钛基多孔HA/SiO2复合涂层的制备及性能研究

为了制得表面多孔且与基材结合强度高的羟基磷灰石(HA)涂层,实验中以正丁醇为分散介质,以SiO2粉末为添加剂,纯钛片为基材,电泳沉积制备羟基磷灰石/二氧化硅/壳聚糖/(HA/SiO2/CS)复合涂层,经后续热处理得到多孔HA/SiO2复合涂层,采用扫描电镜(SEM)、傅立叶红外光谱仪(FT-IR)、X射线衍射仪(XRD)、万能材料试验机对涂层的表面形貌、组成、结构和结合强度进行测试和表征,并通过模拟体液(SBF)浸泡法对复合涂层的生物活性进行评价.结果表明:当悬浮液中的HA/SiO2/CS质量比为1∶1∶1时,制得的HA/SiO2/CS涂层经700℃热处理后获得的HA/SiO2复合涂层孔洞分布均匀,大孔孔径在10～15μm,小孔孔径在1～5μm;涂层与基材的结合强度达到25.5 MPa;多孔HA/SiO2复合涂层在SBF中浸泡7 d后,涂层表面碳磷灰石化;说明实验中添加SiO2所制得的多孔HA/SiO2复合涂层与钛基材结合强度高,且具有良好的生物活性.     

HA/CuO/SrCO3梯度复合涂层的制备及体外生物活性

在羟基磷灰石(HA)悬浮液中, 以正丁醇为分散介质, 三乙醇胺为乳化剂, 成骨微量元素化合物CuO 和SrCO₃作为添加剂, Ti片为基材, 壳聚糖(CS)为造孔剂, 依次通过区带电泳分布并在反向电场作用下电 泳沉积, 得到HA/CS/CuO/SrCO₃复合涂层, 经700 ℃高温煅烧2 h后, 制得HA/CuO/SrCO₃复合涂层. 通过X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)、 场发射扫描电子显微镜(FESEM)、 能量色散光谱仪(EDS)、 劳埃德万能材料试验机、 电化学工作站、 模拟体液培养和抑菌实验等手段对复合涂层进行测试与表征. 结果表明, Ca, Cu和Sr 元素含量在HA/CuO/SrCO₃复合涂层的径向上均呈现梯度分布; 复合涂层与钛基材的结合强度达33.0 MPa; 循环伏安(CV)曲线和Tafel极化曲线测试表明, 复合涂层在N-2-羟乙基哌嗪-N′-2-乙磺酸(HEPES)模拟体液(H-SBF)中电化学性能稳定, 耐腐蚀性较强; 在H-SBF中培养24 d后, 复合涂层表面完全碳磷灰石化; 抑菌实验发现, 复合涂层粉末对大肠杆菌和金黄色葡萄球菌的抑菌率分别为81.82%和71.86%.     

羟基磷灰石/氧化铁复合涂层的制备及其诱导骨生长的生物活性

用电泳沉积法制得羟基磷灰石/壳聚糖/氧化铁(HA/CS/Fe2O3)复合涂层,经700 ℃烧结处理得到HA/Fe2O3复合涂层。 通过SEM、EDS、XRD、FT-IR、电化学和万能材料试验机等对复合涂层的表面形貌、物相组成、抗腐蚀性和结合强度进行了表征和测试,最后采用1.5SBF浸泡法对复合涂层的生物活性进行了评价。 结果表明,当悬浮液中的HA、CS与Fe2O3质量比为100∶100∶1时,所制得的HA/Fe2O3复合涂层表面粗糙,抗腐蚀性强,具有良好的诱导骨生长生物活性,基体与复合涂层结合强度可达27.5 MPa。     

聚富马酸丙二醇酯/羟基磷灰石复合多孔水凝胶的制备及其矿化性能研究

采用二步法合成了可降解的聚富马酸丙二醇酯(poly(propylene fumarate),PPF),并和N-乙烯基吡咯烷酮(N-vinyl pyrrolidone,NVP)共聚,以1,4-二氧六环为溶剂,通过改变溶剂的量制备了溶胀性能不同的PPF水凝胶.采用万能力学测试仪和扫描电子显微镜分别表征了水凝胶的压缩模量和形貌结构.选择20％ PPF和10％ NVP的聚合体系,预掺3％的纳米羟基磷灰石(hydroxyapatite,HA),以氯化钠粒子为致孔剂,制备了孔径在280～450 μm的纳米复合多孔水凝胶,使其压缩模量提高了61％.模拟体液矿化10天的结果显示,磷灰石成核位点的存在和良好的与外界液体环境物质交换的能力,促进了多孔水凝胶表面磷灰石的沉积,说明HA的复合可以有效提高PPF多孔水凝胶的成骨活性.     

水热电沉积羟基磷灰石/Ti复合涂层的研究

在水热电沉积羟基磷灰石（Hydroxyapatite，简称HA）涂层的电解液中加入Ti粉，制备了HA/Ti复合涂层，探讨了Ti粉的加入对涂层结合强度和生物活性的影响，并研究了涂层的热稳定性。结果表明，500 ℃焙烧2 h后，HA/Ti复合涂层的结合强度为18.4 MPa，明显高于纯HA涂层的11.2 MPa；模拟体液浸泡7 d后，涂层表层形成一层碳磷灰石。Ti粉的加入明显提高了涂层的结合强度，又不降低涂层的生物活性。500 ℃焙烧不改变涂层的相组成，焙烧温度高于600 ℃时，HA部分发生分解，Ti氧化为金     

脉冲电化学沉积法制备羟基磷灰石/壳聚糖复合涂层的研究

采用脉冲电化学沉积法在钛金属表面制备出羟基磷灰石/壳聚糖(HA/CS)复合涂层,实现CS与HA在微观尺寸上的复合与杂化.比较了脉冲电位与恒电位模式下复合涂层的形成,研究了电位高低及壳聚糖浓度对复合涂层性能的影响.结果表明,与恒电位模式比较,脉冲电位下制备的涂层较均匀、结晶性好、CS含量高,并且HA与CS杂化程度高.脉冲...     

羟基磷灰石/聚乙烯醇/壳聚糖水凝胶在模拟体液中的力学性能

从仿生学角度出发,将自制的人工角膜支架材料羟基磷灰石/聚乙烯醇/壳聚糖(n-HA/PVA/CS)浸泡在模拟体液中,对材料的含水率及力学性能进行了测试,并利用扫描电镜、X射线衍射仪、电感耦合等离子体原子发射光谱仪及热重分析仪研究了材料在模拟体液中的形貌、晶体结构、元素组成及热稳定性.结果表明,在模拟体液中,n-HA/PVA/CS复合水凝胶的含水率为80%~86%,具有较高的拉伸强度,能承受正常眼压,且热稳定性较好.在浸泡后期,n-HA/CS/PVA复合材料对Ca2+的吸附和释放达到动态平衡;而其表面含有微量的纳米羟基磷灰石沉积,有利于纤维细胞的长入.     

钛表面含硅羟基磷灰石涂层的电化学合成和表征

在含有Ca2+,PO43-以及SiO32-的电解液中,通过电化学恒电位方法,在工作电压为3 V温度为85℃的条件下沉积1 h,于钛表面上制得含硅羟基磷灰石涂层。通过电感耦合等离子体原子发射光谱(ICP)、扫描电镜(SEM)、X-射线衍射(XRD)、探针式轮廓仪(SP)、红外光谱(FTIR)对涂层进行分析。结果表明:电化学恒电位方法可制得Si饱和含量为0.55wt%左右的Si-HA涂层,Si以SiO44-形式取代PO43-进入HA晶格,造成羟基磷灰石中OH-减小以维持电荷平衡。另外,电解液中Si元素的存在抑制涂层中HA晶体的生长,使涂层变薄,且当电解液中nSi/(nSi+nP)达到20%时Si-HA晶体形貌由单独的棒状转变为根部相连的树枝状。     

CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料在SBF中的性能研究

利用溶胶-凝胶生物活性材料粉末二次烧结工艺,制备了CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料,并利用体外实验(in vitro)方法和XRD,SEM及FTIR技术研究了此烧结材料的显微形貌、晶相、生物活性和可降解性能.结果表明,经800℃烧结5 min后,有少量硅磷酸钙[Ca5(PO4)2SiO4,5CPS]析出,在模拟体液(SBF)中浸泡,随着时间的增长,材料表面最初形成的无定形钙磷化合物矿化成碳酸羟基磷灰石(HCA)纳米团簇,并逐渐相互融合形成HCA覆盖层;HCA只在烧结体的玻璃相(SG相)表面生成,在5CPS微晶相表面未发现HCA,该材料在37℃恒温的SBF溶液中具有较高的生物活性和可降解性能.     

不同模拟体液中水化硅酸三钙固化体的体外生物活性行为(英文)

研究水了化硅酸三钙(Ca3SiO5,C3S)固化体的体外生物活性行为。结果表明,干C3S固化体中含有23.97wt%的Ca(OH)2,Ca(OH)2的溶解导致模拟体液(Simulated Body Fluids,SBF)的pH值上升;磷灰石颗粒优先诱导沉积于C3S固化体表面,随后碳酸钙和磷灰石颗粒共同沉积于C3S固化体表面;HCO3-是SBF模拟体液内主要的缓冲离子;Ca(OH)2碳化和CaCO3沉积主要导致SBF的pH值下降。由于离子交换作用的减弱,C3S固化体表面最终被磷灰石完全覆盖,磷灰石的沉积促使SBF的pH值进一步降低。因此,对于C3S和其衍生材料的体外生物活性和生物相容性必须考虑到HCO3-在体内的实际含量和行为。     

电沉积PAMAM/羟基磷灰石复合涂层的研究

电沉积PAMAM/羟基磷灰石复合涂层的研究;羟基磷灰石;聚酰胺胺树枝形聚合物;双电位阶跃技术;电沉积;生物活性     

Superior corrosion protection and in vitro biocompatibility of Na-HAp/CS composite coating on PoPD-coated 316L SS

The synthesis and development of sodium (Na)-substituted hydroxyapatite (HAp)/chitosan (CS) composite using poly (O-phenylenediamine) (PoPD) coating on 316L SS substrate for improving bioactivity and corrosion protection was studied. The surface of Na-HAp/CS/PoPD bilayer coatings on 316L SS substrate was characterized by diverse analytical techniques. The open circuit potential (OCP) measurement, potentiodynamic polarization, and impedance test revealed that the bilayer coating provides excellent protection to the substrate against the corrosion in the simulated body fluid (SBF) solution. This interior layer of the coating acts as a barrier against the release of metal ions from the substrate, which was confirmed by inductively coupled plasma-atomic emission spectroscopy. Besides, the mechanical properties of the coatings were analyzed. From the obtained results, the bilayer coating exhibited greater mechanical strength than the individual coating. An in vitro bioactivity of the coatings was assessed by immersion in the SBF solution at 7–28 days. The apatite formation of bilayer coatings on 316L SS substrate is found to be more bioactive compared with the Na-HAp, PoPD, and Na-HAp/CS. The in vitro biocompatibility test showed no adverse effects, which was proved by the enhanced biocompatibility of the bilayer coating on 316L SS.     

Fabrication and In vitro Bioactivity of Robust Hydroxyapatite Coating on Porous Titanium Implant

Compared witli the traditional dental implant, TixOs■ manufactured by direct laser metal forming(DLMF) technology exhibits improved capability for bone osteointegration due to its porous surface structure, and has achieved remarkable clinical effect. However, like the traditional titanium and other alloyed implants, the porous titanium implant TixOsR also has relatively weak bioactivity. To address this issue, a proper surface modification method may be needed. Hydroxyapatite(HA) has been widely used in implant surface coating for its similar chemical composition to bone tissue and its osteoconductive properties. Thus, combining TixOs■ implants with hydroxyapatite can be an efficient way to enhance their bioactivity. We herewith reported a competent pulsed laser deposition(PLD) method of coating nano-sized HA thin film onto the porous TixOs■ implant. The HA coatings were characterized by means of scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS), X-ray photoelectron spectroscopy(XPS) and focused ion beam(FIB) method, and nanocrystal sized thin HA films were identified on the surface of TixOs■ implants. The low cytotoxicity and improved cell proliferation ability of HA coated implants were further tested and verified using MC 3T3 E1 cells with the consideration of the controlling group. Our results show that a stable and bioactive HA tliin film is able to form on the surtace of the porous titanium implant by PLD method.This may benefit the fiirther clinical application of TixOs■ implants.     

Bonding Strengths of Titania Sol-Gel Derived Coatings on Titanium

Bioactive ceramic coatings have had poor adhesion to substrate. In this study, the bond strength (tensile strength) of titania gel coating to titanium substrate was studied. In the experiments three different pretreatments were used, namely sodium hydroxide corroding, plasma cleaning and titanium nitride coating. Also the effects of heating temperature, heating in vacuum and titanium surface roughness were studied. The sol properties were altered with valeric acid addition. Samples were analysed by SEM-EDX, AES, AFM and tested by bond strength gauge. Those samples in which the titanium surface was precorroded one hour in sodium hydroxide, predeposited by titanium nitride or ground improved the bonding strengths of titania coatings to over 24 MPa. In these samples a fracture occurred at the glue-coating interface.     

Surface characterization and dissolution study of biodegradable calcium metaphosphate coated by sol–gel method

Coatings of biomedical implant surfaces by a bioactive calcium phosphate film render bioactivity to the implant surface and shorten the healing time. In this present study, calcium metaphosphate (CMP) sol was synthesized by sol–gel method and coated onto the titanium alloys (Ti-6Al-4V). CMP sol was first synthesized by reacting Ca(NO₃)₂4H₂O (Sigma–Aldrich 99%, USA) with (OC₂H₅)₃P (Fluka 97%, Japan) in methyl alcohol. A stoichiometric Ca/P ratio of 0.5 was obtained by varying the amounts of the reactants. Sol was then coated on Ti-6Al-4V substrates by spin coating. The coated-specimens were then dried at 70 °C for 24 h, followed by a heat treatment at 650 °C for 1 h. Structural and chemical properties of the coatings were evaluated using XRD, SEM, and EPMA. The dissolution property of the coated-CMP layer was investigated by immersing the samples in the simulated body fluid (SBF) for 1, 3, 7 and 21 days. The concentration of Ca²⁺ released was measured using ICP. After heat treatment, SEM indicated a smooth and uniform CMP layer, with CMP grains of approximately 100 nm. The CMP phase was identified with δ-CMP (JCPDS #9-363). After immersion in SBF, coatings were observed to be roughened and porous. The concentration of Ca²⁺ in SBF was observed to increase over time, indicating continuous dissolution. The presence of titanium oxide phosphate compounds were also observed on CMP surfaces after immersion. It was thus concluded that the ability to control coating properties as well as the need for low heat treatment temperature offers advance for the use of CMP coating by sol–gel process on Ti-6Al-4V implant surfaces.     

有机泡沫浸渍法制备多孔磷灰石-硅灰石(AW)生物活性玻璃陶瓷研究

0引言多孔磷灰石-硅灰石(apatite-wollastonite glass ceramic,AW-GC)生物活性玻璃陶瓷,具有良好的生物活性、骨透导性和一定的可降解性,近年在骨组织工程研究中倍受重视[1￣4]。理想的骨组织修复和支架材料应具备三维立体多孔结构,这种结构有利于细胞粘附增殖、细胞外基质沉积、营养和氧气进入及代谢产物排出,也有利于血管和神经长入[5]。     

脉冲电沉积制备HA/ZrO2纳米复合涂层的稳定性及生物相容性评价

采用脉冲电化学沉积法成功地在生物医用钛金属表面制备出均匀的纳米HA/ZrO₂复合涂层. 通过热处理提高涂层的致密性, 同时保留涂层的微纳结构. 考察了热处理后复合涂层的成分、形貌、生物相容性及生理稳定性. X射线衍射分析表明, 复合涂层成分为HA和ZrO₂. 扫描电镜观察发现, 热处理后复合涂层的致密性有所提高. 研究发现, ZrO₂的加入大大降低了HA/ZrO₂复合涂层中钙离子的释放速度, 提高了HA/ZrO₂复合涂层的生理稳定性. 纳米划痕实验结果表明, HA/ZrO₂复合涂层具有较好的结合强度. 通过培养成骨细胞考察了复合涂层的生物相容性. Alamar Blue检测表明, HA/ZrO₂复合涂层表面细胞黏附及增殖能力较好. ALP检测发现, 热处理后HA/ZrO₂复合涂层表面的细胞分化能力较强. 综合细胞培养结果显示, HA/ZrO₂复合涂层有较好的生物相容性.     

Applying diamond like carbon layer on carbon/carbon composites and its effect on the deposition of hydroxyapatite coating

The biomedical application of carbon/carbon (C/C) composites is limited by lacking bioactivity and releasing carbon debris. Hydroxyapatite (HA) coating has been used to improve the bioactivity of C/C composites, but it cannot reduce the release of carbon debris effectively because of poor wear resistance property. In this work, a wear‐resistant layer of diamond like carbon (DLC) is applied on C/C composites, followed by an ultrasound‐assisted electrochemical deposition to prepare HA coatings. The microstructure, morphology and chemical composition of the DLC layer and the HA coating are characterised by scanning electron microscopy, X‐ray diffraction, energy dispersive spectroscopy (EDS), X‐ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy and Raman spectrum. The bonding strength between the HA coating and the DLC layer modified C/C composites is examined by a tensile test. The results show that the DLC layer has a spherical morphology and provides a uniform surface for the deposition of the HA coating. The HA coating shows flaky morphology with a compact structure. The tensile strength of the HA coating on the DLC layer modified C/C composites is 6.24 ± 0.40 MPa, which is significantly higher than that of HA coating on unmodified C/C composites(3.04 ± 0.20 MPa). Copyright © 2013 John Wiley & Sons, Ltd.