激光熔覆SiO2/La2O3梯度生物陶瓷涂层生物活性研究

目的研究SiO_2含量对钛合金表面激光熔覆梯度生物陶瓷涂层生物活性的影响。方法利用激光熔覆技术,采用梯度成分设计思想,固定涂层中稀土氧化物La_2O_3的添加量,在钛合金TC4表面制备了掺杂不同含量SiO_2的梯度生物陶瓷涂层。采用金相显微镜(OM)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、噻唑蓝(MTT)及荧光素双醋酸酯(FDA)染色等测试手段,研究了SiO_2含量对激光熔覆制备梯度涂层的组织结构和生物活性的影响。结果 SiO_2在激光熔覆过程中可以降低梯度生物陶瓷涂层的开裂敏感性,并起到细化晶粒的作用。当SiO_2掺杂量为2.5%时,激光熔覆过程中诱导合成的HA+CaTiO_3数量最大;当SiO_2掺杂量为7.5%时,模拟体液(SBF)实验表明,涂层的矿化沉积能力最强。MTT测试表明,SiO_2掺杂量为7.5%的涂层细胞增殖数量的OD值最大,细胞能够紧贴涂层表面生长。FDA染色分析表明,SiO_2掺杂量为7.5%的涂层上细胞数量最多,且分布均匀。结论 SiO_2掺杂量深刻影响着生物活性陶瓷相HA和Ca_2SiO_4数量,进而影响生物陶瓷涂层的生物活性。SiO_2掺杂量为7.5%的涂层具有最佳的生物相容性及生物活性。     

Y2O3-CeO2稀土氧化物对激光熔覆生物陶瓷涂层中HA的影响

为降低激光熔覆过程中基材与生物陶瓷涂层之间的热应力,提高涂层与基材的结合强度,选用宽带激光熔覆方法,在TC4合金表面制备一层含HA和β-TCP的梯度活性生物陶瓷涂层。通过金相显微镜、扫描电子显微镜(SEM)和X射线衍射仪(XRD)对在体外模拟体液中浸泡14d后的涂层进行形貌和相组成的研究。结果表明:当Y2O3质量分数为0.6%,CeO2质量分数分别为0%,0.2%,0.4%和0.6%时,生物陶瓷涂层在SBF中浸泡14d后,基材与涂层之间呈良好的冶金结合;涂层表面都有白色球状颗粒生成;且涂层当中HA的生成量各不相同。当CeO2质量分数为0%时几乎不生成HA,为0.2%时HA的生成量最大,而后随着CeO2的含量增加HA生成量减少。说明当Y2O3质量分数为0.6%,CeO2的含量为0.2%时,生物陶瓷涂层具有较好的生物活性。     

稀土含量对Ca-P陶瓷涂层组织及细胞相容性的影响

利用激光熔覆技术在医用钛合金表面制备一层梯度Ca-P陶瓷涂层,并研究了La_2O_3含量对其微观组织结构及细胞相容性的影响。通过OM,XRD,SEM,MTT法及倒置荧光显微镜对Ca-P陶瓷涂层的结合界面、物相、表面形貌,细胞活性及细胞生长形态进行分析。结果表明:Ca-P陶瓷涂层主要含有CaTiO_3、HA、TiO_2、β-TCP等物相。当Ca-P陶瓷涂层中La_2O_3质量分数为0.6%时,在2θ为32~33°附近其XRD图谱中羟基磷灰石(HA)的特征峰较高,表明其生成的生物活性相最多。并且其在模拟体液(SBF)浸泡14天后的表面上生成的HA最多,分布最广。细胞试验表明当La_2O_3质量分数为0.4%~0.6%时,梯度生物陶瓷涂层具有较佳的细胞相容性,有利于细胞的稳定增殖与生长。     

电沉积制备镁合金HA涂层的组织及其可降解性能

采用碱热处理＋电沉积＋碱热处理相结合的工艺,在Mg-4.0Zn-1.0Ca-0.6Zr合金板材表面制备羟基磷灰石（HA）涂层。利用X射线衍射和SEM对涂层的组织和形貌进行了分析,对合金板材及HA涂层板材在SBF溶液中的可降解性能进行了研究,结果表明：通过前碱热处理＋电沉积＋后碱热处理的方法在电沉积温度50℃,电压10 V条件下,在Mg-4.0Zn-1.0Ca-0.6Zr合金板材表面制备出了平整、致密的HA涂层,其Ca/P的比值（1.72）与人骨的（1.67）相近;HA涂层Mg-4.0Zn-1.0Ca-0.6Zr合金板材在SBF溶液腐蚀过程中,发现3 d时腐蚀液穿过HA涂层开始浸蚀基体。随着腐蚀时间的延长,部分点蚀的直径扩大,构成局部腐蚀;HA涂层Mg-4.0Zn-1.0Ca-0.6Zr合金板材在SBF溶液中的初始腐蚀速率低于未涂层的合金板材,其在SBF溶液中的初始pH值的变化低于未涂层的,随降解时间延长,pH变化幅度开始增大,10 d后pH值平均值约为9.2,随后逐步趋于稳定;HA涂层Mg-4.0Zn-1.0Ca-0.6Zr合金板材在SBF溶液中的初始自腐蚀电位与未涂层的相比正移200 mV以上,亦说明了其在SBF溶液中的初始腐蚀速率低于未涂层的,但是随着涂层的脱落将促使腐蚀速率增大。     

等离子喷涂TiO2-CaF2复合涂层的结构及体外生物矿化能力

目的等离子喷涂TiO_2涂层是生物惰性材料,不能与骨组织很好地结合,制备TiO_2-CaF_2复合涂层以提高氧化钛涂层的体外生物矿化能力。方法利用等离子喷涂技术在医用Ti合金表面制备TiO_2-CaF_2复合涂层。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和拉曼光谱仪(Raman)对复合涂层的微观结构进行表征,利用接触角仪、三维轮廓仪和电化学工作站考察复合涂层的接触角、表面粗糙度和耐腐蚀性能。采用模拟体液(SBF)浸泡实验考察复合涂层的体外矿化能力。结果 TiO_2和TiO_2-20%CaF_2涂层主要由金红石型TiO_2构成,其中含有少量的锐钛矿型TiO_2成分。20%CaF_2的掺杂会促进金红石型TiO_2的形成。CaF_2的加入可改变TiO_2涂层的表面形貌,表面粗糙度Ra从4.96μm降低至0.94μm,亲水性也得到增强。TiO_2-CaF_2复合涂层在SBF中的耐腐蚀性能也较TiO_2涂层有所提高。经SBF浸泡28 d后,TiO_2-CaF_2复合涂层表面可沉积类骨磷灰石,显示了较好的体外矿化能力,而TiO_2涂层则无此能力。结论 CaF_2的掺杂可使TiO_2涂层的表面粗糙度下降,亲水性增强,耐腐蚀性增强。体外矿化实验结果表明,TiO_2-CaF_2复合涂层表面可沉积类骨磷灰石,显示了较好的生物活性。     

不同催化剂对镁合金表面SiO_2-ZrO_2涂层耐蚀性的影响

镁合金表面溶胶凝胶涂层存在易析出氢气、涂层缺陷多及防腐性能提升不明显等问题。为改善这些问题利用Ce(NO_3)_3催化制得SiO_2-ZrO_2溶胶并旋涂3层于AZ91D镁合金表面,并与HCl催化制得的镁合金表面SiO_2-ZrO_2溶胶涂层进行对比分析。采用扫描电镜和傅里叶红外光谱等分析涂层微观形貌和化学成分;通过接触角测试涂层亲疏水性;利用极化曲线和电化学阻抗谱对比研究不同催化剂加入的溶胶凝胶层在3.5%NaCl溶液中的耐腐蚀性能。结果显示:与HCl催化制得的镁合金表面SiO_2-ZrO_2溶胶涂层相比,Ce(NO_3)_3催化制得的涂层表面微观缺陷少;接触角由84.2°增大到93.5°;同镁合金基体自腐蚀电流密度1.480×10~(-4) A/cm~2相比,HCl催化和Ce(NO_3)_3催化涂层的自腐蚀电流密度分别为2.562×10~(-6) A/cm~2和7.821×10~(-7) A/cm~2,其耐蚀性提升明显;HCl和Ce(NO_3)_3催化涂层阻抗极化电阻值由镁合金基材的224.9Ω分别增大至4 401Ω和53 888Ω,HCl催化涂层的失效时间为1 d,Ce(NO_3)_3催化涂层失效时间延长为3 d。可见,两种催化剂制备的涂层,Ce(NO_3)_3催化涂层防护更持久,耐蚀性更好。     

溶胶凝胶法制备TiO_2/HA复合生物活性涂层及其体外活性

通过溶胶凝胶法在纯钛基体上制备了羟基磷灰石(HA)/TiO2复合生物活性涂层。HA和TiO2溶胶由前驱体制得,按不同摩尔比直接混合两种溶胶来制备混合溶胶。HA可以提高钛基的生物活性,TiO2可以提高涂层与基体的物理、化学相容性和结合强度。粘结拉伸结果表明,复合涂层与基体结合良好,比纯HA涂层与基体的结合强度提高约47%。复合涂层试样于SBF中浸泡4、7和14d的SEM分析结果表明,复合涂层表面的类骨磷灰石生成量较高。成骨细胞实验结果表明,复合涂层上细胞铺展良好。     

Si基上羟基磷灰石/Al2O3复合生物涂层的制备

采用物理气相沉积(PVD)与阳极氧化与电沉积相结合的复合技术在Si基表面制备了羟基磷灰石(HA)/Al2O3复合生物涂层。采用SEM研究了阳极氧化Al2O3和HA/Al2O3复合生物涂层的形貌,并采用EDS与XRD研究了HA/Al2O3复合生物涂层的组成和物相。结果表明:扩孔处理后阳极氧化的Al2O3孔径约为1.5~3.0μm,电沉积HA的n(Ca)/n(P)约为1.61,最终获得了以HA为外层、HA/Al2O3为中间过渡层、Si为基底的复合材料。其中,HA不仅沉积于阳极氧化Al2O3的孔洞中,且外延生长并覆盖在阳极氧化Al2O3表面,从而在HA外层与HA/Al2O3中间过渡层之间形成了一种T形分布的结构特征,该结构特征将有助于增强HA外层与中间过渡层的界面结合强度。     

钴钼铌对多孔钛合金生物活性的影响

以凝胶注模成形工艺制备的多孔TiCo合金、TiMo合金以及TiNb合金为基体,在其表面沉积以羟基磷灰石(HA)为主的活性物质,研究钛合金中的Co,Mo,Nb分别对涂层生物活性的影响。结果表明:不同合金体系在SBF仿生溶液中出现一些差异,表现在形核生长方式、生长形态和沉积速度:多孔TiCo合金颗粒长大明显,表现出好的生物活性;多孔TiMo合金在短期(15 d)SBF后表面不具备生物活性,但时间增长后(60 d),其表面活化,并具有较快的HA晶粒形核长大速率,表面可形成致密的HA涂层,表现出较好的生物活性;多孔TiNb合金在孔隙内和孔隙周围沉积了较大的Ca-P颗粒并形成较厚的HA涂层,颗粒呈球状生长,但涂层均匀性和完整性较差,降低其表面生物活性;多孔钛合金基体孔隙率的升高和孔径的增大提供了HA晶粒良好的形核长大空间,对于多孔钛合金表面生物活性具有良好的促进作用。     

微弧氧化镁表面钙磷生物涂层的制备及性能

为改善镁合金的骨植性能,采用微弧氧化处理和电沉积钙磷涂层相结合的方法在纯镁表面制备具有生物活性的复合涂层,研究了复合涂层在模拟体液和细胞培养液中的组织结构演化、腐蚀行为、骨形成能力和细胞粘附行为。 微弧氧化镁表面沉积的钙磷相为二水合磷酸氢钙(DCPD)。 电沉积过程中 DCPD 优先在微弧氧化层的通孔和放电通道处形核、随后长大并覆盖微弧氧化层而起到封孔作用。 涂覆后镁的低频阻抗模值在浸泡初期超过了 10⁵ Ω·cm² ,且在 120 h 内基本保持稳定;腐蚀电流密度与纯镁相比下降了约 3 个数量级,复合涂层显著地提高了镁的耐蚀性。 复合涂层在模拟体液和细胞培养液中均表现出了诱导羟基磷灰石(HA)沉积的能力,在细胞培养液中浸泡 14 d 后涂层表面出现球状类骨 HA 组织;细胞黏附试验中,活细胞几乎黏附在整个涂层表面,表现出良好的骨形成能力和细胞活性。     

Mechanical properties of La2O3 doped diamond-like carbon films

Twelve La₂O₃ doped diamond-like carbon (DLC) nanofilms were deposited using unbalanced dual-magnetron sputtering. AFM, XRD, Raman spectroscopy, AES, XPS, TEM, contact surface profiler and nanoindenter were employed to investigate the structure and tribological properties of deposited films. The results show that the La₂O₃ doped DLC films are amorphous. La₂O₃ doping obviously decreases internal stress, and effectively increases the elastic modulus. This results from the dissolving and dissolution of La₂O₃ within the amorphous DLC matrix. Furthermore, the friction coefficient of the doped DLC films decreases, and adhesion strength increases. These are attributed to the lubrication function of La₂O₃ and the formation of transition layer at interface, respectively.     

Microstructure and characterization of La2O3 and CeO2 doped diamond-like carbon nanofilms

Seven kinds of hydrogen-free La₂O₃ and CeO₂ doped DLC films with thickness of 220-280 nm were deposited on Si (100) substrates by unbalanced magnetron sputtering. Nanoparticles with diameter of 20-30 nm are formed on the surface of films. The surface roughness Ra of films is in the range of 1.5-2.0 nm. C, La, Ce and O elements distribute uniformly along the depth direction, and C, La, and Ce elements diffuse into the Si substrate at the interface. X-ray photoelectron spectroscopy confirms that the La₂O₃ and CeO₂ form within the DLC amorphous films, and Raman spectra indicate the obvious amorphous characteristics of DLC films. High-resolution transmission electron microscopy shows the nanocrystallines structure with diameter of 2-3 nm of 16% La₂O₃ and 10% CeO₂ doped DLC films, and Fourier transformation spectroscopy also exhibits the obvious crystalline characteristics. In this work, the microstructure of two kinds of rare earth oxides doped DLC composite films is measured and analyzed.     

Thermal conductivity and thermal cycle life of La2O3 and HfO2 doped ZrO2-Y2O3 coatings produced by EB-PVD

The effects of La₂O₃ and HfO₂ addition on thermal conductivity and thermal cycle life of EB-PVD YSZ coatings were investigated. La₂O₃ and HfO₂ were selected as additives, because they significantly suppress the sintering of YSZ. The developed coating showed low thermal conductivity as well as high resistance to sintering. Burner rig tests confirmed that the developed coating have a superior thermal insulating effect and have a longer life than that of a coating with conventional composition.     

La2O3含量对Al2O3/Cu基复合材料组织与性能的影响

以La₂O₃粉、Al粉、CuO粉为反应物原料、纯铜为基体,采用原位合成技术和近熔点铸造法制备颗粒增强Cu基复合材料,研究La₂O₃对Al-CuO体系制备的Cu基复合材料组织及性能的影响。结果表明：添加La₂O₃可获得纳米Al₂O₃颗粒,且弥散分布于Cu基体中,制备的材料组织更加细小、均匀,其材料的电导率及摩擦磨损性能明显提高。当添加0.6%wtLa₂O₃,复合材料的电导率达到90.2%IACS,磨损量达到最小,相比未添加La₂O₃,其导电率提高10.1%,磨损量减小36.6%。     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

Preparation and properties of sintered molybdenum doped with La2O3/MoSi2

Sintered Mo with the addition of La₂O₃/MoSi₂ was prepared via the process of solid–solid doping + powder metallurgy. X-ray diffraction experiment, hardness test, three-point bending test and high-temperature tensile test were carried out to characterize the samples. The XRD pattern of a typical sample shows that the sintered Mo was mainly composed of Mo, La₂O₃ and Mo₅Si₃. Mo₅Si₃ was probably formed through the reaction between MoSi₂ and the Mo matrix. Densities and fracture toughnesses of both doped Mo and pure Mo were measured and contrasted. Sintered Mo with the addition of 0.2 wt% La₂O₃/MoSi₂ has the highest toughness, while more addition of La₂O₃/MoSi₂ has smaller effect on improving toughness or even embrittles Mo. The results of three-point bending test and high-temperature tensile test show that the bending strength and high-temperature tensile strength of doped Mo are both higher than those of pure Mo. The formation of Mo₅Si₃ improves the high-temperature strength. The La₂O₃/Mo₅Si₃ dispersed in the Mo matrix refined the grains, and thus strengthened the Mo matrix by dispersion strengthening and grain refinement.     

Synthesis of silicate coating by layer-by-layer self-assembly of Yb2O3 and SiO2 particles

Multilayer particle assemblies that contained both Yb₂O₃ and SiO₂ particles were prepared on Si substrates by layer-by-layer self-assembly (LBLSA) as a new non-line-of-sight avenue of producing dense and uniform Yb₂O₃-SiO₂ coating microstructures. Morphological characteristics of the multilayer particle assemblies upon viscous sintering in the temperature range of 1300 to 1350 °C were evaluated in reference to those of multilayer assemblies that only contained SiO₂ or Yb₂SiO₅ particles. A 4-layer 0.5-μm SiO₂ particle assembly could be easily transformed to a dense and continuous coating structure after sintering. In contrast, a 4-layer 1.7-μm Yb₂SiO₅ particle assembly could not be consolidated and densified, as anticipated from the absence of the viscous sintering mechanism provided by the SiO₂ phase. Most of the coatings produced from sintering of Yb₂O₃-SiO₂ (0.5 μm) particles assemblies were dense and continuous with Yb₂Si₂O₇ and Yb₂SiO₅ as two predominant phases. The results suggest the feasibility of producing dense and uniform silicate coating structures by integrating the LBLSA concept with the viscous flow sintering mechanism provided by the SiO₂ particles.     

Al2O3微粉添加量对镁合金微弧氧化膜特性影响研究

为了研究添加Al₂O₃微粉对AZ31A镁合金微弧氧化膜特性影响,在不同浓度Al₂O₃微粉电解液中对其进行了微弧氧化处理。利用扫描电镜(SEM)观察微弧氧化膜形貌,能谱仪(EDS)分析了膜层表面Ca、Mg、O、Al元素分布,X射线衍射仪(XRD)分析了相组成,测定了膜厚、硬度和氧化液中Al₂O₃表面电荷,讨论了掺杂改性机理。结果表明,加入Al₂O₃微粉后,氧化电压随Al₂O₃添加量增加先增加后降低;氧化膜表面孔洞数量和尺寸减小,膜层表面Ca元素分布逐渐减少,成膜效率降低,膜层致密度和表面疏松层硬度提高,氧化膜主要由MgO和MgO₄等相组成。     

Novel thermal barrier coatings based on La2Ce2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Novel thermal barrier coatings based on La₂Ce₂O₇/8YSZ double-ceramic-layer (DCL) systems, which were deposited by electron beam physical vapor deposition (EB-PVD), were found to have a longer lifetime compared to the single layer La₂Ce₂O₇ (LC) system, and even much longer than that of the single layer 8YSZ system under burner rig test. The DCL coating structure design can effectively alleviate the thermal expansion mismatch between LC coating and bond coat, as well as avoid the chemical reaction between LC and Al₂O₃ in thermally grown oxide (TGO), which occurs above 1000 °C as determined by differential scanning calorimetry (DSC) analysis. The failure mechanism of LC/8YSZ DCL coating is mainly due to the sintering of LC coating surface after long-term thermal cycling.