CN1128251C - Bioactive composite Ca-P ceramics/chitosan film on metal surface and electrochemical co-deposition process for preparing it - Google Patents
Bioactive composite Ca-P ceramics/chitosan film on metal surface and electrochemical co-deposition process for preparing it Download PDFInfo
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- CN1128251C CN1128251C CN 00134909 CN00134909A CN1128251C CN 1128251 C CN1128251 C CN 1128251C CN 00134909 CN00134909 CN 00134909 CN 00134909 A CN00134909 A CN 00134909A CN 1128251 C CN1128251 C CN 1128251C
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Abstract
The present invention relates to a method for preparing a complex film layer on the surface of a metal material by an electrochemical deposition method. An electrodeposition solution comprises the components of 0.01 to 0.15 mol/L of Ca (NO3)2, 0.01 to 0.05 mol/L of NH4H2PO4 and 1% to 10% of chitosan solution. The pH value of the solution is from 3.1 to 5.2; the method has the electrodeposition condition that the constant voltage is from 1 to 20V or the constant current is from 1 to 10mA; the temperature is from 30 to 60 DEG C; the deposition time is from 0.1 to 10h. Chitosan is led in calcium and phosphorus ceramics coated on the surface of a metal substrate, which makes the surface of the ceramic complex film layer on the surface of the metal have favorable biocompatibility, favorable bioactivity and favorable biodegradability. The ceramic crystal surface has the advantages of preferred orientation, high degree of crystallization and compact structure. The binding force of the complex film layer and the metal substrate reaches 2.60mpa, which meets the clinical requirement.
Description
The present invention relates to a kind of method that is equipped with high-performance lifestyle medical material with the electrochemical co-deposition legal system.
In recent years, prepare artificial bone-grafting material at titanium-based metal surface-coated Ca-P ceramic coat, owing to have suitable base material mechanical property and good coating biology consistency simultaneously, and receive much attention.Developed multiple method at medical metal surface-coated bioactive ceramic coating, as plasma spraying method, (Wang Yulin etc. such as electrophoretic deposition and electrochemical deposition method, electroplate and finish, 1998,20: 20) at present the most frequently used be to adopt plasma spraying method to apply the Ca-P ceramic coating in the metallic surface, but the high temperature (instantaneous temperature can reach 6000～10000 ℃) of plasma in spraying process can cause hydroxyapatite that serious phase transformation takes place, decompose or be full of cracks, be difficult to obtain and natural bone hydroxyapatite composition, the coat of structural similitude (M Weinlaender, J.mater.Sci.Mater.Med.1992,3:138).Studies show that: the biocompatibility and the biological activity that make hydroxyapatite coating layer with conventional plasma spraying method obviously reduce.Electrochemical deposition method has the preparation condition gentleness, and control is convenient, can obtain the advantage of hydroxyapatite coating layer close with people's osseous tissue on Chemical Composition and crystalline structure.Electrochemical deposition method also can prepare the implant of complex contour, and is more superior than the plasma spraying method of orthoscopic.Yet the ceramic coating with the electrodip process preparation is the calcium phosphor coating at present, and the bonding force of its ceramic coating itself and coating and metal base is relatively poor, thereby has restricted its development for the biological and medicinal implant material of clinical application.
Purpose of the present invention aims to provide that a kind of to be used in metallic surface preparation strong with the bonding force of metal base, and has the electric depositing solution and the electrochemical co-deposition preparation method thereof of the Ca-P ceramics/chitosan composite film of good biological property and mechanical property.
The present invention is said, and to be used in the component that the metallic surface prepares the electric depositing solution of Ca-P ceramics/chitosan composite film be 0.01～0.15mol/L Ca (NO
3)
2, 0.01～0.05mol/L NH
4H
2PO
4And chitosan solution, the solution pH value is 3.1～5.2, chitosan solution accounts for 1%～10% of electric depositing solution total amount.
Said electrochemical co-deposition preparation method is as follows: at first prepare electric depositing solution, with Ca (NO
3)
2And NH
4H
2PO
4Solution mixes the back and adds deionized water, is mixed with to contain Ca (NO
3)
20.01～0.15mol/L, NH
4H
2PO
40.01 the electrolytic solution of～0.05mol/L, regulating electrolyte PH value is 3.1～5.2, adds in electrolytic solution that to account for the electric depositing solution total amount be 1%～10% chitosan.With metal base material surface mechanical grinding, and clean up, with the metal base material is negative electrode, platinum electrode is an anode, adds electric depositing solution, heating, carry out constant voltage or continuous current cathode electrodeposition, its electrochemical deposition condition is constant voltage 1～20V or continuous current 1～10mA, 30～60 ℃ of temperature, depositing time 0.1～10h.
The present invention is at artificial bone-grafting material---and the metallic surface applies and adds natural organic high-molecular chitosan (CTS) in the Ca-P ceramic coat, and its molecular formula is
Chitosan (CTS) is the derivative of chitin, can biological degradation, and no immune response, nontoxic to human body, be a kind of ideal biomaterial for medical purpose.The introducing of chitosan can make ceramic composite membrane surface, metallic surface have good biocompatibility, biological activity and biological degradability.By scanning electronic microscope (SEM), X-ray diffraction (XRD), infrared spectra (FTIR) diffuse-reflectance, x-ray photoelectron spectroscopies (XPS) etc. are to the surface topography of deposition layer, The Nomenclature Composition and Structure of Complexes etc. characterize, proof galvanic deposit pottery crystal face has certain preferred orientation, the degree of crystallinity height of settled layer, crystalline structure is the overlapping ordered arrangement of multi-disc, structure is tight, adopt bonding---the bonding force of stretching experiment measuring composite film and metal base, its bonding force reaches 2.60MPa, improve about 4 times than single Ca-P ceramic electrochemical deposition coating's adhesion, satisfied the mechanics requirement of clinical application substantially.
Fig. 1 is 100 * SEM shape appearance figure of Ca-P ceramics/chitosan composite film.
Fig. 2 is 1000 * SEM shape appearance figure of Ca-P ceramics/chitosan composite film.
Fig. 3 is 3000 * SEM shape appearance figure of Ca-P ceramics/chitosan composite film.
Fig. 4 is the SEM shape appearance figure of simple Ca-P ceramic coat.
Fig. 5 is the XRD diffraction spectrogram.
Fig. 6 is XPS spectrum figure.
The invention will be further described below in conjunction with embodiment.
Embodiment 1: with Ca (NO
3)
2And NH
4H
2PO
4Solution adds the electrolytic solution that ionized water is assigned to 50mL, Ca (NO in the electrolytic solution after mixing
3)
2Concentration is 0.045mol/L, NH
4H
2PO
4Be 0.025mol/L, at room temperature regulating electrolyte PH value with dilute ammonia solution is 3.5, adds the chitosan solution of 2.5mL then in electrolytic solution; With the substrate material surface mechanical grinding of titanium base alloy and clean up, with the titanium base alloy negative electrode, platinum electrode is an anode, adds the above-mentioned electric depositing solution for preparing, constant potential 2.5V is in 30 ℃ of deposit 1h.
With Ca-P ceramics/chitosan composite film and the common Ca-P ceramic comparative analysis of X-ray diffraction (XRD) to obtaining, from the XRD diffraction spectrogram of Fig. 5, can observe the variation of adding chitosan and not adding the deposition layer structure of chitosan, spectral line 2 is not for adding the general calcium phosphorus deposition layer of chitosan among the figure, its major ingredient is the secondary calcium phosphate (DCPD) that contains two crystal water, its peak is strong, and data are compared that certain difference is arranged with standard powder XRD (spectral line 3), illustrate that the ceramic crystal face of galvanic deposit has certain preferred orientation.The position of the diffraction peak of the deposition layer behind the adding chitosan does not change (seeing spectral line 1), but great changes have taken place by force at the relative peak of diffraction peak, especially ° peak of locating is extremely strong in 2 θ=11.7, and this is because the steric hindrance and the inducing action of chitosan on the surface makes DCPD on (020) crystal face tangible preferred orientation be arranged.
Fig. 1～3 are the typical Electronic Speculum pattern of the settled layer different multiples behind the interpolation chitosan, and settled layer is a veiny pattern as seen from the figure, and the degree of crystallinity of settled layer is very high, and its crystal is multilayer chip, and structure is tight between layer and the layer.Can obtain the good vesicular settled layer of crystalline structure by cathode electrodeposition, from biomedical angle, the cell texture that this crystalline structure is good is highly beneficial to the biological activity and the biocompatibility that improve Ca-P ceramic, the settled layer specific surface area is bigger, helps forming large-area synosteosis interface and strong chemical action as embedded material and tissue.The good crystalline structure in surface also helps and promotes interface osteogenic induction effect.And the crystal of the Ca-P ceramic settled layer that simple calcium phosphorus solution obtains is the random (see figure 4) of piling up of monolithic, and is loosely organized.
Fig. 6 is for adding the detected settled layer of chitosan front and rear surfaces power spectrum (XPS) surface N change in concentration, spectral line 1 is for adding the Ca-P ceramic composite film of chitosan, spectral line 2 is not for adding the Ca-P ceramic layer of chitosan, atlas analysis shows, after adding chitosan, at the 398.3ev place, the peak of N1s obviously strengthens, have chitosan in the proof settled layer, chitosan may form organic/inorganic hybrid settled layer with calcium phosphorous compound.
In addition, having adopted bonding---stretching experiment is tested the bonding force of metal base and Ca-P ceramic, uses A-B to consolidate epoxy resin glue bonding sample surface and metal stretching piece soon, after the completely solidified, measures the shearing pulling force of settled layer and substrate with drawing machine.The result shows, with the Ca-P ceramics/chitosan composite film that the electrochemical co-deposition legal system is equipped with, mechanical property is obviously improved, and settled layer has increased about 4 times with the bonding force of substrate than simple Ca-P ceramic coating, reach 2.60MPa, satisfy the mechanics requirement of clinical application substantially.Following table is the experimental data of coating/substrate caking power:
| Sample | Cohesive force (MPa) | The cracking position |
| Calcium phosphorus settled layer | 0.66 | Coating-titanium plate |
| Calcium phosphorus settled layer+(CTS) | 2.60 | Coating-titanium plate |
Embodiment 2: Ca (NO in the electric depositing solution of preparation
3)
2Concentration be 0.01mol/L, NH
4H
2PO
4Be 0.05mol/L, pH value 4.8, chitosan content are 2%, and electrodeposition condition is continuous current 2mA, 45 ℃ of temperature, depositing time 0.5h.All the other are with embodiment 1.
Embodiment 3: with embodiment 1, only change Ca (NO in the electric depositing solution
3)
2Concentration be 0.15mol/L, NH
4H
2PO
4Be 0.01mol/L, pH value 5.2, chitosan content are 10%, and electrodeposition condition is continuous current 5mA, 60 ℃ of depositing temperatures, depositing time 2h.
Claims (5)
1, electric depositing solution is characterized in that its component is 0.01～0.15mol/L Ca (NO
3)
2, 0.01～0.15mol/L5mol/LNH
4H
2PO
4And chitosan, chitosan solution accounts for 1%～10% of electric depositing solution total amount, and the pH value of solution is 3.1～5.2.
2, electric depositing solution as claimed in claim 1 is used for preparing in the metallic surface bioactive composite Ca-P ceramics/chitosan film layer.
3, the preparation method of bioactive composite Ca-P ceramics/chitosan film on metal surface layer is characterized in that at first preparing electric depositing solution, with Ca (NO
3)
2And NH
4H
2PO
4Solution mixes the back and adds deionized water, is mixed with to contain Ca (NO
3)
20.01～0.15mol/L, NH
4H
2PO
40.01 the electrolytic solution of～0.05mol/L, regulating electrolyte PH value is 3.1～5.2, adds in electrolytic solution that to account for the electric depositing solution total amount be 1%～10% chitosan; With metal base material surface mechanical grinding, clean up, with the metal base material negative electrode, platinum electrode is an anode, adds people's electric depositing solution, in 30～60 ℃, constant voltage 1～20V or continuous current 1～10mA carry out cathode electrodeposition, depositing time 0.1～10h.
4, the preparation method of bioactive composite Ca-P ceramics/chitosan film on metal surface layer as claimed in claim 3 is characterized in that the pH value of electrolytic solution is regulated with dilute ammonia solution under room temperature.
5, the preparation method of bioactive composite Ca-P ceramics/chitosan film on metal surface layer as claimed in claim 3 is characterized in that said metal base material is a titanium base alloy.
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|---|---|---|---|
| CN 00134909 CN1128251C (en) | 2000-12-07 | 2000-12-07 | Bioactive composite Ca-P ceramics/chitosan film on metal surface and electrochemical co-deposition process for preparing it |
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|---|---|---|---|
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| CN1128251C true CN1128251C (en) | 2003-11-19 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2002246785A1 (en) * | 2000-12-28 | 2002-08-06 | The Board Of Regents Of The University Of Nebraska | Electrolytic deposition of coatings for prosthetic metals and alloys |
| CN100391557C (en) * | 2003-12-16 | 2008-06-04 | 四川大学 | Biological active material for realizing percutaneous device biological sealing and method for making same |
| CN100383291C (en) * | 2005-01-21 | 2008-04-23 | 四川大学 | Surface activating method of medical metal material |
| CN101352583B (en) * | 2007-07-29 | 2012-03-14 | 山东硅苑新材料科技股份有限公司 | Stephanoporate calcium polyphosphate biological ceramic and preparation method thereof |
| CN101196487B (en) * | 2007-12-25 | 2010-09-08 | 浙江大学 | Method for producing modified electrode by electro-deposition chitosan-ionic liquid-enzyme compound film |
| CN103614756B (en) * | 2013-11-15 | 2015-10-21 | 武汉大学 | A kind of preparation method of hollow multilayer aquagel |
| CN104862757B (en) * | 2015-05-06 | 2017-05-24 | 厦门大学 | Metal surface treatment method based on chitosan and mussel adhesion protein composite membrane |
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