CN1539577A - Nano hud-type bimetal powder of copper and stannum, preparing method and application - Google Patents
Nano hud-type bimetal powder of copper and stannum, preparing method and application Download PDFInfo
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- CN1539577A CN1539577A CNA2003101083395A CN200310108339A CN1539577A CN 1539577 A CN1539577 A CN 1539577A CN A2003101083395 A CNA2003101083395 A CN A2003101083395A CN 200310108339 A CN200310108339 A CN 200310108339A CN 1539577 A CN1539577 A CN 1539577A
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Abstract
A process for preparing the core-shell Cu-Sn nanoparticles includes preparing Cu nanoparticles, dispersing in water, mixing with the solution of stannous chloride under existence of high-molecular protecting agent and thiourea, and displacement reaction to generate a Sn layer on the surface of Cu nanoparticle. It can be used as the additive of extreme-pressure lubricant, powder metallurgy, and different special materials.
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 tin and preparation method thereof, this bimetal powder body can be used as lubricating oil and lubricating grease extreme-pressure anti-friction additive, in powder metallurgy, make additive, or as the raw material or the additive of porous material, anti-biotic material, antifouling paint, electro-conductive material, self-lubricating material, antifriction material, diamond tool and electrical carbon product.
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 [TrenieIznos, 20 (3), 333-338 (Russian) 1999] report that Muscovite scientist adds the discovery that experimentizes in the lubricating oil with copper nanoparticle, lubricity significantly improves, mechanical wear reduced 3-3.5 doubly and friction load be doubled, the tribological property of lubricating oil is good.Yet elemental 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 Red copper 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 gunmetal 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 glass putty 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-bimetallic ruthenium/tin powder 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-bimetallic ruthenium/tin powder.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-bimetallic ruthenium/tin powder in fields such as lubricating oil, antiseptic-germicides.
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 liquid; and the suspension liquid of copper powder mixed with the stannous chloride solution that has macromolecule dispersant and extraordinary cupric coordination agent thiocarbamide to exist; make stannous ion and copper generation replacement(metathesis)reaction; and at the surface portion of copper ultramicron or all coat tin, form a kind of core-shell type copper-bimetallic ruthenium/tin nano-powder.
Technical scheme of the present invention is: nano core-shell type copper-bimetallic ruthenium/tin powder, and it forms component and weight percentage is:
Copper: 80%～92%
Tin: 8%～20%
In said bimetal powder body, the surface portion of copper particle or all coated by tin forms a kind of copper-bimetallic ruthenium/tin powder, and the form of this bimetal powder body particle is spherical or subsphaeroidal, and the single particle size is approximately 50～100nm.
The preparation of above-mentioned nano core-shell type copper-bimetallic ruthenium/tin powder may further comprise the steps:
A, adopt 55～58 pages of document " chemistry circular " the 10th phases in 1996 earlier, the technology of people such as Liu Zhijie, Zhao Bin report prepares 2g nanometer spherical copper powder, and this copper powder is added the suspension liquid that 50ml water dispersed with stirring is evenly made copper powder;
B, then with the mixed solution of the cupric coordination agent thiocarbamide of two hydrated stannous chlorides of the macromolecule dispersant of 5g/L～60g/L, 6g/L～18g/L, 45g/L～90g/L, mix with the suspension liquid of copper powder, according to the proportioning of the decision of the copper-tin content in copper glass putty solution;
C, under 25～80 ℃ condition, stirred 5～30 minutes, can obtain nano core-shell type copper-bimetallic ruthenium/tin powder.
Said macromolecule dispersant is a kind of in the soluble high-moleculars such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), gelatin, Zulkovsky starch, methylcellulose gum, gum arabic.Preferred macromolecule dispersant is polyvinylpyrrolidone (PVP), gelatin.Used solvent is deionized water or distilled water.Solution ratio calculates the consumption of tin protochloride in the solution among the b according to the content proportioning (such as 90: 10,81: 19 etc.) of copper tin in amount of getting of copper powder (such as 2 grams) and the reaction product.
Above-mentioned nano core-shell type copper-bimetallic ruthenium/tin powder 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-germicide, stain control 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, electro-conductive material, self-lubricating composite, antifriction material, diamond tool and electrical carbon product.
The invention has the beneficial effects as follows: copper of the present invention-bimetallic ruthenium/tin powder had both overcome the shortcoming that copper powder is easy to oxidation, tin also has extreme pressure and antiwear behavior as a kind of soft metal simultaneously, copper tin 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 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 additives in addition, to non-corrosivenesss and environmentally friendly such as engine, gear, some metal partss.It is a kind of novel lubricating 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, stain control agent etc., its obvious social benefit.In the application of powder metallurgy etc.,, the existing product performance of gunmetal powder of using are significantly increased and improved effect than the excellent performance of ordinary copper tin alloy powder.Nano core-shell type copper-bimetallic ruthenium/tin the powder of this patent preparation, the substitution method technology of preparing of employing and the application of doing in lubricating oil aspect extreme-pressure anti-friction additive, the anti-biotic material etc. there is no document both at home and abroad and openly report.The present invention prepares a kind of particle with chemical process 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-bimetallic ruthenium/tin powder of oxidation, and is applied to lubricating oil and other is more multi-field (make additive, antiseptic-germicide, stain control agent, conducting powder in powder metallurgy or as the raw material or the additive of porous material, anti-biotic material, antifouling paint, electro-conductive material, self-lubricating material, antifriction material, diamond tool and electrical carbon product).
Description of drawings
Fig. 1 is the electromicroscopic photograph as the pure copper nanoparticle of raw material.
Fig. 2 is the electromicroscopic photograph of nano core-shell type copper of the present invention-bimetallic ruthenium/tin powder.
Fig. 3 is the XRD figure spectrum of nano core-shell type copper of the present invention-bimetallic ruthenium/tin powder.
Embodiment
Below will explain the concrete implementation method of the present invention by embodiment:
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 2 gram nanometer spherical copper powders, and it is even that copper powder is added 50ml water dispersed with stirring;
Macromolecule dispersant PVP content is that 20g/L, two hydrated stannous chloride content are that 7g/L, cupric coordination agent thiocarbamide content are the mixed solution 50ml of 60g/L, under room temperature, stirring condition it is mixed with the copper powder suspension liquid.Reaction times is 10 minutes, with reaction product filtration, washing, drying.Can obtain said core-shell type copper-bimetallic ruthenium/tin nano-powder.
Measure wherein through the gravimetric analysis method that copper content is 90%, tin content is 10%.
By Fig. 1,2 contrasts is that raw material can be prepared sphere or nearly nanometer spherical copper-bimetallic ruthenium/tin powder with the nanometer spherical copper powder as can be known, and the latter's particle is a bit larger tham the former, is the part clad structure.
As shown in Figure 3, only contain two kinds of compositions of copper and tin in the prepared powder, do not have the peak of oxide compound, the antioxidant property that this powder is described is better than the nanometer spherical copper powder as raw material.
Adopting prior art is that reductive agent prepares 2 gram irregular polygon copper powders with the hydrazine hydrate, and it is even that copper powder is added 50ml water dispersed with stirring;
Macromolecule dispersant PVP content is that 20g/L, two hydrated stannous chloride content are that 7g/L, cupric coordination agent thiocarbamide content are the mixed solution 50ml of 60g/L, under room temperature, stirring condition it is mixed with the copper powder suspension liquid.Reaction times is 15 minutes, with reaction product filtration, washing, drying.Can obtain said core-shell type copper-bimetallic ruthenium/tin nano-powder.
Measure wherein through the gravimetric analysis method that copper content is 90%, tin content is 10%.
By its pattern of the prepared powder of transmission electron microscope observation is irregular polygon.The pattern of this explanation raw material copper powder has determined the pattern of copper glass putty.
With reference to embodiment 1 preparation nanometer spherical copper powder 2g, and make suspension liquid 50ml.
Macromolecule dispersant PVP content is that 20g/L, two hydrated stannous chloride content are that 17g/L, cupric coordination agent thiocarbamide content are the mixed solution 50ml of 80g/L, under 60 ℃, stirring condition it is mixed with the copper powder suspension liquid.Reaction times is 10 minutes, with reaction product filtration, washing, drying.Can obtain said core-shell type copper-bimetallic ruthenium/tin nano-powder.
Measure wherein through the gravimetric analysis method that copper content is 81%, tin content is 19%.
By its pattern of the prepared powder of transmission electron microscope observation is spherical or subsphaeroidal, and the single particle size is 50-100nm, is complete clad structure.
With reference to embodiment 1 preparation nanometer spherical copper powder 2g, and make suspension liquid 50ml.
Macromolecule dispersant Zulkovsky starch 25g/L, two hydrated stannous chloride content are that 11g/L, cupric coordination agent thiocarbamide content are the mixed solution 50ml of 60g/L, under 40 ℃, stirring condition it are mixed with the copper powder suspension liquid.Reaction times is 20 minutes, with reaction product filtration, washing, drying.Can obtain said nano core-shell type copper-bimetallic ruthenium/tin powder.
Measure wherein through the gravimetric analysis method that copper content is 88%, tin content is 12%.
By its pattern of the prepared powder of transmission electron microscope observation is subsphaeroidal, and the single particle size is 50-100nm.
Embodiment 5
Method by embodiment 1 prepares core-shell type copper-bimetallic ruthenium/tin nano-powder 0.05g, adds in the 99.95g SN150 base oil, and the powder addition is 0.05%, and heated and stirred was uniformly dispersed it 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 the PB value and is 921N/GB3142 (base oil that does not contain additive is 598N/GB3142), and frictional coefficient is descended to some extent.
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%, heated and stirred was uniformly dispersed it in 1 hour.Tested as can be known by four-ball tester, the maximum no click of this lubricating oil is stung the PB value and is 921N/GB3142 (base oil that does not contain additive is 598N/GB3142).Embodiment 5 compares with embodiment 6, and as lubricated oil additives, the copper glass putty reduces and the stability raising than the consumption of copper powder.
Embodiment 7
Method by embodiment 1,2,4 prepares nano core-shell type copper-bimetallic ruthenium/tin powder 0.1g, and being distributed to the 100ml bacteria concentration is 6.60*10
7(cfu/ml) in the solution, 300r/min concussion one hour is carried out sterilization experiment according to the method for GB15979-2002, and its sterilizing rate is 99.99%.
Claims (8)
1, nano core-shell type copper-bimetallic ruthenium/tin powder, its weight percentage of forming component is:
Copper: 80%～92%
Tin: 8%～20% in said bimetal powder body, and the surface portion of copper particle or all coated by tin forms a kind of nano core-shell type copper-bimetallic ruthenium/tin powder.
2, nano core-shell type copper according to claim 1-bimetallic ruthenium/tin powder is characterized in that: described bimetal powder body single particle size is 50～100nm.
3, nano core-shell type copper according to claim 1 and 2-bimetallic ruthenium/tin powder is characterized in that: the form of described bimetal powder body particle is for spherical or subsphaeroidal.
4, the preparation method of the described nano core-shell type copper of claim 1-bimetallic ruthenium/tin powder, at first prepare the nanometer spherical copper powder, add water and stir and obtain the copper powder suspension liquid, it is characterized in that: the mixed solution of further comprising the steps of a, the macromolecule dispersant with 5g/L～60g/L, two hydrated stannous chlorides of 6g/L～18g/L, the cupric coordination agent thiocarbamide of 45g/L～90g/L etc. mixes with the suspension liquid of copper powder; B, under 25～80 ℃ condition, stirred 5～30 minutes, can obtain nano core-shell type copper-bimetallic ruthenium/tin powder.
5, the preparation method of nano core-shell type copper according to claim 4-bimetallic ruthenium/tin powder is characterized in that: said macromolecule dispersant is a kind of in the soluble high-moleculars such as polyvinylpyrrolidone, polyvinyl alcohol, gelatin, Zulkovsky starch, methylcellulose gum, gum arabic.
6, the preparation method of nano core-shell type copper according to claim 5-bimetallic ruthenium/tin powder is characterized in that: preferred macromolecule dispersant is a kind of in polyvinylpyrrolidone, the gelatin.
7, the described nano core-shell type copper of claim 1-bimetallic ruthenium/tin powder is as the application of lubricating oil and lubricating grease extreme-pressure anti-friction additive.
8, the described nano core-shell type copper of claim 1-bimetallic ruthenium/tin powder is as the application of antiseptic-germicide.
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| CN1299865C (en) * | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nuclear shell structured nano-gold copper powder |
| CN100584743C (en) * | 2006-12-15 | 2010-01-27 | 中国科学院长春应用化学研究所 | Preparation process of nanometer copper complex fiber |
| CN101323020B (en) * | 2008-07-17 | 2011-04-20 | 厦门大学 | Low-melting point core/case type tin-bismuth-copper alloy powder body and preparation thereof |
| CN102554219A (en) * | 2012-01-31 | 2012-07-11 | 云南云天化股份有限公司 | Nanoparticle of copper-tin nuclear shell structure and preparation method for nanoparticle |
| CN103027078A (en) * | 2011-09-29 | 2013-04-10 | 钱陈慧贤 | Antibacterial product containing silver and nickel mixed powder and preparation method of antibacterial product |
| CN103074561A (en) * | 2012-12-11 | 2013-05-01 | 北京矿冶研究总院 | Wide-temperature-range self-lubricating coating material and preparation method thereof |
| CN103753049A (en) * | 2013-12-27 | 2014-04-30 | 哈尔滨工业大学深圳研究生院 | Cu@Sn core-shell-structured high-temperature solder and preparation method thereof |
| CN103769607A (en) * | 2014-02-19 | 2014-05-07 | 四川大学 | Preparation method for nickel-copper nanowire |
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| CN105290418A (en) * | 2015-10-14 | 2016-02-03 | 哈尔滨工业大学深圳研究生院 | Method for cladding surface of micro-nano-copper ball with thick tin layer with weldable thickness |
| CN106433558A (en) * | 2016-09-26 | 2017-02-22 | 麦科勒（滁州）新材料科技有限公司 | Bonding agent for electronic packaging and preparing method thereof |
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| CN1299865C (en) * | 2005-04-26 | 2007-02-14 | 黄德欢 | Preparation method of nuclear shell structured nano-gold copper powder |
| CN100584743C (en) * | 2006-12-15 | 2010-01-27 | 中国科学院长春应用化学研究所 | Preparation process of nanometer copper complex fiber |
| CN101323020B (en) * | 2008-07-17 | 2011-04-20 | 厦门大学 | Low-melting point core/case type tin-bismuth-copper alloy powder body and preparation thereof |
| CN103027078A (en) * | 2011-09-29 | 2013-04-10 | 钱陈慧贤 | Antibacterial product containing silver and nickel mixed powder and preparation method of antibacterial product |
| CN102554219B (en) * | 2012-01-31 | 2014-03-26 | 云南云天化股份有限公司 | Nanoparticle of copper-tin nuclear shell structure and preparation method for nanoparticle |
| CN102554219A (en) * | 2012-01-31 | 2012-07-11 | 云南云天化股份有限公司 | Nanoparticle of copper-tin nuclear shell structure and preparation method for nanoparticle |
| CN104203457B (en) * | 2012-03-30 | 2016-04-13 | 应用纳米粒子研究所株式会社 | Ointment and joint method thereof is belonged to containing copper gasket composite nano-gold |
| CN104203457A (en) * | 2012-03-30 | 2014-12-10 | 应用纳米粒子研究所株式会社 | Composite nanometal paste containing copper filler and bonding method |
| CN103074561A (en) * | 2012-12-11 | 2013-05-01 | 北京矿冶研究总院 | Wide-temperature-range self-lubricating coating material and preparation method thereof |
| CN103753049A (en) * | 2013-12-27 | 2014-04-30 | 哈尔滨工业大学深圳研究生院 | Cu@Sn core-shell-structured high-temperature solder and preparation method thereof |
| CN103753049B (en) * | 2013-12-27 | 2017-02-01 | 哈尔滨工业大学深圳研究生院 | Cu@Sn core-shell-structured high-temperature solder and preparation method thereof |
| CN103769607A (en) * | 2014-02-19 | 2014-05-07 | 四川大学 | Preparation method for nickel-copper nanowire |
| CN104117782A (en) * | 2014-08-11 | 2014-10-29 | 哈尔滨工业大学深圳研究生院 | Novel prefabricated piece high-temperature brazing filler metal and preparation method thereof |
| CN104117782B (en) * | 2014-08-11 | 2017-01-11 | 哈尔滨工业大学深圳研究生院 | Novel prefabricated piece high-temperature brazing filler metal and preparation method thereof |
| CN105290418A (en) * | 2015-10-14 | 2016-02-03 | 哈尔滨工业大学深圳研究生院 | Method for cladding surface of micro-nano-copper ball with thick tin layer with weldable thickness |
| CN106433558A (en) * | 2016-09-26 | 2017-02-22 | 麦科勒（滁州）新材料科技有限公司 | Bonding agent for electronic packaging and preparing method thereof |
| CN113649567A (en) * | 2021-08-19 | 2021-11-16 | 合肥工业大学 | Ag @ SiO2@ Sn three-layer core-shell structure and preparation method thereof |
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