CN1369341A - Superfine tree-shaped silver powder and its preparing process - Google Patents
Superfine tree-shaped silver powder and its preparing process Download PDFInfo
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- CN1369341A CN1369341A CN 01139141 CN01139141A CN1369341A CN 1369341 A CN1369341 A CN 1369341A CN 01139141 CN01139141 CN 01139141 CN 01139141 A CN01139141 A CN 01139141A CN 1369341 A CN1369341 A CN 1369341A
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Abstract
A superfine tree-shaped silver powder, which has 1-10 microns of average conglobation size and 40-300 nm of single branch size, is prepared through preparing superfine copper powder, preparing its suspension, adding high-molecular protected silver ions to it, and displacement reaction between silver ions and copper ions to obtain said silver powder. The said product has high sterilizing rate up to 100%.
Description
Technical field
The present invention relates to a kind of ultrafine metal powders body and preparation method thereof, particularly a kind of pattern is dendritic antibiotic and super fine silver powder conductivity of having.
Background technology
Ultrafine metal particle or ultrafine powder are that atoms metal is assembled the metal cluster that forms, and be both different with metal integral, distinguish to some extent with atoms metal again, and be the metastable state between metal solid and atoms metal.Because the super-refinement of metallics has the advantages that particle diameter is little, surface-area is big, therefore, has a lot of special performances, especially can be used as the catalyzer of a kind of high reactivity, highly selective.There are a lot of documents this to be made detailed report; Zhao Bin, Ma Haiyan have been reported " preparation of silver-colored ultrafine powder " among document " East China University of Science's journal " Vol.22 in addition, No.2 221-226 (1996); " coating technology " 2000,1, Zhao Bin, Zhang Guoqing have reported " application of super fine silver powder in electrically conducting coating " among the 40-44; " precious metal, Vol.19 No.4,1998,50-53 " opens civilian bell-shaped percussion instrument, used in ancient time by troops on march, Zhang Yutian has reported " Ag-carried antibacterial material and goods " and waited preparation method and the silver-colored application in antiseptic-germicide, electrically conducting coating of having introduced particulate state or flaky super fine silver powder respectively.Actual super fine silver powder has multiple pattern, as sphere, sheet, Polygons, dendroid, bar-shaped or the like.Because the difference of pattern, size, its performance is also incomplete same.The anti-microbial property and the conductivity that experiment showed, superfine tree-shaped silver powder are comparatively outstanding.And the technology that above-mentioned document provided can not guarantee that the super fine silver powder that is obtained has dendritic form fully, thereby has influenced the effect of super fine silver powder as antiseptic-germicide and electro-conductive material.Therefore, the technology of preparing of the good superfine tree-shaped silver powder of exploitation conductivity, anti-microbial property has crucial realistic meaning.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of superfine tree-shaped silver powder and preparation method thereof, thereby can not guarantee that to overcome existing in prior technology the super fine silver powder that is obtained has the dendroid form fully and influences its defective as effects such as antiseptic-germicide and conducting powder.
Design of the present invention is such:
At first, in the suspension liquid of superfine cupper powder, add the silver ions of quantitative polymer protection then, make silver ions and copper generation replacement(metathesis)reaction, promptly obtain the fine silver powder of dendritic superfine with reference to the prior art for preparing superfine cupper powder.
Its average aggregate size of fine silver powder of dendritic superfine of the present invention is 1-10 μ m, and the size of single branch is 40nm-300nm.
Described method comprises the steps:
(1) at first adopts document " East China University of Science's journal " Vol.23, " preparation of hydrazine hydrate reduction method and the stability study thereof of superfine cupper powder " disclosed technology of reports such as No.3 372-376 (1997) Zhao Bin, Liu Zhijie prepares superfine cupper powder, and its particle diameter is in the 100nm-10um scope;
(2) be 8-32g/L with protective material content, Silver Nitrate content is that the mixed solution of 0.5mol/L is added drop-wise in the suspension liquid of copper powder, dripping quantity is controlled with the mol ratio ratio of copper with silver, is generally silver: copper=(2～2.5): 1, and be (2～2.2) with the silver-bearing copper ratio: 1 is the best;
(3) 20-40 ℃ of following stirring reaction 0.5～1 hour, adopt conventional method to carry out liquid-solid separation, as filtering or drying etc., can make the dendriform super fine silver powder.
Said macromolecule dispersant is one or more in the soluble high-moleculars such as polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), gelatin, Zulkovsky starch.Protectant effect can guarantee that the pattern of silver powder is dendroid and is superfine powder.The protective material consumption very little, powder is easily reunited; Consumption is too many, then will increase cost.Preferred dispersing agent is PVP, is starch secondly.
The used solvent of step (2) is water or ethanol and composition thereof, and preferred solvent is a water.
Adopt the method for GB15979-1995 that the superfine tree-shaped silver powder that is obtained is carried out antibacterial experiment, the result is: the concentration of silver powder is 100ppm, and bacteria concentration is less than 10
7During/ml the order of magnitude, sterilizing rate can reach 100%.Its conductivity is extremely excellent when making certain electrically conducting coating.Its square resistance can reach 10
-3More than Ω/.Because silver powder preparation method of the present invention is very simple, is easy to suitability for industrialized production, has very wide application prospect.
Description of drawings
Fig. 1 is the electromicroscopic photograph of superfine tree-shaped silver powder.
Fig. 2 is the XRD figure spectrum of superfine tree-shaped silver powder.
Fig. 3 is the thermogravimetric curve of superfine tree-shaped silver powder.
Embodiment
Below by embodiment the relevant details of preparation process is described further.
The preparation of embodiment 1 superfine cupper powder:
Get 37.5g cupric sulfate pentahydrate and 3g PVP adding 150ml deionized water and make it dissolving, other gets the 31.5g hydrazine hydrate and adds the 150ml deionized water.Two kinds of solution are preheated to 65 ℃ respectively, PVP drips of solution with copper sulfate under agitation condition adds in the hydrazine hydrate solution, constant temperature is at 65 ℃, and continue to stir 20 minutes, can get the red-purple powder, after the filtration powder be washed 5 times with deionized water, absolute ethanol washing 3 times, cryodrying (below 40 ℃) or directly air-dry gets superfine cupper powder.Its median size is in the 100nm-10 mu m range.Take by weighing above-mentioned copper powder 0.8g and in the 75ml deionized water, disperse; Other gets Silver Nitrate 4.46g and PVP1.5g is made into 50ml solution.The PVP mixed solution of Silver Nitrate is added drop-wise in the copper powder suspension liquid, and control reaction temperature drips and finishes back continuation stirring 25 minutes at 20 ℃, can get the grey powder.As seen from Figure 1, its pattern of prepared super fine silver powder is a dendroid, and average coacervate is of a size of 8.14 μ m, and single branch sheet size is 55nm.
As seen from Figure 2, only contain the characteristic peak of silver in the XRD figure of the prepared superfine tree-shaped silver powder spectrum, there is no the characteristic peak of copper, replacement(metathesis)reaction is carried out fully, and what make is ultra-fine fine silver powder.
As seen from Figure 3, the superfine tree-shaped silver powder phenomenon that in room temperature to 800 ℃ temperature-rise period, do not increase weight, super fine silver powder is not oxidized, Heat stability is good, and do not contain copper powder, neither copper-silver metal powder.(both all have the weightening finish phenomenon back in this scope.)
Adopt the method for embodiment 1, wherein the consumption of PVP is 4.0g, and the average coacervate of prepared superfine tree-shaped silver powder is of a size of 7.2 μ m.
Embodiment 3
Adopt the method for embodiment 1, change PVP into starch, consumption is 1.0g, and the average aggregation size of prepared superfine tree-shaped silver powder is 6.6 μ m.
Embodiment 4
Adopt the method for embodiment 1, only change temperature of reaction into 40 ℃ from 20 ℃, the average aggregation size of prepared superfine tree-shaped silver powder is 7.1 μ m.
Embodiment 5～6
Adopt the method for embodiment 1, only the proportioning with silver-bearing copper changes 2.1,2.2 into, and the average aggregation size of prepared superfine tree-shaped silver powder is respectively 7.5 μ m, 7.8 μ m.
Embodiment 7～8
Adopt the method for embodiment 1, only change the silver-bearing copper ratio into 1.8 and 1.9, the powder of gained is not a branch shape super fine silver powder, but dendritic ultra-fine copper silver powder.The size of its average coacervate is respectively 7.2 μ m, 7.3 μ m.
Claims (8)
1. a superfine tree-shaped silver powder is characterized in that, its average aggregate size of fine silver powder of this dendritic superfine is 1-10 μ m, and the size of single branch is 40nm-300nm.
2. the preparation method of superfine tree-shaped silver powder as claimed in claim 1 is characterized in that this method comprises the steps:
(1) adopts the prior art for preparing superfine cupper powder;
(2) be 8-32g/L with protective material content, Silver Nitrate content is that the mixed solution of 0.5mo1/L is added drop-wise in the suspension liquid of copper powder, and dripping quantity is a silver: copper=(2～2.5): 1;
(3) stirring reaction adopts conventional method to carry out liquid-solid separation, can make superfine tree-shaped silver powder;
Macromolecule dispersant is one or more in the soluble high-molecular;
The used solvent of step (2) is water or ethanol and composition thereof.
3. the method for claim 1 is characterized in that, the superfine cupper powder particle diameter is 100nm-10um.
4. the method for claim 1 is characterized in that, silver-bearing copper is than being (2～2.2): 1.
5. the method for claim 1 is characterized in that, reaction conditions is: 20-40 ℃, reacted 0.5～1 hour.
6. as the arbitrary described method of claim 1～4, it is characterized in that macromolecule dispersant is one or more in polyvinylpyrrolidone, polyvinyl alcohol, gelatin or the Zulkovsky starch.
7. method as claimed in claim 5 is characterized in that, macromolecule dispersant is PVP.
8. method as claimed in claim 5 is characterized in that, macromolecule dispersant is a starch.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011391413A CN1180909C (en) | 2001-12-20 | 2001-12-20 | Superfine tree-shaped silver powder and its preparing process |
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| CNB011391413A CN1180909C (en) | 2001-12-20 | 2001-12-20 | Superfine tree-shaped silver powder and its preparing process |
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| CN1369341A true CN1369341A (en) | 2002-09-18 |
| CN1180909C CN1180909C (en) | 2004-12-22 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102371357A (en) * | 2011-09-14 | 2012-03-14 | 王利兵 | Method for preparing branch-shaped micro silver with liquid phase method |
| CN104888771A (en) * | 2015-05-15 | 2015-09-09 | 浙江工商大学 | Dendritic nano silver catalyst and preparing method and application thereof |
| CN109222293A (en) * | 2018-08-27 | 2019-01-18 | 江苏阳光股份有限公司 | A kind of production technology of local enhancement antibacterial shirt |
| CN113005561A (en) * | 2019-12-19 | 2021-06-22 | 财团法人工业技术研究院 | Conductive fiber and method for producing same |
| CN113096848A (en) * | 2021-04-09 | 2021-07-09 | 浙江技嘉材料科技有限公司 | Environment-friendly low-resistance low-temperature conductive silver paste and preparation method thereof |
-
2001
- 2001-12-20 CN CNB011391413A patent/CN1180909C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102371357A (en) * | 2011-09-14 | 2012-03-14 | 王利兵 | Method for preparing branch-shaped micro silver with liquid phase method |
| CN104888771A (en) * | 2015-05-15 | 2015-09-09 | 浙江工商大学 | Dendritic nano silver catalyst and preparing method and application thereof |
| CN104888771B (en) * | 2015-05-15 | 2017-03-08 | 浙江工商大学 | A kind of dendritic nano-silver catalyst and its preparation method and application |
| CN109222293A (en) * | 2018-08-27 | 2019-01-18 | 江苏阳光股份有限公司 | A kind of production technology of local enhancement antibacterial shirt |
| CN113005561A (en) * | 2019-12-19 | 2021-06-22 | 财团法人工业技术研究院 | Conductive fiber and method for producing same |
| CN113096848A (en) * | 2021-04-09 | 2021-07-09 | 浙江技嘉材料科技有限公司 | Environment-friendly low-resistance low-temperature conductive silver paste and preparation method thereof |
| CN113096848B (en) * | 2021-04-09 | 2022-12-16 | 浙江技嘉材料科技有限公司 | Environment-friendly low-resistance low-temperature conductive silver paste and preparation method thereof |
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| Publication number | Publication date |
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| CN1180909C (en) | 2004-12-22 |
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