沉积温度对多孔钛表面仿生制备羟基磷灰石的影响

为研究沉积温度对羟基磷灰石涂层生长的影响,制备了不同温度条件下成分恒定的仿生沉积液,并采用纯钛和不同孔径的多孔钛做基体,在其表面仿生沉积羟基磷灰石涂层,再将得到的涂层试样浸泡在标准模拟体液中检测其生物活性.通过X射线衍射仪(XRD)分析涂层物相结构,用金相显微镜、环境扫描电子显微镜(ESEM)表征涂层形貌,利用能谱分析仪(EDS)计算钙磷比.研究表明:基体孔径增大,有利于沉积液进入到孔隙且表面粗糙度相对增大,从而使得HA涂层变得均匀致密;沉积温度由30℃升高至37℃,会加快HA涂层致密均匀的生长,但温度升高到44℃时,HA晶粒变粗大,涂层变得疏松化;模拟体液浸泡后,Ti/HA涂层试样表面有新的HA生成,且Ca/P比接近标准的1.67,表明该Ti/HA涂层试样具有良好的生物活性.适当增大钛基体孔径,提高沉积液温度,可以得到均匀致密的HA生物活性涂层.     

Ti合金表面沉积羟基磷灰石-牛血清蛋白生物活性涂层

通过仿生生长方法,将预处理后的钛片浸入到添加有牛血清蛋白的模拟体液中,使钙磷盐和牛血清蛋白(BSA)共沉积到钛合金的表面,制备生物活性涂层.利用SEM、XRD、红外光谱等对涂层进行了表征,结果表明:BSA通过化学作用和钙磷盐共沉积到基体的表面,并且BSA具有细化涂层晶粒的作用.     

等离子体喷涂氧化钛涂层的生物活性研究

以纳米TiO₂粉末为喷涂原料, 采用大气等离子体喷涂技术在医用钛合金上制备氧化钛涂层. 利用酸和碱溶液对氧化钛涂层表面进行生物活化处理, 体外模拟体液浸泡实验考察涂层的生物活性. 采用XRD、SEM、FTIR、EDS等测试技术对改性前后氧化钛涂层的生物活性进行表征. 结果表明: 氧化钛涂层和钛合金基体的结合强度较高, 其值高达40MPa, 涂层的耐模拟体液腐蚀性优于钛合金. 酸和碱溶液表面改性后的氧化钛涂层经模拟体液浸泡可在其表面生成含有碳酸根的羟基磷灰石(类骨磷灰石), 显示良好的生物活性.     

Ti40Zr10Cu36Pd14大块金属玻璃表面HA/TiO2涂层的制备

Ti40Zr10Cu36Pd14金属玻璃具有较好的玻璃化形成能力和可靠的生物力学性能,但生物活性较差。采用溶胶凝胶法在Ti40Zr10Cu36Pd14金属玻璃表面构建TiO2涂层,并进行水热处理使其具有锐钛矿结构;随后又在模拟体液(SBF)中进行仿生生长实验。采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和激光显微拉曼光谱仪(Raman)等观察和分析涂层表面形貌及物相组成。结果表明,TiO2涂层可改善Ti40Zr10Cu36Pd14金属玻璃试样表面生物活性;在模拟体液中浸泡7天后,覆盖TiO2涂层的金属玻璃可快速诱导磷灰石沉积,在金属玻璃基体表面形成HA/TiO2复合涂层。     

射频磁控溅射制备 HA(+ZrO2+Y2O3)/Ti6Al4V 复合生物活性涂层

采用射频磁控溅射法制备了HA（＋ZrO2＋Y2O3）／Ti6Al4V生物复合涂层．借助于XRD、SEM、FTIR和AFM等对溅射涂层的相组成、微观形貌和界面结合进行了研究，并以模拟体液试验探讨了涂层的生物活性．实验结果表明：磁控溅射的复合涂层呈非晶态，经过退火处理，可以使其转化为晶态；复合涂层的微观表面凹凸不平，并呈现网状结构和较多的孔隙，其孔隙直径约为0．5-2．0μm，孔隙面积占涂层表面积的30％-40％；HA（＋ZrO2＋Y2O3）／Ti6Al4V复合涂层的界面结合强度随（ZrO2＋Y2O3）复合颗粒含量的增大和溅射功率的提高而增强，最高可达59．6MPa．复合涂层在模拟体液中浸泡一段时间后，表面覆盖一层新生物质—含有CO^2-3的类骨磷灰石，其晶粒非常小，它与自然骨中无机相的结构成分相似，表明复合涂层具有良好的生物活性．     

表面改性后AZ31B镁合金在不同模拟体液中的降解性能研究

采用化学沉积法在AZ31B镁合金表面制备了钙磷陶瓷涂层,通过浸泡试验和电化学试验研究了其在3种不同模拟体液(生理盐水、PBS、Hank′s)中的降解性能。结果表明,沉积处理改变了AZ31B镁合金在模拟体液中的降解性能,明显抑制了其降解速度;浸泡后溶液的pH值变化结果和电化学实验结果均表明,在3种不同模拟体液中,表面处理后AZ31B镁合金显示出不同的降解速度,顺序依次为:生理盐水>PBS溶液>Hank′s溶液。     

通过仿生法在硅橡胶表面制备磷灰石薄膜的研究

用CaCl2的乙醇溶液和K2HPO4溶液对硅橡胶进行预处理,将处理过的硅橡胶分别浸渍于模拟体液和钙磷饱和溶液中来制备磷灰石薄膜.利用薄膜X射线衍射、红外吸收光谱和扫描电子显微镜对形成的薄膜进行了表征.结果表明,分别在模拟体液中7d和在钙磷饱和溶液中5d后,硅橡胶表面形成了一层磷灰石薄膜;在模拟体液中的薄膜表面呈网状并分布有许多球状晶粒,在钙磷饱和溶液中的薄膜为结晶良好的片状晶体.     

CaB_6对激光熔覆生物陶瓷涂层组织和生物学性能的影响

为了提高医用钛合金表面激光熔覆羟基磷灰石(HA)涂层的植入稳定性和生物活性,将HA与CaB_6粉末充分混合,采用激光熔覆工艺制备了含硼元素的生物陶瓷涂层。通过X射线衍射仪(XRD)、扫描电镜(SEM)、电化学腐蚀和体外模拟体液(SBF)浸泡实验,对涂层的物相组成、组织形貌、耐腐蚀性和生物活性进行了研究。结果表明,添加CaB_6后熔覆层中产生了物相B_2O_3和CaB_2O_4,同时熔覆层中部组织呈现有序分布的二次枝晶;腐蚀电位下降了294.46 mV,电流密度是未添加CaB_6的4.28倍;在体外SBF浸没实验中,添加CaB_6后,涂层表面沉积的磷灰石均匀分布,浸泡7 d后,形成的矿化磷灰石沉积量最大,涂层表现出较强的矿化作用。CaB_6的添加可以细化晶粒,显著提升生物陶瓷涂层的耐腐蚀性,加强涂层表面的矿化能力。     

钛涂覆多孔羟基磷灰石涂层的制备及其生物活性

在纯钛基体表面通过电泳沉积的方法制得壳聚糖/羟基磷灰石(CS/HA)复合涂层, 然后将复合涂层烧结形成多孔HA涂层。采用SEM对多孔HA涂层的形貌进行观察, XRD分析涂层的物相组成, 粘结拉伸实验测定涂层与基体的结合强度, 1.5倍人体模拟体液(1.5SBF)浸泡测定涂层的生物活性。结果表明: 当悬浮液中CS与HA质量比为1∶1时, 制得的CS/HA复合涂层经过700℃烧结处理, 涂层中CS热分解致孔形成多孔HA涂层, 孔径在10~25 μm, 涂层与基体的结合强度可达19.5 MPa; 在1.5SBF中浸泡5天后, 多孔HA涂层表面完全碳磷灰石化, 呈现较好的生物活性。      

两步电沉积法制备HA-Ti/HA复合涂层的研究

为了提高金属基羟基磷灰石（HA）涂层的结合强度,采用复合电沉积一电沉积两步法在含Ti粉的钙磷电解液中制备HA—Ti／HA复合涂层,对涂层的组分结构、表面形貌、热稳定性、结合强度和生物活性进行了研究．实验结果表明：两步法制备的底层为HA—Ti复合涂层,外层为纯HA涂层的HA—Ti／HA复合涂层既提高了涂层的结合强度,又保证了涂层的生物活性．当涂层中Ti粉的质量分数为51．2wt％时,涂层与基体的结合强度达到21．2MPa,约为纯HA涂层的3倍．模拟体液浸泡7天后,涂层表面即被一层球状碳磷灰石覆盖,具有良好的生物活性,与纯HA涂层相比,复合涂层具有更好的耐蚀性能．     

TC4钛合金微弧氧化因素对生物陶瓷膜中Ca,P相对含量的影响

为了提高钛合金陶瓷膜的生物相容性,采用微弧氧化技术在TC4钛合金表面制备了一层富含Ca,P的生物活性陶瓷膜。采用SEM,EDS,XRD研究了电流密度、溶液中Ca,P摩尔比、添加剂EDTA.2Na浓度对膜层中Ca,P相对含量(原子分数)及Ca,P摩尔比的影响及微弧氧化生物陶瓷膜层的形貌及组成。结果表明:随着电流密度的增大,膜层中的Ca,P相对含量增加,Ca,P摩尔比也逐渐增加;增大溶液中Ca,P摩尔比,膜层中Ca相对含量有所增加,Ca,P摩尔比也逐渐增加;当加入添加剂EDTA.2Na时,膜层中的Ca相对含量显著增加,从而使膜层中Ca,P摩尔比显著增加;氧化膜由致密的内膜层和多孔的外膜层构成,主要由Ca,P,O,Ti,V元素组成,其相成分主要为金红石和板钛矿型TiO2,并含有一定量的非晶相Ca,P化合物。     

表面预氧化镍钛丝微弧氧化涂层的研究

通过微弧氧化法(MAO)在表面预氧化镍钛(NiTi)丝(直径(0)0.5mm)表面制备含Ca、P的均匀微孔涂层,对不同处理时间形成的涂层进行扫描电镜(SEM)形貌观察和电子探针(EPMA)成分分析,并探查了涂层的血液相容性.实验结果表明,表面预氧化的NiTi丝在微弧氧化处理时,随微弧氧化时间的延长,氧化层中Ti/Ni提高,Ca、P含量也提高.微弧氧化20s时,涂层质量较好,微孔均匀分布,微孔孔径1μm左右,表面没有裂纹,而且此时涂层有较好的生物相容性.     

The influence of discharge power and heat treatment on calcium phosphate coatings prepared by RF magnetron sputtering deposition

Ca–P coatings with different Ca/P ratio and composition were successfully prepared by RF magnetron sputtering deposition. The Ca/P ratio, phase composition, structure and morphological properties were characterized by XRD, FTIR, EDS and SEM analyses. All the as-sputtered coatings were amorphous and after IR-irradiation the coatings altered into a crystalline phase. The obtained coatings had a Ca/P ratio that varied from 0.55 to 2.10 and different phase compositions or mixtures of apatite, beta-pyrophosphate and beta-tricalciumphosphate structures were formed. Evidently, the phase compositions of the sputtered coatings are determined not only by the discharge power ratio of the hydroxylapatite and calcium pyrophosphate targets but also by the annealing temperature.     

The influence of target stoichiometry on early cell adhesion of co-sputtered calcium–phosphate surfaces

The nature of the initial interaction between calcium phosphate (Ca–P) thin films and osteoblasts can be influenced by a number of different properties including the phase, crystallinity, stoichiometry and composition of the surface. There is still a strong interest in developing and studying Ca–P surfaces that have the ability to accurately control the osteoblast response. Radio frequency (RF) magnetron sputtering is a technique that allows for accurate control of the properties of deposited Ca–P coatings and has been studied extensively because of this fact. In this work, Ca–P coatings were co-deposited using RF magnetron sputtering in order to study the effect of changing the target stoichiometry on the initial in vitro behavior of MG63 osteoblast-like cells. The samples produced were analysed both as-deposited and after thermal annealing to 500 °C. After annealing XPS analyses of the samples co-deposited using tricalcium phosphate (TCP) materials gave a Ca/P ratio of 1.71 ± 0.01, as compared to those co-deposited from hydroxyapatite (HA) materials, with a Ca/P of 1.82 ± 0.06. In addition to this, the curve fitted XPS data indicated the presence of low levels of carbonate in the coatings. Despite this the XRD results for all of the annealed coatings were shown to be characteristic of pure HA with a preferred 002 orientation. The atomic force microscopy results also highlighted that both types of coatings had surface features of a similar size (200–220 nm). Both surfaces exhibited a degree of surface degradation, even after 1 h of cell culture. However, the TCP derived surfaces showed an enhanced osteoblastic cell response in terms of cell adhesion and cell proliferation in the earlier stages of cell culture than the surfaces deposited from HA. An improvement in the initial cell attachment and a potential for increased cell proliferation rates is viewed as a highly advantageous result in relation to controlling the osteoblast response on these surfaces.     

喷涂距离和喷涂功率对羟基磷灰石涂层的影响

本文以Ｔｉ－６Ａｌ－４Ｖ合金为基体材料,采用等离子喷涂方法,在不同喷涂距离和喷涂功率下制备羟基磷灰石（ＨＡ）涂层,研究喷涂距离和喷涂功率这两个重要的喷涂参数对涂层结构和组成的影响．使用扫描电子显微镜（ＳＥＭ）观察了羟基磷灰石涂层的形貌．涂层的相组成由Ｘ射线衍射谱仪（ＸＲＤ）分析而得．并使用Ｘ射线荧光谱仪（ＸＲＦ）测定了涂层的Ｃａ／Ｐ摩尔比．研究结果表明,喷涂距离对羟基磷灰石涂层的形貌、相组成以及Ｃａ／Ｐ摩尔比有着明显的影响．随着喷涂距离的增大,羟基磷灰石粉末的熔化状态得到改善,涂层的显微结构较为致密．然而,喷涂距离的增大使得涂层的非晶化更加严重,涂层中非晶相含量增大．在实验范围内,喷涂功率对涂层结构和相组成的影响不明显．Ｃａ／Ｐ比测定显示,等离子喷涂羟基磷灰石涂层均为缺磷涂层,Ｃａ／Ｐ比随喷涂距离的增大而降低,随喷涂功率的增大而增大．     

ZrO2改性CaO-SiO2复合生物涂层的制备及表征

以CaO稳定的ZrO2为原料,与适量SiO2在1400℃下反应.制得CazSiO4不同含量(质量分数:20%、40%、60%)的ZrO2改性CaO-SiO2复合粉体,并采用大气等离子体喷涂技术制备涂层.利用X射线衍射(XRD)、电子探针(ETMA)及能量色散谱(EDS)对涂层相组成和形貌进行表征.涂层的体外生物活性和稳...     

电压对钛表面微弧氧化陶瓷层特性的影响

为了提高钛表面的生物活性,利用微弧氧化技术在钛表面制备了含有钙磷的多孔二氧化钛陶瓷层。研究了施加电压对多孔微弧氧化层的平均孔径、表面粗糙度、相成分、钙磷含量以及Ca/P原子比的影响。结果表明,随着微弧氧化电压的升高,平均孔径、表面粗糙度、膜层中钙磷含量以及Ca/P原子比都逐渐增大,膜层的相成分由锐钛矿逐渐向金红石转变,并且膜层中逐渐有羟基磷灰石生成。     

电流密度对复合氧化法制备涂层结构的影响

对TiO2薄膜涂层的结构、形貌、元素组成、硬度进行了观察和测量,研究了电流密度对复合氧化法(即预氧化和微弧氧化复合处理)制备多孔TiO2涂层的结构和性能的影响.结果表明:电流密度对多孔TiO2涂层的结构和性能有很大影响.随着电流密度的增加,涂层的锐钛矿型TiO2含量减少,金红石型TiO2含量增加,涂层表面微孔孔径增加,凹凸起伏变得明显,显微硬度增加,钙磷原子比也发生了变化.当电流密度为20,40,60,80和100 mA/cm2时,涂层的钙磷摩尔比为1.22,1.60,1.89,2.01,2.12.在40 mA/cm2电流密度下可得到结构和性能较理想的多孔TiO2梯度涂层.     

Bioactive Ca–P coating with self-sealing structure on pure magnesium

Bioactive coatings containing Ca and P with self-sealing structures were fabricated on the surface of pure magnesium using micro-arc oxidation technique (MAO) in a specific calcium hydroxide based electrolyte system. Coatings were prepared at three applied voltages, i.e. 360, 410 and 450 V, and the morphology, chemical composition, corrosion resistance and the degradation properties in Hank’s solution of the MAO-coated samples with three different applied voltages were investigated. It was found that all the three coatings showed similar surface morphologies that the majority of micro-pores were filled with compound particles. Both the porous structures and the compound particles were found to contain consistent chemical compositions which were mainly composed of O, Mg, F, Ca and P. Electrochemical tests showed a significant increase in corrosion resistance for the three coatings, meanwhile the coating obtained at 450 V exhibited the superior corrosion resistance owing to the largest coating thickness. The long term immersion tests in Hank’s solution also revealed an effective reduction in corrosion rate for the MAO coated samples, and the pH values of the coated samples always maintained a lower level. Besides, all the three coatings were subjected to a mild and uniform degradation, while the coating obtained at 360 V showed a relatively obvious degradation characteristic and appreciable Ca and P contents on the surfaces of the three coatings were observed after immersion in Hank’s solution. The results of the present study confirmed that the MAO coatings containing bioactive Ca and P elements with self-sealing structures could significantly enhance the corrosion resistance of magnesium substrate in Hanks’ solution with great potential for medical application.     

An innovative auto-catalytic deposition route to produce calcium–phosphate coatings on polymeric biomaterials

The aim of this research is to develop a new methodology to obtain bioactive coatings on bioinert and biodegradable polymers that are not intrinsically bioactive. In this study three types of materials were used as substrates: (i) high molecular weight polyethylene (HMWPE) and two different types of starch based blends (ii) starch/ethylene vinyl alcohol blends, SEVA-C and (iii) starch/cellulose acetate blends, SCA. Two types of baths were originally proposed and studied to produce novel auto-catalytic calcium–phosphate (Ca–P) coatings. Then, the coated surfaces were analyzed by scanning electron microscopy and energy dispersive spectroscopy (SEM/EDS), as produced, and after different immersion periods in SBF. The evolution of Ca and P concentrations was determined by induced-coupled plasma emission (ICP) spectroscopy. The crystalline phases present on the films formed on the different material surfaces, after a certain soaking time, were identified by thin-film X-ray diffraction (TF-XRD). The obtained results indicated that it was possible to coat the materials surfaces with a Ca–P layer with only 60 min of immersion in both types of auto-catalytic solutions. Furthermore, it was possible to observe the clear bioactive nature of the Ca–P coatings after different immersion periods in a simulated body fluid (SBF). The results from TF-XRD confirmed the presence of partially amorphous Ca–P films with clearly noticeable hydroxylapatite peaks. These new methodologies allow for the production of an adherent bioactive film on the polymeric surfaces prior to implantation, which may allow for the development of bone-bonding, bioabsorbable implants and fixation devices. ©2003 Kluwer Academic Publisher