纳米缺钙羟基磷灰石生物陶瓷涂层中相组成和显微结构的控制

研究了低钙磷比溶液电沉积缺钙羟基磷灰石生物陶瓷涂层在水热合成和700℃,800℃,900℃焙烧后的相组成和显微组织结构;用扫描电镜(SEM)、X射线衍射(XRD)和透射电镜(TEM)对涂层进行分析。结果表明:在电沉积液Ca/P比1.30,沉积液温度25℃,电压4V条件下,Ti基体表面沉积了片状和条状HAP和CaHPO4·2H2O混合相涂层;在pH值为12的碱液中,150℃和200℃水热合成4h后涂层由针状纯HAP组成,Ca/P比约为1.61,且随着水热合成温度的升高,晶体结晶度提高,但晶体无明显长大趋势;700℃焙烧后,涂层仍由纯HAP组成,只是晶体因失水而发生团聚;800℃焙烧后,部分HAP发生分解,生成β-Ca3(PO4)2,且HAP与β-Ca3(PO4)2的体积比为90∶10,形貌为块状和板条状,其表面附着许多细小的针状颗粒;900℃焙烧后,β-Ca3(PO4)2的含量增加,HAP与β-Ca3(PO4)2的体积比为74∶26,小颗粒团聚成较大的块状和板条状颗粒。由此制备了对骨组织生长更有利的HAP+β-Ca3(PO4)2双相涂层结构。     

镁合金AZ31表面液相沉积Ca-P生物陶瓷涂层的研究

研究了镁合金AZ31经过预钙吸附和阳极氧化预处理后,在Hank's溶液、Ca(NO3)2和NH4H2PO4混合溶液(简称Ca-P溶液)中制备Ca-P基生物陶瓷涂层的可能性.利用能谱分析仪和X射线衍射仪分析了涂层的化学成分和相组成.结果表明,两种预处理后的AZ31镁合金在Hank's溶液中均不能沉积得到涂层.而在Ca-P溶液中浸泡48 h后,镁合金表面均沉积了Ca-P涂层.其结晶产物主要为透钙磷石(CaHPO4·2H2O)和少量的Ca(H2PO4)2.预钙吸附处理后镁合金表面形成钙的形核点,在Ca-P溶液中沉积所得的涂层均匀致密,由长、宽20～50 μm的片状结晶体组成,结晶体相互咬合交织生长;而阳极氧化处理后的AZ31在Ca-P溶液中沉积所得的涂层则呈竹叶状,且不致密.     

电结晶羟基磷灰石涂层结构的研究

采用电沉积技术,在钛合金表面形成生物涂层。试验结果表明:电流密度由小到大变化时,涂层表面形貌按针状→细晶针状→棒块状发生变化,涂层的孔洞也由小变大,由少变多;单一电流密度下,沉积后涂层的主相为无定形CaHPO4;电流密度交替变化时,形成了大量的三斜晶系CaPO3(OH)相和单斜晶系CaPO3(OH)·H2O,并有少量的HA相生成,经碱处理后,易于生成Ca5(PO4)3(OH)。电流密度交替变化,涂层孔隙结构呈梯度分布,底部组织致密,利于提高涂层与基体的结合强度,表面形成大量的孔洞,利于种植体的植入和HA的生成,促进骨结合。     

声电沉积C/C磷灰石生物活性涂层的超声作用机制

采用声电沉积工艺在炭/炭复合材料表面制备了磷灰石生物活性涂层,借助SEM,EDAX,XRD,FTIR等分析测试手段,考察了超声频率对涂层组成、结构和形貌的影响.结果表明低超声频率时(25 kHz)形成片状羟基磷灰石(Ca10(PO4)6(OH)2(HA));当超声频率升高时(45 kHz或60 kHz)形成棒状磷酸氢钙(CaHPO4·2H2O(DCPD)).随着超声频率的升高,涂层呈紧密堆积并沿(021)、(041)晶面择优生长,涂层厚度和n(Ca)/n(P)逐渐减小,电解液的pH值逐渐升高.超声波对电沉积的作用主要是降低了钙磷相反应能垒和增强了类旋转效应.     

Ti基板上磷酸钙薄膜的电沉积

主要研究电沉积条件如何影响沉积产物磷酸钙涂层的晶相。实验采用金属Ti作为基板,电解液为Ca(NO3)2(45mmol/L)与NH4H2PO4(25mmol/L)的稀混合液,通过改变沉积温度、沉积时间、电解液的pH值等参数,利用XRD、SEM表征沉积产物。结果显示:温度对晶相转变的影响最大,37℃时获得的晶相只有DCPD(CaHPO4·2H2O),当沉积温度升高到60℃时,HAP(Ca10(PO4)(OH)2)相含量增加。沉积时间对沉积产物的晶相类型没有影响。随着pH值的升高,DCPD和OCP(Ca8(HPO4)2(PO4)4·5H2O)相含量均在增加,证明高pH值不仅能影响晶相生长,而且能诱导晶相转变。SEM结果表明,在3V的沉积电压下,都能够得到厚度均匀的沉积涂层,但是以45℃为沉积温度并沉积15min时,Ti基板上得到的磷酸钙盐涂层最均匀,并且得到的HA前躯体比较有利于实验后处理,以得到质量较好的HA涂层。     

电压对AZ31镁合金微弧氧化涂层微观结构及腐蚀性能的影响

为研究过程参数对镁合金微弧氧化涂层的微观结构及耐腐蚀性能的影响,在AZ31镁合金基体上,采用不同电压,在电解液磷酸三钠(Na3PO4)中制备微弧氧化涂层.采用扫描电子显微镜(SEM)及光学显微镜,分析膜层腐蚀前后的微观组织结构;通过X射线衍射仪(XRD)分析涂层样品腐蚀前后的相组成.采用动电位极化曲线和电化学阻抗谱(EIS)测试对涂层的耐腐蚀性能进行评价.结果表明:AZ31镁合金微弧氧化涂层主要由Mg3(PO4)2,MgO,Mg和少量MgAl2O4组成,腐蚀产物由Mg(OH)2,quintinite和Ca10(PO4)6 (OH)2组成.在电压为325 V,频率3 000 Hz,氧化时间为5 min下制备的微弧氧化涂层具有最致密均匀的微观形貌和最小的腐蚀电流密度,因此表现出最强的耐腐蚀性能.     

镁牺牲阳极法制备羟基磷灰石涂层的电化学性能

羟基磷灰石(HA)作为一种最重要的生物材料被成功采用镁牺牲阳极法在Ti6Al4V合金表面合成,以提高该复合材料的电化学抗腐蚀性能。使用电子能谱(EDX)、电子探针(EPMA)、傅里叶红外变换图谱(FTIR)和X射线衍射(XRD)对HA涂层进行分析。结果表明,涂层主要由针状羟基磷灰石晶体组成,Ca/P比为1.4063。浸泡30 d后,HA涂层在汉克氏溶液中晶体变大,在林格氏溶液和台氏溶液中针状晶体分别转变为片状和柱状。通过测试在3 种模拟体液和人血中的开路电位、极化曲线和交流阻抗图谱表明,有HA涂层的Ti6Al4V合金比未涂层的Ti6Al4V合金具有更好的电化学性能     

炭/炭复合材料声电沉积钙磷生物活性涂层的生长机理

通过声电沉积在炭/炭复合材料表面制备钙磷生物活性涂层,采用SEM（带EDAX）,XDR,FTIR研究电沉积时间对钙磷生物活性涂层的形貌、结构和组成的影响.实验结果表明：沉积初始先在炭/炭表面形成无定形层,片状磷酸氢钙（DCPD）在其表面生长,随着电沉积时间的延长,逐渐向针状的羟基磷灰石Ca10（PO4）6（OH）2（HA）转变,涂层厚度和n（Ca）/n（P）不断增加,涂层的结晶度和电解液的pH值下降.涂层为缺钙磷灰石.同时探讨了在炭/炭复合材料表面钙磷生物活性涂层的生长机理.     

工艺参数和热处理对纯钛表面激光熔覆原位合成羟基磷灰石涂层中物相组成的影响

使用CaCO3和CaHPO4混合粉末,在纯钛表面通过激光熔覆原位合成的方法制备羟基磷灰石(Ca10(PO4)6(OH)2,HA)涂层,研究了激光功率,扫描速度和热处理对涂层物相的影响,以期提高涂层中HA的含量。结果表明,低功率下,涂层的主要组成物相为磷酸四钙(Ca4(PO4)2O,TTCP),同时有少量的HA,α-磷酸钙(α-Ca3(PO4)2,α-TCP),CaO和CaTiO3;随功率的增加,涂层中的TTCP,HA和 CaO逐渐减少,只剩下α-TCP和CaTiO3。与功率相比,扫描速度对涂层物相的影响较小。当激光功率为400 W时,不同扫描速度下涂层的物相没有发生明显的变化,主要物相均为TTCP。将涂层在800 ℃下保温5 h,然后随炉冷却,可以使涂层中的TTCP和α-TCP全部转变为HA,进而得到含HA较多的涂层。     

钛基材上电化学沉积羟基磷灰石

通过电沉积法在经过阳极氧化的钛基材表面沉积磷酸钙盐涂层,再经碱热处理使磷酸钙涂层转变为羟基磷灰石涂层。扫描电镜(SEM)观察了阳极氧化后生成的TiO2纳米管的微观结构,以及生成的羟基磷灰石的形貌。X射线衍射仪(XRD)分析了涂层的相组成,同时测定了涂层与基体的结合强度。试验结果表明:电沉积涂层CaHPO4·2H2O经碱处理后转变为羟基磷灰石;电沉积添加双氧水与钛基材经过阳极氧化后使得涂层与基体结合强度有所提高。模拟体液浸泡试验表明涂层具有良好的生物活性。     

Structural, mechanical and corrosion properties of TiOxNy/ZrOxNy multilayer coatings

Results on the deposition and characterization of TiO_xN_y/ZrO_xN_y multilayers, with bilayer periods of 20 and 400 nm, are presented. The coatings were deposited on TiNiNb alloy substrates by the pulsed magnetron sputtering method. The elemental composition, hardness, adhesion and corrosion resistance of the coatings were analyzed.As resulted from the XPS analysis, the individual layers consisted of a mixture of titanium or zirconium oxynitrides and corresponding oxides. X-ray analysis revealed that the coatings were amorphous. Only slight differences between the microhardness and adhesion values of the coatings with small and large bilayer period Λ were found. The experiments also showed that the multilayered coatings improved the corrosion resistance of the uncoated alloy and reduced the amount of ion release in artificial body fluids.     

生物医用NiTi形状记忆合金腐蚀研究进展

镍钛形状记忆合金(NiTi-SMA)具有较好的耐腐蚀和机械性能,在口腔和临床医学中有着大量而广泛的应用。NiTi-SMA腐蚀后释放Ni²⁺会引发细胞毒性和过敏反应,进一步提高NiTi-SMA的耐蚀性是目前生物医学材料领域发展的核心之一。本文对近年来国内外有关口腔医学和临床医学中常用NiTi-SMA的腐蚀研究现状进行了总结,同时也对NiTi-SMA增材制造及表面改性技术进行了评述,以期为开发高性能抗腐蚀生物医用NiTi-SMA提供一定的指导意义。     

Li掺杂Ba(Ti1/7Sn1/7Zr1/7Hf1/7Nb1/7Ga1/7Li(1/7-x))O3高熵陶瓷的制备及介电性能研究

近年来,在高熵合金基础上发展起来的高熵陶瓷逐渐引起了研究者的广泛关注,其出现为开发高性能的无机非金属材料提供了新的设计思路。本文采用固相法制备了BaMO3基钙钛矿型高熵陶瓷Ba(Ti1/7Sn1/7Zr1/7Hf1/7Nb1/7Ga1/7Li(1/7-x))O3 (x = 0, 2.3%, 5.3%, 8.3%, 11.3%),并研究了Li含量对高熵陶瓷物相结构、微观形貌及介电性能的影响。结果表明,Li含量对陶瓷结构的影响不大,陶瓷均保持立方钙钛矿结构,且无杂相产生;陶瓷的晶粒尺寸相对较均匀。当x = 0时,即B位七元等摩尔比Ba(Ti1/7Sn1/7Zr1/7Hf1/7Nb1/7Ga1/7Li1/7)O3高熵陶瓷,其介电常数达到了最大值2920 (@100 Hz),相较于已报道的不掺Li的六元高熵钙钛矿陶瓷Ba(Ti1/6Sn1/6Zr1/6Hf1/6Nb1/6Ga1/6)O3提升了近50倍。     

MOCVD growth and characterizations of BxAl1−xAs and BxAl1−x−yInyAs alloys

Zinc-blende B_xAl_1−xAs and B_xAl_1−x−yIn_yAs alloys have been grown on exactly oriented (0 0 1)GaAs substrates by low pressure metalorganic chemical vapor deposition (LP-MOCVD). The influence of susceptor coating, growth temperature and gas-phase boron mole fraction on boron incorporation into AlAs has been comprehensively investigated. It has been found that boron incorporation into AlAs could be enhanced and the optimal growth temperature range of B_xAl_1−xAs alloys changed from 580 °C to 610 °C when SiC-coated graphite susceptors were replaced by the non-coated ones. In this study, the maximum boron composition x of 2.8% was achieved for the pseudomorphically strained B_xAl_1−xAs alloys. AFM measurements show that RMS roughness of B_xAl_1−xAs alloys increased sharply with the increase of gas-phase boron mole fraction. Raman spectra of B_xAl_1−xAs alloys show a linear increase of the BAs shift with boron composition x. Based on BAlAs deposition, bulk B_xAl_1−x−yIn_yAs (x = 1.9%) quaternary alloy was grown lattice-matched to GaAs successfully. Moreover, 10-period BAlAs/GaAs and BAlInAs/GaAs MQW heterostructures were also demonstrated.     

Ag/LaNixCo1-xO3触点材料的制备及电接触性能研究

本文运用溶胶-凝胶燃烧法合成了双钙钛矿型LaNixCo1-xO3(LNCO)纳米材料,利用粉末冶金和热挤压技术制备了相应的Ag/LNCO触点材料及元件样品。重点考察了不同Ni、Co含量对Ag/LNCO触点材料微观结构、物相组成、物理性能、力学性能及电寿命服役能力的影响,对其电弧侵蚀失效行为进行了研究,并与SnO2粉体增强Ag基触点材料进行对比。结果表明:溶胶凝胶法合成的LNCO纳米颗粒粒径为20-30 nm,经粉末冶金工艺制备的Ag/LaNi0.5Co0.5O3触点材料电学性能和电寿命都优于Ag/SnO2触点材料,其电阻率低至2.10 μΩ?cm,电寿命性能达到51287次。表明Ag/LaNi0.5Co0.5O3触点材料性能较佳,是一种可以取代Ag/CdO的新型触点材料。     

Hydrothermal synthesis of superconductors Ba1−xKxBiO3 and double perovskites Ba1−xKxBi1−yNayO3

Superconductors Ba_1−xK_xBiO₃ and body-centered double perovskites Ba_1−xK_xBi_1−yNa_yO₃ have been selectively synthesized by a facile hydrothermal route. The appropriate ratio and adding sequence of initial reagents, alkalinity, reaction temperature and time are the critical factors that influence the crystal growth of the compounds. The purity and homogeneity of the crystals were detected by the ICP, SEM, EDX and TEM studies. Magnetic measurements show that the superconducting transition temperatures T_C of Ba_1−xK_xBiO₃ decrease from 22 K (for x = 0.35) to 8 K (for x = 0.55) with increasing the K doping level.     

Magnetic phase diagrams of the TbRh2−xPdxPdxSi2 and TbRu2−xPdxSi2 systems

The a.c. susceptibility and high field magnetization on TbRh_2−xPd_xPd_xSi₂ and TbRu_2−xPd_xSi₂ compounds were investigated up to 140 kOe. The (T,x) magnetic phase diagrams were determined. For both systems, an increase in the Pd content causes a decrease in the Néel temperature and changes the magnetization curves.     

High strength and good ductility of casting Al-Cu alloy modified by PrxOy and LaxOy

A modified Al-Cu alloy with high tensile strength and ductility of about 574.0 MPa and 10.4%, respectively, was obtained by adding multiple rare earth oxides (Pr_xO_y and La_xO_y) as modifier. Compared with the unmodified Al-Cu alloy, the tensile strength and ductility of the modified sample were increased by 24.3% and 42.5%, respectively. The improvement both in the strength and ductility may attribute to the finer crystal grains and dendrites, more homogeneously distributed θ′ phase precipitates and the intermetallic compounds formed at the crystal grain boundaries as well as in the space of the dendrites.     

Si3N4/Ti/Cu/Ni/Cu/Ti/Si3N4二次部分瞬间液相连接强度

采用Ti/Cu／Ni中间层对Si3N4陶瓷进行二次部分瞬间液相(PTLP)连接，研究连接工艺参数对Si3N4／Ti/Cu／Ni连接强度的影响，同时研究了连接强度随试验温度的变化规律。结果表明，在该试验条件下，室温连接强度随着二次连接温度的提高和二次保温时间的延长而提高，改变连接工艺参数对Si3N4／Ti/Cu／Ni二次PTLP连接界面反应层厚度无明显影响；连接强度在试验温度400℃时达到最大，随后随试验温度升高，连接强度降低，但在800℃前，其高温强度具有很好的稳定性。