A Sol-Gel Precursor as a Powder Binder for PZT Ceramic Fabrication

A lead zirconate titanate (PZT) precursor sol was prepared by a diol sol-gel route and used as a binder for assisting the uniaxial die pressing of PZT powders. The powders, of composition Pb(Zr_0.52Ti_0.48) O₃, were prepared by a two step mixed oxide route using lead carbonate, zirconia and titania starting powders. The densification characteristics of the powders, which were not milled after the final calcination step, were compared to samples prepared using PVA as a conventional binder. Improved sintering behaviour was observed for the novel sol-gel binder system. For example, using a sol concentration, equivalent to 7 wt% of PZT derived from the binder, pellets of 95% theoretical density were obtained after firing at 1150°C for 4 h, whereas for the same firing conditions, samples blended with PVA resulted in a density of only 78% theoretical.     

Diagramme de phases du systeme binaire AgNO3—RbNO3

Phase diagram of the binary system AgNO₃—RbNO₃ was studied using thermal analysis technique, differential scanning calorimetry and X-ray diffraction. This binary exhibits a congruently melting compound Ag_0.5Rb_0.5NO₃ (m. p.=138°C), an incongruently melting one Ag_0.33Rb_0.66NO3 with two polymorphic varieties, two eutectics at (36 mol% RbNO₃, 128°C) and at (60 mol% RbNO₃, near 134°C) respectively and a peritectic at (60.5 mol% RbNO₃, 141°C). This system contains also three invariant reactions at 164, 222 and 282°C due to the phase transitions of RbNO₃ and another one at 164°C due to the phase transition of AgNO₃.

Ce travail a été présenté aux 32èmes JCAT, tenues à Hammamet, TN, du 12 au 14 Mai 2001.     

A role of BNLT compound addition on structure and properties of PZT ceramics

In this research, effects of lead-free bismuth sodium lanthanum titanate (BNLT) addition on structure and properties of lead zirconate titanate (PZT) ceramics were investigated. PZT ceramics with addition of 0.1–3.0 wt%BNLT were fabricated by a solid-state mixed oxide method and sintering at 1050–1200 °C for 2 h to obtain dense ceramics with at least 96% of theoretical density. X-ray diffraction indicated that complete solid solution occurred for all compositions. Phase identification showed both tetragonal and rhombohedral perovskite structure of PZT with no BNLT phase detected. Scanning electron micrographs of fractured PZT/BNLT ceramics showed equiaxed grain shape with both transgranular and intergranular fracture modes. Addition of BNLT was also found to reduce densification and effectively limited grain growth of PZT ceramic. Optimum Hv and K_IC values were found to be 4.85 GPa and 1.56 MPa.m^1/2 for PZT/0.5 wt%BNLT sample. Among PZT/BNLT samples, room temperature dielectric constant seemed to be improved with increasing BNLT content. The maximum piezoelectric coefficient values were observed in pure PZT ceramic and were slightly decreased in BNLT-added samples. Small reduction of remanent polarization and coercive field in hysteresis loops was observed in BNLT-added samples, indicating a slightly suppressed ferroelectric interaction in this material system.     

Sol-Gel Synthesis of Nanocrystalline PZT Using a Novel System

A simple system has been developed for the preparation of lead zirconate titanate, Pb(Zr _x Ti_{1 – x} )O₃ powders by sol-gel process. To achieve stable and homogeneous precursor solutions, chelating ligands such as acetic acid and acetylacetone have been used for the chemical modification of titanium and zirconium starting precursors. Phase-pure PZT powders were obtained, through a pyrochlore-free pathway, from the amorphous xerogel after heat treatment at 600°C. The formation of the crystalline phase, compositional homogeneity, sinterability, dielectric and piezoelectric characteristics of PZT are reported.     

The Effect of Precursor Chemistry on the Crystallisation and Densification of Sol-Gel Derived Mullite Gels and Powders

Stoichiometric and silica-rich mullite gels and powders were prepared using four different sol-gel methods. Thermal analysis, X-ray powder diffraction and dilatometry techniques were used to investigate the thermal decomposition, crystallisation and sintering of these mullite precursor gels. The method of preparation, by controlled hydrolysis of various mixtures of tetraethylorthosilicate, aluminium sec-butoxide and aluminium nitrate, affected the texture of the gels, producing single-phase or diphasic samples.The crystallisation sequence of the gels depended on the composition and method of preparation. Single phase mullite crystallised from homogeneous gels at 980°C, while diphasic gels initially formed of a mixture of -Al₂O₃ spinel and mullite, or simple -Al₂O₃ spinel, which subsequently transformed to mullite at 1260°C.Dilatometry and density measurement were used to investigate the sintering of compacts formed by pressing powders prepared from gels precalcined at 500°C. Varying the heating rates from 2 to 10°C min^-1 had little effect on the densification to 1500°C. However, the densification rate was sensitive to the degree of crystallinity and the amount and type of phases present at the sintering temperature. The presence of -Al₂O₃ spinel in the structure initially promoted densification, but the sintering rate was reduced considerably after mullite crystallised. Diphasic materials, especially those with an excess amount of silica in the original gel, sintered to higher densities due to the presence of excess silica promoting densification by viscous phase sintering.     

Raman Spectroscopic Investigations of the Effects of Ag+ and Ce3 + Doping on the Densification of Nanoporous Silica Xerogels

Doped and undoped 50 Å porous silica xerogels were heat-treated at various annealing temperatures ranging from 800°C to 1150°C. The heating was performed in air for 1 hour at each temperature. Raman spectroscopy was used to follow the structural changes occurring at various stages of the gel-to-glass transformation, as well as to investigate the effects of metal ions on the densification of these nanoporous silica xerogels. Raman data and density measurements showed that while densification is completely achieved at 1050°C for undoped xerogels, it occurs at 950°C for Ag⁺-doped samples. On the other hand, Ce^{3 +} doping was found to slow down the densification process, with complete densification occurring at 1100°C.     

Effect of sol-gel preparation method on particle morphology in pure and nanocomposite PZT thin films

Double-scale composite lead zirconate titanate Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films of 360 nm thickness were prepared by a modified composite sol-gel method. PZT films were deposited from both the pure sol and the composite suspension on Pt/Al₂O₃ substrates by the spin-coating method and were sintered at 650°C. The composite suspension formed after ultrasonic mixing of the PZT nanopowder and PZT sol at the powder/sol mass concentration 0.5 g mL⁻¹. PZT nanopowder (≈ 40–70 nm) was prepared using the conventional sol-gel method and calcination at 500°C. Pure PZT sol was prepared by a modified sol-gel method using a propan-1-ol/propane-1,2-diol mixture as a stabilizing solution. X-ray diffraction (XRD) analysis indicated that the thin films possess a single perovskite phase after their sintering at 650°C. The results of scanning electron microscope (SEM), energy-dispersive X-ray (EDX), atomic force microscopy (AFM), and transmission electron microscopy (TEM) analyses confirmed that the roughness of double-scale composite PZT films (≈ 17 nm) was significantly lower than that of PZT films prepared from pure sol (≈ 40 nm). The composite film consisted of nanosized PZT powder uniformly dispersed in the PZT matrix. In the surface micrograph of the film derived from sol, large round perovskite particles (≈ 100 nm) composed of small spherical individual nanoparticles (≈ 60 nm) were observed. The composite PZT film had a higher crystallinity degree and smoother surface morphology with necklace clusters of nanopowder particles in the sol-gel matrix compared to the pure PZT film. Microstructure of the composite PZT film can be characterized by a bimodal particle size distribution containing spherical perovskite particles from added PZT nanopowder and round perovskite particles from the sol-matrix, (≈ 30–50 nm and ≈ 100–120 nm), respectively. Effect of the PZT film preparation method on the morphology of pure and composite PZT thin films deposited on Pt/Al₂O₃ substrates was evaluated.     

Die Schmelzdiagramme der Systeme CsN3/Zn(N3)2 und KN3/Zn(N3)2

The phase diagrams of the systems CsN₃/Zn(N₃)₂ and KN₃/Zn(N₃)₂ have been obtained employing the microscopic technique ofL. Kofler andA. Kofler. Within the system CsN₃/Zn(N₃)₂ three eutectics at 148°C, 142°C, and 210°C were found. Besides Cs₂Zn(N₃)₄, melting incongruently in the interval 153°C to 170°C, there exist two further compounds of the most probable composition Cs₃Zn₂(N₃)₇ and CsZn₂(N₃)₅, melting congruently at 170°C and 210°C, resp. In the system KN₃/Zn(N₃)₂ there exist two eutectics at 203°C and 172°C and two compounds, one of them, i.e. K₂Zn(N₃)₄, melting congruently at 206°C, the other one, with composition KZn₃(N₃)₇ or KZn₄(N₃)₉, melting incongruently at 210°C.

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Herrn Professor Dr.Heribert Grubitsch zum 70. Geburtstag gewidmet.     

Quecksilber—Halogensysteme, 3. Mitt.: Das System Hg2J2−Hg2Cl2

The Hg₂I₂–Hg₂Cl₂ phase diagram was constructed by using X-ray and thermal analyses. At room temperature a miscibility gap in the solid state extends from 14 to 89 mole% Hg₂Cl₂ which closes at 212°C. Above 212°C there is a range of complete solid solubility followed at higher temperatures by a three phase region with a minimum in the solidus and liquidus curves at 10 mole% Hg₂Cl₂ and 216°C. A miscibility gap in the liquid state has a critical temperature of 287°C for pure Hg₂I₂ which increases strongly on addition of Hg₂Cl₂.

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Mit 3 Abbildungen     

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.     

Microstructure and properties of sol-gel derived Pb(Zr<Subscript>0.3</Subscript>Ti<Subscript>0.7</Subscript>)O<Subscript>3</Subscript> thin films on GaN/sapphire for nanoelectromechanical systems

Highly (111) oriented, phase-pure perovskite Pb(Zr_0.3Ti_0.7)O₃ (or PZT 30/70) thin films were deposited on single-crystal, (0001) wurtzite GaN/sapphire substrates using the sol-gel process and rapid thermal annealing. The phase, crystallinity, and stoichiometry of annealed PZT films were evaluated by X-ray diffraction and Rutherford backscattering spectroscopy. The atomic force microscopy revealed a smooth PZT surface (rms roughness ∼1.5 nm) with striations and undulations possibly influenced by the nature of the underlying GaN surface. The cross-sectional field-emission scanning electron microscopic images indicated a sharper PZT/GaN interface compared to that of sol-gel derived PZT on (111) Pt/TiO₂/SiO₂/(100) Si substrates. The capacitance-voltage (C-V) characteristics for PZT in the Pt/PZT/GaN (metal-ferroelectric-semiconductor or MFS) configuration were evaluated as a function of annealing temperature and applied voltage. The observed C-V hysteresis stemmed from trapped charge at defect sites within PZT. Also, the lower capacitance density (C/A = 0.35 μF/cm², where A is the area of an electrode) and remnant polarization (P _r ∼ 4 μC/cm²) for PZT in the MFS configuration, compared to the values for PZT in the MFM configuration (Pt/PZT/Pt), were attributed to the high depolarization field within PZT.     

Orientation and Surface Properties of Sol-Gel Derived Y2O3 Films

The orientation, surface and optical properties of sol-gel derived Y₂O₃ films have been investigated. Transparent Y₂O₃ films were prepared on quartz glass substrates by sol-gel processes using YCl₃·6H₂O as a starting material. The water droplet contact angles of the films reached constant values between 79° and 90° after the films were left for 8 to 10 days in air at ambient temperature, indicating that the film surface exhibited hydrophobicity. When 2-(2-methoxyethoxy)ethanol (MEE) was added to the sol, yttria in the films crystallized to a strongly oriented cubic phase at firing temperatures between 400°C and 500°C. The intensity of the XRD peaks increased as the firing temperature was increased to 900°C. However, yttria crystallized to a non-oriented cubic phase when MEE was not used. The refractive index and packing density of the Y₂O₃ films increased from 1.55 to 1.68 and from 0.67 to 0.79, respectively, as the firing temperature was raised from 400°C to 900°C, indicating that sol-gel derived Y₂O₃ films are lower in density than evaporated ones.     

Er3+/Yb3+ Co-Activated Silica-Alumina Monolithic Xerogels

Monolithic silica xerogels doped with different concentrations of Er³⁺, Yb³⁺ and Al³⁺ were prepared by sol-gel route. Densification was achieved by thermal treatment in air at 950°C for 120 h with a heating rate of 0.1°C/min. We studied the luminescence properties of the ⁴I_13/2 ⁴I_15/2 emission band of Er³⁺ as a function of the Al/Er/Yb concentration and we paid particular attention to the alumina effects. Raman spectroscopy and Vis-NIR absorption were used to monitor the degree of densification of the glasses and the residual OH content.     

Preparation and Optical Characterization of Sol-Gel Deposited Pb(Zr0.45Ti0.55)O3 Films

Homogeneous crack-free lead zirconate titanate (Pb(Zr_0.45Ti_0.55)O₃: PZT 45/55) films were prepared by a chemically modified sol-gel process using lead acetate trihydrate, zirconium n-propoxide, and titanium isopropoxide precursors. The coating solutions were modified by the addition of diethanolamine. Single and multilayer films were deposited with a 2000 rpm spin rate on fused silica and MgO(100) substrates. Multiple spin coating with an intermediate heat treatment in air at 400°C for 3 min between coatings was performed to obtain films up to 2 m in thickness. The formation of the tetragonal perovskite structure was found to depend on the intermediate firing temperature, final annealing temperature, and annealing time. A 650°C rapid thermal annealing treatment in oxygen was required to crystallize the PZT film into the perovskite structure. The films were characterized using optical spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and thermo-gravimetry and differential scanning calorimetry (TG-DSC). The optical constants of the PZT films were evaluated from spectral transmittance and reflectance measurements. Optical constants are presented over the visible and near infrared region.     

Phase,crystal struture and sintering behavior of shock-synthesized Pb(Zr0.95Ti0.05)O3 powders

With a cylindrical shock-wave-loading technique, the single perovskite-phase Pb(Zr_0.95Ti_0.05)O₃ powders (PZT 95/5) were synthesized by shock-induced chemical reactions in heterogeneous multi-material powder mixtures of Pb₃O₄, ZrO₂ and TiO₂. The phase and crystal structure of as-synthesized powders were characterized by X-ray diffraction (XRD) and fourier transform infrared (FT-IR) analysis. And the microstructure and electrical properties of PZT 95/5 ceramics prepared with as-synthesized PZT powders at different sintering temperature were analyzed. The results showed that the shock-wave-induced a large quantity of lattice defects and distortion of the crystal structure in the shock-synthesized PZT powders, which could enhance the sintering activity. Thus, the optimal density and electrical properties of PZT ceramics prepared with as-synthesized powders could be obtained at a sintering temperature of 1200–1225 °C for 3 h, significantly lower than the sintering temperature of PZT 95/5 ceramics prepared by conventional solid-state reaction.     

Preparation of PZT Thick Films by an Interfacial Polymerization Method

Pb(Zr_0.53Ti_0.47)O₃ (PZT) films of 10 to 50 m in thickness were prepared by a new sol-gel process using an interfacial polymerization technique. The interfacial polymerization process is that an alkoxide precursor solution is poured on the surface of water in a container to form a gel film at the interface between the two immiscible liquids. The precursor solution was prepared by adding PZT alkoxide solution, PZT powders coated with Pb₅Ge₃O₁₁ (PG), and a surfactant into hexane solvent. After the polymerization at the interface, the gel films were gently placed on a silicon substrate by draining the water in the container. The gel films containing PZT powders were sintered at 950°C for 10 min to obtain crystallized PZT films. The remanent polarization of a PZT thick film was 33.1 C/cm². The piezoelectric d ₃₃ constant measured with a Mach-Zehnder interferometer was 225 pm/V and was independent of frequency from 0.2 to 3 kHz.     

Effect of Metallic Oxides Containing Composite Electrodes on Crystallization and Ferroelectric Properties of Pb(Zr0.52,Ti0.48)O3 Thin Films Deposited by the Sol-Gel Method

In order to suppress polarization fatigue and decrease the leakage current of the PZT capacitor, composite electrodes consisting of MO₂ (RuO_x or IrO_x) as an effective diffusion barrier and considerably large amounts of Pt were deposited by magnetron co-sputtering to yield heterostructured PZT capacitors, Pt/(Pt+MO₂)//PZT(52/48)//(Pt+MO₂)/(Pt+M)/M/Pt/Ti(Ta)/SiO₂/Si(1 0 0), and the crystallinity and the orientation, the morphology of the surface and the cross section, and the composition depth profile of the PZT capacitor were examined by XRD analysis, SEM and AES, respectively, and the ferroelectric properties were measured. The results indicated that by adjusting the distribution and composition of the RuO₂ phase, the polarization loss of the PZT capacitor can be suppressed to as small as 5% after polarization reversals of 10⁹ while maintaining the effective polarization dP_r = P_r* – P_r ^{^} at 15 C/cm². The suppression of the polarization fatigue was found more effective with (Pt+IrO₂) electroding than (Pt+RuO₂) electroding. The leakage current of the PZT capacitor electroded with (Pt+MO₂) was a little larger than that of the PZT capacitor with Pt electrode. The possible reason was suggested.     

X-Ray Absorption and Diffraction Studies of Pr3+, Tb3+ and Er3+-Activated Silica Gels

Rare-earth (Pr³⁺, Tb³⁺, Er³⁺) doped silica xerogels were studied by x-ray absorption spectroscopy and x-ray diffraction. A change of the local environment around rare-earth ions upon xerogel densification at 900–950°C and co-doping with aluminum ions was determined from the rare-earths L₃-edge EXAFS signals. The densification process induces a decrease of the coordination number and a compression and deformation of the first coordination shell, composed of oxygen atoms. The second coordination shell, composed of silicon and/or aluminum ions, also experiences some modification, which is attributed mainly to a shortening of the shell radius. No evidence of clustering of rare-earth ions upon densification was observed. X-ray diffraction data on Tb-doped gels confirm the EXAFS results.     

Synthesis of nanospherical Fe3BO6 anode material for lithium-ion battery by the rheological phase reaction method

This paper developed a novel method, the rheological phase reaction method, to synthesize nanospherical Fe₃BO₆. The sizes and morphologies of products vary with the calcination temperatures. Spherical particles with a uniform size about 40 nm in a monodisperse state were obtained at 800 °C, while the spherical particles with a larger size of 100-500 nm were obtained at 900 °C. The electrochemical properties of these Fe₃BO₆ nanospheres were investigated. Sample synthesized at 800 °C delivers a high reversible capacity above 500 mAh g⁻¹. Sample synthesized at 900 °C possesses relatively good cycleability with a capacity retaining of 376 mAh g⁻¹ after 10 cycles. The measurement of electrochemical impedance spectra for the first time indicated that smaller Fe₃BO₆ nanoparticles intend to give higher impedance of solid-electrolyte interface layer and lower charge-transfer impedance after the first discharge. Additionally, it can be speculated that the increase of resistance charge-transfer is the possible reason for the capacity fading during cycling.     

A study of the reactivity of elemental Cr/Se/Te thin multilayers using X-ray reflectometry, in situ X-ray diffraction and X-ray absorption spectroscopy

The reactivity of [Cr/Se/Te] multilayers under annealing was investigated using X-ray reflectometry, in situ X-ray diffraction, X-ray absorption fine structure (XAFS) measurements and transmission electron microscopy. For all samples, interdiffusion was complete at temperatures between 100 and 300 °C, depending on the repeating tri-layer thickness. A crystalline phase nucleated approximately 20 °C above the temperature where interdiffusion was finished. The first crystalline phase in a binary Cr/Te sample was layered CrTe₃ nucleating at 230 °C. In ternary samples (Se:Te=0.6-1.2), the low-temperature nucleation of such a layered CrQ₃ (Q=Se, Te) phase is suppressed and instead the phase Cr₂Q₃ nucleates first. Interestingly, this phase decomposes around 500 °C into layered CrQ₃. In contrast, binary Cr/Se samples form stable amorphous alloys after interdiffusion and Cr₃Se₄ nucleates around 500 °C as the only crystalline phase. Evaluation of the XAFS data of annealed samples yield Se-Cr distances of 2.568(1) and 2.552(1) Å for Cr₂Q₃ and CrQ₃, respectively. In the latter sample, higher coordination shells around Se are seen accounting for the Se-Te contacts in the structure.