LiNiO2热分解反应动力学研究

用ＤＴＡ和ＸＲＤ研究了ＬｉＮｉＯ_２在空气中的热分解过程为：ＬｉＮｉＯ_２（ｓ）→(６５０～７２０℃)Ｌｉ_２Ｎｉ_８Ｏ_{１０（ｓ）}＋４Ｌｉ_２Ｏ_（ｓ）＋Ｏ_２（ｇ）→(８５０～９５０℃)Ｌｉ_２Ｏ_（ｓ）＋８ＮｉＯ_（ｓ）＋１／２Ｏ_２（ｇ） →(１０００～１１５０℃)ＮｉＯ（ｓ）＋Ｌｉ_２Ｏ_（ｇ）用 Ｄｏｙｌｅ－Ｏｚａｗａ法和 Ｋｉｓｓｉｎｇｅｒ法计算了各反应阶段的表观活化能分别为 ７４７．１８±１．０ ｋＪ·ｍｏｌ^－１、９３２．４６±１．０ ｋＪ·ｍｏｌ^－１和 １１２６．９７±１．０ ｋＪ·ｍｏｌ^－１．用 Ｋｉｓｓｉｎｇｅｒ法确定了反应级数和频率因子,确定了三个阶段的动力学方程分别为 ｄα／ｄt＝１．７３６ｘ１０３９ｅ^{－９００００／Ｔ}（１－α）^{１．０５７}; ｄα／ｄｔ＝１８０６×１０^３９ｅ^{－１１１５００／Ｔ}（１－α）^{０．８４４};ｄα／ｄｔ＝４．２６２×１０４２ｅ^{－１３５０００／Ｔ}（１－α）^{１．２７５}     

掺杂SnO2透明导电薄膜电学及光学性能研究

通过实验测量 ｓｏｌ－ｇｅｌ工艺制备的 Ｓｂ掺杂 ＳｎＯ２薄膜载流子浓度、迁移率、电阻率、膜厚,紫外－可见光区透射率、反射率等性质,详细研究了Ｓｂ掺杂ＳｎＯ_２薄膜电学与光学性能．实验发现,薄膜具有良好的透光性和较高导电性,膜内载流子浓度高达１０^２０ｃｍ^－３,电阻率～１０^－２Ω·ｃｍ,透光率高达 ９０％,ＳｎＯ_２膜禁带宽度 Ｅ_ｇ≈３７～３．８０ｅＶ．     

CoxR1-xAl2O4(R=Zn,Mg)钴蓝颜料反射性能的研究

采用化学共沉淀法成功地制备出适用于彩电显象管内荧光体着色的Ｃｏ_ｘＲ_１－ｘＡｌ_２Ｏ_４（Ｒ＝Ｚｎ、 Ｍｇ, ｘ＝０．８～１．０）钴蓝颜料： ４５０ｎｍ波长处反射率最大提高１８．２％, ６００ｎｍ处反射率最大降低５％。通过对该颜料反射率的影响因素,如掺杂离子类型、掺杂浓度和Ｃｏ^２＋离子浓度的探讨,结论如下：Ｚｎ^２＋、Ｍｇ^２＋改变钴蓝颜料反射性能的作用机理为晶格畸变引起Ｃｏ^２＋３ｄ轨道电子能级分裂程度的变化;对于掺杂离子Ｚｎ^２＋、Ｍｇ^２＋,ｘ下限值分别约为０．８５和０．８．     

复合添加(Ca,Mg)-α-Sialon的晶胞参数研究

利用高分辨率的Ｇｕｉｎｉｅｒ－Ｈａｇｇ相机和计算机控制的底片扫描及数据处理程序系统,测定了复合添加,组份为（Ｃａ_０．５Ｍｇ_０．５）_xＳｉ_{１２－３ｘ}Al_3xＯ_ｘＮ１_６－ｘ（ｘ＝０．３、０．６、１．０和１．４）的α－Ｓｏａｌｏｎ的晶胞参数．材料由热压工艺制备而得．研究结果表明,当ｘ≥１．０时,材料的主晶相为α－Ｓｉａｌｏｎ和含Ｍｇ的ＡlＮ多型体．（Ｃａ,Ｍｇ）－α－Ｓｉａｌｏｎ的晶胞参数明显低于相同组份下的Ｃａ－α－Ｓｉａｌｏｎ的晶胞参数·ＥＤＡＸ的结果进一步给出固溶进入α－Ｓｉａｌｏｎ的包括名义组份中９０％的Ｃａ^＋＋和少量的Ｍｇ^＋＋,而大部分Ｍｇ^＋＋进入ＡlＮ多型体,这一结果为净化α－Ｓｉａｌｏｎ陶瓷的晶界提供了新的有效途径．     

Sol-Gel法制备ZnO压敏陶瓷及其电性

采用溶胶－凝胶（ｓｏｌ－ｇｅｌ）工艺制备ＺｎＯ电压敏陶瓷粉体．探讨其制备的最佳工艺条件：以 Ｚｎ（ＮＯ_３）_２与 ＮａＯＨ为反应前驱物制取胶体, Ｚｎ^２＋浓度控制在 ０．５ｍｏｌ·Ｌ^－１以上, ｐＨ值７．５左右,预烧温度３００℃,陶瓷烧结温度１２００℃;制得的压敏电阻的非线性系数α＝２８;研究了稀土Ｌａ_２Ｏ_３掺杂对该陶瓷电性的影响：低浓度掺杂时,可提高压敏电压,高浓度掺杂时;不呈现压敏特性;对粉体进行了Ｘ射线衍射和透射电镜分析,预烧后得到五元掺杂的ＺｎＯ粉体粒形呈球状,属六方晶系,粒径分布窄,约为４０～８０ｎｍ．     

Ti(IV)在介孔氧化硅MCM-41中的液相移植

以钛酸丁酯为原料,通过液相移植反应,在介孔氧化硅ＭＣＭ－４１中成功地组装了Ｔｉ（ＩＶ）,利用ＸＲＤ、ＴＥＭ、ＥＤＳ、ＦＴ－ＩＲ、Ｎ_２吸附－脱附、^２９Ｓｉ ＭＡＳ ＮＭＲ等多种实验方法对材料进行了表征,并讨论了液相移植反应的机理．实验表明,通过与介孔材料骨架表面Ｑ^３硅原子中的硅醇键（Ｓｉ－ＯＨ）的反应而形成钛－氧－硅（Ｔｉ－Ｏ－Ｓｉ）键,Ｔｉ（ＩＶ）被成功地固定到介孔材料的骨架上面; ９５０～９６０ｃｍ^－１红外共振吸收的加强是Ｓｉ－Ｏ－Ｔｉ键形成的标志．     

Ba0.7Sr0.3TiO3薄膜的制备、结构及性能研究

研究了一种以乙二醇为稳定剂的新的ＢＳＴ前驱液,用ｓｏｌ－ｇｅｌ法在Ｐｔ／Ｔｉ／ＳｉＯ_２／Ｓｉ（１００）基底上成功地制备出具有优良电学性能的Ｂａ_０．７Ｓｒ_０．３　ＴｉＯ_３薄膜．乙二醇的加入有效地增加了前驱液的稳定性,并降低薄膜的结晶温度．利用ＸＲＤ、ＤＴＡ等技术分析了凝胶热处理过程中相变化情况及薄膜厚度与成相的关系．厚度 ２００ｎｍ,Ｏ_２气氛中 ７００℃处理 １５ｍｉｎ后的 ＢＳＴ薄膜具有良好的介电性能,１００ｋＨｚ时介电常数ε＞４００,介电损耗 Ｄ＜０．０２;Ｐ—Ｅ电滞回线说明薄膜具有良好的铁电性能,剩余极化只约为１．４μＣ／ｃｍ^２,矫顽场强 Ｅ_ｃ约为 ４８ｋＶ／ｃｍ．     

Na0.5Bi0.5TiO3-BaTiO3陶瓷的介电和压电性能研究

研究了Ｎａ_０．５Ｂｉ_０．５ＴｉＯ_３和（Ｎａ_０．５Ｂｉ_０．５）_０．９４Ｂａ_０．０６ＴｉＯ_３陶瓷的电滞回线、压电性能和热滞现象·得到（Ｎａ_０．５Ｂｉ_０．５）_０．９４Ｂａ_０．０６ＴｉＯ_３陶瓷的剩余极化Ｐ_ｒ＝１９ｕＣ／ｃｍ^２、矫顽场Ｅ_ｃ＝４．７ｋＶ／ｍｍ．发现用适量的Ｂａ^２＋取代（Ｎａ_０．５Ｂｉ_０．５）^２＋尽管压电性能有所提高,但同时使得材料的温度稳定性大大降低．     

新型复合钙钛矿Ba(SbⅢ,SbⅤ)O3的水热合成和表征

采用水热晶化法制备了Ｂａ（Ｓｂ^Ⅲ,Ｓｂ^Ⅴ）Ｏ_３新型钙钛矿型氧化物,并通过ＸＲＤ、 ＩＲ、ＳＥＭ和ＩＣＰ等方法对产物物相、形貌和组成等进行了表征．结果表明,产物为立方钙钛矿结构,晶胞参数为α＝０．４１５ｎｍ,粒度为１～２μｍ具有一定团聚的多晶粉末．产物中锑为三价和五价两种价态．水热条件对合成影响的研究结果表明, Ｂａ（Ｓｂ^Ⅲ,ｓｂ^Ⅴ）Ｏ_３合成的适宜碱度和ｎ_{Ｓｂ（Ⅴ)}／ｎ_{Ｓｂ（Ⅲ）}分别为 ８～１０Ｍｏｌ／Ｌ ＫＯＨ和 ０～１     

共沉淀法制备掺杂氧化锌压敏陶瓷粉料热力学分析

本文通过对Ｍｅ^ｎ＋（Ｚｎ^２＋;Ｃｒ_３^＋,Ｍｎ^２＋;Ｓｂ^３＋,Ｂｉ^３＋,Ｃｏ^２＋）－ＮＨ_３－ＣＯ_３^２－－Ｈ_２Ｏ体系进行热力学分析的基础上,获得了Ｍｅ－ＮＨ_３－ＣＯ_３^２－Ｈ_２Ｏ体系中的ｌｇ［Ｍ］_T－ｐＨ关系图,得到了用ＮＨ_４ＨＣＯ_３和ＮＨ_３·Ｈ_２Ｏ作沉淀剂,用共沉淀法制备掺杂氧化锌压敏陶瓷粉料时,最佳共沉淀ｐＨ为７．０左右．     

负载钛催化丁二烯本体沉淀聚合的动力学研究

研究了负载钛催化剂引发丁二烯在0～40℃的本位沉淀聚合动力学。结果表明，体系在单体液相未消失之前转化率与时间成直线关系，即聚合速率恒定、表现为稳态聚合，丁二烯本位沉淀聚合的表现活化能为33.5kJ/mol，一定条件下的聚合速率方程为：Rp=kp[Bd]o[Ti]o[Al]o。     

粘土的层间交联和多孔材料的形成条件

本文利用XRD、IR等方法研究2:1型的蒙脱石粘土矿物和聚合羟基铝交联剂的层间交联作用,并对多孔粘土材料的形成条件及过程作初步探讨．结果表明,交联剂浓度、交联温度和洗涤方式等制备条件对多孔粘土材料的形成有较大的影响,稀浓度的交联剂溶液对材料的形成较为有利,交联过程是双向可逆的．     

热处理工艺对多孔TiO2薄膜光催化性能的影响

以十八胺为模板剂,采用溶胶-凝胶法在玻璃基体上制备了多孔TiO2薄膜,研究了热处理工艺对薄膜理化性质及光催化性能的影响。随煅烧温度和煅烧时间的增加,TiO2薄膜表面逐渐形成清晰的孔结构,晶粒尺寸增大。薄膜由锐钛矿型TiO2组成,Ti以Ti 4+的形式存在。制备的TiO2薄膜厚度在200nm左右,薄膜的UV-Vis透射率随煅烧温度的升高呈下降趋势,随煅烧时间的延长先下降而后又上升。多孔TiO2薄膜光催化降解甲基橙结果表明,随煅烧温度升高薄膜的光催化活性增加,在500℃煅烧2h制备的薄膜具有最佳的光催化活性。     

P123对多孔TiN粉体孔结构及电化学性能的影响

以四氯化钛为钛源,P123为模板剂,氰胺为稳定剂,采用溶胶-凝胶法制备多孔TiO 2粉体,再经900℃氨气还原氮化得到多孔TiN粉体。通过XRD,SEM,BET,TEM和SAXD等表征粉体物相组成与微观结构,并采用循环伏安法、交流阻抗法和恒流充放电法测试其电化学性能。结果表明:合成粉体颗粒近似球形,为立方TiN相。相比之下,引入P123时所合成粉体中孔径尺寸为10~50nm的介孔数量增加,并存在孔径大小为2~3nm的微小孔道,同时孔道结构有序性有所提高,这有助于提升TiN粉体的电化学性能。因此,未加入P123合成TiN粉体的比电容仅为81F·g -1 ,内阻 R 1为1.1Ω,离子扩散阻抗 W 1为2.5Ω。引入P123合成TiN粉体的比电容提升到95F·g -1 , R 1和 W 1均有所减小,分别为0.9Ω和0.06Ω。     

Formaldehyde degradation by photocatalytic Ag-doped TiO2 film of glass fiber roving

The photocatalytic Ag doped TiO2 porous films were prepared by sol-gel method and dip coated on glass fiber roving. The sol composed of titanium (IV) isopropoxide, triethanolamine, ethanol and nitric acid followed by calcination of the film at 500 degrees C for 1 hour with a heating rate of 3 degrees C/min. The surface morphology and properties of synthesized TiO2 films were characterized by X-ray diffraction, atomic forced microscope and scanning electron microscope. A laboratory photocatalytic reactor was set up to carry out photoactivity of the prepared catalysts. The results show that TiO2-Ag and TiO2-Ag-TEA porous films give highest rate of formaldehyde gas degradation. It can be noted that triethanolamine exhibits two effects on TiO2 composite films; one is its effect on porous film structure and second is a reverse effect of hindrance of anatase growth.     

丙烯酸十八酯在Nd(P204)3-Al(i-Bu)3催化剂体系中聚合的研究

研究了丙烯酸十八酯(OA)在Nd(P204)3-Al(i-Bu)3催化剂体系中的聚合反应,反应的最佳条件是:以苯为溶剂,［Al］／［Nd］=9(摩尔比),［OA］／［Nd］=162(摩尔比),60 ℃反应6 h,聚合转化率大于90%,所得聚合物的分子量为1.0×105～1.5×105。聚合反应速率与单体浓度、催化剂浓度均呈一级关系,聚合反应的表观活化能为32.5 kJ／mol。     

A two-step sol-gel method for synthesis of nanoporous TiO2

This article reports a study of the effects of synthesis parameters on the preparation and formation of mesoporous titania nanopowders by employing a two-step sol-gel method. These materials displayed crystalline domains characteristic of anatase. The first step of the process involved the hydrolysis of titanium isopropoxide in a basic aqueous solution mediated by neutral surfactant. The solid product obtained from step 1 was then treated in an acidified ethanol solution containing the same titanium precursor to thicken the pore walls. Low pH and higher loading of the Ti precursor in step 2 produced better mesoporosity and crystallinity of titanium dioxide polymorphs. The resultant powder exhibited a high surface area (73.8 m2/g) and large pore volume (0.17 cm3/g) with uniform mesopores. These materials are envisaged to be used as precursors for mesoporous titania films as a wide band gap semiconductor in dye-sensitized nanocrystalline TiO2 solar cells.     

Synthesis and characterization of waterborne polyurethane/organic clay nanocomposites

Stable waterborne polyurethane/organic clay latex was synthesized by ultrasonically-assisted mixing with different clay content. Fourier transform infrared (FT-IR) spectra showed that the interaction between NH and C=O was enhanced with low content organic clay loaded. X-ray diffraction (XRD) results implied that the layered organic clay was exfoliated and the crystallization of the hard domain in the waterborne polyurethane (WPU) matrix was enhanced. Transmission electron microscopy (TEM) images show that the layered clay was exfoliated by WPU molecule. The tensile test shows that the mechanical properties were improved by loading organic clay and the desired addition was 1 wt.%.     

医用多孔金属的制备及其生物活化研究进展

医用多孔金属材料,特别是多孔钛及钛合金能够提供与人体骨组织相匹配的力学性能,并促进骨组织长入以提高其与骨的固定度,在人体硬组织修复与替换方面具有广泛的应用前景。重点围绕多孔钛及钛合金的制备方法及适用于其复杂孔隙结构的表面生物活化方法,综述了各种方法在多孔钛及钛合金上的应用现状。目前适用于多孔钛及钛合金制备的技术主要有粉末冶金法、钛纤维烧结法、自蔓延高温合成法、选区电子束熔化技术和选区激光熔化技术,适用于多孔钛及钛合金表面生物活化的技术主要有溶胶凝胶法、仿生矿化法、电化学沉积法和微弧氧化法。多孔钛及钛合金的力学相容性和表面生物活性需要同时满足临床要求,才能进一步扩大其在医学领域的应用范围。     

Electrosynthesized TiO2 films: dependence of the brookite–anatase ratio on the applied potential

TiO₂ films were produced on ITO using a two-step method: (i) potentiostatic electrosynthesis of an amorphous titanium oxyhydroxide gel and (ii) subsequent crystallization by a thermal treatment (TT). The influence of applied potential on the morphology and on the crystalline structure of the resulting films was studied for three different TT temperatures, using SEM, XRD, and Raman spectroscopy. The films were porous and their morphology was more affected by the potential than by the temperature. The obtained TiO₂ presented a high degree of crystallinity. The brookite–anatase coexistence was observed for all synthesis conditions. Nevertheless, the brookite content decreased for samples synthesized at more negative potentials, irrespective of the TT temperature. A relative estimate of brookite content variation among the prepared samples was obtained from an analysis of Raman spectra, and it was shown to be related with the pH variation during electrosynthesis. This correlation is in accordance with reported dependence of brookite-anatase ratio in sol-gel synthesis, which decreases with an increase in pH.