Microstructural Evolution of Transparent PLZT Ceramics Sintered in Air and Oxygen Atmospheres

Transparent lanthanum-doped lead zirconate titanate (PLZT) ceramics were fabricated by air-pressure sintering. When the PLZT (9/65/35) specimens were sintered in air, the microstructure was not uniform throughout the body; the outer region near the surface was completely dense, while the inner region of the body was porous. The thickness of the outer dense layer increased parabolically with sintering time. When the specimen was sintered in air at 1200°C for 8 h, the thickness of the dense layer was ∼0.25 mm. Therefore, when the specimen had a thickness of <0.5 mm, it was dense and transparent. This difference in microstructure was attributed to the formation of lattice vacancies as a result of PbO evaporation from the surface. The sintering atmosphere also was important in determining the thickness of the dense layer. The thickness was strongly dependent on the oxygen partial pressure of the atmosphere. The oxygen-gas trapped in pores was deemed to migrate easily through the lattice vacancies. By sintering in an oxygen-gas atmosphere at 1200°C for 8 h, a transparent PLZT with thickness up to 2 mm was fabricated.     

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.     

Ferroelectric and Photostrictive Properties of Fine-Grained PLZT Ceramics Derived from Mechanical Alloying

Single-phase lead lanthanum zirconate titanate (PLZT) solid solution powder was synthesized from the constituent oxides at ambient temperature through a mechanical alloying (MA) process and was then densified to fine-grained ceramics by sintering and hot-pressing. The anomalous photovoltaic effect (APV) and photoinduced strain of the resultant PLZT ceramics were investigated and analyzed in association with the influence of grain size. It was found that a photoinduced voltage up to 6000 V·cm⁻¹ can be obtained as the grain size is reduced to 0.42 μm. This is extremely high and about three times that achievable in normal micrometer-grained PLZT ceramics. The maximum photoinduced strain of the PLZT ceramics with an average grain diameter of 0.54 μm reached 0.01%, which is equivalent to electric-field-induced strain of common piezoelectric materials.     

Effects of Crystal-Lattice Distortion on Optical Transmittance of the (Pb, La)(Zr, Ti)O3, System

Optical transmittance and crystal-lattice distortion and their relation were studied in hot-pressed La-doped Pb zirconate-titanate (PLZT) ferroelectric ceramics at the ferroelectric-antiferroelectric morphotropic phase boundary. In the thermally annealed condition, the crystal system of PLZT at the FE-AFE morphotropic phase boundary was pseudotetragonal and similar to the antiferroelectric phase (AFE_β) appearing in Pb(Zr, Ti)O₃ and (Pb, Sr)ZrO₃. Optical transmittance and crystal-lattice distortion change monotonically with respect to the Zr/Ti ratio, and the optical transmittance increases approximately linearly with decreasing lattice distortion. In view of these relations and the temperature dependence of the optical transmittance, it is suggested that light scattering in PLZT ceramics is caused mainly by the variation in refractive index encountered as the light travels from one domain or grain into another.     

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).     

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.     

Optically Transparent Polycrystalline Al2O3 Produced by Spark Plasma Sintering

The spark plasma sintering (SPS) technique was used to produce mid-infrared (IR) transparent alumina with the desired transmittance. An excellent transmittance of 85% has been obtained in a sample sintered at 1300°C for 5 min. The heating rate, sintering time, and annealing have a significant influence on IR transmittance. The improvement in transmission may be attributed to the progressive elimination of residual porosity when applying a slower heating rate, longer sintering time during SPS, and postsinter annealing. It is suggested that localized residual strain/stress at grain boundaries and oxygen vacancy concentration are other factors influencing the optical properties of the SPS-sintered alumina.     

Effect of Manganese Ion Diffusion on the Microstructural Evolution of Lead Lanthanum Zirconate Titanate Ceramic

Microstructural evolution of lead lanthanum zirconate titanate (PLZT) ceramics caused by diffusion of the Mn ion was observed. Specimens with layered structures were fabricated by copressing a PLZT powder (9/65/35) doped with Mn and same PLZT powder without the dopant. When the copressed specimen was sintered at 1200°C in air, the Mn ion diffused out of the doped region. The region originally containing the Mn ions was totally free of pores while all other regions remained porous. The formation of lattice vacancies, as a result of Mn diffusion, was attributed to the enhanced material transport and the resultant rapid densification.     

Defect Structure of PLZT Doped with Mn, Fe, and Al

Practically pore-free Mn-, Fe-, and Al-doped PLZT ceramics were prepared using isostatic hot-pressing. The incorporation of the dopants in the perovskite lattice of PLZT (Pb_0.9La_0.1 |Zr_0.5Ti_o.5O₃₊δ) ceramics was analyzed from measurements of the density, lattice constants, and weight loss during sintering. It was deduced that Mn, Fe, and Al are incorporated as trivalent ions at (Zr, Ti)⁴⁺ sites and that charge compensation is effected by elimination of cation vacancies present in the undoped PLZT.     

Fabrication of Transparent Electrooptic PLZT Ceramics by Atmosphere Sintering

PLZT electrooptic ceramics were fabricated by a unique atmosphere sintering technique. The ceramics produced were significantly more transparent than those obtained by ordinary O₂ sintering methods; in fact, they were comparable in transparency to those obtained by hot-pressing. To achieve good transparency, the powder must be batched with excess PbO, which at the sintering temperature is present as a liquid phase at the grain boundaries. Sintering was conducted at 1200°C for 60 h in an atmosphere containing O₂ and a relatively high partial pressure of lead oxide.     

Densification and microstructure evolution of reactively sintered transparent spinel ceramics

Reactive sintering is an effective and simple method to prepare transparent spinel ceramics. In this research, transparent MgO·nAl₂O₃ (0.98?≤ n?≤?2) spinel ceramics were prepared via reactive sintering in air followed by hot isostatic press (HIP), using MgO and γ-Al₂O₃ powders as raw materials. The influence of composition on densification and microstructure evolution was systemically investigated. More importantly, the relationship between microstructure of presintered samples and final properties of transparent ceramics was singled out. Thermodynamically stable large pores were easily generated in magnesia-rich and stoichiometric samples after presintering in air, causing severe abnormal grain growth during the HIP treatment and poor optical quality of the resulting samples. The presintering temperature of alumina-rich samples widely varied with composition. No large pores were observed in the presintered sample, which was beneficial for the elimination of residual pores in the following HIP process. Highly transparent spinel ceramics with n?=?1.1 and 1.3 were successfully fabricated with the transmittance above 84% even at the short wavelength of 400?nm, close to the theoretical value.     

Fabrication of 0.24Pb(In1/2Nb1/2)O3-0.42Pb(Mg1/3Nb2/3)O3-0.34PbTiO3 transparent ceramics by conventional sintering technique

0.24Pb(In_1/2Nb_1/2)O₃-0.42Pb(Mg_1/3Nb_2/3)O₃-0.34PbTiO₃ transparent ceramics were fabricated by a conventional sintering technique. Through optimization of sintering conditions of calcination and sintering temperatures and time, the obtained ceramics showed high optical transmittance of 53% and 71% at light wavelengths of 1300 and 2000 nm, respectively. The ceramics showed a rhombohedral to tetragonal phase transition at ~120°C and a tetragonal to cubic phase transition at 222°C. These transition temperatures were higher than those of 0.67Pb(Mg_1/3Nb_2/3)-0.33PbTiO₃ ceramics. In addition, the ceramics had a ferroelectric hysteresis loop, a large piezoelectric constant d₃₃ of 407 pC/N, and a planar electromechanical coupling factor k_p of 52%. These results suggest that the transparent ceramics may be used as a temperature-stable, linear electro-optic material.     

Effect of Sintering Atmosphere on Isolated Pores During the Liquid-Phase Sintering of MgO-CaMgSiO4

The shrinkage behavior of isolated pores during the liquidphase sintering of MgO-CaMgSiO₄ at 1650°C in O₂ and N₂ atmospheres has been studied. When 90MgO- 10Ca MgSiO₄ specimens containing artificially produced large spherical pores are sintered in O₂, the liquid and grains flow into the pores as oxygen diffuses out. When sintered in N₂ the pores remain intact even after a long time, because the N₂ gas entrapped in them does not diffuse out. The effect of the sintering atmosphere has also been studied in a fine powder mixture of 80MgO 20CaMgSiO₄ composition. Changing the atmosphere from O₂ to N₂ during the sintering treatment reduces the porosity, probably because of the enhanced oxygen diffusion from the pores. The pores grow when the sintering atmosphere is changed from N₂ to O₂, probably because of oxygen diffusion into the pores from the specimen surface. The practical implication of these results is that changing the atmosphere from O₂ to air during the liquid-phase sintering of oxide ceramics can greatly reduce the porosity.     

Transparent Er2O3 ceramics fabricated by high-pressure spark plasma sintering

Fabrication of transparent Er₂O₃ ceramics was carried out by high-pressure spark plasma sintering (HP-SPS). The color and in-line transmittance of these ceramics was highly sensitive to the sintering parameters. Samples exhibited a strong pink or wine color after sintering at 1150 °C under 600 MPa or 1250 °C under 250 MPa, respectively. This was confirmed to be a result of oxygen vacancies created during the sintering process and high sensitivity of Er₂O₃ to the strong reducing atmosphere in the SPS apparatus. Post-sintering annealing in an air furnace led to elimination of oxygen vacancies and increased transparency. Additionally, the photoluminescence intensity and phosphorescence lifetime of annealed (pink) samples was higher and shorter, respectively, compared to that of the reduced (wine-colored) samples.     

Temperature Dependence of Electric‐induced Light Scattering Performance for PLZT Ceramics

PLZT (7.45/71/29) ceramics with fully dense microstructure and high transmittance were fabricated by a hot‐press sintering method. The effects of temperature on the phase structure, ferroelectric property, and electric‐induced light scattering performance of the PLZT ceramics were examined and analyzed. XRD patterns indicated that the PLZT sample tended to transform from rhombohedral phase to tetragonal phase with the temperature increasing. And the temperature‐dependent ferroelectric hysteresis behavior of the PLZT sample revealed the conversion of a saturated square hysteresis loop to a double‐loop‐like hysteresis loop, accompanied with the significant reduction in coercive field and remnant polarization. Depending on the temperature, the PLZT sample exhibited three different kinds of electric‐induced light scattering performance.     

Effective calcination pretreatment of Lu2O3 powders for LuAG transparent ceramics

Lutetium aluminium garnet (LuAG) ceramics as host materials has been widely used in lighting, laser, displaying and scintillators after doping different rare earth ions. Right selection of raw powder and controlling its characteristics during the preparation can greatly improve the optical quality of transparent ceramics. In this paper, the influence of different pretreatment temperatures of commercial Lu₂O₃ powders in oxygen atmosphere on solid state sintering of LuAG ceramics was systematically investigated. The pretreatment gradually decreased the specific surface area of Lu₂O₃ powders and greatly removed the absorbed impurities, which seriously deteriorated the optical quality before. The mean particle size increased from 4.53 to 5.66 μm, and the in-line transmittance of samples (Thickness = 2 mm) at 1064 nm was 68.4% for the pretreated Lu₂O₃ powder at 1000 °C without any sintering additives. Further increase of pretreatment temperature would lead to the coarsening of Lu₂O₃ powders and the decrease of sintering activity, which finally resulted in a large number of micro pores in LuAG ceramics. These results revealed that the pretreatment of Lu₂O₃ powders has prodigious impact on the optical quality of LuAG transparent ceramics, and the adsorbed materials should be removed as much as possible for their applications in lasers or lighting.     

Translucent α-Sialon Ceramics by Hot Pressing

The single-phase α-sialon ceramics with high optical transmittance have been prepared by hot pressing. The maximum transmittance reached 65.2% and 52.2% in the infrared wavelength region, 58.5% and 40% in the visible region for the samples 1.0 and 1.5 mm thickness, respectively. The material also exhibited good mechanical properties of high hardness (20 GPa) and better fracture toughness (5.1 MPa·m^1/2). Both high optical transmittance and improved toughness of α-sialon ceramics were attributed to the less-grain-boundary glassy phase and the homogeneous microstructure, which was obtained by a proper process and confirmed by SEM and TEM observation, compared to that prepared by ordinary sintering. It is, therefore, expected that the translucent α-sialon ceramics could be a promising optical window material.     

Effects of La2O3 Addition and PbO Excess on the Transmittance of PbZrO3–PbTiO3–Pb(Zn1/3Nb2/3)O3 Ceramics by Spark Plasma Sintering

The effects of La₂O₃ addition and PbO excess on the microstructures and optical properties of PbZrO₃–PbTiO₃–Pb(Zn_1/3Nb_2/3)O₃ (PZ–PT–PZN) ceramics prepared by spark plasma sintering were investigated. When 1 mol% La₂O₃ was added, the highest transmittance of 35% at 700 nm for PZ–PT–PZN ceramics was obtained. The improved transmittance was attributed to the increased relative density and the decreased optical anisotropy. The samples containing more than 1 mol% La₂O₃ showed decreased transmittance, due to the appearance of secondary phases. The transmittance of PZ–PT–PZN ceramics increased slightly to 29% at 700 nm with increasing amount of excess PbO up to 10 mol% and thereafter decreased rapidly.     

Fine-grained transparent MgAl2O4 spinel obtained by spark plasma sintering of commercially available nanopowders

A high transmittance/small grain size combination for pure spinel ceramics from commercially available nanopowders without sintering aids can be obtained by SPS sintering. By using a low heating rate ≤10 °C/min and a sintering temperature ≤1300 °C, a transparent polycrystalline MgAl₂O₄ spinel was fabricated by SPS with an in-line transmission of 74% and 84% for 550 nm (visible) and 2000 nm (NIR) wavelengths respectively. A small average grain size of about 250 nm was obtained and the pores located at the multiple grain junctions have a mean size of about 20 nm. The high in-line transmission is linked not only to the low residual porosity but particularly to the very small size of pores.     

Porous Silicon Nitride Ceramics Prepared by Reduction–Nitridation of Silica

A new method for preparing porous silicon nitride ceramics with high porosity had been developed by carbothermal reduction of die-pressed green bodies composed of silicon dioxide, carbon, sintering additives, and seeds. The resultant porous silicon nitride ceramics showed fine microstructure and uniform pore structure. The influence of SiO₂ particle size and sintering process (sintering temperature and retaining time) on the microstructure of sintering bodies was analyzed. X-ray diffractometry demonstrated the formation of single-phase β-Si₃N₄ via the reaction between silicon dioxide and carbon at high temperature. SEM analysis showed that pores were formed by the banding up of rod-like β-Si₃N₄ grains. Porous Si₃N₄ ceramics with a porosity of 70–75%, and a strength of 5–8 MPa, were obtained.