CN1281689C - Modified zirconium silver-carrying powder and preparation method thereof - Google Patents
Modified zirconium silver-carrying powder and preparation method thereof Download PDFInfo
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- CN1281689C CN1281689C CN 200410000647 CN200410000647A CN1281689C CN 1281689 C CN1281689 C CN 1281689C CN 200410000647 CN200410000647 CN 200410000647 CN 200410000647 A CN200410000647 A CN 200410000647A CN 1281689 C CN1281689 C CN 1281689C
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- zirconium phosphate
- silver powder
- carries
- modified zirconium
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Abstract
The present invention relates to a modified zirconium phosphate silver carrying powder which is prepared by the following method: zirconium phosphate silver carrying powder is thoroughly and evenly mixed with a crystallization accelerating agent which is 3 to 20 wt% of the zirconium phosphate silver carrying powder, is put in the oxygen atmosphere with the oxygen volume content of more than 5v%, and is roasted for 1 to 5 hours at 800 to 1100 DEG C. The crystallization accelerating agent is a mixture of MgO or ZnO or a compound capable of generating the oxide in the roasting process and B2O3 or a compound capable of generating the oxide in the roasting process, and the molar ratio of the B2O3 to the MgO or the ZnO is 0 to 0.3. The modified zirconium phosphate silver carrying powder can be preserved in air for a long time. When mixed with resin, the modified zirconium phosphate silver carrying powder does not discolored, and thus, the problem of discoloration of the zirconium phosphate silver carrying powder when used in industry of textiles, plastic, paper making and the like is essentially improved. The preparation method has the advantages of simple working procedure, easy industrial preparation, no byproduct and no pollution to environment. The modified zirconium phosphate silver carrying powder is applied to enterprises in Shanghai, Hunan and the like at present, and the product quality is superior.
Description
Technical field
The present invention relates to a kind of modified zirconium phosphate and carry silver powder and preparation method thereof.
Background technology
As basic zirconium phosphate (α-Zr (HPO
4)
2H
2When O) being anti-biotic material for the preparation of silver, need between its layer structure, insert silver ion, obtain bedded zirconium phosphate and carry silver powder, and carry out high-temperature process.But this bedded zirconium phosphate carries easily stripping and the oxidation of silver in the silver powder, easy blackening when preserving for a long time in air; And in the high-temperature process that mixes with resin, more can owing to the stripping of silver and oxidation so that the resin variable color.For example, will carry silver powder through the bedded zirconium phosphate that 1000 ℃ of pyroprocessing obtained after 2 hours, and boil in the glycerol of about 300 ℃ of the ethylene glycol of about 200 ℃ of boiling points or boiling points, white powder will soon blackening.And the silver content that bedded zirconium phosphate carries silver powder is more high, and above-mentioned metachromatism is more serious.Obviously, such powder can not satisfy the application of staple fibre and plastic products well.
In order to improve the stability that bedded zirconium phosphate carries silver in the silver powder, the method that adopts is to improve sintering temperature at present, as document 1 (J.Antibac.Antifung.Agents, 21,77,1993) 1200 ℃, or carry in the silver powder product by the zirconium phosphate of making in roasting and to mix other materials, to reduce variable color, as titanium oxide or the zinc oxide of mentioning among the Japanese patent laid-open 7-304620, but effect is all not very good.
Literature research result shows that bedded zirconium phosphate carries silver powder after high temperature (＞700 ℃) roasting, is generally AgZr
2(PO
4)
3, Ag
4P
2O
7, Ag
3PO
4, ZrP
2O
7Between the mixing phase, if improve the silver carrying amount of bedded zirconium phosphate, the AgZr in the product
2(PO
4)
3Principal phase will be become mutually, but still Ag can be contained
3PO
4Phase (Mat.Res.Bull.14,1099,1979).We discover, bedded zirconium phosphate carries the formation of mixed phase in the silver powder sintered product, are the one of the main reasons that causes its silver-colored stripping or oxidation stain.
Summary of the invention
The objective of the invention is to overcome the defective that bedded zirconium phosphate carries the silver powder easy blackout of retention time one length, meeting variable color when resin mixes in air, thereby non-discoloring modified zirconium phosphate carried silver powder when a kind of can mixing in the medium-term and long-term preservation of air or with resin was provided.
Another object of the present invention is to provide described modified zirconium phosphate to carry the preparation method of silver powder.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of modified zirconium phosphate and carry silver powder, it is made by following method: the crystallization promoter that basic zirconium phosphate is carried 3～20wt% of silver powder and its weight fully mixes, in oxygen atmosphere is arranged, 800～1100 ℃ of roastings 1～5 hour, obtain modified zirconium phosphate and carry silver powder; Described crystallization promoter is MgO or ZnO and B
2O
3Mixture, B
2O
3With the mol ratio of MgO or ZnO be 0～0.3.
The median size that described unmodified zirconium phosphate carries silver powder is below the 30 μ m, and silver content is 0.5～12wt%;
Described oxygen atmosphere is arranged is the mixed gas of oxygen content more than 5v%, in the mixed atmosphere as air, nitrogen or argon gas and oxygen.
The granularity of described MgO or ZnO powder is below the 75 μ m.
MgO in the described crystallization promoter or ZnO also can be the compounds that can generate this oxide compound when roasting, as carbonate, the subcarbonate of magnesium or zinc.
B in the described crystallization promoter
2O
3Also can be the compound that can when roasting, generate this oxide, such as boric acid.
The preparation method that the present invention also provides above-mentioned modified zirconium phosphate to carry silver powder, its step comprises:
The crystallization promoter that basic zirconium phosphate is carried 3～20wt% of silver powder and its weight mixes, and in oxygen atmosphere is arranged, 800～1100 ℃ of roastings 1～5 hour, obtains modified zirconium phosphate and carries silver powder; Described crystallization promoter is MgO or ZnO and B
2O
3Mixture, B
2O
3With the mol ratio of MgO or ZnO be 0～0.3.
The median size that described unmodified zirconium phosphate carries silver powder is below the 30 μ m, and silver content is 0.5～12wt%;
Described oxygen atmosphere is arranged is the mixed gas of oxygen volume content more than 5v%, in the mixed atmosphere as air, nitrogen or argon gas and oxygen.
The granularity of described MgO or ZnO powder is below the 75 μ m.
MgO in the described crystallization promoter or ZnO also can be the compounds that can generate this oxide compound when roasting, as carbonate, the subcarbonate of magnesium or zinc.
B in the described crystallization promoter
2O
3Also can be the compound that can when roasting, generate this oxide, such as boric acid.
Modified zirconium phosphate provided by the invention carries silver powder, granularity is all below 100 μ m, compared with the prior art, its advantage is: modified zirconium phosphate provided by the invention carries silver powder through the X-ray diffraction, it is obviously different that its crystalline texture and the basic zirconium phosphate of non-modified carry silver powder, and the basic zirconium phosphate of modification carries AgZr in the X-ray diffracting spectrum of silver powder
2(PO
4)
3Be principal phase mutually, illustrate that the effect of crystallization promoter is obvious.And non-modified is processed the basic zirconium phosphate of (not adding modified component before the sintering) and is carried silver powder and AgZr do not occur
2(PO
4)
3Principal phase, the basic zirconium phosphate that modification is described carries silver powder and can suppress silver-colored stripping or oxidation, makes silver be present in basic zirconium phosphate relatively stablely and carries in the silver powder.Similarly, based on above-mentioned basic reason, modified zirconium phosphate of the present invention carries silver powder and can continue to have blackly in the air midium or long term, and also nondiscoloration when mixing with resin is boiled in the glycerol of about 300 ℃ of the ethylene glycol of about 200 ℃ of boiling points or boiling points and still kept pure white constant.Fundamentally improved the problem that zirconium phosphate carries silver powder variable color when industries such as weaving, plastics, papermaking are used.In addition, preparation method's operation provided by the invention is simple, easy suitability for industrialized production, no byproduct, environmentally safe.In enterprises such as Shanghai, Hunan, use good quality of product at present.
Embodiment
Embodiment 1
Be that the silver-loaded zirconium phosphate powder (particle mean size is 12 μ m) of 3.5wt% is scattered in the 500ml water with the 100g silver content, add carbonic acid ammonia, regulate pH value ≈ 8, adding 15g ZnCl
2Reagent is precipitated thing, after filtration, after the washing, drying, again in mortar with 1.6g B
2O
3After reagent mix is even, be contained in Al
2O
3In the crucible, insert in the high-temperature electric resistance furnace, in the mixed atmosphere of nitrogen and oxygen (oxygen volume content 30%), 850 ℃ of lower roasting 2h naturally cool to room temperature, obtain modified zirconium phosphate and carry silver powder, and particle mean size is 16 μ m.
Embodiment 2
In silver-loaded zirconium phosphate powder (the particle mean size 6.2 μ m) 100g of silver content 9.0%, sneak into MgO reagent (average grain diameter 38 μ m) 8.7g, when mortar or mixer mixing, drip 20wt% boric acid aqueous solution 25ml, after fully mixing, be contained in Al
2O
3In the crucible, insert in the high-temperature electric resistance furnace, in air atmosphere, 950 ℃ of lower roasting 3h naturally cool to room temperature, obtain modified zirconium phosphate and carry silver powder, and particle mean size is 45 μ m.
Embodiment 3
The silver-loaded zirconium phosphate powder (particle mean size 3.0 μ m) of 9.2g silver content 3.0% with after the commercially available ZnO of 0.8g (particle mean size is 38 μ m) fully mixes, with after commercially available boric acid 0.1g fully mixes, is contained in Al again
2O
3In the crucible, insert in the high-temperature electric resistance furnace, in the mixed atmosphere of Ar and oxygen (oxygen content 10%), 800 ℃ of lower roasting 5h naturally cool to room temperature, obtain modified zirconium phosphate and carry silver powder, and particle mean size is 42 μ m.
Embodiment 4
The silver-loaded zirconium phosphate powder (particle mean size 4.1 μ m) of 10.6g silver content 12wt% with after 2.2g basic magnesium carbonate (particle mean size is 38 μ m) fully mixes, is dripped among the 10wt% boric acid aqueous solution 1ml, be contained in Al after fully mixing again
2O
3In the crucible, insert in the high-temperature electric resistance furnace, in the mixed atmosphere of Ar and oxygen (oxygen content 10%), 1000 ℃ of lower roasting 2h naturally cool to room temperature, obtain modified zirconium phosphate and carry silver powder, and particle mean size is 7.8 μ m.
Embodiment 5
The silver-loaded zirconium phosphate powder (particle mean size 4.0 μ m) of 9.0g silver content 6.0% with after 1.0g basic zinc carbonate (particle mean size is 38 μ m) fully mixes, is added 0.16g B again
2O
3Reagent is contained in Al after fully mixing
2O
3In the crucible, insert in the high-temperature electric resistance furnace, in air, 1100 ℃ of lower roasting 1h naturally cool to room temperature, obtain modified zirconium phosphate and carry silver powder, and particle mean size is 25 μ m.
Claims (10)
1, a kind of modified zirconium phosphate carries silver powder, it is made by following method: the crystallization promoter that basic zirconium phosphate is carried 3～20wt% of silver powder and its weight fully mixes, in oxygen atmosphere is arranged, 800～1100 ℃ of roastings 1～5 hour, obtain modified zirconium phosphate and carry silver powder; Described crystallization promoter is MgO or ZnO and B
2O
3Mixture, B
2O
3With the mol ratio of MgO or ZnO be 0～0.3, but do not comprise 0.
2, modified zirconium phosphate as claimed in claim 1 carries silver powder, it is characterized in that, the median size that described zirconium phosphate carries silver powder is below the 30 μ m, and silver content is 0.5～12wt%.
3, modified zirconium phosphate as claimed in claim 1 carries silver powder, it is characterized in that, described oxygen atmosphere is arranged is the mixed gas of oxygen volume content more than 5v%.
4, modified zirconium phosphate as claimed in claim 1 carries silver powder, it is characterized in that, MgO in the described crystallization promoter or the source of ZnO also comprise the compound that can generate this oxide compound when roasting, and its median size is below the 75 μ m.
5, modified zirconium phosphate as claimed in claim 1 carries silver powder, it is characterized in that, the B in the described crystallization promoter
2O
3The source also comprise the compound that can when roasting, generate this oxide.
6, the described modified zirconium phosphate of a kind of claim 1 carries the preparation method of silver powder, and its step comprises:
The crystallization promoter that basic zirconium phosphate is carried 3～20wt% of silver powder and its weight mixes, and in oxygen atmosphere is arranged, 800～1100 ℃ of roastings 1～5 hour, obtains modified zirconium phosphate and carries silver powder; Described crystallization promoter is MgO or ZnO and B
2O
3Mixture, B
2O
3With the mol ratio of MgO or ZnO be 0～0.3, but do not comprise 0.
7, modified zirconium phosphate as claimed in claim 6 carries the preparation method of silver powder, it is characterized in that, the median size that described zirconium phosphate carries silver powder is below the 30 μ m, and silver content is 0.5～12wt%.
8, modified zirconium phosphate as claimed in claim 6 carries the preparation method of silver powder, it is characterized in that, described oxygen atmosphere is arranged is the mixed gas of oxygen volume content more than 5v%.
9, modified zirconium phosphate as claimed in claim 6 carries the preparation method of silver powder, it is characterized in that, MgO in the described crystallization promoter or the source of ZnO also comprise the compound that can generate this oxide compound when roasting, and its median size is below the 75 μ m.
10, modified zirconium phosphate as claimed in claim 6 carries the preparation method of silver powder, it is characterized in that, the B in the described crystallization promoter
2O
3The source also comprise the compound that can when roasting, generate this oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410000647 CN1281689C (en) | 2004-01-15 | 2004-01-15 | Modified zirconium silver-carrying powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410000647 CN1281689C (en) | 2004-01-15 | 2004-01-15 | Modified zirconium silver-carrying powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1640946A CN1640946A (en) | 2005-07-20 |
| CN1281689C true CN1281689C (en) | 2006-10-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410000647 Expired - Fee Related CN1281689C (en) | 2004-01-15 | 2004-01-15 | Modified zirconium silver-carrying powder and preparation method thereof |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504878A (en) * | 2015-11-30 | 2016-04-20 | 东华大学 | Organically modified alpha-ZrP and modification method thereof |
| CN105504877B (en) * | 2015-11-30 | 2018-02-23 | 东华大学 | A kind of organically-modified and loaded metal ion antibacterial α ZrP powders and preparation method thereof |
| CN112674112A (en) * | 2020-12-23 | 2021-04-20 | 深圳市世格赛思医疗科技有限公司 | Silver-loaded zirconium phosphate and preparation method and application thereof |
| CN112913856B (en) * | 2021-02-07 | 2022-02-08 | 上海润河纳米材料科技有限公司 | Anti-agglomeration slow-release inorganic antibacterial material and preparation method thereof |
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| CN1640946A (en) | 2005-07-20 |
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