CN100473422C - Preparation method of nanometer ordered structure biomaterial membranous layer based on super hydro philic/hydro phobic characteristic template - Google Patents
Preparation method of nanometer ordered structure biomaterial membranous layer based on super hydro philic/hydro phobic characteristic template Download PDFInfo
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Abstract
A process for preparing a biologic membrane layer with ordered nanostructure and based on the superhydrophilic/superhydrophobic template includes such steps as electrochemically anodizing on Ti-based material to obtain an ordered TiO2 nanotube array membrane, modifying by FsA-13 to obtain superhydrophobic TiO2 nanotube array membrane, covering with mask, ultraviolet irradiating to obtain a superhydrophiclic pattern, and cathode electrochemical deposition or electrophoretic directional deposition to form a surficial nano-CaP ceramic layer.
Description
Technical field
The present invention relates to the super parent of a kind of utilization/superhydrophobic characteristic template, the method by electrochemical deposition or electrophoretic deposition is in the structurally ordered nano meter biomaterial of the medical metal controlled preparation in surface (calcium phosphorous compound, CaP) new method of rete.
Background technology
Natural bone is the orderly composite of nano-micrometer structure height that is made of by self assembly calcium microcosmic salt and collagen protein, and artificial bio-membrane's material that preparation has the natural bone performance is the target of people's unremitting effort.Traditional bone alternate material can recover the partial function of bone as metal, pottery, medical high polymer.Always there are different shortcoming and defect in single medical metal material or bioceramic material.Biocompatibility and biological activity as metal material are relatively poor, and the ceramic material mechanical property is difficult to meet the demands, so traditional material generally is difficult to satisfy the actual requirement of artificial bone implant.In order to develop the bone alternate material of excellent performance of new generation, people simulate the structure and composition of skeleton, and different homogenous materials is compound, and material advantage separately is integrated in one.The titanio surface is carried out after certain surface oxidation and chemical etching handle, and the titanium surface roughening can be realized the mechanical interlocked of calcium phosphorous compound coating and metallic substrates, and the mechanics that improves coating distributes, and strengthens the adhesion of calcium phosphorous compound coating and substrate.Periodically discontinuous calcium microcosmic salt rete not only can reduce because residual stress and the crackle that the difference of contraction and thermal expansion causes, increase the adhesion of rete and matrix, and can be by the chemical constituent and the structure Design of coating, strengthen the interaction of cell and calcium microcosmic salt rete, improve the biological property and the mechanical property of biomaterial.Electrochemical deposition technique is a kind of nonlinear process, can avoid technical problem such as residual stress and crackle in crystalline phase destruction that traditional high temperature deposition technology may cause, decomposition, the coating.Electrochemical techniques mainly comprise electrochemical deposition technique, the compound codeposition technique of electrochemistry and electrophoretic techniques etc.The electrochemical deposition of calcium microcosmic salt rete is not the electrocrystallization process of traditional concept, but is containing Ca
2+And H
2PO
4 -Solution in, by control cathode reaction, regulate the electrode interface proper pH value, deposit calcium microcosmic salt bioactive ceramics rete at electrode surface.Electrophoretic deposition is charged particle formation of deposits coating at electrode surface under certain DC electric field effect, is the combination of charged particle electrophoresis and two processes of deposition.Electrochemical deposition prepares organic and inorganic composite type biological coating material has remarkable advantages, but still can't really realize the orderly nano-micrometer composite of structure height of the similar natural bone of controlled preparation.
Summary of the invention
The present invention aims to provide a kind of template based on super parent/superhydrophobic characteristic, and the accurate controlled preparation of the nano-micrometer biological composite coating material of implementation structure high-sequential obtains the artificial bone bionic coating material of biocompatibility and biological activity excellence thus.
The said preparation method of the present invention is as follows:
1) with the substrate surface pretreatment, said substrate is titanium or titanium alloy;
2) electrochemical anodic oxidation is carried out in substrate, electrolyte is 0.1～2wt%HF, and preparation voltage is 5～50V, and temperature is 0～25 ℃, and the time is 10～240 minutes, can obtain the nano ordered TiO of one deck at substrate surface
2The nano-tube array rete;
3) sample that step 2 the is obtained FSA-13 methanol solution that is immersed in 0.5～2wt% took out after 1～3 hour, obtained super-hydrophobic TiO down in dry 1～4 hour at 120～160 ℃
2The nano-tube array rete;
4) at the TiO of super-hydrophobicization
2Cover photomask on the nano-tube array rete, through irradiation under ultraviolet ray 5～150 minutes, can substrate surface obtain pattern dimension and pattern and photomask on all four super thin-super hydrophilic pattern;
5) surface that step 3) is obtained have super thin-sample of super hydrophilic pattern carries out cathodic electrochemical deposition, containing 1.05～4.2 * 10
-2Mol [Ca
2+] and 0.625～2.5 * 10
-2Mol [PO
4 3-] calcium microcosmic salt solution in deposit 0.5～30 minute, can obtain to have nano ordered calcium microcosmic salt (CaP) rete with the on all four little pattern of photomask at sample surfaces;
Or with the surface that step 3) obtains have super thin-sample of super hydrophilic pattern carries out the ability cathode electrophoresis deposition, deposit solution is the nanometer hydroxyapatite (Ca that contains 1～10 grams per liter concentration
10(PO
4) (OH)
2, HA) particulate anhydrous organic solvent, control voltage is 5～50V, sedimentation time is 5～300 seconds, promptly obtains to have hydroxyapatite nano rete with the on all four little pattern of photomask at sample surfaces.
In step 1), said surface preparation is to the substrate surface mechanical grinding.
In step 4), said organic solvent is dehydrated alcohol, butanols, amylalcohol etc.
The present invention constructs the structurally ordered nano-calcium-phosphor ceramic coating with special surface pattern and high bioactivity by electrochemistry or electrophoresis orientated deposition on the medical metal surface, and by the orientated deposition of this highly active nano ordered Ca-P ceramic of control at ad-hoc location, the accurate preparation of the little pattern rete of implementation structure ordered nano Ca-P ceramic.Because calcium microcosmic salt crystallite dimension is a nanoscale, and sedimentary calcium microcosmic salt periodic patterns is a micro-meter scale, typically receive-composite film of little secondary structure thereby constitute, to help forming large-area synosteosis interface and strong chemical action power as embedded material and tissue.The present invention can realize the accurate controlled preparation of the composite that the nano-micrometer structure height is orderly, to the orderly composite biological material of design preparation nano-micrometer structure height, provides the high bioactivity bone alternate material of excellent performance to have important potential application foreground.
Description of drawings
The optical microscope photograph of super thin-super hydrophilic membrane that Fig. 1 prepares for embodiment 1 (Nikon, Eclipse ME 600).Scale is 100 μ m among the figure.
Fig. 2 for super thin-the fluorescence microscope photo of super hydrophilic membrane (Motic, AE31).Scale is 100 μ m among Fig. 2.
Fig. 3 for super thin-the optical microscope figure of the super hydrophilic pattern little pattern of calcium microcosmic salt rete that to be template prepare by electrochemical deposition method.
Fig. 4 is the SEM image (a is 500 times, and b is 5000 times) of the little pattern of calcium microcosmic salt rete under Fig. 3 different amplification.
The XRD spectra that Fig. 5 scrapes the back powder for electrochemical deposition calcium microcosmic salt coating and coating relatively (Panalytical X ' pert, Philips).In Fig. 5, abscissa is 2Theta (deg), and spectral line is respectively a, b, and c is labeled as 010 on the spectral line b, and from left to right labelling is respectively 002,241,0.32,260,1.42 on the spectral line c, and T 070, T, T, T represents metallic titanium matrix.
Fig. 6 for super thin-the optical microscope figure of the super hydrophilic pattern little pattern of hydroxyapatite nanoparticle that to be template prepare by electrophoretic deposition.
Fig. 7 is the SEM image (a is 400 times, and b is 10000 times) under Fig. 6 different amplification.
Fig. 8 is a coating XRD spectra under the electrophoretic deposition different time.In Fig. 8, abscissa is 2 Theta (deg), vertical coordinate is intersity (a.u.), and T represents metallic titanium matrix, and represents hydroxyapatite standard spectrogram, electrophoretic deposition time are 15 seconds, 30 seconds and obtained the XRD spectra of rete in 60 seconds respectively for curve a, b, c and d.From left to right labelling is respectively (002), (102), (210), (211), (112), (300), (202), T, T, T, (222), (213) on the curve d.
The specific embodiment
Following examples will the present invention is further illustrated in conjunction with the accompanying drawings.
Embodiment 1: base material adopts the pure titanium plate of 15mm * 20mm * 2mm.Titanium plate surface is after sand papering, and ultrasonic cleaning 10 minutes in acetone, ethanol and three water is successively taken out the back and washed with three water, and airing is stand-by.At ambient temperature, electrochemical anodic oxidation is carried out in substrate, electrolyte is 0.5wt%HF, and preparation voltage is 20V, and the time is 20 minutes, promptly obtains the nano ordered TiO of one deck at substrate surface
2The nano-tube array rete.The FSA-13 methanol solution that sample after the anodic oxidation is immersed in 1wt% took out after 1 hour, obtained super-hydrophobic TiO down in dry 1 hour at 140 ℃
2The nano-tube array rete.At super-hydrophobic TiO
2Cover photomask on the nano-tube array rete, through irradiation under ultraviolet ray 60 minutes, can film surface obtain pattern dimension and pattern with photomask on all four super thin-super hydrophilic pattern.Brighter border circular areas is the super hydrophilic area that ultraviolet lighting is mapped among the visible figure from optical microscope photograph (Fig. 1), and darker zone is for being covered the super-hydrophobic district of ultraviolet light by photomask.Size and the photomask size that can find out pattern thus are identical.The fluorescence microscope photo of Fig. 2 can know that the fluorescein sodium of finding out in the solution mainly is gathered in circular super hydrophilic region, and it (launches tangible green glow at blue light under 450～490nm) the exciting.Pattern dimension is almost consistent with the photomask size.
Containing 0.042 mol Ca (NO
3)
2With 0.025 mol NH
4H
2PO
4, pH value is in 4.2 the electrolyte, the control electric current density is 0.5 milliampere/centimetre
2, with have super thin-be that template is carried out cathodic electrochemical deposition at the bottom of the titanio of super hydrophilic pattern.Sedimentation time is 5 minutes, can obtain the little pattern of nano ordered calcium microcosmic salt rete in the titanio surface.Referring to Fig. 3,4 and table 1.Can find out obviously that from Fig. 3 circular darker super hydrophilic region covers last layer calcium microcosmic salt rete, then do not deposit calcium microcosmic salt rete in other super-hydrophobic zones, and the rete edge contour is clear, thus formed with super thin-the little pattern of the on all four calcium microcosmic salt of super hydrophilic templates (Fig. 1) rete array.From Fig. 4, (Fig. 4 a is 500 times to the SEM image of the little pattern of calcium microcosmic salt rete under the different amplification, Fig. 4 b is 5000 times) can find out obviously further that the calcium microcosmic salt rete that electrochemical deposition obtained in the time of 5 minutes only is deposited on circular super hydrophilic region, size and pattern template are unanimous on the whole.The essential structure unit of calcium microcosmic salt rete is the long ribbon shape crystal of wide hundreds of nanometer, and its direction of growth is the vertical axis along matrix.The XRD spectra that electrochemical deposition coating and coating is scraped the back powder compares, and (the calcium microcosmic salt that Fig. 5 curve a) obtains under electrochemical preparation condition necessarily more as can be known is mainly the form of OCP (OCP) for the XRD spectra (Fig. 5 curve b) that calcium microcosmic salt coating is scraped the back grind into powder and OCP standard spectrogram.XRD spectra (Fig. 5 curve b) the peak position basically identical of OCP rete (Fig. 5 curve c) and its powder relatively, but (010) diffraction maximum of OCP rete obviously weakens, and (002) crystal face has tangible enhancing with respect to other diffraction maximum.Along the growth of (002) crystal face, the direction that promptly is parallel to the c axle has certain preferred orientation in the OCP of electrode surface coating in this explanation, and this is consistent with the result that scanning electron microscope observation obtains.
Embodiment 2: tool super thin-preparation of the nano-tube array rete of super hydrophilic pattern is with embodiment 1, then in the dehydrated alcohol electrolyte that contains 3 grams per liter concentration hydroxyapatite nanoparticles, control voltage is 30V, at ambient temperature, to have super thin-sample of super hydrophilic pattern template carries out the ability cathode electrophoresis deposition.Sedimentation time is 15 seconds, can obtain little pattern of hydroxyapatite nanoparticle in the titanio surface.The result is referring to Fig. 6, and 7 and table 1.Can find out obviously that from Fig. 6 the super hydrophilic region of brighter circle is coated with one deck hydroxyapatite nanoparticle rete, then have only seldom in other super-hydrophobic zones or do not find that substantially the hydroxyapatite nanoparticle rete exists, formed with super thin-the on all four microarray pattern of super hydrophilic templates (Fig. 1).And from Fig. 7 the SEM image of the little pattern of hydroxyapatite nanoparticle under the different amplification (figure a is 400 times, figure b is 10000 times) can find out the hydroxyapatite nanoparticle film that can obtain being deposited on circular super hydrophilic region at electrophoretic deposition in the time of 15 seconds, size is also unanimous on the whole with pattern template.From its high power SEM image as can be seen the hydroxyapatite nanoparticle rete be to pile up by the rhabdolith of wide 20～30 nanometers, long 100～200 nanometers to form.(curve a) for the standard spectrogram of calcium microcosmic salt coating XRD spectra (curve b, c, d) and hydroxyapatite under the different sedimentation times in the comparison diagram 8 (15s, 30s and 60s), the main component of electrophoretic deposition coating is hydroxyapatite (HA) as can be known, illustrates that electrophoretic deposition process is to not influence of the chemical constituent in the solution.Relatively the XRD spectra of the sedimentary HA rete of different time is found the diffraction peak basically identical.But along with the prolongation of sedimentation time, each diffraction maximum of HA rete obviously strengthens, and the diffraction maximum of metallic titanium matrix then has significantly and weakens.The HA coating layer thickness of this explanation electrode surface is along with the prolongation of electrophoretic deposition time has tangible increase.
Table 1
Embodiment 3
Similar to Example 1, its difference is that base material adopts titanium alloy (Ti6Al4V).NaOH with 0.05 mol regulates electrolyte pH=6, and the electric current density of control is 0.1 milliampere/centimetre
2, carry out cathodic electrochemical deposition.Sedimentation time is 5 minutes, obtains the little pattern of nano ordered calcium microcosmic salt (CaP) rete in the titanio surface.
Embodiment 4
Have super thin-preparation of the nano-tube array rete of super hydrophilic pattern is with embodiment 1, its difference is that silicon fluoride (FSA-13) methanol solution that sample is immersed in 2wt% took out after 3 hours, obtains super-hydrophobic TiO down in dry 3 hours at 160 ℃
2The nano-tube array rete.On the TiO2 of super-hydrophobicization nano-tube array rete, cover photomask then, through irradiation under ultraviolet ray 150 minutes, can substrate surface obtain pattern dimension and pattern and photomask on all four super thin-super hydrophilic pattern.Containing 1.05 * 10 at last
-2Mol [Ca
2+] and 6.25 * 10
-3Mol [PO
4 3-] calcium microcosmic salt solution in deposition 30 minutes, can obtain to have nano ordered calcium microcosmic salt (CaP) rete of little pattern at sample surfaces.
Embodiment 5
Base material adopts titanium alloy (Ti6Al4V).NaOH with 0.05 mol regulates electrolyte pH=6, and the electric current density of control is 0.1 milliampere/centimetre
2, carry out cathodic electrochemical deposition.Sedimentation time is 2 minutes.All the other obtain the little pattern of nano ordered calcium microcosmic salt (CaP) rete with embodiment 1 at matrix surface.
Embodiment 6
Base material adopts titanium alloy (Ti-29Nb-13Ta-4.6Zr).NaOH with 0.05 mol regulates electrolyte pH=6, and the electric current density of control is 0.1 milliampere/centimetre
2, carry out cathodic electrochemical deposition.Sedimentation time is 10 minutes.All the other obtain the little pattern of nano ordered calcium microcosmic salt (CaP) rete with embodiment 1 at matrix surface.
Embodiment 7
Similar to Example 2, its difference is that base material adopts titanium alloy (Ti6Al4V), and used deposit solution is the nanometer hydroxyapatite (Ca that contains 10 grams per liter concentration
10(PO
4) (OH)
2, HA) particulate butanols electrolyte is regulated electrolyte pH=5, and control voltage is 50V, apart from 4 centimetres of platinum electrodes, carries out the ability cathode electrophoresis deposition.The room temperature deposit time is 0.5 minute, obtains little pattern of hydroxyapatite nanoparticle in the titanio surface.
Embodiment 8
Similar to Example 2, its difference is that base material adopts titanium alloy (Ti6Al4V).Used deposit solution is the nanometer hydroxyapatite (Ca that contains 1 grams per liter concentration
10(PO
4) (OH)
2, HA) particulate amylalcohol electrolyte is regulated electrolyte pH=5, and control voltage is 5V, carries out the ability cathode electrophoresis deposition apart from 1 centimetre of platinum electrode, and the room temperature deposit time is 5 minutes, obtains little pattern of hydroxyapatite nanoparticle in the titanio surface.
Claims (3)
1. preparation method based on the micro-nanometer ordered structure biomaterial film of super parent/superhydrophobic characteristic template is characterized in that said preparation method is as follows:
1) with the substrate surface pretreatment, said substrate is titanium or titanium alloy;
2) electrochemical anodic oxidation is carried out in substrate, electrolyte is 0.1～2wt%HF, and preparation voltage is 5～50V, and temperature is 0～25 ℃, and the time is 10～240 minutes, promptly obtains the nano ordered TiO of one deck at substrate surface
2The nano-tube array rete;
3) sample that step 2 the is obtained silicon fluoride methanol solution that is immersed in 0.5～2wt% took out after 1～3 hour, obtained super-hydrophobic TiO down in dry 1～4 hour at 120～160 ℃
2The nano-tube array rete;
4) at the TiO of super-hydrophobicization
2Cover photomask on the nano-tube array rete, through irradiation under ultraviolet ray 5～150 minutes, can substrate surface obtain pattern dimension and pattern and photomask on all four super thin-super hydrophilic pattern;
5) surface that step 4) is obtained have super thin-sample of super hydrophilic pattern carries out cathodic electrochemical deposition, containing 1.05～4.2 * 10
-2Mol [Ca
2+] and 0.625～2.5 * 10
-2Mol [PO
4 3-] calcium microcosmic salt solution in deposit 0.5～30 minute, can obtain little pattern and the on all four structurally ordered nanometer calcium microcosmic salt rete of photomask at sample surfaces;
Or with the surface that step 4) obtains have super thin-sample of super hydrophilic pattern carries out the ability cathode electrophoresis deposition, deposit solution is the anhydrous organic solvent that contains the nano-hydroapatite particles of 1～10 grams per liter concentration, control voltage is 5～50V, sedimentation time is 5～300 seconds, promptly obtains little pattern and the on all four structurally ordered nanometer hydroxyapatite nanometer rete of photomask at sample surfaces.
2. as the said a kind of preparation method of claim 1, it is characterized in that said surface preparation is for to clean up substrate surface after mechanical grinding in step 1 based on the micro-nanometer ordered structure biomaterial film that surpasses parent/superhydrophobic characteristic template.
3. as the said a kind of preparation method of claim 1, it is characterized in that said organic solvent is dehydrated alcohol or butanols or amylalcohol in the step 5) based on the micro-nanometer ordered structure biomaterial film that surpasses parent/superhydrophobic characteristic template.
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| CN101991879A (en) * | 2010-11-11 | 2011-03-30 | 奇瑞汽车股份有限公司 | Preparation method of carbon-carbon composite material/hydroxyapatite/polylactic acid biological material |
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| CN105624762B (en) * | 2016-01-15 | 2018-01-12 | 厦门大学 | Method for preparing bioactive composite coating on surface of titanium or titanium alloy |
| CN105798363B (en) * | 2016-03-21 | 2018-07-06 | 大连理工大学 | A kind of micro- pattern processing method of adhesion strength controllable hydrophilic |
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| CN106191830A (en) * | 2016-08-02 | 2016-12-07 | 东华大学 | A kind of have surface hydrophobic and finely receive the preparation method of medical 316L stainless steel of dual structure |
| CN106581744A (en) * | 2016-12-31 | 2017-04-26 | 芜湖孙杨信息咨询有限公司 | Production method of titanium implant surface composite coating used for stomatology department |
| CN109125809A (en) * | 2018-08-21 | 2019-01-04 | 华南理工大学 | To inhibit bacterial growth and promote the titanium surface and preparation method thereof of protein adherence |
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