等离子体表面改性的双相磷酸钙陶瓷在SBF中类骨磷灰石形成的研究

由于材料表面类骨磷灰石的形成是材料是否具有生物活性的关键因素。因此,本文研究了等离子体活化改性的双相钙磷陶瓷(HA／TCP)在模拟体液(SBF)中形成类骨磷灰石的表面形貌、组成和结构,并探讨活化和沉积的机理。结果发现等离子体处理的HA／TCP更容易形成类骨磷灰石。其机理是等离子体中的高能、高活性的粒子轰击HA／TCP,使其表面刻蚀和粗化,也使HA／TCP晶体产生畸变活化,从而增加了钙磷陶瓷的溶解性,易使局部钙、磷离子浓度达到过饱和,有利于类骨磷灰石的成核和生长。表明等离子体表面改性提高了材料的活性。有利于促进骨的形成和生长。     

生物陶瓷及其复合材料表面诱导类骨磷灰石层形成的研究

钙磷生物材料表面类骨磷灰石层的形成对其植入体内诱导新骨生成起非常重要的作用.本实验采用2倍模拟体液(2×SBF)为介质,通过仿生浸泡的方法研究了羟基磷灰石(HA)陶瓷及其复合材料羟基磷灰石/聚乳酸(HA/PLA)、羟基磷灰石/聚己內脂(HA/PCL)、羟基磷灰石/丝素(HA/SF)和羟基磷灰石/壳聚糖(HA/CS)表面诱导类骨磷灰石层形成的差异.实验结果表明,HA陶瓷及其复合材料在2×SBF溶液中仿生浸泡7d后,各样品表面均有一层厚度不同的类骨磷灰石层生成.并且该类骨磷灰石层的结晶度较低,晶粒较细(15～30nm),与人体自然骨无机物的结构非常类似.其中,在这4种复合材料中,HA/CS和HA/SF复合材料中因丝素蛋白和壳聚糖富含多种功能基团,能有效促进类骨磷灰石晶体的形核和生长,因而诱导类骨磷灰石生成的能力最强,显示其良好的生物活性.     

Sol-gel原位相转变矿化制备纳米羟基磷灰石/壳聚糖复合支架材料

为了模拟天然骨组织的结构和成分, 以羟基磷灰石(HA)为钙磷源, 以壳聚糖(CS)为大分子基质材料, 在酸性环境中形成均相溶液, 通过Sol-gel相转变矿化方法和陈化处理, 原位构建了纳米HA/CS复合多孔支架材料, 研究了共沉积时体系的pH值和陈化时间对支架压缩强度、晶相组成及形貌等的影响。结果表明体系pH为10和11时, 支架的力学强度远高于未矿化壳聚糖支架强度, 但是随着体系pH的升高强度逐渐下降。XRD分析结果表明陈化处理有利于磷酸钙盐向HA转化, 随着陈化时间的延长, 纳米HA沿c轴择优生长。SEM观察显示支架材料具有相互贯穿的多孔结构, 纳米级的短棒状或颗粒状HA晶体颗粒均匀分散在孔壁上, 随着陈化处理以及陈化时间的延长, 形成致密的纳米无机/有机均匀复合体。这种快速深度矿化方法为骨支架材料的制备提供了新思路。      

多巴胺辅助牙本质沉积羟基磷灰石研究

本研究报道了一种新颖的、模拟口腔环境的仿生修复牙齿的方法。利用具有良好生物相容性的多巴胺在牛牙牙本质表面自聚合形成聚多巴胺层(PDA)使牙本质表面功能化, 进而诱导羟基磷灰石从模拟唾液中向牙本质表面沉积。XPS、XRD、SEM和EDS表征分析表明: 聚多巴胺层的涂覆有利于牙本质表面羟基磷灰石晶体的结晶生长, 可提高羟基磷灰石再矿化层与牙本质表面的结合力; 多巴胺溶液浓度为2 mg/mL时, 牙本质表面聚多巴胺层的沉积效果最佳。     

在类仿生溶液中电沉积羟基磷灰石涂层的性能

在类仿牛溶液中用电沉积法在阳极氧化处理后的钛基体上电沉积均一的羟基磷灰石涂层,研究了阳极氧化处理后对HA涂层耐蚀性能、沉积效率和结合强度的影响.结果表明:用该方法沉积的HA涂层结构单元的排列与人骨类似,具有优良的生物诱导性能.经过阳极氧化后钛表面生成均匀的纳米孔洞结构,增强了与HA涂层的机械结合和涂层的阻抗值,提高了涂层的结合强度和耐腐蚀性能.同时,在类仿生溶液中二氧化钛吸附羟基,通过库仑力和氢键作用大大提高了沉积效率,并因其纳米孔洞结构促进HA的形核,形成更加细小、致密的针状HA晶体结构,提高了涂层的结合强度和耐腐蚀性能.     

氟化钠处理对炭/炭复合材料磷灰石生物活性涂层的影响

通过声电沉积工艺在炭/炭复合材料表面制备钙磷生物活性涂层, 采用扫描电镜、 X射线能谱仪、 X射线衍射仪、 红外光谱等方法研究了氟化钠处理前后钙磷生物活性涂层的形貌、 结构和组成。实验结果表明: 氟化钠能促进磷酸三钙转化为含氟羟基磷灰石(FHA), 并提高涂层结晶度; 经氟化钠处理后, 羟基磷灰石(HA)的(112)、 (300)衍射峰明显增强, 涂层是HA和FHA的混合物。氟化钠处理前后涂层表面形貌均为片状晶体, 但处理后其颗粒尺寸增大; 氟化钠处理后涂层与基体的结合强度略有增强, 结合强度可达4.08MPa, 涂层氟的含量为4.59wt％。分析了炭/炭复合材料表面HA转变为FHA的反应机制。采用氟化处理HA制备FHA涂层时, 应加入磷酸盐保持整个反应过程的pH值不变。      

碳纳米管的表面改性与羟基磷灰石的包覆

通过TEM、FTIR及XRD等检测手段对原位合成法制备羟基磷灰石/碳纳米管复合材料过程中碳管的表面改性及影响羟基磷灰石包覆的因素进行了系统探讨. 研究表明, 浓酸处理后, 碳纳米管表面产生大量官能团; 阴离子表面活性剂十二烷基磺酸钠(SDS)的加入提高了碳纳米管与水的相容性; 实验中随着(NH₄)₂HPO₄溶液的加入, 羟基磷灰石原位沉积并形成包覆层. 结果发现: 碳纳米管的表面改性、适当的pH值和陈化温度是得到羟基磷灰石连续包覆层的关键因素.     

声电沉积透钙磷石和羟基磷灰石涂层动力学对比研究

借助声电沉积技术，在碳／碳复合材料表面制备了生物活性透钙磷石和羟基磷灰石涂层。采用分析天平称量了不同温度和时间的涂层重量，通过理论分析研究了涂层沉积的动力学规律。结果表明随时间温度增加，涂层的质量增加。透钙磷石和羟基磷灰石沉积都受扩散过程控制，并且得出羟基磷灰石的扩散活化能是7．24Kcal／mol，透钙磷石的扩散活化能很小，在本实验范围内不能求出，但通过比较分析，可知透钙磷石的扩散活化能远小于羟基磷灰石涂层，因此从理论上揭示了声电沉积工艺中，透钙磷石优先羟基磷灰石涂层沉积的本质原因。     

不同pH值NaOH溶液对钛材微弧氧化膜水热处理后性能的影响

采用NaOH溶液对钛材表面含Ca,P微弧氧化膜进行水热处理能提高其医学性能,过去从水热处理工艺方面的探讨不多。在纯钛表面制备了含Ca,P的微弧氧化膜,并采用不同pH值的NaOH溶液进行水热处理制得了羟基磷灰石（HA）/TiO₂复合微弧氧化陶瓷层。分别采用X射线衍射（XRD）、扫描电镜（SEM）观察、能谱（EDS）分析、显微硬度及接触角测量等方法对水热处理前后陶瓷膜的化学成分、微观形貌、润湿性和显微硬度进行了研究。结果表明:含Ca,P氧化膜经NaOH溶液于210℃水热处理,其表面可以形成结晶度较高的棒状HA;随着溶液pH值升高,HA晶粒数量不断增加,晶粒长度逐渐减小,HA层逐渐细化和均匀;溶液pH值高于12.0时,氧化膜发生破坏并导致HA剥落;溶液pH值和温度分别为10.5和210℃时水热处理效果最好。     

pH值和缓冲剂对水热电化学沉积HA/TiO_2涂层的影响

以微弧氧化后的钛合金为基体,采用水热电化学法制备了HA/TiO2涂层。利用SEM、XRD对涂层的表面形貌、物相组成进行了表征分析,通过pH微探针原位探测电极/电解液界面pH值的变化,研究了pH值和缓冲剂对水热电化学沉积HA/TiO2涂层的影响。研究结果表明,微弧氧化膜有利于水热电化学沉积HA,得到的HA晶体分布均匀、致密。当电解液pH值在2~8时,pH值升高有利于提高水热电化学沉积HA的结晶度,并促使HA沿(002)晶面生长。在水热电化学沉积HA过程中,电极表面的pH值随沉积时间的增加先升高后逐渐降低;而溶液中的pH值随沉积时间的增加逐渐降低。pH值和缓冲剂对涂层HA晶体形貌有明显影响,加入缓冲剂后得到的HA晶体端面呈六边形棒状结构,晶体表面光滑、结晶完整。     

微波辅助法制备镁合金的植酸镁/羟基磷灰石复合涂层及其耐蚀性能

采用微波辅助法在AZ31镁合金表面制备了植酸镁/羟基磷灰石(PA/HA)复合涂层。利用FESEM、EDS、XRD和电化学性能测试等方法表征涂层的表面形貌、物相组成以及耐蚀性能,探究了植酸溶液的pH值对PA/HA复合涂层形貌及耐蚀性能的影响,并通过浸泡实验研究了镁合金及PA/HA复合涂层在模拟体液(SBF)中的降解矿化行为。结果表明:在植酸预处理中,植酸溶液的pH=5.0时制备得到的PA/HA复合涂层表面均匀、无裂纹,与镁合金基底的界面结合良好;并且在此pH值下PA/HA复合涂层包覆镁合金样品的交流阻抗最大,自腐蚀电流密度最小,说明其耐蚀性最好。在SBF中,PA/HA复合涂层能够快速诱导磷灰石的生成,并显著提高镁合金基底的耐蚀性能。     

Preparation of layered bioceramic hydroxyapatite/sodium titanate coatings on titanium substrates using a hybrid technique of alkali-heat treatment and electrochemical deposition

Bioceramic hydroxyapatite/sodium titanate coating on sandblasted titanium substrate was fabricated by a three-step process. At first, the sandblasted titanium substrate was coated with a flake-like sodium titanate layer by alkali-heat treatment. In the second step, the alkali-heat treated titanium substrate was hydrothermal treated at 180 °C for 4 h with calcium solutions. In the third step, the hydroxyapatite (HA) coating was deposited onto the hydrothermal treated layer via electrochemical deposition method. The surface topography and roughness of the coatings were determined by field emission scanning electron microscope (FESEM) and a mechanical contact profilometer, respectively. The surface compositions were evaluated by X-ray diffraction (XRD), energy-dispersive X-ray spectrum (EDS), and X-ray photoelectron spectroscopy (XPS). The EDS, XPS, and XRD analysis confirm the presence of element Ca, Ca²⁺, and CaTiO₃ on sodium titanate layer after hydrothermal treatment with Ca(NO₃)₂ solution, respectively. FESEM micrograph shows the rod/needle-shaped crystallites are highly densely packed on the calcium-ion-containing layer with an average size of ~50 nm in diameter. The results indicate that the sodium titanate layer containing Ca²⁺ ions possesses higher ability to induce HA formation compared with the pure sodium titanate layer. It is revealed that surface composition plays an important role in the electrochemical deposition of HA. The calcium-ion-containing layer probably makes the nucleation of HA easy and effectively promotes orientated growth of HA on flake-like sodium titanate surface. The sodium titanate layer possesses a lower corrosion current density and a higher corrosion potential than sandblasted-Ti substrate. The sodium titanate layer should act as a barrier to the release of metal ions from metallic substrate to physiological solutions and thus reducing the electrochemical reaction rate.     

沉积温度对多孔钛表面仿生制备羟基磷灰石的影响

为研究沉积温度对羟基磷灰石涂层生长的影响,制备了不同温度条件下成分恒定的仿生沉积液,并采用纯钛和不同孔径的多孔钛做基体,在其表面仿生沉积羟基磷灰石涂层,再将得到的涂层试样浸泡在标准模拟体液中检测其生物活性.通过X射线衍射仪(XRD)分析涂层物相结构,用金相显微镜、环境扫描电子显微镜(ESEM)表征涂层形貌,利用能谱分析仪(EDS)计算钙磷比.研究表明:基体孔径增大,有利于沉积液进入到孔隙且表面粗糙度相对增大,从而使得HA涂层变得均匀致密;沉积温度由30℃升高至37℃,会加快HA涂层致密均匀的生长,但温度升高到44℃时,HA晶粒变粗大,涂层变得疏松化;模拟体液浸泡后,Ti/HA涂层试样表面有新的HA生成,且Ca/P比接近标准的1.67,表明该Ti/HA涂层试样具有良好的生物活性.适当增大钛基体孔径,提高沉积液温度,可以得到均匀致密的HA生物活性涂层.     

Effects of the nano-tubular anodic TiO2 buffer layer on bioactive hydroxyapatite coating

We studied the effect of nano-tubular anodic TiO2 buffer layers on hydroxyapatite (HA) coating. The pulsed laser deposition (PLD) method was used to deposit HA on a well arranged nano-tubular anodic TiO2 (NT-ATO) buffer layer prepared by an electrochemical anodization technique. The surface morphology and chemical composition of HA coatings were characterized by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and contact angle measurement. We found that crystalline HA coatings show well arranged porous morphologies with a favorable surface wettability. We also found that an anodic nano-tubular TiO2 buffer layer with a relatively short tube length shows a better coating morphology. The deposition process of HA on the nanotubular TiO2 buffer layer was also proposed.     

HA-SrCO_3-SiO_2复合涂层的制备及其生物活性

为制得在力学性能和生物活性方面都较为优异的羟基磷灰石(HA)复合涂层,首先,通过添加二元成骨微量元素化合物SrCO_3和SiO_2,以壳聚糖为造孔剂,采用电泳沉积的方法辅以高温烧结制得HA-SrCO_3-SiO_2复合涂层;然后,使用FTIR、XRD、SEM、EDS、万能材料试验机和电化学工作站对复合涂层进行测试与表征,并通过1.5倍离子浓度模拟体液的浸泡培养评价HA-SrCO3-SiO2复合涂层的生物活性。结果表明:HA-SrCO_3-SiO_2复合涂层与基体间的结合强度达28.6 MPa;在模拟体液中浸泡培养7d后,复合涂层表面完全碳磷灰石化,说明该复合涂层具有比单一掺杂成骨微量元素化合物复合涂层及纯HA涂层更为优异的生物活性。所得结论表明制得的HA-SrCO_3-SiO_2复合涂层有望开发成为新一代人工骨替代材料。     

Electrophoretic deposition of HA/MWNTs composite coating for biomaterial applications

A composite coating of hydroxyapatite (HA)/multi-walled carbon nanotubes (MWNTs) has been fabricated by electrophoretic deposition (EPD). The nano powders of HA and MWNTs were dispersed in ethanol with total concentration of 0.005 g/mL and MWNTs 20% and 30% contents (wt). And the pH value of suspension was adjusted in a range from 4 to 5. After stabilization the mixture was ultrasonically treated for 3 h to form a stable suspension. Prior to the electrophoretic deposition, the titanium substrate was hydrothermally treated at 140 in NaOH (10 mol/L) solution for 6 h. A titanium sheet and circinal net of stainless steel were used as a cathode and an anode respectively, and a constant deposition voltage of 30 V was applied for 50-60 s in the EPD process. The thickness of the coatings was controlled from 10 mum to 20 mum. The samples of composite coating were then sintered in a resistance tube furnace in flowing argon at 700 for 2 h. The structure of the as prepared coating was characterized by SEM and XRD, and the bonding force of the coating/substrate was measured by an interfacial shear strength test. It is shown that the bonding strengths between the coating and the titanium substrate is as high as 35 MPa. The cell culture experiments indicate that the prepared composite coating of HA/MWNTs possesses good biocompatibility.     

钛涂覆多孔羟基磷灰石涂层的制备及其生物活性

在纯钛基体表面通过电泳沉积的方法制得壳聚糖/羟基磷灰石(CS/HA)复合涂层, 然后将复合涂层烧结形成多孔HA涂层。采用SEM对多孔HA涂层的形貌进行观察, XRD分析涂层的物相组成, 粘结拉伸实验测定涂层与基体的结合强度, 1.5倍人体模拟体液(1.5SBF)浸泡测定涂层的生物活性。结果表明: 当悬浮液中CS与HA质量比为1∶1时, 制得的CS/HA复合涂层经过700℃烧结处理, 涂层中CS热分解致孔形成多孔HA涂层, 孔径在10~25 μm, 涂层与基体的结合强度可达19.5 MPa; 在1.5SBF中浸泡5天后, 多孔HA涂层表面完全碳磷灰石化, 呈现较好的生物活性。      

Modulation effects of collagen ? on the structure of electrochemically deposited hydroxyapatite coating

In this work, collagen ? was introduced as an additive to the dilute electrolyte used for direct electrochemical deposition of hydroxyapatite (HA) coating, and its modulation effects on the morphology and crystal structure of the HA coating were examined by SEM and XRD, respectively. Collagen I-modified HA coating was found to exhibit a micro-porous structure, formed by the ordered arrangements of ultra-fine HA crystals. The crystal structure of the modified HA coating was demonstrated to be similar to that of the natural bone. Further compositional studies using FTIR spectroscopy supported the integration of the collagen into the HA coating.     

电流密度对水热电化学沉积HA涂层性能的影响

在含0.15mol/L HF,2mol/L H_3PO_4的水溶液中对Ti6Al4V基体进行阳极氧化处理,然后在0.02mol/L CaCl_2,0.012mol/L K_2HPO_4·3H_2O,0.139mol/L NaCl的电解液中采用水热电化学沉积方法在预处理的Ti_6Al_4V基体表面制备羟基磷灰石(HA)涂层。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能谱仪(EDS)、台阶仪和万能材料试验机等研究沉积过程中电流密度大小对HA涂层物相、微观形貌、厚度、生物活性及结合强度的影响。结果表明:采用水热电化学沉积方法在不同电流密度下均制备出了HA涂层,涂层表现为分层生长,部分晶体呈花簇状。HA的厚度随电流密度的增加先增大后减小,在1.25mA/cm~2时达到最大为26.4μm,此时涂层最为致密,与基体的结合强度最高,约为20.0MPa。模拟体液(SBF)浸泡实验能较快诱导类骨磷灰石(CHA)的生成,最大直径达到7~8μm,表明涂层具有较好的生物活性。     

Formation of hydroxyapatite coating using novel chemo-biomimetic method

A novel chemo-biomimetic method was developed to deposit hydroxyapatite (HA), simulating the porous nano-scale structure and chemical composition of natural bone. Electrochemical activation in NaOH solution, a prerequisite process to heterogeneously nucleate hydroxyapatite in this investigation, creates nano-scale porous structure on the surface of Ti6Al4V alloy. XPS analysis confirmed that the surface of activated Ti6Al4V substrate converted to TiO(2) during activation, existing in the form of hydrated TiO(2). Benefiting from the biocompatible top-layer of hydrated TiO(2) and the favorable alkaline surface chemistry created through the electrochemical activation, the HA coating nucleates heterogeneously and grows continuously on the activated substrate resembling the nano-scale porous bone-like structure. The coating was characterized using XRD, SEM/FESEM/EDX, TEM and FTIR, and was confirmed as pure hydroxyapatite. A coating thickness of 50 mum was achieved, which is preferable and acceptable for medical implant application to promote bone ingrowth, thus enhancing fixation and biocompatibility of implant surface.