CN103160790B - Method of preparing biology activity composite thin film on surface of titanium alloy - Google Patents
Method of preparing biology activity composite thin film on surface of titanium alloy Download PDFInfo
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- CN103160790B CN103160790B CN201110428111.9A CN201110428111A CN103160790B CN 103160790 B CN103160790 B CN 103160790B CN 201110428111 A CN201110428111 A CN 201110428111A CN 103160790 B CN103160790 B CN 103160790B
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Abstract
The invention discloses a method of preparing biology activity composite thin film on surface of titanium alloy. Specifically, the titanium alloy which is processed before the convention is placed in a multi-sphere ion plating-magnetic control sputtering composite gas phase sedimentation vacuum system. A data link control (DLC) thin film with Ti as a transition layer is sedimentated. The composite thin film is composed of a titanium alloy base body, the DCL thin film and a casein phosphoric acid peptide activity egg white surface layer in sequence. A series of excellent qualities of the titanium alloy as the base body material are maintained by the thin film. The biology activity and the tribology performance are improved.
Description
Technical field
The present invention relates to a kind of method preparing biological activity laminated film at titanium alloy surface, specifically adopt the chemical process of physical gas phase deposition technology and multistep assembling to obtain gradient multilayer diamond-like, phosphopeptide caseinate biological activity laminated film at titanium alloy surface.
Background technology
Titanium or titanium alloy more and more receives the concern of medical researchers with features such as good biocompatibility, low density, low elastic modulus (80-100GPa).Therefore titanium or titanium alloy joint prosthesis (such as hip joint, knee joint, elbow joint, ankle joint etc.) and dummy have been widely used in body bone tissue reparation and orthomorphia.Now widely used Ti-6Al-4V has the features such as intensity is high, ductility is good.But its wear resistance and biological activity poor, even if with the ultra high molecular polyethylene as articular fossa soft material to mill, also can produce abrasive dust, abrasive dust can bring out bone resorption, thus causes aseptic loosening of prosthesis and cause displacement to lose.Secondly after biomaterial implants, what occur at first is the absorption of organic molecule (mainly protein molecule) at material surface, generates adsorption layer, just can bring out further physiological response more afterwards on organic molecule adsorption layer.Therefore, the surface treatment of titanium alloy is extremely important.
The research of current titanium alloy surface process mainly comprises physical treatment (sandblasting, ion implantation etc.), chemical treatment (acid etching, differential arc oxidation, electrochemical deposition, alkali heat-treatment etc.), but for biological treatment, namely the research of sticking of surface biological albumen is less.Titanium alloy surface only has some organic molecule of absorption just can activate some cells in surrounding tissue and have an effect, and promotes the propagation of cell and the activation of composition-factor.
Therefore, how to improve titanium alloy wear resisting property and biological activity, thus make it be applied to biomedical sector more widely as biological implantation material, there is important clinical meaning.
Summary of the invention
The object of this invention is to provide a kind of method with the titanium alloy surface film of wear resisting property and good biological activity, improve tribological property and the biological activity of titanium alloy with this, make up its deficiency in clinical application.
A kind of method preparing biological activity laminated film at titanium alloy surface, it is characterized in that the titanium alloy after conventional pre-treatment being placed in multi-arc ion coating-magnetron sputtering compound vapour deposition vacuum system, deposition take Ti as the DLC film of transition layer, and concrete steps are:
A, titanium alloy and Ti-6Al-4V plating piece surface sputtering clean, and titanium alloy substrate is placed in multi-arc ion coating-magnetron sputtering compound vapour deposition vacuum system, argon gas flow 500sccm, bias voltage is 1.3KV, and target current is 12A, and the treatment time is 15min;
B, multi-arc ion coating Ti transition layer, metal Ti target is negative electrode, and working gas is argon gas, and flow is 70sccm, bias voltage 800V, treatment time 5 ~ 10min;
C, multi-arc ion coating deposition DLC, working gas is methane, and flow is 200sccm bias voltage is 800V, and dutycycle is 80%, and the treatment time is 40min;
The modification of the poly-Dopamine HCL film in D, DLC surface, Dopamine HCL is added in Tris-HCl buffered soln, abundant stirring makes Dopamine HCL dissolve completely, then by surface deposition, this solution put into by the Ti-6Al-4V substrate of DLC film, after stirred at ambient temperature, print is taken out, puts into deionized water for ultrasonic process, then use deionized water rinsing, last nitrogen dries up;
E, modify phosphopeptide caseinate (CPP) further on the DLC surface modifying poly-Dopamine HCL film, sample through D step process is immersed in phosphopeptide caseinate solution, rinse with PBS after left at room temperature, vacuum-drying, finally obtains DLC/CPP composite bio-active film at Ti-6Al-4V substrate surface.
In E step, the concentration of phosphopeptide caseinate solution is 9-11g/L.
The laminated film of preparation, is made up of titanium alloy substrate, DCL film, phosphopeptide caseinate activated protein top layer successively.Film had both maintained a series of one's best qualities of titanium alloy as body material, turn improved its biological activity and tribological property.
The present invention has prepared the frictional coefficient of the titanium alloy of DLC/CPP biological activity laminated film well below common alloy of titanium on surface, dry friction coefficient is lower than 0.08, (friction-wear test adopts ball-on-disc wear test machine to evaluate, adopt the mode reciprocatingly slided, load is 5N, and friction pair is the Si of Φ 5mm
3n
4ball).
The DLC/CPP biological activity laminated film adopting the present invention to obtain, has excellent tribological property and biological activity.Its feature is that the DLC film of the performance by having high rigidity and a series of excellence such as high-wearing feature and low-friction coefficient and efficiency promote that human body combines to the absorption of calcium and the CPP of utilization, has prepared DLC/CPP biological activity laminated film.Titanium alloy through this laminated film modification has had excellent tribological property and biological activity concurrently, overcomes the shortcomings such as wear resistance that conventional titanium alloy exists in clinical application and biological activity difference.Thus meet it as the requirement of biological implantation material in clinical application.
Titanium alloy surface working method of the present invention belongs to vacuum plasma and Chemical self-assembly category, and environmental protection can not to environment.Surface grafting activated protein method is simple, does not need that specific equipment is easy and simple to handle, process stabilizing, can realize batch production.Therefore this technology has good using value in biomedical materials field.
Accompanying drawing explanation
Fig. 1 is the comparison of different treatment titanium alloy surface osteoblastic proliferation rate.We have carried out related biological performance comparison with the titanium alloy not carrying out surface modification, and as shown in Figure 1, titanium alloy surface DLC/CPP biological activity laminated film has excellent biological activity to result.
Embodiment
Embodiment 1
Get 1 × 1cm
2size Ti-6Al-4V sheet, Ti-6Al-4V sheet surface DLC/CPP biological activity complex thin film structure is Ti-6Al-4V matrix/DLC layer/CPP layer, treatment process carries out according to following steps: Ti-6Al-4V substrate is carried out conventional oil removing cleaning by (1), then in acetone and ethanolic soln, carries out ultrasonic cleaning successively; (2) Ti-6Al-4V substrate is placed in multi-arc ion coating-magnetron sputtering compound vapour deposition vacuum system, and carry out argon plasma sputter clean, argon gas flow is 500sccm, and bias voltage is 1.3KV, and target current is 12A, and the treatment time is 15min; (2) multi-arc ion coating Ti transition layer, metal Ti target is negative electrode, and working gas is argon gas, and flow is 70sccm, bias voltage 800V, treatment time 5 ~ 10min; (3) multi-arc ion coating deposition DLC, working gas is methane, and flow is 200sccm bias voltage is 800V, and dutycycle is 80%, and the treatment time is 40min; (4) modification of the poly-Dopamine HCL film in DLC surface, weigh 80mg Dopamine HCL and add the Tris-HCl buffered soln 40mL prepared, abundant stirring makes Dopamine HCL dissolve completely, then by surface deposition, this solution put into by the Ti-6Al-4V substrate of DLC film, after stirred at ambient temperature 2h, print is taken out, puts into deionized water for ultrasonic 1min, then use a large amount of deionized water rinsing, last nitrogen dries up; (5) phosphopeptide caseinate (CPP) is modified further on the DLC surface modifying poly-Dopamine HCL film, sample through previous step process is immersed in the phosphopeptide caseinate solution of the 10g/L be mixed with, rinse with PBS after left at room temperature overnight, vacuum-drying.Finally obtain DLC/CPP composite bio-active film at Ti-6Al-4V substrate surface.
Claims (2)
1. prepare the method for biological activity laminated film at titanium alloy surface for one kind, it is characterized in that the titanium alloy after conventional pre-treatment being placed in multi-arc ion coating-magnetron sputtering compound vapour deposition vacuum system, deposition take Ti as the DLC film of transition layer, and concrete steps are:
A, titanium alloy and Ti-6Al-4V plating piece surface sputtering clean, and titanium alloy substrate is placed in multi-arc ion coating-magnetron sputtering compound vapour deposition vacuum system, argon gas flow 500sccm, bias voltage is 1.3KV, and target current is 12A, and the treatment time is 15min;
B, multi-arc ion coating Ti transition layer, metal Ti target is negative electrode, and working gas is argon gas, and flow is 70sccm, bias voltage 800V, treatment time 5 ~ 10min;
C, multi-arc ion coating deposition DLC, working gas is methane, and flow is 200sccm bias voltage is 800V, and dutycycle is 80%, and the treatment time is 40min;
The modification of the poly-Dopamine HCL film in D, DLC surface, Dopamine HCL is added in Tris-HCl buffered soln, abundant stirring makes Dopamine HCL dissolve completely, then by surface deposition, this solution put into by the Ti-6Al-4V substrate of DLC film, after stirred at ambient temperature, print is taken out, puts into deionized water for ultrasonic process, then use deionized water rinsing, last nitrogen dries up;
E, modify phosphopeptide caseinate further on the DLC surface modifying poly-Dopamine HCL film, sample through D step process is immersed in phosphopeptide caseinate solution, rinse with PBS after left at room temperature, vacuum-drying, finally obtains DLC/CPP composite bio-active film at Ti-6Al-4V substrate surface.
2. the method for claim 1, is characterized in that the concentration of phosphopeptide caseinate solution in E step is 9-11g/L.
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| CN101469408A (en) * | 2007-12-25 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Method for depositing diamond-like carbon film on stainless steel substrate |
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| CN101469408A (en) * | 2007-12-25 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Method for depositing diamond-like carbon film on stainless steel substrate |
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| Title |
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| Preparation of DLC gradient biomaterials by means of plasma source ion implant-ion beam enhanced deposition;G.F. Yin;《Thin Solid Films》;19991231;全文 * |
| 聚多巴胺基复合薄膜研究取得新进展;陈东;《功能材料信息》;20101231;第7卷(第5-6期);全文 * |
| 钛合金表面壳聚糖-酪蛋白磷酸肽生物复合薄膜的制备及性能研究;王琳;《中国优秀硕士学位论文全文数据库 医药卫生科技辑》;20111115(第11期);摘要 * |
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