ratio be 1: 4 and CuSO 4With NH 4HCO 3Mol ratio be to determine NH at 1: 2 4HCO 3Amount; Al 2O 3Al among the-Cu 2O 3Massfraction less than 5%;
Tensio-active agent: Sodium hexametaphosphate 99, concentration are 0.5mg/L;
Operation steps: A, will be by the NH of above-mentioned requirements configuration 4Al (SO 4) 2And CuSO 4Mother liquor adds in the reactor, adds Sodium hexametaphosphate 99 simultaneously, till mechanical stirring is extremely dissolved;
B, with precipitation agent NH 4HCO 3Speed with 10ml/min splashes in the mother liquor, after treating all to drip off, continues to stir 0.5 hour, with the guarantee system homogenizing, and finally generates NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Colloidal sol;
With colloidal sol ageing 8 hours, remove supernatant liquid under C, the room temperature, centrifuge dehydration gets NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Gel gets aqueous precursor gel with the centrifugal dealcoholysis in 4 hours of soaked in absolute ethyl alcohol gel, repeats this alcohol and washes process more than 3 times;
D, under 50 ℃, the gel after the dealcoholysis is slowly dried, ground 100 orders or 200 mesh sieves, NH 4Al (OH) 2CO 3-Cu 2(OH) 2CO 3Precursor powder;
E, under 1100~1200 ℃, calcining precursor powder 0.5~1 hour ground 200 orders or 400 mesh sieves, nanometer Al 2O 3-CuO composite powder;
(2) then, reduction Al 2O 3-CuO gets Al 2O 3-Cu composite powder:
In 350 ℃ methyl alcohol or hydrogen reducing atmosphere, reduce and got Al in 0.5~1 hour 2O 3-Cu composite powder;
(3) last, be cold-pressed into base, normal pressure-sintered:
With Al 2O 3-Cu composite powder is cold-pressed into base on pressing machine, selecting pressure for use is 100kN, two-sided colding pressing more than 6 times; Sinter molding in 800~850 ℃ of sintering ovens obtains Cu-base composites immediately.
7. a kind of chemical precipitation method of utilizing according to claim 6 obtains the method that composite powder prepares Cu-base composites, it is characterized in that: the excessive NH of every 1L mother liquor 4HCO 3Solution 5~10ml.
8. a kind of chemical precipitation method of utilizing according to claim 6 obtains the method that composite powder prepares Cu-base composites, and it is characterized in that: the sintering time fibrous root of blank in sintering oven decides according to its thickness, the per 1 millimeter sintering of equivalent depth 10 minutes.
9. a kind of chemical precipitation method of utilizing according to claim 6 obtains the method that composite powder prepares Cu-base composites, and it is characterized in that: the weight of Sodium hexametaphosphate 99 is 2/10000ths of reactant copper sulfate, exsiccated ammonium alum and bicarbonate of ammonia weight.
CNB2006100410980A 2006-07-22 2006-07-22 Method for preparing copper base composite material by chemical precipitation method to obtain composite powder Expired - Fee Related CN100395360C (en)

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CN103173645B (en) * 2013-03-25 2014-09-17 北京科技大学 Preparation method of dispersedly strengthened aluminum-based composite material
CN103981381B (en) * 2014-05-15 2017-05-17 厦门理工学院 Method for preparing nano aluminum oxide dispersion enhanced copper-base composite material according to sol-gel method
CN104117684B (en) * 2014-08-11 2016-06-22 郴州市金贵银业股份有限公司 A kind of preparation method of tin-oxygen-silver electric contact material
CN105350104B (en) * 2015-12-01 2017-10-27 东华大学 A kind of preparation method of Mesoporous zirconium phosphate loaded copper oxide antibacterial polyethylene alcohol fiber
CN108285708A (en) * 2017-07-14 2018-07-17 合肥文胜新能源科技有限公司 A kind of solar energy heat absorbing coating
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CN107546279A (en) * 2017-07-14 2018-01-05 合肥文胜新能源科技有限公司 A kind of solar panel antireflective coating
CN111462939A (en) * 2020-04-08 2020-07-28 安徽壹石通材料科技股份有限公司 Nano-alumina-enhanced silver-based electrical contact material and preparation method thereof

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