An Investigation Demonstrating the Feasibility of Microwave Sintering of Base-Metal-Electrode Multilayer Capacitors

A microwave sintering technique has been developed for base-metal electrode (BME) multilayer ceramic capacitors (MLCCs). Commercial green chips of size 0603 MLC with nickel electrodes were sintered in a microwave field. With a specially designed susceptor/insulation package to optimize coupling and uniformity of heating, a number of sintering experiments were conducted in the temperature range of 1200 to 1250∘C in a multimode microwave cavity operating at 2.45 GHz under a partially reducing atmosphere. Microstructure of the microwave processed MLCCs was investigated with both SEM and TEM techniques. The dielectric properties of the microwave sintered MLCCs were measured and compared with those sintered using conventional process at 1320∘C and lower pO₂’s ≈ 10^{− 9} atms. The results demonstrate that nickel electrodes remain metallic after microwave sintering even though the pO₂’s were relatively high and would thermodynamically favor NiO. The microwave sintered samples showed a dense, fine and uniform microstructure. The properties of the microwave-sintered samples were comparable to the conventionally sintered samples. The microwave processing was found to have enhanced sintering kinetics of the BME MLCCs, lowering sintering temperature by about 100∘C and also the processing time by about 90%.     

SrLnAlO4 (Ln=Nd and Sm) Microwave Dielectric Ceramics

SrLnAlO₄ (Ln=Nd and Sm) ceramics with K₂NiF₄ structure were prepared by a solid state reaction approach, and their microwave dielectric characteristics were evaluated together with the microstructures. The single phase dense SrNdAlO₄ and SrSmAlO₄ ceramics were obtained by sintering at 1450–1475°C and 1475–1500°C, respectively, and the good microwave dielectric characteristics were achieved: (1) = 17.8, Q · f = 25,700 GHz, _f = –9 ppm/°C for SrNdAlO₄; and (2) = 18.8, Q · f = 54,880 GHz, _f = 2 ppm/°C for SrSmAlO₄ dense ceramics. The Qf value significantly increased with increasing sintering temperature.     

Synthesis of NASICON with New Compositions for Electrochemical Carbon Dioxide Sensors*

Powders and pellets of new NASICON compositions have been synthesized using a mixed inorganic-organic sol-gel synthesis, by the preliminary formation of a pre-hydrolized TEOS xerogel. The investigated compositions can be described by the general formula Na₃Zr_2-(x/4)Si_2-xP_1+xO₁₂, obtained by keeping the Na concentration constant (= 3) at the optimum value reported for ionic conductivity, with x = 0 (the usual NASICON composition), 0.667, and 1.333. The xerogels were calcined at various temperatures in the range 400–1200°C. The powder samples were analyzed by TG/DTA, BET measurements, XRD, and SEM. The powders calcined at 500°C were sintered into pellets at 1100°C for 6 h. The sintering behavior of the pellets was investigated by dilatometric measurements and SEM observations. The sinterability increased with increasing x value. Dense samples of the new compositions were obtained by sintering at only 1100°C. This is attributed to the occurrence of liquid phase sintering. The electrical conductivity of the NASICON sintered bodies was measured by ac impedance spectroscopy. The conductivity decreased with decreasing c₀ lattice parameter of the hexagonal structure or increasing x value. The CO₂ gas sensors, using as electrolyte the dense samples of the new NASICON compositions, showed good EMF response that was very close to the theoretical value, even for the sample with x = 1.333 that showed much lower conductivity.     

Phase compositions and microwave dielectric properties of MgTiO<Subscript>3</Subscript>-based ceramics obtained by reaction-sintering method

MgTiO₃-based microwave dielectric ceramics were prepared successfully by reaction sintering method. The X-ray diffraction patterns of the sintered samples revealed a major phase of MgTiO₃-based and CaTiO₃ phases, accompanied with Mg₂TiO₄ or MgTi₂O₅ determined by the sintering temperature and time. The microwave dielectric properties had a strong dependence of sintering condition due to the different phase compositions and the microstructure characteristics. The ceramics sintered at 1360 °C for 4 h exhibited good microwave dielectric properties: a dielectric constant of 20.3, a high quality factor of 48,723 GHz (at 9GHz), and a temperature coefficient of resonant frequency of ?1.8 ppm/^oC. The obtained results demonstrated that the reaction-sintering process is a simple and effective method to prepare the MgTiO₃-based ceramics for microwave applications.     

Piezoelectric and Magnetoelectric Properties of Lead Zirconate Titanate/Ni-Ferrite Particulate Composites

Piezoelectric and magnetoelectric properties of magnetoelectric particulate composites with Lead Zirconate Titanate (PZT) and Ni-ferrite were investigated. The maximum magnetoelectric voltage coefficient, (dE/dH)_max, increased with higher sintering temperature up to 1250°C. Composites sintered at 1300°C, had dissolution of Fe ions into PZT, or interdiffusion between PZT and ferrite. Connectivity of the ferrite particles and sintering temperature were important factors for fabrication of this particulate composite. The composite added with 20 wt.% amount of Ni-ferrite, sintered at 1250°C for 2 hours, had the highest magnetoelectric voltage coefficient of 115 mV/cm · Oe at room temperature. This value is comparable to that of the BaTiO₃-CoFe₂O₄ based composites reported by Philips laboratory, and is 44% higher than other magnetoelectric particulate composites.     

Electrical properties of conventional and microwave sintered lead free magnetoelectric composites

Abstract

Here we report comparison of dielectric properties of composition synthesized by microwave and conventional sintering. Microwave sintering requires less time and temperature to achieve the same quality of materials as sintered by conventional route. The material sample was prepared by conventional solid state method and sintered in conventional & microwave furnace. Sintered samples were then subjected to XRD analysis. X-ray diffraction revealed the formation of single phase material. The dielectric and ferroelectric properties were recorded for both the samples and properties were found to improve in microwave sintered samples. There is also a significant improvement in density by microwave processing.     

Improved giant dielectric properties in microwave flash combustion derived and microwave sintered CaCu 3 Ti 4 O 12 ceramics

The nanocrystals of CaCu3Ti4O12 ceramic were prepared by microwave flash combustion technique. The microwave sintering of powders was optimized to 1025 − 1075 °C for 20 min with heating and cooling rate of 50 °C/min. Microstructural evaluation of sintered sample was carried out using SEM. The dielectric properties were measured in the frequency range 10–2 × 106 Hz and the temperature range 30–100 °C. The CCTO sample sintered at 1075 °C had giant dielectric constant 53,300 at 100 Hz. It was observed that dielectric constant was greatly increased on a slight increase in sintering temperature. Modulus and impedance analysis were performed to explore the observed unusual dielectric response. Grain and grain boundary resistance were observed as 8 Ω and 350,000 Ω, respectively. The grain boundary activation energy for electro-conduction was calculated as 0.65 eV by using the characteristic frequencies in cole-cole plots. It was noticed that the thermally activated charge carriers had long-range mobility.     

TLM simulation of microwave hybrid sintering of multiple samples in a multimode cavity

Microwave heating technology is a powerful mean to ensure successful sintering of ceramic materials. In sintering experiments, low loss insulators, conductors and high‐loss ceramics are microwaved so as to get optimal mechanical and structural properties. It is known that low‐loss ceramic materials such alumina and zirconia exhibit long waiting time before reaching a critical coupling temperature at which microwaves can be readily absorbed. On the other hand, some ceramics such as silicon carbid have a high loss factor and therefore can be used as a process stimulus for microwave sintering of microwave transparent ceramics. Furthermore, successful sintering experiments often require the use of carefully designed insulating structure in order to minimize thermal gradients caused by heat loss from surfaces. All these problems have led to the introduction of microwave hybrid heating (MHH) schemes using higher dielectric loss susceptors, insulation or coating. Since MHH depend mainly on human expertise, the optimization of sintering experiments will certainly benefit from numerical simulations. The transmission line matrix (TLM) is used to study two MHH schemes where both a susceptor and an insulating matrix were, respectively, used as process stimulus for microwave heating of multiple alumina samples within a three‐dimensional multimode cavity. The effects of such MHH schemes and target settings on electric field distribution and power absorption rates are reported in this paper. Copyright © 2003 John Wiley & Sons, Ltd.     

LiFePO4/C的微波法制备和性能

用微波法制备了LiFePO4和LiFePO4/C材料。分析了不同的微波烧结时间与材料结构和性能的关系。材料经微波烧结3 min,XRD图谱中出现了Fe2O3杂质,时间更长时则不出现Fe2O3杂质。充放电测试结果表明:烧结8 min的LiFe-PO4/C材料0.1C的首次放电比容量达140.0 mAh/g,但高倍率放电比容量衰减严重;烧结5 min的材料在1.0C放电倍率下,比容量超过了95.0 mAh/g。     

Modified Citrate Gel Techniques to Produce ZnO-Based Varistors (Part II—Electrical Characterisation)

The electrical characteristics of doped ZnO pellets prepared by novel, modified citrate gel routes and the conventional mixed oxide route were compared. The mixed oxide route produced rather inhomogeneous materials at the sintering temperatures employed in this study (970 °C and 1000 °C). In contrast, the modified citrate gel routes enabled some control over the location of the minority components incorporated into the ZnO. By positioning these components according to their function, varistor pellets with higher nonlinearity coefficients, higher characteristic voltages and slightly higher energy absorption abilities than those of the conventional mixed-oxide route were prepared. Differences in the electrical characteristics of varistors prepared by different routes but with apparently similar microstructures was taken to indicate successful control over the compositional homogeneity.     

The Influence of Bi2O3 and Sb2O3 on the Electrical Properties of ZnO-Based Varistors

This work presents a study of the influence of both Bi content and Sb/Bi ratio on the electrical characteristics of a commercial-type ZnO varistor. In contrast to previous studies two nonlinear coefficients, the breakdown fields and energy absorption abilities were measured after sintering at 970°C or 930°C. The Bi-content was varied from 0.9 to 1.8 at% while the Sb/Bi ratio was varied from 0.8 to 1.5, leading to values of up to 104 for the nonlinear coefficient 1, 1100 V mm^–1 for the breakdown field and 1137 J cm^–3 for the energy absorption ability. The highest value was measured for the highest Bi-content and the lowest Sb/Bi ratio and vice versa. The breakdown field E _V increased with lower sintering temperature, increased Sb/Bi ratio (at a given Bi-content) and increased Bi-content (at a given Sb/Bi ratio). The energy absorption coefficient increased at the higher sinter temperature and with lower Sb and Bi concentrations.The observed effects were related to the amount of spinel phase (Zn₇Sb₂O₁₂) formed during the sintering process and the amount of liquid phase present during early stages of the sintering process.     

Aging and Annealing Effects of ZnO Thin Films on GaAs Substrates Deposited by Pulsed Laser Deposition

Zinc oxide (ZnO) thin films were deposited on GaAs (100) substrates at different temperatures in the pulsed laser deposition (PLD) system. From the measurements of X-ray diffraction (XRD) at room temperature, 300–500°C were found to be good condition for the crystallization of the thin films. From the photoluminescence (PL) measurements, 500°C was found to be the optimized temperature for its optical property. Samples grown at 100, 200, 300, and 400°C showed near band-edge (NBE) emissions and deep-level emissions. The intensity of deep-level emissions decreased as time goes on, which is believed to originate from oxygen vacancies or zinc interstitials in thin films. While for the sample grown at 500°C, bright NBE emissions were observed at room temperature, and no deep-level emissions observed. This means that the high-optical-quality thin film was grown at 500°C. At the same time, annealing process of ZnO thin films grown at room temperature was carried out in PLD chamber. It was found that the annealing temperature of 600°C has strong effects on its PL. Aging and annealing effects in ZnO thin films grown on GaAs substrates by PLD were observed for the first time.     

Microwave dielectric properties of B2O3-added Li2MgTiO4 ceramics for LTCC applications

Li₂MgTiO₄ (LMT) ceramics which are synthesized using a conventional solid-state reaction route. The LMT ceramic sintered at 1250°C for 4 h had good microwave dielectric properties. However, this sintering temperature is too high to meet the requirement of low-temperature co-fired ceramics (LTCC). In this study, the effects of B₂O₃ additives and sintering temperature on the microstructure and microwave dielectric properties of LMT ceramics were investigated. The B₂O₃ additive forms a liquid phase during sintering, which decreases the sintering temperature from 1250°C to 925°C. The LMT ceramic with 8 wt% B₂O₃ sintered at 925°C for 4 h was found to exhibit optimum microwave dielectric properties: dielectric constant 15.16, quality factor 64,164 GHz, and temperature coefficient of resonant frequency -28.07 ppm/°C. Moreover, co-firing of the LMT ceramic with 8 wt% B₂O₃ and 20 wt% Ag powder demonstrated good chemical compatibility. Therefore, the LMT ceramics with 8 wt% B₂O₃ sintered at 925°C for 4 h is suitable for LTCC applications.     

La2O3–B2O3–TiO2 Glass/BaO–Nd2O3–TiO2 ceramic for high quality factor low temperature co-fired ceramic dielectric

A conventional BaO–Nd₂O₃–TiO₂ ceramic of microwave dielectric material was added to rare-earth derived borate glasses (La₂O₃–B₂O₃–TiO₂) for use as LTCC (low temperature co-fired ceramic) materials. The sintering behavior, phase evaluation, and microwave dielectric properties were investigated. It was found that increasing the sintering temperature from 750 to 850 °C led to increases in shrinkage and microwave dielectric properties (≈15 for ?_r , >10,000 GHz for Q*f₀ and >94 ppm/ °C for τ _f at 7–8 GHz for resonant frequency). The results suggest that a composite with suitable additives for τ _f could feasibly be developed as a material for LTCC applications.     

Mixed Electronic-Ionic Conductivity of Cobalt Doped Cerium Gadolinium Oxide

The effect of small amounts (<5 mol %) of cobalt oxide on the electrical properties of cerium oxide solid solutions has been evaluated. Ce_0.8Gd_0.2O_2-x (CGO) powder with an average crystallite size of 20 nm served as a model substance for the electrolyte material with a high oxygen ion conductivity and low electronic conductivity in its densified state. Doping the CGO powder by transition metal oxides (MeO) with concentrations below 2 mol % did not change the ionic conductivity nor the electrolytic domain boundary. After long sintering times (2 h) at temperatures above 900°C, MeO and CeO₂ form solid solutions. However, short sintering times or high dopant concentrations lead to an electronic conducting grain boundary phase short circuiting the ionic conductivity of the CGO grains. Choosing proper doping levels, sintering time and temperature allows one to tailor mixed conducting oxides based on CGO. These materials have potential use as electrolytes and/or anodes in solid oxide fuel cells and ion separation membranes.     

Fabrication of microinductor using Nanocrystalline NiCuZn ferrites

The nanocrystalline Ni_0.53Cu_0.12Zn_0.35Fe₂O₄ was prepared using microwave hydrothermal (M-H) method at a low temperature of 160 °C/30 min. As synthesized powders were characterized using XRD and TEM. The powders were sintered using microwave sintering methods at different sintering temperatures i.e. 750 °C/30 min, 800 °C/30 min, 850 °C/30 min 900 °C/30 min and 950 °C/30 min respectively. The sintered samples were characterized using XRD and SEM. The complex permittivity (ε*) and permeability (μ*) have been measured in the frequency range of 100 kHz to 1.8 GHz. The micro inductors were fabricated with the help of microwave sintered sample by using screen-printing method and co-firing. The electrical properties such as inductance and Quality factor of the prepared inductors were measured over a wide frequency range.     

Synthesis and characterization of novel Ca2Zn4Ti15O36 microwave ceramics derived from sol-gel powder

A novel microwave dielectric ceramics with composition of Ca₂Zn₄Ti₁₅O₃₆ (CZT) have been synthesized at different sintering temperatures, using citrate sol-gel derived powder. The sintering behavior and the phase identification of the powders were evaluated using differential thermal analysis-thermo gravimetric analysis and X-ray powder diffraction analysis techniques. The phase of CZT can be observed in the powder calcined at 900 °C. The single-phase of CZT, however, can only be obtained at sintering temperature of 1,000 °C or above. The single-phase CZT ceramics can be sintered into dense at 1,100 °C, exhibiting excellent microwave dielectric properties of ? _r?=?48.1, Q?×?f?=?27,000 GHz, and τ _f?=?+53.5 ppm/°C. The effects of sintering temperature on the density, microstructure, and dielectric properties of the sintered ceramics were investigated. The mechanism responsible for the change of dielectric properties with sintering temperature was also discussed.     

Processing of (La,Sr)(Ga,Mg)O3 Solid Electrolyte

The preparation of La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ (LSGM) powders by the mixed oxide route requires significantly longer annealing times of about 60 h compared to the combustion synthesis and Pechini method which requires less than 6 h. In comparison to the mixed oxide route the soft chemical synthesis methods produce significantly smaller grain sizes after solid-state reactive sintering, which is due to the significantly shorter annealing times in order to achieve well crystallized ceramics. It is emphasized that at 1400°C in air single phase LSGM samples with the composition La_0.8Sr_0.2Ga_0.8Mg_0.2O₃ could be prepared neither by the mixed oxide route nor the combustion synthesis or the Pechini method, but only at higher temperatures, for example 1500°C. Taking the results of the dilatometric studies for processing of LSGM ceramics into account, it is obviously that sinter temperatures of above 1300°C in air are required in order to prepare dense LSGM ceramics.     

微波烧结Ni-Zn铁氧体软磁材料的初步研究

采用微波高温烧结炉对Ni-Zn铁氧体软磁材料进行公斤级烧结工艺研究.结果表明,运用微波烧结可以实现Ni-Zn铁氧体材料烧结过程中的快速升温,短时保温,不仅大大降低能源消耗,缩短工艺周期,而且提高了Ni-Zn铁氧体软磁材料物理及机械性能.     

PMN-PFN Relaxor Ferroelectric Ceramics by a Reaction-Sintering Process

Pb((Mg_1/3Nb_2/3)_0.6(Fe_1/2Nb_1/2)_0.4)O₃ (PMFN) perovskite relaxor ferroelectric ceramics produced by reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Mg(NO₃)₂, Fe(NO₃)₃ and Nb₂O₅ was pressed into pellets and sintered directly. PMFN ceramics of 100% perovskite phase were obtained. Density of 7.84 g/cm³ (95% of theoretical value) was obtained after sintered at 1250°C for 2 h. Grain sizes of 3–6 m were formed after 2 h sintering at 1150–1250°C. Dielectric constant at room temperature under 10 kHz reaches 22400 after sintered at 1250°C for 2 h.