脉冲频率及占空比对3D打印Ti6Al4V合金表面生物活性涂层的影响

采用微弧氧化法,在恒定电压下,使用不同的脉冲频率及脉冲占空比,在3D打印Ti6Al4V合金表面制备生物活性涂层。利用扫描电子显微镜、能谱仪、电化学工作站、涡流膜厚仪、Image J软件和划痕仪等对涂层进行结构、性能以及微观形貌表征,研究脉冲频率和脉冲占空比对涂层的影响。结果表明：随着脉冲频率的增加,涂层的平均孔径、Ca/P比、表面粗糙度和厚度均逐渐减小,孔隙率变化不明显;耐腐蚀性先得到改善后变差;涂层与基体的结合力逐渐变大。随着脉冲占空比增大,涂层的平均孔径、孔隙率、Ca/P比、厚度逐渐变大;耐腐蚀性能呈现先好后差的趋势;涂层与基体的结合力逐渐变弱。     

In vitro bioactivity and cytocompatibility of porous scaffolds of bioactive borosilicate glasses

The bioactive borosilicate scaffolds （R2O-RO-B2O3-SiO2-P2O5） with four different contents of borate were fabricated by replication technique. The bioactivity, degradability and the cytotoxicity of the scaffolds were studied in this paper. The porosity of the scaffolds was found to be 73%-80%, and the pore size was in the range of 200-300 μm. The porous scaffolds immersed in 0.02 mol.L^-1 K2HPO4 solution were transformed into hydroxyapatite. And it is notable that the D-AIk-2B, D-AIk-3B-scaffolds were covered by hydroxyapatite layers after 7 h-immersion, which proved their high bioactivity. In the cell adhesion test, cells could be seen growing well on the scaffolds, showing stretched morphology and obvious pseudopodia, and only the high cumulative concentration of B ions released from the D-AIk-3B-scaffold samples had an inhibition effect on cell proliferation. But the inhibition effect could be alleviated by diluting the extract solution to a certain concentration （dilution ratio： 1：8）. Therefore, after suitable pretreatment, the porous borosilicate bioactive glass scaffold can be a desirable candidate for bone tissue engineering.     

聚多巴胺对氧化处理后钛合金表面沉积羟基磷灰石的影响

利用阳极氧化法和微弧氧化法分别对医用钛合金表面进行处理,再经聚多巴胺薄膜表面修饰后,利用仿生溶液矿化法制备羟基磷灰石生物活性涂层,并研究聚多巴胺对经不同氧化处理的医用钛合金生物诱导沉积能力的影响;采用场发射扫描电子显微镜、X射线光电子能谱仪和X射线衍射仪对经不同氧化处理及其生物诱导沉积羟基磷灰石涂层的表面形貌、元素组成和相结构进行表征分析.结果表明：阳极氧化和微弧氧化处理后的钛合金表面分别形成了纳米管和微米孔结构;再经聚多巴胺修饰后,可以显著提高羟基磷灰石涂层的生物诱导沉积能力,而且使得羟基磷灰石的排列致密、规则.     

人胚胎骨髓基质干细胞的长期培养及体外成骨特性

研究了人胚胎骨髓基质干细胞(hBMSCs)在体外长期培养时的基本特性和向成骨细胞的分化能力。结果表明：前三代hBMSCs多数呈长梭形,生长快速,增殖能力强;而后几代细胞变得比较扁平,生长缓慢,增殖能力下降;至第六代,细胞已失去增殖能力。每一代细胞生长均分为延滞期、对数生长期和稳定期,延滞期一般为6～7d,对数生长期为4～5d,最后是稳定期。前三代细胞对数生长期的群体倍增时间(PD71)基本相同,而第四代细胞的PDT略有上升,第五代细胞的PDT最大。在体外扩增能力方面,前三代细胞均可以扩增18倍左右,而第四、第五代细胞则下降至11倍、5倍。实验结果表明扩增后的细胞经过诱导可以形成钙化小结,与未诱导细胞相比碱性磷酸脂酶(ALP)活性显著提高。     

铝合金表面有色钛/锆转化膜的成膜机理及性能

为了解决工业生产中钛/锆转化膜无色的问题,通过向含钛/锆的处理液中加入单宁酸及成膜促进剂,在铝合金表面制备了有色钛/锆转化膜.采用X射线能谱仪、扫描电镜、傅里叶变换红外光谱仪、X射线衍射仪、X射线光电子能谱仪和电化学工作站对转化膜的形成过程、形貌、组织结构、耐蚀性等进行了分析.结果表明:在铝合金表面成功制备出了金黄色、耐蚀性优异的转化膜,其主要成分是Na3AlF6,其次是单宁酸水解产物的金属络合物以及少量Al2O3.3H2O、TiO2等;膜的形成可分为Na3AlF6晶体成核、生长和金属络合物的沉积3个阶段;转化膜的腐蚀电流密度由基体的5.894μA/cm2下降到0.283μA/cm2,耐蚀性明显提高.     

沉积温度对纯钛表面制备Cu掺杂羟基磷灰石涂层的影响

在钛和钛合金表面制备羟基磷灰石（hydroxyapatite, HAp）涂层能够显著提升其生物活性。HAp中进一步掺杂Cu，可以获得抗菌效果，有效避免术后感染。为研究温度对纯钛表面制备Cu掺杂羟基磷灰石（CuHAp）涂层形貌的影响，采用电化学沉积的方法，在不同温度下制备CuHAp涂层。采用扫描电子显微镜、能量色散X射线光谱仪、X射线衍射仪对涂层的表面形貌、元素含量和物相组成进行表征。结果表明：随着沉积温度的升高，沉积过程中的电流密度也随之增大。沉积温度由25 ℃升高至45 ℃，会加快CuHAp涂层致密均匀的生长；但温度升高到55 ℃时，CuHAp涂层变得疏松，并且出现裂纹。沉积温度低于45 ℃时，Ca+Cu与P的物质的量比小于1.67，有利于骨生长。适当提高沉积温度，可以得到均匀致密的CuHAp涂层。     

High-temperature oxidation resistance of ceramic coatings on titanium alloy by micro-arc oxidation in aluminate solution

Ceramic coatings with aluminum titanuate (Al₂TiO₅) were prepared on Ti–6Al–4V alloy using pulsed bi-polar Micro-arc Oxidation (MAO). The micromorphology and phase composition of the micro-arc-oxidition ceramic coatings on the titanium alloy were characterized by X-ray powder diffraction (XRD), and scanning electron microscopy (SEM) respectively. The results revealed that the distinct discharge channels and pores on the surface of the micro-arc-oxidition coatings appeared, and these channels were connected in the molten state. The electrolyte concentration was inversely proportional to the coating hardness; additionally, the coating prepared with sodium aluminate and sodium hypophosphite concentrations of 4 ?g/L and 0.5 ?g/L, respectively, was the most refined after high-temperature sintering, and it was demonstrated to better prevent oxidation. Increasing the electrolyte concentration coincided with fluctuating coating thermal shock resistance. The thermal shock resistance of the coating respectively prepared with sodium aluminate, and the sodium hypophosphite concentrations of 4 ?g/L and 0.5 ?g/L was the highest. Additionally, the high-concentration coatings performed significantly better than the low-concentration coatings. The oxidation resistance of the coating samples was also significantly higher than that of the TC4 titanium alloy substrate. The adhesion strength between the coatings and the substrate with and without the sealing treatment was measured by tensile tests. Then, the high-temperature oxidation performance of the coating samples with and without the sealing treatment was investigated by conducting a high-temperature oxidation experiment at a calcinating temperature of 500 ?°C. The results indicate that the adhesion strength between the coatings and substrate was high for the as-prepared and sealed micro-arc oxidation samples regardless of whether they were calcined. The high-temperature oxidation mass increase curves for the sealed and unsealed coating samples calcined at 500 ?°C for 500 ?h revealed that the high-temperature-oxidation-induced mass increase of the coating samples sealed with a sodium silicate solution was much lower than that of the titanium alloy substrate. Thus, the sealing treatment significantly improved the high-temperature oxidation resistance of the TC4 titanium alloy. Lastly, the high-temperature oxidation behavior at 500 ?°C was analyzed and discussed.     

In vitro antibacterial and osteogenic properties of plasma sprayed silver-containing hydroxyapatite coating

The objective of the present investigation was to characterize the antibacterial and osteogenic properties of plasma sprayed silver-containing hydroxyapatite （HA/Ag） coating in vitro. HA/Ag coating was deposited via vacuum plasma spraying. The concentration of silver ions released from HA/Ag coating, the efficacy of the HA/Ag coating against bacterial biofilm development, the effect of the HA/Ag coating on early adhesion and ossification of osteoblast cells in vitro was measured. The silver ion concentration released from the HA/Ag coating was between the minimum inhibitory concentration to bacteria and the cytotoxic concentration. Bacterial biofilm inhibition studies indicated an antibacterial activity on the HA/Ag coating surface when compared with hydroxyapatite （HA） coating alone. Moreover, it was demonstrated that osteoblast cell adhesion and mineralization occurred on the HA/Ag coating surface during the testing period. We conclude that the vacuum plasma sprayed HA/Ag coating possesses good antibacterial capability and osteogenic properties in vitro and represents a promising candidate for coating orthopedic implants.     

处理频率对TC4钛合金微弧氧化膜特性的影响

利用自制多功能微弧氧化膜的制备系统对TC4钛合金进行表面处理, 通过扫描电镜(SEM)和X射线衍射仪(XRD)研究脉冲频率(f)对氧化膜生长特性、 表面形貌和相组成的影响. 结果表明, 当f≤2 000 Hz时, 成膜速率随f增加迅速减小; 当2 000 Hz＜f＜4 000 Hz时, 成膜速率随f增加而减小的趋势变缓; 当f≥4 000 Hz时, 成膜速率不随f发生变化. 该氧化膜表面多孔, 随f的增加, 膜表面微孔尺寸逐渐减少, 微孔密度逐渐增加. 膜层主要由锐钛矿和金红石相TiO2及少量不饱和氧化物TiO2-x（0.02＜x＜0.07）相组成, 其中锐钛矿和金红石相TiO₂的相对含量随f的变化不明显, 而TiO_2-x的相对含量当f≤2 000 Hz时较高, 当f＞2 000 Hz时, TiO_2-x的相含量明显减少.      

基于8-羟基喹啉荧光敏感化合物的铝合金腐蚀监测技术

利用8-羟基喹啉(8HQ)与铝离子鳌合后形成的鳌合物——8-羟基喹啉铝(AlQ3)能发出强荧光的特性,开发了一种有效地铝合金涂层下腐蚀的监测技术.研究了铝离子浓度及pH对8-羟基喹啉铝(AlQ3)的吸光度及荧光特性的影响.发现了8HQ与Al3+鳌合生成的AlQ3荧光强度随Al3+浓度的变化规律.成功地将8-羟基喹啉加载在LY12铝合金表面,并以透明环氧树脂涂层覆盖.所制备的试样经盐雾腐蚀后表面出现明显的荧光斑点,荧光斑点处用光学显微镜观测可见腐蚀现象,而在可见光下观测并未有明显变化.研究表明:随着腐蚀时间延长,腐蚀程度加深,试样表面荧光现象增强.     

Coating mechanism of nano-TiO<Subscript>2</Subscript> films on the surface of ultra-fine calcined coal kaolin particles

A new type of mineral composite was made by calcined coal kaolin. The interaction mechanism of an inorganic modification reagent TiOSO₄ with the surface of ultra-fine calcined coal kaolin particles (substrate) was studied by X-ray photoelectron spectroscopy. The results show that chemisorption exists in the phase boundary between the modification agent and the substrate surface, while physical adsorption occurs on the modification layers of hydrate titanium dioxide. The interaction force was calculated and analyzed according to DLVO theory between ultra-fine calcined coal kaolin particles and hydrate titanium dioxide nano-particles in the modification system. It is shown that the both electrostatic force and van der Waals force are attractive, and the coacervation between ultra-fine calcined coal kaolin particles and hydrate titanium dioxide nano-particles leads to the coating of hydrate titanium dioxide on the surface of ultra-fine calcined coal kaolin particles.     

La-Mg-Ni系A2B7型贮氢合金表面包覆铜及其电化学性能

以A2B7型贮氢合金La1.5Mg0.5Ni7为研究对象,研究未包覆和表面包覆Cu以及对包覆铜的贮氢合金进行再包覆Ni、Co处理的合金电极电化学性能.实验结果表明,表面包覆Cu和Cu-Ni后的贮氢合金电极循环稳定性有所提高,而包覆Cu-Co的合金电极稳定性较差,但电极容量有所提高.线性极化扫描和电化学阻抗图谱分析结果表明,包覆Cu、Cu-Co及Cu-Ni处理改善合金电极的交换电流密度I0,降低电化学阻抗,说明包覆处理改善合金表面的电催化活性,加快合金表面电荷的迁移速率,从而提高高倍率放电能力.     

多孔Ti-45Nb合金的微观组织与力学性能研究

新型多孔Ti-Nb合金因为具有良好的生物相容性,在硬组织植入材料领域中受到关注。本文利用纯Ti和Nb粉采用粉末烧结法制备多孔Ti-45Nb合金。通过造孔剂NH4HCO3调控多孔钛合金的孔隙度、孔隙尺寸、孔隙形貌、弹性模量和抗压强度。研究结果表明:随着造孔剂含量的增加,多孔Ti-45Nb合金的孔隙度和孔隙尺寸增大,孔隙连通性增加;弹性模量和抗压强度减小。多孔Ti-45Nb合金的孔隙特性和力学性能满足硬组织植入材料的基本要求。     

钛合金经皮植入式假肢骨内固定植入体表面经生物陶瓷改性后与骨整合的研究

通过对钛合金经皮植入式假肢的的骨内固定植入体表面进行生物陶瓷改性,以研究经改性过的植入体与其宿主骨整合的能力.采用羟基磷灰石喷涂和微弧氧化两种生物陶瓷改性工艺,对骨内固定植入体进行改性处理,将改性过的植入体植入山羊后腿胫骨,术后8周取标本行组织学观察,见两种生物陶瓷改性的植入体均可与宿主骨形成严密整合.计算宿主骨组织与植入体整合率,发现经生物陶瓷表面改性的植入体与宿主骨组织整合率显著高于未经生物改性的对照组植入体(p＜0.01),而羟基磷灰石喷涂组和微弧氧化组与宿主骨整合率的差别无统计学意义(p＞0.05),说明羟基磷灰石和微弧氧化两种陶瓷层都具有很强的诱导骨生成能力,经其表面改性的骨内固定植入体能与宿主骨形成紧密整合.     

硬脂酸改性处理TC4钛合金微弧氧化膜层耐蚀性的研究

在Ti₆Al₄V合金微弧氧化膜层上采用硬脂酸改性处理实现了陶瓷膜层的疏水化转变，显著提高了钛合金的耐蚀性能。利用接触角测试仪、扫描电子显微镜（SEM）、能谱仪（EDS）和傅里叶变换红外光谱仪（FT-IR）对膜层的润湿性、稳定性、微观结构和化学组成进行了分析，并通过动电位极化曲线和电化学阻抗分析了其腐蚀行为。结果表明，改性处理得到的疏水微弧氧化膜层试样能有效修复微弧氧化膜层缺陷，提高钛合金的耐蚀性能，说明硬脂酸改性处理与微弧氧化技术相结合有助于拓宽微弧氧化技术在钛合金上的应用。     

Microstructure and Corrosion Resistance of Cr7C3/γ-Fe Ceramal Composite Coating Fabricated by Plasma Cladding

A new type in situ Cr7C3/γ-Fe ceramal composite coating was fabricated on substrate of hardened and tempered grade C steel by plasma cladding with Fe-Cr-C alloy powders. The ceramal composite coating has a rapidly solidified microstructure consisting of primary Cr7C3/γ- and the Cr7C3/γ-Fe eutectics, and is metallurgically bonded to the degree C steel substrate. The corrosion resistances of the coating in water solutions of 0.5 mol/L H2SO4 and 3.5% NaCl were evaluated utilizing the electrochemical polarization corrosion-test method. Because of the inherent excellent corrosion-resisting properties of the constituting phase and the rapidly solidified homogeneous microstructure, the plasma clad ceramal composite coating exhibits excellent corrosion resistance in the water solutions of 0.5 mol/L H2SO4 and 3.5% NaCl.     

Calcium carbonate nanoparticles promote osteogenesis compared to adipogenesis in human bone-marrow mesenchymal stem cells

Rhombohedron-like and fusiform calcium carbonate nanoparticles were fabricated using a new method. Their geometry was controlled by varying the mixing speed and ratio of ethanol versus water in reaction system. The calcium carbonate nanoparticles(CCNPs) have slight effect on viability of human bone-marrow mesenchymal stem cells(hBMSCs) with dose-dependent and shape-dependent, but they can significantly promote osteogenic differentiation of hBMSCs in vitro by 10–37% increase of alkaline phosphatase(ALP) activity, 9–36% growth of collagen secretion and 1.13–1.83 folds upregulation of osteogenesis-related genes, even at lower dose ranges(5–20 μg/ml). The efficacity of promoting osteogenesis depends on the shape and dose of CCNPs. Furthermore,adipogenesis was inhibited by less accumulation of lipid droplets, lower triglyceride(TG) secretion and downregulation of adipogenesis-related genes. These findings improve the understanding of effects CCNPs on hBMSCs fate towards osteoblasts or adipocytes and have meaningful impact for combining use of CCNPs and hBMSCs in tissue engineering and regenerative medicine fields.     

Investigation of the Ce-Mn conversion coating on 6063 aluminium alloy

In this paper, the sustainable Ce-Mn chemical conversion coating was fabricated on 6063 aluminium alloy by means of Ce(NO₃)₃ and KMnO4 as the inhibitors and NaF as the accelerator. The morphologies, composition and valence state of the coating were analyzed by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS), respectively. The results indicated that the Ce-Mn conversion coating was formed. The anticorrosion of the coating was evaluated in 3.5 wt.% NaCl aqueous solution at room temperature by using polarization curve and electrochemical impedance spectroscopy (EIS). It indicated that the treated surface presented better anticorrosion behavior in chloride media than on the original material surface. The corrosion resistance of Ce-Mn conversion coating was about equal to the trivalent chromium conversion coating.     

羟基磷灰石涂层的骨结合行为

使用等离子喷涂技术，在钛合金表面制备了羟基磷灰石涂层。采用动物实验的方法，研究羟基磷灰石涂层的生物相容性。生物力学实验结果表明，使用羟基磷灰石涂层，可以显著提高骨组织与种植体的界面结合强度。扫描电镜观察显示，羟基磷灰石涂层与骨组织形成骨性结合，而钛合金种植体与骨组织之间存在纤维组织结构。两种不同的界面结构，是导致种植体与骨组织结构强度差异的主要原因。