CN102672168B - Preparation method for core-shell structural nickel-silver bimetallic powder - Google Patents
Preparation method for core-shell structural nickel-silver bimetallic powder Download PDFInfo
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- CN102672168B CN102672168B CN201210003622.0A CN201210003622A CN102672168B CN 102672168 B CN102672168 B CN 102672168B CN 201210003622 A CN201210003622 A CN 201210003622A CN 102672168 B CN102672168 B CN 102672168B
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Abstract
The invention relates to the technical field of the preparation of metal powder materials and particularly discloses a preparation method for core-shell structural nickel-silver bimetallic powder. The preparation method comprises the following steps of: adding nickel powder and a dispersing agent in an ethanol-water mixed solvent, and stirring to obtain a nickel powder dispersing solution; preparing hydrazine hydrate solution with the hydrazine hydrate concentration of 2.5 mol/L, and adjusting the pH value of the hydrazine hydrate solution to more than 10 to obtain a reducing agent solution; mixing the nickel powder dispersing solution with the reducing agent solution to obtain a reaction solution A; dropwise adding an ammonia-silver solution in the reaction solution A and reacting for 70-100 minutes to obtain turbid liquid; performing centrifugal separation, washing and vacuum-drying the obtained solid to obtain the core-shell structural nickel-silver bimetallic powder. The preparation method provided by the invention has simple process; the obtained core-shell structural nickel-silver bimetallic powder has the advantages of controllable thickness of a silver coating layer, narrow distribution of grain diameter, good dispersing property and high vibrating density.
Description
Technical field
The present invention relates to metal powder material preparing technical field, be specifically related to a kind of preparation method of core-shell structural nickel-silver bimetallic powder.
Background technology
Metal dust is a kind of important raw material, both can directly disperse to use, also can be compressing and sinter block materials into by it, can also make film material etc.For modern electronics industry, multilayer ceramic capacitor (Multilayer ceramic capacitors is called for short MLCC) has become the main product of capacitor industry, is widely used in communication, computer and consumer electronics product.One of main development direction of MLCC shows as the lowpriced metallization of electrode, and namely adopt the base metal of low price to replace the expensive noble metal such as palladium, silver to reduce costs, interior electrode can save the cost of 2 ~ 5 times after lowpriced metallization.Nickel is cheap and easy to get, and have higher fusing point and good electric conductivity, high frequency stability is better than gold, silver, and with most of solder compatible, not diffusion or the reaction in ceramic dielectric when sintering, not affecting ceramic dielectric performance, is ideal inner electrode.But nickel powder is oxidizable generation non-conductor oxide-film at high temperature, therefore, to nickel powder modifying surface, improving its high-temperature oxidation resistance is solve one of important approach of electrode base metalization.
For the problem of oxidation of nickel powder in MLCC electrode and electromagnetic shielding material, in order to improve the high-temperature oxidation resistance of nickel powder, the existing report adopting the method for nickel powder electroplate to improve the antioxygenic property of nickel powder at present.Silver-plated nickel powder not only can improve the antioxygenic property of nickel powder, and can lead the prerequisite decline low electrode of performance, the cost of electric slurry not affecting it.The electroless plating technology of the technique that nickel powder surface clad silver adopts at present mainly nickel powder, first in nickel powder Electroless copper, then by copper and silver ion displacement reaction silver-plated.The method complex process, needs repeatedly to wash, filter, and is unfavorable for the reduction of the stable of properties of product and production cost.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of core-shell structural nickel-silver bimetallic powder.
In order to realize above object, the technical solution adopted in the present invention is: a kind of preparation method of core-shell structural nickel-silver bimetallic powder, comprises the following steps:
(1) nickel powder, dispersant are joined in ethanol-water mixed solvent, then water-bath is placed in, bath temperature is kept to be 50 DEG C, stir, obtained nickel powder dispersion soln, in described nickel powder dispersion soln, the concentration of nickel powder is 25.0g/l, and in described nickel powder dispersion soln, the concentration of dispersant is 8.33g/l;
(2) mixed with water by reducing agent hydrazine hydrate, obtained concentration of hydrazine hydrate is the hydrazine hydrate aqueous solution of 2.5mol/L, regulates more than the pH value to 10 of hydrazine hydrate aqueous solution, obtains reductant solution;
(3) by described nickel powder dispersion soln with described reductant solution with volume ratio nickel powder dispersion soln: reductant solution=2.4: 1 mixes, obtain reactant liquor A, in described reactant liquor A, drip silver ammino solution 50ml react, controlling the reaction time is 70 ~ 100 minutes, obtain suspension, centrifugation, gained solid, through washing, vacuum drying, obtains core-shell structural nickel-silver bimetallic powder.
The spherical nickel particulate that described nickel powder is 1.0 μm by average grain diameter forms.
Described dispersant is PVP or sodium tartrate.
In described ethanol-water mixed solvent, the volume ratio of second alcohol and water is: ethanol: water=2: 5.
The preparation method of core-shell structural nickel-silver bimetallic powder provided by the invention passes through thermodynamic analysis, select suitable reducing agent and reaction system, when fully suppressing displacement reaction, realize at nickel powder surface direct electroless plating silver, namely liquid phase reduction is adopted, directly at metal nickel powder electroplate, in ethanol-water system, take hydrazine hydrate as reducing agent, displacement reaction is suppressed by the control of reaction condition, silver ammino solution is made preferentially Liquid reduction reaction process to occur, in plating process, argent ion in solution is deposited on matrix surface by constantly reducing, obtain the core-shell type Ni-Ag bimetallic powder body roughly the same with pattern with former nickel powder particle diameter.
The preparation method of core-shell structural nickel-silver bimetallic powder provided by the invention adopts that particle diameter is less, the nickel powder of narrow diameter distribution, good dispersion makes matrix; Because matrix nickel powder itself can serve as catalyst, matrix surface is without the need to carrying out sensitization, activation process.The preparation method of core-shell structural nickel-silver bimetallic powder provided by the invention has the following advantages: it is directly coated that the present invention adopts Electroless Plating to carry out nickel powder, avoid in the past complicated technique, be conducive to the reduction of the stable of properties of product and production cost; In plating process, adopt dripping method new technology, quantitatively, continuously add silver ammino solution, carry out under making reaction maintain low metal ion concentration always, efficiently solve the difficult problem hindering powder electroless large-scale production; The pattern that the pattern of Ni-Ag bimetallic powder body is controlled to change into the nickel powder preparation process of relative maturity by the present invention controls; By the thickness of silver-colored addition controlling diaphragm.
Adopt the core-shell structural nickel-silver bimetallic powder that the inventive method is obtained, its silver coating thickness is controlled, and narrow diameter distribution, good dispersion, tap density is high.The Ni-Ag bimetallic powder body adopting the inventive method to obtain maintains original pattern of nickel powder, and powder dispersity is good, and soilless sticking phenomenon produces.The surperficial silver content of Ni-Ag bimetallic powder body obtained after secondary is coated can reach more than 90%, and silver forms continuous print silverskin on nickel particle surface, forms the Ni-Ag bimetallic powder body of nucleocapsid structure.Known by DSC-TG atlas analysis, the initial oxidation resistance temperature of Ni-Ag bimetallic powder body obtained after secondary is coated has and promotes by a relatively large margin, high-temperature oxidation resistance also significantly improves, and for serving as electrocondution slurry under Ni-Ag bimetallic powder body hypothermia, electromagnetic wave absorption material provides possibility.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1 Raw nickel powder;
Fig. 2 is the SEM figure of once coated core-shell structural nickel-silver bimetallic powder obtained in the embodiment of the present invention 1;
Fig. 3 is the XRD collection of illustrative plates of once coated core-shell structural nickel-silver bimetallic powder obtained in the embodiment of the present invention 1;
Fig. 4 is the XRD collection of illustrative plates of the coated core-shell structural nickel-silver bimetallic powder of secondary obtained in the embodiment of the present invention 1;
Fig. 5 is the SEM figure of once coated core-shell structural nickel-silver bimetallic powder obtained in the embodiment of the present invention 2;
Fig. 6 is the DSC-TG collection of illustrative plates of the embodiment of the present invention 2 Raw nickel powder;
Fig. 7 is the DSC-TG collection of illustrative plates of the coated core-shell structural nickel-silver bimetallic powder of secondary obtained in the embodiment of the present invention 2.
Detailed description of the invention
Embodiment 1
The preparation method of the present embodiment core-shell structural nickel-silver bimetallic powder, comprises the following steps:
(1) 25g nickel powder, 8.33g dispersant PVP are joined in 1L ethanol-water mixed solvent, then water-bath is placed in, bath temperature is kept to be 50 DEG C, stir 1 hour, mixing speed 500rpm, obtained nickel powder dispersion soln, the spherical nickel particulate that wherein nickel powder is 1.0 μm by average grain diameter forms, and in ethanol-water mixed solvent, the volume ratio of second alcohol and water is: ethanol: water=2: 5;
(2) mixed with water by reducing agent hydrazine hydrate, obtained concentration of hydrazine hydrate is the hydrazine hydrate aqueous solution of 2.5mol/L, regulates the pH value to 11 of hydrazine hydrate aqueous solution, obtains reductant solution;
(3) by nickel powder dispersion soln with reductant solution with volume ratio nickel powder dispersion soln: reductant solution=2.4: 1 mixes, obtain reactant liquor A, in reactant liquor A, drip silver ammino solution 50ml react, controlling the reaction time is 70 minutes, obtain suspension, centrifugation, gained solid, through washing, vacuum drying, obtains once coated core-shell structural nickel-silver bimetallic powder.
Replace the nickel powder in the present embodiment step (1) with once coated core-shell structural nickel-silver bimetallic powder, the core-shell structural nickel-silver bimetallic powder that secondary is coated can be prepared, namely comprise the following steps:
(1) core-shell structural nickel-silver bimetallic powder once coated for 25g, 8.33g dispersant PVP are joined in 1L ethanol-water mixed solvent, then water-bath is placed in, bath temperature is kept to be 50 DEG C, stir 1 hour, mixing speed 500rpm, obtained dispersion soln, in ethanol-water mixed solvent, the volume ratio of second alcohol and water is: ethanol: water=2: 5;
(2) mixed with water by reducing agent hydrazine hydrate, obtained concentration of hydrazine hydrate is the hydrazine hydrate aqueous solution of 2.5mol/L, regulates the pH value to 11 of hydrazine hydrate aqueous solution, obtains reductant solution;
(3) by dispersion soln with reductant solution with volume ratio dispersion soln: reductant solution=2.4: 1 mixes, obtain reactant liquor A, in reactant liquor A, drip silver ammino solution 50ml react, controlling the reaction time is 70 minutes, obtain suspension, centrifugation, gained solid, through washing, vacuum drying, obtains the core-shell structural nickel-silver bimetallic powder that secondary is coated.
Fig. 1 is the SEM figure of the present embodiment nickel powder material, and as can be seen from Figure 1, nickel powder material is spheric granules, uniform particle sizes, average grain diameter 1.0 μm, and distributed area is narrow; Fig. 2 is the SEM figure of the once coated core-shell structural nickel-silver bimetallic powder that the present embodiment obtains, as can be seen from Figure 2, once coated core-shell structural nickel-silver bimetallic powder maintains original pattern of nickel powder material, average grain diameter is 1.2 μm, powder dispersity is good, and soilless sticking phenomenon produces; Fig. 3 is the XRD collection of illustrative plates of the once coated core-shell structural nickel-silver bimetallic powder that the present embodiment obtains, as can be seen from Figure 3, Ag and Ni characteristic peak is had in diffraction maximum, show that nickel powder is through coated, define Ni-Ag bimetallic powder, the once coated core-shell structural nickel-silver bimetallic powder surface silver content that the present embodiment obtains reaches 32.53%, illustrates surperficial except containing except silver atoms, also there is nickle atom, silver does not have to form continuous print silverskin on nickel particle surface; Fig. 4 is the XRD collection of illustrative plates of the coated core-shell structural nickel-silver bimetallic powder of obtained secondary, as can be seen from Figure 4, the surperficial silver content of the core-shell structural nickel-silver bimetallic powder that obtained secondary is coated can reach 90.96%, although nickle atom also exists, but proportion is very little, silver atoms account for absolute predominance, and silver defines continuous print silverskin on nickel particle surface.
Embodiment 2
The preparation method of the present embodiment core-shell structural nickel-silver bimetallic powder, comprises the following steps:
(1) 25g nickel powder, 8.33g dispersant sodium tartrate are joined in 1L ethanol-water mixed solvent, then water-bath is placed in, bath temperature is kept to be 50 DEG C, stir 1 hour, mixing speed 500rpm, obtained nickel powder dispersion soln, the spherical nickel particulate that wherein nickel powder is 1.0 μm by average grain diameter forms, and in ethanol-water mixed solvent, the volume ratio of second alcohol and water is: ethanol: water=2: 5;
(2) mixed with water by reducing agent hydrazine hydrate, obtained concentration of hydrazine hydrate is the hydrazine hydrate aqueous solution of 2.5mol/L, regulates the pH value to 12 of hydrazine hydrate aqueous solution, obtains reductant solution;
(3) by nickel powder dispersion soln with reductant solution with volume ratio nickel powder dispersion soln: reductant solution=2.4: 1 mixes, obtain reactant liquor A, in reactant liquor A, drip silver ammino solution 50ml react, controlling the reaction time is 100 minutes, obtain suspension, centrifugation, gained solid, through washing, vacuum drying, obtains once coated core-shell structural nickel-silver bimetallic powder.
Replace the nickel powder in the present embodiment step (1) with once coated core-shell structural nickel-silver bimetallic powder, prepare the core-shell structural nickel-silver bimetallic powder that secondary is coated, comprise the following steps:
(1) core-shell structural nickel-silver bimetallic powder once coated for 25g, 8.33g dispersant sodium tartrate are joined in 1L ethanol-water mixed solvent, then water-bath is placed in, bath temperature is kept to be 50 DEG C, stir 1 hour, mixing speed 500rpm, obtained dispersion soln, in ethanol-water mixed solvent, the volume ratio of second alcohol and water is: ethanol: water=2: 5;
(2) mixed with water by reducing agent hydrazine hydrate, obtained concentration of hydrazine hydrate is the hydrazine hydrate aqueous solution of 2.5mol/L, regulates the pH value to 12 of hydrazine hydrate aqueous solution, obtains reductant solution;
(3) by dispersion soln with reductant solution with volume ratio dispersion soln: reductant solution=2.4: 1 mixes, obtain reactant liquor A, in reactant liquor A, drip silver ammino solution 50ml react, controlling the reaction time is 100 minutes, obtain suspension, centrifugation, gained solid, through washing, vacuum drying, obtains the core-shell structural nickel-silver bimetallic powder that secondary is coated.
Fig. 5 is the SEM figure of the once coated core-shell structural nickel-silver bimetallic powder that the present embodiment obtains, as can be seen from Figure 5, the once coated core-shell structural nickel-silver bimetallic powder that the present embodiment obtains is spheric granules, distributed area is narrow, average grain diameter 1.2 μm, good dispersion property, does not have agglomeration to occur.Fig. 6 is the DSC-TG collection of illustrative plates of the present embodiment nickel powder material, Fig. 7 is the DSC-TG collection of illustrative plates of the coated core-shell structural nickel-silver bimetallic powder of the present embodiment secondary, as can be seen from Figure 6, the initial oxidation temperature of nickel powder material is 290.45 DEG C, 732.62 DEG C time, weightening finish is up to 25.89%, after this no longer increase weight, therefore the high-temperature oxidation resistance of nickel powder material is very poor; As can be seen from Figure 7, the initial oxidation temperature of the core-shell structural nickel-silver bimetallic powder that the present embodiment secondary is coated is 389.36 DEG C, 732.62 DEG C time, weightening finish reaches maximum, weightening finish 7.584%, as can be seen here, the coated initial oxidation resistance temperature of core-shell structural nickel-silver bimetallic powder of the present embodiment secondary significantly promotes, about lifting 100 DEG C, high-temperature oxidation resistance also significantly improves.Because the initial oxidation resistance temperature of the coated core-shell structural nickel-silver bimetallic powder of secondary significantly promotes, for serving as electrocondution slurry under its low temperature, electromagnetic wave absorption material provides possibility.
In order to obtain the core-shell structural nickel-silver bimetallic powder that covered effect is good, high-temperature oxidation resistance is excellent, preparation method 1-2 time of core-shell structural nickel-silver bimetallic powder provided by the invention can be repeated.
Claims (4)
1. a preparation method for core-shell structural nickel-silver bimetallic powder, is characterized in that, comprises the following steps:
(1) nickel powder, dispersant are joined in ethanol-water mixed solvent, then water-bath is placed in, bath temperature is kept to be 50 DEG C, stir, obtained nickel powder dispersion soln, in described nickel powder dispersion soln, the concentration of nickel powder is 25.0g/l, and in described nickel powder dispersion soln, the concentration of dispersant is 8.33g/l;
(2) mixed with water by reducing agent hydrazine hydrate, obtained concentration of hydrazine hydrate is the hydrazine hydrate aqueous solution of 2.5mol/L, regulates more than the pH value to 10 of hydrazine hydrate aqueous solution, obtains reductant solution;
(3) by described nickel powder dispersion soln with described reductant solution with volume ratio nickel powder dispersion soln: reductant solution=2.4: 1 mixes, obtain reactant liquor A, in described reactant liquor A, drip silver ammino solution 50ml react, controlling the reaction time is 70 ~ 100 minutes, obtain suspension, centrifugation, gained solid, through washing, vacuum drying, obtains core-shell structural nickel-silver bimetallic powder.
2. the preparation method of core-shell structural nickel-silver bimetallic powder according to claim 1, is characterized in that, the spherical nickel particulate that described nickel powder is 1.0 μm by average grain diameter forms.
3. the preparation method of core-shell structural nickel-silver bimetallic powder according to claim 1, is characterized in that, described dispersant is PVP or sodium tartrate.
4. the preparation method of core-shell structural nickel-silver bimetallic powder according to claim 1, is characterized in that, in described ethanol-water mixed solvent, the volume ratio of second alcohol and water is: ethanol: water=2: 5.
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| CN103008674A (en) * | 2013-01-08 | 2013-04-03 | 安徽工业大学 | Nickel/copper oxide composite nanometer wave absorbing material and preparation method thereof |
| CN103567437A (en) * | 2013-10-11 | 2014-02-12 | 国家钽铌特种金属材料工程技术研究中心 | Preparation method of nickel powder with high tap density and degree of crystallinity |
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| CN106378448B (en) * | 2016-09-20 | 2019-03-19 | 杨海波 | A kind of nickel powder silver clad surface for circuit brake material is modified |
| CN108296478A (en) * | 2018-01-11 | 2018-07-20 | 宁波广新纳米材料有限公司 | Silver-nickel powder and preparation method thereof and electrocondution slurry containing the silver-nickel powder |
| CN111468739A (en) * | 2020-03-26 | 2020-07-31 | 浙江师范大学 | Magnetic recyclable Ni-coated Ag core-shell structure composite nanoparticle, preparation method thereof and dye degradation method |
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