A Comparison of the Nanostructure of Lead Zirconate,Lead Titanate and Lead Zirconate Titanate Sols

Sol-gel processing has been widely used for the fabrication of lead zirconate titanate (PZT) thin films. To successfully and consistently make high quality thin films for different applications, we must develop a fundamental understanding of the structures of the sols. In this study, the characters of lead titanate (PT) and lead zirconate (PZ)sols were studied by measuring the rheological properties and particle sizes in them and comparing their behaviours. The average particle sizes in unhydrolysed PT, PZ and PZT sols are 11.5, 1.0, and 6.0 nm, respectively. PT sol has the highest rate of hydrolysis. It gels at about 24 h after hydrolysis. PZ and PZT sols have a quite similar feature in hydrolysis. The reasons for the differences in the hydrolysis behaviour of the different types of sol are discussed in terms of a model which indicates that the inhomogeneous sols consist of 5 to 6 nm PT particles surrounded by much smaller PZ particles, which tend to dominate the sol behaviour.     

Studies of Lead Zirconate Titanate Sol Ageing Part I: Factors Affecting Particle Growth

The formation and growth of polymeric particles during the hydrolysis and condensation of PbZr_0.3Ti_0.7O₃ (PZT 30/70) precursor solutions have been studied as functions of time by using photon correlation spectroscopy (PCS). Particle shape was deduced by measuring the rheological properties of the sols and was found to remain chain-like during sol ageing. Various factors that affect the ageing of PZT sols have been investigated. Ethylene glycol (EG) was found to greatly accelerate the hydrolysis and condensation of the acid-modified Pb-free Zr/Ti solutions but had little effect on the particle growth for the Pb-containing PZT sols. Temperature and H₂O concentration were found to have major effects on the ageing behaviors. The higher the temperature and H₂O concentration, the higher the particle growth rates and the faster the sol gels.     

Preparation of Lead Zirconate Titanate Ceramic Fibers by Sol-Gel Method

PZT fibers with the nominal composition of Pb(Zr_0.53Ti_0.47)O _x have been successfully drawn by the sol-gel techniques. Ti(O·i–C₃H₇)₄, Zr(O·n–C₄H₉)₄, and Pb(O₂C₈H₁₅)₂ were used as the starting materials. The rheological conditions for continuous gel fiber drawing were determined. Thermal and microstructural evolutions of gel fibers were investigated by X-ray diffraction and Fourier-transform infrared spectroscopy. Perovskite crystalline fibers without breakage were obtained by a two-stage heat treatment on the gel fibers up to 600°C in air. Bending strength of the fibers decreases with the increase of the fiber diameter and is ranged from 10 to 30 MPa.     

Study of the Lead Environment in Liquid and As-Dried Precursors of PZ, PT and PZT Thin Films

The environment of lead and zirconium atoms in liquid and as-dried precursors for PbZrO3 (PZ), PbTiO3 (PT) and Pb1.1Zr0.53Ti0.47O3 (PZT) thin film deposition were analyzed by EXAFS. The sols were prepared by 2-methoxyethanol route with lead acetate and lead oxide as lead sources. Pb—O—M (M = Zr and/or Ti, depending on the sol composition) linkages were determined in all sols. The choice of lead source weakly influences the lead environment, and strongly influences that of zirconium in both PZ and PZT sols. By drying lead oxide based sols the Pb–M correlation is moderately reduced in PZ, PT and is strongly reduced in PZT.     

Ferroelectric Properties of Modified Lead Titanate Thin Films Obtained by a Sol-Gel Method

Calcium substituted lead titanate thin films have been prepared by a sol-gel method, deposited by spin-coating, and thermally treated so as to obtain a perovskite structure. Two types of thermal treatments were given, differing in the heating rate, which in conventional treatments was of some 10°C/min, and in rapid treatments >500°C/min. With rapid heating, materials are obtained in which greater polarizations are commuted and bias fields are smaller. This, together with the fact that additional (undesired) phases are not observed by X-ray diffractometry when rapid treatments are used, shows that these are to be preferred over conventional treatments.     

Study by Rutherford Backscattering Spectroscopy of the Heterostructure of Lead Titanate Thin Films

A depth profile analysis of modified lead titanate thin films was performed by means of Rutherford Backscattering Spectroscopy (RBS). These films were deposited from sol-gel synthesized solutions onto platinized silicon substrates and crystallized by thermal treatments at temperatures of about 650°C. The chemistry of the solution and the thermal treatment for crystallization affect the heterostructure of the resulting films. Losses of lead and formation of substrate-film interfaces are produced during the crystallization of the films. These film characteristics determine their ferroelectric response.     

Seeding Effects in the Sol-Gel Preparation of Lead Zirconate Titanate (PZT) Powders

Lead zirconate titanate, Pb(Zr, Ti)O₃ (PZT), crystallizes in a perovskite form from an intermediate pyrochlore phase and the effects of the presence of perovskite seeds have been considered. PZT powders have been obtained from lead acetate and Zr and Ti alkoxides using a sol-gel process involving a chemical modification by acetylacetone. Perovskite seeds have been introduced during the process by means of colloidal suspensions in acetylacetone. The seeding effects have been evidenced from DTA and XRD measurements, the formation temperature of pure perovskite phase being lowered by 50°C with 5 wt% seeds. More dense powder microstructure is observed in presence of seeds. Work performed within the Concerted European Action on Sol-Gel Processing for Advanced Industrial Material Technologies, Contract No. BRE2, CT92.0137.     

纤维钛酸铅/纳米钛酸铅晶体复合陶瓷材料性能研究

钛酸铅（PbTiO3）在常温下属于典型的钙钛矿结构,其居里温度高达490℃,介电常数小,压电性能高,压电各向异性大,是一种优良的高温高频的压电材料,但因其轴向比c/a=1.063和矫顽场大,难于极化,在冷却过程四方至立方的相变中易出现微细裂纹,有时甚至破碎,所以制备纯相致密的PbTiO3陶瓷存在烧结上的困难,且因陶瓷本身固有的脆性,使其优良的电性能很难得到充分的开发和利用。PbTiO3的应用通常是通过掺杂改性而获得的。而掺杂改性会对其电性能产生不良的影响。如能寻找一种有效的方法,即改善其烧结特性,又不影响其电性能,而且能制得致密的PbTiO3陶瓷,则对PbTiO3的研究与应用具有重要的意义。     

用X线荧光衍射法和原子吸收光谱法测定油漆中的铅含量

为勘查环境铅暴露的来源并评价其状况，应用K层X线荧光衍射法（XRF）对84张木制桌面表面油漆中的铅含量进行了测定。并应用原子吸收光谱法定量分析了8类18种液体油漆及12种内墙剥脱涂料中可溶性铅的含量。结果发现：所有桌面油漆的铅含量≤0．7mg／cm2，在正常范围内。但是，90年代以前生产的木质桌面表面油漆层中的铅含量明显高于90年代生产产品。液体油漆中铅含量为1．03×10－6～32800×10－6，其中超标者有3种，占16．7％，均为用于金属表面的防锈漆。内墙剥脱涂料中的铅含量为105×10－6～1430×10－6，均在正常范围内。结果提示：①应用便携式XFR检测桌面油漆中的铅含量，是一种快速、实用、准确的方法，非常有利于进行铅源的实地勘查；②除了少数几种工业用防锈漆以外，民用油漆，包括内墙涂料、家具、地板及桌面上用的油漆中的铅含量均未超标。但由于本调查未涉及80年代及更早时期的木质家具，老建筑中使用的油漆的铅污染情况如何，还有待进一步地勘查和研究。     

Adsorption of Eu(III) on titanate nanotubes studied by a combination of batch and EXAFS technique

The effects of pH,contact time and natural organic ligands on radionuclide Eu(Ⅲ) adsorption and mechanism on titanate nanotubes(TNTs) are studied by a combination of batch and extended X-ray absorption fine structure(EXAFS) techniques.Macroscopic measurements show that the adsorption is ionic strength dependent at pH < 6.0,but ionic strength independent at pH > 6.0.The presence of humic acid(HA) /fulvic acid(FA) increases Eu(Ⅲ) adsorption on TNTs at low pH,but reduces Eu(Ⅲ) adsorption at high pH.The results of EXAFS analysis indicate that Eu(Ⅲ) adsorption on TNTs is dominated by outer-sphere surface complexation at pH < 6.0,whereas by inner-sphere surface complexation at pH > 6.0.At pH < 6.0,Eu(Ⅲ) consists of ～ 9 O atoms at REu?O ≈ 2.40  in the first coordination sphere,and a decrease in NEu-O with increasing pH indicates the introduction of more asymmetry in the first sphere of adsorbed Eu(Ⅲ).At long contact time or high pH values,the Eu(Ⅲ) consists of ～2 Eu at REu-Eu ≈ 3.60  and ～ 1 Ti at REu-Ti ≈ 4.40 ,indicating the formation of inner-sphere surface complexation,surface precipitation or surface polymers.Surface adsorbed HA/FA on TNTs modifies the species of adsorbed Eu(Ⅲ) as well as the local atomic structures of adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids.Adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids forms both ligand-bridging ternary surface complexes(Eu-HA/FA-TNTs) as well as surface complexes in which Eu(Ⅲ) remains directly bound to TNT surface hydroxyl groups(i.e.,binary Eu-TNTs or Eu-bridging ternary surface complexes(HA/FA-Eu-TNTs)).The findings in this work are important to describe Eu(Ⅲ) interaction with nanomaterials at molecular level and will help to improve the understanding of Eu(Ⅲ) physicochemical behavior in the natural environment.     

Infrared spectroscopic study of microwave-sintered Pb(Zr,Ti)O<Subscript>3</Subscript>-based ceramics

Infrared spectroscopy is often used to monitor the formation of the perovskite phase during the preparation of lead zirconate titanate (PZT) thin films and fibres and also to detect phase transitions. Infrared spectroscopy has rarely been used to investigate bulk samples or thick films of PZT. In this study, the first results of infrared investigations of microwave-sintered PZT and PZT reinforced with powdered copper are presented and compared with results from thermally heated samples. The infrared spectra show the typical Zr/TiO₆ metal–oxygen octahedral vibrational modes in the range 750 to 450 cm⁻¹. This band is broadened for the pure PZT samples at higher sintering temperatures. A shift of the peak to lower wave numbers with increasing temperatures can be proven for pure PZT samples, but not for the Cu-reinforced PZT samples.     

手控注射式钛酸锶钡多孔球富集器分离富集-火焰原子吸收法测定水中铅和镉

以D311树脂为模板,采用溶胶-凝胶法制备了纳米钛酸锶钡多孔球,用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和傅立叶变换红外光谱仪(FTIR)进行了表征.考察了Pd2+和Cd2+的吸附和解脱条件.将微球装柱,制成注射式富集器,研究了此富集器对水中痕量Pd2+和Cd2+的富集性能.结果表明: 此法合成的多孔球,由钙钛矿结构的纳米钛酸锶钡组成,晶体平均粒径为21 nm,球体表面布满了不规则的纳米孔洞.当pH 4～7时,此多孔球对水中的Pd2+和Cd2+具有很强的吸附能力,静态吸附容量分别为61.9和14.8 mg/g.由多孔球装柱制成的手控注射式富集器,可成功实现对水中Pd2+和Cd2+的同时吸附.用2 mol/L HNO3洗脱后,火焰原子吸收测定.建立了手控注射式纳米钛酸锶钡富集器分离富集、FAAS法测定水中痕量Pd2+和Cd2+的新方法.此方法对Pd2+和Cd2+的检出限分别为0.099和0.0034 μg/L.用于水样中痕量Pd2+和Cd2+的富集和原子吸收测定,回收率分别为97.8%～106.5%和93.0%～100.7%.     

纳米钛酸钙粉体的制备及其对水中铅和镉的吸附行为

采用柠檬酸络合溶胶-凝胶法制备了纳米钛酸钙粉体. 以X射线衍射(XRD)、透射电子显微镜(TEM)和傅立叶变换红外光谱(FTIR)对其进行了表征. 考察了该纳米粉体对水中重金属铅和镉的吸附性能, 并以镉离子为例, 系统地研究了吸附热力学和动力学. 结果表明, 该法合成的钛酸钙为钙钛矿结构的纳米粉体, 粒径大小受灼烧温度的影响, 灼烧温度越高, 粉体平均粒径越大, 600 ℃灼烧2 h条件下, 粉体的平均粒径最小, 约为20 nm. 当介质的pH值为4～8时, 钛酸钙对水中的铅和镉具有很强的吸附能力. 其对镉离子的吸附行为符合Langmuir 吸附等温模型和HO准二级动力学方程式, 吸附过程焓变(ΔH)为39.312 kJ&#8226;mol－1, 各温度下的自由能变(ΔG)均小于零, 熵变(ΔS)均为正值, 吸附过程的活化能(Ea)为20.359 kJ&#8226;mol－1. 该吸附过程是自发的吸热物理过程. 被吸附的铅和镉均可用1 mol&#8226;L－1的硝酸完全洗脱回收. 对铅和镉的富集因子均超过200. 将其应用于水中痕量铅和镉的吸附富集和测定, 回收率分别为96.3%～107.2%和93.5%～104.0%, 与石墨炉原子吸收光谱法测定结果一致.     

醇盐水解法制备钛酸铅微粉的机理研究

采用ＴＧ－ＤＴＡ、ＸＲＤ、ＩＲ等手段研究了醇盐水解法制备的钛酸铅微粉的晶化行为，并用化学分析方法对微粉中可溶铅含量做了研究。结果表明，未昌化微粉中Ｐｂ以无定形ＰｂＴｉＯ３和无定形ＰｂＯ两种形式存在，当热处理温度达到晶化温度区间（４３０￣４７０℃）时，无定形ＰｂＴｉＯ３向结晶型ＰｂＴｉＯ３的转化和无定形ＰｂＯ与ＴｉＯ２间的反应同时发生。     

Determination of Particle Size and Shape during the Hydrolysis of Pb(Zr0.3Ti0.7)O3 Precursor Solutions

The formation and growth of polymeric particles during the hydrolysis and condensation of PbZr_0.3Ti_0.7 O₃ (PZT 30/70) sol-gel precursor solutions have been investigated by using photon correlation spectroscopy (PCS), small angle X-ray scattering (SAXS) and by measuring their rheological properties. The measurements showed that the growth of the particles in the transition of PZT sol to gel followed a simple polymerisation process. Solution A (containing by-products) and Solution B (by-products removed) displayed a similar plot of logarithmic viscosity against logarithmic time, indicating that the particles in both solutions have similar structures after hydrolysis. The changes in viscosity and particle size with time were described by single logarithmic growth models. However, the increasing rate of logarithmic particle size in Solution B is higher than that in Solution A. A model for the form of the aggregates is discussed which is applicable to PZT organometal-particle aggregation process in systems with acetic acid as a modifier.     

(K_(0.485)Na_(0.485)Li_(0.03))NbO_3-Pb(Zr_(0.53)Ti_(0.47))O_3陶瓷的介电铁电性能

采用传统电子陶瓷工艺制备新型钙钛矿体系(1-x)(K_(0.485)Na_(0.485)Li_(0.03))NbO_3-Pb(Zr_(0.53)Ti_(0.47))O_3陶瓷,研究了该体系陶瓷的介电铁电性能.X射线衍射分析表明:所有陶瓷样品都具有单一的钙钛矿结构,在0.65≤x≤0.75时,出现明显的正交相和四方相的准同型相界区.测试结果表明:陶瓷具有高介电常数.低介质损耗,良好的温度稳定性;获得了饱和的电滞回线,显示了优良的铁电性能.尤其在x=0.75时各项性能达到最佳,其中介电常数ε_r=1590,介电损耗tan δ=0.017,居里温度T_c=295℃,剩余极化强度P,=28.6 μC·cm~(-1),矫顽场强E_c=0.89 kV·mm~(-1).     

0-3型PZT/P[VDF(77)-TrFE(23)]铁电复合物的非线性介电系数

用自建的非线性介电测试装置测得了０ － ３ 型ＰＺＴ／Ｐ［ＶＤＦ（７７） － ＴｒＦＥ（２３）］ 铁电复合物厚片在不同场强和温度下的线性和非线性介电系数。对于ＰＺＴ 体积含量Φ＞ ０ ．３ 的复合物,介电系数ε１ 随测试场强的升高显著增大。在Φ＜ ０ ．１ 时,可用Ｍａｘｗｅｌｌ－ Ｇａｒｎｅｔｔ 方程拟合实验结果。Ｂｒｕｇｇｅｍａｎ 方程适合于低电场（ ＜ １ ＭＶ／ｍ ） 下复合物介电系数的预测。随着退极化场系数Ｌｚ 的改变,用Ｙａｍａｄａ 模型可拟合不同场强下复合物介电系数随Φ的变化关系。ε１ 的温度依赖性显示了明显的热滞后效应。Φ值增大导致升温过程的居里温度Ｔｃ 降低。Φ＜ ０ ．３ 时,三阶非线性介电系数ε３ 随测试场强的升高而减小,而Φ＞ ０ ．４ 试样的ε３ 在６ＭＶ／ｍ 场强下出现极小值。高Φ值的复合物具有较大的ε３ 。高ＰＺＴ 含量的复合物在相变区出现较大的ε３值。ε３ 温度谱同样显示了与ε１ 类似的表观热滞后现象。     

Crystallization and Microstructure of (Sm, Pb)TiO3 Thin Films Prepared from Sol-Gel Synthesized Solutions

A sol-gel route is developed for the synthesis of samarium modified lead titanate precursor solutions. The solutions are used for the deposition of thin films. After thermal treatment of the films, two crystalline phases are observed by X-ray diffraction analysis: an undesirable pyrochlore phase and a ferroelectric perovskite. These two phases are clearly distinguished in the film microstructure, showing a fined grained fraction of pyrochlore anda-axis oriented rosette grains of perovskite. The development of these phases as well as the evolution of the perovskite/pyrochlore ratio in the films is related to the chemistry of the synthesized solutions and the thermal treatment used for crystallization.     

Multielement XRF Semimicroanalysis of Pb(Zr,Ti)O3 Type Ferroelectric Ceramic Materials Doped with Pb(Nb,Mn)O3 and Bi2O3 by the Thin Layer Method

A method of wavelength-dispersive XRF analysis of Pb(Zr,Ti)O₃ type ferroelectric ceramics doped with Pb(Nb,Mn)O₃ and Bi₂O₃ is presented. The major elements Pb, Zr, Ti and minor elements Nb, Mn, Bi were determined. Matrix effects were minimized by using the thin layer method. Standards of the same chemical composition but varied masses were prepared to simplify calibration. To minimize errors resulting from inhomogeneity of a mass per unit area, the internal standard was used. Preparation of the sample consisted in digesting 25mg of the materials (with nickel as the internal standard) in sulfuric acid, evaporating to dryness and digesting in nitric acid and hydrogen peroxide, filling up to 25mL, and dropping 0.5mL of the solution onto a substrate. Standard samples were prepared by dropping different amounts of the multielement solution onto the substrate. The residual standard deviation for the reference sample of mass from 0.25mg to 0.7mg was within the range of 0.001–0.009mg (correlation coefficient 0.998–0.999) for major elements and within the range of 0.00003–0.0009mg (correlation coefficient 0.989–0.993) for minor elements. The detection limits for 0.5mg samples were within the range of 0.015%–0.35% for manganese and zirconium, respectively.     

Determination of Possible Olefin Interference in the Analysis of Lead in Gasoline by Atomic Absorption Spectroscopy

Abstract

Atomic absorption spectroscopy has been used to determine the concentration of lead in gasoline. The method employs the use of iodine to “level” the variation in response of different lead alkyls. It has been reported that this method is useless when applied to real gasolines, possibly because of the interference of iodine with olefins in the gasoline. The work performed here shows that olefins do not interfere with the lead analysis even when the concentration of olefins is 254 times that of iodine in the test gasoline.