CN104947097A - Method for preparing calcium hydrophosphate micro-nanofiber conversion coating on pure-titanium surface - Google Patents
Method for preparing calcium hydrophosphate micro-nanofiber conversion coating on pure-titanium surface Download PDFInfo
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Abstract
The invention relates to a method for preparing a calcium hydrophosphate micro-nanofiber conversion coating on a pure-titanium surface. A method that under the proper pH-value condition, a chemical conversion solution carries out chemical conversion treatment on the pure-titanium surface is adopted, and a chemical conversion solution is a solution composed of the proper amount of phosphoric acid, compounds containing calcium ions, zinc ions and dihydrogen phosphates, and an accelerant; and according to chemical conversion treatment, a pure-titanium sample obtained after proper activation treatment and surface adjustment is coupled with pure iron, then, ultrasonic field manufacturing and water bath heating are carried out, and the calcium hydrophosphate micro-nanofiber conversion coating on the pure-titanium surface is obtained. A phase of the conversion coating prepared on the pure-titanium surface through the method is a CaHPO4 2H2O crystal, and a crystal aggregate can induce and promote formation of hydroxyapatite (HA) in simulated body fluid; and the formed conversion coating is of a micro-nano fiber-shaped structure close to a human body multi-level micro-nano structure, and the method has the important significance in regulating and controlling cells, the tissue reaction and the like.
Description
Technical field
The present invention relates to a kind of preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film, belong to Surface Modification of Metallic Biomaterials technical field.
Background technology
Dicalcium phosphate dihydrate (CaHPO
42H
2o) because of close with organism calcified tissue chemical substance and be proved to be there is good biocompatibility, and it is nontoxic without immunological rejection, there is absorbability, in bone mineralisation process, play good Integrated implant effect, be widely used in the biomedical sector such as dentistry, surgical plastic.There are some researches prove and secondary calcium phosphate can be converted into hydroxyapatite (HA) by precipitation from homogeneous solution (PFHS) method, many investigators it can be used as the presoma forming HA rete.Pure titanium Young's modulus and bone photo closely, and have higher specific tenacity and corrosion resisting property, are widely used in Reparation and Reconstruction operation (as tumor resection, fracture, joint replacement, edentulous jaw etc.) as retainer.But titanium belongs to bio-inert material, for obtaining good implant Integrated implant, to titanium surface modify and modification be always research focus.Prepare one deck secondary calcium phosphate conversion film on pure titanium surface, and this rete possesses the structure similar or close with human body level micro-nano weave construction, to raising its biocompatibility and biological activity significant.
Discovery is consulted by lot of documents and data, the current research for the calcic cycling of elements film preparation of pure titanium surface is less both at home and abroad, have research at present at other metals as Mg and alloy surface thereof define secondary calcium phosphate conversion film by chemical conversion process, as document " H.Du, Z.Wei, H.Wang, E.Zhang, L.Zuo, L.Du, Surface microstructure and cell compatibility of calcium silicate and calcium phosphate composite coatings on Mg-Zn-Mn-Ca alloys for biomedical application, Colloids Suf.B:Biointerfaces 83 (2011) 96-102. " report one phosphoric acid, water glass, the phosphate solution of nitrocalcite mixed preparing prepares the method for the conversion film of phosphoric acid hydrogen calcium thing phase at Mg alloy surface, Mg alloy belongs to active metal, in film process Mg participate in chemical reaction compare be easy to transform.But titanium belongs to inert metal, and there is stable oxide film in surface, and in conversion process, Ti does not participate in reaction, therefore adopts general conversion fluid and method for transformation to be difficult to film forming.It is worth mentioning that patent CN103952745A discloses a kind of method preparing hot-dipping galvanized coating on titanium surface, but calcic conversion film is not mentioned, especially for the secondary calcium phosphate conversion film forming micro-nano-scale filamentary structure on pure titanium surface, the report of domestic and international data of literatures is not retrieved at present.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film, adopting ultrasonic field and heating in water bath booster action to obtain dominant is the conversion film of secondary calcium phosphate mutually, conversion film even compact, there is the micro nanometer fiber shape structure close with human body multi-layer micro-nano structure, CaHPO
42H
2o thing phase and micro-nano fiber structure significant for regulating cell and tissue reaction etc.
In order to achieve the above object, the technical scheme that the present invention takes is:
It is as follows that a kind of preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film comprises step:
(1) mix by phosphoric acid with containing calcium ion, zine ion, the compound of dihydrogen phosphate ions and promotor, obtain chemical conversion base soln;
(2) in above-mentioned chemical conversion base soln, add iron powder, slaking 12-24h at 20-25 DEG C, cross leaching supernatant liquor, i.e. slaking liquid;
(3) activation treatment and surface adjustment are carried out to pure Titanium base;
(4) matrix that step (3) obtains is put into slaking liquid, be carry out chemical conversion treatment under the condition of 5.00 in pH value, obtain secondary calcium phosphate micro nanometer fiber conversion film.
Preferably, in step (1), the feed composition of described chemical conversion base soln is: H
3pO
49-18g/L, Ca (H
2pO
4)
2h
2o 6-15g/L, Zn (H
2pO
4)
22H
2o 1-4g/L, NaNO
31-3g/L, NaNO
22-5g/L.
Preferably, in step (2), in often liter of chemical conversion base soln, the add-on of iron powder is 2-7g.
Preferably, the concrete steps of activation treatment described in step (3) and surface adjustment are: the HF solution (aqueous solution of hydrofluoric acid) the pure Titanium base of having polished being put into 2wt%, 15s is activated at 20 ~ 25 DEG C, with deionized water, the pure Titanium base after activation is rinsed for several times, the pure Titanium base rinsed is put into colloidal titanium solution (containing titanium phosphate colloidal solution), in 20 ~ 25 DEG C of lower surface adjustment 30s.
Preferably, slaking liquid pH value is regulated with phosphoric acid or sodium hydroxide solution in step (4).
Preferably, in step (4), the condition of described chemical conversion treatment is under 55-65 DEG C of condition, pure titanium sample is coupled with pure iron, after first acting on 5-15min in 250w ultrasonic field, then water-bath leaves standstill 15-30min, keeps treatment temp constant.
Pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film prepared by above-mentioned method.
Pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film prepared by the present invention can be used for preparing biomaterial.
The invention has the beneficial effects as follows:
(1) method of the present invention is utilized to be CaHPO mutually at the thing of the conversion film of pure titanium surface preparation
42H
2o crystal, this crystal aggregates can be induced and be promoted the formation of hydroxyapatite (HA) in simulated body fluid.
(2) conversion film utilizing method of the present invention to prepare has the micro nanometer fiber shape structure close with human body multi-layer micro-nano structure, significant for regulating cell and tissue reaction etc.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of pure titanium surface phosphoric acid hydrogen calcium chemical conversion film prepared by reference the present invention.
Fig. 2 is the field emission scanning electron microscope image of pure titanium surface micronano threadiness secondary calcium phosphate chemical conversion film prepared by reference the present invention.
Embodiment
For making the present invention become apparent, hereby with a preferred embodiment, and accompanying drawing is coordinated to be described in detail below.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
The preparation method of a kind of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film described in the present embodiment, its concrete steps are as follows:
(1) by 85wt%H
3pO
47ml/L, Ca (H
2pO
4)
2h
2o 8g/L, Zn (H
2pO
4)
22H
2o 1.55g/L, NaNO
32g/L, NaNO
22g/L mixes successively, is mixed with chemical conversion solution.
(2) reduced iron powder 5g/L is joined in chemical conversion solution, leave standstill slaking 16h at ambient temperature, cross leaching supernatant liquor.
(3) H is used
3pO
4the pH value regulating chemical conversion base soln with NaOH is 5.00.
(4) the pure Titanium base of having polished is put into the HF solution of 2wt%, 15s is activated under room temperature condition, with deionized water, the pure Titanium base after activation is rinsed for several times, the pure Titanium base rinsed is put into colloidal titanium solution (containing titanium phosphate colloidal solution), room temperature condition lower surface adjustment 30s.
(5) the pure titanium sample processed through step (4) is coupled with pure iron, first in 250w ultrasonic field, acts on 15min, leave standstill chemical conversion 15min afterwards, keep invert point to be 55 DEG C.
(6) step (5) products therefrom flowing water is rinsed 5min, dry under room temperature, obtain pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film.
Embodiment 2
The preparation method of a kind of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film described in the present embodiment, its concrete steps are as follows:
(1) by 85wt%H
3pO
48ml/L, Ca (H
2pO
4)
2h
2o 9g/L, Zn (H
2pO
4)
22H
2o 2g/L, NaNO
32.5g/L, NaNO
22.5g/L mixes successively, is mixed with chemical conversion solution.
(2) reduced iron powder 6g/L is joined in chemical conversion solution, leave standstill slaking 18h at ambient temperature, cross leaching supernatant liquor.
(3) H is used
3pO
4the pH value regulating chemical conversion base soln with NaOH is 5.00.
(4) the pure Titanium base of having polished is put into the HF solution of 2wt%, 15s is activated under room temperature condition, with deionized water, the pure Titanium base after activation is rinsed for several times, the pure Titanium base rinsed is put into colloidal titanium solution (containing titanium phosphate colloidal solution), room temperature condition lower surface adjustment 30s.
(5) the pure titanium sample processed through step (4) is coupled with pure iron, first in 250w ultrasonic field, acts on 10min, leave standstill chemical conversion 20min afterwards, keep invert point to be 60 DEG C.
(6) step (5) products therefrom flowing water is rinsed 5min, dry under room temperature, obtain pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film.
Embodiment 3
(1) by 85wt%H
3pO
410ml/L, Ca (H
2pO
4)
2h
2o 15g/L, Zn (H
2pO
4)
22H
2o 4g/L, NaNO
33g/L, NaNO
24g/L mixes successively, is mixed with chemical conversion solution.
(2) reduced iron powder 7g/L is joined in chemical conversion solution, leave standstill slaking 24h at ambient temperature, cross leaching supernatant liquor.
(3) H is used
3pO
4the pH value regulating chemical conversion base soln with NaOH is 5.00.
(4) the pure Titanium base of having polished is put into the HF solution of 2wt%, 15s is activated under room temperature condition, with deionized water, the pure Titanium base after activation is rinsed for several times, the pure Titanium base rinsed is put into colloidal titanium solution (containing titanium phosphate colloidal solution), room temperature condition lower surface adjustment 30s.
(5) the pure titanium sample processed through step (4) is coupled with pure iron, first in 250w ultrasonic field, acts on 20min, leave standstill chemical conversion 20min afterwards, keep invert point to be 65 DEG C.
(6) step (5) products therefrom flowing water is rinsed 5min, dry under room temperature, obtain pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (8)
1. a preparation method for pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film, is characterized in that, comprise step as follows:
(1) mix by phosphoric acid with containing calcium ion, zine ion, the compound of dihydrogen phosphate ions and promotor, obtain chemical conversion base soln;
(2) in above-mentioned chemical conversion base soln, add iron powder, slaking 12-24h at 20-25 DEG C, cross leaching supernatant liquor, i.e. slaking liquid;
(3) activation treatment and surface adjustment are carried out to pure Titanium base;
(4) matrix that step (3) obtains is put into slaking liquid, be carry out chemical conversion treatment under the condition of 5.00 in pH value, obtain secondary calcium phosphate micro nanometer fiber conversion film.
2. the preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film as claimed in claim 1, it is characterized in that, in step (1), the feed composition of described chemical conversion base soln is: H
3pO
49-18g/L, Ca (H
2pO
4)
2h
2o 6-15g/L, Zn (H
2pO
4)
22H
2o 1-4g/L, NaNO
31-3g/L, NaNO
22-5g/L.
3. the preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film as claimed in claim 1, it is characterized in that, in step (2), in often liter of chemical conversion base soln, the add-on of iron powder is 2-7g.
4. the preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film as claimed in claim 1, it is characterized in that, the concrete steps of activation treatment described in step (3) and surface adjustment are: the HF solution pure Titanium base of having polished being put into 2wt%, 15s is activated at 20 ~ 25 DEG C, with deionized water, the pure Titanium base after activation is rinsed for several times, the pure Titanium base rinsed is put into colloidal titanium solution, in 20 ~ 25 DEG C of lower surface adjustment 30s.
5. the preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film as claimed in claim 1, is characterized in that, regulates slaking liquid pH value in step (4) with phosphoric acid or sodium hydroxide solution.
6. the preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film as claimed in claim 1, it is characterized in that, in step (4), the condition of described chemical conversion treatment is under 55-65 DEG C of condition, pure titanium sample is coupled with pure iron, first in 250w ultrasonic field, act on 5-15min, then water-bath leaves standstill 15-30min, keep treatment temp constant.
7. pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film prepared by the method as described in claim 1-6.
8. pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film according to claim 7 is preparing the application in biomaterial.
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| CN106498397A (en) * | 2016-11-16 | 2017-03-15 | 中国科学院深圳先进技术研究院 | A kind of method in titanio implant surface in-situ construction multi-stage nano topological structure that is lost based on salt |
| CN106521466A (en) * | 2016-09-18 | 2017-03-22 | 山东大学 | Preparation method for inducing titanium or titanium alloy surface chemical conversion film by virtue of electric coupling |
| CN106620852A (en) * | 2016-10-09 | 2017-05-10 | 江苏科技大学 | Method for preparing dicalicium phosphate anhydrous (DCPA) bioceramic coating on surface of pure titanium |
| CN107338425A (en) * | 2017-06-22 | 2017-11-10 | 山东大学苏州研究院 | A kind of preparation method of the titanium surface bioactivity conversion film of phosphate containing strontium |
| 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 |
| CN110158020A (en) * | 2019-04-09 | 2019-08-23 | 山东大学 | A kind of method of ultrasonic wave added induction heating preparation nanostructure oxidation film |
| CN110770368A (en) * | 2017-06-22 | 2020-02-07 | 日本帕卡濑精株式会社 | Magnesium-containing metal material with film |
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| CN105568272A (en) * | 2015-12-18 | 2016-05-11 | 山东大学 | Method for regulating and controlling physical phases of zinc and calcium conversion films on pure-titanium surfaces by aid of pH (potential of hydrogen) value |
| CN111926316A (en) * | 2015-12-25 | 2020-11-13 | 日本帕卡濑精株式会社 | Surface conditioner, magnesium material or magnesium alloy material with coating film, and method for producing same |
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| CN111926316B (en) * | 2015-12-25 | 2022-03-01 | 日本帕卡濑精株式会社 | Surface conditioner, magnesium material or magnesium alloy material with coating film, and method for producing same |
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| CN106620852A (en) * | 2016-10-09 | 2017-05-10 | 江苏科技大学 | Method for preparing dicalicium phosphate anhydrous (DCPA) bioceramic coating on surface of pure titanium |
| CN106498397B (en) * | 2016-11-16 | 2019-04-09 | 中国科学院深圳先进技术研究院 | A method of based on salt erosion in titanium-based implant surface in-situ construction multi-stage nano topological structure |
| CN106498397A (en) * | 2016-11-16 | 2017-03-15 | 中国科学院深圳先进技术研究院 | A kind of method in titanio implant surface in-situ construction multi-stage nano topological structure that is lost based on salt |
| CN110770368A (en) * | 2017-06-22 | 2020-02-07 | 日本帕卡濑精株式会社 | Magnesium-containing metal material with film |
| CN107338425A (en) * | 2017-06-22 | 2017-11-10 | 山东大学苏州研究院 | A kind of preparation method of the titanium surface bioactivity conversion film of phosphate containing strontium |
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| CN110117784B (en) * | 2019-05-10 | 2020-07-14 | 山东大学 | Preparation method of hydroxyapatite conversion film on surface of pure titanium |
| 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 |
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