含氟、锌、银的羟基磷灰石涂层的制备及其生物学效应的研究

发布时间：2019-03-21 17:41

【摘要】：生物材料是最具发展潜力的材料,其中羟基磷灰石(Ca10(PO4)6(OH)2HA)以其优良的生物相容性和分子结构与人体骨组织分子结构高度相似性成为最具有代表性的骨修复和骨替代材料,常被用于医用金属材料的表面改性涂层[1]。而在众多的金属材料中,钛合金以其优良的抗腐蚀性能和力学性能,已经得到了广泛的临床应用,如Ti6A14V、Ti6A17Nb等常被应用于人体硬组织植入物如人工关节、骨折固定器等领域[2、3]。因此目前研究最多的就是将HA以薄膜的形式涂到钛合金表面,制备出兼具有生物活性,而且力学性能和抗腐蚀性能优良的新型材料[4]。但新型材料在实际的运用中出现了一系列新的问题。比如羟基磷灰石在人体内的降解速率太快[5],导致其在体内过早失效；部分植入材料和骨替代材料术后患者出现感染症状,而导致手术失败。通过添加部分微量元素,可以在很大程度上改善上述缺陷。加入微量元素氟,以氟替代羟基磷灰石中的羟基,可以在很大程度上降低材料的溶解度,延长材料使用寿命；加入微量元素银,以银替代小部分羟基磷灰石的钙,可以提高材料的抗菌性能,降低术后患者的感染风险；另外锌元素的加入对成骨细胞的增殖有直接刺激作用,同时对破骨细胞有一定的抑制作用,可以提高羟基磷灰石的生物活性。因此,同时将三种元素加入到羟基磷灰石中,制备出一种新型的生物材料,有着良好的应用前景和实际意义。通过查阅大量文献和相关专业的资料的基础上,最终确定以HPF6、AgN03和Zn(NO3)2·6H2O作为氟引入剂和银、锌的添加剂。将一定量的Ca(NO3)2和P205分别溶于乙醇中经搅拌后充分溶解。制备出Ca(NO3)2和P205的乙醇溶液后,将两种溶液按照一定的比例混合。然后将三种添加剂按照严格的顺序加入上述混合液中,回流24小时后形成涂膜液,采用浸渍-提拉技术,在钛合金基板上涂覆一层有特定氟、锌、银含量的羟基磷灰石薄膜,以满足理想生物材料的需求。本论文在研究含三种元素的羟基磷灰石(X-HA)的薄膜的同时,对含氟羟基磷灰石(FHA)、载锌羟基磷灰石(Zn-HA)、载银羟基磷灰石(Ag-HA)的制备和相关性能也做了一定的研究。本实验采用XRD、XPS、SEM等技术对所有制备的薄膜材料进行了薄膜晶相组成、表面形貌以及微量元素的加入对HA的影响和微量元素相互之间的影响进行了分析。用模拟体液浸泡来观察新材料的抗溶解性能、用MTT比色法测定新材料对成骨细胞增殖的刺激作用、用材料对大肠埃希菌的抗菌性测定新材料的抗菌性能。本论文获得的具体结果如下： 1)通过溶胶-凝胶法能够成功制备出理想的新型生物材料X-HA。 2)微量添加剂的加入并未影响到HA分子的形成。 3)氟离子成功进入到HA分子中取代了羟基的位置,锌离子和银离子部分进入到HA分子中取代了HA分子中钙离子的位置。 4)新材料中银离子、锌离子的加入并未影响新材料的抗溶解性能。 5)新材料中锌离子、氟离子的加入并未影响到新材料的抗菌性能。 6)新材料的刺激成骨细胞增殖作用受到一定影响,但是较纯HA,还是有明显的改进。
[Abstract]:The biological material is the most promising material, in which the hydroxyapatite (Ca10 (PO4)6 (OH) 2HA) is the most representative bone repair and bone substitute material with its excellent biocompatibility and molecular structure and the molecular structure of human bone tissue. A surface-modified coating[1], which is often used for medical metallic materials. In many metal materials, titanium alloy has been widely used in the fields of hard tissue implants such as artificial joint and fracture fixer, such as Ti6A14V, Ti6A17Nb, etc. Therefore, at most, the HA is applied to the surface of the titanium alloy in the form of a thin film, and the novel material[4] with excellent biological activity and excellent mechanical property and corrosion resistance is prepared. But the new material has a series of new questions in the practical application Problems. For example, the rate of degradation of the hydroxyapatite in the human body is too fast[5], resulting in premature failure in the body, partial implantation of the material and the presence of symptoms of infection in the patient after the replacement of the bone, leading to surgical loss by adding some of the trace elements, it is possible to improve the above-mentioned deficiency to a large extent A trace element fluorine is added to replace the hydroxyl in the hydroxyapatite, so that the solubility of the material can be greatly reduced, the service life of the material is prolonged, the trace element silver is added, the calcium of the small-part hydroxyapatite is replaced with silver, and the antibacterial property of the material can be improved. The addition of the zinc element has direct stimulation to the proliferation of the osteoblast, and at the same time, the osteoclast has a certain inhibition effect, and the biological activity of the hydroxyapatite can be improved. Therefore, three elements are added into the hydroxyapatite, a novel biological material is prepared, and the novel biological material has good application prospect and practical meaning. It is defined that HPF6, AgN03 and Zn (NO3) 2.6H2O are used as the fluorine-introducing agent and the silver and the zinc on the basis of consulting a large number of documents and relevant professional data. adding a certain amount of Ca (NO3)2 and P205 in ethanol, stirring, and charging; And dissolving. After the ethanol solution of Ca (NO3)2 and P205 is prepared, the two solutions are mixed according to a certain ratio. mixing, adding the three additives into the mixed solution in a strict sequence, refluxing for 24 hours to form a coating solution, and coating a layer of the hydroxyapatite film with a specific fluorine, zinc and silver content on the titanium alloy substrate to meet the ideal biological material by adopting the dipping-pulling technology The preparation and related properties of hydroxyapatite (HA), zinc-loaded hydroxyapatite (Zn-HA) and silver-loaded hydroxyapatite (Ag-HA) were also studied. The film phase composition, surface morphology and trace element addition to HA and the effect of trace elements on HA were studied by XRD, XPS and SEM. The effect of the new material on the proliferation of the osteoblast was measured by means of the MTT colorimetric method, and the antibacterial activity of the new material was determined by MTT colorimetric method. The antibacterial properties of the material. The specific results obtained are as follows:1) It can be successfully prepared by the sol-gel method A new type of biological material X-HA. the in did not affect the formation of the HA molecule.3) The fluoride ion was successfully removed from the HA molecule the position of the hydroxyl group, the zinc ion and the silver ion part enter the HA, in that molecule, the position of the calcium ion in the HA molecule is replace, and 4) the silver ion in the new material, The addition of zinc ions does not affect the anti-dissolution performance of the new material. The addition of fluorine ions does not affect the antibacterial performance of the new material.6) The stimulation of the new material stimulates the proliferation of the osteoblast.
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2012
【分类号】：R318.08

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