Effect of composition and grain size on dielectric,ferroelectric and induced strain behavior of PLZT/ZrO2 composites

Lead lanthanum zirconate titanate ceramics (PLZT) are well known for their excellent dielectric, piezoelectric and ferroelectric properties. In this study, PLZT 9/70/30, 9/65/35 and 9/60/40 ceramics were prepared by vibro-milling mixed-oxide method. All compositions of powders were uniaxial pressed in pellets and sintered at the temperatures of 1200–1275 °C with various soaking times of 2, 4 and 6 h. The X-ray diffraction (XRD) patterns confirmed that all the PLZT samples had perovskite structure with ZrO₂ as a second phase and PLZT/ZrO₂ composite structure was formed. Dielectric behavior at the frequency of 1 kHz showed broad peak indicating relaxor ferroelectric behavior and the difference of the temperature at maximum dielectric at different frequencies increased when Zr:Ti ratio increased. Polarization with electric field (P-E loop) at room temperature showed that when Zr:Ti ratio increased, the coercive field decreased resulting from crystal structure change from tetragonal to rhombohedral. Induced strain with electric field depended on microstructure where the value of S_max/E_max tended to decrease with increasing grain size. It can be concluded that dielectric and ferroelectric behavior predominantly depended on composition of PLZT ceramics and induced strain behavior predominantly depended on grain size of PLZT ceramics.     

Effects of Preparation Conditions on the Structural and Optical Properties of Spark Plasma-Sintered PLZT (8/65/35) Ceramics

Transparent lanthanum-doped lead zirconate titanate (PLZT) ceramics with high density were fabricated using spark plasma sintering (SPS), a recently developed hot-pressing method. A wet–dry combination method was used to prepare the fine PLZT powders. The average grain size of the PLZT ceramics was less than 1 μm, because of a relatively low sintering temperature and a very short sintering time. The transmittance of PLZT ceramics increased with an increase of calcination temperature up to 700°C and then it slightly decreased with further increase of calcination temperature. The transmittance strongly depended on the SPS temperature and heat-treatment temperature. The pellet sintered at 900°C for 10 min and heat treated at 800°C for 1 h with a thickness of 0.5 mm showed a transmittance of 31% at a wavelength of 700 nm. The relationships between the transmittance and the microstructure were investigated.     

Fabrication of Transparent Lead Lanthanum Zirconate Titanate Ceramics from Fine Powders by Two-Stage Sintering

Transparent lead lanthanum zirconate titanate (PLZT) ceramics were fabricated from fine powders using an inexpensive two-stage sintering technique. The powders were prepared by hydrolysis from low-cost inorganic precursors. In the two-stage sintering method, uniaxially pressed green pellets were densified to nearly theoretical values in an oxygen gas atmosphere during the first-stage sintering, at 1000°C for 1 h, and then residual, free lead oxide in the pellets was removed by second-stage sintering at 1100°C for 12 h. Transparent ceramic with an average grain size of 1.6 μm and a porosity of 1.3% was obtained. The transparency and dielectric characteristics of the present samples were compared with those of hot-pressed samples: The study of the polarization–field hysteresis loops of the present samples yielded a remanent polarization of 6.8 μC/m² and a coercive field of 1.6 kV/cm. The low coercive field of PLZT ceramics could potentially reduce the driving voltage of electrooptic devices in many applications.     

Delectric properties of single grain in PLZT ferroelectric ceramics

The hot pressed and grain-grown transparent ceramics with maximum grain size 80∼100 μm provides the possibility of investigating the dielectric properties of single grain from ceramic specimens. The ion milling technique was employed to separate the grains. The dielectric permittivities of single grain of PLZT have been measured. It is found that the range of dielectric constant of single grains in unpoled state is larger than that of the bulk ceramic. Poling in both single grains and bulk ceramics reduces the dielectric constant in the poling direction, and increases it in the direction perpendicular to the poling field. The anisotropy of dielectric permittivity for PLZT 8/65/35 is calculated from the single grain data.     

Study of Fracture Behavior of Very Fine-Grained Silicon Carbide Ceramics

Dense, fine-grained silicon carbide (SiC) ceramics were fabricated by a hot-pressing technique using pyrolyzed polycarbosilane powders. Hot-isostatic pressing treatments were also applied to some of these hot-pressed samples. The grainsize range of the obtained sintered bodies was from 0.2 to 1.4 μm, which was much finer than that of ordinary sintered SiC ceramics. Relationships among sintering conditions, microstructures, and fracture toughness of the obtained ceramics were investigated. A clear grain-size dependence of fracture toughness was observed in this very fine-grain region (0.2 to 1.4 μm). Fracture toughness showed its maximum (5.1 MPa.m^1/2) at the average grain size of ∼0.7 μm. Also, the fracture toughness of the samples having similar grain sizes increased with increasing relative density.     

Grain-Size Dependence of Sliding Wear in Tetragonal Zirconia Polycrystals

Using a pin-on-plate tribometer with the reciprocating motion of SiC against yttria-doped tetragonal zirconia polycrystal (Y-TZP) plates, the friction and wear of Y-TZP ceramics were investigated as a function of grain size in dry N₂ at room temperature. The results showed that the overall wear resistance increased as the grain size of Y-TZP ceramics decreased. For grain sizes ≤0.7 μm, the wear results revealed a Hall-Petch type of relationship ( d ^−1/2) between wear resistance and grain size. In this case, the main wear mechanisms were plastic deformation and microcracking. For grain sizes ≥0.9 μm, the wear resistance was proportional to the reciprocal of the grain diameter. In this regime, delamination and accompanying grain pullout were the main mechanisms. In this case, the phase transformation to monoclinic zirconia had a negative effect on the wear resistance of TZP ceramics. The coefficient of friction tended to be higher for fine-grained TZP-SiC couples than for coarse-grained TZP-SiC couples, whereas, for a specific regime of grain size, the coefficient of friction was almost independent of the grain size.     

Textured PMN–PT and PMN–PZT

A promising way to improve the performance of piezoelectric ceramics is grain orientation by templated grain growth. In this work lead-based piezoelectric ceramics Pb(Mg_1/3Nb_2/3)_0.68Ti_0.32O₃ (PMN–32PT) and Pb(Mg_1/3Nb_2/3)_0.42(Ti_0.638Zr_0.362)_0.58O₃ (PMN–37PT–21PZ) ceramics were textured via templated grain growth process. For texturization (001)-oriented BaTiO₃ (BT) platelets (approximately 10 μm × 10 μm × 2 μm) were utilized as templates. The texturized ceramics were accomplished by aligning the templates by tape casting. The template growth into the matrix resulted in textured ceramics with Lotgering factors between 0.94 and 0.99 for both compositions. Consequences of the texture are enhanced dielectric and piezoelectric properties. Unipolar strain-field measurements of textured ceramics showed 0.25% strain s ₃₃ at 3 kV/mm. Large signal d ₃₃^* of up to 878 pm/V were determined directly from strain measurements. Compared with randomly oriented ceramics in texturized samples unipolar strain s ₃₃ and large signal d ₃₃^* was enhanced by a factor of up to 1.8.     

Microstructural Control for Strengthening of Silicon Carbide Ceramics

Fine-grained (<1 μm) silicon carbide ceramics with high strength were obtained by using ultrafine (∼90 nm) β-SiC starting powders and a seeding technique for microstructural control. The microstructures of the as-hot-pressed and annealed ceramics without α-SiC seeds consisted of fine, uniform, and equiaxed grains. In contrast, the annealed material with seeds had a uniform, anisotropic microstructure consisting of elongated grains, owing to the overgrowth of β-phase on α-seeds. The strength, the Weibull modulus, and the fracture toughness of fine-grained SiC ceramics increased with increasing grain size up to ∼1 μm. Such results suggested that a small amount of grain growth in the fine grained region (<1 μm) was beneficial for mechanical properties. The flexural strength and the fracture toughness of the annealed seeded materials were 835 MPa and 4.3 MPa·m^1/2, respectively.     

Microstructure Development in Low-Antimony Oxide-Doped Zinc Oxide Ceramics

The grain growth of ZnO ceramics sintered with low additions of Sb₂O₃ (<500 ppm of Sb) was investigated. Additions of Sb<250 ppm resulted in a coarse-grained microstructure with large ZnO grains (55–70 μm), much larger than the grain size of ZnO ceramics without any Sb₂O₃ addition (45 μm). The addition of 500 ppm of Sb resulted in a fine-grained microstructure with an average ZnO grain size of about 12 μm. The results are explained by an inversion-boundary (IB) -induced grain-growth mechanism. The grain-growth exponent has a value of about 2 as long as the grains containing IBs grow at the expense of IB-free grains. It increases to about 4 after the IB-containing grains impinge on each other, and achieves values above 10 for additions of 500 ppm of Sb when IBs nucleate in nearly all the ZnO grains so that grains with IBs prevail in the microstructure at an early stage in the grain-growth process.     

Anomalous Grain Growth in PLZT Ceramics

The isothermal grain growth of PLZT ceramics with various La concentrations from 0 to 10 at. % is studied. For all La concentrations, the sintering time (t) dependence of grain size (D) is expressed in the normal grain growth formula, Dⁿ= Kt. The constants n and K greatly depend on the La contents. These facts indicate that there are several grain growth mechanisms related to the La concentrations in PLZT ceramics.     

Effect of the ac Field Level on the Aging of the Dielectric Response in Polycrystalline BaTiO3

BaTiO₃ ceramics with grain sizes from 0.6 to 60 μm and relative densities of 89% to 92% were prepared by hot forging and conventional sintering from very pure-oxalate-derived powder. The aging of both the dielectric constant and the dielectric loss was examined at weak and strong fields with respect to grain size and frequency. It was concluded that the main aging mechanism is the aging of hysteretic domain wall motion for coarse-grained ceramics. At grain size of less than 1 μm, the lack of frequency and E _AC dependence, along with a lower aging rate, suggests that domain motions or hysteretic domain wall motions are restricted in finegrained ceramic BaTiO₃ and contribute little to the aging.     

Sintering and Properties of Monazite-Type CePO4

Monazite-type CePO₄ powder (average grain size 0.3 μm) was dry-pressed to disks or bars. The green compacts began to sinter above 950°C. Relative density ≧ 99% and apparent porosity <1% were achieved when the specimens were sintered at 1500°C for 1 h in air. The linear thermal expansion coefficient and thermal conductivity of the CePO₄ ceramics were 9 × 10⁻⁶/°C to 11 × 10⁻⁶/°C (200° to 1300°C) and 1.81 W/(m · K) (500°C), respectively. Bending strength of the ceramics (average grain size 4 μm) was 174 ± 28 MPa (room temperature). The CePO₄ ceramics were cracked or decomposed by acidic or alkaline aqueous solutions at high temperatures.     

Effect of Grain Size on Diffusion-Induced Grain-Boundary Migration in Ba(Zn1/3Nb2/3)O3 Ceramics

Diffusion-induced grain-boundary migration (DIGM) in Ba(Zn_1/3Nb_2/3)O₃ (BZN) ceramics was investigated with small (3.0 μm) and large (31. 4 μm) grain size specimens. The specimens were embedded in Nb₂O₅ or ZnO powders and then heat-treated at 1250° and 1310°C, respectively. The grain boundaries of the small grain size specimens were immobile, while those of the large grain size specimens migrated away from their centers of curvature. From the observed difference in migration behavior depending on grain size, the magnitude of the driving force for the DIGM was estimated.     

Synthesis of Dense Lead Titanate Ceramics with Submicrometer Grains by Spark Plasma Sintering

Dense PbTiO₃ ceramics consisting of submicrometer-sized grains were prepared using the spark-plasma-sintering (SPS) method. Hydrothermally prepared PbTiO₃ (0.1 μm) was used as a starting powder. The powder was densified to ≳98% of the theoretical X-ray density by the SPS process. The average grain size of the spark-plasma-sintered ceramics (SPS ceramics) was ≲1 μm, even after sintering at 900°–1100°C, because of the short sintering period (1–3 min). The measured permittivity of the SPS ceramics showed almost no frequency dependence over the range 10¹–10⁶ Hz, mainly because pores were absent from the ceramics. The coercive field of the SPS ceramics was somewhat higher than that of conventionally sintered ceramics, which could be attributed to the small-grained microstructures of the SPS ceramics.     

Two-Stage Sintering of Alumina with Submicrometer Grain Size

This work verifies the applicability of two-stage sintering as a means of suppressing the final stage grain growth of submicrometer alumina. The first heating step should be short at a relatively high-temperature (1400°–1450°C) in order to close porosity without significant grain growth. The second step at temperatures around 1150°C facilitates further densification with limited grain growth. Fine-grained alumina with a relative density of 98.8% and a grain size of 0.9 μm was prepared by two-stage sintering. A standard sintering process resulted in ceramics with identical relative density and a grain size of 1.6 μm.     

Superplastic Flow in Fine-Grained Alumina

Dense polycrystalline alumina having an average grain size of 1.6 μm was deformed to true strains of up to 60% in simple uniaxial compression at 1693 K without significant cavitation. A strain rate of ∼2 × 10⁻⁴ s⁻¹ was obtained at a uniaxial stress of ∼30 MPa. Such a reasonable flow stress at such high strain rates and a relatively low temperature raises a real possibility of isothermal superplastic forging of alumina ceramics. The mechanism of deformation was identified to be diffusion creep with grain boundaries as the dominant diffusion path. The specimens suffered considerable grain growth during deformation. Part of the grain growth resulted from time and temperature, but the majority was induced by deformation strain.     

Fine-Grained Silicon Nitride Ceramics Prepared from β-Powder

Fine β-powder with an average particle size of 0.28 μm was prepared by grinding and centrifugal sedimentation of sub-micrometer β-powder. Fine- and uniform-grained ceramics were fabricated from the powder by hot pressing. The average grain size of the ceramic was 0.21 μm. It was shown that this kind of microstructure was desirable for the matrix of in situ composite. It was also shown that the ceramics could be superplastically deformed at a temperature as low as 1500°C.     

Influence of Microstructure on the Electrical Properties of Iron-Substituted Calcium Titanate Ceramics

CaTi_0.8Fe_0.2O_3–δ ceramics with grain sizes that varied from 2 to 10 μm were obtained and studied using SEM, TEM, Mössbauer spectroscopy, impedance spectroscopy, and electrochemical oxygen permeability measurements. Smaller grains developed a core–shell microstructure that consisted of a pure CaTiO₃ core and an iron-rich microdomain structure at the shell. The effect of grain size on electronic conductivity was negligible. The ionic conductivity was higher for the ceramics with core–shell grains, which suggested that fast oxygen transport along microdomain walls may have occurred. For the homogeneous ceramics, the ionic conductivity decreased with decreased grain size, in which case the grain boundary represented an additional resistance, probably because of the depletion of oxygen vacancies.     

Controlled Oxygen Partial Pressure Sintering of (Pb,La)(Zr,Ti)O3 Ceramics

Transparent PLZT(7/60/40) ceramics with large piezoelectric coefficients were obtained using a two-step sintering process with controlled oxygen partial pressure. Specifically, low-oxygen-pressure and low-temperature sintering were used in the first step, followed by a high-oxygen-pressure, high-temperature sintering cycle. High-density ceramics with small grain sizes of about 3 µm were prepared. As a result, k _p= 0.71, k ₃₃= 0.78, d ₃₃= 850 × 10^-12 C/N, and a transparency of 15% (λ= 610 nm, thickness of 1 mm) have been achieved; 20% improvement of d ₃₃ was gained compared to conventional processed PLZT ceramics ( d ₃₃= 710 × 10^-12 C/N).     

Influence of ZrO2 Grain Size and Content on the Transformation Response in the Al2O3─ZrO2 (12 mol% CeO2) System

Based on experimental and modeling studies, the rate of increase in the martensite start temperature M _s for the tetragonal-to-monoclinic transformation with increase in zirconia grain size is found to rise with decrease in ZrO₂ content in the zirconia-toughened alumina ZTA system. The observed grain size dependence of M _s can be related to the thermal expansion mismatch tensile (internal) stresses which increase with decrease in zirconia content. The result is that finer zirconia grain sizes are required to retain the tetragonal phase as less zirconia is incorporated into the alumina, in agreement with the experimental observations. At the same time, both the predicted and observed applied stress required to induce the transformation are reduced with increase in the ZrO₂ grain size. In addition, the transformation-toughening contribution at temperature T increases with increase in the M _s temperature brought about by the increase in the ZrO₂ grain size, when T > M _s. In alumina containing 20 vol% ZrO₂ (12 mol% CeO₂), a toughness of ∼10 MPa. √m can be achieved for a ZrO₂ grain size of ∼2 μm ( M _s∼ 225 K). However, at a grain size of ∼2 μm, the alumina–40 vol% ZrO₂ (12 mol% CeO₂) has a toughness of only 8.5 MPa. √m ( M _s∼ 150 K) but reaches 12.3 MPa. ∼m ( M _s∼ 260 K) at a grain size of ∼3 μm. These findings show that composition (and matrix properties) play critical roles in determining the ZrO₂ grain size to optimize the transformation toughening in ZrO₂-toughened ceramics.