CN105862095A - Bioactive coating and preparation method thereof - Google Patents
Bioactive coating and preparation method thereof Download PDFInfo
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- CN105862095A CN105862095A CN201610387046.2A CN201610387046A CN105862095A CN 105862095 A CN105862095 A CN 105862095A CN 201610387046 A CN201610387046 A CN 201610387046A CN 105862095 A CN105862095 A CN 105862095A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
- C25D5/06—Brush or pad plating
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
Abstract
The invention discloses a bioactive coating and a preparation method thereof. The structure of the coating is a matrix/CS-SrHA. The preparation method comprises the following specific steps: (1) preparing SrHA powder by a homogeneous co-precipitation-hydrothermal process; (2) preparing a CS-SrHA plating solution; (3) pre-treating the surface of the matrix; (4) performing brush electroplating of the CS-SrHA plating solution on the surface of the matrix; and (5) soaking in SBF (Simulated Body Fluid). The invention has the following beneficial effects: the coating combines the flexibility and toughness of chitosan and the strength and hardness of hydroxyapatite, and good matching between bioactivity and metal materials is realized. By adopting the brush electroplating technology, the preparation time of the coating can be remarkably shortened, and the production efficiency is improved while the time cost is reduced; and the coating after brush electroplating is soaked in the SBF, so that the morphology change of the coating can be observed, and osteogenesis fibering of the coating can be greatly enhanced through a simulated bionic technology.
Description
Technical field
The present invention relates to bioactivity coatings prepare, particularly by the method for Brush Plating at Ti6A14V is prepared on surface
CS-SrHA bioactivity coatings.
Background technology
Bio-medical material is the abbreviation of biomaterial, is to carry out diagnosis and treatment for organism, repair and replace its disease damage group
Knit, organ or promote the novel High-tech Material of its performance.Constantly progress and key science and technology along with Novel medical technology
Important breakthrough, biomaterial be increasingly becoming the whole world scientist and relevant scholar fall over each other research and development focus material it
One.Metallic biomaterial is one of Present clinical most widely used load material, has the highest mechanical strength and resisting fatigue
Characteristic.Such as cobalt alloy, titanium alloy and the rustless steel of body implanting material, it is frequently utilized for artificial artificial limb, artificial skelecton joint, human body
Inside-fixture product etc..
Strontium (Sr) is one of micro elements needed by human, and strontium and calcium are congeners in the periodic table of elements.The atom of strontium
Radius is the atomic radius that 1.94nm is slightly larger than calcium, and size difference is less than 15%.Ca in strontium substituted hydroxy apatite structure2+Can
Form displaced type solid solution strontium-doped hydroxyapatite Ca10-nSrn(PO4)6(OH)2, due to atomic radius and character between two elements
Difference, the replacement of strontium makes the original lattice of HA be distorted, and changes the crystallinity of HA and biological degradability and increases anti-
Compressive Strength.Mixing the strontium mass fraction strontium containing hydroxyapatite good biocompatibility less than 20%, self-bone grafting ability is excellent, biological fall
Solution is good, can obtain satisfied bone defects and repair result after implanting.
Technique of brush plating has simple to operate, and technique is flexible, and coating speed is fast, bond strength high.And can be
Uniform coating is prepared on complex-shaped surface, and occupied ground is little, has broad application prospects.
Research shows, amino and hydroxyl on chitosan are the groups with reactivity, therefore can be changed by chemistry
Property is allowed to have New function.Chitosan is mainly manifested in adhesion, activation and facilitation, suppression to the impact of body cell
Effect.Chitosan-phospholipid complex can well promote that epithelial cell increases, and promotes osteoblastic proliferation.Chitosan/containing strontium hydroxyl
Base apatite composite coating had both possessed toughness and the flexibility of chitosan, had also possessed the intensity of hydroxyapatite itself with hard
Degree, can prepare the two good combination and meet the Novel bone material instantly required.
Ti6A14V matrix surface Brush Plating method prepares CS-SrHA bioactive coating material, and there is not been reported both at home and abroad.
Summary of the invention
In order to meet the demand of the preferable coating of preparation, the invention provides a kind of bioactivity coatings and preparation method thereof,
By Brush Electroplating Technique, optimize the surface pre-treating process of matrix, at titanium alloy-based surface Brush Plating CS-SrHA.Pass through mould
Intend body fluid and soak observation coating morphology and skeletonization situation.
In order to realize foregoing invention purpose, the invention provides the preparation process of a kind of strontium containing hydroxyapatite, content of strontium
Mass fraction in made plating solution is 9%-16%.
The present invention, according to mechanism of electrodeposition, selects graphite plated pen as anode, and workpiece to be plated is as negative electrode.Utilize oxidation also
Former reaction principle deposits desired coating.After power on, water produces H at anode electrolysis2And OH-
2H2O+2e-=H2+OH- (1)
The OH that electrolysis produces-The PH that can make solution raises, it is therefore desirable to regulation plating voltage controls electric current density thus controls
PH near anode, the OH that electrolysis produces-With H2PO4 -There is reversible reaction and generate HPO in the change according to environmental PH4 2-
OH-+H2PO4 - H2O+HPO4 2- (2)
Along with electrolysis carries out solution PH rising, in solution, HPO42-concentration can be gradually increased, and is that reaction (3) is to generating Ca1- xSrxHPO4·2H2O moves in direction, and anode surface deposits Ca1-xSrxHPO4·2H2O。
HPO4 2-+Ca2++Sr2++2H2O=Ca1-xSrxHPO4·2H2O (3)
Meanwhile, the chitosan owing to protonating in brush plating liquid also reacts with OH-, so chitosan also can become at anode
Separate out.
OH-+CS-NH3+=CS-NH2+H2O (4)
To achieve these goals, the concrete thought of the present invention is: a kind of bioactivity coatings, described coating structure is base
Body/CS-SrHA.
Described coating structure is Ti6A14V/ CS-SrHA。
SrHA used is prepared by homogeneous coprecipitation-hydro-thermal method.
In order to goal of the invention is better achieved, the present invention also provides for the preparation method of a kind of bioactivity coatings, specifically walks
Suddenly include:
(1) homogeneous coprecipitation-hydro-thermal method prepares SrHA powder；
(2) configuration of CS-SrHA plating solution；
(3) matrix surface pretreatment；
(4) at matrix surface Brush Plating CS-SrHA plating solution；
(5) SBF simulated body fluid soaks.The components unchanged of SBF simulated body fluid, controls coating soak time in body fluid, detection
The performance of coating.
Described step (1) homogeneous coprecipitation-hydro-thermal method prepares SrHA powder, and concrete steps include:
A, selection NH4H2PO4As phosphorous raw material, Ca (NO3)2·4H2O、Sr(NO3)2As metal ion source;By 94.4g-
Ca (the NO of 177.0g3)2·4H2Sr (the NO of O and 76.8g-144.0g3)2It is dissolved in 500ml deionized water and is configured to mixed solution
One；
B, by 46.0g-92.0gNH4H2PO4It is dissolved in 500ml deionized water and being sufficiently stirred for, obtain solution two, and solution two is existed
Being slowly dropped under magnetic agitation state in mixed solution one, obtain solution three, the described last mole ratio of solution three is (Ca+
Sr)/P=1.67；
C, the pH value utilizing 1:1 ammonia to regulate solution three are 9-10, after PH is stable, continue to stir under omnipotent magnetic stirrer
3-5h, then room temperature stands 12-24h, obtains solution four；
D, solution four proceed to hydrothermal treatment consists 5-10h in the autoclave of 120-150 DEG C, obtain solution five；
E, solution five standing poured out in D step be cooled to room temperature carry out sucking filtration, washing 2-3 time after, filtering residue puts into 100-120
Grinding after being dried 24h in DEG C drying baker, then sieve with 400 mesh sieve, collection is finally given by the powder of 400 mesh sieve
SrHA powder.
The configuration of described step (2) CS-SrHA plating solution, concrete steps include:
A, measuring chitosan CS 36.5-94.5g, glacial acetic acid 10-15ml puts into mix and blend preparation in 200-350ml distilled water
Become mixed solution a；
B, take citric acid 30-60g, ammonium sulfate 20-40g, add 100-250ml distilled water and stir, by ammonia volume ratio 2:1
Solution regulation pH value be 2.2-2.5, be configured to compound complex agent；
C, taking 20-30ml boric acid solution as buffer agent, the compound complex agent adding the configuration of step b stirs, then will step
The mixed solution a of rapid a configuration is poured slowly into, and uniformly mixes to obtain solution b, and described boric acid solution mass concentration is 30%；
D, take 0.2-0.5g dodecyl sodium sulfate and pour mix homogeneously in the solution b that step c obtains into as surfactant,
Solution c；
E, to step d configuration solution c in add 24-40g sodium hypophosphite NaH2PO2Stir 5-15 minute, be subsequently adding
SrHA powder 80-150g, after being heated to 30-50 DEG C and continuing to stir 15-30min, regulates pH after obtaining solution d, solution d cooling
Value is 3.7-6.9, obtains CS-SrHA plating solution；Chitosan mass fraction in CS-SrHA plating solution is 5%-10%, and SrHA is at CS-
Mass fraction in SrHA plating solution is that the pH value hydrochloric acid of 9%-16%, CS-SrHA plating solution is adjusted with the solution of ammonia volume ratio 2:1
Joint.
Described step (3) substrate pretreated, concrete steps include:
1. chemistry abatement processes: cleaned up by matrix deionized water, dries and is placed in platter, dip acetone with absorbent cotton
Behind wiping plating surface, then with deionized water rinsing, dry, to be plated；
2. electricity is clean processes:
The clean liquid of brush plating electricity on the matrix after chemistry abatement processes, brush-plating technique is: electrode just connects, brushing plating voltage 10-12V,
Brush plating time 20-40S, with relative velocity 6-24m/min unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
The clean liquid of electricity includes following components: sodium hydroxide 20-30g/L tertiary sodium phosphate 40-60g/L sodium carbonate 20-25g/L, acetic acid
0.2-0.5g/L, sodium hypophosphite 0.2-0.5g/L, sodium chloride 1.8-2.9g/L, surplus is water；The pH value of the clean liquid of electricity is 11-
13；
3. activation processing: first No. 2 activating solutions of brush plating, then brush plating 3 activation in step 2. matrix after electricity processes only
Liquid,
No. 2 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10-12V, brush plating time 20-40S, with relative velocity
6-24m/min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
No. 3 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10-12V, brush plating time 20-40S, with relative velocity
6-24m/min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating.
Described step (4) is at matrix surface Brush Plating CS-SrHA mixing plating solution, and concrete steps include:
Brush plating CS-SrHA plating solution on the matrix after substrate pretreated, during brush plating, process conditions are that electrode just connects, and first use 16-
18V voltage launch as surprise attack brush plating 5-10S, and then under brushing plating voltage 11-14V, brush plating time more than 60S, with relative velocity 6m/min-
The unidirectional brush plating of 11m/min, brush plating liquid CS-SrHA plating solution pH value is 3.7-6.9；Matrix distilled water after brush plating cleans.
Described matrix is Ti6A14V titanium alloy substrate.
The detection of coating: SBF simulated body fluid soaks, specifically:
1. the chemical composition of SBF solution and adding amount of medicines
SBF solution includes following component: NaCl 6.6674-6.6683g/1000ml, NaHCO3 2.2679-2.2682g/
1000ml, KCl 0.2235-0.2238g/1000ml, K2HPO4·3H2O 0.2281-0.2284g/1000ml, MgCl2·6H2O
0.3058-0.3061g/1000ml, CaCl20.2270-0.2273g/1000ml, Na2SO4 0.0709-0.0712g/
1000ml, surplus is water；
According to described consumption successively by NaCl, NaHCO3、KCl、K2HPO4·3H2O、MgCl2·6H2O、CaCl2、Na2SO4It is dissolved in
In deionized water, it is subsequently adding hydrochloric acid and trishydroxymethylaminomethane obtains solution Z, then the PH of the solution Z of configuration is adjusted to
7.4, finally coating is soaked 7 days in SBF simulated solution, observe surface topography.
Described hydrochloric acid content in solution Z is 40ml/1000ml, and described trishydroxymethylaminomethane contains in solution Z
Amount is 6.057g/1000ml.
1:1 ammonia refers to strong aqua ammonia (the most commercially available strong aqua ammonia, containing ammonia 28%～29%) and water and mixes with volume ratio for 1:1 and join
The solution of system
The solution of ammonia volume ratio 2:1: be strong aqua ammonia (the most commercially available strong aqua ammonia, containing ammonia 28%～29%) with water with volume ratio as 2:1
The solution of mixed preparing
The technical scheme that the embodiment of the present invention provides has the benefit that the coating structure of the present invention is matrix/CS-
SrHA, coating of the present invention combines flexibility and the toughness of chitosan, the intensity of hydroxyapatite and hardness, has obtained biological activity
Matched well with metal material.Utilizing Brush Electroplating Technique, the coating of preparation can significantly shorten preparation time, improves and produces effect
Rate reduces time cost.The complete simulated body fluid of coating brush plating soaks, and both can observe the morphology change of coating, can pass through again
Class bionics techniques makes the skeletonization fibroid of coating be greatly improved.
Detailed description of the invention
Decompose too fast in human body for current HA coating, easily cause sheet and cave in so that the material implanted quickly loses
Effect；Coating is the highest with basal body binding force；Bone mass cells is difficult to the series of problems such as propagation.The present invention provides a kind of CS-SrHA raw
The preparation method of thing active coating.
NH4H2PO4Lark prestige Science and Technology Ltd., ACS level reagent C AS No.:7722-76-1
Ca(NO3)2·4H2O Chemical Reagent Co., Ltd., Sinopharm Group, AR CAS No.:13477-34-4
Sr(NO3)2Shanghai Xi Long biochemical technology company limited, AR CAS No.:10042-76-9
Chitosan: Chemical Reagent Co., Ltd., Sinopharm Group, CAS No.:9012-76-4
Citric acid: CAS No.:77-92-9 Shanghai Xi Long biochemical technology company limited, AR
Ammonium sulfate: CAS No.:7783-20-2 Chemical Reagent Co., Ltd., Sinopharm Group, AR
Glacial acetic acid: anhydrous acetic acid, organic compound.It is frozen into ice-like when low temperature, is commonly called as glacial acetic acid, the chemistry examination of traditional Chinese medicines group
Agent company limited: CAS No.:64-19-7
Boric acid Chemical Reagent Co., Ltd., Sinopharm Group CAS No.:11113-50-1, solid
Dodecyl sodium sulfate CAS No.:151-21-3 Chemical Reagent Co., Ltd., Sinopharm Group, CP
Sodium hypophosphite NaH2PO2: CAS No.7681-51-0 Chemical Reagent Co., Ltd., Sinopharm Group, AR
No.:67-64-1 days white Chemical Groups of acetone: CAS, analytical pure
Tertiary sodium phosphate: Chemical Reagent Co., Ltd., Sinopharm Group, CP CAS No.:7601-54-9
Sodium carbonate: Chemical Reagent Co., Ltd., Sinopharm Group CAS No.:479-19-8
Acetic acid CAS No.:72196-32-8: this hundred full Chemical Co., Ltd.
Trishydroxymethylaminomethane: CAS No.:77-86-1, this hundred full Chemical Co., Ltd.
K2HPO4·3H2O Chemical Reagent Co., Ltd., Sinopharm Group, CP CAS No.:16788-57-1
MgCl2·6H2O Chemical Reagent Co., Ltd., Sinopharm Group, AR CAS No.:7791-18-6
CaCl2Chemical Reagent Co., Ltd., Sinopharm Group, CP CAS No.:10043-52-4
Na2SO4Chemical Reagent Co., Ltd., Sinopharm Group, AR CAS No.:7757-82-6
KCl Chemical Reagent Co., Ltd., Sinopharm Group, CAS No.:7447-40-7
NaHCO3 Shanghai Aladdin biochemical technology limited company, CAS No.:144-55-8
No. 2 activating solutions are salt acid type Qingdao Peng Xuda Electronics Equipment Co., Ltd (Linyi Rui Tai sufacing company limited)
No. 3 activating solutions are Fructus Citri Limoniae acid type Qingdao Peng Xuda Electronics Equipment Co., Ltd (the auspicious safe limited public affairs of sufacing in Linyi
Department)
Boric acid solution autogamy mass concentration 30%, i.e. 4.85mol boric acid is dissolved in 700ml water.
Embodiment 1
The preparation method of bioactivity coatings, concrete steps include:
(1) homogeneous coprecipitation-hydro-thermal method prepares SrHA powder；
A, selection NH4H2PO4As phosphorous raw material, Ca (NO3)2·4H2O、Sr(NO3)2As metal ion source;By 98.5g's
Ca(NO3)2·4H2Sr (the NO of O and 80.2g3)2It is dissolved in 500ml deionized water and is configured to mixed solution one；
B, by 54.7gNH4H2PO4It is dissolved in 500ml deionized water and being sufficiently stirred for, obtain solution two, and solution two is stirred at magnetic force
Mixing and be slowly dropped in mixed solution one under state, obtain solution three, the described last mole ratio of solution three is (Ca+Sr)/P=
1.67；The Ca of mole ratio (Ca+Sr)/P=1.67 ie in solution three kinds2+ And Sr2+Molal quantity sum be dihydrogen phosphate ions
1.67 times of molal quantity;
C, the pH value utilizing 1:1 ammonia to regulate solution three are 9, after PH is stable, continue to stir 5h under omnipotent magnetic stirrer,
Then room temperature stands 24h, obtains solution four；
D, the solution four stood is proceeded to hydrothermal treatment consists 10h in the autoclave of 120 DEG C, obtain solution five；
E, solution five standing poured out in D step be cooled to room temperature carry out sucking filtration, washing 3 times after, filtering residue put into 100 DEG C be dried
Grind after being dried 24h in case, then sieve by 400 mesh sieve and finally give SrHA powder.
(2) configuration of CS-SrHA plating solution:
A, measuring chitosan CS 36.5g, glacial acetic acid 10ml puts into mix and blend in 350ml distilled water and is configured to mixed solution a；
B, take citric acid 30g, ammonium sulfate 20g, add 100ml distilled water and stir, regulate with the solution of ammonia volume ratio 2:1
PH value is 2.4, is configured to compound complex agent；
C, taking 20ml boric acid solution as buffer agent, the compound complex agent adding the configuration of step b stirs, then by step a
The mixed solution a of configuration is poured slowly into, and uniformly mixes to obtain solution b, and the mass concentration of boric acid solution is 30%；
D, take 0.2g dodecyl sodium sulfate and pour mix homogeneously in the solution b that step c obtains into as surfactant, obtain solution
c；
E, to step d configuration solution c in add 24g sodium hypophosphite NaH2PO2Stir 15 minutes, be subsequently adding SrHA powder
80g, after being heated to 50 DEG C and continuing to stir 30min, cooling regulation solution ph is 4.5, obtains CS-SrHA plating solution；Chitosan
Mass fraction in CS-SrHA plating solution is 5%, and SrHA mass fraction in CS-SrHA plating solution is 11.0%, pH value hydrochloric acid
Regulate with the solution of ammonia volume ratio 2:1.
(3) matrix surface pretreatment；
1. chemistry abatement processes: by Ti6A14V titanium alloy substrate deionized water cleans up, and dries and is placed in platter, uses
After absorbent cotton dips acetone wiping plating surface, then with deionized water rinsing, dry, to be plated；
The most only process:
The clean liquid of brush plating electricity on Ti6A14V titanium alloy substrate, brush-plating technique is: electrode just connects, brushing plating voltage 10V, the brush plating time
20S, with relative velocity 14m/min unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
The clean liquid of electricity includes following components: sodium hydroxide 30g/L tertiary sodium phosphate 60g/L sodium carbonate 25g/L, acetic acid 0.2g/L, secondary Asia
Sodium phosphate 0.2g/L, sodium chloride 2.9g/L, surplus is water；The pH value of the clean liquid of electricity is 11；
3. activation processing: first No. 2 activating solutions of brush plating in step 2. Ti6A14V titanium alloy substrate after electricity processes only, so
No. 3 activating solutions of rear brush plating,
No. 2 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10V, brush plating time 30 S, with relative velocity 14m/
Min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
No. 3 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10V, brush plating time 30 S, with relative velocity 14m/
Min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating.
(4) at matrix surface Brush Plating CS-SrHA plating solution；
Brush plating CS-SrHA plating solution on the Ti6A14V titanium alloy substrate after substrate pretreated, during brush plating, process conditions are electrode
Just connecing, first launch a surprise attack brush plating 5S with 16V voltage, then under brushing plating voltage 12 V, brush plating time 120S, with relative velocity 11m/
The unidirectional brush plating of min, the matrix distilled water after brush plating cleans.
(5) SBF simulated body fluid soaks, the components unchanged of body fluid, controls coating soak time in body fluid, detects coating
Performance.
1. the chemical composition of SBF solution and adding amount of medicines
NaCl 6.6677g/1000ml, NaHCO32.2681g/1000ml, KCl 0.2235g/1000ml, K2HPO4·3H2O
0.2282/1000ml, MgCl2·6H2O 0.3061g/1000ml, CaCl20.2273g/1000ml, Na2SO4 0.0711g/
1000ml, surplus is water；
According to described consumption successively by NaCl, NaHCO3、KCl、K2HPO4·3H2O、MgCl2·6H2O、CaCl2、Na2SO4It is dissolved in
In deionized water, it is subsequently adding hydrochloric acid and trishydroxymethylaminomethane obtains solution Z, then the PH of the solution Z of configuration is adjusted to
7.4, finally coating is soaked 7 days in SBF simulated solution, observe surface topography.Hydrochloric acid content in solution Z is 40ml/
1000ml, trishydroxymethylaminomethane content in solution Z is 6.057g/1000ml.
Result: XRD analysis coating substance phase structure, Ti, SrHA diffraction maximum is sharp-pointed, CS diffraction maximum disperse width.Simulated body fluid
After middle immersion, SEM observes coating surface is voids and pits, and coating soaks front surface in simulated body fluid micro-crack, splits after immersion
Stricture of vagina disappears, and generates one layer of new compacted zone with a large amount of deposits.Its EDS result is shown as Ca, P, O composition.Cross section SEM
Show that coating is tightly combined with matrix；Coating layer thickness is about 9 μm, and the adhesion of employing scarification testing coating and matrix is
80.3MPa。
Embodiment 2
The preparation method of bioactivity coatings, concrete steps include:
(1) homogeneous coprecipitation-hydro-thermal method prepares SrHA powder；
A, selection NH4H2PO4As phosphorous raw material, Ca (NO3)2·4H2O、Sr(NO3)2As metal ion source;By 157.6g's
Ca(NO3)2·4H2Sr (the NO of O and 128.2g3)2It is dissolved in 500ml deionized water and is configured to mixed solution one；
B, by 87.6g NH4H2PO4It is dissolved in 500ml deionized water and being sufficiently stirred for, obtain solution two, and by solution two at magnetic force
Being slowly dropped under stirring in mixed solution one, obtain solution three, the described last mole ratio of solution three is (Ca+Sr)/P=
1.67；
C, the pH value utilizing 1:1 ammonia to regulate solution three are 10, after PH is stable, continue to stir under omnipotent magnetic stirrer
3h, then room temperature stands 12h, obtains solution four；
D, the solution four stood is proceeded to hydrothermal treatment consists 5h in the autoclave of 150 DEG C, obtain solution five；
E, solution five standing poured out in D step be cooled to room temperature carry out sucking filtration, washing 2 times after, filtering residue put into 120 DEG C be dried
Grind after being dried 24h in case, then sieve by 400 mesh sieve and finally give SrHA powder.
(2) configuration of CS-SrHA plating solution:
A, measuring chitosan CS 67 g, glacial acetic acid 12 ml puts into mix and blend in 300ml distilled water and is configured to mixed solution a；
B, take citric acid 43g, ammonium sulfate 31g, add 135ml distilled water and stir, regulate with the solution of ammonia volume ratio 2:1
PH value is 2.2, is configured to compound complex agent；
C, taking 27ml boric acid solution as buffer agent, the compound complex agent adding the configuration of step b stirs, then by step a
The mixed solution a of configuration is poured slowly into, and uniformly mixes to obtain solution b；
D, take 0.3 g dodecyl sodium sulfate and pour mix homogeneously in the solution b that step c obtains into as surfactant, obtain molten
Liquid c；
E, to step d configuration solution c in add 32 g sodium hypophosphite NaH2PO2Stir 5 minutes, be subsequently adding SrHA powder
124g, is heated to 30 DEG C and continues to stir after 30min, and adjusting pH value after cooling is 5.2 to obtain CS-SrHA plating solution；Chitosan exists
Mass fraction in CS-SrHA plating solution is 7.9%, and SrHA mass fraction in CS-SrHA plating solution is 14.6%, and CS-SrHA plates
The pH value hydrochloric acid of liquid regulates with the solution of ammonia volume ratio 2:1.
(3) matrix surface pretreatment；
1. chemistry abatement processes: by Ti6A14V titanium alloy substrate deionized water cleans up, and dries and is placed in platter, uses
After absorbent cotton dips acetone wiping plating surface, then with deionized water rinsing, dry, to be plated；
The most only process:
The clean liquid of brush plating electricity on Ti6A14V titanium alloy substrate, brush-plating technique is: electrode just connects, brushing plating voltage 10V, the brush plating time
20S, with relative velocity 14m/min unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
The clean liquid of electricity includes following components: sodium hydroxide 30g/L tertiary sodium phosphate 60g/L sodium carbonate 25g/L, acetic acid 0.2g/L, secondary Asia
Sodium phosphate 0.2g/L, sodium chloride 2.9g/L, surplus is water；The pH value of the clean liquid of electricity is 11；
3. activation processing: first No. 2 activating solutions of brush plating in step 2. Ti6A14V titanium alloy substrate after electricity processes only, so
No. 3 activating solutions of rear brush plating,
No. 2 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10V, brush plating time 30 S, with relative velocity 14m/
Min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
No. 3 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10V, brush plating time 30 S, with relative velocity 14m/
Min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating.
(4) at matrix surface Brush Plating CS-SrHA plating solution；
Brush plating CS-SrHA plating solution on the Ti6A14V titanium alloy substrate after substrate pretreated, during brush plating, process conditions are electrode
Just connecing, first launch a surprise attack brush plating 10S with 16V voltage, then under brushing plating voltage 12 V, the brush plating time, 300S was with relative velocity 11m/
The unidirectional brush plating of min, brush plating liquid CS-SrHA plating solution pH value is 5.2；Matrix distilled water after brush plating cleans.
(5) SBF simulated body fluid soaks, the components unchanged of body fluid, controls coating soak time in body fluid, detects coating
Performance.
1. the chemical composition of SBF solution and adding amount of medicines
NaCl 6.6677g/1000ml, NaHCO32.2681g/1000ml, KCl 0.2235g/1000ml, K2HPO4·3H2O
0.2282/1000ml, MgCl2·6H2O 0.3061g/1000ml, CaCl20.2273g/1000ml, Na2SO4 0.0711g/
1000ml, surplus is water;
By medicine provide order and consumption is dissolved in deionized water, and molten as buffering with hydrochloric acid and trishydroxymethylaminomethane
Liquid, is adjusted to 7.4 by configuration solution PH, close with blood of human body.Then coating is soaked 7 days in SBF simulated solution, observe surface
Pattern.Hydrochloric acid content in solution Z is 40ml/1000ml, and trishydroxymethylaminomethane content in solution Z is 6.057g/
1000ml。
Result: XRD analysis coating substance phase structure, Ti, SrHA diffraction maximum is sharp-pointed, CS diffraction maximum disperse width, has a small amount of
TiO2Diffraction maximum.After soaking in simulated body fluid, SEM observes coating surface is voids and pits, along with the increase of SrHA content, coating
Soaking front surface in simulated body fluid and have obvious crackle, after immersion, crackle disappears, and generates one layer of new compacted zone with big
Amount dendroid deposit.Its EDS result is shown as Ca, P, O composition.Cross section SEM shows that coating is tightly combined with matrix；Thick coating
Degree is about 13 μm, and the adhesion using scarification testing coating and matrix is 101.7MPa.
Embodiment 3
The preparation method of bioactivity coatings, concrete steps include:
(1) homogeneous coprecipitation-hydro-thermal method prepares SrHA powder；
A, selection NH4H2PO4As phosphorous raw material, Ca (NO3)2·4H2O、Sr(NO3)2As metal ion source;By 118.0g's
Ca(NO3)2·4H2Sr (the NO of O and 96.0g3)2It is dissolved in 500ml deionized water and is configured to mixed solution one；
B, by 65.6gNH4H2PO4It is dissolved in 500ml deionized water and being sufficiently stirred for, obtain solution two, and solution two is stirred at magnetic force
Mixing and be slowly dropped in mixed solution one under state, obtain solution three, the described last mole ratio of solution three is (Ca+Sr)/P=
1.67；
C, the pH value utilizing 1:1 ammonia to regulate solution three are 10, after PH is stable, continue to stir under omnipotent magnetic stirrer
5h, then room temperature stands 20h, obtains solution four；
D, the solution four stood is proceeded to hydrothermal treatment consists 7h in the autoclave of 130 DEG C, obtain solution five；
E, solution five standing poured out in D step be cooled to room temperature carry out sucking filtration, washing 3 times after, filtering residue put into 100 DEG C be dried
Case grinds after being dried 24h, then sieves by 400 mesh sieve and finally gives SrHA powder.
(2) configuration of CS-SrHA plating solution:
A, measuring chitosan CS94.5g, glacial acetic acid 15ml puts into mix and blend in 200ml distilled water and is configured to mixed solution a；
B, take citric acid 60g, ammonium sulfate 40g, add 220ml distilled water and stir, regulate with the solution of ammonia volume ratio 2:1
PH value is 2.5, is configured to compound complex agent；
C, taking 30ml boric acid solution as buffer agent, the compound complex agent adding the configuration of step b stirs, then by step a
The mixed solution a of configuration is poured slowly into, and uniformly mixes to obtain solution b；
D, take 0.5g dodecyl sodium sulfate and pour mix homogeneously in the solution b that step c obtains into as surfactant, obtain solution
c；
E, to step d configuration solution c in add 40g sodium hypophosphite NaH2PO2Stir 15 minutes, be subsequently adding SrHA powder
150g, is heated to 30 DEG C and continues to stir after 15min, and regulating pH value after cooling is 6.1 to obtain CS-SrHA plating solution；Chitosan exists
Mass fraction in CS-SrHA plating solution is 10%, and SrHA mass fraction in CS-SrHA plating solution is 15.9%, CS-SrHA plating solution
The solution regulation of pH value hydrochloric acid and ammonia volume ratio 2:1.
(3) matrix surface pretreatment；
1. chemistry abatement processes: by Ti6A14V titanium alloy substrate deionized water cleans up, and dries and is placed in platter, uses
After absorbent cotton dips acetone wiping plating surface, then with deionized water rinsing, dry, to be plated；
The most only process:
The clean liquid of brush plating electricity on Ti6A14V titanium alloy substrate, brush-plating technique is: electrode just connects, brushing plating voltage 10V, the brush plating time
20S, with relative velocity 14m/min unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
The clean liquid of electricity includes following components: sodium hydroxide 30g/L tertiary sodium phosphate-60g/L sodium carbonate 25g/L, acetic acid 0.2g/L, secondary Asia
Sodium phosphate 0.2g/L, sodium chloride 2.9g/L, surplus is water；The pH value of the clean liquid of electricity is 11；
3. activation processing: first No. 2 activating solutions of brush plating in step 2. Ti6A14V titanium alloy substrate after electricity processes only, so
No. 3 activating solutions of rear brush plating,
No. 2 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 12V, brush plating time 30 S, with relative velocity 14m/
Min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
No. 3 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 12V, brush plating time 30 S, with relative velocity 14m/
Min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating.
(4) at matrix surface Brush Plating CS-SrHA plating solution；
Brush plating CS-SrHA plating solution on the Ti6A14V titanium alloy substrate after substrate pretreated, during brush plating, process conditions are electrode
Just connecing, first launch a surprise attack brush plating 5S with 16V voltage, then under brushing plating voltage 12V, brush plating time 300S, with relative velocity 11m/min
Unidirectional brush plating, brush plating liquid CS-SrHA plating solution pH value is 6.1；Matrix distilled water after brush plating cleans.
(5) SBF simulated body fluid soaks, the components unchanged of body fluid, controls coating soak time in body fluid, detects coating
Performance.
1. the chemical composition of SBF solution and adding amount of medicines
NaCl6.6677g/1000ml, NaHCO32.2681g/1000ml, KCl 0.2235g/1000ml, K2HPO4·3H2O
0.2282g/1000ml, MgCl2·6H2O 0.3061g/1000ml, CaCl20.2273g/1000ml, Na2SO4 0.0711g/
1000ml, surplus is water;
By medicine provide order and consumption is dissolved in deionized water, and add hydrochloric acid and trishydroxymethylaminomethane as slow
Punching, is adjusted to 7.4 by the solution PH of configuration, close with blood of human body.Then coating is soaked 7 days in SBF simulated solution, observe table
Face pattern.Hydrochloric acid content in solution Z is 40ml/1000ml, and trishydroxymethylaminomethane content in solution Z is 6.057g/
1000ml。
Result: XRD analysis coating substance phase structure, Ti, SrHA diffraction maximum is sharp-pointed, and CS diffraction maximum disperse width has TiO2With
TCP phase generates.After soaking in simulated body fluid, SEM observes coating surface is voids and pits, and along with the increase of SrHA content, coating exists
Soaking front surface in simulated body fluid and have obvious crackle and particle aggregation phenomenon, after immersion, crackle disappears, and generate one layer new
Compacted zone is with a large amount of dendroid deposits.Its EDS result is shown as Ca, P, O composition.Cross section SEM shows that coating is tied with matrix
Close closely；Coating layer thickness is about 14 μm, and the adhesion using scarification testing coating and matrix is 83.4MPa.
Comparative example 1
Plasma spraying method prepares HA bioactivity coatings, basic step: with plasma flame flow as thermal source, utilizes plasma gun
The plasma jet produced is by powder heating and accelerates, and is melting or is spraying to matrix surface formation coating under molten condition.Deng
Plasma spray is linear process, is difficult to prepare desired coating at complicated surface of the work；In preparation process, problem is high, and HA and titanium close
Auri isolator CTE differs greatly, and has the biggest residual stress during cooling；In Plasma Spraying Process Using, HA easily decomposes.
Ining contrast to plasma spraying method and prepare HA bioactivity coatings, Brush Plating is the most flexible.Plasma spray is painted with line
Property technique, be difficult to prepare desired coating on complex part surface, and Brush Plating to be adapted to various titanium alloy articular bone surface raw
The plating of thing coating.Although the coated substrate that the adhesion of the HA coating after plasma spraying and matrix is prepared than technique of brush plating
Big about the 500MPa of adhesion, but preparation temperature is too high, in the case of HA and the titanium alloy-based coefficient of volume expansion differ greatly, cooling
Time can leave residual stress, HA, as medium temperature is too high and decompose, causes coating failure.Preparation temperature under technique of brush plating
Degree just more than 100 degree, and constantly wash away workpiece surface temperature along with substantial amounts of plating solution and ensured.
Comparative example 2
Mineralising biomimetic method prepares FHA-SrHA coating, basic step: under low temperature state, and titanium alloy is put into simulation mineralising body fluid
In, growth 6-8 week naturally.Although the coating biocompatibility that this method prepares is best, but process cycle is very long, general 1 to 2 month
Coating layer thickness is thick at several um.The FHA-SrHA coating prepared with biomimetic method, general coating and basal body binding force 10MPa with
Under, the FHA-SrHA coating prepared compared to biomimetic method, general coating prepared by Brush Plating method and basal body binding force can improve 8
To 10 times.
Comparative example 3
Coprecipitation prepares CS-HA coating, by H3PO4Aqueous solution becomes solution with chitosan acetic acid solutions, then is added drop-wise to Ca
(OH)2Suspension is prepared nanometer hydroxyapatite CS/HA composite.The chitosan of protonation is at Ca (OH)2Solution sinks
Analysis, H simultaneously3PO4With Ca (OH)2React, i.e. the two co-precipitation.Ining contrast to Brush Plating CS-HA coating, this method is utilizing
Particle aggregation can be produced during electro-deposition configuration plating solution.Particle aggregation just has pitting corrosion, during use on building-up process floating coat surface
Stress concentration can be produced and cause material processing technique difficulty, shorten service life.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. a bioactivity coatings, it is characterised in that described coating structure is matrix/CS-SrHA.
Bioactivity coatings the most according to claim 1, it is characterised in that described coating structure is Ti6A14V/ CS-
SrHA。
The preparation method of bioactivity coatings the most according to claim 1 and 2, it is characterised in that concrete steps include:
(1) homogeneous coprecipitation-hydro-thermal method prepares SrHA powder；
(2) configuration of CS-SrHA plating solution；
(3) matrix surface pretreatment；
(4) at matrix surface Brush Plating CS-SrHA plating solution；
(5) SBF simulated body fluid soaks.
4. according to the arbitrary described preparation method of claim 1-3, it is characterised in that described step (1) homogeneous coprecipitation-
Hydro-thermal method prepares SrHA powder, and concrete steps include:
A, by the Ca (NO of 94.4g-177.0g3)2·4H2Sr (the NO of O and 76.8g-144.0g3)2It is dissolved in 500ml deionized water
It is configured to mixed solution one；
B, by 46.0g-92.0gNH4H2PO4It is dissolved in 500ml deionized water and being sufficiently stirred for, obtain solution two, and solution two is existed
Being slowly dropped under magnetic agitation state in mixed solution one, obtain solution three, the described last mole ratio of solution three is (Ca+
Sr)/P=1.67；
C, the pH value utilizing 1:1 ammonia to regulate solution three are 9-10, after pH is stable, continue to stir under omnipotent magnetic stirrer
3-5h, then room temperature stands 12-24h, obtains solution four；
D, solution four is proceeded to hydrothermal treatment consists 5-10h in the autoclave of 120-150 DEG C, obtain solution five；
E, solution five standing poured out in D step be cooled to room temperature carry out sucking filtration, washing 2-3 time after, filtering residue puts into 100-120
Grind after being dried 24h in DEG C drying baker, then sieve, collect and finally give SrHA powder by the powder of 400 mesh sieves.
5., according to the arbitrary described preparation method of claim 1-4, it is characterized in that, joining of described step (2) CS-SrHA plating solution
Putting, concrete steps include:
A, measuring chitosan CS 36.5-94.5g, glacial acetic acid 10-15ml puts into mix and blend preparation in 200-350ml distilled water
Become mixed solution a；
B, take citric acid 30-60g, ammonium sulfate 20-40g, add 100-250ml distilled water and stir, by ammonia volume ratio 2:1
Solution regulation pH value be 2.2-2.5, be configured to compound complex agent；
C, taking 20-30ml boric acid solution as buffer agent, the compound complex agent adding the configuration of step b stirs, then will step
The mixed solution a of rapid a configuration is poured slowly into, and uniformly mixes to obtain solution b, and described boric acid solution mass concentration is 30%；
D, take 0.2-0.5g dodecyl sodium sulfate and pour mix homogeneously in the solution b that step c obtains into as surfactant,
Solution c；
E, to step d configuration solution c in add 24-40g sodium hypophosphite NaH2PO2Stir 5-15 minute, be subsequently adding
SrHA powder 80-150g, regulates pH after obtaining solution d, solution d cooling after being heated to 30-50 DEG C and continuing to stir 15-30min
Value is 3.7-6.9, obtains CS-SrHA plating solution；Chitosan mass fraction in CS-SrHA plating solution is 5%-10%, and SrHA is at CS-
Mass fraction in SrHA plating solution is that the pH value hydrochloric acid of 9%-16%, CS-SrHA plating solution is adjusted with the solution of ammonia volume ratio 2:1
Joint.
6., according to the arbitrary described preparation method of claim 1-5, it is characterized in that, described step (3) substrate pretreated, specifically
Step includes:
1. chemistry abatement processes: cleaned up by matrix deionized water, dries and is placed in platter, dip acetone with absorbent cotton
Behind wiping plating surface, then with deionized water rinsing, dry, to be plated；
2. electricity is clean processes:
The clean liquid of brush plating electricity on the matrix after chemistry abatement processes, brush-plating technique is: electrode just connects, brushing plating voltage 10-12V,
Brush plating time 20-40S, with relative velocity 6-24m/min unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
The clean liquid of electricity includes following components: sodium hydroxide 20-30g/L, tertiary sodium phosphate 40-60g/L, sodium carbonate 20-25g/L, acetic acid
0.2-0.5g/L, sodium hypophosphite 0.2-0.5g/L, sodium chloride 1.8-2.9g/L, surplus is water；The pH value of the clean liquid of electricity is 11-
13；
3. activation processing: first No. 2 activating solutions of brush plating, then brush plating 3 activation in step 2. matrix after electricity processes only
Liquid,
No. 2 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10-12V, brush plating time 20-40S, with relative velocity
6-24m/min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
No. 3 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10-12V, brush plating time 20-40S, with relative velocity
6-24m/min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating.
7. according to the arbitrary described preparation method of claim 1-6, it is characterized in that, described step (4) is at matrix surface brush
Plating CS-SrHA mixing plating solution, concrete steps include:
Brush plating CS-SrHA plating solution on the matrix after substrate pretreated, during brush plating, process conditions are that electrode just connects, and first use 16-
18V voltage launch as surprise attack brush plating 5-10S, and then under brushing plating voltage 11-14V, brush plating time more than 60S, with relative velocity 6m/min-
The unidirectional brush plating of 11m/min；Matrix distilled water after brush plating cleans.
8. according to the arbitrary described preparation method of claim 1-7, it is characterized in that, described matrix is Ti6A14V titanium alloy substrate.
9., according to the arbitrary described preparation method of claim 1-8, it is characterized in that, described step (5) SBF analogue body immersion
Bubble, concrete steps include:
SBF solution includes following component: NaCl 6.6674-6.6683g/1000ml, NaHCO3 2.2679-2.2682g/
1000ml、KCl 0.2235-0.2238g/1000ml、K2HPO4·3H2O 0.2281-0.2284g/1000ml、MgCl2·6H2O
0.3058-0.3061g/1000ml、CaCl2 0.2270-0.2273g/1000ml、Na2SO4 0.0709-0.0712g/
1000ml, surplus is water；
According to described consumption successively by NaCl, NaHCO3、KCl、K2HPO4·3H2O、MgCl2·6H2O、CaCl2、Na2SO4It is dissolved in
In deionized water, it is subsequently adding hydrochloric acid and trishydroxymethylaminomethane obtains solution Z, then the PH of the solution Z of configuration is adjusted to
7.4, finally coating is soaked 7 days in SBF simulated solution.
10. according to the arbitrary described preparation method of claim 1-9, it is characterized in that, described hydrochloric acid content in solution Z is
40ml/1000ml, described trishydroxymethylaminomethane content in solution Z is 6.057g/1000ml.
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Application publication date: 20160817 |