CN1401243A - Silver-carried fluor apatite antimicrobials and its preparation method - Google Patents
Silver-carried fluor apatite antimicrobials and its preparation method Download PDFInfo
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- CN1401243A CN1401243A CN 02129370 CN02129370A CN1401243A CN 1401243 A CN1401243 A CN 1401243A CN 02129370 CN02129370 CN 02129370 CN 02129370 A CN02129370 A CN 02129370A CN 1401243 A CN1401243 A CN 1401243A
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- antimicrobials
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Abstract
An Ag-carried fluor apatite as antibacterial agent is prepared through coprecipitation to prepare amorphous, nanoparticles of Ag-carried fluor apatite and high-temp calcining. Its advantages are high resistance to high temp (more than 1350 deg.C) and not colouring and yellowing of its products.
Description
Technical field
The present invention relates to a kind of inorganic antiseptic and preparation thereof, relate in particular to a kind of silver-carried fluor apatite antimicrobials and preparation method thereof.
Background technology
The exploitation of inorganic antiseptic results from the concern of medical profession to bacterial infection.The mid-80, for improving the antibiotic durability of antibiotic fabric, the product river fuel corporation of Japan adopts the method for zeolite ion exchange, inorganic solid support and heavy metal ion combination have been prepared inorganic antiseptic first, from then on, this inorganic solid support and heavy metal ion are developed in conjunction with the technology for preparing inorganic antiseptic and extend, and have obtained using widely in the manufacturing of antibacterial product.
In the antibiotic property metal ion, because silver ion (Ag
+) have antibiotic wide spectrum, germicidal efficiency height, characteristics such as be difficult for developing immunity to drugs, therefore, silver ion is widely used in the inorganic antiseptic.Yet in actual applications, all silver base inorganic antibacterial agents all exist problem painted easily, variable color; Simultaneously, can to lose its antibacterial ability under high temperature action also be a problem demanding prompt solution to antibacterial agent.These problems derive from same reason: carrier is to Ag
+Load capacity strong inadequately, thereby under situations such as illumination or heating, Ag
+The constraint that will shake off carrier is perhaps with O
2In conjunction with generating Ag
2Metachromatism takes place in O; Perhaps from carrier, dissipate, make antibacterial agent lose antibacterial ability.The quality of the resistance to elevated temperatures of antibacterial agent is a sign weighing its year of silver-colored ability.
Phosphorus ash stone such as hydroxyapatite, fluor-apatite carrier not only has very strong ion exchange performance, and loaded metal ion that can be a large amount of.The maximum characteristics of phosphorus ash stone antibacterial agent are exactly to have higher resistance to elevated temperatures and discoloration-resisting, can be applied in the antibacterial products such as anti-bacteria ceramic that need the higher temperature requirement, simultaneously in the processing of antibacterial product and use, be difficult for as other silver base inorganic antibacterial agent, taking place common metachromatism.
The performance of argentum-carried hydroxylapatite inorganic antiseptic and other common antibacterial agents relatively is shown in table 1.Data show in the table 1, in several frequently seen inorganic carrying silver antimicrobials, warm tolerance with argentum-carried hydroxylapatite is best, because its excellent heat resistance, so during Hybrid Heating moulding such as argentum-carried hydroxylapatite and ceramic glaze, coating, synthetic fibers, synthetic resin, goods never degenerate, not painted, non-yellowing, its warm tolerance reaches as high as 1200 ℃, and this is that other several antibacterial agents hardly match.However, it still can not satisfy resistant to elevated temperatures needs in the practical application.
Relatively trade name main component heat-resisting safety is water-soluble at plastics for the various carrying silver antimicrobials performances of table 1
The property big white mouse acute in consumption
(℃) oral, LD
50(wt%)
(mg/kg) Zeomic carries silver (zinc) 600 5000 PPB levels 0.5～1
Zeolite Novaron carries silver-colored phosphatase 11 000 2000 PPB levels 0.5～1
Zirconium Apaciaer carries silver-colored hydroxyl 1,200 5000 PPB levels 0.5～1
Apatite WA291 carries silver-colored phosphoric acid 600 5000 PPB levels 0.5～1
Salt antibacterial glass セ ラ phosphoric acid silver 900 4900 PPB levels 0.5～1 ミ ッ Network pottery
Summary of the invention
The purpose of this invention is to provide a kind of silver-carried fluor apatite antimicrobials and preparation method thereof, this antibacterial agent not only has the never degenerating of argentum-carried hydroxylapatite antibacterial agent goods, advantage such as not painted, non-yellowing, and can further improve its resistance to elevated temperatures.
A kind of silver-carried fluor apatite antimicrobials provided by the invention has following physicochemical characteristic:
(1) outward appearance: white powder
(2) chemical formula: Ag
xCa
10-x(PO
4)
6F
2(wherein X≤0.55)
(3) under 1350 ℃ of high temperature,, Escherichia coli and staphylococcus aureus still had 100% antibacterial effect to the powder that obtains after the thermal treatment in 3 hours of this antibacterial agent
The preparation method of silver-carried fluor apatite antimicrobials provided by the present invention is: at first with the synthetic unformed silver-carried fluor apatite nanometer grade powder of chemical coprecipitation, as precursor, this precursor is carried out high-temperature calcination, its concrete operations step is as follows:
(1). with Na
3PO
4With two kinds of components of NaF is to be dissolved in an amount of alcohol-water solution at 3: 1 making solution A in molar ratio, and the control pH value is 10～11;
(2). with Ca (NO
3)
24H
2O and AgNO
3Two kinds of components are to be dissolved in proper amount of deionized water wiring solution-forming B at 10: 1 in molar ratio;
(3). at room temperature solution B is added in the solution A of high-speed stirred, control pH value is 7～8, until obtaining translucent precipitation, precipitate through centrifugal, alcohol is washed, freezing, dry, obtain armorphous nano level precursor powder;
(4). with the thermal treatment 2～3.5 hours under 800 ℃～1000 ℃ conditions of described powder, finally obtain silver-carried fluor apatite antimicrobials.
In the present invention, adopt fluor-apatite as carrier material.Fluor-apatite is to Ag
+The load effect come from ion exchange between them, Ag
+By the Ca in the ion exchange replacement fluor-apatite
2+Thereby, by the fluor-apatite load.But because these two kinds of ionic charge differences, and the ionic radius (Ag that also differs greatly
+Radius is 0.126nm, Ca
2+Radius is 0.099nm), differ each other above 15%, so Ag
+To Ca
2+Replacement mostly occur on the surface of carrier, be difficult to enter into intracell and go, thus its year silver-colored poor effect.Yet, can impel the Ag of carrier surface by high temperature action
+Deeply be diffused into intracell and go, thereby obtain the more stable silver-colored effect of carrying, this is the reason that the high-temperature calcination process can be put forward high silver supported effect.Powder is carried out high-temperature calcination, not only can promote Ag
+To the diffusion of carrying silver-colored internal crystal framework, also Ag can take place simultaneously
+Dissipation.When carrying out high-temperature calcination for a common year aluminium powder, Ag
+The phenomenon that dissipation takes place is very outstanding, is unfavorable for carrying out high-temperature calcination.So in the present invention, prepared unformed silver-carried fluor apatite nano-powder specially as presoma, it is a kind of nano-powder that is in unformed shape, and it not only has very strong adsorption effect, can adsorb a large amount of Ag
+, also be in a kind of upper state simultaneously, have extremely strong reactivity, under the high-temperature calcination effect, be in the nano silver-carrying fluor-apatite powder of unformed shape, deform by lattice, thereby make Ag
+Be deep into intracell, reached and carried silver-colored effect preferably.
The silver-carried fluor apatite antimicrobials that the present invention is prepared, after 3 hours, antibacterial agent all has 100% antibacterial effect to Escherichia coli and staphylococcus aureus through 1350 ℃ of high temperature treatment, and its resistance to elevated temperatures is considerably beyond like product.
Embodiment
Embodiment 1:
The concrete operations step is as follows:
(1). get 0.006mol Na
3PO
4And 0.002molNaF, be dissolved in the 500ml alcohol-water solution, be solution A, adjusting pH value is 10;
(2). get 0.01mol Ca (NO
3)
24H
2O and 0.001mol AgNO
3, be dissolved in the 10mL deionized water, be solution B;
(3). under the normal temperature, solution B is directly joined in the solution A that is in the high-speed stirred state, brown muddiness appears in solution at the beginning, disappears again after 1 second at once, obtains translucent precipitation at last, and adjusting reaction back system pH is 7;
(4). obtain precipitation by high speed centrifugation, carry out freeze drying after alcohol is washed repeatedly, obtain a kind of cotton-shaped powder of white light weight;
(5). above-mentioned powder is carried out 3 hours thermal treatment under 800 ℃, obtain final antibacterial agent, be white powder.Test effect and data:
Test data 1: the content of calcium constituent and silver element in the antibacterial agent:
Test data 2: anti-bacteria test result (the test bacterial classification is Escherichia coli)
Test data 3: anti-bacteria test result (the test bacterial classification is a staphylococcus aureus)
| Sample | Ag(wt％) | Ca(wt％) | Ag(mol)/(Ca+ Ag)(mol) |
| Antibacterial agent | 3.41 | ?41.9 | 0.029 |
| Sample | The sample clump count | Bacteriostasis rate | Antibacterial effect is estimated |
| Comparative sample (pure ha) | 319 | ?0％ | There is not antibiotic effect |
| Antibacterial agent | 0 | ?100％ | Antibacterial effect is arranged |
| Sample | The sample clump count | Bacteriostasis rate | Antibacterial effect is estimated |
| Comparative sample (pure ha) | 258 | ?0％ | There is not antibiotic effect |
| Antibacterial agent | 0 | ?100％ | Antibacterial effect is arranged |
Embodiment 2:
The concrete operations step is as follows:
(1). get 0.012mol Na
3PO
4And 0.004molNaF, be dissolved in the 1000ml alcohol-water solution, be solution A, control solution pH value is 11;
(2). get 0.02mol Ca (NO
3)
24H
2O and 0.002mol AgNO
3, be dissolved in the 20mL deionized water, be solution B;
(3). under the normal temperature, solution B is directly joined in the solution A that is in the high-speed stirred state, brown muddiness appears in solution at the beginning, disappears again after 1 second at once, obtains translucent precipitation at last, and adjusting reaction back system pH value is 8;
(4). obtain precipitation by high speed centrifugation, carry out freeze drying after alcohol is washed repeatedly, obtain a kind of cotton-shaped powder of white light weight.
(5). above-mentioned powder is carried out 2.5 hours thermal treatment under 1000 ℃, obtain final antibacterial agent, be white powder.
The present invention is raw materials used, and to be commercially available analysis pure, without being further purified.
Test effect and data:
Test data 1: the content of calcium constituent and silver element in the antibacterial agent:
Test data 2: anti-bacteria test result (the test bacterial classification is Escherichia coli)
Test data 3: anti-bacteria test result (the test bacterial classification is a staphylococcus aureus)
| Sample | Ag(wt％) | Ca(wt％) | Ag(mol)/(Ca+ Ag)(mol) |
| Antibacterial agent | 3.40 | ?42.0 | ?0.028 |
| Sample | The sample clump count | Bacteriostasis rate | Antibacterial effect is estimated |
| Comparative sample (pure ha) | 322 | ?0％ | There is not antibiotic effect |
| Antibacterial agent | 0 | ?100％ | Antibacterial effect is arranged |
| Sample | The sample clump count | Bacteriostasis rate | Antibacterial effect is estimated |
| Comparative sample (pure ha) | 264 | ?0％ | There is not antibiotic effect |
| Antibacterial agent | 0 | ?100％ | Antibacterial effect is arranged |
Claims (2)
1. silver-carried fluor apatite antimicrobials is characterized in that having following physicochemical characteristic:
(1) outward appearance: white powder
(2) chemical formula: Ag
xCa
10-x(PO
4)
6F
2X≤0.55 wherein)
(3) under 1350 ℃ of high temperature, the powder that this antibacterial agent thermal treatment was obtained after 3 hours still has 100% antibacterial effect to Escherichia coli and staphylococcus aureus.
2. one kind prepares the method for silver-carried fluor apatite antimicrobials according to claim 1, and this method is carried out as follows:
(1) with Na
3PO
4With two kinds of components of NaF is to be dissolved in an amount of alcohol-water solution at 3: 1 making solution A in molar ratio, and the control pH value is 10～11;
(2) with Ca (NO
3)
24H
2O and AgNO
3Two kinds of components are to be dissolved in proper amount of deionized water wiring solution-forming B at 10: 1 in molar ratio;
(3) at room temperature solution B is added in the solution A of high-speed stirred, control pH value is 7～8, until obtaining translucent precipitation, precipitate through centrifugal, alcohol is washed, freezing, dry, obtain armorphous nano level precursor powder;
(4) with the thermal treatment 2～3.5 hours under 800 ℃～1000 ℃ conditions of described powder, finally obtain silver-carried fluor apatite antimicrobials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02129370 CN1267006C (en) | 2002-09-06 | 2002-09-06 | Silver-carried fluor apatite antimicrobials and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02129370 CN1267006C (en) | 2002-09-06 | 2002-09-06 | Silver-carried fluor apatite antimicrobials and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1401243A true CN1401243A (en) | 2003-03-12 |
| CN1267006C CN1267006C (en) | 2006-08-02 |
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ID=4746214
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02129370 Expired - Fee Related CN1267006C (en) | 2002-09-06 | 2002-09-06 | Silver-carried fluor apatite antimicrobials and its preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333107C (en) * | 2005-07-18 | 2007-08-22 | 北京工业大学 | Preparation method for discoloration tolerant antibacterial material of silver-loaded titanium phosphate |
| CN100403907C (en) * | 2004-05-30 | 2008-07-23 | 云南大学 | Inorganic bactericidal agent and its use |
| CN100549109C (en) * | 2007-06-15 | 2009-10-14 | 中国科学院上海硅酸盐研究所 | A kind of anti-bacterial carboxy apatite composite coating, preparation method and application |
| CN105271160A (en) * | 2015-09-24 | 2016-01-27 | 河南科技大学 | Preparation method of nano-fluorapatite biomaterial |
| CN115321821A (en) * | 2022-08-24 | 2022-11-11 | 珠海聚暖新型材料科技有限公司 | Antibacterial ceramic glaze and preparation method thereof |
-
2002
- 2002-09-06 CN CN 02129370 patent/CN1267006C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100403907C (en) * | 2004-05-30 | 2008-07-23 | 云南大学 | Inorganic bactericidal agent and its use |
| CN1333107C (en) * | 2005-07-18 | 2007-08-22 | 北京工业大学 | Preparation method for discoloration tolerant antibacterial material of silver-loaded titanium phosphate |
| CN100549109C (en) * | 2007-06-15 | 2009-10-14 | 中国科学院上海硅酸盐研究所 | A kind of anti-bacterial carboxy apatite composite coating, preparation method and application |
| CN105271160A (en) * | 2015-09-24 | 2016-01-27 | 河南科技大学 | Preparation method of nano-fluorapatite biomaterial |
| CN115321821A (en) * | 2022-08-24 | 2022-11-11 | 珠海聚暖新型材料科技有限公司 | Antibacterial ceramic glaze and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1267006C (en) | 2006-08-02 |
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