CN106435690A - Micro-arc oxidation solution for titanium alloy strontium-containing biological coating and application of micro-arc oxidation solution - Google Patents
Micro-arc oxidation solution for titanium alloy strontium-containing biological coating and application of micro-arc oxidation solution Download PDFInfo
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Abstract
The invention discloses a micro-arc oxidation solution for a titanium alloy strontium-containing biological coating. The micro-arc oxidation solution contains Sr(OH)2 with the concentration being 1-3 g/L or Sr(OH)2.8H2O with the concentration being 2-6 g/L, Na2SiO3 with the concentration being 4-8 g/L, NaH2PO4 with the concentration being 2-4 g/L, triethanolamine with the concentration being 2-4 g/L, Na2B4O7 with the concentration being 1-2 g/L and glycerol with the concentration being 5-10 ml/L, and a solvent is deionized water. The invention further provides application of the micro-arc oxidation solution. Titanium alloy is added into the micro-arc oxidation solution, a direct current pulse power source is adopted, voltage is controlled at 200-600 V, the current density is 0.1-0.4 A/dm<2>, the solution temperature is lower than 60 DEG C, time is 20-120 min, and the strontium-containing biological coating is formed on the surface of the titanium alloy. Compared with other medial titanium alloy surface treatment technology, the micro-arc oxidation solution has the beneficial effects of being high in treatment efficiency, firm in combination of a film layer and a base body and the like. Besides, because strontium, phosphorus and other active elements are added into the film layer, the biological activity is superior to that of an existing titanium alloy micro-arc oxidation treatment method.
Description
Technical field
The invention belongs to materialogy field, relate to a kind of titanium alloy, specifically a kind of titanium alloy biological coating containing strontium
Microarc oxidation solution and application.
Background technology
Cranial defect and fracture have become a kind of serious social concern affecting health of people and life.Current Bone Defect Repari is raw
It is few to there is quantity in thing material, and description is complete, be difficult to meet the deficiencies such as clinical operation needs.Therefore, research and development bone is repaiied
Multiple material not only can cure the health of the disabled, and has huge economic results in society.For Bone Defect Repari and replacement
Material in have Metal and Alloy, bioceramic, polymer, composite and humans and animals bone derivative etc..In bone and pass
Under the stress condition of joint system complex, do not require nothing more than repair materials and have no side effect, have biological safety and it is necessary to have enough
Mechanical strength and can be securely joined with green bone.
Titanium and titanium alloy are because having the features such as low-density, low modulus, high intensity, excellent biocompatibility and corrosion resistance
And obtain in technical field of biological material and be increasingly widely applied, it is mainly used as artificial knee joint, femoral joint, dental implant, tooth
Root and artificial tooth metallic support etc..Although titanium and alloy thereof are widely popularized in medical implant field, but the structure of titanium and titanium alloy
Differ greatly with bone tissue with character, chemistry key generally can not be occurred with bone tissue as bioactive materials to be combined, i.e.
It is bio-inert material, can form fibr tissue interlayer in titanium, titanium alloy and biological tissue interface, makes implant that pine to occur
Dynamic, cause implant to lose efficacy.Therefore, with titanium and titanium alloy as the reparation alternate material of tooth and bone it is necessary to solve it and biological live
The problem of property difference.Differential arc oxidation is a kind of surface modification new technology in recent years developed, and can be closed at titanium or titanium by differential arc oxidation
Gold surface generates one layer of porous oxide ceramic membrane containing a certain amount of calcium P elements, and the surface of this ceramic membrane has porous knot
Structure.Micro-arc oxidation films from element form, the element of existing parent metal and alloy thereof, also have the element in solution；
From phase composition, the oxide of the various structures with oxygen or with the ionic reaction generation in solution for the matrix element is the master of film layer
Body phase, also has the various oxide being formed by alloying element in matrix and intermetallic compound simultaneously.Titanium or titanium alloy are through micro-
Its abrasion resistance properties, decay resistance is not only increased after arc oxidation processes；In solution, calcium, phosphonium ion are direct by reaction simultaneously
Penetrate in ceramic layer, exist with amorphous calcium phosphate form, add titanium alloy biologically active.
On the other hand, in recent years, non radioactive element strontium is led in medical science as the required important trace element of skeleton
The application in territory is increasingly paid close attention to by people.Now there are some researches show that strontium has the double of suppression bone information and promoting bone growing simultaneously
Recast is used：Strontium can heavily be absorbed by suppressing osteoclast proliferation to reduce bone and pass through stimulated osteoblastic proliferation promotion bone shape
Become.Strontium can strengthen the duplication of preosteoblast and osteoblastic functional activation, including the synthesis of bone matrix and alkaline phosphatase
The activity of enzyme.Strontium can reduce the generation of osteoclast mark in Differentiation of Bone Marrow Cells, suppresses the differentiation of osteoclast,
Reduce the activity to bone resorption for the osteoclast.Strontium can also stimulate mesenchymal stem cells MSCs and other cell Osteoblast Differentiation, because of
And strontium and mix strontium active material, on bone tissue engineer and planting body coating, there is higher using value.
New through looking into, retrieve containing the strontium bone renovating material relevant with the application and the relevant patent of titanium alloy differential arc oxidation altogether
As follows：
The patent of Application No. CN201410848994 disclose a kind of strontium-doped calcium phosphate salt polymer base bone renovating material and
Preparation method.Described strontium-doped calcium phosphate salt polymer base bone renovating material is by porous polymer support and is deposited on this support
Strontium-doped calcium phosphate salt constitute.This invention is to prepare strontium-doped calcium phosphate salt polymer base Bone Defect Repari material by electrochemical deposition technique
Material, time-consumingly short, simple to operate, this invention, with porous polymer support as substrate, saves the original loose structure of support.But
Being to use porous polymer support in this invention, intensity is relatively low, is only suitable for cannot act as bone renovating material implanting
Body, thus its application is subject to certain restrictions.
Application No. CN201610063539 patent discloses the system of a kind of Bone Defect Repari porous strontium doping hydroxyapatite material
Preparation Method, by strontium doping hydroxyapatite powder（50%~80%）With ammonium hydrogen carbonate pore creating material powder（50%~20%）Mixing, mixing
Through being mechanically pressed into block pressed compact after Jun Yun, then pressed compact is put into graphite jig, inserts discharge plasma sintering stove and be sintered,
I.e. obtain Bone Defect Repari porous strontium doping hydroxyapatite material.Bone Defect Repari prepared by this application porous strontium doping hydroxy-apatite
Stone material is without adding any binding agent and template, and composition is pure without objectionable impurities, and porosity is controlled between 20 ~ 40%, fall
Solve speed suitable, there is good osteogenic induction ability, and simple for process, rapidly and efficiently, with low cost and be easy to real
Existing industrialized production, may be used for biological hard tissue regeneration or the bone impairment renovation material rebuild.But, this invention obtains
Being porous strontium doping hydroxyapatite material, intensity is relatively low, and being only suitable for equally can not be on implant as bone renovating material.
Application No. CN200710017716 patent discloses the reparation of a kind of applicable human body load Cranial defect or strengthens solid
Fixed high strength and tenacity degradable strontium calcium superphosphate composite bone cement and preparation method thereof.The bone cement Solid raw materials taked is high crystalline
Ca4(PO4)2O pottery, SrHPO4、CaHPO4Mixed-powder, solidification liquid is the phosphoric acid,diluted aqueous solution, and the toughened unit of interpolation is anti-for height
The biocompatibility degradable macromolecule fiber of tensile strength, selected from poly lactic coglycolic acid fiber, acid fiber by polylactic or
Polyglycolic acid fiber or other medical absorbable sutures, enhancement unit is Ca after curing reaction4(PO4)2O residue pottery
Grain.It is toughness reinforcing modified with later stage degradation, strontium etc. multiple that this preparation method has merged ceramic particle In-sltu reinforcement, biodegradable fiber initial stage
Technology, obtains a kind of novel high strength and tenacity degradable strontium calcium superphosphate composite bone cement under class physiological environment.This material has good
Biocompatibility well, biologically active, osteoconductive and degradation property.The method uses multiple method to carry out bone cement by force
Toughening, has certain supporting role to human body load bone, but this technology can not be used directly on titanium implants.
Application No. CN201510290989 patent discloses a kind of polymethyl methacrylate (PMMA) composite bone cement
Precursor, described composite bone cement precursor includes solid phase pulvis and solidification liquid, and wherein, solid phase pulvis includes strontium borate biological glass
Glass, polymethyl methacrylate powder and polymerization initiator, solidification liquid includes methyl methacrylate and polymerization activator, solid phase
The quality of pulvis is the 50 ~ 80% of solid phase pulvis and solidification liquid quality sum.Present invention also offers a kind of polymethylacrylic acid
The preparation method of methyl esters composite bone cement, this composite bone cement combines strontium borate biological glass and simple PMMA bone cement
Performance, has excellent biologically active, biological degradability and biocompatibility and a mechanical strength matching with bone, thus
Promote that Bone Defect Repari method has reached more good effect, but this technology can not be used directly on titanium implants equally.
The patent of Application No. CN200910308780.5 discloses the preparation method of a kind of titanium alloy micro-arc oxide coating.
The method is as follows：By titanium alloy bipolar pulse mao power source power be 5kw～6kw, voltage be 250V～400V, frequently
Rate be 200Hz～400Hz, dutycycle under conditions of be 8%～15% containing sodium metasilicate 10～20g/L, sodium phosphate 10～
20g/L, sodium fluoride 2～5g/L, Boratex 2～5g/L, oxidation processes 5 minutes in glycerine 5～10ml/L electrolyte aqueous solution～
30 minutes, obtaining the differential arc oxidation coating that thickness is 3 μm～15 μm, the differential arc oxidation coating of gained and matrix are firmly combined with, tool
There is good abrasion resistance properties.This technology can be used for titanium alloy, but when being used on implant, the osteoinductive of this coating is not enough.
The patent of Application No. CN201110179072 discloses the differential of the arc oxygen of a kind of titanium alloy growth in situ wear-resistant coating
Change solution and application thereof.Described solution is KOH, Na2SiO3, NaF, triethanolamine and Na2B4O7Solution in deionized water.We
The microarc oxidation solution of the titanium alloy wear-resistant coating in method fast filming under higher voltage and current, thus significantly improve
The growth efficiency of oxide-film, and the wear-resistant coating hardness being formed after differential arc oxidation is high, reaches more than HV700, coating has higher
Growth efficiency, hardness and the wearability of coating are higher.But differential arc oxidation layer not calcic prepared by the solution in the method, phosphorus,
Strontiums etc. can promote the element of new bone growth, thus oxide layer biologically active is not enough.
The patent of Application No. CN201110354339 discloses a kind of metal implant bioactive layer and preparation side thereof
Medical metal is planted as anode differential arc oxidation in special treatment fluid by method, and described microarc oxidation solution is contained by every liter：3~
6g sodium metasilicate, 3 ~ 6g calcium acetate, 2 ~ 4g sodium dihydrogen phosphate, 2 ~ 4g potassium hydroxide, 2 ~ 4g sodium fluoride.The method is at metal implant
Surface is prepared bioactivity coatings and is had technique simply, and treatment effeciency is high, and process layer is high with the bond strength of metal implant, painting
Promote bone uptake element containing calcium phosphorus etc. in Ceng thus the advantage such as biologically active is good.But the microarc oxidation solution in the method contains
It is made up of substantial amounts of calcium ion, phosphate anion and hydroxide ion, be easily formed calcium phosphate or calcium hydroxide precipitation and affect place
Reason effect.
Content of the invention
For above-mentioned technical problem of the prior art, the invention provides the differential of the arc of a kind of titanium alloy biological coating containing strontium
Oxidation solution formula and application thereof, microarc oxidation solution formula and the application thereof of described this titanium alloy biological coating containing strontium are wanted
Solve the not strong technical problem of titanium alloy biologically active of the prior art.
The invention provides the microarc oxidation solution of a kind of titanium alloy biological coating containing strontium, by the one-tenth packet of following concentration
Become：
Sr(OH)21～3g/L；
Na2SiO34～8g/L；
NaH2PO42～4g/L；
Triethanolamine 2～4 g/L；
Na2B4O71～2g/L；
Glycerine 5～10 ml/L；
Solvent is deionized water.
Further, described Sr (OH)2By Sr (OH)2•8H2O replaces, Sr (OH)2•8H2The concentration of O is 2～6 g/L.
Further, the microarc oxidation solution of a kind of titanium alloy biological coating containing strontium of the present invention, by the one-tenth of following concentration
It is grouped into：
Sr(OH)22g/L；
Na2SiO36g/L；
NaH2PO43g/L；
Triethanolamine 3 g/L；
Na2B4O71.5g/L；
Glycerine 7.5ml/L；
Solvent is deionized water.
Further, the microarc oxidation solution of described a kind of titanium alloy biological coating containing strontium, it is characterised in that by as follows
The one-tenth of concentration is grouped into：
Sr(OH)2•8H2O 4g/L；
Na2SiO36g/L；
NaH2PO43g/L；
Triethanolamine 3g/L；
Na2B4O71.5g/L；
Glycerine 7.5ml/L；
Solvent is deionized water.
The preparation method of the microarc oxidation solution of above-mentioned a kind of titanium alloy biological coating containing strontium of the present invention, be by more than
Material stirs after adding deionized water, obtains the microarc oxidation solution of a kind of titanium alloy biological coating containing strontium of the present invention.
Present invention also offers the using method of the microarc oxidation solution of above-mentioned a kind of titanium alloy biological coating containing strontium, will
Titanium alloy is placed in oxidation processes in the microarc oxidation solution of titanium alloy biological coating containing strontium, uses direct current pulse power source, voltage 200
～600 V, it is 0.1～0.4 A/dm that titanium alloy processes surface current density2, electrolyte temperature is less than 60 DEG C, processes 20～120
Min, through rinsing after taking-up, is dried, forms the titanium alloy of biological coating containing strontium.
The microarc oxidation solution of a kind of titanium alloy biological coating containing strontium of the present invention is high at 200～600 V for titanium alloy
Containing materials such as sodium metasilicate in differential arc oxidation under voltage, and this process, the flash-over characteristic for the treatment of fluid can be improved, thus oxide layer is raw
Long speed is high.In prior art, titanium alloy is about tens volts at anodised voltage, and after processing 1 hour, the thickness of coating is general
All over less than 10 m, and the treatment fluid of the present invention is used to carry out the oxide layer that differential arc oxidation was formed after 20 minutes at titanium alloy surface
Thickness i.e. can reach 10 more than m, is incorporated into the composition in solution in oxide layer, the change original surface composition of titanium alloy,
Structure and performance.
Present invention improves over solution formula, add the element such as strontium and phosphorus in the solution, these elements can enter oxide layer,
Adding the self-bone grafting performance processing layer, compared with the process layer without strontium and phosphorus, the ability of its induction apatite deposition improves
About 50～110%.In addition, the chemical raw material valency that the microarc oxidation solution of a kind of titanium alloy biological coating containing strontium of the present invention uses
Lattice are low, therefore, use the method to process the advantage that implantation titanium alloy has low cost.
Titanium alloy prescription for the treatment of liquid and apply this solution titanium alloy surface is carried out differential arc oxidation obtain biological coating side
Method, it is adaptable to process titanium alloy implant.
The present invention compares with prior art, and its technological progress is significant.The present invention and other medical titanium alloy surface
Treatment technology is compared, and has the advantages such as treatment effeciency height, film layer and matrix are firmly combined with.It is additionally, since in film layer and add strontium
With phosphorus isoreactivity element, biologically active is better than existing titanium alloy differential arc oxidation treatment method, it is adaptable to process titanium alloy and plant
Enter body.
Brief description
Fig. 1 is titanium alloy and the process layer side shape appearance figure of Application Example 1 gained.
Fig. 2 is that the titanium alloy of Application Example 1 gained processes layer surface topography map.
Fig. 3 is the phosphorus ash that the titanium alloy of Application Example 1 gained soaks one week post processing layer induction and deposition through simulated body fluid
Stone shape appearance figure.
Detailed description of the invention
It below by embodiment and combine accompanying drawing the present invention is expanded on further, but is not limiting as the present invention.
Mao power source used by the present invention, WHD-30,30 kilowatts, Institute for Research and Technology of Harbin Institute of Technology；
A kind of microarc oxidation solution of the titanium alloy biological coating containing strontium of the present invention to selected titanium alloy sample at DC pulse
Carry out differential arc oxidation on power supply；
Simulated body fluid collocation method used by the present invention and using method see (Liu Xuanyong. biomedical titanium material and surface thereof change
Property. Chemical Industry Press, 2009, P145）
The present invention uses the quality of the apatite of deposition in unit are after soaking one week in simulated body fluid to evaluate coating
Self-bone grafting ability.
Titanium alloy sample in the embodiment of the present invention selects Ti-6Al-4V alloy, but is not limiting as a kind of titanium of the present invention
The microarc oxidation solution of alloy biological coating containing strontium process on other titanium alloys in application.
Embodiment 1
A kind of microarc oxidation solution of titanium alloy biological coating containing strontium, the Sr (OH) containing 1 g in i.e. every liter solution2, 4 g
Na2SiO3, the NaH of 2 g2PO4, the triethanolamine of 2 g, the Na of 1 g2B4O7With the glycerine of 5 ml/L, prepared by deionized water
Solution is become to stir.
Application Example 1
Titanium alloy sample selects Ti-6Al-4V alloy, with the differential of the arc oxygen of a kind of titanium alloy biological coating containing strontium of embodiment 1 gained
Change solution on direct current pulse power source, carry out differential arc oxidation acquisition biological coating to selected titanium alloy sample.Titanium alloy is placed in
In the microarc oxidation solution of titanium alloy biological coating containing strontium.
In micro-arc oxidation process, controlling voltage 200 V, dutycycle is 10 %, and current density is 0.1 A/dm2, electrolyte
Temperature is less than 50 DEG C, and the time is 20 min, and the titanium alloy sample surface after process forms biological coating, then with after clean water
Natural drying.
Acquisition biological coating side pattern such as Fig. 1 after above-mentioned Ti-6Al-4V alloy treatment, as can be seen from Figure 1
Coating layer thickness about 13 m.Wear-resistant coating surface topography such as Fig. 2 is obtained after Ti-6Al-4V alloy differential arc oxidation, permissible from Fig. 2
Find out that coating has loose structure.
Biological coating after the Ti-6Al-4V alloy treatment of final gained, after simulated body fluid soaks one week, apatite
Deposition be 6.2 mg/cm2.
Application Example 2
Titanium alloy sample selects Ti-6Al-4V alloy, with the differential of the arc oxygen of a kind of titanium alloy biological coating containing strontium of embodiment 1 gained
Change solution on direct current pulse power source, carry out differential arc oxidation acquisition biological coating to selected titanium alloy sample.Titanium alloy is placed in
In the microarc oxidation solution of titanium alloy biological coating containing strontium.
Micro-arc oxidation process controls voltage 300 V, and dutycycle is 20 %, and current density is 0.2 A/dm2, electrolyte temperature
Less than 60 DEG C, the time is 40 min, and titanium alloy sample surface after process forms biological coating, then with natural after clean water
It is dried.
Coating layer thickness about 20 m of the above-mentioned acquisition after Ti-6Al-4V alloy treatment.Ti-6Al-4V alloy differential of the arc oxygen
Obtain biological coating after change and there is loose structure.
Biological coating after the Ti-6Al-4V alloy treatment of final gained, after simulated body fluid soaks one week, apatite
Deposition be 6.8 mg/cm2.
Embodiment 2
A kind of microarc oxidation solution of titanium alloy biological coating containing strontium, the Sr (OH) containing 3 g in i.e. every liter solution2, 8 g
Na2SiO3, the NaH of 4 g2PO4, the triethanolamine of 4 g, the Na of 2 g2B4O7With the glycerine of 10 ml/L, prepared by deionized water
Solution is become to stir.
Application Example 3
Titanium alloy sample selects Ti-6Al-4V alloy, with the differential of the arc oxygen of a kind of titanium alloy biological coating containing strontium of embodiment 2 gained
Change solution on direct current pulse power source, carry out differential arc oxidation acquisition biological coating to selected titanium alloy sample.Titanium alloy is placed in
In the microarc oxidation solution of titanium alloy biological coating containing strontium.
Micro-arc oxidation process control voltage 400 V dutycycle is 10 %, and current density is 0.3 A/dm2, electrolyte temperature
Less than 50 DEG C, processing 80 min, the titanium alloy sample surface after process forms biological coating, is more naturally done by after clean water
Dry.
Acquisition biological coating thickness about 28 m after above-mentioned Ti-6Al-4V alloy treatment.The Ti-6Al-4V of gained closes
Biological coating after gold process, after soaking one week in simulated body fluid, the deposition of apatite is 6.7 mg/cm2.
Application Example 4
Titanium alloy sample selects Ti-6Al-4V alloy, with the differential of the arc oxygen of a kind of titanium alloy biological coating containing strontium of embodiment 2 gained
Change solution on direct current pulse power source, carry out differential arc oxidation acquisition biological coating to selected titanium alloy sample.
Titanium alloy is placed in the microarc oxidation solution of titanium alloy biological coating containing strontium.
Micro-arc oxidation process controls voltage 600 V, and dutycycle is 20 %, and current density is 0.4 A/dm2, electrolyte temperature
Less than 60 DEG C, the time is 120 min, and titanium alloy sample surface after process forms biological coating, then with natural after clean water
It is dried.
Acquisition biological coating thickness about 36 m after above-mentioned Ti-6Al-4V alloy treatment.The Ti-6Al-of final gained
Biological coating after 4V alloy treatment, after soaking one week in simulated body fluid, the deposition of apatite is 8.1 mg/cm2.
Comparative example
A kind of titanium alloy does not contains strontium and phosphorus microarc oxidation solution, the Na containing 6 g in every liter of solution2SiO3, three ethanol of 3 g
Amine, the Na of 1.5 g2B4O7It with the glycerine of 7.5 ml/L, is configured to solution by deionized water and stirs.
Titanium alloy sample selects Ti-6Al-4V alloy, does not contains strontium and phosphorus microarc oxidation solution to institute with comparative example 1 gained
The titanium alloy sample of choosing carries out differential arc oxidation on direct current pulse power source and obtains biological coating.
It is placed in titanium alloy in above-mentioned solution.
Micro-arc oxidation process controls voltage 400V, and dutycycle is 20 %, and current density is 0.3 A/dm2, electrolyte temperature
Less than 60 DEG C, the time is 20 min, and titanium alloy sample surface after process forms biological coating, then with natural after clean water
It is dried.
The above-mentioned acquisition biological coating after Ti-6Al-4V alloy treatment after simulated body fluid soaks one week, apatite
Deposition be 4.2 mg/cm2.
Above-mentioned specific embodiment is used only to illustrate the present invention, rather than limits the invention, in the present invention
Spirit and claims in, any modifications and changes that the present invention is made, both fall within the protection model of the present invention
Enclose.
Claims (5)
1. the microarc oxidation solution of a titanium alloy biological coating containing strontium, it is characterised in that be grouped into by the one-tenth of following concentration：
Sr(OH)21～3g/L；
Na2SiO34～8g/L；
NaH2PO42～4g/L；
Triethanolamine 2～4 g/L；
Na2B4O71～2g/L；
Glycerine 5～10 ml/L；
Solvent is deionized water.
2. the microarc oxidation solution of a kind of titanium alloy biological coating containing strontium as claimed in claim 1, it is characterised in that：Described
Sr(OH)2By Sr (OH)2•8H2O replaces, Sr (OH)2•8H2The concentration of O is 2～6 g/L.
3. the microarc oxidation solution of a kind of titanium alloy biological coating containing strontium as claimed in claim 1, it is characterised in that by as follows
The one-tenth of concentration is grouped into：
Sr(OH)22g/L；
Na2SiO36g/L；
NaH2PO43g/L；
Triethanolamine 3 g/L；
Na2B4O71.5g/L；
Glycerine 7.5ml/L；
Solvent is deionized water.
4. the microarc oxidation solution of a kind of titanium alloy biological coating containing strontium as claimed in claim 2, it is characterised in that by as follows
The one-tenth of concentration is grouped into：
Sr(OH)2•8H2O 4g/L；
Na2SiO36g/L；
NaH2PO43g/L；
Triethanolamine 3 g/L；
Na2B4O71.5g/L；
Glycerine 7.5ml/L；
Solvent is deionized water.
5. the using method of the microarc oxidation solution of a kind of titanium alloy biological coating containing strontium described in claim 1 or 2, its feature
It is：Titanium alloy is placed in oxidation processes in the microarc oxidation solution of titanium alloy biological coating containing strontium, uses direct current pulse power source,
Voltage 200～600 V, it is 0.1～0.4 A/dm that titanium alloy processes surface current density2, electrolyte temperature is less than 60 DEG C, processes 20
～120 min, through rinsing after taking-up, are dried, form the titanium alloy of biological coating containing strontium.
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| CN110629270A (en) * | 2019-09-17 | 2019-12-31 | 广东省医疗器械研究所 | Preparation method of strontium-containing biological film layer |
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| CN116676039A (en) * | 2023-05-26 | 2023-09-01 | 中山大学 | Titanium alloy surface gradient antifouling coating and preparation method and application thereof |
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