CN1314821C - In-situ chemical process of preparing zircmia reinforced copper-base composite material - Google Patents
In-situ chemical process of preparing zircmia reinforced copper-base composite material Download PDFInfo
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- CN1314821C CN1314821C CNB2005100150777A CN200510015077A CN1314821C CN 1314821 C CN1314821 C CN 1314821C CN B2005100150777 A CNB2005100150777 A CN B2005100150777A CN 200510015077 A CN200510015077 A CN 200510015077A CN 1314821 C CN1314821 C CN 1314821C
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Abstract
The present invention relates to an in-situ chemical method for preparing a nanometer zirconium oxide reinforced copper base composite material, which belongs to the preparing technology of copper base composite materials. The method of the present invention comprises the following processes: yttrium nitrate hexahydrate and zirconium chloroxide octahydrate are added to a mixed solution of alcohol and water, and ammonia water is dropped in the mixed solution; then, the mixed solution is kept still for a period of time, and Cu(NO3)2.3Hi2O is added; after complete stirring, the Cu(NO3)2.3Hi2O and the mixed solution are dissolved together; after being dried and heated, the mixed solution is calcined to prepare the mixed powder with a particle diameter of CuO and ZrO2; the mixed powder of CuO and ZrO2 is prepared by the reduction of hydrogen gas; the prepared mixed powder is initially pressed, sintered and repressed to obtain a ZrO2 /Cu nanometer composite material. The present invention has the advantages that because the wettability of nanometer zirconium dioxide is good in copper powder and dispersion is homogeneous, the hardness of the prepared material is high, and electrical performance is good. When the mass percentage content of the zirconium dioxide is 5%, microhardness can reach more than 125 which is 80%IACS greater relative to electric conductivity.
Description
Technical field
The present invention relates to a kind of in-situ chemical and prepare the method that nano zircite strengthens Cu-base composites, belong to the technology of preparing of Cu-base composites.
Background technology
The high-intensity high-conductivity copper based composites is the new function material that a class has excellent comprehensive performance, has both had good electroconductibility, has high intensity and resistance to elevated temperatures again.But,, reduced the electroconductibility of Cu-base composites to a certain extent owing to the introducing of the second phase particle.For preparing the Cu-base composites of excellent property, the selection of wild phase is vital.The dispersion-strengthened effect of nano zircite is obvious, high high-temp stability is good, and thermal expansion is comparatively approaching with copper, special crystalline structure makes it to become the important electron material, good mechanical performance and heat physical properties are the wild phases of preparation high strength high conductivity Cu-base composites excellent performance.This research mainly concentrates on nano zircite as wild phase, adopt the in-situ chemical prepared the high electricity of the high strength zirconium white of leading strengthen Cu-base composites, adopt the matrices of composite material of this kind method preparation good with enhancing body wetting property, the interface contaminating impurity is few.
Summary of the invention
The object of the present invention is to provide a kind of in-situ chemical to prepare the method that nano zircite strengthens Cu-base composites, preparation technology is simple for this method, prepared excellent material performance.
The present invention is realized that by following technical proposals a kind of in-situ chemical prepares the method that nano zircite strengthens Cu-base composites, it is characterized in that comprising following process:
(1) with six water Yttrium trinitrates and eight water zirconium oxychlorides with mol ratio 0.04～0.06: it is that being made into eight water zirconium oxychloride concentration is the solution of 0.1～0.3mol/L in 1～2: 1 the mixing solutions that 1 ratio joins ethanol and water ratio.
(2) titration ammoniacal liquor is 9.0～9.8 to pH in step (1) gained solution, generation Zr (OH)
4, Y (OH)
3Mix gelatinous precipitate.After leaving standstill 6～12h, press Cu: (ZrO
2+ Cu) mass ratio is 92～98% to add Cu (NO
3)
2.3H
2O dissolves together after stirring fully.
(3) being after 20～50 ℃/min is heated to 150～400 ℃ of dryings to step (2) gained mixed solution with temperature rise rate, is that 15～25 ℃/min is warming up to 500～650 ℃ of calcinings in temperature rise rate again, and generating particle diameter is that 2～15 μ mCuO and particle diameter are 10～30nmZrO
2Powder mix.Be that 8～15 ℃/min rises to 550～700 ℃ with temperature rise rate again, and be 2～3ml/s reduction, 30～60min that generating particle diameter is that 0.5～5 μ mCu and particle diameter are 15～40nmZrO with hydrogen flowing quantity
2Powder mix.
(4) to the powder mix of step (3) preparation through 400～600MPa first pressing, dwell time 30～60s is that 15～20 ℃/min rises to 900～1000 ℃ through temperature rise rate again, 1.5～2.5h sintering, presses again at 0.8～1.2GPa at last, dwell time is 30～60s, obtains ZrO
2/ Cu nano composite material.
The present invention has the following advantages:
Because nano zircite wetting property in copper powder is uniformly dispersed, thereby prepared material hardness height, good electrical property.When zirconium white quality percentage composition was 5%, microhardness can reach more than 125, and relative conductivity is greater than 80%IACS.
Description of drawings
Fig. 1 adopts the microhardness and the relative conductivity graphic representation of the different content zirconium oxide composite material that the present invention prepares.
The anti-softening temperature graphic representation of the zirconic matrix material of the different content that Fig. 2 adopts the present invention to prepare.
The 8%ZrO that Fig. 3 adopts the present invention to prepare
2The SEM figure of/Cu composite powder, the white small-particle among the figure is a zirconium white, all the other dark circles spheroidal particle are copper.
The 5%ZrO that Fig. 4 adopts the present invention to prepare
2The SEM figure of/Cu matrix material
Embodiment
Embodiment one
It is that the concentration that makes gained eight water zirconyl chloride solutions is 0.1mol/L in 2: 1 the mixing solutions that the ratio of 0.035g six water Yttrium trinitrates and 1.05g eight water zirconium oxychlorides is joined 24ml alcohol water ratio, titration ammoniacal liquor to pH be 9.0, generate Zr (OH)
4, Y (OH)
3Mix gelatinous precipitate.Behind the precipitation 6h, add the Cu (NO of 28.83g again
3)
2.3H
2O dissolves together after stirring fully.Is after 20 ℃/min rises to 150 ℃ of dryings with mixed solution with temperature rise rate, is that 15 ℃/min is heated to 500 ℃ of calcining 1h with temperature rise rate again, generates 5 μ mCuO, 10nmZrO
2Powder mix.With temperature rise rate is that 8 ℃/min rises to 550 ℃, is to generate 2 μ mCu, 15nmZrO behind the reduction 60min in the 2ml/s hydrogen at hydrogen flowing quantity
2Powder mix.Powder mix after the pressurize 50s first pressing, is that 15 ℃/min rises to 900 ℃ with temperature rise rate through 400MPa again, and sintering 2.5h obtains 5%ZrO at last after the multiple pressure that through the 0.8GPa dwell time is 60s
2/ Cu nano composite material.
Embodiment two
It is that the concentration that makes gained eight water zirconyl chloride solutions is 0.3mol/L in 1: 1 the mixing solutions that the ratio of 0.025g six water Yttrium trinitrates and 0.85g eight water zirconium oxychlorides is joined 8.8ml alcohol water ratio, titration ammoniacal liquor to pH be 9.0, generate Zr (OH)
4, Y (OH)
3Mix gelatinous precipitate.Behind the precipitation 6h, add the Cu (NO of 39.67g again
3)
2.3H
2O dissolves together after stirring fully.Is after 30 ℃/min rises to 200 ℃ of dryings with mixed solution with temperature rise rate, is that 18 ℃/min is heated to 550 ℃ of calcining 1h with temperature rise rate again, generates 5 μ mCuO, 10nmZrO
2Powder mix.With temperature rise rate is that 8 ℃/min rises to 600 ℃, is to generate 2 μ mCu, 20nmZrO behind the reduction 45min in the 3ml/s hydrogen at hydrogen flowing quantity
2Powder mix.Powder mix after the pressurize 45s first pressing, is that 18 ℃/min rises to 950 ℃ with temperature rise rate through 500MPa again, and sintering 2h obtains 3%ZrO at last after the multiple pressure that through the 1GPa dwell time is 45s
2/ Cu nano composite material.
Embodiment three
It is that the concentration that makes gained eight water zirconyl chloride solutions is 0.3mol/L in 2: 1 the mixing solutions that the ratio of 0.045g six water Yttrium trinitrates and 1.85g eight water zirconium oxychlorides is joined 19.13ml alcohol water ratio, titration ammoniacal liquor to pH be 9.5, generate Zr (OH)
4, Y (OH)
3Mix gelatinous precipitate.Behind the precipitation 12h, add the Cu (NO of 30.71g again
3)
2.3H
2O dissolves together after stirring fully.Is after 30 ℃/min rises to 180 ℃ of dryings with mixed solution with temperature rise rate, is that 20 ℃/min is heated to 650 ℃ of calcining 1h with temperature rise rate again, generates 10 μ mCuO, 20nmZrO
2Powder mix.With temperature rise rate is that 8 ℃/min rises to 650 ℃, is to generate 3.5 μ mCu, 25nmZrO behind the reduction 30min in the 2.5ml/s hydrogen at hydrogen flowing quantity
2Powder mix.Powder mix after the pressurize 60s first pressing, is that 20 ℃/min rises to 975 ℃ with temperature rise rate through 400MPa again, and sintering 2h obtains 8%ZrO at last after the multiple pressure that through the 1.2GPa dwell time is 60s
2/ Cu nano composite material.
Claims (1)
1. an in-situ chemical prepares the method that nano zircite strengthens Cu-base composites, it is characterized in that comprising following process:
(1) with six water Yttrium trinitrates and eight water zirconium oxychlorides with mol ratio 0.04～0.06: 1 ratio joins in the mixing solutions that ethanol and water ratio are 1: 1 or 2: 1, and being made into eight water zirconium oxychloride concentration is the solution of 0.1～0.3mol/L;
(2) titration ammoniacal liquor is 9.0～9.8 to pH in step (1) gained solution, generation Zr (OH)
4, Y (OH)
3Mix gelatinous precipitate, leave standstill 6～12h after, press Cu: (ZrO
2+ Cu) mass ratio is 92～98% to add Cu (NO
3)
2.3H
2O dissolves together after stirring fully;
(3) being after 20～50 ℃/min is heated to 150～400 ℃ of dryings to step (2) gained mixed solution with temperature rise rate, is that 15～25 ℃/min is warming up to 500～650 ℃ of calcinings in temperature rise rate again, and generating particle diameter is that 2～15 μ mCuO and particle diameter are 10～30nmZrO
2Powder mix; Be that 8～15 ℃/min rises to 550～700 ℃ with temperature rise rate again, and be 2～3ml/s reduction, 30～60min that generating particle diameter is that 0.5～5 μ mCu and particle diameter are 15～40nmZrO with hydrogen flowing quantity
2Powder mix;
(4) to the powder mix of step (3) preparation through 400～600MPa first pressing, dwell time 30～60s is that 15～20 ℃/min rises to 900～1000 ℃ through temperature rise rate again, 1.5～2.5h sintering, presses again at 0.8～1.2GPa at last, dwell time is 30～60s, obtains ZrO
2/ Cu nano composite material.
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| CNB2005100150777A CN1314821C (en) | 2005-09-13 | 2005-09-13 | In-situ chemical process of preparing zircmia reinforced copper-base composite material |
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| CNB2005100150777A CN1314821C (en) | 2005-09-13 | 2005-09-13 | In-situ chemical process of preparing zircmia reinforced copper-base composite material |
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| CN1740356A CN1740356A (en) | 2006-03-01 |
| CN1314821C true CN1314821C (en) | 2007-05-09 |
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| CN100409982C (en) * | 2006-10-27 | 2008-08-13 | 桂林工学院 | Method for preparing high temperature phase nano zirconium oxide powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401802A (en) * | 2002-04-10 | 2003-03-12 | 昆明理工大学 | Method for mfg. nanograin crystal reinforced copper based material |
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|---|---|---|---|---|
| CN1401802A (en) * | 2002-04-10 | 2003-03-12 | 昆明理工大学 | Method for mfg. nanograin crystal reinforced copper based material |
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