Effect of microwave sintering on the microstructure and electric properties of (Zn,Mg)TiO3-based multilayer ceramic capacitors

In this study, the effects of microwave sintering on the sintering behaviour, microstructure and silver diffusion of (Zn,Mg)TiO₃-based multilayer ceramic capacitors (ZMT MLCCs) with pure silver electrodes were investigated. The energy dispersive spectroscopy results showed that the silver ions diffused into the dielectric layer significantly when the ZMT MLCC was sintered with conventional processing at 900 °C. However, sintering of ZMT MLCC at 900 °C using microwave processing was found to effectively suppress silver ion diffusion into the dielectric layer. The concentration of silver ions was identified by wavelength dispersive spectroscopy, which showed that the Ag ion concentrations for conventional and microwave sintering are approximately 1.0 at.% and below 0.4 at.%, respectively. The observed difference may be due to different kinetics between conventional and microwave sintering.     

Multilayer bender-type PZT-PZN actuator by co-extrusion process

A multilayer flextensional bender-type actuator, which was composed of five piezoelectric layers and one passive conducting layer, was fabricated using a co-extrusion process. A low-temperature sinterable PZN-PZT was used for the piezoelectric layer. The conducting inner electrode layers and passive bottom layer were fabricated by dispersing silver particles in the PZN-PZT matrix. For the co-extrusion process, piezoelectric and conducting feedrods were made separately by mixing them with polymers, which was followed by the formation of the initial feedrods. The initial feedrods were co-extruded through a reduction die to produce a continuous multilayer sheet. The binder was burnt out and, the multilayer green bodies were then sintered at 900 °C. The design was suitable not only for applying a high electric field with inner electrodes, but also for inducing a residual tensile stress on the piezoelectric layer. A multilayer actuator with dimensions of 50 mm × 20 mm × 0.84 mm generated a displacement of approximately 400 μm at 400 V, which is more than twice the displacement of a simple two-layer actuator with the same dimensions.     

Investigation of thin film end-termination on multilayer ceramic capacitors with base-metal-electrode

The thin film of copper, chromium and titanium as end-termination studies were performed on multilayer ceramic capacitors (MLCCs) based on BaTiO₃ ceramic with nickel internal electrodes. A green sheet was prepared by tape casting using the X7R/BME powders. Nickel paste was attached to the green sheet as an internal electrode. After lamination, the green chips were sintered at 1300 °C for 2 h, then the external electrodes were sputtered as thin films for end-termination. There is no extra curing process, so that thermal shock of the MLCCs is reduced. To improve the adhesion between thin film end-termination and dielectric body, chromium and titanium were applied as media in this study. The mechanical and electrical properties of the MLCCs were investigated subsequently. The results showed that end-termination with chromium/copper has good performances on electrical and mechanical properties of MLCC, compared to conventional end-termination.     

Electrophoretic deposition and sintering of thin/Thick PZT films

Electrophoretic deposition (EPD) is a simple, rapid, and low cost method for forming dense lead zirconate titanate (PZT) films down to 5 μm from particulate precursors. The three main steps of this process are: (1) formation of a charged suspension of the starting PZT powder; (2) deposition of the powder particles on an electrode under the influence of a dc electric field; and (3) fluxing and constrained sintering of the resulting particulate deposit at 900°C to form a dense continuous film. A 10 μm film formed using this process exhibited a polarization hysteresis equivalent to that of a bulk sample formed from the same starting powder, with a remnant polarization of 33 μC cm⁻².     

Constrained sintering of 8 mol% Y2O3 stabilised zirconia films

Constrained sintering kinetics of 8 mol% Y₂O₃/92 mol% ZrO₂ (8YSZ) films approximately 10–15 μm thick screen-printed on dense YSZ substrates, and the resulting stress induced in the films, were measured in the temperature range 1100–1350 °C. The results are compared with those reported earlier for 3YSZ films.Both materials behave similarly, although there are differences in detail. The constrained densification rate was greatly retarded compared with the unconstrained densification rate due to the effect of the constraint on the developing anisotropic microstructure (3YSZ) and, in the case of 8YSZ, considerable grain growth. The stress generated during constrained sintering was typically a few MPa. The apparent activation energies for free sintering, constrained sintering, creep and grain growth are found to cover a wide range (135–670 kJ mol^?1) despite all probably being mainly controlled by grain boundary cation diffusion.     

Tape casting and characterization of Li2.08TiO3-LiF glass free LTCC for microwave applications

Li_2.08TiO₃-LiF Glass-free Low temperature co-fired ceramic (LTCC) green tapes were prepared by tape casing technique. The rheology of the slurry was characterized using rheometer. The slurry exhibited pseudoplastic behavior. The sintering kinetics of the green tape was investigated using heating microscope. The sintering activation energy was determined to be ∼173 kJ/mol. The green tape could be densified at 900 °C/2 h. Microwave dielectric properties of the sintered tape were characterized in a split-post dielectric resonator using a network analyzer. The ceramic sheet with thickness of 0.11 mm demonstrated good microwave dielectric properties: ε_r = 22.4 and Q × f = 35,490 GHz. The cross sectional microstructure of the cofired multilayer stack was observed by scanning electron microscopy (SEM). The green tape demonstrated good chemical and shrinkage compatibilities with Ag electrode during sintering process. The thermal expansion coefficient and thermal conductivity of the ceramic is 22.4 ppm/∘C and 4.75 W m⁻¹ K ⁻¹, respectively.     

Piezo-spectroscopic characterization of alumina-aluminium titanate laminates

A multilayered alumina-aluminium titanate composite was prepared by a colloidal route from aqueous suspensions. The structure of the laminate was symmetric and constituted of two external Al₂O₃ layers (width ≅ 1750 μm), one central Al₂O₃ layer (width ≅ 1200 μm) and two intermediate thin (width ≅ 315–330 μm) Al₂O₃–Al₂TiO₅ layers.Additional monolithic materials with the same compositions as those of the layers were fabricated as reference materials. Young's modulus of the monoliths was determined by three point bending. Dilatometry determinations were performed on green specimens, following the same heating and cooling schedules as those used for sintering the laminate, in order to determine the actual dimensional changes on cooling after sintering. The dimensional changes of the sintered specimens on heating and on cooling were also determined. Microscopic distributions of residual stresses were evaluated by fluorescence piezo-spectroscopy, and they revealed the existence of weak tensile and compressive hydrostatic stresses in the aluminium titanate and alumina layers, respectively. The level and sign of these stresses was in good agreement with those predicted based on analysis of the Young's modulus and the dimensional variations during cooling after sintering of the monoliths with the same compositions as those of the layers. Dimensional variations during cooling after sintering were different from those for sintered materials, which presented hysteresis between heating and cooling. In spite of the presence of compressive residual stresses in the external layers of the laminate, strength values of notched samples of the laminated specimens were lower than those for monoliths of the same composition as the external layers.     

CO2 laser peeling of Al2O3 ceramic and an application for the polishing of laser cut surfaces

A laser controlled fracture peeling technique is demonstrated to smooth the Al₂O₃ ceramic surface without thermal damages. It was found that a chip can be separated and curled from the ceramic surface during a focused CO₂ continuous wave (CW) laser dual-scanning. The thickness of the curled chip is ～50 μm and the formed subsurface roughness (R_a ≈ 2 μm) is close to the surface machined by mechanical breaking (R_a = 1.84 μm). The chip formation is attributed to the controlled fracture by the residual tensile stress in the recast layer, whereas the chip curling only occurs when the melting depth is shallower than the position of lateral cracks. The peeling technique can be applied to polish the cut surface of laser fusion cutting in ceramics. The polished cut surface (R_a = 2.18 μm) is free from recast, crack and heat effects. The microstructure is similar to the base material. The material removal rate during polishing is up to 0.125 mm³/s.     

Fabrication of sub-micrometer MgO transparent ceramics by spark plasma sintering

Transparent MgO ceramics were fabricated by spark plasma sintering (SPS) of the commercial MgO powder using LiF as the sintering additive. Effects of the additive amount and the SPS conditions (i.e., sintering temperature and heating rate) on the optical transparency and microstructure of the obtained MgO ceramics were investigated. The results showed that LiF facilitated rapid densification and grain growth. Thus, the MgO ceramics could be easily densified at a moderate temperature and under a low pressure. In addition, the transparency and microstructure of the MgO ceramics were found to be strongly dependent on the temperature and heating rate. For the MgO ceramics sintered at 900 °C for 5 min with the heating rate of 100 °C/min and the pressure of 30 MPa from the powders with 1 wt% LiF, the average in-line transmittance reached 85% in the range of 3 – 5 μm, and the average grain size is ∼0.7 μm.     

Improvement in the Temperature Stability of a BaTiO3-Based Multilayer Ceramic Capacitor by Constrained Sintering

In this study, a self-constrained BaTiO₃ material system, composed of a low-fire BaTiO₃-based X7R (Δ C / C ±15% within −55° to 125°C) MLCC dielectric and a high-fire, BaTiO₃-based X7R MLCC dielectrics eliminated sintering aid that are laminated on both sides of the BaTiO₃-based X7R MLCC, has been developed. The temperature dependence of capacitance of the BaTiO₃-based X7R MLCC is significantly improved to satisfy X8R requirements over the entire temperature range studied (Δ C / C ±15% within –55° to 150°C) using the self-constrained sintering. The curie temperature of BaTiO₃-based X7R MLCC increases on increasing the thickness of the constraining layers. Compared with the specimen fired by free sintering, a substantial reduction in grain size, leading to a decrease in dielectric constant, was observed in the specimen fired by constrained sintering with the thickness of the constraining layer being 170 μm. The increase in Curie temperature and decrease in grain size of the specimen fired by constrained sintering can be explained in terms of the presence of in-plane tensile stress. The in-plane tensile stress that introduces a friction force between the multilayer matrix and the nonshrinkage constraining layers to suppress the in-plane shrinkage and to inhibit the rate of grain growth was formed during constrained sintering.     

Particle size effects in flash sintering

The study of 3 mol% yttria stabilized zirconia (3YSZ) with different particle sizes provides new insights into flash sintering. Four powders, all with the same crystallite size but various particle size were investigated: described as nominally 1 μm (D80 = 0.51 μm, meaning 80 vol% has a size less than 0.51 μm), 2 μm (D80 = 0.90 μm), 5 μm (D80 = 2.11 μm) and 10 μm (D80 = 3.09 μm). While the furnace temperature for flash sintering, at a field of 100 V cm^?1, increased from 920 °C to 1040 °C with particle size, the specimen temperature in all instances remained at ～1200 °C. The quantum increase in density decreased with larger particles. The grain size distribution of conventionally and flash sintered specimens remained similar, with some evidence of a preponderance of nanograins in the flash sintered specimens. Joule heating was well below the temperatures that would have been required for sintering in a few seconds. An explanation based upon the nucleation of Frenkel pairs is proposed.     

Microstructure and dielectric characteristics of Nb2O5 doped BaTiO3-Bi(Znl/2Til/2)O3 ceramics for capacitor applications

The effects of Nb₂O₅ addition on the dielectric properties and phase formation of 0.8BaTiO₃-0.2Bi(Zn_l/2Ti_l/2)O₃ (0.8BT-0.2BZT) ceramics were investigated. The desired perovskite phase was achieved with Nb₂O₅ doping levels being in the range of 0.5 wt.%–3.0 wt.%. The 0.8BT-0.2BZT ceramics doped with 1.5 wt.% Nb₂O₅ was found to possess a moderate dielectric constant (ε = 1170) and low dielectric loss (tanδ = 1%) at room temperature and 1 kHz frequency, showing a flat dielectric behavior over the temperature range of −55 °C–200 °C. Based on this composition, the X9R-MLCC (multilayer ceramic capacitor) with Ag0.7-Pd0.3 electrode was sintered at 1060 °C. The optimized capacitance of the MLCC is 26.5 nF, with dielectric loss tanδ of 0.9% and electrical resistance of 4.50 × 10¹¹ Ω at room temperature, leading to a high time constant of 11,900 s, decreasing to 175 s at 200 °C, being one order higher than those of commercial X7R MLCC. In addition, the equivalent series resistance (ESR) was found to be on the order of 0.2 mΩ at 2 MHz, much lower than that of the DC Bus Capacitor Bank for the automotive inverters (where the desired characteristic is <3 mΩ). All these characteristics of the newly developed MLCC will benefit the high temperature and high power capacitor applications.     

Microwave dielectric properties of the (BaxSr1−x)TiO3 thin films on alumina substrate

Barium strontium titanate, (Ba_xSr_1?x)TiO₃ (BST) thin films have been prepared on alumina substrate by sol–gel technique. The X-ray patterns analysis indicated that the thin films are perovskite and polycrystalline structure. The interdigital electrode with 140 nm thickness Au/Ti was fabricated on the film with the finger length of 80 μm, width of 10 μm and gaps of 5 μm. The temperature dependence of dielectric constant of the BST thin films in the range from ?50 °C to 50 °C was measured at 1 MHz. The dielectric properties of the BST thin films were measured by HP 8510C vector network analyzer from 50 MHz to 20 GHz.     

Yb3+ doped Lu2O3 transparent ceramics by spark plasma sintering

Transparent ceramics of 10% Yb doped Lu₂O₃ was fabricated by spark plasma sintering. The operating vital parameters in yielding transparency and mutual effects of sintering, pressure, dwell time, heating rate and annealing temperature on microstructure have been investigated. Fully compacted specimens were obtained at 1250 °C and the average grain size increased from few nm up to 5 μm until 1700 °C, above which abnormal grain growth was witnessed. The post-annealing of sintered ceramics at 1200 °C removes discoloration and improves transparency. The ceramics prepared at 1700 °C with dwell time of 5 min and heating rate at 50 °C/min shows the maximum transmittance with a thickness of 2 mm of 55% at a wavelength of 2 μm.     

Influence of sintering on microstructure and electrical properties of ZnO-based multilayer varistor (MLV)

The effect of sintering on microstructure, dielectric property and varistor property of ZnO-based multilayer varistor (MLV) were investigated. The results show that an optimum microstructure of ZnO-based MLV can be obtained when sintering at 950 °C/1.5 h. The reaction between ZnO and Sb₂O₃ is noted. Also, the segregation of Bi₂O₃ to the inner electrode and thus the reaction of Bi₂O₃ with Pd are observed. The V_B and α value of ZnO-based MLV can be controlled in a straightforward manner through the control of grain size. The decrease in V_B directly relates to the grain growth of ZnO grains when increasing the sintering temperatures from 900 to 1050 °C. Moreover, the increase of capacitance with sintering temperature may mainly result from the coalescence of ZnO matrix grains. The energy absorption capabilities in terms of electro-static discharge (ESD) and peak current (PC) measurements of ZnO-based MLV are reported. The optimum varistor properties of ZnO-based MLV can be obtained when sintering at 950 °C.     

Surface stress measurement with interference microscopy of thick homoepitaxial single-crystal diamond layers

In this article, we present a study of surface stress measurements of a thick single-crystal diamond (SCD) layer (110 μm) deposited onto a high-temperature high-pressure (HTHP) Ib substrate. The measurement is based on observations of the deformation of the backside of the HTHP substrate due to internal stress that varies as the thickness of the SCD layer is modified by ion-beam etching. The deformation is obtained from the height-distribution analysis of interference microscopy (IM) observation. The results show that the tensile surface stress σ increases linearly with SCD-layer thickness with t_f according to σ = 0.065t_f MPa/μm. The tensile surface stress may be attributed to the intrinsic stress that originates from the lattice mismatch between the CVD-diamond layer and the HTHP-Ib substrate. The increased internal stress is a principle cause of crack formation of the crystal.     

Fabrication and phase transition of La2−xLuxZr2O7 transparent ceramics

A series of transparent ceramics with the composition of La_2−xLu_xZr₂O₇ (x = 0−2.0) were prepared by solid-state reactive sintering in vacuum. With the increase of Lu content (x), phase transition from pyrochlore to defective fluorite occurred and a two-phase region existed in the range of x = 0.6−1.2. Grain sizes of the pyrochlore phase dominated samples (x < 0.5) were 11−14 μm, and that of the defective fluorite phase dominated samples were larger than 60 μm. However, grain sizes of the samples in the two-phase region were smaller than 3 μm. The La_0.8Lu_1.2Zr₂O₇ ceramic with the smallest grain size (∼2.5 μm) reached a highest in-line transmittance of 72.4% at 1100 nm among all the samples.     

Fabrication of porous silicon carbide ceramics with high porosity and high strength

Unique porous SiC ceramics with a honeycomb structure were fabricated by a sintering-decarburization process. In this new process, first a SiC ceramic bonded carbon (SiC/CBC) is sintered in vacuum by spark plasma sintering, and then carbon particles in SiC/CBC are volatized by heating in air at 1000 °C without shrinkage. The honeycomb structure has at least two different sizes of pores; ∼20 μm in size resulting from carbon removal; and smaller open pores of 2.1 μm remaining in the sintered SiC shell. The total porosity is around 70% and the bulk density is 0.93 mg/m³. The bending and compressive strengths are 26 MPa, and 105 MPa, respectively.     

High power density in a piezoelectric energy harvesting ceramic by optimizing the sintering temperature of nanocrystalline powders

Piezoelectric energy harvesting is the research hotspot in the field of new energy, and its core is to prepare piezoelectric ceramics with high transduction coefficient (d₃₃ × g₃₃) and large mechanical quality factor (Q_m) as well. In addition, the miniaturization of the piezoelectric energy harvester also requires the material to have a submicron fine grain structure. In this work, submicron-structured ternary system, MnO₂-doped Pb(Zn_1/3Nb_2/3)O₃-Pb(Zr_0.5Ti_0.5)O₃ was constructed by pressureless sintering of nanocrystalline powders, which has been synthesized for the first time by high-energy ball milling route thereby evading the calcination stage. The microstructure and the energy harvesting characteristics were tailored through changing the sintering temperature. It was found that 1000 °C sintered fine-grained specimen (mean grain size ∼0.95 μm) showed the maximum d₃₃ × g₃₃ value of 9627 × 10⁻¹⁵ m²/N, meanwhile Q_m was as large as 774, which was almost seven times larger than pure counterpart. In the mode of the cantilever-type energy harvester, a high power density of 1.5 μW/mm³ were obtained for 1000 °C sintered specimen at a low resonance frequency of 90 Hz and acceleration of 10 m/s², which were further increased to 29.2 μW/mm³ when the acceleration increased to 50 m/s², showing the potential applications as a next generation high power multilayer energy harvester.     

Effect of atmosphere and sintering time on the microstructure and mechanical properties at high temperatures of α-SiC sintered with liquid phase Y2O3–Al2O3

The influence that the atmosphere (N₂ or Ar) and sintering time have on microstructure evolution in liquid-phase-sintered α-SiC (LPS-α-SiC) and on its mechanical properties at high temperature was investigated. The microstructure of the samples sintered in N₂ was equiaxed with a grain size of 0.70 μm and a density of 98% of the theoretical value regardless of the sintering time. In contrast, samples sintered in Ar had an elongated-grain microstructure with a density decreasing from 99 to 95% and a grain size increasing from 0.64 to 1.61 μm as the sintering time increased from 1 to 7 h. The mechanical behaviour at 1450 °C showed the samples sintered in nitrogen to be brittle and fail at very low strains, with a fracture stress increasing from 400 to 800 MPa as the sintering time increased. In contrast, the samples sintered in Ar were quasi-ductile with increasing strain to failure as the sintering time increased, and a fracture stress strongly linked to the form and size of the grains. These differences in the mechanical properties of the two materials are discussed in the text. During mechanical tests, a loss of intergranular phase takes place in a region, between 50 and 150 μm thick, close to the surface of the samples—the effect being more important in the samples sintered in Ar.