CN104195531A - Method for depositing bionic hydroxyapatite (HA) on zinc phosphate conversion coating surface - Google Patents
Method for depositing bionic hydroxyapatite (HA) on zinc phosphate conversion coating surface Download PDFInfo
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- CN104195531A CN104195531A CN201410433268.4A CN201410433268A CN104195531A CN 104195531 A CN104195531 A CN 104195531A CN 201410433268 A CN201410433268 A CN 201410433268A CN 104195531 A CN104195531 A CN 104195531A
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Abstract
The invention relates to a method for depositing bionic hydroxyapatite (HA) on a zinc phosphate conversion coating surface, which comprises the following steps: preparing a simulated body fluid, in which the solute concentrations are as follows: 8.035-16.07g/L sodium chloride, 0.355-0.71g/L sodium bicarbonate, 0.225-0.45g/L potassium chloride, 0.231-0.462g/L dipotassium hydrogen phosphate dihydrate, 0.311-0.622g/L magnesium chloride hexahydrate, 39-58.5mL/L 1mol/L hydrochloric acid, 0.292-0.584g/L calcium chloride and 0.072-0.144g/L sodium sulfate; and cleaning a stainless steel sample of which the surface is provided with the zinc phosphate chemical conversion coating, putting the cleaned sample into the simulated body fluid, putting in a 36-38 DEG C thermostatic water bath oscillator, immersing for 0.5-30 days, taking out, cleaning with deionized water, and drying to obtain the HA coating. The composite coating is beneficial to enhancing the corrosion resistance of the stainless steel implant, has excellent biological activity, and implements early healing and long-term stability of the stainless steel implant.
Description
Technical field
The present invention relates to a kind of method at zinc phosphate conversion film surface biomimetic deposited hydroxyl apatite, belong to bio-medical material surface modification field.
Background technology
Hydroxyapatite (HA) due to its good biocompatibility, biological activity, nontoxic, receive much concern with the advantage such as synosteosis is firm always.Bionical sedimentation is prepared hydroxyapatite and is had that technique is simple, cost is low, can on the matrix of out-of-shape and porous, form the advantages such as uniform coating has been widely used in multiple material.Zinc phosphate (Hopeite, H) is the principal crystalline phase of zinc phosphate bone cement, receives much concern because it has the active and bone formation performance of good biological.That zinc phosphate conversion film (HPCC) has is water insoluble, corrosion resistance and good, the surface modification of the advantage widespread use tool metallic substance such as firm of being combined with matrix, can play protection matrix, suppress harmful ion and discharge, give the effects such as matrix biological activity.Due to HA structurally with bone in inorganic salt more approaching, at HPCC surface deposition one deck, HA will further improve its biological activity and skeletonization effect.Due to the crystal grain of zine ion energy refinement HA, improve mechanical property; Zine ion adds the growth that can suppress HA crystal in HA, reduce degree of crystallinity, improve biological activity, so Zn-HA becomes study hotspot (Shundong Miao, Wenjian Weng, Kui Cheng, et al, Sol-gel preparation of Zn-doped fluoridated hydroxyapatite films, Surface and Coating Technology 198 (2005) 223-226).About HPCC surface biomimetic deposition HA, current only report is exactly at zinc phosphate surface electrical deposition HA coating (S.M.A.Shibli, A.C.Jayalekshmi, Development of phosphate inter layered hydroxyapatite coating for stainless steel implants, Applied Surface Science 254 (2008) 4103 – 4110), and have not been reported at the direct bionical deposition HA in HPCC surface by simulated body fluid (SBF) method.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency and a kind of method at zinc phosphate conversion film surface biomimetic deposited hydroxyl apatite is provided, the method is significant for the biological applications of stainless steel surface zinc phosphate conversion film.Promoter action by HPCC surface micro/nano-scale hole to deposition, utilizes the present invention can be directly at HPCC surface deposition HA, and whole preparation process is simple, pollution-free, cost is low.
The technical scheme that the present invention takes is:
In a method for zinc phosphate conversion film surface biomimetic deposited hydroxyl apatite, comprise that step is as follows:
(1) prepare zinc phosphate chemical conversion film at stainless steel surface;
(2) surface there is is the stainless steel sample of zinc phosphate chemical conversion film use respectively acetone, dehydrated alcohol and washed with de-ionized water totally for subsequent use;
(3) preparation simulated body fluid, wherein solute concentration is sodium-chlor 8.035-16.07g/L, sodium bicarbonate 0.355-0.71g/L, Repone K 0.225-0.45g/L, hydrogen phosphate dihydrate dipotassium 0.231-0.462g/L, magnesium chloride hexahydrate 0.311-0.622g/L, 1mol/L hydrochloric acid 39-58.5mL/L, calcium chloride 0.292-0.584g/L, sodium sulfate 0.072-0.144g/L;
(4) bionical deposition: the sample after step (2) is cleaned is put into simulated body fluid, puts into the water bath with thermostatic control vibrator of 36-38 DEG C, soaks after 0.5-30 days, and taking-up washed with de-ionized water, dries, and obtains hydroxyapatite HA rete.
The described stainless steel of step in above-mentioned preparation method (1) is preferably 316 stainless steels.
The method of preparing zinc phosphate chemical conversion film can be existing method, preferred following method:
(a) preparation conversion fluid: 25g/L zinc oxide, 30ml/L nitric acid, 15ml/L phosphoric acid, 5g/L nitrocalcite, 5g/L citric acid; And need to use 5g/L straight iron powder slaking conversion fluid 24h;
(b) first by stainless steel base at room temperature, carry out acid etching 10min with the phosphoric acid of 7wt%; Subsequently, at room temperature activate 30s with colloidal titanium; Finally, matrix is put into conversion fluid, at 75 DEG C, pH value is 2.75, and after chemical conversion 30min, water rinses and obtains zinc phosphate chemical conversion film.In the middle of each step, all fully clean with deionized water.
In the preparation of the simulated body fluid described in step in above-mentioned preparation method (3), prepare in strict accordance with ISO/FDIS 23317 standards.
In bionical deposition process described in step (4), required experiment container is Plastic Bottle; The volume of required simulated body fluid SBF and the surface-area (250mm of sample in experimentation
2) 1/10th ratio be 1:1-10, required concussion frequency is 60-100 time/min, needs every 24h to change a simulated body fluid SBF in bionical deposition process.
Beneficial effect of the present invention is:
(1) the HA coating that the present invention prepares, evenly fine and close, transform rete with zinc phosphate and be combined firmly; And HA surface presents porousness, pore distribution is comparatively even.The vesicular structure on HA surface will promote its surperficial process such as cell response and bone formation rate.
(2) after deposition HA, formed the compound coating of H/HA at stainless steel surface, this kind of compound coating is conducive to improve the corrosion resistance nature of stainless steel implant, effectively suppresses the corrosion of matrix and the stripping of harmful ion; There is good bioactive composite film, can promote osteogenesis, realize getting up early healing and the long-term stability of stainless steel implant.
(3) compound coating of H/HA has higher biological activity and corrosion resistance nature: the advantage of the zinc phosphate layer (H) of lower floor is to have higher corrosion resistance nature and higher bonding force, and stainless steel base is formed to protection; Zinc phosphate has good biological activity and bone formation performance.The HA layer biological activity on top layer is good, and the vesicular structure of nanostructure that its surface forms is conducive to adhesion and the propagation of cell.
(4) HPCC is completely different mutually from the thing of micro-arc oxidation films.The preparation of zinc phosphate conversion film and HA adopts simple simulated body fluid to soak, and depositing temperature is 37 ± 1 DEG C; On micro-arc oxidation films, depositing HA is to adopt hydro-thermal reaction method, and reaction conditions is 100-600 DEG C of Water Under thermal response 0.5-4.0h, and reaction medium is the HA suspension liquid of 0.025-100g/L.The advantage of zinc phosphate conversion film surface HA Film preparation is that method is simple, and the HA of deposition is in conjunction with good, and HA film surface has typical nanostructure, and this method is significant to the biological applications of zinc phosphate conversion film.
Brief description of the drawings
Fig. 1 is the field emission scanning electron microscope figure of the chemical conversion film prepared with reference to the embodiment of the present invention 1.
Fig. 2 is the field emission scanning electron microscope figure of the chemical conversion film prepared with reference to the embodiment of the present invention 2.
Embodiment:
Below in conjunction with embodiment, preparation method of the present invention is described further.
Embodiment 1
(1) prepare zinc phosphate chemical conversion film at stainless steel surface;
(2) clean: have the stainless steel sample of zinc phosphate chemical conversion film to use respectively acetone, dehydrated alcohol and washed with de-ionized water totally for subsequent use on surface;
(3) preparation SBF solution: sodium-chlor 12.0525g/L, sodium bicarbonate 0.5325g/L, Repone K 0.3375g/L, hydrogen phosphate dihydrate dipotassium 0.3465g/L, magnesium chloride hexahydrate 0.4665g/L, 1mol/L hydrochloric acid 58.5mL/L, calcium chloride 0.438g/L, sodium sulfate 0.108g/L;
(4) bionical deposition: the sample after cleaning is put into the simulated body fluid of 200mL, in the water bath with thermostatic control vibrator of 37 DEG C, soaked after 9 days, taking-up washed with de-ionized water, dries, and obtains HA rete.
Embodiment 2
(1) prepare zinc phosphate chemical conversion film at stainless steel surface;
(2) clean: have the stainless steel sample of zinc phosphate chemical conversion film to use respectively acetone, dehydrated alcohol and washed with de-ionized water totally for subsequent use on surface;
(3) preparation SBF solution: sodium-chlor 12.0525g/L, sodium bicarbonate 0.5325g/L, Repone K 0.3375g/L, hydrogen phosphate dihydrate dipotassium 0.3465g/L, magnesium chloride hexahydrate 0.4665g/L, 1mol/L hydrochloric acid 58.5mL/L, calcium chloride 0.438g/L, sodium sulfate 0.108g/L;
(4) bionical deposition: the sample after cleaning is put into the simulated body fluid of 25mL, in the water bath with thermostatic control vibrator of 37 DEG C, soaked after 15 days, taking-up washed with de-ionized water, dries, and obtains HA rete.
Embodiment 3
(1) prepare zinc phosphate chemical conversion film at stainless steel surface;
(2) clean: have the stainless steel sample of zinc phosphate chemical conversion film to use respectively acetone, dehydrated alcohol and washed with de-ionized water totally for subsequent use on surface;
(3) preparation SBF solution: sodium-chlor 8.035g/L, sodium bicarbonate 0.355g/L, Repone K 0.225g/L, hydrogen phosphate dihydrate dipotassium 0.231g/L, magnesium chloride hexahydrate 0.311g/L, 1mol/L hydrochloric acid 39mL/L, calcium chloride 0.292g/L, sodium sulfate 0.072g/L;
(4) bionical deposition: the sample after cleaning is put into the simulated body fluid of 25mL, in the water bath with thermostatic control vibrator of 37 DEG C, soaked after 7 days, taking-up washed with de-ionized water, dries, and obtains HA rete.
Claims (6)
1. in a method for zinc phosphate conversion film surface biomimetic deposited hydroxyl apatite, it is characterized in that, comprise that step is as follows:
(1) prepare zinc phosphate chemical conversion film at stainless steel surface;
(2) surface there is is the stainless steel sample of zinc phosphate chemical conversion film clean up for subsequent use;
(3) preparation simulated body fluid, wherein solute concentration is sodium-chlor 8.035-16.07g/L, sodium bicarbonate 0.355-0.71g/L, Repone K 0.225-0.45g/L, hydrogen phosphate dihydrate dipotassium 0.231-0.462g/L, magnesium chloride hexahydrate 0.311-0.622g/L, 1mol/L hydrochloric acid 39-58.5mL/L, calcium chloride 0.292-0.584g/L, sodium sulfate 0.072-0.144g/L;
(4) bionical deposition: the sample after step (2) is cleaned is put into simulated body fluid, puts into the water bath with thermostatic control vibrator of 36-38 DEG C, soaks after 0.5-30 days, and taking-up washed with de-ionized water, dries, and obtains hydroxyapatite HA rete.
2. a kind of method at zinc phosphate conversion film surface biomimetic deposited hydroxyl apatite according to claim 1, is characterized in that, described stainless steel is 316 stainless steels.
3. a kind of method at zinc phosphate conversion film surface biomimetic deposited hydroxyl apatite according to claim 1, is characterized in that, the method for preparing zinc phosphate chemical conversion film is:
(a) preparation conversion fluid: 25g/L zinc oxide, 30ml/L nitric acid, 15ml/L phosphoric acid, 5g/L nitrocalcite, 5g/L citric acid; And need to use 5g/L straight iron powder slaking conversion fluid 24h;
(b) first by stainless steel base at room temperature, carry out acid etching 10min with the phosphoric acid of 7wt%; Subsequently, at room temperature activate 30s with colloidal titanium; Finally, matrix is put into conversion fluid, at 75 DEG C, pH value is 2.75, and after chemical conversion 30min, water rinses and obtains zinc phosphate chemical conversion film.
4. a kind of method at zinc phosphate conversion film surface biomimetic deposited hydroxyl apatite according to claim 1, is characterized in that, 1/10th ratio of the volume of required simulated body fluid and the surface-area of sample is 1:1-10.
5. a kind of method at zinc phosphate conversion film surface biomimetic deposited hydroxyl apatite according to claim 1, is characterized in that, the required concussion frequency of step (4) is 60-100 time/min.
6. a kind of method at zinc phosphate conversion film surface biomimetic deposited hydroxyl apatite according to claim 1, is characterized in that, needs every 24h to change a simulated body fluid in bionical deposition process.
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Cited By (3)
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| WO2018188338A1 (en) * | 2017-04-14 | 2018-10-18 | 华南理工大学 | Whitlockite coating constructed on surface of calcium phosphate-based bioceramic substrate and preparation method therefor |
| CN110117784A (en) * | 2019-05-10 | 2019-08-13 | 山东大学 | A kind of preparation method of pure titanium surface hydroxyl apatite conversion film |
| CN113174592A (en) * | 2021-04-20 | 2021-07-27 | 北京科技大学 | Preparation and application of coating for improving biocompatibility of medical zinc/zinc alloy surface |
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| CN101417145A (en) * | 2008-12-04 | 2009-04-29 | 山东大学 | Bracket material for bone tissue engineer and preparation method thereof |
| CN103924226A (en) * | 2014-04-25 | 2014-07-16 | 山东大学 | Preparation method of zinc phosphate chemical conversion coating in hierarchical structure |
| CN103952745A (en) * | 2014-05-08 | 2014-07-30 | 山东大学苏州研究院 | Method for preparing zinc phosphate conversion coating on surface of titanium |
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| CN101417145A (en) * | 2008-12-04 | 2009-04-29 | 山东大学 | Bracket material for bone tissue engineer and preparation method thereof |
| CN103924226A (en) * | 2014-04-25 | 2014-07-16 | 山东大学 | Preparation method of zinc phosphate chemical conversion coating in hierarchical structure |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018188338A1 (en) * | 2017-04-14 | 2018-10-18 | 华南理工大学 | Whitlockite coating constructed on surface of calcium phosphate-based bioceramic substrate and preparation method therefor |
| US11389564B2 (en) | 2017-04-14 | 2022-07-19 | South China University Of Technology | Whitlockite coating constructed on surface of calcium phosphate-based bioceramic substrate and preparation method therefor |
| CN110117784A (en) * | 2019-05-10 | 2019-08-13 | 山东大学 | A kind of preparation method of pure titanium surface hydroxyl apatite conversion film |
| CN110117784B (en) * | 2019-05-10 | 2020-07-14 | 山东大学 | Preparation method of hydroxyapatite conversion film on surface of pure titanium |
| CN113174592A (en) * | 2021-04-20 | 2021-07-27 | 北京科技大学 | Preparation and application of coating for improving biocompatibility of medical zinc/zinc alloy surface |
| CN113174592B (en) * | 2021-04-20 | 2021-12-03 | 北京科技大学 | Preparation and application of coating for improving biocompatibility of medical zinc/zinc alloy surface |
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