羟基磷灰石涂层的制备研究

以五氧化二磷、无水乙醇、硝酸钙为原料,通过溶胶-凝胶法制备羟基磷灰石涂层.选用2mm/s的速度浸渍提拉载玻片,在载玻片上进行涂膜,经60℃干燥后在650℃保温3h,可在载玻片上得到羟基磷灰石涂层.研究结果表明:制备溶胶合适的配比为nCa(NO3)2·4H2O:nP2O5=10:3,即Ca/P原子比=5:3(约等于1.67).     

羟基磷灰石和含氟羟基磷灰石涂层的制备技术

羟基磷灰石(HA)生物陶瓷涂层被认为是目前最好的用于替代人体硬组织的一种生物医用材料,具有很高的外科应用价值.含氟羟基磷灰石(FHA)涂层由于比羟基磷灰石涂层的溶解度低、热膨胀系数小且生物活性好,有着更为广泛的应用前景.对羟基磷灰石及其涂层的各种制备方法进行了概述,同时介绍了溶胶-凝胶法制备含氟羟基磷灰石涂层的技术特点,并对未来的发展前景进行了分析.     

羟基磷灰石涂层的制备

本文以五氧化二磷、无水乙醇、硝酸钙为原料,通过溶胶-凝胶法制备羟基磷石灰涂层。选用2mm/s的速度浸渍提拉载玻片,在载玻片上进行涂膜,经60℃干燥后在650℃烧结保温3h,可在载玻片上得到羟基磷灰石涂层。研究结果表明:制备溶胶合适的配比为Ca(NO3)22·4H2O:P2O5(摩尔比)=10:3,即Ca/P原子比=5:3(约等于1.67)。     

电泳沉积用羟基磷灰石稳定悬浮液的制备

研究了羟基磷灰石粉体粒径、粉体预烧温度、陈化时间、分散溶剂、悬浮液固含量对羟基磷灰石悬浮液稳定性的影响,通过测定Zeta电位,吸光度等参数表征悬浮液稳定性,对悬浮液电泳沉积的涂层进行SEM表面形貌及粘结-拉伸结合强度的表征.结果表明:悬浮液颗粒越小,Zeta电位越高;对羟基磷灰石粉体预烧800℃,Zeta电位明显提高,且有利于涂层与基体的结合;悬浮液陈化48 h后,颗粒荷电性最佳,可得致密均匀的涂层;以乙二醇为分散溶剂可制备稳定的悬浮液,但乙醇溶剂更有利于涂层的电泳沉积;悬浮液固含量控制为20g/L时,涂层质量较好.     

氧化石墨烯/羟基磷灰石涂层对镁合金耐腐蚀性的影响

采用仿生法在改性模拟体液中于镁合金表面制备了羟基磷灰石(HA)涂层和氧化石墨烯/羟基磷灰石(GO/HA)复合涂层。利用扫描电子显微镜(SEM)和X射线衍射(XRD)对两种涂层进行了形貌和结构表征,通过析氢量测量、极化曲线和交流阻抗等方法分别研究了裸镁合金、含HA涂层及GO/HA涂层镁合金在pH为7.4的模拟体液(SBF)和3.5%NaCl溶液中的腐蚀行为。结果表明,氧化石墨烯增加了羟基磷灰石涂层的致密性,含GO/HA复合涂层的AZ91镁合金耐腐蚀性能最好,相对于裸镁合金,其腐蚀电流密度降低了一个数量级,析氢量降低了52%。     

钛合金表面TiO2-FHA-HA梯度生物陶瓷涂层的制备

采用溶胶-凝胶工艺在经过微弧氧化预处理的钛基体表面制备二氧化钛(TiO2)-含氟羟基磷灰石(FHA)-羟基磷灰石(HA)梯度结构的生物陶瓷涂层.采用X射线衍射检测了涂层的相组成,采用扫描显微镜观察了梯度涂层的形貌,采用划痕法测定了涂基结合力,结果表明:所制备的涂层是均匀和致密的具有梯度结构的TiO2-FHA-HA涂层;与单一的HA涂层相比梯度的引入显著提高了涂基结合力.生物溶解性实验结果显示了溶解速度FHA小于HA,这就表明了可以通过梯度设计来提高涂层的植入寿命.     

碳酸根替代对磷灰石块体和涂层生物矿化的影响研究

应用体外实验方法(in vitro)研究了不同碳酸根替代量的磷灰石块体和电泳沉积涂层的生物矿化性能,通过XRD和SEM等手段分别研究了块体和电泳涂层样品的生物矿化过程.研究结果表明,碳酸根掺杂形成的磷灰石结晶程度差、晶粒尺寸小,利于块体的烧结致密及在SBF溶液中表面类骨碳酸羟基磷灰石矿化层(HCA)的形成.然而,碳酸根掺杂大大减少了涂层中气孔孔径和孔隙率,不利于矿化层的沉积生长,削弱了涂层的生物矿化性能.     

纳米羟基磷灰石的溶胶-凝胶制备及其特性研究

采用溶胶-凝胶法制备羟基磷灰石的前体物--无定形磷酸钙(ACP),并进行晶化处理得到纳米羟基磷灰石(HAP).在Ca/P＝1.67的条件下,Ca(OEt)2和H3PO4在乙醇溶液中发生反应,合成ACP凝胶体.采用化学滴定法、透射电镜(TEM),X射线衍射法(XRD),BET,傅立叶红外吸收光谱分析法(FTIR)对晶化处理前后的ACP粉料进行的性能测试表明:溶胶-凝胶法制备的HAP粉料具有粒度小、晶化处理活性高、相纯度和结晶度优良的特点.     

电化学沉积制备多孔羟基磷灰石泡沫复合材料

以多孔聚氨酯泡沫为基体,经过预处理、电化学沉积等工艺制备了具有三维多孔网状结构的、高空隙率的羟基磷灰石泡沫复合材料,将羟基磷灰石涂层浸泡在模拟体液SBF中进行浸泡实验,通过扫描电子显微镜(SEM)、X射线衍射(XRD)和红外分析仪(FTIR)等技术对羟基磷灰石涂层进行了表征。实验结果表明:在合适的条件下可得到纯羟基磷灰石涂层;随着温度的升高,晶体端面边长和长度逐渐增大;涂层在模拟体液SBF中浸泡24h后,涂层表面生成了很多球状磷灰石颗粒相互堆积,磷灰石颗粒尺寸明显增大。     

两种电化学方法对制备羟基磷灰石涂层的差异性研究

通过恒电流和脉冲电流技术在钛基表面制备磷酸钙,然后经热碱处理得到羟基磷灰石(HAP)涂层。利用X射线衍射(XRD)、红外光谱(FT-IR)和扫描电镜(SEM)等手段对涂层的结构及形貌进行了表征,并对涂层的耐腐蚀性进行了研究。结果表明,恒电流与脉冲电流技术均可在钛基表面电沉积羟基磷灰石涂层,所得的2种涂层均具有良好的生物相容性;与恒电流方法制得的涂层相比,脉冲电流技术制得的涂层更均匀、致密,与基体结合强度较高,在模拟体液中表现出较好的耐腐蚀性。     

多孔双相钙磷钛合金微弧氧化膜层的制备及生物相容性

为克服钛合金生物膜层单一相的缺陷,以Ti6A14V合金为基体,用微弧氧化法制得具有双相钙磷复合陶瓷膜层(BCP)的钛合金器件.通过控制工作液成分制得由不同比例的β-磷酸三钙(β-TCP)和羟基磷灰石(HA)组成的多孔性复合膜层.研究了电源占空比对BCP膜孔隙率和孔径大小的影响.采用能谱仪和X射线衍射仪分析了BCP膜层的...     

羟基磷灰石/TiO2复合涂层在模拟脑脊液中生物相容性（英文）

应用阳极氧化法在Ti-6Al-4V钛合金（TC4）表面制备了多孔TiO2涂层,在TiO2涂层表面电沉积制备了羟基磷灰石（hydroxyapatite,HA）/TiO2复合涂层,用实验用人工脑脊液（artificial cerebrospinal fluid,ACSF）体液模拟人体的脑脊液,以TC4和TiO2涂层为对比,研究了HA/TiO2涂层在浸泡过程中发生的物理化学变化,考察了HA/TiO2复合涂层抑制钛合金中元素Al和V的析出情况。结果表明：3种样品随浸泡时间的延长遵循的生长规律为：HA成核→HA晶粒长大→HA晶粒相互团簇形成一体→涂层逐渐扩大覆盖到整个基体表面;TC4,TiO2以及HA/TiO2涂层在ACSF中都能够诱导HA的生成,表现出了良好的生物活性。检测浸泡后溶液中Al和V的浓度可知,阳极氧化法制备的TiO2涂层对于Al,V元素的析出起到了一定的抑制作用,能够进一步提高钛合金的生物相容性。

Abstract：

Porous TiO2 coating was prepared on Ti-6Al-4V titanium alloy （TC4） substrate by the potentiostatic anodic oxidation method,and hydroxyapatite （HA） coating was prepared on the surface of TiO2 coating by the electrodeposition method to form HA/TiO2 composite coating. By using artificial cerebrospinal fluid （ACSF） to simulate human cerebrospinal fluid,the physicochemical changes of the HA/TiO2 coatings when soaked in ACSF were studied and compared with TC4 and TiO2 coating. Its inhabitation effects on Al and V were also studied. The results show that these three samples follow such a growth pattern：HA nucleation forma-tion,crystal growth,agglomeration,coatings formation. The bioactivity of TC4,TiO2 coating and TiO2/HA composite coating can be induced by the formation of HA in ACSF. According to the concentration of Al and V in ACSF,the TiO2 coating formed by anodic oxidation could inhibit the element precipitation more or less,and enhance the biocompatibility of titanium alloy.     

医用钛合金微弧氧化膜的制备及其生物相容性研究

利用微弧氧化技术在Ti合金表面制备了医用羟基磷灰石(HA)膜,研究了HA膜在模拟体液中的生物相容性,通过SEM观察了HA膜在模拟体液中浸泡不同时间的表面形貌,并利用EDs测试了HA膜浸泡前后的Ca、P原子分数.结果表明,HA膜在模拟体液中浸泡后,体液的pH变化不大,而经过溶解-重结晶,新生成的HA晶粒发育更完整,更利于...     

微弧氧化-电泳沉积一步法制备羟基磷灰石/TiO2复合涂层

采用微弧氧化-电泳沉积一步法在钛表面生成了羟基磷灰石(HA)/TiO2复合涂层。探讨了电解液中乙醇含量的不同对涂层表面形貌、相组成及抗腐蚀能力的影响。结果表明:乙醇含量为25%时,涂层中HA的含量最高,其抗腐蚀能力最强。     

In vitro assessment of zinc apatite coatings on titanium surfaces

In this paper, coatings of hydroxyapatite partially substituted with zinc (ZnHA) were produced on titanium substrates by a two-step hydrothermal process using a precursor solution rich in calcium, phosphate and zinc. Activation of titanium surfaces was performed by oxidation with an acidic HF/HNO₃ solution. The coated substrates were then converted into HA by immersion in an alkali 0.1 M NaOH solution. The ZnHA samples were characterized by several techniques and their in vitro behavior was studied in comparison to hydroxyapatite (HA) and titanium (Ti-control) samples. A uniform and homogeneous calcium-deficient carbonate apatite coating was obtained for all samples, both doped and undoped with zinc. The percentage of zinc incorporated in the coatings is 7 at%, and the Ca/P ratio is 1.61(±0.01) for both types of samples, suggesting that Zn is incorporated substitutionally, replacing Ca atoms into the HA structure. The incorporation of Zn in the HA structure changed the crystals morphology, reduced crystals sizes and decreased the deposition rate showing that zinc is an inhibitor of the growth of HA crystal. X-ray diffraction showed that HA is the single crystalline phase present after alkali treatment. The coating adhesion strength was evaluated in terms of the critical load (Lc) obtained from scratch tests and no significant difference was found between the two tested groups, indicating the good adhesion of ZnHA to Ti substrates. The in vitro response of human osteoblasts (HOB) exposed to the surfaces of HA and ZnHA coatings was evaluated. The results of Live/Dead tests showed cell viability for all samples surfaces, but the adhesion and proliferation tests showed that ZnHA samples presented better adhered and spread cells compared with HA. ZnHA coatings presented cells with elongated or polygonal shapes and clearly more spread than HA. Quantitative analysis showed that there was a significantly higher number of cells adhered to ZnHA coatings compared to HA, indicating the zinc incorporation stimulates osteoblast proliferation.     

医用钛合金表面羟基磷灰石/二氧化锆梯度复合涂层的制备

用恒电流沉积方法分别在ZrO(NO3)2电解液和由Ca(NO3)2及NH4H2PO4组成的电解液中制备出羟基磷灰石/二氧化锆(HA/ZrO2)梯度医用复合涂层.通过扫描电镜观察,研究了沉积电流和沉积时间对涂层形貌的影响.结果表明,当沉积电流为11.1 mA,沉积时间为400 s时,在锆电解液中可获得均匀的钛基Zr(OH...     

Sol–gel derived nanostructure hydroxyapatite powder and coating: aging time optimisation

Abstract

The aim of this work was to evaluate the effect of aging time on the formation and phase purity of nanostructure hydroxyapatite powder and coating. Hydroxyapatite powder and coating were prepared by sol–gel method using calcium nitrate and phosphorous pentoxide as starting materials. Precursor sols were dip coated onto the pure titanium substrates. The coated plates were aged in different aging times and dried. Finally, samples were calcinated at 600 and 700°C. Thermal behaviour, phase formation, surface morphology and interfacial coherency were investigated by thermogravitometry analysis, X-ray diffraction and scanning electron microscope. Results showed that a solution aging time of at least 24 h was required to achieve monophasic nanostructure hydroxyapatite powder and coating. Hydroxyapatite structure of coating was obtained at 600°C, and a β-tricalcium phosphate phase was formed at 700°C. The effect of sintering temperatures on crystallite size of the coatings was not significant.     

改进酸碱联合处理法制备钛基羟基磷灰石活性涂层(英文)

为了制备理想的钛基羟基磷灰石(hydroxyapatite,HA)生物活性涂层,对钛合金表面分别采用酸处理、碱处理和酸碱联合处理,经过预钙化和热处理后,于模拟体液中进行HA沉积试验.采用X射线粉末衍射仪分析HA涂层的化学组成,以扫描电镜观察所得涂层的表面形态.结果表明:酸碱联合处理法是理想的钛合金表面处理法,所得表面呈多孔状,表面粗糙,对HA涂层沉积和结合强度的改善极为有利;模拟体液法所得涂层主要由HA组成,沉积物为云团状或球状;与相关文献比较,涂层HA含量高,没有裂纹,并且在钛基金属表面形成了片状晶体,均匀覆盖于金属表面,球状颗粒间有空隙存在,有利于新骨形成和牢固的结合.     

钛植入合金表面电化学沉积掺镁羟基磷灰石涂层

以Ca(NO3)2、(NH4)2HPO4和Mg(NO3)2为原料,采用电化学沉积法在医用钛合金表面制备了掺镁羟基磷灰石涂层,研究了电沉积工艺条件对掺镁羟基磷灰石涂层表面形貌的影响。结果表明,当电流密度为1.0mA/cm2,温度为65°C,pH为4.5,n(Mg):n(Ca)=1:3,电沉积时间为1300s时,得到了均匀致密的晶须状涂层。X射线衍射分析表明,烧结后的掺镁羟基磷灰石涂层中Mg2+取代了Ca2+,使HA涂层的晶格发生了变化。