CN115074796B - Titanium alloy surface coating and preparation method thereof - Google Patents
Titanium alloy surface coating and preparation method thereof Download PDFInfo
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- 239000011574 phosphorus Substances 0.000 claims description 6
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- 229910000883 Ti6Al4V Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 12
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Classifications
-
- 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
- C25D9/02—Electrolytic coating other than with metals with organic 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
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Abstract
The invention discloses a titanium alloy surface coating and a preparation method thereof. The method comprises the following steps: pretreating the surface of a titanium alloy matrix; preparing a chitosan coating on the surface of the pretreated titanium alloy matrix by adopting a constant potential electrochemical deposition method by taking chitosan solution as electrolyte; and preparing the hydroxyapatite coating on the surface of the chitosan coating by adopting a constant potential electrochemical deposition method by taking a solution containing calcium ions and phosphate ions as an electrolyte. According to the invention, the chitosan coating and the hydroxyapatite coating are sequentially prepared on the surface of the biomedical titanium alloy by adopting a constant potential electrochemical deposition method, so that the titanium alloy with the chitosan coating and the hydroxyapatite double-layer coating is obtained, the prepared titanium alloy with the double-layer coating fully plays various advantages of three materials, has excellent biocompatibility, antibacterial property and corrosion resistance, and integrally shows mechanical properties matched with bones, and meanwhile, the adhesive force of the coating on a substrate is greatly improved due to the introduction of chitosan.
Description
Technical Field
The invention relates to the field of biomedical titanium alloy material surface modification, in particular to a titanium alloy surface coating and a preparation method thereof.
Background
Biomedical titanium and titanium alloys have excellent mechanical properties and have been demonstrated to have mechanical compatibility matching with human bones and good biocompatibility, and thus are widely used as a main clinical application material for hard tissues such as bones and dental implants. However, biomedical titanium and titanium alloys have poor osseointegration ability due to their biological inertness, and at the same time, their antibacterial and corrosion resistance properties are further improved. In order to enable biomedical titanium and titanium alloy to adapt to complex physiological environments of human bodies, the biomedical titanium and titanium alloy are required to be subjected to surface modification so as to improve the performances of the biomedical titanium and titanium alloy, and the biomedical titanium and titanium alloy can be better adapted to clinical application.
Calcium phosphate is the most important inorganic constituent of biological hard tissue and is present in bone and teeth in the form of Hydroxyapatite (HA). The artificially synthesized hydroxyapatite ceramic has excellent bioactivity, bone induction capacity and biocompatibility, can form chemical bonding with bone tissue, and can induce the growth of bone tissue. However, the brittleness of hydroxyapatite limits its use in heavy-duty bones, and is therefore generally used for active ingredients in composite materials, particulate fillers directly incorporated into human tissues, and coatings on metal implants, etc.
Chitosan (CS) is the only natural basic polysaccharide present in nature, in the crustacean shell, the insect cuticle and the fungal cell wall. Chitosan has excellent physicochemical and biological properties such as good biocompatibility, non-toxicity, antibacterial properties, and significant affinity with proteins, etc. The excellent performance of chitosan promotes the chitosan to be a reliable natural bioactive material, and the chitosan is widely applied in the fields of medical treatment, pharmaceutical industry, tissue engineering, agriculture and the like. Chitosan is also insoluble in water, alkali and general organic solvents due to its own characteristics, but due to the presence of-NH in its structural units 2 Groups are very reactive with acids to form salts so they can be dissolved in many dilute mineral acids or some common organic acid.
Disclosure of Invention
The invention aims to provide a titanium alloy surface coating and a preparation method thereof, and the obtained biomedical titanium alloy surface coating has excellent bioactivity, biocompatibility and antibacterial property, and the binding force between the coating and a substrate and the corrosion resistance are enhanced. The biomedical titanium alloy with the chitosan and hydroxyapatite double-layer coating on the surface can be effectively applied to orthopedic implants.
The technical scheme of the invention is as follows:
in a first aspect of the invention, a method for preparing a titanium alloy surface coating is provided, wherein the preparation method comprises the following steps:
providing a titanium alloy substrate;
pretreating the surface of the titanium alloy matrix;
preparing chitosan solution;
preparing a solution containing calcium ions and phosphate ions;
preparing a chitosan coating on the surface of the pretreated titanium alloy matrix by adopting a constant potential electrochemical deposition method by taking the chitosan solution as an electrolyte;
and preparing the hydroxyapatite coating on the surface of the chitosan coating by adopting a constant potential electrochemical deposition method by taking the solution containing calcium ions and phosphate ions as electrolyte.
Optionally, the step of pre-treating the surface of the titanium alloy substrate specifically includes: and sequentially polishing, degreasing, etching and activating the surface of the titanium alloy matrix.
Optionally, the step of preparing the chitosan solution specifically includes:
adding glacial acetic acid into water to obtain an acetic acid solution, wherein the volume fraction of acetic acid in the acetic acid solution is 1-3%;
adding chitosan powder into the acetic acid solution, stirring until the solution is clear, and removing insoluble substances to obtain a chitosan solution, wherein the mass fraction of chitosan in the chitosan solution is 1-5%.
Optionally, the molecular weight of the chitosan is 40000-500000, and the deacetylation degree is more than or equal to 91%.
Optionally, the step of preparing the solution containing calcium ions and phosphate ions specifically includes: dissolving soluble calcium salt and soluble phosphate in water to obtain a solution containing calcium ions and phosphate ions; wherein the molar ratio of the calcium element to the phosphorus element in the solution containing the calcium ions and the phosphate ions is 1-3, and the concentration of the calcium ions in the solution containing the calcium ions and the phosphate ions is 4.0-6.0 mmol/L.
Alternatively, the soluble calcium salt is Ca (NO 3 ) 2 ·4H 2 O, the soluble phosphate is (NH) 4 ) 2 HPO 4 。
Optionally, the step of preparing the chitosan coating on the surface of the pretreated titanium alloy substrate by adopting a potentiostatic electrochemical deposition method by taking the chitosan solution as an electrolyte comprises the following steps: placing the pretreated titanium alloy matrix in an electrolytic cell of a three-electrode system, wherein the electrolyte is the chitosan solution, performing electrochemical deposition under constant potential, and preparing a chitosan coating on the surface of the pretreated titanium alloy matrix;
wherein the time of the electrochemical deposition is 1800-7200 s, and the deposition potential of the electrochemical deposition is-3V.
Optionally, the step of preparing the hydroxyapatite coating on the surface of the chitosan coating by adopting an electrochemical deposition method by taking the solution containing calcium ions and phosphate ions as electrolyte comprises the following steps: placing a titanium alloy substrate with a chitosan coating on the surface in an electrolytic cell of a three-electrode system, performing electrochemical deposition on the solution containing calcium ions and phosphate ions at a constant potential, and preparing a hydroxyapatite coating on the chitosan coating surface of the titanium alloy substrate;
wherein the time of the electrochemical deposition is 1800-7200 s, and the deposition potential of the electrochemical deposition is-3V.
Optionally, wherein the electrochemical deposition is performed in a constant temperature water bath at 35 ℃ to 40 ℃.
In a second aspect of the invention, a titanium alloy surface coating is provided, wherein the titanium alloy surface coating is prepared by the preparation method of the titanium alloy surface coating.
The invention has the following beneficial effects:
(1) The biomedical titanium alloy surface coating prepared by the invention has lamellar structure, compact structure among layers and even distribution. The structure can obviously improve the specific surface area of the material, is very beneficial to the adhesion, spreading and proliferation of osteoblasts, and can promote the formation of new bones. Meanwhile, the chitosan coating is prepared firstly, then the hydroxyapatite coating is prepared on the basis of the chitosan coating, and the chitosan is used as a transition layer between the substrate and the hydroxyapatite coating, so that the adhesive force of the prepared biomedical titanium alloy surface coating on the substrate is obviously enhanced compared with that of the traditional coating.
(2) The biomedical titanium alloy surface coating prepared by the invention is prepared by introducing hydroxyapatite and chitosan on a titanium alloy substrate, fully utilizes the advantages of three materials of the titanium alloy substrate, the hydroxyapatite and the chitosan, not only ensures that the whole titanium alloy has mechanical compatibility matched with bones, but also has excellent biocompatibility and antibacterial property, and simultaneously has better corrosion resistance, and the adhesive force of the coating on the substrate is greatly improved due to the introduction of the chitosan, thus having important practical application value in the aspects of implants and the like.
(3) The biomedical titanium alloy surface coating prepared by the method is a constant potential electrochemical deposition method, the method is simple to operate, the preparation process is stable, parameters and control variables can be effectively regulated in the operation process, and the method can be applied to the surface of any substrate with complex shape. Meanwhile, the method almost generates no waste substances in the application process, has high preparation efficiency and can be industrialized.
Drawings
FIG. 1 is a schematic cross-sectional structure of a biomedical titanium alloy Ti6Al4V substrate with a chitosan & hydroxyapatite bilayer coating on the surface prepared in example 1.
Fig. 2 is an SEM image of the chitosan & hydroxyapatite bilayer coating prepared in example 1 at different magnifications.
Detailed Description
The invention provides a titanium alloy surface coating and a preparation method thereof, which are used for making the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a preparation method of a titanium alloy surface coating, which comprises the following steps:
providing a titanium alloy substrate;
pretreating the surface of the titanium alloy matrix;
preparing chitosan solution;
preparing a solution containing calcium ions and phosphate ions;
preparing a chitosan coating on the surface of the pretreated titanium alloy matrix by adopting a constant potential electrochemical deposition method by taking the chitosan solution as an electrolyte;
and preparing the hydroxyapatite coating on the surface of the chitosan coating by adopting a constant potential electrochemical deposition method by taking the solution containing calcium ions and phosphate ions as electrolyte.
Most of the surface coatings prepared in the prior art are of a net-shaped structure, and are different from the surface coatings prepared in the prior art, the biomedical titanium alloy surface coatings prepared in the embodiment have lamellar structures, and the layers are compact in structure and even in distribution. The lamellar structure of the coating has a plurality of overlapped and orderly arranged lamellar structure, compact structure and strong crystal orientation. The structure can obviously improve the specific surface area of the material, and can form a large-area bone-combining interface with a human body as an implant coating, thereby being very beneficial to the adhesion, spreading and proliferation of osteoblasts and promoting the formation of new bones. While the conventional surface coating is a network structure, which achieves pore connectivity at the expense of mechanical strength of the material, the special lamellar structure of this embodiment can provide excellent mechanical properties, and can improve resistance to physical and chemical damage, thereby prolonging the service life thereof and realizing long-acting application. Meanwhile, the adhesive force of the prepared biomedical titanium alloy surface coating on the substrate is obviously enhanced compared with that of the traditional coating, and the prepared biomedical titanium alloy surface coating has better corrosion resistance and can better meet the requirements of implant coatings.
The reason why the present embodiment has good corrosion resistance is as follows: the chitosan coating is deposited first, and then the chitosan coating can be used as a coating with barrier effect, which can reduce the possibility of corrosive ions penetrating the coating, thereby improving the corrosion resistance. And then a hydroxyapatite coating is deposited on the substrate, chitosan is combined with the hydroxyapatite coating through chelation and hydrogen bonding, and hydroxyapatite molecules are good adsorbents of organic molecules, so that the hydroxyapatite coating has good adhesive force on the polymer coating. Thus, the synergistic effect of the chitosan & hydroxyapatite bilayer coating as the final coating on the titanium alloy substrate will produce better corrosion resistance. In addition, as the chitosan and hydroxyapatite double-layer coating is of a lamellar structure, compared with the traditional reticular structure coating, the porosity is reduced, and the lamellar structure is staggered and tiled to form another compact barrier, so that an external corrosion medium is difficult to enter a channel of the titanium alloy matrix, and the corrosion resistance is greatly improved.
Wherein, the reaction process of chitosan coating formation:
2H 2 O+2e - ＝H 2 +2OH -
the reaction process of forming the hydroxyapatite coating comprises the following steps:
electrochemical half reaction: 2H (H) 2 O+2e - ＝H 2 +2OH -
Acid group reaction:
according to the embodiment, biomedical titanium alloy is used as a matrix, a constant potential electrochemical deposition method is adopted to sequentially prepare a chitosan coating and a hydroxyapatite coating on the surface of the biomedical titanium alloy matrix, so that the titanium alloy with the surface provided with a chitosan coating and a hydroxyapatite coating double-layer coating (marked as a chitosan and hydroxyapatite double-layer coating) is obtained, the prepared titanium alloy with the double-layer coating fully plays various advantages of the three materials of the titanium alloy matrix, the hydroxyapatite and the chitosan, has excellent biocompatibility, antibacterial property and corrosion resistance, and integrally shows mechanical properties matched with bones, and meanwhile, the adhesive force of the coating on the matrix is greatly improved due to the introduction of the chitosan. Therefore, the titanium alloy with the chitosan and hydroxyapatite double-layer coating prepared by the potentiostatic electrochemical deposition method has important practical application value.
The biomedical titanium alloy surface coating prepared by the embodiment adopts a potentiostatic electrochemical deposition method, the method is simple to operate, the preparation process is stable, parameters and control variables can be effectively regulated in the operation process, and the method can be applied to any substrate surface with complex shape. Meanwhile, the method almost generates no waste substances in the application process, has high preparation efficiency and can be industrialized.
In addition, the constant potential electrochemical deposition method is carried out under mild conditions, so that the problem of thermal stress does not exist between the titanium alloy substrate and the coating interface, the problems of phase change, embrittlement and the like caused by the existing high-temperature preparation method are effectively avoided, and the bonding strength between the substrate and the coating is enhanced; meanwhile, the electrochemical deposition process is a nonlinear process, and the coating can be prepared on the surface of the substrate with a complex shape.
In one embodiment, the titanium alloy substrate is a Ti6Al4V substrate or the like, but is not limited thereto.
In one embodiment, the step of pre-treating the surface of the titanium alloy substrate specifically includes: and sequentially polishing, degreasing, etching and activating the surface of the titanium alloy matrix.
Further, the polishing process specifically includes: sequentially use 180 # 、400 # 、800 # 、1500 # And 2000 # The surface of the titanium alloy matrix is polished by the water sand paper.
Further, the degreasing treatment specifically includes: and (3) carrying out oil removal treatment on the surface of the polished titanium alloy matrix by adopting acetone, and then carrying out ultrasonic cleaning for 2-5 times for 8-15 minutes each time.
Further, the etching process specifically includes: and placing the deoiled titanium alloy matrix in an acid solution for etching treatment, wherein the temperature of the etching treatment is 50-65 ℃, and the etching treatment time is 4-6 hours.Wherein the acidic solution may be H 2 SO 4 HCl and H 2 The volume ratio of the mixed solution of O is 1:1:1.
further, the activation treatment specifically includes: and (3) placing the etched titanium alloy matrix in an activating solution for activation treatment, wherein the temperature of the activation treatment is 50-65 ℃, and the time of the activation treatment is 1-1.5 hours. Wherein the activating solution can be NaOH solution with the concentration of 3.5-5 mol/L.
After each of the above steps of polishing, degreasing, etching and activating, the titanium alloy substrate is ultrasonically cleaned with deionized or distilled water at room temperature.
In one embodiment, the step of preparing the chitosan solution specifically includes:
adding glacial acetic acid into water to obtain an acetic acid solution, wherein the volume fraction of acetic acid in the acetic acid solution is 1-3%;
adding chitosan powder into the acetic acid solution, stirring until the solution is clear, and removing insoluble substances to obtain a chitosan solution, wherein the mass fraction of chitosan in the chitosan solution is 1-5%.
In one embodiment, the chitosan has a molecular weight of 400000 ～ 500000 and a degree of deacetylation of greater than or equal to 91%.
In one embodiment, the step of preparing a solution containing calcium ions and phosphate ions specifically includes: dissolving soluble calcium salt and soluble phosphate in water to obtain a solution containing calcium ions and phosphate ions; wherein the molar ratio of the calcium element to the phosphorus element in the solution containing the calcium ions and the phosphate ions is 1-3, and the concentration of the calcium ions in the solution containing the calcium ions and the phosphate ions is 4.0-6.0 mmol/L.
In one embodiment, the soluble calcium salt is Ca (NO 3 ) 2 ·4H 2 O (analytically pure), the soluble phosphate being (NH) 4 ) 2 HPO 4 (analytically pure).
In one embodiment, the step of preparing the chitosan coating on the surface of the pretreated titanium alloy substrate by adopting a potentiostatic electrochemical deposition method by taking the chitosan solution as an electrolyte comprises the following steps:
placing the pretreated titanium alloy matrix in an electrolytic cell of a three-electrode system, wherein the electrolyte is the chitosan solution, performing electrochemical deposition under constant potential, and preparing a chitosan coating on the surface of the pretreated titanium alloy matrix;
wherein the time of the electrochemical deposition is 1800-7200 s, and the deposition potential of the electrochemical deposition is-3V.
Further, the electrochemical deposition is performed in a constant temperature water bath at 35-40 ℃.
Further, the three-electrode system comprises a working electrode, a counter electrode and a reference electrode, wherein the working electrode is a pretreated titanium alloy matrix, the counter electrode is a metal plate (such as a platinum plate), and the reference electrode is a saturated calomel electrode.
Further, the titanium alloy substrate with the chitosan coating is prepared by flushing the surface with deionized water immediately after the deposition is completed, and then drying by cold air.
In one embodiment, the step of preparing the hydroxyapatite coating on the surface of the chitosan coating by adopting a potentiostatic electrochemical deposition method by taking the solution containing calcium ions and phosphate ions as an electrolyte specifically comprises the following steps: placing a titanium alloy substrate with a chitosan coating on the surface in an electrolytic cell of a three-electrode system, performing electrochemical deposition on the solution containing calcium ions and phosphate ions at a constant potential, and preparing a hydroxyapatite coating on the chitosan coating surface of the titanium alloy substrate;
wherein the time of the electrochemical deposition is 1800-7200 s, and the deposition potential of the electrochemical deposition is-3V.
Further, the electrochemical deposition is performed in a constant temperature water bath at 35-40 ℃.
Further, the three-electrode system comprises a working electrode, a counter electrode and a reference electrode, wherein the working electrode is a titanium alloy matrix with a chitosan coating on the surface, the counter electrode is a metal plate (such as a platinum plate), and the reference electrode is a saturated calomel electrode.
Further, the titanium alloy with the chitosan and hydroxyapatite double-layer coating is washed by deionized water immediately after the deposition is finished, and is dried by cold air.
In the embodiment, the chitosan and hydroxyapatite double-layer coating is prepared on the surface of the biomedical titanium alloy matrix by performing constant potential electrochemical deposition on the biomedical titanium alloy matrix. The titanium alloy with the chitosan and hydroxyapatite double-layer coating prepared by the method fully plays roles of three materials, namely a medical titanium alloy matrix, hydroxyapatite and chitosan. The biomedical titanium alloy has better mechanical property and has proved to have good biocompatibility; the hydroxyapatite is used as the main component of human bone tissue, calcium and phosphorus can be released out of the surface of the material to be absorbed by the body tissue after being implanted into the body, and new tissue can be grown, so that the hydroxyapatite has higher bioactivity and good biocompatibility; the chitosan not only can improve the binding force between the coating and the matrix, but also has excellent antibacterial performance, and has been widely used in the fields of food additives, biomedical applications and the like. The titanium alloy with the chitosan and hydroxyapatite double-layer coating prepared by the method combines the advantages of three materials and can be effectively applied to orthopedic implants.
The invention is further illustrated by the following specific examples.
Example 1
The first step: pretreatment is carried out on the surface of the biomedical titanium alloy matrix
(1) The biomedical titanium alloy Ti6Al4V is used as a matrix, and a cutting machine is adopted to cut the Ti6Al4V alloy plate into small square pieces with the dimensions of 10mm multiplied by 1 mm.
(2) Sequentially use 180 # 、400 # 、800 # 、1500 # And 2000 # The surface of the Ti6Al4V alloy plate is polished by the water sand paper, and the polished surface is ultrasonically cleaned by deionized water for 15min at room temperature.
(3) And (3) degreasing the polished Ti6Al4V alloy plate by using acetone, performing ultrasonic cleaning for 3 times, cleaning for 10min each time, and performing ultrasonic cleaning for 15min by using deionized water at room temperature after degreasing.
(4) Etching the deoiled Ti6Al4V alloy plate by using a chemical etching method, wherein the solution adopted by etching is an acidic solution, and the specific volume ratio is 1:1: 1H 2 SO 4 HCl and H 2 And (3) carrying out ultrasonic cleaning on the mixed solution of O at room temperature for 15min by using deionized water after etching, wherein the temperature of the etching treatment is 60 ℃ and the etching treatment time is 5 h.
(5) And (3) performing activation treatment on the etched Ti6Al4V alloy plate by using an activating solution, wherein the activating solution is a NaOH solution with the concentration of 4mol/L, the activation treatment temperature is 60 ℃, the activation treatment time is 1h, and the activated Ti6Al4V alloy plate is ultrasonically cleaned by using deionized water for 15min at room temperature.
(6) And (5) drying with cold air for later use.
And a second step of: preparing chitosan solution
(1) 20mL of glacial acetic acid is measured and added into deionized water to reach 1000mL, and an acetic acid solution with the volume fraction of 2% is prepared.
(2) And preparing chitosan solution according to the mass-volume ratio. 1.0g of chitosan powder (available from Shanghai Kangshen Biotechnology Co., ltd.) having a molecular weight of 500000 and a degree of deacetylation of-95% was added to 1000mL of an acetic acid solution to prepare a chitosan solution having a mass fraction of 1%.
(3) Dissolving and stirring until the solution is clear, and filtering out insoluble matters to obtain chitosan solution.
And a third step of: preparing a solution containing calcium ions and phosphate ions
(1) The solution containing calcium ion and phosphate ion adopts high purity substance with purity of determined value as solute, and Ca (NO) can be selected as soluble calcium salt 3 ) 2 ·4H 2 O, analytically pure; soluble phosphate is selected from (NH) 4 ) 2 HPO 4 Purity is analytically pure. The ultrapure water is used as a solvent, is prepared by a weight-capacity method in a clean laboratory with the room temperature of 20+/-2 ℃.
(2) 0.2000g of Ca (NO) was weighed out in a molar ratio of calcium element to phosphorus element of 1.67 3 ) 2 ·4H 2 O and 0.0930g (NH) 4 ) 2 HPO 4 Dissolving in ultrapure water, and fixing the volume to 1000mL. The prepared solution had a calcium concentration of 5mmol/L and a phosphorus concentration of 3mmol/L, and was subjected to quantitative verification by ion chromatography.
(3) Stirring thoroughly to obtain a uniform solution containing calcium ions and phosphate ions.
Fourth step: preparation of chitosan and hydroxyapatite double-layer coating by constant potential electrochemical deposition
(1) Firstly, placing the Ti6Al4V alloy plate pretreated in the first step into an electrolytic cell of a three-electrode system, wherein electrolyte is a uniform chitosan solution prepared in the second step, taking the pretreated Ti6Al4V alloy plate as a working electrode, a platinum plate as a counter electrode and a saturated calomel electrode as a reference electrode, and performing constant potential electrochemical deposition in a constant-temperature water bath at 37 ℃. Wherein, the deposition potential is-1.3V, and the deposition time is 3600s.
(2) And (3) immediately washing a sample with deionized water after the deposition is finished, and drying by cold air to obtain the Ti6Al4V alloy plate with the chitosan coating on the surface.
(3) Then placing the Ti6Al4V alloy plate with the surface provided with the chitosan coating in an electrolytic cell of a three-electrode system, wherein the electrolyte is a uniform solution containing calcium ions and phosphate ions prepared in the third step, the Ti6Al4V alloy plate with the surface provided with the chitosan coating is used as a working electrode, a platinum plate is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and performing constant potential electrochemical deposition in a constant-temperature water bath at 37 ℃. Wherein, the deposition potential is-1.3V, and the deposition time is 3600s.
(4) And (5) immediately after the deposition is finished, washing the sample with deionized water, and drying by cold air.
Fig. 1 is a schematic cross-sectional view of a biomedical titanium alloy Ti6Al4V substrate with a chitosan & hydroxyapatite bilayer coating on the surface prepared in this example. The morphology and the components of the chitosan and hydroxyapatite double-layer coating prepared in the embodiment are characterized, the corresponding scanning electron microscope images are shown in fig. 2, and a and b in fig. 2 are microcosmic morphology images under different magnifications. As can be seen from SEM images, the prepared double-layer coating has a lamellar structure, is formed by stacking layers one by one, has a compact structure between the layers, and has a thickness of about 40 nm. The lamellar structure of the coating has a plurality of overlapped and orderly arranged lamellar structure, compact structure and strong crystal orientation. It is also evident from SEM images that the coating has a large reaction area, as an implant coating, it can form a large area of bone-bonding interface with the human body, and the good crystal structure of the surface is beneficial to promote osteogenesis.
The adhesion of the double-layer coating is tested by a cross-hatch test standard GB/T9286-1998. The sample was conditioned for 24 hours at (23.+ -. 2), (50.+ -. 5)% RH to make the cutter perpendicular to the sample surface, apply force to the cutter uniformly, cut on the coating at a uniform cut rate with a 1mm scribe pitch and a 6X 6 number of scribes. Adhesive tape is applied, the adhesive tape used here being Mitigbang 405. After the cross-hatch test, it was observed that the cut edge of the sample surface coating was completely smooth, no lattice was dropped, and the adhesion was 0 grade. The prepared coating has excellent adhesive force and meets the requirement of implant coating.
In summary, the invention provides a titanium alloy surface coating and a preparation method thereof. According to the invention, a constant potential electrochemical deposition method is adopted, chitosan and hydroxyapatite are sequentially deposited and attached on a titanium alloy matrix, and the prepared double-layer coating has a lamellar structure. The obtained titanium alloy with the chitosan and hydroxyapatite double-layer coating has excellent bioactivity, biocompatibility, antibacterial property and corrosion resistance, and the binding force between the coating and a matrix is enhanced. The titanium alloy with the chitosan and hydroxyapatite double-layer coating can be effectively applied to orthopedic implants.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (2)
1. A method for preparing a titanium alloy surface coating, which is characterized by comprising the following steps:
providing a titanium alloy substrate;
pretreating the surface of the titanium alloy matrix;
preparing chitosan solution;
preparing a solution containing calcium ions and phosphate ions;
preparing a chitosan coating on the surface of the pretreated titanium alloy matrix by adopting a constant potential electrochemical deposition method by taking the chitosan solution as an electrolyte;
preparing a hydroxyapatite coating on the surface of the chitosan coating by adopting a constant potential electrochemical deposition method by taking the solution containing calcium ions and phosphate ions as electrolyte; the titanium alloy surface coating is a chitosan and hydroxyapatite double-layer coating, the double-layer coating has a lamellar structure, the layers have a compact structure, and the distribution is uniform;
the method specifically comprises the following steps of preprocessing the surface of the titanium alloy matrix: sequentially polishing, degreasing, etching and activating the surface of the titanium alloy matrix;
the step of preparing chitosan solution specifically comprises the following steps:
adding glacial acetic acid into water to obtain an acetic acid solution, wherein the volume fraction of acetic acid in the acetic acid solution is 1-3%;
adding chitosan powder into the acetic acid solution, stirring until the solution is clear, and removing insoluble substances to obtain a chitosan solution, wherein the mass fraction of chitosan in the chitosan solution is 1-5%;
the molecular weight of the chitosan is 400000 ～ 500000, and the deacetylation degree is more than or equal to 91%;
the preparation method of the solution containing calcium ions and phosphate ions comprises the following steps: dissolving soluble calcium salt and soluble phosphate in water to obtain a solution containing calcium ions and phosphate ions; wherein the molar ratio of the calcium element to the phosphorus element in the solution containing the calcium ions and the phosphate ions is 1-3, and the concentration of the calcium ions in the solution containing the calcium ions and the phosphate ions is 4.0-6.0 mmol/L;
the soluble calcium salt is Ca (NO) 3 ) 2 ·4H 2 O, the soluble phosphate is (NH) 4 ) 2 HPO 4 ；
The chitosan solution is used as electrolyte, and a constant potential electrochemical deposition method is adopted to prepare a chitosan coating on the surface of the pretreated titanium alloy substrate, which comprises the following steps: placing the pretreated titanium alloy matrix in an electrolytic cell of a three-electrode system, wherein the electrolyte is the chitosan solution, performing electrochemical deposition under constant potential, and preparing a chitosan coating on the surface of the pretreated titanium alloy matrix;
wherein the time of the electrochemical deposition is 1800-7200 s, and the deposition potential of the electrochemical deposition is-3V;
the step of preparing the hydroxyapatite coating on the surface of the chitosan coating by adopting a potentiostatic electrochemical deposition method by taking the solution containing calcium ions and phosphate ions as electrolyte comprises the following steps: placing a titanium alloy substrate with a chitosan coating on the surface in an electrolytic cell of a three-electrode system, performing electrochemical deposition on the solution containing calcium ions and phosphate ions at a constant potential, and preparing a hydroxyapatite coating on the chitosan coating surface of the titanium alloy substrate;
wherein the time of the electrochemical deposition is 1800-7200 s, and the deposition potential of the electrochemical deposition is-3V;
the electrochemical deposition is carried out in a constant temperature water bath at 35-40 ℃.
2. A titanium alloy surface coating, characterized in that the titanium alloy surface coating is prepared by the preparation method of the titanium alloy surface coating in claim 1.
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| CN101381881A (en) * | 2007-09-05 | 2009-03-11 | 西南交通大学 | Method for preparing hydroxylapatite/chitosan composite coating by pulse electrochemical deposition |
| CN103272269A (en) * | 2013-05-30 | 2013-09-04 | 上海师范大学 | Hydroxyapatite/chitosan composite coating and preparation method thereof |
| CN114404652A (en) * | 2022-01-19 | 2022-04-29 | 河北科技师范学院 | Method for preparing chitosan intermediate layer on surface of medical magnesium alloy |
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| CN101381881A (en) * | 2007-09-05 | 2009-03-11 | 西南交通大学 | Method for preparing hydroxylapatite/chitosan composite coating by pulse electrochemical deposition |
| CN103272269A (en) * | 2013-05-30 | 2013-09-04 | 上海师范大学 | Hydroxyapatite/chitosan composite coating and preparation method thereof |
| CN114404652A (en) * | 2022-01-19 | 2022-04-29 | 河北科技师范学院 | Method for preparing chitosan intermediate layer on surface of medical magnesium alloy |
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