CN103160790A - 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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- CN103160790A CN103160790A CN2011104281119A CN201110428111A CN103160790A CN 103160790 A CN103160790 A CN 103160790A CN 2011104281119 A CN2011104281119 A CN 2011104281119A CN 201110428111 A CN201110428111 A CN 201110428111A CN 103160790 A CN103160790 A CN 103160790A
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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 for preparing the 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 medical research personnel's concern with characteristics 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 characteristics such as intensity is high, ductility is good.But its wear resistance and biological activity are relatively poor, though with as the ultra high molecular polyethylene of articular fossa soft material to mill, also can produce abrasive dust, abrasive dust can bring out bone resorption, thereby causes aseptic loosening of prosthesis and cause displacement to lose.Secondly after biomaterial implants, occur at first be organic molecule (being mainly protein molecule) in the absorption of material surface, generate adsorption layer, just can bring out further physiological response again on the organic molecule adsorption layer afterwards.Therefore, the surface treatment of titanium alloy is very important.
The at present research processed of titanium alloy surface mainly comprises physical treatment (sandblast, ion implantation etc.), chemical treatment (acid etching, differential arc oxidation, electrochemical deposition, alkali thermal treatment etc.), but for biological treatment, i.e. the surface biological albumen research of sticking 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, thereby make it be applied to more widely biomedical sector as biological implantation material, have important clinical meaning.
Summary of the invention
The purpose of this invention is to provide a kind of method with titanium alloy surface film of wear resisting property and good biological activity, with this tribological property and biological activity that improves titanium alloy, make up its deficiency in clinical application.
A kind of method for preparing the biological activity laminated film at titanium alloy surface, it is characterized in that to be placed in the compound vapour deposition vacuum system of multi-arc ion coating-magnetron sputtering through the titanium alloy after conventional pre-treatment, the DLC film of deposition take Ti as transition layer, concrete steps are:
A, titanium alloy are that Ti-6Al-4V plating piece surface sputtering cleans, and the titanium alloy substrate is placed in the compound vapour deposition vacuum system of multi-arc ion coating-magnetron sputtering, and argon gas flow 500sccm, bias voltage are 1.3KV, and target current is 12A, and the treatment time is 15min;
B, multi-arc ion coating Ti transition layer, the 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 that the 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, fully stirring dissolves Dopamine HCL fully, then with surface deposition the Ti-6Al-4V substrate of DLC film put into this solution, after stirring under room temperature, print is taken out, put into deionized water for ultrasonic and process, then use deionized water rinsing, last nitrogen dries up;
E, further modify phosphopeptide caseinate (CPP) on the DLC surface of modifying poly-Dopamine HCL film, to immerse through the sample of D step process in phosphopeptide caseinate solution, standing rinse with PBS afterwards under room temperature, vacuum-drying obtains DLC/CPP composite bio-active film at the Ti-6Al-4V substrate surface at last.
In the E step, the concentration of phosphopeptide caseinate solution is 9-11g/L.
The laminated film of preparation is made of titanium alloy substrate, DCL film, phosphopeptide caseinate activated protein top layer successively.Film had both kept a series of one's best qualities of titanium alloy as body material, had improved again its biological activity and tribological property.
The present invention has prepared the frictional coefficient of titanium alloy of DLC/CPP biological activity laminated film well below common alloy of titanium on the surface, dry friction coefficient is lower than 0.08, (friction-wear test adopts the ball-on-disc wear test machine to estimate, the mode that employing reciprocatingly slides, load is 5N, and friction pair is the Si of Φ 5mm
3N
4Ball).
The DLC/CPP biological activity laminated film that adopts the present invention to make has excellent tribological property and biological activity.Its characteristics are that DLC film and the efficiency that will have the performance of a series of excellences such as high rigidity and high-wearing feature and low-friction coefficient promote that human body combines to the absorption of calcium and the CPP of utilization, have prepared DLC/CPP biological activity laminated film.Titanium alloy through this laminated film modification had excellent tribological property and biological activity concurrently, overcome the shortcomings such as wear resistance that conventional titanium alloy exists in clinical application and biological activity be poor.Thereby satisfy its requirement in clinical application as biological implantation material.
Titanium alloy surface working method of the present invention belongs to vacuum plasma and Chemical self-assembly category, and environmental protection can be 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.
Description of drawings
Fig. 1 is the comparison of different treatment titanium alloy surface osteoblastic proliferation rate.We have carried out associated biomolecule with the titanium alloy that does not carry out surface modification and have learned performance comparison, result as shown in Figure 1, titanium alloy surface DLC/CPP biological activity laminated film has excellent biological activity.
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: (1) carries out conventional oil removing cleaning with the Ti-6Al-4V substrate, then carries out successively ultrasonic cleaning in acetone and ethanolic soln; (2) the Ti-6Al-4V substrate is placed in the compound vapour deposition vacuum system of multi-arc ion coating-magnetron sputtering, carries out the argon plasma sputter clean, and the 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 are 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 that the 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, weighing 80mg Dopamine HCL adds the Tris-HCl buffered soln 40mL for preparing, fully stirring dissolves Dopamine HCL fully, then with surface deposition the Ti-6Al-4V substrate of DLC film put into this solution, after stirring 2h under room temperature, print is taken out, put into deionized water for ultrasonic 1min, then use a large amount of deionized water rinsings, last nitrogen dries up; (5) modifying the further phosphopeptide caseinate (CPP) of modifying in DLC surface of poly-Dopamine HCL film, to immerse through the sample that previous step is processed in the phosphopeptide caseinate solution of the 10g/L that is mixed with, rinse vacuum-drying under room temperature after hold over night with PBS.Obtain DLC/CPP composite bio-active film at the Ti-6Al-4V substrate surface at last.
Claims (2)
1. method for preparing the biological activity laminated film at titanium alloy surface, it is characterized in that to be placed in the compound vapour deposition vacuum system of multi-arc ion coating-magnetron sputtering through the titanium alloy after conventional pre-treatment, the DLC film of deposition take Ti as transition layer, concrete steps are:
A, titanium alloy are that Ti-6Al-4V plating piece surface sputtering cleans, and the titanium alloy substrate is placed in the compound vapour deposition vacuum system of multi-arc ion coating-magnetron sputtering, and argon gas flow 500sccm, bias voltage are 1.3KV, and target current is 12A, and the treatment time is 15min;
B, multi-arc ion coating Ti transition layer, the 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 that the 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, fully stirring dissolves Dopamine HCL fully, then with surface deposition the Ti-6Al-4V substrate of DLC film put into this solution, after stirring under room temperature, print is taken out, put into deionized water for ultrasonic and process, then use deionized water rinsing, last nitrogen dries up;
E, further modify phosphopeptide caseinate on the DLC surface of modifying poly-Dopamine HCL film, to immerse through the sample of D step process in phosphopeptide caseinate solution, standing rinse with PBS afterwards under room temperature, vacuum-drying obtains DLC/CPP composite bio-active film at the Ti-6Al-4V substrate surface at last.
2. the method for claim 1, the concentration that it is characterized in that phosphopeptide caseinate solution in the E step is 9-11g/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108853604A (en) * | 2018-06-06 | 2018-11-23 | 湖北大学 | A method of quickly eliminating bone implant surface bacteria biomembrane using near-infrared |
| CN114481074A (en) * | 2022-04-06 | 2022-05-13 | 中南大学湘雅医院 | Magnesium alloy surface coating material and application thereof |
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| US20100034495A1 (en) * | 2005-08-01 | 2010-02-11 | Aktiebolaget Skf | Bearing and method of producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100034495A1 (en) * | 2005-08-01 | 2010-02-11 | Aktiebolaget Skf | Bearing and method of producing the same |
| 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 |
Non-Patent Citations (3)
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| G.F. YIN: "Preparation of DLC gradient biomaterials by means of plasma source ion implant-ion beam enhanced deposition", 《THIN SOLID FILMS》, 31 December 1999 (1999-12-31) * |
| 王琳: "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", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》, no. 11, 15 November 2011 (2011-11-15) * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108853604A (en) * | 2018-06-06 | 2018-11-23 | 湖北大学 | A method of quickly eliminating bone implant surface bacteria biomembrane using near-infrared |
| CN108853604B (en) * | 2018-06-06 | 2020-11-27 | 湖北大学 | Method for rapidly eliminating bacterial biofilm on surface of bone implant by utilizing near infrared |
| CN114481074A (en) * | 2022-04-06 | 2022-05-13 | 中南大学湘雅医院 | Magnesium alloy surface coating material and application thereof |
| CN114481074B (en) * | 2022-04-06 | 2022-06-17 | 中南大学湘雅医院 | Magnesium alloy surface coating material and application thereof |
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