Effects of microwave heating on dielectric and piezoelectric properties of PZT ceramic tapes

Commercial lead zirconate titanate (PZT) perovskite powders were used to fabricate ceramic tape and then sintered by microwave and conventional methods. Both dielectric and piezoelectric properties of PZT ceramic tapes were studied in terms of sintering process. X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) show the PZT perovskite phase with smaller grain size and dense microstructure can be obtained at a lower sintering temperature by microwave process. It was also observed that shrinkage ratio and bulk density of the tapes sintered at 800 °C were obtained about 19% and 7.46 g/cm³ by the microwave heating method, respectively, that is corresponding to those values of sintered PZT tapes at 950 °C by conventional process. Moreover, the dielectric constant and maximum permittivity are increased about 30% as compared with conventional processing method. The experimental results demonstrated that the characteristics of the PZT tapes could be significantly improved by microwave heating method. These results demonstrate that such a simple approach can upswing the piezoelectric and dielectric properties of these tapes by using microwave process with a short heating time.     

Al2O3/Y-TZP and Y-TZP materials fabricated by stacking layers obtained by aqueous tape casting

A processing method for production of multilayer ceramics by laminating stacked green ceramic tapes with help of adhesive layer and pressing at room temperature was extended. Ceramic tapes with two compositions within the system alumina/yttria stabilized zirconia (Y-TZP) (alumina–40 vol.% Y-TZP and 100 vol.% Y-TZP), obtained from aqueous ceramic slurries by tape casting procedure were employed in this work. The optimum conditions to fabricate pieces made of six tapes with same composition, and to obtain defect free sintered materials, by varying the level of pressure applied, was investigated. For this purpose, previously selected composition of adhesive layer and type of pre-treatment of tapes were used.The analysis of engineering stress–apparent strain curves recorded during the lamination process was done to control the formation of cracks within the pieces under pressure. Optimization of the pressure range was performed by the analysis of the green density change as a function of pressure. The cross section observation by optical and scanning electron microscopy of sintered ceramic pieces was carried out to assure the control of the process. Fabricated pieces were subjected to testing by Impulse Excitation Technique (IET) and Vickers indentation in order to evaluate the adequacy of the fabrication procedure and to analyse the possible effects of interfaces. Dense pieces with maximum sizes of the defects of the same level as those of the microstructural ones and without interface effects on the elastic and mechanical behaviour were obtained.     

High piezoelectric properties of BaTiO3-xLiF ceramics sintered at low temperatures

BaTiO₃-xLiF ceramics were prepared by a conventional sintering method using BaTiO₃ powder about 100 nm in diameter. The effects of LiF content (x) and sintering temperature on density, crystalline structure and electrical properties were investigated. A phase transition from tetragonal to orthorhombic symmetry appeared as sintering temperatures were raised from 1100 °C to 1200 °C or as LiF was added from 0 mol% to 3 mol%. BaTiO₃-6 mol% LiF ceramic sintered at 1000 °C exhibited a high relative density of 95.5%, which was comparable to that for pure BaTiO₃ sintered at 1250 °C. BaTiO₃-4 mol% LiF ceramic sintered at 1100 °C exhibited excellent properties with a piezoelectric constant d₃₃ = 270 pC/N and a planar electromechanical coupling coefficient k_p = 45%, because it is close to the phase transition point in addition to high density.     

Effect of nano-sized PbO on the transport critical current density of (Bi1.6Pb0.4Sr2Ca2Cu3O10)/Ag tapes

The effect of nano-sized PbO (10–30 nm) addition on the transport critical current density, J_c of (Bi_1.6Pb_0.4)Sr₂Ca₂Cu₃O₁₀ (PbO)_x (x=0–0.15 wt%) was investigated. J_c of PbO added pellet samples showed the maximal value at x=0.05 wt%. Using this result, Ag-sheathed (Bi_1.6Pb_0.4)Sr₂Ca₂Cu₃O₁₀ (PbO)_x/Ag tapes (x=0 and 0.05 wt %) were fabricated by the powder-in-tube (PIT) method. The tapes were sintered for 50 h and 100 h at 845 °C. The temperature dependence of J_c for the non-added and PbO added tapes in applied field was investigated. J_c of the non-added tapes was 4510 A/cm² at 40 K and 949 A/cm² at 77 K. J_c of (Bi_1.6Pb_0.4)Sr₂Ca₂Cu₃O₁₀ (PbO)_0.05/Ag tape sintered for 100 h was 26,800 A/cm² at 40 K and 10,700 A/cm² at 40 K, which was higher than the tapes sintered for 50 h (8590 A/cm² at 40 K and 1880 A/cm² at 77 K). Nano-sized PbO added tapes sintered for 100 h showed a higher J_c (more than 10 times) under magnetic field (0–0.75 T) compared with the non-added tape. A combined effect of enhanced flux pinning and improved microstructure led to the significant increase in J_c of the nano-sized PbO added tapes.     

Fabrication and characterization of Li1+x−yNb1−x−3yTix+4yO3 substrates using aqueous tape casting process

An aqueous system for tape casting Li_1+x−yNb_1−x−3yTi_x+4yO₃ (LNT) ceramics was developed using poly(vinyl alcohol) (PVA) binder, ethylene alcohol (EG) plasticizer and ammonium salt of polycarboxylate (PCA-NH₄) dispersant. The zeta potential measurement showed that the isoelectric point of the LNT particles moved slightly toward more acid region after the dispersant absorbed on the particles, while the zeta potential increased significantly. The rheological test indicated that the ceramic slurry exhibited a typical pseudoplastic behavior without thixotropy. The effect of solid loading on the properties of the green tapes was investigated. The increase in the solid loading increased the tensile strength and the green density of the tapes. TGA analysis indicated that the organic additives in the green tapes can be completely removed by heat treatment at 600 °C. SEM micrographs showed that the microstructure of the green and sintered tapes was homogeneous.     

Fabrication and electrical properties of Pb(Co1/3Nb2/3)O3 ceramics

Pb(Co_1/3Nb_2/3)O₃ (PCN) ceramics have been produced by sintering PCN powders synthesized from lead oxide (PbO) and cobalt niobate (CoNb₂O₆) with an effective method developed for minimizing the level of PbO loss during sintering. Attention has been focused on relationships between sintering conditions, phase formation, density, microstructural development, dielectric and ferroelectric properties of the sintered ceramics. From X-ray diffraction analysis, the optimum sintering temperature for the high purity PCN phase was found at approximately 1050 and 1100 °C. The densities of sintered PCN ceramics increased with increasing sintering temperature. However, it is also observed that at very high temperature the density began to decrease. PCN ceramic sintered at 1050 °C has small grain size with variation in grain shape. There is insignificant change of dielectric properties with sintering temperature. The P–E hysteresis loops observed at −70 °C are of slim-loop type with small remanent polarization values, which confirmed relaxor ferroelectric behavior of PCN ceramics.     

Yttria-stabilized zirconia closed end tubes prepared by electrophoretic deposition

The electrophoretic deposition technique was used for the preparation of ZrO₂:8 mol% Y₂O₃ (yttria-stabilized zirconia, 8YSZ) closed end tubes for application in high temperature oxygen sensing devices. The 8YSZ ceramic suspensions with different average particle sizes were investigated looking for the best conditions for electrophoretic deposition of thin wall closed end ceramic tubes. High deposition rate of the ceramic particles onto graphite were obtained with isopropanol as solvent and 4-hydroxybenzoic acid as dispersant, with good surface quality of the deposited layer. The green tubes were dried and sintered at 1500 °C, and their properties were analyzed by X-ray diffraction for determination of the structural phases, scanning probe microscopy for observation of grain morphology, and impedance spectroscopy for evaluation of the oxide ion electrical resistivity. Pt/YSZ tube/Pt electrochemical cells were assembled for exposure to oxygen in the 60-650 ppm range using an electrochemical YSZ oxygen pump and sensor system. The signal response of the electrophoretic deposited sensor was similar to the response of the sensor of the oxygen pump. Several thin wall 4 mm diameter × 30 mm length closed end tubes may be obtained in a single operation, showing the ability of this technique for processing large quantities of tubular solid electrolytes with electrical properties suitable for use in high temperature devices.     

Fabrication of transparent neodymium-doped yttrium aluminum garnet ceramics by high solid loading suspensions

Dense neodymium-doped yttrium aluminum garnet (Nd:YAG) transparent ceramic was obtained by slip casting and solid-state reaction. The colloidal behavior of the aqueous suspensions of neodymia, yttria, and alumina mixed powders using Dispex A as dispersant was investigated. The variation in zeta potential due to pH alteration was studied. The isoelectric point (IEP) was at pH 4.5 and 4 for the specimens with and without Dispex A, respectively. The optimal dispersion conditions were achieved for the suspensions at pH 9.6 with 0.4 wt% Dispex A. The green body prepared by slip casting was vacuum sintered from 1200 °C to 1750 °C. The grain size of the sintered body increased, and the pore size decreased with increasing sintering temperature. Pore-free Nd:YAG transparent ceramic with a grain size of 5–10 μm was obtained by sintering at 1750 °C for 10 h. The in-line transmittance of the annealed specimen reached 80.8% at 1064 nm.     

Yttria stabilized zirconia formed by micro ceramic injection molding: Rheological properties and debinding effects on the sintered part

Micro Ceramic Injection Molding (μCIM) is a near net-shape process to produce smaller and intricate parts at a competitive cost. The application of nano-sized ceramic powder in μCIM has the advantages of fine grain size growth and good surface finish. However, the nano size effect causes agglomeration and low powder loadings, which result in defects during the μCIM process and in the sintered components. This study extensively investigated the debinding and sintering of yttria-stabilized zirconia (YSZ), as well as its rheological properties, using polypropylene (PP) as the primary binder and palm stearin as the secondary binder. 50 nm Yttria stabilized zirconia (YSZ) powders were mixed with palm stearin and PP at a powder loading of 37–43 vol%. The results of rheological studies showed that the feedstock had a dilatant flow characteristic and a viscosity of around 10–40 Pa s. Feedstock with 38 vol% powder loading had the lowest activation energy of 9.48 kJ/mol. The green part of the injected feedstock had flexural strength ranging from 13 to16 MPa, within which the feedstock with 43 vol% powder loading had the highest green density. Solvent debinding was carried out at three temperatures (50, 60, and 70 °C) using heptane. A large porous region was clearly identified at 70 °C compared with 50 °C. A debinding split furnace with argon gas was used to remove PP at 450 °C for 4 h. The debound samples did not shrink when 94%–98% of the binder system was removed. All debound samples sintered at 1350 °C and 41 vol% had the highest mechanical properties with hardness of 900 HV and a flexural strength of 400 MPa.     

Suspension stability and sintering influence on yttria-stabilized zirconia fabricated by colloidal processing

The stability of nano-zirconia 3YSZ powder in suspension was extensively studied by the colloidal method, and the optimum sintering temperature of the green sample fabricated through slip casting was determined. Zirconia suspensions with 10 vol% powder loading were prepared with distilled water, and HNO₃ was used to adjust the pH of the suspension to pH 1–6. All of the suspensions were subjected to sedimentation test, and the results showed that the suspensions adjusted to pH 2 had the lowest sediment volume. This finding indicates that a suspension with pH 2 produces higher packing density. Viscosity test was carried out for the suspensions added with dispersant ranging from 0.3 wt% to 0.7 wt% polyethyleneimine (PEI) with and without pH adjustment. The suspension containing 0.5 wt% PEI with pH 2 adjustment produced the lowest viscosity because of interparticle bond breakage in the aggregates, thus forming colloidally stable suspensions. The zirconia suspension containing 0.5 wt% PEI and whose pH was adjusted to pH 2 was chosen to be slip casted into cylindrical shape. Green samples were sintered at various sintering temperatures that ranged from 1100 °C to 1500 °C through a two-step sintering method. The sample sintered at 1500 °C was found to be porosite-free, and its highest relative density was 99.6% of the theoretical density. Morphological studies detected pores in the microstructure of the samples sintered at low sintering temperatures (1100 and 1200 °C). By contrast, the samples sintered at 1400 and 1500 °C were fully densified. However, the grain size of the sample sintered at 1500 °C was 230 nm, which indicated excessive grain growth. The Vickers hardness of the sample sintered at 1400 °C was found to be highest (12.9 GPa) and comparable to results found in the literature.     

Preparation of boron carbide–aluminum composites by non-aqueous gelcasting

Gelcasting is an attractive forming process to fabricate ceramic parts with near-net-shape. In the present work, non-aqueous gelcasting of boron carbide (B₄C)–aluminum (Al) composites was studied. A stable B₄C–Al slurry with solids loading up to 55 vol.% for gelcasting was prepared. The slurry was solidified in situ to green body with the mean value of relative density of 64% and flexural strength of 21 MPa. The SEM images showed that powders in green body compact closely by the connection of polymer networks. B₄C–Al samples were also obtained by the process of gelcasting and sintering at 1300 °C for 1 h in 0.1 MPa Ar atmosphere. The average bulk density of sintered body was 2.05 g cm⁻³.     

Two-step sintering of fine alumina–zirconia ceramics

This work investigates the feasibility to the fabrication of high density of fine alumina–5 wt.% zirconia ceramics by two-step sintering process. First step is carried out by constant-heating-rate (CHR) sintering in order to obtain an initial high density and a second step is held at a lower temperature by isothermal sintering aiming to increase the density without obvious grain growth. Experiments are conducted to determine the appropriate temperatures for each step. The temperature range between 1400 and 1450 °C is effective for the first step sintering (T₁) due to its highest densification rate. The isothermal sintering is then carried out at 1350–1400 °C (T₂) for various hours in order to avoid the surface diffusion and improve the density at the same time. The content of zirconia provides a pinning effect to the grain growth of alumina. A high ceramic density over 99% with small alumina size controlled in submicron level (0.62–0.88 μm) is achieved.     

Microstructure evaluation of sintered combustion-derived fine powder NiO–YSZ

Citrate–nitrate combustion synthesis was used for the preparation of NiO–YSZ. The main advantage of the preparation method used was reflected in the fact that after the synthesis both phases NiO and YSZ were randomly distributed on a nanometre level. The prepared NiO–YSZ powder composites were shaped, sintered and reduced to Ni–YSZ and subsequently submitted to microstructure investigations. Relative sintered densities higher than 90% were obtained at sintering temperatures as low as 1200 °C. A sintering temperature 1200 °C was also recognized as the preparation temperature that provided the smallest Ni grains in the final Ni–YSZ cermet with an average Ni-particle diameter as low as 0.27 μm.     

Direct coagulation casting of YSZ powder suspensions using MgO as coagulating agent

Direct coagulation casting (DCC) of aqueous 8 wt% yttria stabilized zirconia (YSZ) powder suspensions prepared using ammonium poly(acrylate) dispersant has been studied using MgO as coagulating agent. Small amount (<0.1 wt% based on YSZ) of MgO powder dispersed in the YSZ powder suspension at ∼5 °C set the suspension in to stiff wet-coagulated body when exposed to room temperature (30 °C) due to the reaction between ammonium poly(acrylate) and MgO. MgO concentration equivalent to react with dispersant did not coagulate the YSZ powder suspension though it precipitate the whole ammonium poly(acrylate) dispersant as Mg-poly(acrylate). This is because of the ability of the YSZ powder to disperse in water at alkaline pH (∼9.5) without any dispersant by electrostatic mechanism. The YSZ powder suspensions form stiff coagulated bodies at MgO concentration double or more of the equivalent amount required for reacting with the dispersant. Setting of the YSZ powder suspension is due to the heterocoagulation of the YSZ particles and MgO particles added in excess of the equivalent amount to react with the dispersant, having opposite surface charges. The wet-coagulated body showed relatively high compressive yield strength (155 kPa) and Young’s modulus (3.1 MPa). The green bodies prepared by humidity controlled drying of the wet-coagulated bodies sintered to >98% TD at 1550 °C.     

Rheology of aqueous mullite-starch suspensions

One of the forming methods developed for the manufacture of porous materials by direct consolidation, in which a ceramic suspension consolidates into non-porous molds (e.g. metal molds) by thermogelation of an organic agent, uses starch as both consolidator/binder of the ceramic suspension and pore former at high temperature. Changes in the rheological behavior of the aqueous suspensions are produced by starch gelatinization thermal process. This process as well as the presence of both the ceramic particles and added processing additives, influences the kinetics of green ceramic body formation and its microstructural features.In this work, the thermogelling behavior of mullite aqueous suspensions (40 vol.%; 0.45 wt.% of a polyacrylic polyelectrolyte as dispersant) containing 10 vol.% of different native starches (potato, cassava, and corn) was studied by dynamic rheology in order to determine the experimental conditions that must be used for forming mullite green bodies by thermal consolidation. Viscoelastic properties (G′ and G″) as a function of temperature (30-95 °C) and deformation (0.1-625.0% at 40 °C) were determined by temperature sweep tests and dynamic strain sweep tests, respectively. From these tests, and considering previous results of the rheological behavior of starch suspensions, we analyzed the influence of ceramic particles on the starch gelatinization process and the strength of the developed gels. On the other hand, shear flow properties of aqueous mullite-starch suspensions were also analyzed to obtain information on the rheological behavior of the suspensions at room temperature.     

Processing and properties of ZrB2-SiC composites obtained by aqueous tape casting and hot pressing

ZrB₂-SiC composites with different SiC content were prepared through aqueous tape casting and hot pressing. The influences of dispersant, SiC content and binder content on the rheological properties of slurries were investigated and the conditions for preparing stable ZrB₂-SiC suspensions were optimized. After tape casting and drying, the green ZrB₂-SiC tapes showed good flexibility, lubricious surface and homogeneous microstructure. The ZrB₂ ceramics could be densified to 97.2% after hot-pressing, while the ZrB₂ containing 20 and 30 vol% SiC ceramics were nearly fully densified (>99%). The sintered ZrB₂-20 vol% SiC ceramic had improved mechanical properties compared with ZrB₂ ceramic. Further increase in SiC content resulted in lower flexural strength and fracture toughness. SEM and TEM showed a fine microstructure with a clear grain boundary. The fracture mode changed from intragranular type for ZrB₂ to both intragranular and intergranular type for ZrB₂-SiC composites.     

High-pressure sintered yttria stabilized zirconia ceramics

Fast densification of 8YSZ ceramics under a high pressure of 4.5 GPa was carried out at different temperatures (800, 1000, 1450 °C), by which a high relative density above 92% could be obtained. FT-Raman spectra indicate that the 8YSZ underwent a phase transition from partially tetragonal to partially cubic phase as temperatures increase from 1000 to 1450 °C when sintering under high pressure. The electrical properties of the samples under different high-pressure sintering conditions were measured by complex impedance method. The total conductivity of 0.92 × 10⁻² S cm⁻¹ at 800 °C has been obtained for 8YSZ under high pressure at 1450 °C, which is about 200 °C lower than that of the samples prepared by conventional pressureless sintering.     

Synthesis of nanocrystalline 8 mol% yttria stabilized zirconia by the oleate complex route

Nanocrystalline 8 mol% yttria stabilized zirconia (YSZ) powder has been synthesized by the oleate complex route. Oleate complexes of zirconium and yttrium were formed in the hexane rich layer by the reaction of sodium oleate with zirconyl chloride and yttrium chloride at the interface of the two ternary solutions in water–ethanol–hexane system. The zirconyl oletae and yttrium oleate complexes on heating decomposed to oxide through the formation of carbonate intermediates. The powder obtained by calcination at 600 °C for 2 h was cubic YSZ with surface area of 42 m²/g. The YSZ powder contained primary particles of ∼300 nm size and the primary particles were aggregate of crystallites of 5–10 nm. The compacts prepared from the YSZ powder were sintered to ∼99% TD (theoretical density) at 1400 °C. The sintered YSZ had a low average grain size of 0.73 μm.     

Improved Compaction in Multilayer Capacitor Fabrication

The most common defects found in multi-layer ceramic capacitors are derived from residual porosity formed when solvents and binders are released from a ceramic green body. Without a well-controlled compaction technique, defects between sheets in the stacked body are often present, leading to lamination problems. This paper suggests alternative approaches, using compaction applied before and/or after the process of binder burnout with the intention of reducing the number of stacking-generated defects and the volume of voids formed after binder burn-out. Barium titanate tapes and stacked multilayer electroded discs have been investigated and characterised by microstructural examination and density measurement. The resulting properties are described, and the behaviour of the multi-layers discussed in terms of the microstructure and processing procedures. It is shown that the porosity content of sintered samples compacted at 300 MPa is approximately half that of samples compacted at 30 MPa when both are sintered at 1300°C for 2 h. A further improvement of densification can be achieved by a postcompaction treatment after binder burn out.     

Cold chemical lamination of ceramic green tapes

The cold chemical lamination (CCL) is a new technique of bonding ceramic green tapes into one 3D structure. Instead of a standard thermo-compression method, new solvent-based lamination is presented. A film of a special chemical agent is put on the green tape surface. The solvent melts the surface. Then the tapes are stacked. The bonding of the green tapes is made at a room temperature. The new method is used for joining green tapes of the low temperature co-fired ceramics (LTCC). A quality of the bonding depends on the solvent type. The cold chemical lamination is examined on two types of the LTCC tapes: DuPont 943 and DuPont 951. Six types of the solvents are analyzed in the paper. The bonding quality and geometry of the test structures are examined. The lamination quality is investigated by the scanning electron microscope.