CN102525827A - Method for preparing medical titanium material with long-acting antibacterial property and good biocompatibility - Google Patents
Method for preparing medical titanium material with long-acting antibacterial property and good biocompatibility Download PDFInfo
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Abstract
The invention discloses a method for preparing a medical titanium material with long-acting antibacterial property and good biocompatibility. The method comprises the following steps of: firstly forming a titanium dioxide nanotube array with regular and orderly height on the surface of the titanium material by anodic oxidation process; then adding a silver salt solution into the titanium dioxide nanotubes by spin-coating process, and heating at a high temperature to make the silver salt decompose into sliver nanoparticles in the titanium dioxide nanotubes; and finally modifying the material surface with a quaternary ammonium salt QAS, to obtain the final product of medical titanium material with long-acting antibacterial property and good biocompatibility. The preparation method is simple, does not need a special equipment and has a low preparation cost.
Description
Technical field
The invention belongs to field of medical materials, relate to a kind of method for preparing of functionalization titanium material.
Background technology
Titanium or titanium alloy has and the proximate elastic modelling quantity of people's bone, good corrosion resistance, excellent biological compatibility and processing characteristics, begins just to be widely used in dental implant, artificial joint and tooth implant frame etc. as embedded material from the seventies.Bacterial infection is one of modal reason of biomaterial graft failure.If receive severe infections, just need the taking-up implant to lay equal stress on and newly perform the operation.Therefore, ideal implant not only needs excellent biological compatibility, and needs durable antibacterial performance.
Previously result of study shows, suitable nanotube caliber and pipe range can promote cell function; Titania nanotube has good antibacterial performance after adding carried with antibiotics, but because antibiotic rapid release can not reach persistent antibacterial effect; Titania nanotube has more persistent antibacterial ability behind the silver loaded nano-particle, but pair cell has certain toxicity.
Summary of the invention
In view of this; The object of the present invention is to provide a kind of medical titanium material with long acting antibiotic performance and good biocompatibility and preparation method thereof, operating process is simple, need not special installation; Preparation cost is low, and products obtained therefrom has long acting antibiotic performance and excellent biological compatibility.
For achieving the above object, the present invention provides following technical scheme:
1. have the method for preparing of the medical titanium material of long acting antibiotic performance and good biocompatibility, may further comprise the steps:
A. the titanium material is cleaned and obtain clean metal surface;
B. the orderly Nano tube array of titanium dioxide of titanium material surface formation rule that adopts anodizing to obtain at step a;
C. the titanium material that obtains with the mode treatment step b of silver salt solution through spin coating gets in the titania nanotube silver salt, makes the silver salt that gets in the titania nanotube be decomposed to form silver nano-grain through heat again;
D. the titanium material surface that step c is obtained was with irradiation under ultraviolet ray 1 ~ 3 hour; Drip dimethyl stearyl [3-(trimethoxy is silica-based) propyl group] ammonium chloride (QAS) solution on titanium material surface again; Heat treated forms the QAS decorative layer, promptly gets the medical titanium material with long acting antibiotic performance and good biocompatibility.
Preferably, said step a used acetone, isopropyl alcohol and methanol ultrasonic cleaning 10 ~ 20 minutes successively with the titanium material, and reuse water cleans 2 ~ 4 times, drying for standby.
Preferably; Said step b is that the titanium material that obtains with step a is as anode; Platinum is as negative electrode, to use concentration be 0.25 ~ 0.30 mol/L, with volume ratio as glycerin-water mixed liquid of 1:1 as the ammonium fluoride solution of solvent as electrolyte, anodic oxidation reactions is 30 ~ 60 minutes under constant voltage 30V condition; Titanium material after the processing cleans, drying for standby.
Preferred, said step b be use concentration as 0.27mol/L, with volume ratio as glycerin-water mixed liquid of 1:1 as the ammonium fluoride solution of solvent as electrolyte, anodic oxidation reactions is 30 minutes under constant voltage 30V condition.
Preferably, said step c is the titanium material that obtains with the silver salt solution of the saturated concentration mode treatment step b through spin coating, and the spin coating number of times is 10 ~ 30 times, and is each earlier with 450 ~ 550 rev/mins of spin coatings 15 ~ 30 seconds, again with 1000 ~ 2000 rev/mins of spin coatings 10 ~ 20 seconds; Titanium material after the processing cleans, drying, under 470 ~ 550 ℃, inert gas shielding condition, heats 2 ~ 4 hours again, cools off subsequent use.
Preferred, said step c uses concentration to carry out spin coating as the silver nitrate solution of 1mol/L, and the spin coating number of times is 30 times, and is each earlier with 450 rev/mins of spin coatings 18 seconds, again with 1500 rev/mins of spin coatings 12 seconds; Titanium material after the processing cleans, after the drying, heating is 3 hours under 500 ℃, argon shield condition.
Preferably; Said steps d is titanium material surface that step c is obtained with irradiation under ultraviolet ray 1 ~ 3 hour; Drip mass fraction again on titanium material surface and be 0.4 ~ 0.6% QAS solution, 80 ℃ of heating 16-24 hour promptly get the medical titanium material with long acting antibiotic performance and good biocompatibility.
Preferred, said steps d is titanium material surface that step c is obtained with irradiation under ultraviolet ray 2 hours, drips mass fraction again on titanium material surface and be 0.5% QAS solution, and 80 ℃ were heated 20 hours.
2. the product that adopts above-mentioned method for preparing to make is the medical titanium material with long acting antibiotic performance and good biocompatibility.
In the above-mentioned method for preparing, step b adopts anodizing to prepare Nano tube array of titanium dioxide.In anode oxidation process, many factors can influence the formation of nano-tube array, for example electrolyte system, oxidation voltage etc., and different preparation conditions possibly obtain having the nano-tube array of different-shape characteristic.The present invention investigates electrolyte system, comprises ammonium fluoride glycerin system, Fluohydric acid. aqueous systems and ammonium fluoride glycerin
/Water (volume ratio is 1:1) system.The result shows, prepares the Nano tube array of titanium dioxide of identical caliber pipe range with ammonium fluoride glycerin system, needs long period and high voltage; Prepare Nano tube array of titanium dioxide with the Fluohydric acid. aqueous systems, the pattern of nano-tube array is difficult to control; And use the ammonium fluoride glycerin
/Water (volume ratio is 1:1) system prepares Nano tube array of titanium dioxide, can more easily control the caliber pipe range of nanotube through changing approach such as oxidation voltage; Therefore, electrolyte system preferred fluorinated ammonium glycerin of the present invention
/Water (volume ratio is 1:1) system.The concentration of ammonium fluoride can influence the form of the titania nanotube that is generated, and research shows, adopting concentration is 0.25 ~ 0.30 ammonium fluoride electrolyte of 0.27 mol/L particularly, and prepared titania nanotube has good form.The present invention also investigates oxidation voltage, is respectively 5,10,15,20,25,30,40V.The result shows that the caliber of the little titania nanotube that then generates of oxidation voltage is little, is unfavorable for the loading of silver nano-grain; Rising along with oxidation voltage; The caliber of titania nanotube increases, and when oxidation voltage during greater than 40V, titania nanotube is destroyed; Therefore, the preferred oxidation voltage of the present invention is 30V.
Step c adds silver salt solution in the titania nanotube to through spin-coating method.Spin-coating method can rely on the action of gravity of porous tubular structured capillarity of nanotube itself and silver salt solution itself, and it is inner to make silver salt get into nanotube, and utilizes the centrifugal force that produces when rotating that silver salt is evenly distributed in body.Influence the principal element that silver salt distributes in body silver salt solution concentration, spin coating number of times and spin speed etc. are arranged.For the silver loaded nano-particle is in titania nanotube effectively, silver salt solution concentration of the present invention is preferably saturated concentration.In the certain numerical value scope, the spin coating number of times is many more, and it is many more to get into the inner silver salt of body.The centrifugal force that spin speed produces too slowly is not enough, if spin speed is very fast when just having begun, silver salt can be thrown out of and can not well be loaded in the nanotube.Result of study of the present invention shows, adopts the high concentration silver salt solution, uses earlier than the spin coating of low velocity reuse fair speed, and the more number of times of spin coating could effectively load silver salt to titania nanotube interior (Fig. 1).
Steps d increases the chemical active radical on titanium material surface earlier through ultra violet lamp, drip QAS solution again, makes its chemical active radical reaction surperficial with the titanium material under the heat treated condition, finally forms the QAS decorative layer on titanium material surface.The QAS solution concentration is too low, titanium material surface can not be covered by QAS fully, and then influence antibacterial effect; The QAS solution concentration is too high, and then to titanium material surface, QAS is intermolecular also id reaction can to take place QAS, forms unnecessary waste except that partially grafted.The present invention studies demonstration, and the mass fraction of QAS solution is preferably 0.4 ~ 0.6%, and more preferably 0.5%.
Beneficial effect of the present invention is: the present invention at first generates highly regular Nano tube array of titanium dioxide through anodizing on titanium material surface; Through spin-coating method silver salt solution is added in the titania nanotube then; Heat makes silver salt in nanotube, be decomposed to form silver nano-grain; Use quaternary ammonium salt QAS decorative material surface at last, made a kind of medical titanium material that has long acting antibiotic performance and good biocompatibility simultaneously, method for preparing is simple; Need not special installation, preparation cost is low.
Description of drawings
Fig. 1 is the field emission scanning electron microscope figure that silver loads in the titania nanotube under the different condition; Wherein A is low concentration silver salt, low speed-high speed spin coating; B is high concentration silver salt, less spin coating number of times, and C is high concentration silver salt, high speed spin coating, and D is high concentration silver salt, low speed-high speed spin coating.
Fig. 2 is the field emission scanning electron microscope figure on the titanium material surface of process different disposal; Wherein A is the titanium material that is untreated; B is " titania nanotube " vertical view, and C is " titania nanotube " sectional view, and D is " titania nanotube silver " vertical view; E is " titania nanotube silver " sectional view (arrow has been indicated the silver nano-grain in titania nanotube), and F is " titania nanotube silver QAS " vertical view.
Fig. 3 is the energy spectrum analysis figure on the titanium material surface of process different disposal, and wherein A is " titania nanotube ", and B is " a titania nanotube silver ", and C is " titania nanotube silver QAS ".
Fig. 4 is the activity of rat osteoblast on the titanium material surface of process different disposal; Wherein * representes and the relatively p < 0.05 of titanium material that is untreated; * representes and the relatively p < 0.01 of titanium material that is untreated; # represent with " titania nanotube " relatively p 0.05, and & represent with " titania nanotube silver " relatively p < 0.05 ， && representes and " titania nanotube silver " p < 0.01 relatively.
The specific embodiment
In order to make the object of the invention, technical scheme and advantage clearer, will combine accompanying drawing that the preferred embodiments of the present invention are carried out detailed description below.
Embodiment 1. has the preparation of the medical titanium material of long acting antibiotic performance and good biocompatibility
A. the pretreatment of titanium material: the titanium material was used acetone, isopropyl alcohol and methanol ultrasonic cleaning 20 minutes successively, reuse washed with de-ionized water 3 times, 40 ℃ of dryings, subsequent use;
B. the structure of Nano tube array of titanium dioxide: ammonium fluoride is used glycerin-water mixed solution dissolving of volume ratio as 1:1, process the ammonium fluoride solution that concentration is 0.27mol/L, as electrolyte; The titanium material that step a is obtained is as anode, and platinum is put in the above-mentioned ammonium fluoride electrolyte as negative electrode, and anodic oxidation reactions is 30 minutes under constant voltage 30V condition; Titanium material water after the processing cleans 5 times, and 40 ℃ of dryings are subsequent use; Gained titanium material abbreviates " titania nanotube " as;
C. the loading of silver nano-grain: the titanium material that step b is obtained is fixed on the spin coater (spin-coater); Dripping concentration on titanium material surface is the silver nitrate solution of 1mol/L, and each 20 μ L are earlier with 450 rev/mins of spin coatings 18 seconds; With 1500 rev/mins of spin coatings 12 seconds, repeat spin coating 30 times again; Titanium material water after the processing cleans 5 times, drying at room temperature, and heating 3 hours under 500 ℃, argon shield condition is again cooled off subsequent use; Gained titanium material abbreviates " titania nanotube silver " as;
D. the modification of quaternary ammonium salt: the titanium material surface that step c is obtained was with irradiation under ultraviolet ray 2 hours; Drip mass fraction again on titanium material surface and be 0.5% QAS solution 20 μ L; 80 ℃ were heated 20 hours; Promptly get medical titanium material, abbreviate " titania nanotube silver QAS " as with long acting antibiotic performance and good biocompatibility.
The field emission scanning electron microscope figure on gained titanium material surface is as shown in Figure 2 after above-mentioned each step process; It is thus clear that after step b handles; Vertical arrangement, regular Nano tube array of titanium dioxide have been formed on titanium material surface, the about 110nm of the caliber of titania nanotube wherein, the about 900nm of pipe range; After step c handled, the silver nano-grain of loading had fraction to be present between the surface and tube and tube of nanotube, and major part is present in titania nanotube inside; After steps d was handled, titania nanotube was partly covered by QAS.
The energy spectrum analysis figure on gained titanium material surface is as shown in Figure 3 after above-mentioned each step process; It is thus clear that compare with the titanium material after step b handles; Titanium material after step c handles contains 5% the silver element of having an appointment; Description of step c has loaded silver nano-grain effectively in titania nanotube inside, and the content of silicon, nitrogen and chlorine element obviously increases in the titanium material after the steps d processing, explains at " titania nanotube silver " material surface and has successfully modified QAS.
A. the pretreatment of titanium material: the titanium material was used acetone, isopropyl alcohol and methanol ultrasonic cleaning 20 minutes successively, reuse washed with de-ionized water 3 times, 40 ℃ of dryings, subsequent use;
B. the structure of Nano tube array of titanium dioxide: ammonium fluoride is used glycerin-water mixed solution dissolving of volume ratio as 1:1, process the ammonium fluoride solution that concentration is 0.25mol/L, as electrolyte; The titanium material that step a is obtained is as anode, and platinum is put in the above-mentioned ammonium fluoride electrolyte as negative electrode, and anodic oxidation reactions is 45 minutes under constant voltage 30V condition; Titanium material water after the processing cleans 5 times, and 40 ℃ of dryings are subsequent use; Gained titanium material abbreviates " titania nanotube " as;
C. the loading of silver nano-grain: the titanium material that step b is obtained is fixed on the spin coater (spin-coater); Dripping concentration on titanium material surface is the silver nitrate solution of 1mol/L, and each 20 μ L are earlier with 500 rev/mins of spin coatings 30 seconds; With 1000 rev/mins of spin coatings 20 seconds, repeat spin coating 20 times again; Titanium material water after the processing cleans 5 times, drying at room temperature, and heating 3 hours under 500 ℃, argon shield condition is again cooled off subsequent use; Gained titanium material abbreviates " titania nanotube silver " as;
D. the modification of quaternary ammonium salt: the titanium material surface that step c is obtained was with irradiation under ultraviolet ray 3 hours; Drip mass fraction again on titanium material surface and be 0.6% QAS solution 20 μ L; 80 ℃ were heated 24 hours; Promptly get medical titanium material, abbreviate " titania nanotube silver QAS " as with long acting antibiotic performance and good biocompatibility.
Embodiment 3. has the preparation of the medical titanium material of long acting antibiotic performance and good biocompatibility
A. the pretreatment of titanium material: the titanium material was used acetone, isopropyl alcohol and methanol ultrasonic cleaning 20 minutes successively, reuse washed with de-ionized water 3 times, 40 ℃ of dryings, subsequent use;
B. the structure of Nano tube array of titanium dioxide: ammonium fluoride is used glycerin-water mixed solution dissolving of volume ratio as 1:1, process the ammonium fluoride solution that concentration is 0.30mol/L, as electrolyte; The titanium material that step a is obtained is as anode, and platinum is put in the above-mentioned ammonium fluoride electrolyte as negative electrode, and anodic oxidation reactions is 60 minutes under constant voltage 30V condition; Titanium material water after the processing cleans 5 times, and 40 ℃ of dryings are subsequent use; Gained titanium material abbreviates " titania nanotube " as;
C. the loading of silver nano-grain: the titanium material that step b is obtained is fixed on the spin coater (spin-coater); Dripping concentration on titanium material surface is the silver nitrate solution of 1mol/L, and each 20 μ L are earlier with 550 rev/mins of spin coatings 15 seconds; With 2000 rev/mins of spin coatings 10 seconds, repeat spin coating 10 times again; Titanium material water after the processing cleans 5 times, drying at room temperature, and heating 3 hours under 500 ℃, argon shield condition is again cooled off subsequent use; Gained titanium material abbreviates " titania nanotube silver " as;
D. the modification of quaternary ammonium salt: the titanium material surface that step c is obtained was with irradiation under ultraviolet ray 1 hour; Drip mass fraction again on titanium material surface and be 0.4% QAS solution 20 μ L; 80 ℃ were heated 16 hours; Promptly get medical titanium material, abbreviate " titania nanotube silver QAS " as with long acting antibiotic performance and good biocompatibility.
Experimental example 1. has the medical titanium material of long acting antibiotic performance and good biocompatibility to colibacillary inhibition ability
Get embodiment 1 through " titania nanotube ", " the titania nanotube silver " and " titania nanotube silver QAS " that obtains after the different disposal and " titania nanotube QAS " material that obtains according to embodiment 1 step a, b, d processing; With irradiation under ultraviolet ray antibacterial in 2 hours; Drip escherichia coli suspension 40 μ L at material surface,, vibrate strongly with sterilized water 4mL then and washed 5 minutes respectively at 37 ℃ of cultivations 1,7,21 and 30 day; Wash the antibacterial that sticks to material surface; Get cleaning mixture 100 μ L and smear flat board, cultivated 24 hours for 37 ℃, the counting bacterium colony also calculates antimicrobial efficiency.The result sees table 1, and " titania nanotube silver " all has the long acting antibiotic performance with " the silver-colored QAS of titania nanotube " these two kinds of materials, and along with the release approach exhaustion of silver, " titania nanotube QAS " material still has good antibacterial ability.
The titanium material of table 1 process different disposal is to colibacillary inhibition ability
Experimental example 2. has the medical titanium material of long acting antibiotic performance and good biocompatibility to the active influence of rat osteoblast
Get embodiment 1 " titania nanotube ", " titania nanotube silver " and " titania nanotube silver QAS " material and titanium material that is untreated (abbreviating " titanium material " as) through obtaining after the different disposal; At material surface inoculation neonate rat skull osteoblast, inoculum density is 40000/cm
2, use and to contain the DMEM culture medium culturing that volume fraction is 10% NBCS, changed liquid in per 2 days; Cultivated respectively 4 days and 7 days, every then hole adds MTT 100 μ L, cultivates 4 hours for 37 ℃; Supernatant is abandoned in suction, and every again hole adds DMSO 0.5mL, measures absorbance in wavelength 490nm place with ELIASA.The result sees Fig. 1; Rat osteoblast is cultivated 4 days and 7 days on " titania nanotube silver " material cytoactive is minimum; Show that this material has certain cytotoxicity, and after this material surface has been modified QAS, the cytoactive of cultivating 4 days and 7 days has all obtained significant raising; Explain that " titania nanotube silver QAS " material has excellent biological compatibility, can promote osteoblastic growth.
Explanation is at last; Above embodiment is only unrestricted in order to technical scheme of the present invention to be described; Although through invention has been described with reference to the preferred embodiments of the present invention; But those of ordinary skill in the art should be appreciated that and can make various changes to it in form with on the details, and the spirit and scope of the present invention that do not depart from appended claims and limited.
Claims (9)
1. have the method for preparing of the medical titanium material of long acting antibiotic performance and good biocompatibility, it is characterized in that, may further comprise the steps:
A. the titanium material is cleaned and obtain clean metal surface;
B. the orderly Nano tube array of titanium dioxide of titanium material surface formation rule that adopts anodizing to obtain at step a;
C. the titanium material that obtains with the mode treatment step b of silver salt solution through spin coating gets in the titania nanotube silver salt, makes the silver salt that gets in the titania nanotube be decomposed to form silver nano-grain through heat again;
D. the titanium material surface that step c is obtained was with irradiation under ultraviolet ray 1 ~ 3 hour; Dripping dimethyl stearyl [3-(trimethoxy is silica-based) propyl group] ammonium chloride on titanium material surface again is QAS solution; Heat treated forms the QAS decorative layer, promptly gets the medical titanium material with long acting antibiotic performance and good biocompatibility.
2. the method for preparing with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 1; It is characterized in that; Said step a used acetone, isopropyl alcohol and methanol ultrasonic cleaning 10 ~ 20 minutes successively with the titanium material, and reuse water cleans 2 ~ 4 times, drying for standby.
3. the method for preparing with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 1; It is characterized in that; Said step b is that the titanium material that obtains with step a is as anode; Platinum is as negative electrode, to use concentration be 0.25 ~ 0.30mol/L, with volume ratio as glycerin-water mixed liquid of 1:1 as the ammonium fluoride solution of solvent as electrolyte, anodic oxidation reactions is 30 ~ 60 minutes under constant voltage 30V condition; Titanium material after the processing cleans, drying for standby.
4. the method for preparing with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 3; It is characterized in that; Said step b be use concentration as 0.27mol/L, with volume ratio as glycerin-water mixed liquid of 1:1 as the ammonium fluoride solution of solvent as electrolyte, anodic oxidation reactions is 30 minutes under constant voltage 30V condition.
5. the method for preparing with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 1; It is characterized in that; Said step c is the titanium material that obtains with the silver salt solution of the saturated concentration mode treatment step b through spin coating; The spin coating number of times is 10 ~ 30 times, and is each earlier with 450 ~ 550 rev/mins of spin coatings 15 ~ 30 seconds, again with 1000 ~ 2000 rev/mins of spin coatings 10 ~ 20 seconds; Titanium material after the processing cleans, drying, under 470 ~ 550 ℃, inert gas shielding condition, heats 2 ~ 4 hours again, cools off subsequent use.
6. the method for preparing with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 5; It is characterized in that; Said step c uses concentration to carry out spin coating as the silver nitrate solution of 1mol/L; The spin coating number of times is 30 times, and is each earlier with 450 rev/mins of spin coatings 18 seconds, again with 1500 rev/mins of spin coatings 12 seconds; Titanium material after the processing cleans, after the drying, heating is 3 hours under 500 ℃, argon shield condition.
7. the method for preparing with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 1; It is characterized in that; Said steps d is titanium material surface that step c is obtained with irradiation under ultraviolet ray 1 ~ 3 hour; Drip mass fraction again on titanium material surface and be 0.4 ~ 0.6% QAS solution, 80 ℃ of heating 16-24 hour promptly get the medical titanium material with long acting antibiotic performance and good biocompatibility.
8. the method for preparing with medical titanium material of long acting antibiotic performance and good biocompatibility according to claim 7; It is characterized in that; Said steps d is titanium material surface that step c is obtained with irradiation under ultraviolet ray 2 hours; Drip mass fraction again on titanium material surface and be 0.5% QAS solution, 80 ℃ of heating 20 hours.
9. the medical titanium material that adopts each said method for preparing of claim 1 to 8 to make with long acting antibiotic performance and good biocompatibility.
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| CN102758202A (en) * | 2012-08-11 | 2012-10-31 | 西北有色金属研究院 | Method for preparing biomedical titanium and titanium alloy surface antibacterial coatings |
| CN103041976A (en) * | 2012-12-25 | 2013-04-17 | 苏州大学附属第二医院 | Method for preparing argentiferous antibacterial coating on surface of CoCr alloy material for oral use |
| CN103526259A (en) * | 2013-10-08 | 2014-01-22 | 广州中国科学院先进技术研究所 | Titanium alloy operation apparatus surface treatment technology |
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| CN102758202A (en) * | 2012-08-11 | 2012-10-31 | 西北有色金属研究院 | Method for preparing biomedical titanium and titanium alloy surface antibacterial coatings |
| CN103041976A (en) * | 2012-12-25 | 2013-04-17 | 苏州大学附属第二医院 | Method for preparing argentiferous antibacterial coating on surface of CoCr alloy material for oral use |
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| CN106086989A (en) * | 2016-07-20 | 2016-11-09 | 中南大学 | A kind of titania modified by Argentine nanotube composite anode and preparation method thereof |
| CN106086989B (en) * | 2016-07-20 | 2018-06-19 | 中南大学 | A kind of titania modified by Argentine nanotube composite anode and preparation method thereof |
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| CN109267137A (en) * | 2018-10-12 | 2019-01-25 | 厦门大学 | A kind of preparation method of the surface graded nano silver of medical titanium |
| CN111705347A (en) * | 2020-06-05 | 2020-09-25 | 西北工业大学 | Method for preparing titanium nanotube iodine coating by chemical vapor deposition method and application |
| CN111705347B (en) * | 2020-06-05 | 2021-11-30 | 西北工业大学宁波研究院 | Method for preparing titanium nanotube iodine coating by chemical vapor deposition method and application |
| CN112076348A (en) * | 2020-07-22 | 2020-12-15 | 浙江大学 | Medical metal surface anti-infection and osseointegration promotion coating, preparation method and application |
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