CN101209493A - Nano core-shell type copper-nickel bimetal powder body and preparing method and application thereof - Google Patents
Nano core-shell type copper-nickel bimetal powder body and preparing method and application thereof Download PDFInfo
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Abstract
The invention relates to a bimetal powder of copper and nickel and a preparation method thereof. The invention solves the defect of easy oxidation of the simple substance nanometer copper powder and improves the use effect of the ordinary copper nickel composite powder. Referring to the prior art, the invention firstly prepares a nanometer copper powder, the copper powder is stirred and dispersed homogeneously in the water, and suspension liquid of the copper powder is prepared; the suspension liquid of the copper powder is blended with the nickel sulfate solution comprising macromolecule protective agent and special copper coordination agent thiourea so as to cause a replacement reaction between nickel ion and the copper; surfaces of the ultrafine copper particles are partly or all coated with the nickel, thus forming the core-shell copper-nickel bimetal nanometer powder. The bimetal powder can be taken as lubricant, lubricating grease extreme pressure-antiwear additives, additives in powder metallurgy, or as porous materials, antibacterial materials, antifouling coatings, conductive materials, magnetic materials, self-lubricating materials, antifriction materials, diamond tools, and raw materials or additives of electrical carbon products.
Description
Technical field
The invention belongs to the technical field of bimetal powder body and preparation thereof and application, relate in particular to bimetal powder body of a kind of copper and mickel and its production and application.
Technical background
Nano-powder is owing to have the physics and the chemical property of the unexistent uniqueness of many traditional materials, thereby obtained paying attention to widely, becomes one of heat subject of current research both at home and abroad.Nano material is applied in the lubricating oil research field that the multidisciplinary intersection of application prospect is arranged very much especially.According to document [Trenie Iznos, 20 (3), 333-338 (Russian) 1999] report that Muscovite scientist adds the discovery that experimentizes in the lubricating oil with copper nanoparticle, greasy property significantly improves, mechanical wear reduced 3-3.5 doubly and friction load be doubled, the tribological property of lubricating oil is good.Yet simple substance nanometer copper is easy to oxidized in air.55~58 pages of document " chemistry circular " the 10th phases in 1996, people such as Liu Zhijie, Zhao Bin have reported that copper nanoparticle will be oxidized to khaki cuprous oxide under the situation of air drying.This has limited copper nanoparticle in each Application for Field such as lubricating oil and lubricating grease.General copper nickel composite powder is used also wider at present, can be used as the raw material or the products such as additive and additive for powder metallurgy of antifouling, diamond, electrical carbon product, if but adopt nanometer copper-nickel powder effect to significantly improve.
Summary of the invention
It is oxidized easily in air that one of technical problem that will solve required for the present invention is to solve the simple substance copper nanoparticle, and a kind of oxidized nano core-shell type copper-nickel bimetal powder body that is difficult for is provided.
Two of the technical problem that will solve required for the present invention is to disclose a kind of preparation cost preparation method lower, that be easy to realize industrialized nano core-shell type copper-nickel bimetal powder body.
Three of the technical problem that will solve required for the present invention is to disclose the application of said nano core-shell type copper-nickel bimetal powder body in fields such as lubricating oil, conductive materials.
Design of the present invention is such:
At first with reference to a kind of nanometer spherical copper powder of prior art for preparing; then this copper powder dispersed with stirring in water is evenly made the copper powder suspension; and the suspension of copper powder mixed with the nickel sulfate solution that has macromolecule dispersant and extraordinary cupric coordination agent thiocarbamide to exist; make nickel ion and copper generation displacement reaction; and at the surface portion of copper ultramicron or all coat nickel, form a kind of core-shell type copper-nickel bimetal nano-powder.
Technical scheme of the present invention is: nano core-shell type copper-nickel bimetal powder body, and it forms component and weight percentage is: copper: 60%~90%, nickel: 10%~40%;
In said bimetal powder body, the surface portion of copper particle or all coated by nickel forms a kind of copper-nickel bimetal powder body, and the form of this bimetal powder body particle is spherical or subsphaeroidal, and the single particle size is approximately 10~100nm.
Most preferred composition component and weight percentage are: copper: 70%~80%, and nickel: the preparation of 20%~30% above-mentioned nano core-shell type copper-nickel bimetal powder body may further comprise the steps:
A, copper powder is mixed with water, obtain the suspension of copper powder;
Said copper powder can adopt commercially available product, preferably adopts 55~58 pages of document " chemistry circular " the 10th phases in 1996, and the technology preparation of people such as Liu Zhijie, Zhao Bin report is a kind of nanometer spherical copper powder, and particle diameter is 30~80 nanometers;
In the copper powder suspension, the content of copper powder is 2~5g/100ml;
B, then with the coating aqueous solution that contains nickel, under 75~90 ℃ condition, stirred 5~30 minutes, can obtain the nano core-shell type copper-nickel bimetal powder.
In the said covering liquid that contains nickel, the content of macromolecule dispersant is 5g/L~60g/L, and the content of six hydration nickel sulfate is 13g/L~54g/L, and the content of cupric coordination agent thiocarbamide is 45g/L~90g/L;
Specifically can be according to the proportioning of the copper nickel content in copper nickel powder decision solution, solution ratio calculates the consumption of nickelous sulfate in the solution among the b according to the content proportioning (such as 90: 10,81: 19 etc.) of copper nickel in the amount of getting (such as 4 grams) of copper powder and the product.
Said macromolecule dispersant is a kind of in the soluble high-moleculars such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), gelatin, soluble starch, methylcellulose, Arabic gum.Preferred macromolecule dispersant is polyvinylpyrrolidone (PVP), gelatin.Used solvent is deionized water or distilled water.
Above-mentioned nano core-shell type copper-nickel bimetal powder body can be used as the additive in lubricating oil and lubricating grease extreme-pressure anti-friction additive, the powder metallurgy, can be used as antiseptic, anti-fouling agent, conducting powder etc. and directly use, also can be used as raw material or additive and make application such as anti-biotic material, antifouling paint, conductive material, magnetic material, self-lubricating composite, antifriction material, diamond tool and electrical carbon product.
The invention has the beneficial effects as follows: copper-nickel bimetal powder of the present invention had both overcome the shortcoming that copper powder is easy to oxidation, nickel also has extreme pressure and antiwear behavior as a kind of metal simultaneously, copper nickel adds it in the lubricating oil to after forming metal powder, and its extreme pressure and antiwear behavior can further improve.The ratio nano copper lubricating oil additive has improved extreme pressure anti-wear, stability and has reduced consumption.Can also satisfy the requirement of the appearance transparent of lubricating oil simultaneously, oily muddy phenomenon not occur.This powder is an inorganic additive in addition, to non-corrosiveness and environmentally friendly such as engine, gear, some metal parts.It is a kind of novel lube oil additive, has good wear-resistant, antifriction and energy-saving and environmental protection effect, and considerable economic is arranged.In addition, this powder is done the application of antibiotic powder, anti-fouling agent etc., its obvious social benefit.In the application of powder metallurgy etc.,, the existing properties of product of copper nickel composite powder of using are significantly increased and improved effect than the excellent performance of ordinary copper nickel composite powder.The nano core-shell type copper-nickel bimetal powder of this patent preparation, the displacement method technology of preparing of employing and the application of doing in lubricating oil aspect extreme-pressure anti-friction additive, the conductive material etc. there is no document both at home and abroad and openly report.The present invention prepares a kind of particle with chemical method to be not more than 100 nanometers, narrow diameter distribution, pattern is for spherical or subsphaeroidal and be difficult for the nano core-shell type copper-nickel bimetal powder body of oxidation, and is applied to lubricating oil and other is more multi-field (make additive, antiseptic, anti-fouling agent, conducting powder in powder metallurgy or as the raw material or the additive of porous material, anti-biotic material, antifouling paint, conductive material, magnetic material, self-lubricating material, antifriction material, diamond tool and electrical carbon product).
Description of drawings
Fig. 1 is the size distribution of the nano core-shell type copper-nickel bimetal powder body of embodiment 1.
Fig. 2 is the electromicroscopic photograph of the nano core-shell type copper-nickel bimetal powder body of embodiment 1.
The specific embodiment
Below will explain the concrete implementation method of the present invention by embodiment:
Embodiment 1
At first adopt 55~58 pages of document " chemistry circular " the 10th phases in 1996, the technology of people such as Liu Zhijie, Zhao Bin report prepares 4 gram nanometer spherical copper powders, and it is even that copper powder is added 100ml water dispersed with stirring;
Macromolecule dispersant PVP content is that 16g/L, six hydration nickel sulfate content are that 13.3g/L (nickel theoretical content in powder is 10%), cupric coordination agent thiocarbamide content are the mixed liquor 120ml of 67g/L, under 80 degree, stirring condition it is mixed with the copper powder suspension.Reaction time is 15 minutes, with product filtration, washing, drying.Can obtain said core-shell type copper-nickel bimetal nano-powder.
By Fig. 1,2 contrasts is that raw material can be prepared sphere or nearly nanometer spherical copper-nickel bimetal powder with the nanometer spherical copper powder as can be known, and the latter's particle is a bit larger tham the former, is clad structure.
Embodiment 2
With reference to embodiment 1 preparation nanometer spherical copper powder 4g, and it is even that copper powder is added 100ml water dispersed with stirring; Other makes macromolecule dispersant PVP content is that 16g/L, cupric coordination agent thiocarbamide content are 67g/L, and six hydration nickel sulfate content is that the mixed liquor 120ml. of 20g/L (nickel theoretical content in powder is 15%) mixes it under 80 ℃ of stirring condition with the copper powder suspension.Reaction time is 15 minutes, with product filtration, washing, drying.Can obtain said core-shell type copper-nickel bimetal nano-powder.
Laser particle analyzer is tested the particle diameter of prepared powder, and the average grain diameter of particle is 70nm.Particle is a clad structure.
Embodiment 3
With reference to embodiment 1 preparation nanometer spherical copper powder 4g, and it is even that copper powder is added 100ml water dispersed with stirring; Other makes macromolecule dispersant PVP content is that 16g/L, cupric coordination agent thiocarbamide content are that 67g/L, six hydration nickel sulfate content are the mixed liquor 120ml of 26.6g/L (nickel theoretical content in powder is 20%), under 80 ℃, stirring condition it is mixed with the copper powder suspension.Reaction time is 20 minutes, with product filtration, washing, drying.Can obtain said nano core-shell type copper-nickel bimetal powder body.
Laser particle analyzer is tested the particle diameter of prepared powder, and the average grain diameter of particle is 60nm.Particle is a clad structure.
But the nanometer copper-nickel powder of nickel content 30%, 40% etc. in the same method powder process body
Embodiment 4
Method by embodiment 2 prepares the core-shell type copper-nickel bimetal nano-powder, and only reaction temperature changes 90 degree into.Resulting nano core-shell type copper-nickel bimetal powder body is through the particle diameter of laser particle analyzer test powder, and the average grain diameter of particle is 65nm.Particle is a clad structure.
Embodiment 5
Method by embodiment 2 prepares core-shell type copper-nickel bimetal nano-powder 0.015g, adds in the 99.99g SN500 base oil, and the powder addition is 0.015%, adds thermal agitation and it is uniformly dispersed in 1 hour.By the four-ball tester experiment as can be known, this powder has good extreme pressure and antiwear behavior, and maximum no click is stung P
BValue is 980N/GB3142 (base oil that does not contain additive is 647N/GB3142).
Embodiment 6
With reference to embodiment 3 preparation nanometer spherical copper-nickel powder 0.015g, add in the 99.99g 15W40 engine oil, the powder addition is 0.015%, adds thermal agitation and it is uniformly dispersed in 1 hour.By the four-ball tester experiment as can be known, the maximum no click of this lubricating oil is stung P
BValue is 1254N/GB3142 (additive oil is not 745N/GB3142).
Embodiment 7
With reference to embodiment 1 preparation nanometer spherical copper powder 0.1g, add in the 99.9g SN150 base oil, the powder addition is 0.1%, adds thermal agitation and it is uniformly dispersed in 1 hour.By the four-ball tester experiment as can be known, maximum no click is stung P
BValue is 921N/GB3142 (base oil that does not contain additive is 598N/GB3142).As the extreme-pressure anti-friction additive of lubricating oil, the consumption of nanometer copper-nickel powder ratio nano copper powder reduces and stability increases.
Annotate: the application of nano core-shell type copper-nickel bimetal powder body is used identical with common copper-nickel composite powder powder.As in powder metallurgy, making additive, antiseptic, anti-fouling agent, conducting powder or as the raw material of porous material, anti-biotic material, antifouling paint, conductive material, magnetic material, self-lubricating material, antifriction material, diamond tool and electrical carbon product or make additive.Here differ and one illustrated for example.
Claims (11)
1. nano core-shell type copper-nickel bimetal powder body, its weight percentage of forming component is:
Copper: 60%~90%, nickel: 10%~40%.
2. nano core-shell type copper-nickel bimetal powder body according to claim 1 is characterized in that: its weight percentage of forming component is:
Copper: 70%~80%, nickel: 20%~30%.
3. nano core-shell type copper-nickel bimetal powder body according to claim 1 is characterized in that: described bimetal powder body single particle size is 10~100nm.
4. nano core-shell type copper-nickel bimetal powder body according to claim 1 and 2 is characterized in that: in said bimetal powder body, the surface portion of copper particle or all coated by nickel is a kind of copper-nickel bimetal powder body.
5. nano core-shell type copper-nickel bimetal powder body according to claim 1 is characterized in that: the form of described bimetal powder body particle is for spherical or subsphaeroidal.
6. the preparation method of the described nano core-shell type copper-nickel bimetal powder body of claim 1 mixes copper powder with water, obtains the suspension of copper powder;
B, then with the coating aqueous solution that contains nickel, under 75~90 ℃ condition, stir, can obtain the nano core-shell type copper-nickel bimetal powder.
7. method according to claim 6 is characterized in that, said copper powder is a kind of nanometer spherical copper powder, and particle diameter is 40~80 nanometers.
8. method according to claim 6 is characterized in that in the copper powder suspension that the content of copper powder is 2~5g/100ml.
9. method according to claim 6 is characterized in that, in the said covering liquid that contains nickel, the content of macromolecule dispersant is 5g/L~60g/L, and the content of six hydration nickel sulfate is 13g/L~54g/L, and the content of cupric coordination agent thiocarbamide is 45g/L~90g/L.
10. the preparation method of nano core-shell type copper-nickel bimetal powder body according to claim 6 is characterized in that: said macromolecule dispersant is a kind of in the soluble high-moleculars such as polyvinylpyrrolidone, polyvinyl alcohol, gelatin, soluble starch, methylcellulose, Arabic gum.
11. the described nano core-shell type copper-nickel bimetal powder body of claim 1 is as making additive in lubricating oil and lubricating grease extreme-pressure anti-friction additive, the powder metallurgy, or as the raw material of porous material, anti-biotic material, antifouling paint, conductive material, magnetic material, self-lubricating material, antifriction material, diamond tool and electrical carbon product or make Application of Additives.
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