纯钛表面微弧氧化法制备含羟基磷灰石氧化膜的实验研究

应用微弧氧化技术在纯钛表面制备含羟基磷灰石的氧化物膜.在氧化过程中,将钛试件放入含Ca、P电解液中,用直流脉冲电源处理.用扫描电镜(SEM)观察试件的表面和横断面形貌,X射线能谱(EDS)及X射线衍射(XRD)分析其元素成分和晶相结构.结果表明微弧氧化处理后,纯钛表面生成微孔结构的氧化膜,膜层厚度约20μm,由O、Ti、Ca和P四种元素组成.膜层表面有分布不均匀的火山丘状的微孔分布,直径小于5μm.膜层表面的钙磷原子比为1.63,界面处的钙磷原子比为0.51.膜层由金红石型和锐钛矿型二氧化钛及少量结晶相羟基磷灰石组成.微弧氧化技术在纯钛表面生成了内层致密外层多孔的晶相二氧化钛膜,同时含有少量羟基磷灰石,表明该技术在人工种植牙和人工骨关节等领域具有良好的医学应用前景.     

纯钛表面不同厚度微弧氧化膜的形貌及相结构分析

本研究采用微弧氧化(micro-arc oxidation,MAO)技术,并通过控制微弧氧化处理时间,在经过抛光和清洗的商业纯钛表面分别获得5、10和20μm的TiO2及相关钛氧化物陶瓷膜层。利用扫描电镜(scanning electron microscopy,SEM)分析表征膜层厚度及表面形貌,X线衍射(X-ray diffraction,XRD)分析表征膜层晶相组成。结果表明:5μm厚的MAO膜,表面呈多孔状,较为平整,孔径较小。XRD谱线中除了突出的钛基体衍射峰外,只出现了锐钛矿的衍射峰。膜厚为10μm时,表面形貌与5μm相似,但孔径大小分布更为均匀,在2μm左右。XRD谱线中钛峰强度下降,出现了金红石型TiO2的衍射峰,但仍以锐钛矿型TiO2占主导地位。膜厚为20μm时,表面孔径进一步增大,达到4～6μm,同时可见陶瓷层表面有的地方出现了破损和裂纹。XRD谱线中钛峰弱小,金红石和锐钛矿型TiO2的衍射峰仍然分别存在,但所占比例发生变化,同时还出现了Ca(Ti2P3O12)2、CaTi O3的衍射峰。除此之外,不同膜层厚度的表面粗糙度也有较大差异。膜层厚度的改变能够显著影响MAO陶瓷层的特性,通过改变...     

钛表面微弧氧化涂层的细胞生物活性

背景：微弧氧化技术可改善钛或钛合金的表面特征。 目的：研究纯钛表面微弧氧化涂层的表面性能及其对MC3T3-E1细胞早期黏附、增殖及成骨能力的影响。 方法：将46个直径10 mm、厚度2 mm圆盘状纯钛试件分为实验组和对照组。实验组置于含0.02 mol/Lβ-甘油磷酸二钠盐及0.2 mol/L乙酸钙的电解液中进行微弧氧化处理,对照组对试件进行机械抛光。扫描电子显微镜观察试件表面形貌,X射线能谱分析检测涂层表面钙磷比,X射线衍射分析检测涂层晶相构成。将MC3T3-E1细胞接种在两组试件表面,1,2,4 h电镜下观察细胞形态,在2,4,7 d通过CCK-8方法检测细胞增殖,并于7,14 d检测碱性磷酸酶活性。 结果与结论：经微弧氧化处理后,钛表面形成粗糙多孔的钙磷涂层,微弧氧化涂层主要元素为Ca、P、O及Ti,微弧氧化膜层主要由氧化钛、钛酸钙、磷酸钙及偏磷酸钙构成。电镜观察显示1 h 微弧氧化涂层表面细胞已伸出伪足,4 h呈现较典型的细胞形态。细胞在微弧氧化处理钛表面4,7 d的细胞增殖和7,14 d的碱性磷酸酶活性高于对照组。表明微弧氧化技术生成的粗糙多孔钙磷涂层能显著促进MC3T3-E1细胞的早期黏附、增殖及成骨活性。     

不同多肽修饰方法对纯钛微弧氧化膜层性能的影响

背景：理论上推测钛基-微弧氧化陶瓷膜-精氨酸-甘氨酸-天冬氨酸(RGD)序列多肽的结合模式应具较好的力学和生物学性能。 目的：观察不同修饰方法固定RGD多肽后,钛基体微弧氧化膜层表面的微观结构和细胞增殖。 方法：取纯钛与微弧氧化纯钛试件共90枚,分3种方法固定RGD多肽,分别为RGD多肽物理吸附修饰纯钛组、RGD多肽物理吸附修饰微弧氧化组与RGD多肽化学偶联修饰微弧氧化组,每组30枚。应用荧光显微镜观察3组试件表面接枝效果,采用X射线光电子能谱扫描检测试样表面的RGD多肽含量。将3组试件分别与小鼠骨髓基质细胞培养,光镜观察各时间点的细胞黏附及增殖情况。 结果与结论：3组试样表面有大小不一、数量不等的绿色荧光亮点,在单位视野中,RGD多肽化学偶联修饰微弧氧化组荧光最强,提示此组试件接枝了更多的多肽。RGD多肽物理吸附修饰纯钛组试样表面仅含少量或微量多肽,RGD多肽物理吸附修饰微弧氧化组含多肽量居中,RGD多肽化学偶联修饰微弧氧化组含肽量最高。3组试件均无明显的细胞毒性,但RGD多肽化学偶联修饰微弧氧化组细胞生长情况最好。表明化学偶联法可以较好地将RGD多肽固定在含微弧氧化膜层的纯钛试样表面,无明显细胞毒性,有利于细胞的生长增殖。中国组织工程研究杂志出版内容重点：生物材料;骨生物材料; 口腔生物材料; 纳米材料; 缓释材料; 材料相容性;组织工程全文链接：     

钛合金表面微弧氧化涂层理化性能及表面形貌研究

目的研究Ti．6A1—4V合金表面微弧氧化（MAO）涂层的表面形貌及理化性能。方法将Ti-6A1-4V合金置于含0．02mol／Lβ-甘油磷酸二钠盐及0．2mol／L乙酸钙的电解液中进行MAO处理后,通过扫描电子显微镜（SEM）观察涂层表面形貌及截面形貌;X线能谱分析（EDX）检测涂层表面钙磷比;X射线衍射分析（XRD）检测涂层晶相构成;纳米压痕试验测量涂层的微弹性模量及微硬度。结果经MAO处理后,钛合金表面形成粗糙多孔的氧化膜;XRD显示涂层主要由锐钛矿相TiO2、金红石相Ti02和羟基磷灰石（HAP）构成;EDX及纳米压痕试验测得膜层的钙磷比为1．64,弹性模量和微硬度分别为（32．07±7．07）GPa和（1．49±0．68）GPa。结论通过MAO技术可制备出具备良好理化性能的含HAP的涂层。     

不同多肽修饰方法对纯钛微弧氧化膜层性能的影响CSCD

背景:理论上推测钛基-微弧氧化陶瓷膜-精氨酸-甘氨酸-天冬氨酸(RGD)序列多肽的结合模式应具较好的力学和生物学性能。目的:观察不同修饰方法固定RGD多肽后,钛基体微弧氧化膜层表面的微观结构和细胞增殖。方法:取纯钛与微弧氧化纯钛试件共90枚,分3种方法固定RGD多肽,分别为RGD多肽物理吸附修饰纯钛组、RGD多肽物理吸附修饰微弧氧化组与RGD多肽化学偶联修饰微弧氧化组,每组30枚。应用荧光显微镜观察3组试件表面接枝效果,采用X射线光电子能谱扫描检测试样表面的RGD多肽含量。将3组试件分别与小鼠骨髓基质细胞培养,光镜观察各时间点的细胞黏附及增殖情况。结果与结论:3组试样表面有大小不一、数量不等的绿色荧光亮点,在单位视野中,RGD多肽化学偶联修饰微弧氧化组荧光最强,提示此组试件接枝了更多的多肽。RGD多肽物理吸附修饰纯钛组试样表面仅含少量或微量多肽,RGD多肽物理吸附修饰微弧氧化组含多肽量居中,RGD多肽化学偶联修饰微弧氧化组含肽量最高。3组试件均无明显的细胞毒性,但RGD多肽化学偶联修饰微弧氧化组细胞生长情况最好。表明化学偶联法可以较好地将RGD多肽固定在含微弧氧化膜层的纯钛试样表面,无明显细胞毒性,有利于细胞的生长增殖。     

电参数对钛微弧氧化膜层理化性能及细胞相容性的影响

目的:研究纯钛微弧氧化电参数（脉冲宽度及脉冲频率）的改变对膜层表面形貌、理化性能及成骨细胞生物行为的影响。 方法:对喷砂酸蚀钛片进行微弧氧化处理,通过脉宽及频率的变化,研究其对膜层的表面形貌、摩擦性能、耐腐蚀性等影响,分析得出不同表面形貌所对应的参数条件（脉冲频率400 Hz、脉冲宽度60 μs微弧氧化组为A组,脉冲频率500 Hz、脉冲宽度60 μs微弧氧化组为B组,脉冲频率500 Hz、脉冲宽度75 μs的微弧氧化组为C组）,进一步比较在该参数下的微弧氧化膜的耐腐蚀性及成骨细胞在其表面的粘附、增殖情况及细胞形态。 结果:电镜下3组试件表面均形成粗糙多孔的膜层,且A组纯钛微弧氧化膜表面粗糙度最高;C组所制备的微弧氧化膜层耐腐蚀性能及耐磨性优于A、B两组。细胞粘附及增殖实验A、B、C各组之间差异有统计学意义（P<0.05）,实验表明A组表面成骨细胞粘附及增殖均优于B、C两组。 结论:脉冲宽度及频率变化对微弧氧化膜层表面生物活性及理化性能均有影响,当脉冲频率400 Hz、脉冲宽度60 μs时,膜层表面的细胞生长最佳。     

紫外光激发纯钛光催化作用对降解能力和体外矿化能力的影响*

背景：紫外光因其照射纯钛表面可以引起表面亲水性的显著提高,近几年作为一种新的钛表面处理手段成为研究的热点。 目的：探讨紫外光激发纯钛表面光催化作用引起的降解能力和体外矿化能力。 方法：打磨抛光纯钛和微弧氧化纯钛表面接受紫外光处理,通过亚甲基蓝降解实验检测紫外光激发纯钛表面光催化作用,体外浸泡模拟体液评价体外诱导磷灰石能力。酶标仪检测12 h时亚甲基蓝溶液吸光度值;2周时扫描电镜观察纯钛表面磷灰石沉积后形貌,X射线衍射仪检测表面晶相。 结果与结论：紫外光激发微弧氧化纯钛表面产生的光催化降解作用强于打磨抛光纯钛表面(P < 0.05),微弧氧化纯钛表面经紫外光照射后体外矿化能力显著增强。提示紫外光作为一种新的钛表面处理方法,可以增强材料生物活性。 关键词：光催化;钛;牙种植体;降解;矿化 doi:10.3969/j.issn.1673-8225.2012.08.012     

退火处理不同管径TiO2纳米管表面成纤维细胞的生物学行为

文题释义：TiO₂纳米管阵列：利用阳极氧化方法在纯钛板表面生成的一薄层TiO₂结构。即以钛或钛合金为阴极以铂片为阳极,在含氟电解液中通过电化学方法产生的自组装TiO₂纳米管层,可通过控制阳极氧化的电压来精确控制纳米管的管径,阳极氧化的时间会影响纳米管的长度。与光滑的钛表面相比,TiO₂纳米管显著增大了表面积,提高了材料的亲水性和表面能,增加了对纤维粘连蛋白和玻璃粘连蛋白等胞外蛋白大分子的吸附,同时纳米管状结构具有加载药物和生物因子等潜能。 退火处理：退火是一种金属热处理工艺,即将金属缓慢加热到一定温度保持足够的时间,然后以适宜速度冷却。TiO₂存在3种不同的晶型结构：非晶态、锐钛矿和金红石相态。常温制备的TiO₂纳米管为非晶态,经过退火处理,控制退火处理的温度,TiO₂晶型结构转变为锐钛矿或金红石。一般情况下,400-600 ℃的退火可形成锐钛矿,600-750 ℃的退火可形成金红石相。 背景：前期研究发现不同管径钛纳米管对植体表面细胞的黏附和生长影响不同。 目的：分析退火处理不同管径TiO₂纳米管对成纤维细胞生物学行为的影响。 方法：在5 V和20 V电压下分别采用阳极氧化方法在抛光纯钛表面制备TiO₂纳米管,并行退火处理。将纯钛试样分为6组：抛光纯钛组、5 V纳米管组、20 V纳米管组、退火处理抛光纯钛组、退火处理5 V纳米管组、退火处理20 V纳米管组,利用场发射扫描电镜观察试样表面形貌。各组试样表面接种成纤维细胞,采用胞核染色计数方法分析培养60,120 min时试样表面细胞的黏附数,利用扫描电镜观察培养1 d时的细胞形态,MTT法检测培养1,3,5 d后试样表面细胞的增殖情况,天狼星红苦味酸染色法分析培养3 d时细胞的胶原纤维分泌情况。 结果与结论：①退火处理对钛表面TiO₂纳米管形貌及管径无明显影响;②5,20 V纳米管组表面的细胞黏附数量少于抛光纯钛组;退火处理增加了抛光纯钛表面的成纤维细胞黏附数量,减少了5,20 V纳米管表面的细胞黏附数量;③退火处理增强了抛光纯钛表面成纤维细胞的活性,降低了5,20 V纳米管表面的细胞活性;④5,20 V纳米管组表面的细胞增殖活性低于抛光纯钛组;退火处理提高了抛光纯钛表面的细胞增殖活性,减少了5,20 V纳米管表面的细胞增殖活性;⑤5,20 V纳米管组表面细胞的胶原纤维分泌量高于抛光纯钛组;退火处理提高了抛光纯钛表面的细胞胶原分泌量,减少了5,20 V纳米管表面的细胞胶原分泌量;⑥结果表明,TiO₂纳米管不同程度地抑制成纤维细胞的黏附、伸展和增殖,退火处理可增强这种抑制作用;TiO₂纳米管不同程度增强成纤维细胞的胶原分泌功能,退火处理抑制了这种增强效果。 ORCID: 0000-0002-3358-5856(李红彩) 中国组织工程研究杂志出版内容重点：生物材料;骨生物材料; 口腔生物材料; 纳米材料; 缓释材料; 材料相容性;组织工程     

微弧氧化/电化学沉积钙磷涂层纯钛种植体的骨内植入

背景：近年来已有对微弧氧化/电化学沉积技术制备涂层在材料性能方面的相关报道,但对这种材料植入体内的性能研究较少见。 目的：观察纯钛种植体经微弧氧化/电化学沉积处理后的骨结合和新骨形成情况。 方法：通过微弧氧化/电化学沉积方法在纯钛上制备含钙磷元素的涂层,然后将该种植体和纯钛种植体分别植入羊两侧胫骨种植窝内,于动物处死前15,5 d分别进行注射四环素进行四环素标记。术后4,12周分别进行X射线、扫描电镜及激光共聚焦观察。 结果与结论：两侧X射线表现相似,种植体周围均无明显阴影,骨小梁排列和骨质密度与宿主骨基本一致。术后4周时,在电镜下可观察到两组种植体和骨组织之间均有间隙,部分见骨性结合;术后12周时,微弧氧化/电化学沉积种植体组可形成新骨,并且新骨与种植体和原来骨组织结合紧密,涂层与钛基体没有明显间隙,纯钛种植体组也可见新骨生成,但可看到明显裂隙。激光共聚焦观察显示,微弧氧化/电化学沉积种植体组双标记带间距离及骨矿化沉积率均高于纯钛种植体组(P < 0.05)。表明微弧氧化/电化学沉积处理可增强纯钛种植体的骨结合能力及新骨形成。     

Improved biological performance of Ti implants due to surface modification by micro-arc oxidation

The surface of a titanium (Ti) implant was modified by micro-arc oxidation (MAO) treatment. A porous layer was formed on the Ti surface after the oxidation treatment. The phase and morphology of the oxide layer were dependent on the voltage applied during the oxidation treatment. With increasing voltage, the roughness and thickness of the film increased and the TiO(2) phase changed from anatase to rutile. During the MAO treatment, Ca and P ions were incorporated into the oxide layer. The in vitro cell responses of the specimen were also dependant on the oxidation conditions. With increasing voltage, the ALP activity increased, while the cell proliferation rate decreased. Preliminary in vivo tests of the MAO-treated specimens on rabbits showed a considerable improvement in their osseointegration capability as compared to the pure titanium implant.     

Preparation of bioactive titanium metal via anodic oxidation treatment

Titania with specific structures of anatase and rutile was found to induce apatite formation in vitro. In this study, anodic oxidation in H(2)SO(4) solution, which could form anatase and rutile on titanium metal surface by conditioning the process, was employed to modify the structure and bioactivity of biomedical titanium. After the titanium metal was subjected to anodic oxidation treatment, thin film X-ray diffraction and scanning electron microscopy results showed the titanium metals surfaces were covered by porous titania of anatase and/or rutile. In simulated body fluid (SBF), the titanium anodically oxidized under the conditions with spark-discharge could induce apatite formation on its surface. The induction period of apatite formation was decreased with increasing amount of either anatase or rutile by conditioning the anodic oxidation. After the titanium metal, anodically oxidized under the conditions without spark-discharge, was subjected to heat treatment at 600 degrees C for 1 h, it could also induce apatite formation in SBF because the amount of anatase and/or rutile was increased by the heat treatment. Our results showed that induction of apatite-forming ability on titanium metal could be attained by anodic oxidation conjoined with heat treatment. So it was believed that anodic oxidation in H(2)SO(4) solution was an effective way to prepare bioactive titanium.     

Photoexcited formation of bone apatite-like coatings on micro-arc oxidized titanium

A novel method to rapidly deposit bone apatite-like coatings on titanium implants in simulated body fluid (SBF) is proposed in this article. The processing was composed of two steps; for example, micro-arc oxidation (MAO) of titanium to form titania films, and UV-light illumination of the titania-coated titanium in SBF. The morphology, crystalline structure, and bond strength of the MAO films were investigated as a function of the applied voltage (in the range of 250-400 V) by using scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectrometry, Fourier transform infrared spectroscopy, adhesion-tensile test, and scratch test. Results showed that the MAO films were porous and nanocrystalline with pore sizes varying from 1 to 3 microm and grain sizes varying from 10-20 to 70-80 nm; the predominant phase in titania films changed from anatase to rutile, and the bond strength of the films decreased from 43.4 to 32.9 MPa as the applied voltage increased from 250 to 400 V. After UV-light illumination of the films in SBF for 2 h, bone apatite-like coating was deposited on the MAO film formed at 250 V. The bond strength of the apatite/titania bilayer was about 44.2 MPa. However, no apatite was observed on the MAO film formed at 400 V after UV-light illumination.     

Characteristic and in vitro bioactivity of a microarc-oxidized TiO(2)-based coating after chemical treatment

Microarc oxidation (MAO) was used to prepare a TiO(2)-based coating containing Ca and P on titanium alloy. An alkali treatment was developed to modify the surface of the MAO coating to improve the apatite-forming ability of the coating. The chemically treated MAO coating exhibits a modified layer, with the main constituents being O, Ti, Ca and Na, showing anatase. The modified MAO coating shows a rough and porous morphology containing numerous nanoflakes of approximately 100nm thickness. During the alkali treatment process, P on the surface of the MAO coating shows a main dynamic process of dissolution; however, Ca exhibits a re-deposition process as well as dissolution. The formation of the modified layer could be explained by this mechanism: negatively charged HTiO(3)(-) ions are formed on the MAO coating due to the attack of OH(-) ions on the TiO(2) phase. The HTiO(3)(-) ions could incorporate sodium from the alkali solution and calcium from the alkali solution and MAO coating. The apatite-forming ability of the MAO coating is improved remarkably by the simple chemical treatment, since the surface of the alkali-treated MAO coating could provide abundant Ti-OH groups probably formed by ionic exchanges between (Ca2+, Na+) ions of the alkali-treated MAO coating and H3O+ ions of a simulated body fluid (SBF). Moreover, Ca released from the alkali-treated MAO coating increases the degree of supersaturation of SBF, promoting the formation of apatite. The apatite induced by the alkali-treated MAO coating possesses carbonated structure and pore networks on the nanometer scale.     

Osteoblast-like cell adhesion on porous silicon-incorporated TiO2 coating prepared by micro-arc oxidation

Silicon-incorporated TiO(2) coating (Si-TiO(2) ) was prepared on titanium (Ti) by micro-arc oxidation (MAO) technique in the Ca, P, Si-containing electrolyte. The surface topography, phase, and element composition of the coatings were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy-dispersive X-ray spectrometry (EDS), respectively. Osteoblast-like MC3T3-E1 cells were cultured on the surface of the coatings to evaluate their adhesion behavior. The obtained results showed that Si element was successfully incorporated into the porous TiO(2) coating, which did not alter apparently the surface topography and phase composition of the coating. The adhesion of the MC3T3-E1 cells on Si-incorporated TiO(2) coating was significantly enhanced compared with the Si-free TiO(2) coating and pure Ti plates. In addition, the enhanced cell adhesion may at least partly be mediated by integrin β1-FAK signal transduction pathway. The present work suggests that the Si-TiO(2) coating is worth further consideration for orthopedic implant applications.     

纯钛种植体表面微弧氧化涂层的生物相容性

背景：各种纯钛种植体表面微弧氧化涂层效果不尽相同。 目的：观察3种不同微弧氧化涂层种植体钛片对小鼠成骨细胞的细胞增殖、碱性磷酸酶活性和β1-integrin的基因表达水平的影响。 方法：采用国际常用小鼠成骨细胞系(MC3T3-E1),3种不同涂层钛片作为影响因素,纯钛作为对照,采用MTT法和电镜法观察细胞附着和细胞增殖,PNPP法测定碱性磷酸酶的活性,RT-PCR法检测β1-integrin在小鼠成骨细胞中的表达。 结果与结论：MTT值、碱性磷酸酶值、β1-integrin的基因表达水平和电镜观察均显示含钙、磷、镁、锌元素的二氧化钛涂层钛片生物相容性最好,含钙磷盐的二氧化钛涂层钛片次之,二氧化钛涂层钛片最差。小鼠成骨细胞在其多孔,含有钙、磷、镁、锌元素表面的黏附及增殖最优。     

Corrosion test, cell behavior test, and in vivo study of gradient TiO2 layers produced by compound electrochemical oxidation

This paper describes efforts to improve implant biocompatibility and durability by applying a hybrid technique using composite oxidation. Pure titanium was used as the substrate material. A porous oxide film as the outer layer was produced by micro-arc oxidation and a dense oxide film as the inner layer was produced by pre-anodic oxidation. In this study, physicochemical characteristics, corrosion test, cell attachment behavior, and in vivo studies were used to compare this gradient layer with untreated titanium. The results revealed that the gradient layer was composed of two layers of oxide films which were made up of rutile and anatase and the surface was porous with calcium and phosphor. The corrosion resistance of the gradient layer was improved remarkably, which was about three times the values for titanium and two times the value for the dense layer. The cell-material interaction study indicated that L929 cells seeded and cultured on the gradient layer appeared to attach well and the rate of proliferation was the greatest. The study in vivo showed that the gradient layer had good biocompatibility. This gradient layer provides a material with high corrosion resistance, bioactivity, and biological properties suitable for tissue engineering applications.