CN101485901A - Method for preparing hydroxyapatite/nano silver antimicrobial composite coating by pulse electrochemical deposition - Google Patents
Method for preparing hydroxyapatite/nano silver antimicrobial composite coating by pulse electrochemical deposition Download PDFInfo
- Publication number
- CN101485901A CN101485901A CN 200810147664 CN200810147664A CN101485901A CN 101485901 A CN101485901 A CN 101485901A CN 200810147664 CN200810147664 CN 200810147664 CN 200810147664 A CN200810147664 A CN 200810147664A CN 101485901 A CN101485901 A CN 101485901A
- Authority
- CN
- China
- Prior art keywords
- composite coating
- pulse
- electrochemical deposition
- hydroxyapatite
- nano silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a method for preparing a hydroxyapatite/nano silver antibacterial composite coating through pulse electrochemical deposition, which comprises: using a calcium salt, phosphate, silver nitrate and a proper amount of coordination agent to prepare electrolyte with certain concentration and pH value, and performing electrodeposition in a electrolytic cell provided with a three-electrode system; taking a saturated calomel electrode as a reference electrode, a platinum sheet as a counter electrode and biological medical metal to be coated as a working electrode, wherein the pulse high electric potential is 0 volt, the pulse low electric potential is -2.0 volts, the pulse width is 100 seconds, and the deposition time is 2 hours; and depositing compositions in the coating on a base material in a mode of ions, uniformly dispersing nano silver generated during deposition in the composite coating, and finally preparing the hydroxyapatite/nano silver antibacterial composite coating.
Description
Affiliated technical field
The present invention relates to the method for modifying on a kind of biomaterial for medical purpose surface, especially be applicable to the preparation of the biomedical metal material face coat that the human body bone injury is repaired.
Background technology
The infection of biomaterial is than the significant effects factor in the surgical operation.In biomaterial and the medical equipment, the use of silver has been become a kind of effective ways of inhibition antibacterial.Silver-colored and silver-colored chemical compound has higher antibiotic property, can kill up to 16 kinds of antibacterials, comprises escherichia coli and Staphylococcus albus etc.Characteristics such as silver antibacterial agent is because low to the toxicity of human body cell, and the heat stability height of self, volatility are lower are paid close attention to widely.The appearance of nanometer silver makes silver antibacterial agent show superpower antibacterial ability, becomes one of focus of present biological antibiotic investigation of materials.The hydroxyapatite of synthetic [HA, Ca
10(PO
4)
6(OH)
2] identical with the inanimate matter composition of natural bone, therefore structural similarity has good biological activity and biocompatibility, is widely used as bone defect repair and bone clinically and fills shaping material.The silver-colored apatite that carries based on the preparation of the advantage of hydroxyapatite and nanometer silver, calcium phosphate series pottery excellent biological compatibility and biological activity had both been inherited, utilize the direct bactericidal action of Ag itself simultaneously, make the HA/nano-Ag composite coating have good anti-microbial property.
At titanium and the medical metal-based surface of other biological deposition calcium phosphate series of biologic active coating is a kind of common methods, fully combine metal material and biological active ceramic material advantage separately, both had the high intensity of metal material, toughness, again the good biological property and the biocompatibility of biologically active ceramic material.The preparation method of carrying the right coating of silver-colored phosphorus ash has plasma spraying method, sol-gel process, electrochemical deposition method etc.Plasma spraying method is owing to temperature in the experimentation is too high, and apatite decomposes, and reduces the biocompatibility and the biological activity of composite coating.The deficiency that sol-gel process exists is to exist in the gel a large amount of micropores, will overflow again in the product dry run many gases and Organic substance, and make product produce contraction, influence the bulk properties of coating.Electrochemical deposition method has advantages such as simple equipments, all the property covered is good, cost is low, speed is fast, technology is easy, becomes one of focus of biological coating research.
In recent years, the existing report that adopts electrochemical deposition to prepare calcium microcosmic salt bioactive ceramics/silver-colored composite coating.
Liu Rongfang etc. adopt one-step method constant current mode prepared by electrodeposition HA/Ag composite coating, and its method is to add the Ag powder in the electrolyte of electro-deposition hydroxyapatite (HA) coating.This method deficiency is to exist a large amount of Ag particle agglomerations at coating surface, and Ag powder skewness, and this will influence the anti-microbial property of composite coating.Employing two-step method constant current mode electrodeposition processes such as Xiao Xiufeng prepare the HA/Ag composite coating, its method is: at first, by presoma at constant current mode deposition HA, place NaOH solution to soak then and obtain HA, cross in the silvering solution at nicotinic acid at last, surface with HA is substrate, galvanostatic deposition Ag granule.Its as a result deficiency be the surface that silver-colored granule just is present in coating, this will cause a large amount of silver-colored particle detachment in surface in body.In general, the report of document adopts single constant current (or constant voltage mode) to carry out a step deposition or two step depositions mostly.Yet there are some shortcomings in these methods, and are bigger as silver-colored particle grain size in the coating, and silver-colored skewness.
Above shortcoming in view of prior art, the purpose of this invention is to provide and a kind ofly prepare the composite coating method at the bio-medical metal material surface, promptly adopt pulse electrodeposition to prepare hydroxyapatite/nano silver antimicrobial composite coating, this method has overcome the shortcoming of said method, improved the uniformity of composite coating, the silver-colored particle grain size of Jiang Diing has realized the uniform distribution of nanometer silver in hydroxyapatite coating layer widely.Thereby on micro-scale, realized the evenly compound of hydroxyapatite and nanometer silver, obtained to have the biomedical antimicrobial composite material of excellent comprehensive performance.
Summary of the invention
A kind of pulse electrochemical deposition prepares the method for hydroxyapatite/nano silver antimicrobial composite coating, with calcium salt, phosphate and silver nitrate is that raw material is electrochemically-deposited in the bio-medical metal surface through pulse and prepares uniform HA/nano-Ag antimicrobial composite coating, comprises the steps:
(1) as the bio-medical metal of matrix through surface treatment.
(2) with analytical pure calcium salt, phosphate, silver nitrate and cysteine, use dissolved in distilled water respectively; Get four water-calcium nitrate, ammonium di-hydrogen phosphate and obtain uniform calcium phosphorus solution with mixing behind the water dissolution respectively; Add cysteine then in silver nitrate aqueous solution slowly, gained solution joins in the described calcium phosphorus solution, regulates pH=4.0 with ammonia, mixes, and obtains even electrolyte at last.
(3) in described electrolyte, be reference electrode with the saturated calomel electrode, platinized platinum is a counter electrode, the bio-medical metal for the treatment of coating is a working electrode, carries out electrochemical deposition in the electrolysis bath of three-electrode system.
The technological parameter of electrochemical deposition is: pulse high potential: 0V, pulse electronegative potential :-2.0V, pulsewidth: 100s, sedimentation time: 2h.
Whole process of preparation is all finished under the condition of room temperature or heated at constant temperature (below 40 ℃).
Compared with prior art, the invention has the beneficial effects as follows:
At first, whole electrochemical deposition process adopts the method for pulse potential to substitute single constant current or constant potential method, this improved advantage is to utilize the concentration polarization of the relaxation reduction negative electrode of potential pulse, and when adopting constant current or potentiostatic electrodeposition, because deposition ion convergence negative electrode constantly is deposited, thereby causes concentration polarization inevitably.And in the pulse electrodeposition process, when current lead-through, fully react near the ion of negative electrode, its concentration also descends significantly; But crossing one section pulse frequency range, electric current is cut off, and near the ion concentration of negative electrode is recovered.Therefore, adopt the pulse electrodeposition method can improve current efficiency, make the coating crystallization closely, firmly, good uniformity, coating is smooth.
Secondly, the cysteine complexant that adds in the electrolyte makes that free concentration of silver ions reduces greatly in the electrolyte, obtains nano level silver.Silver ion and phosphate is codeposition under the effect of impulse electric field, the complex uniform distribution, and no agglomeration finally obtains the even composite coating of hydroxyapatite/nanometer silver antimicrobial.
At last, this method adopts a step sedimentation, nanometer silver is embedded among the calcium microcosmic salt coating equably, solve silver particles and covered silver particles that calcium microcosmic salt coating surface the causes problem that comes off that is, effectively reduce the problem of silver-colored particle detachment, prolong the antibiotic time, finally improve the antibacterial effect of composite coating.
The bio-medical metal that need are handled carries out still removing greasy dirt and other spot of material surface earlier before the operation of above step, makes between coating and the ground and can more combine closely.The cleaning of above-mentioned substrate, drying.
Description of drawings is as follows
The XRD figure spectrum of Fig. 1 embodiment of the invention 1 hydroxyapatite/nano silver antimicrobial composite coating.
The SEM photo of Fig. 2 embodiment of the invention 1 hydroxyapatite/nano silver antimicrobial composite coating.
The EDS of Fig. 3 embodiment of the invention 1 hydroxyapatite/nano silver antimicrobial composite coating can spectrogram.
Fig. 4 embodiment of the invention 1 hydroxyapatite/nano silver antimicrobial composite coating face scanner uni section elemental line scan picture.
The light microscopic photo of Fig. 5 embodiment of the invention 1 hydroxyapatite/qualitative antibacterial experiment of nano silver antimicrobial composite coating.
The electromicroscopic photograph of the cellular morphology of Fig. 6 embodiment of the invention 1 hydroxyapatite/nano silver antimicrobial composite coating.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) gets the titanium plate as working electrode, acid, alkali surface treatment again after conventional acetone is ultrasonic.
(2) get the 0.5g silver nitrate and be dissolved in an amount of distilled water, again to the cysteine that wherein adds 0.2g lentamente;
(3) get four water-calcium nitrate 0.394g, ammonium di-hydrogen phosphate 0.115g, mix with dissolved in distilled water, again (2) are gently added wherein, be mixed with the electrolyte that the pH=4.0 cumulative volume is 1000ml, beaker placed on the magnetic stirring apparatus stir, obtain even electrolyte at last;
(4) with the even electrolyte in (3), be reference electrode with the saturated calomel electrode, the platinum sheet is a counter electrode, the bio-medical metal for the treatment of coating is a working electrode, carries out electro-deposition in the electrolysis bath of three-electrode system.Relevant parameter is: pulse high potential: 0V, pulse electronegative potential :-2.0V, pulsewidth: 100s, sedimentation time: 2h.
Pattern, composition, antibiotic property and the biocompatibility etc. of present embodiment gained coating material are seen accompanying drawing.
Fig. 1 is the XRD figure spectrum of HA/Ag composite coating.Show that composite coating is by hydroxyapatite and money phase composition.
Fig. 2 is the SEM picture of HA/Ag composite coating.As can be seen, coating is uniform nanometer-size die.
Fig. 3 is that the EDS of HA/Ag composite coating can spectrogram.As can be known, contain three kinds of elements of Ca, P and Ag in the composite coating.
Fig. 4 is that first vegetarian noodles scanner uni section elemental line scan of HA/Ag composite coating can spectrogram.(a) the face scintigram of Ca element in the coating; (b) the face scintigram of P element in the coating; (c) the face scintigram of Ag element in the coating; (d) coating section elemental line scan figure, curve is followed successively by from top to bottom among the figure: the line of Ca element distributes; The line of Ag element distributes; The line of P element distributes; The line of Ti element distributes.Unit's vegetarian noodles scans as can be known, and composite coating surface C a, P, Ag are evenly distributed.Distribute as can be known in conjunction with the section element line simultaneously, Ag is evenly distributed in composite coating.Promptly successfully prepare the even compound HA/Ag composite coating of HA and Ag.
Fig. 5 is a HA/Ag composite coating antibacterial experiment picture qualitatively, and (a) and (b) are that Staphylococcus albus is respectively in the antibiotic situation of HA/Ag composite coating surface, HA coating surface; (c), (d) is that escherichia coli are respectively in the antibiotic situation of HA/Ag composite coating surface, HA coating surface.As can be seen, after composite coating surface action a period of time, escherichia coli kill fully with the bacterium liquid of concentration, and Staphylococcus albus falls to also having only small amount of residual.Proof HA/Ag composite coating has sterilizing ability preferably to these two strains, and colibacillary sterilizing ability is higher than Staphylococcus albus.The step of antibacterial experiment:
(1) activation of thalline:
On aseptic workbench, an amount of sterilized LB culture medium to be poured in the flat board, the bacterial classification inoculation of getting 50 μ l then with spreader with antibacterial coating evenly, was put under 37 ℃ of the constant incubators on culture medium, constant temperature culture 12 hours.
(2) preparation of bacteria suspension:
Get an amount of step 1 with inoculating loop and cultivate 12 hours postactivated good thalline, put into the test tube that fills 10ml liquid LB culture medium.Then, the test tube that inoculation is good is put into 37 ℃, in the shaking table of 200rmp, cultivates 12 hours.Adopt the concentration of gradient dilution method test bacterium liquid subsequently, and adjusting concentration is 1 * 10
8Individual/ml.
(3) add sample
With 3 the every group test tubes that contain 10ml phosphate buffer (PBS) of having sterilized, be divided into two groups, add the above-mentioned bacteria suspension of 100 μ l respectively.Then two groups of samples (HA/Ag composite coating, HA coating) are put into test tube respectively,, cultivated 12 hours in the shaking table of 200rmp at 37 ℃.
(4) observe
Draw the aforesaid liquid of 100 μ l with liquid-transfering gun, coat on the solid medium, put into constant incubator and cultivated 12 hours, observe the growing state of antibacterial, record is analyzed and is taken pictures.
Conclusion: with the contrast of pure HA coating as can be seen:
(1) the Staphylococcus albus amount of bacteria is 100 μ l, bacterial concentration 1 * 10
8Under the condition of individual/ml, cultivate after 12 hours, the HA/Ag composite coating has bactericidal effect preferably to Staphylococcus albus, and some single bacterium colonies are only sporadicly distributing on the composite coating surface.
(2) the escherichia coli amount of bacteria is 100 μ l, bacterial concentration 1 * 10
8Under the condition of individual/ml, cultivate after 12 hours, the HA/Ag composite coating has the good sterilization effect to escherichia coli, and coating surface does not observe antibacterial, is 100 μ l in amount of bacteria, bacterial concentration 1 * 10
8Sterilizing rate almost reaches 100% under the condition of individual/ml.
Fig. 6 is the SEM picture of cell at HA/Ag composite coating surface different time.Cell is better at the surface adhesion of HA/Ag composite earth layer in the time of 1 day, can obviously see the pseudopodium of cell.Cell almost completely spreads over material surface after 3 days.From cellular morphology and sprawl situation as can be known, the cell well-grown, HA/Ag has better biocompatibility.
Comprehensive above experimental result as can be known, the pulse electrodeposition method is successfully prepared HA and the even compound HA/nano-Ag antimicrobial composite coating of Ag.The HA/nano-Ag antimicrobial composite coating has well good anti-microbial property and better biocompatibility simultaneously.
Embodiment 2
The ammonium di-hydrogen phosphate of embodiment 1 is changed etc. into the NaH of molar concentration
2PO
4, carry out electrochemical deposition, other conditions are constant.
The ammonium di-hydrogen phosphate of embodiment 1 is changed etc. into the KH of molar concentration
2PO
4, carry out electrochemical deposition, other conditions are constant.
Embodiment 4
Calcium chloride with molar concentrations such as the four water-calcium nitrate among the embodiment 1 change into carries out electrochemical deposition, and other conditions are constant.
More than the preparation process of each embodiment all finish at ambient temperature, and before deposition, to prepare homodisperse electrolyte.
Adopt basic scheme of the present invention can do some expansions routinely as the case may be in reality is implemented: calcium ion can also be by CaCl in the synthos solution
2Obtain; The bio-medical metal can be by pure titanium, titanium alloy (as Ti6A14V), and rustless steel is taken on.
The HA/nano-Ag antimicrobial composite coating of electrochemical deposition method preparation provided by the invention, because whole electrochemical deposition process is to adopt impulse electric field, the use of complexant cysteine in addition makes electrolyte stable.Whole electrochemical deposition process is simple, and the goods cycle is short, need not add dispersant, catalyst.Can access the bio-medical antimicrobial coating of good combination property.
Claims (4)
1, a kind of pulse electrochemical deposition prepares the method for hydroxyapatite/nano silver antimicrobial composite coating, with calcium salt, phosphate and silver nitrate is that raw material is electrochemically-deposited in the bio-medical metal surface through pulse and prepares uniform HA/nano-Ag antimicrobial composite coating, comprises the steps:
(1) as the bio-medical metal of matrix through surface treatment;
(2) with analytical pure calcium salt, phosphate, silver nitrate and cysteine, use dissolved in distilled water respectively; Get four water-calcium nitrate, ammonium di-hydrogen phosphate and obtain uniform calcium phosphorus solution with mixing behind the water dissolution respectively; Add cysteine then in silver nitrate aqueous solution slowly, gained solution joins in the described calcium phosphorus solution, regulates pH=4.0 with ammonia, mixes, and obtains even electrolyte at last;
(3) in described electrolyte, be reference electrode with the saturated calomel electrode, platinized platinum is a counter electrode, the bio-medical metal for the treatment of coating is a working electrode, carries out electrochemical deposition in the electrolysis bath of three-electrode system;
The technological parameter of electrochemical deposition is: pulse high potential: 0V, pulse electronegative potential :-2.0V, pulsewidth: 100s, sedimentation time: 2h.
2, prepare the method for hydroxyapatite/nano silver antimicrobial composite coating according to the described a kind of pulse electrochemical deposition of claim 1, it is characterized in that, phosphate radical at least can be by obtaining in following a kind of material in the described synthos solution: NH
4H
2PO
4, KH
2PO
4, NaH
2PO
4
3, prepare the method for hydroxyapatite/nano silver antimicrobial composite coating according to the described a kind of pulse electrochemical deposition of claim 1, it is characterized in that, calcium ion at least can be by obtaining in following a kind of material in the described synthos solution: CaCl
2, Ca (NO
3)
2
4, prepare the method for hydroxyapatite/nano silver antimicrobial composite coating according to the described a kind of pulse electrochemical deposition of claim 1, it is characterized in that, treat that the bio-medical metal of coating can be following a kind of material at least: pure titanium, titanium alloy, rustless steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810147664 CN101485901B (en) | 2008-11-25 | 2008-11-25 | Method for preparing hydroxyapatite/nano silver antimicrobial composite coating by pulse electrochemical deposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810147664 CN101485901B (en) | 2008-11-25 | 2008-11-25 | Method for preparing hydroxyapatite/nano silver antimicrobial composite coating by pulse electrochemical deposition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101485901A true CN101485901A (en) | 2009-07-22 |
| CN101485901B CN101485901B (en) | 2012-12-19 |
Family
ID=40889061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810147664 Expired - Fee Related CN101485901B (en) | 2008-11-25 | 2008-11-25 | Method for preparing hydroxyapatite/nano silver antimicrobial composite coating by pulse electrochemical deposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101485901B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101791433A (en) * | 2010-03-24 | 2010-08-04 | 吉林大学 | Molecular sieve antibacterial coating with pure titanium or titanium alloy surface and preparation method thereof |
| DE102010025533A1 (en) | 2010-06-29 | 2011-12-29 | Heraeus Medical Gmbh | Method and device for bone growth promoting coating |
| EP2468923A1 (en) | 2010-12-23 | 2012-06-27 | Heraeus Medical GmbH | Surface coating method and coating device |
| CN102560590A (en) * | 2012-02-14 | 2012-07-11 | 陕西科技大学 | Anode in-situ electrochemical method for preparing hydroxyapatite coating |
| CN102677125A (en) * | 2012-06-13 | 2012-09-19 | 西北有色金属研究院 | Preparation method of active antibacterial composite coating on surface of titanium and titanium alloy medical instrument |
| CN104788022A (en) * | 2015-03-31 | 2015-07-22 | 哈尔滨工业大学 | Preparation method and application of flaky nano-silver electrochromic film |
| CN104790007A (en) * | 2015-04-21 | 2015-07-22 | 浙江大学 | Method for preparing mineral collagen coating on surface of medical implantation body |
| CN105019004A (en) * | 2015-07-09 | 2015-11-04 | 新疆师范大学 | Preparation method of electric-spun PLLA/Ag antibacterial composite membrane |
| CN105112967A (en) * | 2015-09-11 | 2015-12-02 | 西南交通大学 | Preparation method of conductive coating layer having bone induction and antibacterial performances |
| CN105970266A (en) * | 2016-05-25 | 2016-09-28 | 西南交通大学 | Device and method for preparing multi-element doping calcium phosphorus in high throughput mode |
| CN108144112A (en) * | 2018-03-05 | 2018-06-12 | 湖北大学 | A kind of preparation method in composite coating of the surface of metal titanium with synergetic antibacterial effect |
| CN108508077A (en) * | 2018-05-29 | 2018-09-07 | 四川维思达医疗器械有限公司 | A kind of method of electrode operating condition in determining calcium phosphate electrochemical coating |
| CN112843330A (en) * | 2020-12-31 | 2021-05-28 | 吉林大学 | Composite material for implant and method for producing same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101156963A (en) * | 2007-11-08 | 2008-04-09 | 浙江大学 | Method for preparing similar bone bioactivity coatings medical material by galvano-chemistry method |
| CN101294297A (en) * | 2008-06-12 | 2008-10-29 | 中山大学 | Process for producing silver-hydroxyapatite nano-composite material |
-
2008
- 2008-11-25 CN CN 200810147664 patent/CN101485901B/en not_active Expired - Fee Related
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101791433A (en) * | 2010-03-24 | 2010-08-04 | 吉林大学 | Molecular sieve antibacterial coating with pure titanium or titanium alloy surface and preparation method thereof |
| 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 |
| DE102010025533A1 (en) | 2010-06-29 | 2011-12-29 | Heraeus Medical Gmbh | Method and device for bone growth promoting coating |
| EP2402042A2 (en) | 2010-06-29 | 2012-01-04 | Heraeus Medical GmbH | Method and device for coating promoting bone growth |
| CN102309780A (en) * | 2010-06-29 | 2012-01-11 | 贺利氏医疗有限公司 | Be used to promote the method and apparatus of the coating of bone growth |
| US9592319B2 (en) | 2010-06-29 | 2017-03-14 | Heraeus Medical Gmbh | Method and device for coating of a medical implant |
| CN102309780B (en) * | 2010-06-29 | 2014-10-29 | 贺利氏医疗有限公司 | Method and device for coating promoting bone growth |
| US9028907B2 (en) | 2010-06-29 | 2015-05-12 | Heraeus Medical Gmbh | Method and device for coating of a medical implant |
| EP2468923A1 (en) | 2010-12-23 | 2012-06-27 | Heraeus Medical GmbH | Surface coating method and coating device |
| DE102010055561A1 (en) | 2010-12-23 | 2012-06-28 | Heraeus Medical Gmbh | Coating method and coating device |
| US9878346B2 (en) | 2010-12-23 | 2018-01-30 | Heraeus Medical Gmbh | Device for coating regions of a medical implant |
| US8895098B2 (en) | 2010-12-23 | 2014-11-25 | Heraeus Medical Gmbh | Coating method and coating device |
| CN102560590B (en) * | 2012-02-14 | 2015-01-28 | 陕西科技大学 | Anode in-situ electrochemical method for preparing hydroxyapatite coating |
| CN102560590A (en) * | 2012-02-14 | 2012-07-11 | 陕西科技大学 | Anode in-situ electrochemical method for preparing hydroxyapatite coating |
| CN102677125A (en) * | 2012-06-13 | 2012-09-19 | 西北有色金属研究院 | Preparation method of active antibacterial composite coating on surface of titanium and titanium alloy medical instrument |
| CN102677125B (en) * | 2012-06-13 | 2014-12-17 | 西北有色金属研究院 | Preparation method of active antibacterial composite coating on surface of titanium and titanium alloy medical instrument |
| CN104788022A (en) * | 2015-03-31 | 2015-07-22 | 哈尔滨工业大学 | Preparation method and application of flaky nano-silver electrochromic film |
| CN104790007A (en) * | 2015-04-21 | 2015-07-22 | 浙江大学 | Method for preparing mineral collagen coating on surface of medical implantation body |
| CN104790007B (en) * | 2015-04-21 | 2017-03-29 | 浙江大学 | The preparation method of the mineralized collagen coating of medical metal implant surfaces |
| CN105019004A (en) * | 2015-07-09 | 2015-11-04 | 新疆师范大学 | Preparation method of electric-spun PLLA/Ag antibacterial composite membrane |
| CN105112967A (en) * | 2015-09-11 | 2015-12-02 | 西南交通大学 | Preparation method of conductive coating layer having bone induction and antibacterial performances |
| CN105970266A (en) * | 2016-05-25 | 2016-09-28 | 西南交通大学 | Device and method for preparing multi-element doping calcium phosphorus in high throughput mode |
| CN108144112A (en) * | 2018-03-05 | 2018-06-12 | 湖北大学 | A kind of preparation method in composite coating of the surface of metal titanium with synergetic antibacterial effect |
| CN108508077A (en) * | 2018-05-29 | 2018-09-07 | 四川维思达医疗器械有限公司 | A kind of method of electrode operating condition in determining calcium phosphate electrochemical coating |
| CN108508077B (en) * | 2018-05-29 | 2020-04-03 | 四川维思达医疗器械有限公司 | Method for determining working conditions of electrode in calcium phosphate electrochemical coating |
| CN112843330A (en) * | 2020-12-31 | 2021-05-28 | 吉林大学 | Composite material for implant and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101485901B (en) | 2012-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101485901B (en) | Method for preparing hydroxyapatite/nano silver antimicrobial composite coating by pulse electrochemical deposition | |
| Panda et al. | A comprehensive review on the preparation and application of calcium hydroxyapatite: A special focus on atomic doping methods for bone tissue engineering | |
| Maimaiti et al. | Stable ZnO-doped hydroxyapatite nanocoating for anti-infection and osteogenic on titanium | |
| Huang et al. | Strontium and copper co-substituted hydroxyapatite-based coatings with improved antibacterial activity and cytocompatibility fabricated by electrodeposition | |
| Huang et al. | Antibacterial efficacy, corrosion resistance, and cytotoxicity studies of copper-substituted carbonated hydroxyapatite coating on titanium substrate | |
| Sun et al. | Electrophoretic deposition of colloidal particles on Mg with cytocompatibility, antibacterial performance, and corrosion resistance | |
| Honda et al. | In vitro and in vivo antimicrobial properties of silver-containing hydroxyapatite prepared via ultrasonic spray pyrolysis route | |
| Đošić et al. | In vitro investigation of electrophoretically deposited bioactive hydroxyapatite/chitosan coatings reinforced by graphene | |
| CN101381881A (en) | Method for preparing hydroxylapatite/chitosan composite coating by pulse electrochemical deposition | |
| Karthika et al. | Retracted Article: Fabrication of divalent ion substituted hydroxyapatite/gelatin nanocomposite coating on electron beam treated titanium: mechanical, anticorrosive, antibacterial and bioactive evaluations | |
| CN111035803A (en) | Titanium implant material with anti-infection and osseointegration promoting functions and preparation method thereof | |
| Qiao et al. | Gallium loading into a polydopamine-functionalised SrTiO3 nanotube with combined osteoinductive and antimicrobial activities | |
| Huang et al. | Physicochemical, osteogenic and antimicrobial properties of graphene oxide reinforced silver/strontium-doped hydroxyapatite on titanium for potential orthopedic applications | |
| Wang et al. | Osteogenic and antiseptic nanocoating by in situ chitosan regulated electrochemical deposition for promoting osseointegration | |
| Chen et al. | Hydroxyapatite coatings with oriented nanoplate and nanorod arrays: Fabrication, morphology, cytocompatibility and osteogenic differentiation | |
| CN101156963A (en) | Method for preparing similar bone bioactivity coatings medical material by galvano-chemistry method | |
| CN110042392B (en) | Preparation method of composite coating with excellent biocompatibility and antibacterial property on surface of medical implant | |
| Lee et al. | Silver ion-exchanged sodium titanate and resulting effect on antibacterial efficacy | |
| CN105617460A (en) | Method for preparing nontoxic antibacterial coating on surface of medical implant material | |
| Hsueh et al. | Synergistic effects of collagen and silver on the deposition characteristics, antibacterial ability, and cytocompatibility of a collagen/silver coating on titanium | |
| Liu et al. | In simulated body fluid performance of polymorphic apatite coatings synthesized by pulsed electrodeposition | |
| Wang et al. | Accelerated fabrication of antibacterial and osteoinductive electrospun fibrous scaffolds via electrochemical deposition | |
| Zhang et al. | A novel La3+ doped MIL spherical analogue used as antibacterial and anticorrosive additives for hydroxyapatite coating on titanium dioxide nanotube array | |
| CN109385658A (en) | Hydroxyapatite nano stick array configuration coating of titanium-based surface multiple element codope and its preparation method and application | |
| Karthika | Biocompatible iron and copper incorporated nanohydroxyapatite coating for biomedical implant applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121219 Termination date: 20151125 |