CN100551450C - A kind of preparation method of antiseptic biological active titanium coating - Google Patents
A kind of preparation method of antiseptic biological active titanium coating Download PDFInfo
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- CN100551450C CN100551450C CNB2007100414011A CN200710041401A CN100551450C CN 100551450 C CN100551450 C CN 100551450C CN B2007100414011 A CNB2007100414011 A CN B2007100414011A CN 200710041401 A CN200710041401 A CN 200710041401A CN 100551450 C CN100551450 C CN 100551450C
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Abstract
The present invention relates to a kind of antibacterial bioactivity coating and preparation method, it is characterized in that adopting NaOH solution and contain Ag
+Supersaturation calcium phosphate solution is handled the titanium coating, makes it have biological activity and anti-microbial property concurrently.The antiseptic biological active titanium coating of preparation contains Ag
+Ion concentration is 0.01-0.1mM, and making step is: adopt earlier the vacuum plasma spray technology, under optimized parameters (table 1) condition titanium powder is being deposited on the metallic matrix (as titanium alloy) that cleans with sandblast.Prepared titanium coating immerses in the 3-10M NaOH solution, at 20-80 ℃ of insulation 12-48h down, takes out the back with deionized water ultrasonic cleaning 2-6 time, and each 3-10 minute, dry 12-48h under 20-80 ℃ then.Dried titanium coating immerses and contains Ag
+The calcium phosphate supersaturated solution, 20-37 ℃ of following insulation 12-60h is then at 100-150 ℃ of dry 2-6h down.The titanium coating of preparation shows antibiotic resistance performance and does not have obvious cytotoxicity.
Description
Technical field
The present invention relates to a kind of antimicrobial form plasma spray coating biological active titanium coating and preparation method, belong to the medical bio coatings art.
Background technology
In metal implant surface preparation plasma spray coating titanium coatings such as titanium or titanium alloy, be to improve itself and the bonded common method of osseous tissue.Coarse titanium coating surface can increase the contact area between implant and osseous tissue, increases the mechanical packing interaction between bone and the porous surface, and therefore the shear strength of implant and bone interface obviously improves.The sclerous tissues's implants such as artificial joint that are coated with plasma spray coating titanium coating have obtained clinical practice.Yet the titanium coating belongs to the biologically inert coating, does not have a biological activity, and the growth of osseous tissue is not promoted inducing action, and its clinical result of use still remains to be improved.
In order to improve the biological fixation effect of titanium coating, give its biological activity, Recent study has been developed and multiple the method for activation processing has been carried out on the titanium surface, and studying more is that chemical method is carried out surface treatment.Chemical treatment can make titanium coating biologically active.Yet the titanium coating surface of biologically active may provide environment for growth, the breeding of antibacterial, has increased possibility of infection.In order more effectively to protect from infection, suppress pathogen such as antibacterial, mycete in its superficial growth, can in coating, load antibacterial.Silver is as a kind of the most frequently used inorganic antiseptic, has advantages such as efficient, safety, has a broad antifungal spectrum, is widely used in the antibacterial product.The titanium coating is being carried out when bioactivation handles, if can load and contain silver material, forming design of the present invention so then be expected to prepare the titanium coating that has biological activity and anti-microbial property concurrently.
Summary of the invention
Based on the good mechanical performance of titanium coating and the advantages such as broad-spectrum antiseptic of silver salt, the object of the present invention is to provide a kind of antibiotic property biological active titanium coating and preparation method, specifically the present invention intends adopting chemical method that vacuum plasma spray titanium coating is carried out surface modification, make its both biologically active, have anti-microbial property again.
Specific embodiment of the present invention is as follows: adopt earlier the vacuum plasma spray method, under optimized parameters (table 1) condition titanium powder is being deposited on the metallic matrix (as titanium alloy) that cleans with sandblast.Prepared titanium coating immerses in the 3-10M NaOH solution, at 20-80 ℃ of insulation 12-48h down, takes out the back with deionized water ultrasonic cleaning 2-6 time, and each 3-10 minute, dry 12-48h under 20-80 ℃ then.Dried titanium coating immerses and contains Ag
+The calcium phosphate supersaturated solution, 20-37 ℃ of following insulation 12-60h, then 100-150 ℃ down dry 2-6h get final product.
Table 1 spray parameters scope
Slpm: standard liter/min
Contain Ag
+Calcium phosphate supersaturated solution process for preparation as follows: take by weighing NaNO successively
3, Ca (NO
3)
24H
2O, K
2HPO
43H
2O forms solution, with trihydroxy aminomethane and HNO
3At the pH value of 20-37 ℃ of following regulator solution to 7.40-7.50.Then with silver salt (AgNO for example
3) add in the oversaturated calcium phosphate solution, make Ag
+Concentration is 0.01-0.1mM.
This shows that antiseptic biological active titanium coating provided by the invention contains Ag
+Ion concentration is 0.01-0.1mM.
Described titanium coating is to be matrix with the titanium alloy, adopts the vacuum plasma spray coating method that titanium valve is deposited on the matrix.
Ag provided by the invention
+The titanium coating of ion modification has antibiotic resistance performance.Find that through the closely connected method antibacterial tests of thin film the antibiotic rate of above-mentioned modification titanium coating provided by the invention increases (see figure 1) with the increase of silver content.Simultaneously, Ag provided by the invention
+(compound method is seen S.Cho to the titanium coating of ion modification, K.Nakanishi, T.Kokubo in simulated body fluid, et al.J Am Ceram Soc.1995, soak after 2 days 78:1769-1774), the surface can generate the bone like apatite layer (see figure 2), shows that coating has good biological activity.The vitro cytotoxicity test shows, through Ag
+The titanium coating (CA0.1) that concentration is not more than behind the supersaturation calcium phosphate solution modification of 0.1mM does not have obvious cytotoxicity.The Ag that the MTT colorimetry detects
+The CA0.1 coating toxicity rank that concentration is not more than behind the supersaturation calcium phosphate solution modification of 0.1mM is 0, and the cell pattern is seen Fig. 3.
Description of drawings
Fig. 1 cultivates through 24h, and modification titanium coating is to the antibiotic rate of escherichia coli, Pseudomonas aeruginosa and staphylococcus aureus.
Fig. 2 modification titanium coating immerses the SEM figure of simulated body fluid after 2 days.
Fig. 3 MTT colorimetry detects the cellular morphology in the test of CA0.1 vitro cytotoxicity.Positive control has very strong toxicity, and negative control does not have toxicity.
Bacterium colony photo behind Fig. 4 CA, CA0.02, CA0.06 and the CA0.1 test specimen surface 24h culture of bacteria.
(a) escherichia coli; (b) Pseudomonas aeruginosa; (c) staphylococcus aureus
The specific embodiment
Further illustrate substantive distinguishing features of the present invention and obvious improvement below by embodiment, but limit the present invention absolutely not.
Embodiment 1:
Utilize the vacuum plasma spray method to prepare the titanium coating, it is immersed in the 5M NaOH solution,, take out the back with deionized water ultrasonic cleaning 3 times at 60 ℃ of insulation 24h down, each 5 minutes, 40 ℃ of dry 24h down then.Preparation contains Ag
+The supersaturation calcium phosphate solution of ion 0.02mM: take by weighing 12.0700g NaNO successively
3, 0.8856g Ca (NO
3)
24H
2O, 0.3423g K
2HPO
43H
2O, 0.0034gAgNO
3, put into the 1000ml deionized water, use HNO under 25 ℃
3PH value to 7.42 with 6.0600g trihydroxy aminomethane accent solution.The titanium coating of alkali treatment immerses in the supersaturation calcium phosphate solution, and 25 ℃ are incubated 48h down, then dry 2h under 120 ℃.Sample number into spectrum is CA0.02.
Through Ag
+Titanium coating CA0.02 after the modification is respectively 98%, 94% and 63% to the antibiotic rate of escherichia coli, Pseudomonas aeruginosa and staphylococcus aureus.The bacterium colony photo is seen Fig. 4 behind the 24h culture of bacteria of test specimen surface.According to regulation among the standard GB 15979-1995 " product antibacterial and bactericidal property and stability test method ", bacteriostasis rate 〉=50% can report that product has bacteriostasis, thereby can assert that CA0.02 titanium coating has good antibacterial effect to positive bacterias such as gram negative bacterias such as escherichia coli, Pseudomonas aeruginosa and staphylococcus aureuses.The vitro cytotoxicity rank that the MTT colorimetry detects CA0.02 is 0, shows no obvious cytotoxicity.
Embodiment 2:
Employing contains preparation with top identical method preparation and contains Ag
+The supersaturation calcium phosphate solution of ion 0.06mM.Then adopt the step identical to be prepared into and contain Ag with embodiment 1
+Modification titanium coating CA0.06.The CA0.06 coating is respectively 99%, 99% and 95% to the antibiotic rate of escherichia coli, Pseudomonas aeruginosa and staphylococcus aureus.The bacterium colony photo is seen Fig. 4 behind the 24h culture of bacteria of test specimen surface.The result shows that the CA0.06 coating has good antibacterial effect to positive bacterias such as gram negative bacterias such as escherichia coli, Pseudomonas aeruginosa and staphylococcus aureuses.The vitro cytotoxicity rank that the MTT colorimetry detects CA0.06 is 0, shows no obvious cytotoxicity.
Claims (8)
1, a kind of preparation method of antibacterial bioactivity coating is characterized in that adopting chemical method that vacuum plasma spray titanium coating is carried out surface modification, and concrete processing step is:
1. adopt the vacuum plasma spray coating method earlier, titanium powder is deposited on the titanium alloy substrate, prepare the titanium coating;
2. the titanium coating that 1. step is prepared immerses in the NaOH solution, is incubated under 20-80 ℃ of condition;
3. insulation is taken out the back with deionized water ultrasonic cleaning 2-6 time, then in 20-80 ℃ of dry 12-48h;
4. dried titanium coating immerses and contains Ag
+Ion concentration is the calcium phosphate supersaturated solution of 0.01-0.1mM, and 20-37 ℃ of insulation is at last at 100-150 ℃ of dry 2-6h.
2, by the preparation method of the described antibacterial bioactivity coating of claim 1, it is characterized in that the vacuum plasma spray coating described in step 1., the technological parameter that titanium valve is deposited on the titanium alloy substrate is plasma gas Ar and H
2Flow be respectively 35-45 standard liter/min and 7-16 standard liter/min, powder carrier gas Ar flow is the 1.0-3.0 standard liter/min, spray distance is 200-300mm, powder feeding rate is 10-30g/min, vacuum is the 100-300 millibar.
3,, it is characterized in that the titanium coating immerses in the 3.0-10MNaOH solution by the preparation method of the described antibacterial bioactivity coating of claim 1.
4, by the preparation method of the described antibacterial bioactivity coating of claim 1, it is characterized in that the 2. described temperature retention time of step is 12-48h.
5, by the preparation method of the described antibacterial bioactivity coating of claim 1, it is characterized in that the 3. described deionized water ultrasonic cleaning of step each 3-10 minute.
6, by the preparation method of the described antibacterial bioactivity coating of claim 1, it is characterized in that the 4. described supersaturation calcium phosphate of step solution is by NaNO
3, Ca (NO
3)
24H
2O, K
2HPO
43H
2O forms, and pH value is 7.40-7.50; Described Ag
+Be AgNO
3
7, by the preparation method of the described antibacterial bioactivity coating of claim 6, the pH value that it is characterized in that supersaturation calcium phosphate solution is with trihydroxy aminomethane and HNO
3Under 20-37 ℃, regulate.
8, by the preparation method of the described antibacterial bioactivity coating of claim 1, it is characterized in that temperature retention time is 12-60h under the 4. described 20-37 ℃ of condition of step.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602008002145D1 (en) * | 2007-01-15 | 2010-09-23 | Accentus Medical Plc | METAL IMPLANTS |
| US20110046747A1 (en) * | 2009-02-19 | 2011-02-24 | Kelvin Wai Kwok Yeung | Antibacterial surface and method of fabrication |
| CN101791433B (en) * | 2010-03-24 | 2012-11-14 | 吉林大学 | Molecular sieve antibacterial coating with pure titanium or titanium alloy surface and preparation method thereof |
| CN101869725B (en) * | 2010-06-25 | 2013-06-12 | 昆明贵金属研究所 | Antibacterial bioactivity composite coating comprising nano Ag particles and preparation method |
| CN101972490A (en) * | 2010-10-28 | 2011-02-16 | 中国科学院上海硅酸盐研究所 | Anti-degradation antibacterial biological coating, and preparation method and application thereof |
| CN108095843A (en) * | 2017-12-25 | 2018-06-01 | 大连三生科技发展有限公司 | A kind of antibacterial tooth-implanting base station |
| CN108144117A (en) * | 2017-12-25 | 2018-06-12 | 大连三生科技发展有限公司 | A kind of tooth-implanting base station |
| CN108144118A (en) * | 2017-12-25 | 2018-06-12 | 大连三生科技发展有限公司 | A kind of preparation method of antibacterial tooth-implanting base station |
| CN107898648A (en) * | 2017-12-25 | 2018-04-13 | 大连三生科技发展有限公司 | A kind of complex implanted false teeth |
| CN108158679A (en) * | 2017-12-25 | 2018-06-15 | 大连三生科技发展有限公司 | A kind of preparation method of complex implanted false teeth |
| CN110066577A (en) * | 2019-04-30 | 2019-07-30 | 中国船舶重工集团公司第七二五研究所 | Titanium alloy and carbon fibre composite bonding insulating coating and its adhering method |
| CN111821506A (en) * | 2020-06-16 | 2020-10-27 | 温州医科大学附属口腔医院 | Preparation of strontium/silver nano-coating modified bone bionic titanium implant |
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| CN1816645A (en) * | 2003-07-01 | 2006-08-09 | 法国圣戈班玻璃厂 | Method for deposition of titanium oxide by a plasma source |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1816645A (en) * | 2003-07-01 | 2006-08-09 | 法国圣戈班玻璃厂 | Method for deposition of titanium oxide by a plasma source |
Non-Patent Citations (4)
| Title |
|---|
| Chemical composition and biocompatibility of Ti-Ag-O filmsprepared by ion beam assisted deposition. X.Wang et al.surface&coating Technology,Vol.185. 2004 * |
| Influence of surface modifications to titanium onantibaceerialactivity in vitro. M.Yoshinari et al.Biomatreials,Vol.22. 2001 * |
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