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.     

钛合金表面电泳沉积氟羟基磷灰石涂层

采用沉淀法制备了氟掺杂的氟羟基磷灰石(FHA,Ca_(10)(PO_4)_6OH_(2–x)F_x(x=0~2))粉体,并采用电泳沉积在钛合金(Ti_6Al_4V)表面制备了FHA涂层。通过改变沉积电压、时间及电极间距获得不同沉积量的涂层,采用X射线衍射、扫描电子显微镜研究了电压、时间、电极间距以及热处理对涂层形貌、物相组成和涂基结合强度的影响,确定制备FHA涂层的最佳沉积工艺和热处理制度。结果表明:控制沉积电压15 V、沉积时间1 min、电极间距1 cm的条件下沉积涂层并在N_2气氛下900℃保温1 h热处理可制得涂层质量好,涂基结合强度高的FHA生物陶瓷涂层。     

电沉积含氟羟基磷灰石/纳米二氧化钛复合涂层的表征与性能研究

根据含氟羟基磷灰石(FHA)陶电沉积瓷技术,将纳米二氧化钛微粒加入电解液中,在钛基体表面进行电化学复合共沉积,获得了含氟羟基磷灰石复合纳米TiO2涂层(FHA/n-TiO2).对FHA/n-TiO2纳米复合涂层进行了真空烧结处理,并通过X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(IR)、X射线光电子能谱(XPS...     

固相离子交换法制备碳酸羟基磷灰石涂层的研究

通过涂覆-烧结法在氧化铝(Al2O3)基体上制备羟基磷灰石(HA)/氟羟基磷灰石(FHA)双层涂层,然后采用固相离子交换法在湿CO2气氛中对HA表层进行碳酸化处理。XRD、FTIR和SEM测试结果表明:FHA中间层能有效地抑制HA与Al2O3的反应,湿CO2气氛中的湿气有利于分解相的恢复,而碳酸根能进入到表面涂层结构内部,形成A型替代为主的碳酸羟基磷灰石(CHA)。所获得的双层涂层具有多孔粗糙的表面,但与Al2O3基体结合紧密。     

氧化铝基体上羟基磷灰石/氟羟基磷灰石双层涂层的制备及性能

通过涂覆-烧结法在氧化铝(Al_2O_3)表面制得羟基磷灰石(HA)/氟羟基磷灰石(FHA)双层涂层,HA和FHA重复沉积在氧化铝基体上形成均匀涂层,然后在1300 ℃进行热处理.在此过程中,如果没有FHA中间层,HA会和Al_2O_3发生严重的反应,形成磷酸三钙和钙铝化合物.SEM、XRD及粘接拉伸试验表明:FHA中间层能有效地抑制HA与Al_2O_3的反应,所获得的双层涂层具有多孔粗糙的表面,但与Al_2O_3基体结合紧密.涂层经1300 ℃热处理后,其结合强度约为30 MPa.     

生物活性梯度涂层中羟基磷灰石的相转变与结构稳定性

重点研究了生物活性梯度涂层中羟基磷灰石高温结构稳定性。探讨了羟基磷灰石在喷涂和热处理过程中的相变化,对比研究了不同热处理条件对羟基磷灰石晶体稳定性和羟基恢复的影响。发现经等离子喷涂后的生物活性梯度涂层中的羟基磷灰石结晶程度明显降低,并出现β－ＴＣＰ杂相。羟基磷灰石晶体中的羟基已完全分解脱落。适当条件的热处理可使喷涂涂层中的磷酸三钙转变为羟基磷灰石,晶体中的羟基可大部分恢复,其中大气热处理比真空热处     

等离子体喷涂生物陶瓷涂层

综合介绍了文献及中国科学院上海硅酸盐研究所在等离子体喷涂生物涂层方面的近期研究进展。羟基磷灰石涂层已在临床上获得应用,但使用效果仍然受其较低的结合强度和结晶度所制约。通过优化喷涂工艺和制备羟基磷灰石基复合涂层,可有效提高羟基磷灰石涂层的结合强度和结晶度。此外,为了获得综合性能优良的植入体材料,制备了多种新型的生物活性陶瓷涂层。纳米氧化钛涂层经合适工艺的后处理可具有良好的生物活性,由于其与钛合金基体有较高的结合强度,在体液环境下具有高稳定性和生物相容性,使纳米氧化钛涂层成为一种具有发展前景的植入体涂层候选材料。新型生物活性硅酸钙涂层具有良好的生物活性,与骨组织能形成有效结合。此外,对这些新型涂层的生物活性机制也做了必要的描述。     

HA生物活性陶瓷涂层制备方法研究进展

阐述了国内外学者对金属基羟基磷灰石生物活性涂层的研究状况,论述了羟基磷灰石涂层的制备方法,认为该材料是最具有发展前景的生物硬组织替代材料之一。     

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.     

钛合金表面制备羟基磷灰石生物陶瓷涂层研究进展

钛合金表面制备羟基磷灰石生物陶瓷涂层以其优异的力学性能和生物活性,成为近年来材料学家研究的热点医用材料之一。本文综述了在钛合金表面制备羟基磷灰石生物陶瓷涂层的研究进展,特别是在提高涂层结合强度和涂层结晶度方面的最新研究成果,展望了钛合金表面制备羟基磷灰石生物涂层复合材料的发展趋势和前景。     

Surfactant-free electrochemical synthesis of fluoridated hydroxyapatite nanorods for biomedical applications

Fluoridated hydroxyapatite (FHA) [Ca₁₀(PO₄)₆F_x(OH)_2−x, x = 0–2] is believed to be a promising calcium phosphate (CaP) to replace pure hydroxyapatite (HA) for next-generation implants, owing to its better biocompatibility, higher antibacterial activity, and lower solubility. Notably, the shape and size of the CaP crystals play key roles in their performance and can influence their applications. One-dimensional (1D) FHA nanorods are important CaP materials which have been widely used in regenerative medicine applications such as restorative dentistry. Unfortunately, the traditional synthesis methods for FHA nanorods either employ surfactants or take a relatively long time. In this study, we aimed to propose a facile synthesis route to fabricate FHA nanorods without any surfactants using an electrochemical deposition method for the first time. This study focused on preparing FHA nanorods without the assistance of any surfactant, unlike the traditional synthesis methods, to avoid chemical impurities. FHA nanorods with lengths of 124–2606 nm, diameters of 28–211 nm, and aspect ratios of 4.4–21.8 were synthesized using the electrochemical method, followed by a heat treatment. For the as-synthesized FHA nanorods, the Ca/P ratio was 1.60 and the atomic concentration of F was 2.06 at.%. An ultrastructure examination revealed that each FHA nanorod possessed long-range order, good crystallinity, and a defect-free lattice with a certain crystallographic plane orientation along the whole rod. In short, we propose a novel, surfactant-free, cost-saving, and more efficient route to synthesize FHA nanorods which can be widely applied in multiple biomedical applications, including drug delivery, bone repair, and restorative dentistry.     

The Effect of the Two‐Step Sintering Process on Consolidation of Fluoridated Hydroxyapatite and its Mechanical Properties and Bioactivity

The aim of this work was to evaluate the effect of the two‐step sintering process on consolidation of fluoridated hydroxyapatite (FHA). In addition, the effect of fluorine content on sinterability, mechanical properties, and bioactivity of FHA bulks was studied. Nanostructured FHA bulks were obtained under the conditions of 1000 and 900°C for the initial and secondary temperatures, respectively, without any structural decomposition. In addition, by increasing the fluorine content, the sinterability of FHA bulks was decreased and the hardness of FHA bulks was improved. Moreover, FHA bulks showed acceptable bioactivity.     

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.     

Conversion of HA on NT-C/C Composites from Ultrasonic Induction Heating Deposited Monetite to FHA Coating by an Alkaline Followed by NaF Solution Hydrothermal Treatment Methods

An ultrasonic induction heating (UIH) deposited monetite coating on (NH₄)₂S₂O₈ treated (NT) C/C composites was subjected to a hydrothermal treatment to form a hydroxyapatite (HA) coating. This HA coating was then placed in a NaF solution and hydrothermally treated a second time to produce a fluorinated hydroxyapatite (FHA) coating. The structure, morphology and chemical composition of the HA and FHA coatings were characterized by XRD, FTIR, XPS SEM and EDS, and the adhesiveness of the two coatings to the NT-C/C substrates was evaluated by a scratch test. The results showed that after the NaF treatment, the FHA coating was a mixture of FHA and HA with some calcium oxides, and the FHA showed a higher degree of crystallization than the HA coating though the morphologies were similar. In addition, the EDS-determined Ca/P atomic ratio for the FHA coating was about 1.78 which was larger than 1.69 ratio of the HA coating. The bonding strength of the HA coating on C/C could reach a critical load of 60.3 N, while that of the as-prepared F-containing HA coating only had a critical load of 42.4 N. The reason of the lower adhesion for the FHA coating than that for the HA coating is suggested to be correlated with the constituent and structure of the two coatings.     

Deposition of Nanostructured Fluorine‐Doped Hydroxyapatite Coating from Aqueous Dispersion by Suspension Plasma Spray

In this study, we prepared an aqueous dispersion of fluorine‐doped hydroxyapatite (FHA) nanoparticles by a wet chemical method. For the first time, the as‐prepared aqueous dispersion of FHA nanoparticles was directly used as suspension for depositing nanostructured FHA coating on stainless steel substrate by suspension plasma spray (SPS) method. Field‐emission scanning electron microscopy images confirm that the coating was nanostructured. X‐ray Diffraction pattern, Fourier‐transform infrared spectroscopy, and Raman spectra show that the as‐sprayed coating was FHA phases. The experimental result confirmed that OH^? and F^? ions have been well kept in FHA crystal lattice and structural integrity has been maintained during SPS process by using an aqueous dispersion of FHA nanoparticles. The potentiodynamic polarization and electrochemical impedance spectroscopy results prove that the nanostructured FHA coating can greatly enhance the anticorrosion performance of stainless steel in phosphate‐buffered saline solution.     

Al（OH）3@Zn（OH）2双层包覆氧化铁黄合成及其耐热性能研究

采用共沉淀法对铁黄颜料进行Al（OH）₃/Zn（OH）₂双层异相包覆,提升其耐热性能,并通过XRD、TG-DTA、FT-IR、SEM&EDS等手段对包覆前后铁黄颜料的微观结构进行表征。研究结果表明,包覆质量分数为40%的Al（OH）₃时铁黄颜料的耐热性能较好;第二层包覆Zn（OH）₂,最优包覆质量分数为30%,样品在240 ℃时色差值为1.84。XRD测试结果表明,Al（OH）₃和Zn（OH）₂包覆并没有改变氧化铁黄的特征峰,两者可能以无定形态包覆在铁黄粒子表面。SEM、EDS、FT-IR测试表明,Al（OH）₃/Zn（OH）₂已成功对铁黄颜料进行了包覆;此外,还出现了片状结构对应Al（OH）₃自身成核现象,包锌后出现了团聚现象。TG-DTA表征显示,包覆后样品升温脱水分两步,低温吸热峰对应包覆层物质的脱水,高温吸热峰偏向更高温度,对应包覆颜料耐热性能的提升。     

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.     

氟羟基磷灰石烧结体的热物性和抗折强度研究

以湿化学法制备了不同氟替代量的氟羟基磷灰石(FHA,Ca10(PO4)6(OH)2-2xF2x,0相似文献