多孔钛支架表面羟基磷灰石的仿生生长

以纯钛粉为原料,采用选区激光烧结(SLS)技术制备不同孔隙率仿生人工骨试样。测试烧结试样表面抗压强度,将试样表面处理后,在4倍模拟体液(SBF)中浸泡,利用X射线衍射、扫描电子显微镜和能谱分析表面涂层的物相组成,观察多孔试样的表面、纵切面及孔内涂层形貌,计算表面涂层的钙磷比。讨论了激光扫描速率和扫描间距对试样孔隙率的影响。结果表明:SLS可以获得内部连通微孔结构的试样。经过4倍模拟体液中浸泡8 d,在2组试样外表面及孔内均产生类骨磷灰石涂层,实现了HA钙磷涂层的三维生长。孔隙率较高的试样抗压强度为117 MPa,其表面诱导羟基磷灰石沉积的能力更强,且表面涂层的钙磷比与自然骨更接近,涂层的综合性能更好。     

La_2O_3对激光熔覆生物陶瓷涂层生物活性的影响

采用梯度宽带激光熔覆技术在钛合金(TC4)基体表面制备生物陶瓷涂层,研究不同含量稀土氧化物La_2O_3的加入对浸泡在模拟体液(SBF)中的生物陶瓷涂层生物活性的影响。结果表明,稀土氧化物La_2O_3在激光熔覆生物陶瓷过程中具有诱导合成HA+β-TCP的作用,在模拟体液(SBF)中浸泡相同时间,当La_2O_3含量为0.6 wt%时,合成HA+β-TCP的数量最多,生物陶瓷涂层生物活性更好。     

富含钙磷的多孔氧化钛膜及其生物活化机理

在不同电压下,钛经微弧氧化在表面形成富含钙磷的多孔氧化钛膜。通过模拟体液浸泡实验检测磷灰石的形成以确定样品的生物活性。实验结果表明：不同电压制备的微弧氧化样品在模拟体液浸泡后,只有400 V和450 V的样品表面生成磷灰石层,说明高电压制备的样品具有生物活性;而低电压制备的微弧氧化样品在模拟体液中浸泡长达50 d仍未见到任何物质沉积,表明其不具有生物活性。分析认为,粗糙多孔的表面虽有利于磷灰石的成核,但高电压下出现的CaTiO_3相及其水解吸引钙、磷沉积才是磷灰石形成的主要原因。     

羟基磷灰石/TiO_2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。     

纳米羟基磷灰石/聚氨酯支架材料体外的生物活性和降解性

采用纳米羟基磷灰石(hydroxyapatite,HA)粉体与聚氨酯(polyurethane,PU)复合,制备了多孔HA/PU支架材料,通过模拟体液(simulated bodyfluid,SBF)浸泡试验评估支架材料的降解性和生物活性.用等离子体原子发射光谱仪测定了浸提液中钙离子浓度变化,评估钙离子在支架材料表面的沉积;用电子天平测定了支架材料浸泡前后的质量损失,分析材料的降解性.用X射线衍射、红外光谱分析支架材料浸泡前后结构组成变化,并用扫描电镜观察其表面形貌特征.结果表明:HA/PU支架材料在SBF中,随浸泡时间的延长,材料均有不同程度的降解,PU的降解主要来自于水解.随着PU的降解,表面HA含量增加、溶液中的Ca,P离子过饱和,并与水解的基团成核,在支架材料表面形成一层结晶性较差的钙磷层,使得复合支架随着浸泡时间的延长而表现出最佳的体外生物活性.     

两步电化学法制备羟基磷灰石/氧化铝复合生物涂层的研究

研究旨在开发一种可应用于医用金属表面生物学改性的复合生物陶瓷涂层。通过先阳极氧化、再电沉积的两步电化学方法成功制备了羟基磷灰石(hydroxyapatite,HA)／Al2O3复合生物涂层。利用扫描电子显微镜(SEM)研究了阳极氧化Al2O3(anodic aluminum oxide,AAO)膜的表面形貌与HA／Al2O3复合涂层的表面及截面形貌结构;用X射线衍射仪(XRD)、Fourier变换红外光谱仪(FT-IR)与能谱仪(EDS)表征了复合涂层的物相组成;用等离子原子发射光谱仪(ICP-AES)和粘接拉伸试验分别测定涂层在模拟体液(SBF)中的体外行为和浸渍后涂层间的结合强度,结果表明：所制备的HA含有少量碳酸根,在SBF中呈现优良的稳定性并能诱导新的磷灰石层的形成;HA底部嵌入AAO膜的孔洞中形成互锁界面,经模拟体液处理后两者之间结合强度为3．2MPa。     

以葡萄糖为造孔剂制备多孔羟基磷灰石涂层

采用电泳沉积方法在钛基材表面制得羟基磷灰石(hydroxyapatite,HA)/葡萄糖复合涂层,经烧结处理得到多孔HA涂层。采用红外光谱仪、扫描电镜、X射线衍射和热重分析表征了涂层的组成、表面形貌、物相组成及热稳定性,黏结-拉伸实验测定涂层与基体的结合强度,人体模拟体液(simulated body fluid,SBF)浸泡测定涂层的生物亲合性。结果表明:经700℃烧结处理,复合涂层中的葡萄糖微粒热分解得到多孔HA涂层,孔径为2～20μm,涂层与基体的结合强度可达17.6MPa;在1.5倍SBF(各离子浓度为SBF的1.5倍)中浸泡5d后,多孔HA涂层表面碳磷灰石化,呈现良好的生物亲合性。     

镁合金表面MAO/HA/CNTs涂层的电化学腐蚀性能

笔者采用化学沉淀法制备羟基磷灰石/碳纳米管复合粉体(HA/CNTs),并将这种复合粉体作为电解液的添加剂,采用微弧氧化的方法制备镁合金表面羟基磷灰石/碳纳米管(MAO/HA/CNTs)复合涂层。然后对制备的复合粉体分别采用扫描电子显微镜(SEM)、傅里叶红外光谱(FTIR)、X射线衍射分析(XRD)和电化学工作站研究其表面形貌、物相组成、以及对微弧氧化图层表面形貌和在模拟体液(SBF)中可以承受腐蚀的不同能力。研究结果显示,复合粉体在微弧氧化过程中均匀地沉积在镁合金表面,有很好的保护作用。所制备的羟基磷灰石/碳纳米管(HA/CNTs)复合粉体结晶良好,无任何杂质;电化学工作站中,MAO/HA/CNTs样品的腐蚀电位为-0.2～-2.0 V,通过在模拟体液中浸泡了7 d之后,其表面沉积了大量的亚纳米级的颗粒沉淀物,通过实验对镁基体和MAO样品进行试验,发现镁基体相比于MAO样品,具有的耐腐蚀性比较好,生物活性比较高。     

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.     

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%。     

Long-term corrosion resistance and fast mineralization behavior of micro-nano hydroxyapatite coated magnesium alloy in vitro

To improve the long-term corrosion resistance of biodegradable AZ31 magnesium alloy, the micro-nano structural hydroxyapatite (HA) coating was fabricated on AZ31 substrate by hydrothermal treatment. The compact and high crystallinity HA coating prepared at 120 °C had excellent electrochemical properties. Moreover, the cell viability experiment revealed that the micro-nano structure coating was conducive to the viability and proliferation of MC3T3-E1 osteoblasts. The immersion experiment in simulated body fluid (SBF) solution showed that the micro-nano structural HA coatings could quickly induce the production of HA mineralization, and then the mineralization evolved into a compact mineralized layer on the surface of coated sample, which provided a long-term protection for the specimen. Even after 147 days of immersion, the coated samples remained the relatively complete macroscopic shape, the corrosion rates were lower than 0.500 mm/y and the pH values of the SBF solution maintained in the range of 7.10–7.80, suggesting when these coated AZ31 magnesium alloys were used as degradable biomaterial implants, they could provide a long-term mechanical support during the healing of damaged bones.     

Effect of suspension medium on the electrophoretic deposition of hydroxyapatite nanoparticles and properties of obtained coatings

The suspensions of hydroxyapatite (HA) nanoparticles were prepared in different alcohols. The zeta potential of HA nanoparticles was the highest in butanolic suspension (65.65 mV) due to the higher adsorption of RCH₂OH₂⁺ species via hydrogen bonding with surface P3OH group of HA. Electrophoretic deposition was performed at 20 and 60 V/cm for different times. Deposition rate was faster in low molecular weight alcohols due to the higher electrophoretic mobility of HA nanoparticles in them. The coating deposited from butanolic suspension had the highest adhesion strength and corrosion resistance in SBF solution at 37.5 °C. The surface of this coating was covered by apatite after immersion in SBF solution for 1 week.     

Influence of a hard transition layer on the microstructure and properties of diamond-like carbon/hydroxyapatite composite coating prepared by magnetron sputtering

The nanostructured diamond-like carbon/hydroxyapatite composite coating (DLC/HA) was deposited using magnetron sputtering technique with a densely packed columnar cross-sectional structure and a uniform granular surface morphology. After heat treatment, the amorphous structure of the coating was transformed into a crystal structure. Nanohardness and scratch tests results demonstrated the DLC transition layer significantly enhanced the nanohardness of Ti6Al4V substrates from 4.8 GPa to 10.4 GPa, and increased critical load from 16.6 N (pure HA layer) to 26.5 N (DLC layer) without obvious brittle fracture, flaking and delamination. Electrochemical and immersion tests results demonstrated that DLC/HA composite coatings with a dense gradient transition interlayer had better corrosion resistance and could prevent harmful metal ions being released into the SBF solution more effectively than single HA coatings. Furthermore, active Ca²⁺ ions can be rapidly released from the coating surface during initial immersion in the SBF solution, and facilitated the formation of bone-like apatite.     

Development of HA-CNTs composite coating on AZ31 Magnesium alloy by cathodic electrodeposition. Part 2: Electrochemical and in-vitro behavior

The carbon nano-tubes (CNTs) reinforced hydroxyapatite (HA), with various functionalized CNTs concentration ranging from 0 to 1.5?wt%, were deposited on AZ31 magnesium alloy by direct and pulse cathodic electrodeposition methods. The corrosion resistance of the coatings was tested in simulated body fluid (SBF) using different electrochemical methods such as open circuit potential, polarization and electrochemical impedance spectroscopy. The in-vitro behavior, changes in solution pH as well as the amount of evolved hydrogen of these coatings were also evaluated during five days immersion in SBF. The results indicated that the pulse deposited HA having 1% CNTs coating was the optimum condition which decreased the corrosion current density of AZ31 magnesium alloy from 44.25?µA/cm² to 0.72?µA/cm². Moreover, it stabilized the alkalization behavior of AZ31 alloy and caused a tenfold decrease in the amount of hydrogen generation in SBF. Additionally, the formation of new hydroxyapatite layer on the surface of the pre-exist coatings after five days immersion in SBF was confirmed by SEM characterization.     

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...     

Biomimetic apatite deposited on microarc oxidized anatase-based ceramic coating

Biomimetic apatite was formed on a microarc oxidized (MAO) anatase-based coating containing Ca and P in a simulated body fluid (SBF). At the process of the SBF immersion (0–96 h), the Ca and P of the MAO coating dissolve into the SBF, increasing the supersaturation degree near the surface of the MAO coating, which could promote the formation and growth of apatite. After SBF immersion for 7 days, the surface of the MAO coating was modified slightly. The entire surface immersed for 14 days was covered by an apatite coating. The apatite possesses carbonated structure, controllable crystallinity and pore networks. The results indicate that the MAO coating formed in an electrolyte containing phosphate and EDTA–Ca chelate complex possesses good apatite-forming ability.     

Electrodeposition of hydroxyapatite coating on magnesium for biomedical applications

The effectiveness of hydroxyapatite (HA) coating prepared by electrodeposition technique in improving the corrosion resistance of commercially pure magnesium (CP-Mg) in simulated body fluid (SBF) is addressed. The coating formed in as-deposited condition is identified as dicalcium phosphate dehydrate (DCPD) (Brushite), which is converted to HA after immersion in 1?M NaOH at 80°C for 2?h. The XRD patterns and FTIR spectra confirm the formation of DCPD and HA. During electrodeposition, the H₂PO₄ ^? ion is reduced and the reaction between Ca²⁺ ions and the reduced phosphate ions leads to the formation of DCPD, which is converted to HA following treatment in NaOH. The deposition of HA coating enables a threefold increase in the corrosion resistance of CP-Mg. The ability to offer a significant improvement in corrosion resistance coupled with the bioactive characteristics of the HA coating establish that electrodeposition of HA is a viable approach to engineer the surface of CP-Mg in the development of Mg-based degradable implant materials.     

The effect of surface treatment on CaP deposition of Ti6Al4V open cell foams in SBF solution

The effects of alkali and nitric acid surface treatment and acid etching on the CaP deposition of an open cell Ti6Al4V foam (60% porous and 300–500 μm in pore size) developed for biomedical applications were investigated in a simulated body fluid (SBF) solution for 14-day. The surface roughness of the foam specimens ground flat surfaces was measured in nano-metric scale before and after SBF immersion using an atomic force microscope (AFM). A significant increase in the surface roughness of alkali treated foam specimen after SBF immersion indicated a smaller crystal size CaP deposition, which was also confirmed by the AFM micrographs. The microscopic evaluation clearly showed that alkali treatment and nitric acid treatment induced a continuous, uniform CaP deposition on the cell wall surfaces of the foam (interior of cells). While in untreated foam specimen the cells are filled with CaP precipitates and acid etching did not produce a continuous coating layer on particles interior of the cells. The coating layer thickness was ～3 μm in alkali treated foam specimens after 14-day of SBF immersion, while nitric acid treatment induced relatively thinner coating layer, 0.6 μm.