不同烧结温度下中空羟基磷灰石微球的物相、组织与织构性能的研究

利用锂钙硼玻璃的原位转化反应制备了表面由介孔组成的中空羟基磷灰石(HAP)微球。研究了不同烧结温度对微球的物相、组织、织构等性能的影响。通过X射线衍射仪(XRD)、扫描电镜(SEM)、比表面积分析仪、压汞仪与化学分析方法研究了不同烧结温度下中空HAP微球的物性与特征。结果表明,所制备的微球由缺钙HAP组成。随着烧结温度的提高,微球的结晶性能提高,晶粒尺寸增加。烧结温度700℃时,缺钙HAP发生分解,生成磷酸三钙新物相。所制备的HAP微球(90℃热处理)球壳由2～40nm的介孔组成,平均孔径最小。随着烧结温度的提高,平均孔径增加。烧结温度900℃时,微球表面出现微米级的小孔。所制备的中空HAP微球(90℃热处理)的比表面积最大,总孔体积最大,随着烧结温度的增加,比表面积与总孔体积减少。调节烧结温度,可获得不同物相、表面形貌、比表面积、总孔体积与小孔孔径的中空HAP微球,有利于获得具有缓释速率可在一定范围内调节的生物医用材料。     

壳聚糖原位复合纳米羟基磷灰石缓释微球

利用高压微囊成型装置,以壳聚糖为有机基质,通过原位复合纳米羟基磷灰石,制备载淫羊藿苷复合微球,构建一种新型载药复合微球。结果表明:制得的复合微球形态圆整,粒径约为200μm且分布均匀;原位形成的羟基磷灰石达到纳米级;复合微球对淫羊藿苷形成了良好的包覆,并对成骨细胞具有促进增殖的作用。     

均匀沉淀法制备多孔羟基磷灰石球晶

以生物碳酸钙作为钙源,采用均匀沉淀法,制备多孔羟基磷灰石(HA)球晶。利用SEM、XRD、FT-IR和光学显微镜研究球晶的形貌、尺寸、成分和相组成。结果表明,球晶由片状含碳酸HA纳米晶体组成,平均直径为5～15μm,大小均匀、分散性好、结构精致、对称性好。在正交偏光镜间球晶呈现黑十字消光,用补色法则测得为正光性球晶。     

表面活性剂对超声喷雾法制备的纳米羟基磷灰石粉体性能影响

在常温常压下,以硝酸钙(Ca(NO3)2·4H2O)和磷酸氢二铵((NH4)2HPO4)为原料,分别将其作为钙与磷的先驱体,运用超声喷雾法特种工艺技术制备羟基磷灰石(HAP)纳米粉体。探讨在制备工艺过程中添加柠檬酸、甘氨酸、葡萄糖和TX-104种表面活性剂对制备的羟基磷灰石纳米粉体的分散性能、粒度、均匀性及形貌等的影响情况。结果表明,所有表面活性剂的加入对粉体的产物相没有影响,但对制备出的纳米羟基磷灰石粉体的分散效果均有一定的影响,在本反应体系中当甘氨酸适量加入时,对纳米羟基磷灰石粉体能起到很好的分散作用;而等量柠檬酸的加入反而加剧了纳米HAP颗粒的团聚。从扫描电镜照片看出,在未加活性剂时,HAP大多呈现椭圆的、30～40nm的颗粒;加入甘氨酸后,有利于HAP颗粒的细化与均匀,而葡萄糖与TX-10的加入则使粒度变大,并易造成局部团聚。并从物化基本原理出发初步探讨与解释上述表面活性剂对HAP产物所造成影响的原因。     

利用冷冻干燥原位构筑仿生型纳米羟基磷灰石、壳聚糖多孔支架材料

在目前仿生制备骨缺损修复材料研究的基础上,利用冷冻干燥技术结合原位复合方法在成分仿生的基础上进行结构仿生制备骨缺损修复材料.充分利用壳聚糖的溶解、沉析和羟基磷灰石形成特性,在室温下实现了纳米羟基磷灰石在多孔支架中的纳米分散.研究结果表明,利用冷冻干燥原位构筑的多孔支架材料拥有很好的相互贯穿多孔连通结构,孔径分布为100～136 μm,孔隙率达到96.1%.此外,原位形成的纳米羟基磷灰石(95 nm)对于多孔支架还起到了纳米增强作用,支架表现出良好的力学性能,可以根据不同缺损形状实现随意赋行.体外生物活性测试表明,该支架材料具有很好的生物活性,是一种优越的潜在骨缺损修复支架材料.     

脉冲电沉积涂覆纳米羟基磷灰石的多孔Mg-Zn支架材料的体外生物降解能力和生物相容性(英文)

研究纳米羟基磷灰石(HAP)涂覆的多孔Mg-2Zn(质量分数,%)支架材料的生物降解能力和生物相容性。采用脉冲电沉积制备羟基磷灰石涂层。对涂覆HAP的支架在碱性溶液中进行后处理来改善其生物降解性和生物相容性。研究支架和HAP涂层的显微组织和成分以及它们在模拟体液(SBF)中的降解和细胞毒性。经过碱溶液处理后的涂层由几乎垂直于基体的直径小于100 nm的针状HAP组成,具有和天然骨头相似的成分,浸泡在SBF中后,产物为HAP、(Ca,Mg)3(PO4)2和Mg(OH)2。涂覆HAP和经过处理碱处理后的支架比未涂覆HAP的支架具有更高的生物相容性和细胞存活性。MG63细胞粘附在涂覆HAP和经过碱处理后的支架的表面并增殖,使这些支架有望应用于医学。结果表明:纳米HAP的脉冲电沉积和碱处理可有效改善多孔Mg-Zn支架的生物降解能力和生物相容性。     

中空二氧化硅微球的尺寸控制制备及草甘膦释放(英文)

以硅酸钠为硅源,聚苯乙烯与苯乙烯-甲基丙烯酸共聚乳液为模板,制备直径为249～1348nm的不同尺寸的中空二氧化硅微球。在给定二氧化硅与乳液模板质量比的前提下,中空二氧化硅微球直径与壳厚度随着乳液模板直径的增加而增加。中空二氧化硅微球直径与壳厚度也随着二氧化硅与乳液模板质量比的增加而增加。苯乙烯-甲基丙烯酸共聚乳液模板表面存在羧基有利于形成致密、均匀的二氧化硅微球球壳。中空二氧化硅球壳具有介孔结构和大的比表面积。将草甘膦用作释放模型化合物时,其释放速率可通过改变球壳厚度而进行调节。     

钛表面种籽层水热沉积制备羟基磷灰石生物涂层

为了获得与基体结合强度高、生物活性好的羟基磷灰石(HAP)涂层,通过种籽层水热沉积方法在钛合金表面生长HAP,首先纳米尺寸的钙磷盐通过微弧氧化技术在钛金属表面形成,此种籽层在随后的水热沉积过程中促进了HAP的诱导沉积。讨论了络合剂和种籽层对HAP的形貌和结构的调控。采用此方法制备的生物活性梯度涂层无裂纹、涂层厚度分布均匀,与基体具有高的结合强度,HAP呈现良好的结晶性,并具有沿c轴的择优取向,此HAP涂层表现出优良的生物活性,有利于促进骨的生长。     

相组成对含CO3^2-的双相钙磷陶瓷表面类骨磷灰石形成的影响

钙磷陶瓷表面形成的类骨磷灰石层对材料诱导新骨生成起非常重要的作用。利用体外模拟装置首次研究了新工艺制备的含CO3^2-的双相HA／β-TCP多孔陶瓷相组成对表面类骨磷灰石形成的影响。结果表明，具有不同相组成的该种陶瓷因CO3^2-的存在，导致类骨磷灰石晶体的形成时间有不同程度的提前。并且相组成在β-TCP含量较低时(HA／β-TCP之比为9／1)，该陶瓷也能在较短的作用时间内形成类骨磷灰石晶体。此外还有缺钙羟基磷灰石晶体的形成。类骨磷灰石晶体的形成情况随β-TCP含量的增加而越来越好。且相组成以HA／β-TCP比值为6／4时类骨磷灰石的形成情况最好。相组成的优化有利于该陶瓷材料骨诱导性的提高，进而有利于骨缺损的快速修复。     

烧结对羟基磷灰石微球微观结构和性能的影响

利用扫描电镜(SEM)、激光粒度分析仪(LDPSA)、X射线衍射仪(XRD)以及比表面积分析仪(SSA)等检测方法,研究了烧结对于羟基磷灰石微球的微观结构、形貌以及粒径、比表面积和孔隙率等性能的影响.结果表明,经800℃热处理,微球的比表面积、孔隙率及其表面形貌均会发生明显的变化;经1000℃烧结后,部分羟基磷灰石相发生热分解,生成较多的的杂质相,如α-磷酸三钙(α-TCP)和β-磷酸三钙(β-TCP).     

添加Zn对自反应淬熄法制备Mn-铁氧体空心微珠相结构与性能的影响

采用自反应淬熄法制备了Mn-铁氧体复合空心微珠,分析了自蔓延反应体系中添加Zn元素对制备空心微珠的形貌、相结构和电磁参数的影响。结果表明,制备的粉末大部分为球状空心微珠,粒径在微米范围,少量自蔓延反应不完全的团聚颗粒未能球化,形成不规则颗粒。Zn的引入使得微珠成分转变为以Mn0.5Zn0.5Fe2O4铁氧体为主,提高了Mn-铁氧体复合空心微珠的微波电磁损耗,使吸收峰向高频移动。     

Fabrication of Mono-dispersed Hollow Titania Nanospheres with Enhanced Photocatalytic Property

采用阳离子聚苯乙烯(PS)微球为模板,以钛酸丁酯为前驱体经溶胶凝胶反应制备了TiO2/PS复合微球,并经高温煅烧得到单分散中空TiO2纳米微球。采用扫描电镜(SEM)、透射电镜(TEM)、红外光谱仪(FT-IR)、X射线衍射仪(XRD)和紫外-可见分光光度计(UV-VIS DRS)对复合和中空微球的结构和光催化性能进行了表征。结果表明,经高温煅烧后TiO2中空微球尺寸相对于复合微球收缩了约25%,其粒径约为100 nm;中空微球壳层厚度可随钛酸丁酯用量而变化,壳层呈锐钛矿和金红石混晶结构,同时中空微球表现出比P25纳米TiO2更强的甲基橙光降解特性。     

Facile hydrothermal synthesis and characteristics of B-doped TiO2 hybrid hollow microspheres with higher photo-catalytic activity

The boron doped titanium oxide hybrid hollow microspheres were easily prepared by hydrothermal method. The scanning and transmission electron microscopy images demonstrated that the hybrid hollow microspheres possessed smooth outer shell and hollow interior. Their crystal structure, chemical state, amount of surface active groups and spectral response region were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectra and UV-Vis diffuse reflection spectra, respectively. Methylene blue aqueous solution served as a target pollutant to evaluate the photo-catalytic activity under simulated sunlight. It turned out a higher photo-catalytic activity of boron doped hybrid hollow microspheres, comparing with the undoped ones.     

火焰干燥法制备低结晶度羟基磷灰石微球(英文)

利用火焰干燥法将3种不同性质的羟基磷灰石(HA)料浆分别制得不同结构的微球。通过透射电镜(TEM)、X线衍射仪(XRD)和扫描电镜(SEM)分别研究不同磷灰石料浆中颗粒的微观结构、所得HA微球的相组成及其表面形貌,进而分析料浆性质及干燥工艺参数对所得HA微球结构的影响。TEM结果表明,随着磷灰石料浆反应陈化时间的延长,其中的纳米颗粒形貌由球状的非晶态转变为针状的纳米晶态;低温条件下HA料浆的结晶程度明显降低。XRD结果表明:火焰干燥所得3种HA微球的结晶程度和其对应料浆的结晶程度一致。SEM结果显示:去氨水后的纯HA料浆经火焰干燥所得微球的球形度最好,含有氨水的HA料浆所得微球具有表面开口的空心结构,而冰水混合物料浆所得HA微球球形度最差。     

Fabrication of hydroxyapatite microspheres with poor crystallinity using a novel flame-drying method

Three kinds of hydroxyapatite (HA) microspheres were prepared using a flame-drying method. The morphologies and selected area diffraction of HA slurries were determined by TEM. The phase composition, and morphologies were studied by TEM, X-ray diffractometer (XRD), scanning electron microscope (microstructure, SEM), respectively. The TEM result shows that the slurries are composed of nano-particle HA. With the aging time of HA slurry prolonging, the morphology of HA particle changes from spherical ACP (amorphous calcium phosphate) to rod-like acicular nano-crystal morphology. Low temperature can also cause the crystallinity degree of HA slurry decrease obviously. The XRD result shows that the crystallinity of HA microspheres prepared from three kinds of HA slurry is consistent with its corresponding slurry. The SEM result shows that the sphericity of the microspheres prepared by pure HA slurry without ammonia water is the best among three kinds of microspheres, then the HA slurry containing ammonia solution forms the hollow microspheres with open pore, and ice-water mixture flurry.     

基于空心氧化铝微球造孔的陶瓷结合剂金刚石砂轮

研究空心氧化铝微球质量分数和粒径（0.2, 0.4, 0.6 mm）对砂轮的总气孔率、抗弯强度、硬度和微观结构的影响，制备以空心氧化铝微球为造孔剂的陶瓷结合剂金刚石砂轮，并研究砂轮对石英玻璃的磨削性能。结果表明:随着空心氧化铝微球质量分数增加，砂轮总气孔率升高，抗弯强度和硬度降低；空心氧化铝微球质量分数相同时，其粒径越小，砂轮的总气孔率越高，抗弯强度和硬度越低；制备的空心氧化铝微球陶瓷结合剂金刚石砂轮可用于磨削石英玻璃，加工后石英玻璃的表面粗糙度从0.5113 μm降至0.0206 μm。      

新型可充锂-空气电池的纳米刺状α-MnO_2/Pd空心微球催化剂(英文)

利用NaBH4溶液还原PdCl2的方法在具有纳米刺状表面的α-MnO2中空微球上沉积Pd,制备一种α-MnO2/Pd核壳型复合催化剂作为新一代可充锂-空气电池的催化剂。TEM、XRD和EDS等方法的分析结果表明,在催化剂中纳米Pd颗粒均匀地分布在刺状α-MnO2中空微球表面,Pd在催化剂中的质量分数约为8.88%。充放电测试结果表明,与纳米刺状的α-MnO2中空微球催化剂相比,α-MnO2/Pd复合催化剂提高了空气电极的能量转化效率和充放电循环性能。由Super P碳材料和所制备的α-MnO2/Pd复合催化剂所构成的空气电极在0.1mA/cm2电流密度下的首次放电比容量可以达1220 mA·h/g,经13次充放电循环后的容量保持率为47.3%。该纳米刺状α-MnO2/Pd核壳型复合催化剂是一种有前途的空气电池催化剂。     

Hierarchical CuO hollow microspheres: Controlled synthesis for enhanced lithium storage performance

In this work, hierarchical CuO hollow microspheres were hydrothermally prepared without use of any surfactants or templates. By controlling the formation reaction conditions and monitoring the relevant reaction processes using time-dependent experiments, it is demonstrated that hierarchical CuO microspheres with hollow interiors were formed through self-wrapping of a single layer of radically oriented CuO nanorods, and that hierarchical spheres could be tuned to show different morphologies and microstructures. As a consequence, the formation mechanism was proposed to proceed via a combined process of self-assembly and Ostwald's ripening. Further, these hollow microspheres were initiated as the anode material in lithium ion batteries, which showed excellent cycle performance and enhanced lithium storage capacity, most likely because of the synergetic effect of small diffusion lengths in building blocks of nanorods and proper void space that buffers the volume expansion. The strategy reported in this work is reproducible, which may help to significantly improve the electrochemical performance of transition metal oxide-based anode materials via designing the hollow structures necessary for developing lithium ion batteries and the relevant technologies.     

Controllable preparation of hierarchical NiO hollow microspheres with high pseudo-capacitance

Nickel oxide (NiO) hollow microspheres with hierarchical structure were fabricated through a process consisting of a self-assembling, hydrothermal reaction and calcination. The prepared NiO hollow microspheres composed of many nanoflakes, are about 2-3 μm in diameter. The length of the NiO flakes, having clear edges, is about 500-700 nm, while the thickness is only about 40-50 nm. This indicates that the NiO microspheres possess a hierarchical structure that can provide porous channels to facilitate the transmission of both electrons and electrolyte ions. NiO microspheres exhibit a high specific capacitance of about 1340 F/g at a current density of 1 A/g and high capacitance retention about 96.5% after 1000 cycles. What's more, the conductive mechanism of nickel oxide for electrochemical capacitor electrodes was also studied.     

Effect of Atmosphere on Synthesizing Hollow Ceramic Microspheres by Self-reactive Flame Quenching Technology

In order to obtain high comprehensive performance hollow ceramic microspheres (HCMs), used Al-Cr2O3 as the main reaction system, HCMs were prepared by Self-reactive flame quenching technology in Ar2 and N2 atmosphere respectively. Effects of the two different atmospheres on synthesizing HCMs were studied. Results show that in Ar2 atmosphere, because of incomplete reaction of agglomerate powders, porous particles with hollow structure and smooth-faced HCMs constitute the products. However in N2 atmosphere, because agglomerate powders react completely, all of them become smooth-faced HCMs. Results above show that experiment atmosphere is a important parameter to synthesize HCMs and to a great extent influences reaction process of agglomerate powders in the flame field.