纳米珍珠质/Ⅰ型胶原复合支架结构及活性研究

研究了纳米珍珠质/I型胶原复合支架的组成结构及对MC3T3-E1前成骨细胞的影响。应用扫描电镜、X射线衍射,光谱法进行组成结构,钙离子和多肽释放测试。将MC3T3-E1前成骨细胞在复合支架上进行培养,测定细胞增殖率,碱性磷酸酶及I型胶原蛋白的表达。结果表明,纳米珍珠质/I型胶原复合支架呈多孔状结构,能缓慢释放游离钙离子和多肽。MC3T3-E1细胞生长良好,碱性磷酸酶、胶原蛋白表达水平明显提高。复合支架对MC3T3-E1细胞成骨活性有明显的促进作用。     

AZ31镁合金表面含纳米羟基磷灰石微弧氧化涂层的制备及性能研究

目的改善AZ31镁合金的耐腐蚀性能及生物活性。方法使用微弧氧化技术,分别在以六偏磷酸钠为主盐的电解液和以六偏磷酸钠为主盐、以纳米羟基磷灰石(HA)为添加剂的电解液中,在AZ31镁合金表面制备了微弧氧化涂层。通过扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)表征了涂层的微观形貌、元素特征和相组成。通过电化学方法和浸泡实验考察了涂层的耐蚀性。通过细胞实验评价了两种涂层的细胞相容性。结果电解液中的HA可以进入到微弧氧化涂层中,含HA的微弧氧化涂层较不含HA的更致密,且有封孔现象。电化学方法及浸泡实验结果表明,含HA的微弧氧化涂层的耐腐蚀性能更好。细胞表面粘附实验和细胞增殖实验也表明,经表面纳米HA微弧氧化处理后的AZ31镁合金生物相容性更好,且对MC3T3-E1细胞的增殖有促进作用。结论六偏磷酸钠电解液中添加纳米HA,可以在AZ31镁合金表面制备出含HA的微弧氧化涂层,且其耐腐蚀性能和生物活性均优于不含HA的微弧氧化膜。     

CVI C／C复合材料及其表面HA涂层成骨细胞体外响应行为对比研究

采用声电化学工艺在CVI C／C复合材料表面制备了HA涂层，分别用SEM，XPS，EDAX和XRD表征了CVI C／C和HA的表面形貌、组成和结构，同时对比了成骨细胞在其表面的粘附、增殖和碱性磷酸酶活性的表达。制备的HA涂层为球状形貌，由纳米片状晶体构成。细胞培养初期，粘附于HA涂层表面的细胞数与CVI C／C表面的细胞数无显著差别，成骨细胞在CVI C／C表面易铺展在孔的边缘，8h后粘附于HA表面的成骨细胞数显著多于CVI C／C表面。HA涂层提高了细胞的增殖能力，成骨细胞碱性磷酸酶在HA涂层表面的表达也优于CVI C／C材料。结果表明，声电化学制备的HA涂层提高了CVI C／C材料的生物活性和生物相容性，可以加速成骨细胞的粘附、增殖、分化和成熟。成骨细胞在材料表面的粘附机制是由多因素综合作用的，材料的表面形貌和生物活性在细胞粘附过程的早期发挥着重要作用。     

脉冲电化学沉积制备n-HA/ZrO2复合涂层

用脉冲电化学沉积法在生物医用钛金属表面成功制备了纳米RA/ZrO2复合涂层,涂层中的成分均以离子形式沉积到基材上,得到ZrO2均匀分布的HA/ZrO2复合涂层.脉冲电位为-3.5 V时有利于离子的沉积结晶,有利于复合涂层的沉积.复合涂层的成分、结构、形貌及生物活性等的研究结果表明:复合涂层烧结前成分为HA、OCP及碱式硝酸锫,高温烧结后得到均匀致密HA/ZtO2复合涂层.检测表明HA/ZrO2复合涂层能够诱导磷灰石生成,具有较好的生物活性.     

等离子喷涂制备HA/MO纳米管复合涂层及性能分析

目的提高生物医用钛合金涂层的结合力与生物活性。方法采用阳极氧化法在Ti-10Mo-28Nb-3Zr-6Ta合金表面先制备纳米氧化管,接着通过等离子喷涂法在纳米氧化层表面喷涂HA生物涂层,制备HA/MO纳米管复合涂层,对合金进行表面改性。在等离子喷涂法制备复合涂层时,通过改变喷涂电压和喷涂距离,对涂层的显微结构和物相组成进行探究,获得最佳制备工艺参数,同时对最佳工艺参数制备的复合涂层,通过电化学工作站实验、自动划痕仪测试、仿生矿化法试验和MTT法(四唑盐比色法)试验,分别评价复合涂层的耐腐蚀性能、附着力、生物活性和细胞毒性。结果在钛合金用阳极氧化法预处理的前提下,通过等离子喷涂制备HA/MO纳米管复合涂层,当喷涂电压为40V、喷涂距离为100mm时,制备出的HA/MO纳米管复合涂层涂覆均匀,涂层厚度在50μm左右,耐蚀性得到提高,结合力最佳,为14.8 N。HA/MO纳米管复合涂层具有良好的生物活性,通过培养细胞进行毒性实验,HA/纳米管复合涂层试样的毒性分级为0级,对细胞无影响,且从细胞增殖速率分析,试样表现出优异的细胞活性,对细胞的增长速率促进效果最好。结论 HA/MO纳米管复合涂层可以有效提高耐蚀性和结合强度,同时提高材料的生物活性。     

溶胶凝胶法制备TiO_2/HA复合生物活性涂层及其体外活性

通过溶胶凝胶法在纯钛基体上制备了羟基磷灰石(HA)/TiO2复合生物活性涂层。HA和TiO2溶胶由前驱体制得,按不同摩尔比直接混合两种溶胶来制备混合溶胶。HA可以提高钛基的生物活性,TiO2可以提高涂层与基体的物理、化学相容性和结合强度。粘结拉伸结果表明,复合涂层与基体结合良好,比纯HA涂层与基体的结合强度提高约47%。复合涂层试样于SBF中浸泡4、7和14d的SEM分析结果表明,复合涂层表面的类骨磷灰石生成量较高。成骨细胞实验结果表明,复合涂层上细胞铺展良好。     

纯钛表面两步电化学法制备载银多孔涂层

在医用纯钛表面先采用阳极氧化法制备TiO2纳米管预涂层,然后通过AgNO3溶液浸泡和紫外光照射处理实现银颗粒在预涂层上的固定,再经过微弧氧化处理制备出载银多孔涂层。利用扫描电子显微镜(SEM)、能谱仪(EDS)、X射线光电子能谱(XPS)对涂层表面形貌、载银量、银元素纵向分布及特征进行了表征,并通过金黄色葡萄球菌检验了涂层的抗菌性能。结果表明:两步电化学法可以在纯钛表面制备出含银量较高的多孔涂层,涂层中银元素大部分以纳米颗粒形式存在,涂层表面和最外层Ag元素主要以氧化物的形式存在,而沿涂层法向向内Ag单质与Ag氧化物共存,且涂层具有良好的抗菌性能。     

钛基表面PDLLA/ZnO纳米阵列材料的制备及生物学性能

采用水热生长法,在钛基表面制备高度有序、尺寸可控的氧化锌纳米棒阵列,再通过静电吸附的方法在其表面自组装一层具有良好生物相容性的聚乳酸生物涂层。利用SEM,MTT,LDH方法对细胞形态和生物活性进行表征。结果表明,氧化锌阵列上细胞形态呈圆形,无铺展现象。而经聚乳酸修饰过的材料表面MC3T3细胞外基质铺展较好,细胞分泌的丝状伪足嵌入了阵列结构的空隙中,并且表面细胞数量最多,细胞活性明显高于氧化锌纳米棒及纯钛片。结果表明,聚乳酸涂层提高了氧化锌阵列的生物相容性,为细胞生长提供适宜的微环境,有效促进了细胞的黏附与增殖。     

纯钛材与大变形纯钛材微弧氧化-水热合成复合陶瓷膜层的细胞相容性研究

采用微弧氧化-水热法分别在纯钛材及大变形纯钛材表面制备了TiO_2/HA复合陶瓷膜层,从细胞毒性实验、细胞增殖实验、细胞黏附实验等方面评价膜层的细胞相容性。结果表明:纯钛材与大变形纯钛材微弧复合陶瓷膜层均无细胞毒性。与纯钛材微弧复合陶瓷膜层相比,大变形纯钛材微弧复合陶瓷膜层表面粗糙度更适宜,结晶形核的HA晶粒的形状及Ca/P比更接近人骨HA,更能有效促进成骨细胞的黏附和铺展,随着培养时间的延长,成骨细胞双层重叠生长结构更为明显。成骨细胞在大变形纯钛材微弧复合陶瓷膜层表面各时间点的吸光度值均更高,细胞相容性更好。     

钛合金表面GO/纳米ZnO复合涂层的制备及性能

为了有效解决生物医用钛合金长期植入人体后,易发生细菌感染和面临有害金属离子释放的问题,采用水热反应和涂覆方法,分别在聚多巴胺(PDA)预处理的Ti6Al4V合金表面制备了氧化石墨烯涂层(GP/T)和氧化石墨烯/纳米氧化锌复合涂层(GZP/T)。系统分析了2种涂层的物相结构、微观形貌及其在林格氏液中的耐腐蚀性能和在大肠杆菌环境中的抗菌性能。结果表明:聚多巴胺发挥“双面胶”桥接作用,有效增强了涂层与基底间的化学键合;GP/T涂层抗菌率随着GO浓度增大而增大;GZP/T纳米复合涂层相较Ti6Al4V基材具有优异的耐蚀性,该复合涂层中ZnO起主要抗菌作用。     

生物活性多孔钽支架的构建及其初步生物学评价

表面生物活性涂层构建是提升金属内植物骨整合能力的有效途径,本研究利用电化学沉积技术在多孔钽支架表面构建生物活性羟基磷灰石(HA)涂层。通过接触角和比表面积测试发现,HA涂层的构建显著提升了多孔钽表面亲水性,并增加了其比表面积。利用模拟体液浸泡试验评估支架生物活性,发现仅浸泡3天后,多孔钽支架表面就已被类骨磷灰石沉积所覆盖。建成骨细胞培养模型,通过激光共聚焦观察及细胞增殖测试发现,所有支架均具有良好的细胞相容性。并且,细胞共培养5天后,HA涂层化多孔钽支架表面细胞的增殖率分别是未改性材料组和空白对照组的1.1和1.4倍,呈现了更大的促细胞增殖潜力。本研究中所制备的生物活性多孔钽支架具备快速诱导类骨磷灰石沉积能力,能够促进成骨细胞在其表面的贴附和增殖,在骨修复领域具有较大的临床应用前景。     

Effects of Zn Content on Crystal Structure, Cytocompatibility, Antibacterial Activity, and Chemical Stability in Zn-Modified Calcium Silicate Coatings

In our previous study, Zn-modified calcium silicate coatings possess not only excellent chemical stability but also well antibacterial activity. Still, effects of zinc content on these properties and cytocompatibility remain unclear. In this paper, two kinds of Zn-modified calcium silicate coatings (ZC0.3, ZC0.5) were fabricated on Ti-6Al-4V substrates via plasma spraying technology. X-ray diffraction results and transmission electron microscopy observations showed that the ZC0.5 coating was composed of pure hardystonite (Ca₂ZnSi₂O₇) phase, while, besides Ca₂ZnSi₂O₇ phase, the amorphous CaSiO₃ phase was also detected in the ZC0.3 coating. Chemical stability in Tris-HCl buffer solution and antibacterial activity of the Zn-modified calcium silicate coatings increased with an increase in zinc content. In vitro cytocompatibility evaluation demonstrated that the proliferation and alkaline phosphatase activity and collagen type I (COLI) secretion of osteoblast-like MC3T3-E1 cells on Zn-modified coatings were significantly enhanced compared to the Zn-free coating and Ti-6Al-4V control, and no cytotoxicity appeared on Zn-modified coatings. The better antibacterial activity and the enhanced capability to promote MC3T3-E1 cells differentiation of Zn-modified coatings should be attributed to the slow and constant Zn²⁺ releasing from the coatings.     

纳米硫化铋-锌复合镀膜的制备及其抗菌性能研究

目的将锌镀层与具有光催化抗菌性能的纳米粒子复合,实现对锌镀层的改性,成功制备一种具有光催化抗菌性能的功能性复合镀层。方法通过向弱酸性硫酸盐锌镀液中加入梯度浓度具有可见光催化杀菌性能的硫化铋纳米粒子,在20#碳钢表面利用恒电流法一步成功制备了系列硫化铋-锌复合镀膜。利用电化学工作站监测了沉积过程中的沉积电位,分别记录沉积前和沉积后的样品质量并测量沉积面积,通过计算,确定了沉积过程的电流效率。通过扫描电子显微镜(SEM)、X-射线晶体衍射仪(XRD)及电子能谱仪(EDS)对镀层进行了形貌及成分分析,采用大肠杆菌作为代表性的细菌,检测了复合镀膜的抗菌性能。结果与纯锌镀膜相比,硫化铋的加入显著促进了(100)晶相的晶体生长,而抑制了(102)晶相的晶体生长,使镀膜形貌由标准六方晶系变为块状晶体;硫化铋的加入使沉积电位变得更正,且随硫化铋添加量的增加,变正增幅变大;硫化铋的加入使电沉积过程的电流效率与纯锌镀膜的电流效率相比增大了5%左右,但硫化铋的添加量对电流效率的影响不大;硫化铋-锌复合镀膜在可见光下对大肠杆菌具有良好的抗杀性能,且硫化铋的复合量越高,抗菌效果越好。结论通过笔者提出的电沉积方法,硫化铋可成功复合到了锌镀膜中,从而使硫化铋-锌复合镀膜获得了良好的抗菌性能,最终发现当镀液中硫化铋质量浓度为2 g/L时,硫化铋在锌镀层中的复合量最高,抗菌性能最好。     

Silver-Doped Hydroxyapatite Coatings Deposited by Suspension Plasma Spraying

Pure hydroxyapatite suspension was produced by wet chemical synthesis. Using a hybrid water-stabilized torch, a series of HA coatings were produced on SS304 and Ti6Al4V substrates and their properties were characterized by SEM, EDX and XRD techniques. After deposition, the amorphous phase content reached 6-10% and the coatings retained 75-82% of crystalline HA phase. Their thickness reached 145 μm. To understand the wear behavior of the coatings, pin-on-disc tribology evaluation was performed. Additionally, a set of HA coatings was prepared with pure metallic Ag content. This formed by in situ chemical decomposition of AgNO₃ added into the HA suspension. The Ag was dispersed evenly within the coatings in the form of submicron-sized particles situated predominantly along the HA splats boundaries with a total Ag content of 8 wt.%. Given the antibacterial properties of Ag, such result presents a promising step forward in the hard tissue replacement research.     

Fabrication and Characterization of Suspension Plasma-Sprayed Fluoridated Hydroxyapatite Coatings for Biomedical Applications

Fluoridated hydroxyapatite (FHA) coatings were prepared on a Ti substrate using a suspension plasma spraying technique. The crystalline phases and chemical compositions of the coatings were characterized using x-ray diffraction, Fourier transform infrared spectroscopy, and x-ray photoelectron spectroscopy. The analysis confirmed that the coating consisted of an FHA phase. The corrosion behavior in simulated body fluid was studied using potentiodynamic polarization tests, and the results indicated that the FHA coating greatly enhanced the corrosion resistance of the Ti substrate. The chemical stability of the FHA coatings was assessed by evaluating the release of Ca²⁺ ions. The results indicated that the substitution of fluorine into the hydroxyapatite (HA) structure had a positive effect on the dissolution resistance of the HA. The antibacterial activity was investigated using a surface-plating method; the results revealed that the antibacterial activity of the FHA coating was greater than that of the pure HA coatings. During cell culture tests, the FHA coating did not exhibit cytotoxicity toward the osteoblast cell line, and the cell proliferation was comparable with that of the HA coatings. The antibacterial activity and cell culture results suggested that the plasma-sprayed FHA coating possesses good antibacterial qualities, but is biocompatible with osteoblasts. The promising features of the FHA coating render it suitable for orthopedic and dental applications.     

AZ91镁合金表面电化学沉积羟基磷灰石涂层的制备及其耐蚀性

采用电化学沉积方法在AZ91镁合金表面制备了羟基磷灰石(HA)涂层,研究了电沉积工艺参数对羟基磷灰石涂层形貌和相组成的影响,并通过腐蚀浸泡试验、极化曲线测试等方法对该涂层的耐蚀性进行了研究。结果表明:当溶液pH为4.5,温度为60℃时,涂层的致密性最好,呈放射状的结构,主要成分为HA相,涂层的厚度约为60~70μm,与基体结合较好;HA涂层对镁合金基体具有较好的保护作用,显著提高了基体合金在生理溶液中的耐蚀性。     

低压沉积-微弧氧化制备钛金属HA-TiO2复合膜层

采用低压沉积-微弧氧化法,在钛金属表面直接制备了具有生物活性的HA-TiO2复合膜层,通过XRD和SEM分别分析了膜层的相结构和表面形貌,探讨了沉积参数对膜层中HA含量与表面形貌的影响.结果表明:低压沉积处理是微弧氧化法制备HA-TiO2复合膜层的必要条件;复合膜层主要由金红石型和锐钛矿型TiO2及HA组成,HA以白色...     

Characterization of plasma-sprayed hydroxyapatite/TiO2 composite coatings

To enhance the bonding between hydroxyapatite (HA) coating and titanium alloy substrate, HA/TiO₂ composite coatings have been fabricatedvia plasma spraying. Bonding strength evaluation, simulated body fluid tests, and cell culturein vitro were carried out to characterize the composite coatings. The results obtained showed that the addition of TiO₂ to HA coating improved the bonding strength of the coating significantly. After being immersed in simulated body fluid (SBF) for a period, the surfaces of HA/TiO₂ composite coatings were completely covered by carbonate-containing apatite, which indicated that the coatings possess good bioactivity. Thein vitro cell culture indicated good cytocompatibility for HA/TiO₂ composite coatings.