CN101139663A - Preparation method of silver nickel composite material - Google Patents
Preparation method of silver nickel composite material Download PDFInfo
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- CN101139663A CN101139663A CNA200710009688XA CN200710009688A CN101139663A CN 101139663 A CN101139663 A CN 101139663A CN A200710009688X A CNA200710009688X A CN A200710009688XA CN 200710009688 A CN200710009688 A CN 200710009688A CN 101139663 A CN101139663 A CN 101139663A
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- silver
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- nickel composite
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Abstract
A preparation method for silver-nickel composite material is provided, which relates to silver-nickel composite material. The utility model provides a preparation method for a scattered silver-nickel composite material., the synthesizing of Ag2NiO2 crystal including the steps of that: mixing nickel nitrate solution with silver nitrate solution, adding them into sodium hydroxide solution and retaining heat of the reacted solution under 230 to 270 DEG C for at least 72 h, thus getting the Ag2NiO2 crystal; deacidizing the Ag2NiO2 crystal under H2+N2 atmosphere; carrying out ball grinding to the deacidized product from Ag2NiO2 crystal to get micro nanometer silver-nickel compound powder; tabletting the micro nanometer silver-nickel compound powder and sintering them under an atmosphere of protective gas. As silver and nickel atoms are arranged during synthesizing `Ag2NiO2, mixing of them at atom level is possible and the prepared silver-nickel composite material, nickel is evenly distributed in the silver substrate. The invention has simple process, short period and low cost, which is applicable for industrialized production.
Description
Technical field
The present invention relates to a kind of silver nickel composite material, especially relate to a kind of employing reduction Ag
2NiO
2Crystal prepares the method for silver nickel composite material.
Background technology
Because the contact resistance of silver-colored nickel (AgNi) matrix material is low and stable, be easy to processing, and silver has favorable conductive and heat conductivility, and nickel has good erosion-resisting characteristics, and therefore silver-colored nickel (AgNi) matrix material is a contact material first-selected in the low capacity control apparatus.But have shortcomings such as resistance fusion welding can differ from, Ag was alternate when its reason was arcing is easy to take place seam.For this reason, make Ni mutually evenly, to be distributed in the Ag matrix to disperse be a present important development direction.But under equilibrium conditions, Ag and the solid solubility between the Ni when solid-state are minimum, and the maximum solid solution degree of Ni in Ag is 0.2at.%Ni, and the maximum solid solution degree of Ag in Ni is 1at.%Ag, and exist liquid phase two to be separated when high temperature.Therefore, preparing AgNi matrix material that disperse distributes by traditional method is unusual difficulty.At present, most of research work mainly utilizes physical method to prepare Ag, Ni composite nano-powder.Japan Nevesi and Behrens (Nevesi I et al., Behavior of the Ni Component of AgNiContacts in Switching Processes[A], Proceedings of 13
ThICEC[C], Piscateway:IEEE, 1986) attempted high speed/height and cut off ball milled fine powder and the Ag powder of Ni disperseed compoundization preparation AgNi alloy, improved structure property to a certain extent.Zhao Ze very waits (Zhao Z L, Zhao Y, Niu Y et al, Synthesis and characteristics ofconsolidated nanocrystalline two-phase Ag50Ni50 alloy by hot pressing[J], Journal of Alloys andCompounds, 2000,307 (1-2) 254-258) use high-energy ball milling-pressure sintering to make Ag
50Ni
50(massfraction) Nanoalloy has proved that mechanical alloying can obtain that crystal grain is tiny, the nanometer crystal alloy of compact structure.Adopting novel method and process aspect, (Zheng Fuqian such as Zheng Fuqian, Xie Ming, Liu Jianliang etc., the mechanical alloying of Ag-10Ni alloy [J], precious metal, 1998,19 (4): 1-3) utilize the chilling atomizing to make the AgNi coated composite powder, and then moulding is handled in mechanical alloying, it is tiny and disperse is distributed in the tissue in the Ag matrix to obtain Ni, and the electricity of contact and mechanical property are all increased.But the poly-partially phenomenon of Ni often appears in the AgNi matrix material of physical method preparations such as employing mechanical alloying.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of silver nickel composite material of disperse distribution.
The present invention includes following steps.
1) Ag
2NiO
2Crystalline is synthetic: nickel nitrate solution is mixed with silver nitrate solution, join in the sodium hydroxide solution again, being incubated reacted solution at least in 230～270 ℃, 72h promptly gets Ag
2NiO
2Crystal;
2) at H
2+ N
2Under the atmosphere, reduction Ag
2NiO
2Crystal;
3) with Ag
2NiO
2Crystalline reduzate ball milling obtains the micro nanometer silver nickle composite powder;
4) with micro nanometer silver nickle composite powder compressing tablet, sintering under protective atmosphere.
Press mass ratio, the content of nickel nitrate solution, silver nitrate solution and sodium hydroxide solution is 1: (1～1.7): (10～12).
The concentration of nickel nitrate solution, silver nitrate solution and sodium hydroxide solution is respectively 0.4～0.7mol/L, 0.3～0.8mol/L, 8～12mol/L.
In step 2) in, the reductive gas velocity is 15～35ml/min, and reduction temperature is controlled at 450～600 ℃, and the recovery time is 2h at least.
In step 3), Ag
2NiO
2Crystalline reduzate ball milling can carry out at planetary ball mill.
In step 4), the operating pressure of compressing tablet is 310～380MPa, and sintering temperature is controlled at 500～900 ℃, and sintering time is 1～6h.Protective atmosphere is preferably the hydrogen atmosphere protection.
The silver nickel composite material that the present invention is prepared is because at synthetic Ag
2NiO
2Therefore silver, nickle atom are arranged in the process, can be realized the two mixing on atomic level, so the prepared distribution of silver nickel composite material nickel in silver matrix of this method is more even.Simultaneously, preparation technology involved in the present invention is simple, the cycle is short, cost is low, is applicable to suitability for industrialized production.
Description of drawings
Fig. 1 is the prepared Ag of the embodiment of the invention
2NiO
2Crystalline XRD figure spectrum.In Fig. 1, X-coordinate is diffraction angle 2 Θ, and ordinate zou is diffracted intensity Intensity.
Fig. 2 is the XRD figure spectrum of reduction back AgNi composite granule in the embodiment of the invention 1 preparation process.In Fig. 2, X-coordinate is diffraction angle 2 Θ, and ordinate zou is diffracted intensity Intensity.
Fig. 3 is the face scanning analysis figure of the AgNi composite granule after the reduction in the embodiment of the invention 1 preparation process, in Fig. 3, (a) is the sem photograph of AgNi composite granule, (b) is corresponding Ag distribution diagram of element, (c) is corresponding Ni distribution diagram of element.
Fig. 4 is the sem photograph (* 10000) of the AgNi composite granule of ball milling 5h after having reduced in the embodiment of the invention 1 preparation process.
Fig. 5 is the sem photograph (* 1500) of the embodiment of the invention 2.
Fig. 6 is that the EDS of the embodiment of the invention 2 can spectrogram.In Fig. 6, X-coordinate is energy (eV), and ordinate zou is intensity (counting rate).
Fig. 7 is the sem photograph (* 1500) of the embodiment of the invention 3.
Fig. 8 is that the EDS of the embodiment of the invention 3 can spectrogram.In Fig. 8, X-coordinate is energy (eV), and ordinate zou is intensity (counting rate).
Embodiment
The invention will be further described below in conjunction with example and accompanying drawing.
Embodiment 1
The nickel nitrate solution of 2.5ml0.5mol/L and the silver nitrate solution of 5ml0.5mol/L are mixed, join in the sodium hydroxide solution of 10ml10mol/L then while stirring, reacted solution is packed in the stainless steel hydro-thermal still, insulation 72h can obtain Ag in 230 ℃ again
2NiO
2Crystal.Ag
2NiO
2Crystal is put into tube furnace and is adopted 6.9%H
2+ N
2Reducing gas at 500 ℃ of following reduction 3h, wherein gas velocity is 25ml/min.After treating that sample is reduced to room temperature, reduzate is put into planetary ball mill every ball milling 30min under 500r/min by ratio of grinding media to material at 20: 1 stop 15min, total ball milling time is 5h.The silver-colored nickle composite powder that ball milling is obtained depresses to the small thin slices that diameter is 8mm at 330MPa, then under hydrogen shield at 600 ℃ of sintering 3h, obtain sample.
Adopt X-ray diffraction, Electronic Speculum that thing phase, form and the element of product are analyzed, can obtain Ag
2NiO
2The diffracting spectrum (referring to Fig. 1, Fig. 2) of crystalline diffracting spectrum and reduction back AgNi composite granule, by the distribution at peak as can be known, 500 ℃ down reduction 3h only have the diffraction peak of Ag and Ni, illustrate that reduction is complete; By face scanning analysis figure (referring to Fig. 3) as can be seen, the distribution of Ag, Ni is more even in the composite granule behind the hydrogen reducing; The shape of the AgNi composite granule behind the ball milling 5h is more irregular as can be seen by electromicroscopic photograph (referring to Fig. 4), and particle diameter is at 5～10 μ m.
Embodiment 2
Condition by embodiment 1 prepares Ag
2NiO
2Crystal is then Ag
2NiO
2Crystal is put into tube furnace and is adopted 6.9%H
2+ N
2Reducing gas at 500 ℃ of following reduction 3h, wherein gas velocity is 25ml/min.After treating that sample is reduced to room temperature, reduzate is put into planetary ball mill every ball milling 30min under 500r/min by ratio of grinding media to material at 20: 1 stop 15min, total ball milling time is 5h.The silver-colored nickle composite powder that ball milling is obtained depresses to the small thin slices that diameter is 8mm at 330MPa, then under hydrogen shield at 800 ℃ of sintering 3h, obtain sample.The scanning electron microscope picture of sample and its energy spectrum analysis figure see Fig. 5, Fig. 6.The darker part main component of color is Ni in Fig. 5, and the more shallow part main component of color is Ag, and as can be seen from Figure 5, Ni compares and is distributed in equably in the Ag matrix., approaching by the ratio that can calculate AgNi among energy spectrum analysis Fig. 6 with the ratio of AgNi in the crystal near 2: 1.
Embodiment 3
Condition by embodiment 1 prepares Ag
2NiO
2Crystal is then Ag
2NiO
2Crystal is put into tube furnace and is adopted 6.9%H
2+ N
2Reducing gas at 480 ℃ of following reduction 3h, wherein gas velocity is 25ml/min.After treating that sample is reduced to room temperature, reduzate is put into planetary ball mill every ball milling 30min under 500r/min by ratio of grinding media to material at 20: 1 stop 15min, total ball milling time is 5h.The silver-colored nickle composite powder that ball milling is obtained depresses to the small thin slices that diameter is 8mm at 330MPa, then under hydrogen shield at 600 ℃ of sintering 3h, obtain sample.The scanning electron microscope picture of sample and its energy spectrum analysis figure see Fig. 7, Fig. 8.The darker part main component of color is Ni in Fig. 7, the more shallow part main component of color is Ag, as can be seen from Figure 7, Ni compares and is distributed in equably in the Ag matrix, and the distribution of Ni is than the more disperse of distribution of Ni in the sample tissue that is obtained among the embodiment 2., approaching by the ratio that can calculate AgNi among energy spectrum analysis Fig. 8 with the ratio of AgNi in the crystal near 2: 1.
Embodiment 4～6
Except that the concentration that adopts different nickelous nitrate, Silver Nitrate and sodium hydroxide solution, other conditions are all identical with embodiment 1 among the embodiment 4～6.Wherein, the solubility of nickel nitrate solution is 0.4mol/L among the embodiment 4, and the solubility of silver nitrate solution is 0.5mol/L, and the concentration of sodium hydroxide solution is 8mol/L; The solubility of nickel nitrate solution is 0.7mol/L among the embodiment 5, and the solubility of silver nitrate solution is 0.8mol/L, and the concentration of sodium hydroxide solution is 12mol/L; The solubility of nickel nitrate solution is 0.5mol/L among the embodiment 6, and the solubility of silver nitrate solution is 0.7mol/L, and the concentration of sodium hydroxide solution is 10mol/L.
The concentration of nickel nitrate solution, silver nitrate solution and sodium hydroxide solution is to Ag
2NiO
2The crystalline productive rate has certain influence, but little to tissue topography's influence of final product AgNi composite block material.
Embodiment 7,8
Except that adopting different crystal synthesis temperatures, other conditions are all identical with embodiment 1 among the embodiment 7,8.Wherein, embodiment 7 and 8 crystal synthesis temperature are respectively 250,270 ℃.
The crystal synthesis temperature is only to Ag
2NiO
2The crystalline productive rate is influential, and is little to tissue topography's influence of final product AgNi composite block material.
Except that adopting different crystal reduction temperatures, other conditions are all identical with embodiment 1 among the embodiment 9,10.Wherein, embodiment 9 and 10 crystal reduction temperature are respectively 450,600 ℃.
Reduction Ag under 450 ℃ and 600 ℃
2NiO
2Crystal all can obtain the AgNi composite granule, and reduces and all compare fully, and the AgNi distribution is all compared evenly in the powder after the reduction simultaneously.
Embodiment 11,12
Except that adopting different sintering temperatures, other conditions are all identical with embodiment 2 among the embodiment 11,12.Wherein, embodiment 11 and 12 sintering temperature are respectively 500,900 ℃.
Sintering temperature is bigger to the influence of the tissue topography of composite block material and density.Sintering temperature is high more, and the density of block materials is high more, but the poly-partially phenomenon aggravation of Ni, organizing of material is inhomogeneous more.
Claims (8)
1. the preparation method of a silver nickel composite material is characterized in that may further comprise the steps.
1) Ag
2NiO
2Crystalline is synthetic: nickel nitrate solution is mixed with silver nitrate solution, join in the sodium hydroxide solution again, being incubated reacted solution at least in 230～270 ℃, 72h promptly gets Ag
2NiO
2Crystal;
3) at H
2+ N
2Under the atmosphere, reduction Ag
2NiO
2Crystal;
3) with Ag
2NiO
2Crystalline reduzate ball milling obtains the micro nanometer silver nickle composite powder;
4) with micro nanometer silver nickle composite powder compressing tablet, sintering under protective atmosphere.
2. the preparation method of a kind of silver nickel composite material as claimed in claim 1 is characterized in that by mass ratio, and the content of nickel nitrate solution, silver nitrate solution and sodium hydroxide solution is 1: 1～1.7: 10～12.
3. the preparation method of a kind of silver nickel composite material as claimed in claim 1 is characterized in that the concentration of nickel nitrate solution, silver nitrate solution and sodium hydroxide solution is respectively 0.4～0.7mol/L, 0.3～0.8mol/L, 8～12mol/L.
4. the preparation method of a kind of silver nickel composite material as claimed in claim 1 is characterized in that in step 2) in, the reductive gas velocity is 15～35ml/min, and reduction temperature is 450～600 ℃, and the recovery time is 2h at least.
5. the preparation method of a kind of silver nickel composite material as claimed in claim 1 is characterized in that in step 3) Ag
2NiO
2Crystalline reduzate ball milling carries out at planetary ball mill.
6. the preparation method of a kind of silver nickel composite material as claimed in claim 1 is characterized in that in step 4), and the operating pressure of compressing tablet is 310～380MPa.
7. the preparation method of a kind of silver nickel composite material as claimed in claim 1 is characterized in that sintering temperature is 500～900 ℃, and sintering time is 1～6h.
8. the preparation method of a kind of silver nickel composite material as claimed in claim 1 is characterized in that protective atmosphere is the hydrogen atmosphere protection.
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|---|---|---|---|
| CNB200710009688XA CN100489130C (en) | 2007-10-19 | 2007-10-19 | Preparation method of silver nickel composite material |
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|---|---|---|---|
| CNB200710009688XA CN100489130C (en) | 2007-10-19 | 2007-10-19 | Preparation method of silver nickel composite material |
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|---|---|
| CN101139663A true CN101139663A (en) | 2008-03-12 |
| CN100489130C CN100489130C (en) | 2009-05-20 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104439249A (en) * | 2014-12-30 | 2015-03-25 | 桂林电器科学研究院有限公司 | Method for processing sheet silver nickel electric contact material |
| CN104493180A (en) * | 2014-12-30 | 2015-04-08 | 桂林电器科学研究院有限公司 | Preparation method of flakey or rivet-shaped silver and nickel electrical contact material |
| CN104493173A (en) * | 2014-12-30 | 2015-04-08 | 桂林电器科学研究院有限公司 | Preparation method of flakey or rivet-shaped silver and tungsten electrical contact material |
| CN104493170A (en) * | 2014-12-30 | 2015-04-08 | 桂林电器科学研究院有限公司 | Preparation method of flakey or rivet-shaped silver and tungsten electrical contact material |
| CN108439492A (en) * | 2018-04-16 | 2018-08-24 | 沈阳建筑大学 | A kind of Ag doped with nano nickel oxide raw powder's production technology |
| CN108441668A (en) * | 2018-04-13 | 2018-08-24 | 上海和伍复合材料有限公司 | A kind of silver tungsten contact material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4904457B2 (en) * | 2005-03-31 | 2012-03-28 | Ｄｏｗａエレクトロニクス株式会社 | Alkaline battery positive electrode material, method for producing the same, and alkaline battery positive electrode material |
-
2007
- 2007-10-19 CN CNB200710009688XA patent/CN100489130C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104439249A (en) * | 2014-12-30 | 2015-03-25 | 桂林电器科学研究院有限公司 | Method for processing sheet silver nickel electric contact material |
| CN104493180A (en) * | 2014-12-30 | 2015-04-08 | 桂林电器科学研究院有限公司 | Preparation method of flakey or rivet-shaped silver and nickel electrical contact material |
| CN104493173A (en) * | 2014-12-30 | 2015-04-08 | 桂林电器科学研究院有限公司 | Preparation method of flakey or rivet-shaped silver and tungsten electrical contact material |
| CN104493170A (en) * | 2014-12-30 | 2015-04-08 | 桂林电器科学研究院有限公司 | Preparation method of flakey or rivet-shaped silver and tungsten electrical contact material |
| CN104493180B (en) * | 2014-12-30 | 2016-08-24 | 桂林电器科学研究院有限公司 | A kind of lamellar or the preparation method of rivet type silver nickel electric contact material |
| CN108441668A (en) * | 2018-04-13 | 2018-08-24 | 上海和伍复合材料有限公司 | A kind of silver tungsten contact material and preparation method thereof |
| CN108439492A (en) * | 2018-04-16 | 2018-08-24 | 沈阳建筑大学 | A kind of Ag doped with nano nickel oxide raw powder's production technology |
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| CN100489130C (en) | 2009-05-20 |
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