CN102936141A - Silver-containing antimicrobial bioceramic, and preparation method and application thereof - Google Patents
Silver-containing antimicrobial bioceramic, and preparation method and application thereof Download PDFInfo
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- CN102936141A CN102936141A CN201210486800XA CN201210486800A CN102936141A CN 102936141 A CN102936141 A CN 102936141A CN 201210486800X A CN201210486800X A CN 201210486800XA CN 201210486800 A CN201210486800 A CN 201210486800A CN 102936141 A CN102936141 A CN 102936141A
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Abstract
The invention relates to a silver-containing antimicrobial bioceramic, and a preparation method and application thereof. The preparation method comprises the following steps: doping certain amounts of nano or/and micron metal silver powder into the ceramic raw material to prepare a ceramic blank, and sintering a common oxygen or oxygen increase environment to form the ceramic capable of releasing silver ions. The ceramic can release silver ions in a liquid and organism environment, and can continuously release silver ions along with the gradual degradation of the material to form a slow release antibacterial action. The technique can control the silver content and structure (porous, compact and porous/compact composite ceramic) of the ceramic, and can prepare granular, geometrical and anatomical ceramics. The silver-containing antimicrobial bioceramic is applicable to the fields of biomedicine, water treatment, gas filtration and the like, and can be used independently or compounded with other substances.
Description
A kind of silver-containing antibacterial biological ceramics, preparation method and application thereof
Technical field
Invention relates to a kind of silver-containing antibacterial biological ceramics, specifically discharges the material of silver ions at the biological ceramics embodied energy, can discharge silver ions in liquid and body environment, reaches and stablizes effective anti-microbial effect.And can be with the progressively degraded of material the silver ions sustained release, form the slowly-releasing anti-microbial effect.This pottery can be used in the fields such as biomedicine, water treatment and gas filtration.
Background technology
Use the antibiotic therapy bacterial infection and accepted extensively by people, and receive good effect.But, along with the generation of the anti-medicine of bacterium and resistance, just even more serious to the worry that hospitalized patients is brought.This kind phenomenon has the trend that increases the weight of to develop in recent years, scientists call on urgently Ying Shen with or use less microbiotic.Yet people have been forgotten the silver salt of eighties of last century widespread use (as: Silver Nitrate etc.) sterilant.Silver ions has good germicidal action, almost can not produce anti-medicine or drug-resistant effect to bacterium., the silver ions of super metering can produce infringement to human body cell and tissue, and therefore, silver-colored measure control must be very strict.
Infection of bone is obstinate disease of medical circle, can cause the patient disabled all the life, and especially the damaged companion of bone infects that and just makes the matter worse.Its reason is that bacterium invades in the osseous tissue, and systemic antibiotic is difficult to reach effective concentration at diseased region.Diluted by blood and body fluid or take away and local application is very fast, also just be difficult to prove effective.And, very easily produce the reaction of anti-medicine or resistance.So people's imagination makes its existing medicament slow release effect by with in the antimicrobial substance composite material carrier, and the damaged filling of bone and repair are arranged again.Commonly used is with the bioabsorbable carrier material composite antibiotic at present, is this mode such as patent ZL200810044887.9 and ZL03114597.3, however their complex manufacturing technology, product can't be sterilized, and the uncertain factor of result for the treatment of is more.In addition, because local use antibiotic concentration is too high and overlong time, can increase the generation of the anti-medicine of bacterium or resistance.
Silver has broad-spectrum antimicrobial, efficient sterilizing, be difficult for the advantages such as resistance and take the course of its own, and eye is incorporated into can avoids antibiotic excessive use in the anti-biotic material.Therefore, industry is that the research and development of anti-biotic material is more and more paid attention to silver, especially at medical instruments field.By the whole bag of tricks such as ion exchange method, scorification and absorption methods, zeolite, phosphoric acid salt, soluble glass, tobermorite and silica gel etc. are combined with silver, make various silver-series antibacterial agents, use these antiseptic-germicides and made the various Ag-carried antibacterial products such as antibacterial fiber, antibiotic plastic, anti-bacteria ceramic, antibiotic glass and anti-bacteria stainless steel.The argentiferous biomaterial can be divided into two classifications, and the one, be coated with on the material structure surface or silver-plated, 100 micro materials particles are soaked in 5% silver nitrate solution dry silver-containing antibacterial material that forms such as patent U.S.7597900.Patent U.S.6283308 is coating silver nitrate solution in the micropore ceramics, liquid by the time discharge silver ions.Patent ZL 200620023048.5 is coated with silver oxide on the spheres of ceramic surface.Patent ZL 200710015808.7 is soaked in coupling agent modified porous ceramics in the nano silver colloidal sol, makes with drying after the alcohol wash.Above-mentioned technique only is embodied in material surface has silver ions to discharge, and may begin burst size larger, and limited duration.Another is the silver salt that mixes in material, patent U.S.5, and 151,122nd, in ceramic material powder, mix the liquefaction metal-salt and comprise silver, copper and zinc salt, sinter the argentiferous pottery into through 800-1300 ℃.In tricalcium phosphate and hydroxylapatite ceramic preparation process, mix silver suboxide or Silver Nitrate in addition, form the silver-containing antibacterial pottery.Yet because the technologic defective of above-mentioned patent, effective anti-microbial effect is stablized in very difficult formation.Therefore, the slow-release time of how improving technique and prolonging silver ions is to need one of problem that solves.
Summary of the invention
Theory of the present invention is to mix quantitative nano level or/and micron order argent powder is prepared ceramic body in ceramic raw material, and sintering forms and contains the pottery that can discharge the silver ions material in normal oxygen or oxygenation environment.This pottery can discharge silver ions in liquid and body environment, reach to stablize effective anti-microbial effect.And with the progressively degraded of material, and the silver ions sustained release forms the slowly-releasing anti-microbial effect.
The object of the present invention is to provide a kind of preparation technology of silver-containing antibacterial biological ceramics, its feature can be controlled silver content and the silver ions burst size of preparation pottery.And can make different size, shape and structure.Its structure can be porous ceramics, ceramic of compact and porous and fine and close composite ceramics.Its form can be particle, geometry and anatomic form.
Another object of the present invention is to provide the application of above-mentioned pottery in the fields such as biomedicine, water treatment and gas filtration.It uses separately, also can unite use with other material.
The argent powder granularity that pottery of the present invention uses is 10 nanometers to 1000 micron, and its content in pottery is 0.1% to 40%.
But pottery degradable material of the present invention, but also degradable material not.Its principal phase raw material can be hydroxyapatite, tricalcium phosphate, Calucium Silicate powder, calcium carbonate, aluminum oxide, zirconium white, titanium dioxide, aluminum-spinel etc., also their mixture more than 2 kinds or 2 kinds.
Ceramic sintering temperature of the present invention is controlled at 600 ℃ to 1600 ℃, and sintering environment oxygen level is 20% to 80%, and sintering pressure is at 1 to 2000 normal atmosphere, and sintering time was at 2 to 10 hours.
Processing parameter of the present invention has good operability, and those skilled in the art can carry out processing parameter setting and process control according to following principle:
1) the argent powder with raw material powder and set amount is placed in the pipe of milling, and adds 20% to 80% pure water and the son of milling in right amount again, mills 1 to 10 hour at the Horizontal mill machine, configures mobile good ceramic slurries.
2) after simple or/and pore-forming material mixes with ceramic slurries, be filled in the mould that sets, through 25 to 90 ℃ of oven dry 6 to 24 hours, the demoulding formed ceramic body.
3) with ceramic body 200 to 400 ℃ of binder removals 12 to 48 hours in draft glue discharging furnace, get rid of the organism of base substrate.
4) base substrate behind the binder removal is placed in the sintering oven, in oxygen level 20% to 80% and pressure 1 to 2000 atmospheric environment, through 600 to 1600 ℃ of sintering 2 to 10 hours, formed the silver-containing antibacterial biological ceramics.
Description of drawings
Fig. 1. contain the rectangle tricalcium phosphate compact substance biological ceramics entity photo of 5% nanometer silver.
Fig. 2. contain the biological local porcelain scanning electron microscope (SEM) photograph of making pottery of 5% nanometer silver tricalcium phosphate compact substance.
Fig. 3. contain the partial sweep Electronic Speculum figure of 5% micron silver-colored tricalcium phosphate compact substance biological ceramics.
Fig. 4. contain the cylindrical tricalcium phosphate porous bio-ceramic entity photo of 5% micron silver.
Fig. 5. contain the microstructure scanning electron microscope (SEM) photograph of the tricalcium phosphate porous bio-ceramic of 5% micron silver.
Fig. 6. contain the rectangle Calucium Silicate powder porous bio-ceramic photo of 2% nanometer silver.
Understand above-mentioned and other advantage and feature of the present invention for better, the present invention will be further elaborated by non-limiting example.
Embodiment
Embodiment 1: the silver powder of 190 gram tricresyl phosphate calcium powders and 10 grams, 20 nanometers is placed in the milling tank, adds 80 gram pure water and the sons of milling in right amount again, milled 3 hours at the Horizontal mill machine, be configured to ceramic slurries.Again slurry filling is arrived in the gypsum mold (20 * 20 * 40 millimeters), form ceramic body through the demoulding in 4 hours of 50 ℃ of dryings.(20% contains oxygen and 1 normal atmosphere) forms the rectangle tricalcium phosphate compact substance biological ceramics (Fig. 1 and 2) that contains 5% nanometer silver through 1000 ℃ of sintering 4 hours in sintering oven subsequently.
Embodiment 2: 285 gram tricresyl phosphate calcium powders and the 15 silver powder water that restrain 1.5 microns are placed in the pipe of milling, add 120 gram pure water and the sons of milling in right amount again, milled 3 hours at the Horizontal mill machine, be configured to ceramic slurries.Again slurry filling is arrived in the gypsum mold (20 * 20 * 40 millimeters), form ceramic body through the demoulding in 4 hours of 50 ℃ of dryings.Subsequently in sintering oven (20% contains oxygen and 1 normal atmosphere) through 1000 ℃ of sintering 4 hours, form the rectangle tricalcium phosphate compact substance biological ceramics (Fig. 3) that contains 5% micron silver.
Embodiment 3: the slurries of 40ml embodiment 1 and the spherical PMMA particle of 50ml (diameter 500-600 micron) are stirred be filled in the gypsum mold (diameter 15 and high 20 millimeters) after being mixed, form ceramic body through the demoulding in 4 hours of 50 ℃ of dryings.Subsequently in draft glue discharging furnace through 300 ℃ of binder removals 12 hours, (20% contains oxygen and 1 normal atmosphere) forms the cylindrical tricalcium phosphate porous bio-ceramic (Figure 4 and 5) that contains 5% micron silver through 1000 ℃ of sintering 4 hours in sintering oven again.
Embodiment 4: 98 gram calcium silicate powders and the 2 silver powder water that restrain 1.0 microns are placed in the pipe of milling, add 40 gram pure water and the sons of milling in right amount again, milled 3 hours at the Horizontal mill machine, be configured to ceramic slurries.In ceramic slurries, add in the stainless steel mould that is filled into 10 * 20 * 30 millimeters after the 120 spherical PMMA particles of gram (diameter 500-600 micron) stirrings are mixed, form ceramic body in 70 ℃ of oven dry demoulding in 12 hours.Got rid of organism in 12 hours through 300 ℃ of bakings again in draft glue discharging furnace, (oxygen contains 20% and 1 normal atmosphere) forms the cube compact substance Calucium Silicate powder biological ceramics that contains 2% micron silver through 1000 ℃ of sintering 4 hours in sintering oven subsequently.
Embodiment 5: respectively 5 gram 5% nanometer silver potteries (embodiment 1) and 5% micron silver pottery (embodiment 2) are immersed in the 10ml purified water, sampling after 48 hours is by the burst size of ICP quantitative analysis silver ions.The result shows that two kinds of silver-colored potteries soak and all have silver ions to discharge, and the burst size (174ppm/g) of micron silver pottery is apparently higher than nanometer silver pottery (76ppm/g).
Claims (9)
1. the present invention relates to a kind of silver-containing antibacterial biological ceramics, and preparation technology, its principle is to mix nano level or/and micron order argent powder is prepared ceramic body in ceramic raw material, and sintering forms the pottery that closes the silver ions h substance in normal oxygen or oxygenation environment.This pottery can discharge silver ions in liquid and body environment, reach to stablize effective anti-microbial effect.And with the progressively degraded of material the silver ions sustained release, form the slowly-releasing anti-microbial effect.
2. according to claim 1, the granularity of described argent powder is 10 nanometers to 1000 micron.
3. according to claim 1, the content of described argent powder in pottery is 0.1% to 40%.
4. according to claim 1, described ceramic major raw material can be hydroxyapatite, tricalcium phosphate, Calucium Silicate powder, calcium carbonate, aluminum oxide, zirconium white, titanium dioxide, aluminum-spinel etc., also their mixtures more than 2 or 2.
5. according to claim 1 to 4, described sintering temperature is 600 ℃ to 1600 ℃, and the oxygen amount of closing that sintered ring is domestic is 20% to 80%, and sintering pressure is at 1 normal atmosphere to 2000 normal atmosphere, and sintering time was at 2 to 10 hours.
6. according to claim 1 to 5, described ceramic structure can be porous ceramics, ceramic of compact, porous and fine and close composite ceramics.
7. according to claim 1 to 6, described ceramic form can be particle, geometry and anatomic form.
8. according to claim 1 to 7, but described pottery degradable material also can be non-degradable material.
9. according to claim 1 to 8, described pottery is with application that can be in the fields such as biomedical, water treatment and gas filtration.It uses separately, and also compound other material uses.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104996464A (en) * | 2015-07-24 | 2015-10-28 | 中山市瑞佳厨房电器有限公司 | Preparing method of nano-silver sheet for sterilization of water and nano-silver sheet |
| CN105036717A (en) * | 2015-07-24 | 2015-11-11 | 合肥凯士新材料贸易有限公司 | Flake alumina porous ceramic used for packaging high-power LED and preparation method thereof |
| CN105272172A (en) * | 2015-10-15 | 2016-01-27 | 郭进标 | Composite ceramic and preparation method thereof |
| WO2016062233A1 (en) * | 2014-10-21 | 2016-04-28 | Silverloy Company Limited | Antibacterial product and antibacterial structure |
| CN105776535A (en) * | 2016-05-19 | 2016-07-20 | 沈阳理工大学 | Preparation method of sustained-release nickel-element biological ceramsite |
| CN106278256A (en) * | 2015-03-31 | 2017-01-04 | 丁永新 | Hardness and anti-wear performance preferable wear-resisting zirconia pottery |
| CN109020513A (en) * | 2018-09-18 | 2018-12-18 | 广东蓝狮医疗科技有限公司 | A kind of preparation method of the aluminium oxide-zirconium oxide long acting antibiotic bioceramic of nano oxidized Copper-cladding Aluminum Bar |
| CN109773183A (en) * | 2019-04-08 | 2019-05-21 | 长沙集智创新工业设计有限公司 | A kind of medical metal ceramic material and preparation method thereof |
| CN111377729A (en) * | 2020-03-21 | 2020-07-07 | 杭州书瓷手作文化创意有限公司 | Environment-friendly biological ceramic material and preparation method thereof |
| WO2021120353A1 (en) * | 2019-12-20 | 2021-06-24 | 上海贝奥路生物材料有限公司 | Metal prosthesis of composite porous biological ceramic, and preparation method therefor |
| EP3334282B1 (en) | 2015-08-14 | 2022-12-21 | Imertech Sas | Inorganic particulate containing antimicrobial metal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407412A (en) * | 2007-10-11 | 2009-04-15 | 郑开明 | Nano composite active biological ceramic powder and processing process thereof |
| CN101797521A (en) * | 2009-06-15 | 2010-08-11 | 牛智勇 | Method for preparing catalytic and sterile material |
-
2012
- 2012-11-26 CN CN201210486800XA patent/CN102936141A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407412A (en) * | 2007-10-11 | 2009-04-15 | 郑开明 | Nano composite active biological ceramic powder and processing process thereof |
| CN101797521A (en) * | 2009-06-15 | 2010-08-11 | 牛智勇 | Method for preparing catalytic and sterile material |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016062233A1 (en) * | 2014-10-21 | 2016-04-28 | Silverloy Company Limited | Antibacterial product and antibacterial structure |
| CN106278256A (en) * | 2015-03-31 | 2017-01-04 | 丁永新 | Hardness and anti-wear performance preferable wear-resisting zirconia pottery |
| CN104996464A (en) * | 2015-07-24 | 2015-10-28 | 中山市瑞佳厨房电器有限公司 | Preparing method of nano-silver sheet for sterilization of water and nano-silver sheet |
| CN105036717A (en) * | 2015-07-24 | 2015-11-11 | 合肥凯士新材料贸易有限公司 | Flake alumina porous ceramic used for packaging high-power LED and preparation method thereof |
| EP3334282B1 (en) | 2015-08-14 | 2022-12-21 | Imertech Sas | Inorganic particulate containing antimicrobial metal |
| CN105272172A (en) * | 2015-10-15 | 2016-01-27 | 郭进标 | Composite ceramic and preparation method thereof |
| CN105776535B (en) * | 2016-05-19 | 2018-11-02 | 沈阳理工大学 | A kind of preparation method of sustained release nickel element biological ceramic particle |
| CN105776535A (en) * | 2016-05-19 | 2016-07-20 | 沈阳理工大学 | Preparation method of sustained-release nickel-element biological ceramsite |
| CN109020513A (en) * | 2018-09-18 | 2018-12-18 | 广东蓝狮医疗科技有限公司 | A kind of preparation method of the aluminium oxide-zirconium oxide long acting antibiotic bioceramic of nano oxidized Copper-cladding Aluminum Bar |
| CN109773183A (en) * | 2019-04-08 | 2019-05-21 | 长沙集智创新工业设计有限公司 | A kind of medical metal ceramic material and preparation method thereof |
| CN109773183B (en) * | 2019-04-08 | 2021-08-27 | 长沙集智创新工业设计有限公司 | Medical metal ceramic material and preparation method thereof |
| WO2021120353A1 (en) * | 2019-12-20 | 2021-06-24 | 上海贝奥路生物材料有限公司 | Metal prosthesis of composite porous biological ceramic, and preparation method therefor |
| CN111377729A (en) * | 2020-03-21 | 2020-07-07 | 杭州书瓷手作文化创意有限公司 | Environment-friendly biological ceramic material and preparation method thereof |
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Application publication date: 20130220 |