Microwave versus conventional sintering: Estimate of the apparent activation energy for densification of α-alumina and zinc oxide

A comparative study between the conventional and 2.45 GHz microwave multimode sintering behavior of insulator (α-Al₂O₃) and semi-conductive ceramic (ZnO) was systematically investigated. The apparent activation energy of nonisothermal sintering was determined by way of the Arrhenius plot of densification data at constant heating rates (CHR) and the concepts of Master Sintering Curves (MSCs), respectively. During microwave densification process, the apparent activation energy was about 90 kJ/mol less than the value for conventional sintering of Al₂O₃ applying these two estimation methods. However, an opposite result was obtained in the case of ZnO, although its densification process had been also accelerated by microwave as well as Al₂O₃. The significant differences in activation energy give a good proof of the difference in diffusion mechanism induced by the electromagnetic field underlying microwave sintering.     

Microwave-Assisted Synthesis and Sintering of NZP Compounds

We have identified the high microwave susceptibility of the sodium di-hydrogen phosphate monohydrate (NHPM), NH₂PO₄·H₂O. This acid phosphate of sodium can be heated to >900°C when exposed to 2.45 GHz microwave radiation. Using NHPM and microwave energy, a novel single-step synthesis of many important crystalline NZP compounds has been accomplished in a very short time. Interestingly, the combination of microwaves and nonstoichiometric oxide precursors for the preparation of NZP materials is found to reduce the reaction temperatures and enhance the reaction kinetics further. The microwave synthesis method is found to be simple and fast, minimizing the loss of volatile chemical species from the reaction. A microwave-assisted procedure for the rapid sintering of NZP compounds has also been demonstrated. Densification (>97%) has been achieved in <30 min at sintering temperature much lower than normally required in conventional processes. Finer microstructure and better densification are the main advantages of the microwave sintering in this study.     

Microwave Sintering of Alumina at 2.45 GHz

The sintering kinetics and microstructural evolution of alumina tubes (∼17 mm length, ∼9 mm inner diameter, and ∼11 mm outer diameter) were studied by conventional and microwave heating at 2.45 GHz. Temperature during microwave heating was measured with an infrared pyrometer and was calibrated to ±10°C. With no hold at sintering temperature, microwave-sintered samples reached 95% density at 1350°C versus 1600°C for conventionally heated samples. The activation energy for microwave sintering was 85 ± 10 kJ/mol, whereas the activation energy for conventionally sintered samples was 520 ± 14 kJ/mol. Despite the difference in temperature, grains grew from ∼1.0 μm at 86% density to ∼2.6 μm at 98% density for both conventionally sintered and microwave-sintered samples. The grain size/density trajectory was independent of the heating source. It is concluded that the enhanced densification with microwave heating is not a consequence of fast-firing and therefore is not a result in the change in the relative rates of surface and grain boundary diffusion in the presence of microwave energy.     

Densification and microstructure evolution of Y-Tetragonal Zirconia Polycrystal powder during direct and hybrid microwave sintering in a single-mode cavity

The densification and microstructure changes of 2 mol% yttria-stabilized zirconia nanopowder have been investigated during direct and hybrid microwave sintering. Microwave heating tests were achieved in a resonant single-mode cavity at 2.45 GHz and a cylindrical SiC susceptor was used for hybrid sintering experiments. Constant heating rate runs (25 °C/min) were controlled by adjusting the position of a sliding piston at constant forward microwave power. The temperature on the upper surface of the specimen was measured with an infrared camera. The final densities and the microstructures observed by SEM were compared to those of conventionally sintered materials. Homogeneous microstructures have been obtained by hybrid heating whereas direct microwave heating led to rather heterogeneous microstructures due to thermal gradients. Nevertheless, microwave-sintered materials always exhibited higher final densities for a given sintering temperature. This significant enhancement of the densification process was particularly observed in the intermediate sintering stage (1200–1350 °C range). Besides, grain growth was found to be mainly influenced by the sintering temperature rather than by the heating mode.     

Comparative Study of Microwave Sintering of Zinc Oxide at 2.45, 30, and 83 GHz

Temperature gradients that develop in ceramic materials during microwave heating are known to be strongly dependent on the applied microwave frequency. To gain a better understanding of this dependence, identical samples of ZnO powder compacts were microwave heated at three distinct widely separated frequencies of 2.45, 30, and 83 GHz and the core and surface temperatures were simultaneously monitored. At 2.45 GHz, the approximately uniform "volumetric" heating tends to raise the temperature of the sample as a whole, but the interior becomes hotter than the exterior because of heat loss from the surface. At 30 and 83 GHz, this interior to exterior temperature difference was found to be reversed, especially for high heating rates. This reversal resulted from increased energy deposition close to the sample's surface associated with reduced skin depth. A model for solving Maxwell's equations was incorporated into a newly developed two-dimensional (2-D) heat transport simulation code. The numerical simulations are in agreement with the experimental results. Simultaneous application of two or more widely separated frequencies is expected to allow electronic tailoring of the temperature profile during sintering.     

Fully coupled electromagnetic‐thermal‐mechanical comparative simulation of direct vs hybrid microwave sintering of 3Y‐ZrO2

Direct and hybrid microwave sintering of 3Y‐ZrO₂ are comparatively studied at frequency of 2.45 GHz. Using the continuum theory of sintering, a fully coupled electromagnetic‐thermal‐mechanical (EMTM) finite element simulation is carried out to predict powder samples deformation during their microwave processing. Direct and hybrid heating configurations are computationally tested using advanced heat transfer simulation tools including the surface to surface thermal radiation boundary conditions and a numeric proportional‐integral‐derivative regulation (PID). The developed modeling framework shows a good agreement of the calculation results with the known experimental data on the microwave sintering of 3Y‐ZrO₂ in terms of the densification kinetics. It is shown that the direct heating configuration renders highly hot spot effects resulting in nonhomogenous densification causing processed specimen's final shape distortions. Compared with the direct heating, the hybrid heating configuration provides a reduction of the thermal inhomogeneity along with a densification homogenization. As a result of the hybrid heating, the total densification of the specimen is attained without specimen distortions. It is also shown that the reduction of the sample size has a stabilization effect on the temperature and relative density spatial distributions.     

Pressure-assisted microwave sintering: A rapid process to sinter submicron sized grained MgAl2O4 transparent ceramics

This work focuses on the development of an original process based on a 2.45 GHz single-mode microwave cavity equipped with a uniaxial press, to sinter transparent spinel MgAl₂O₄ ceramic in air. The samples were conventionally pre-sintered to a density of 90% TD before microwave sintering to the final stage of densification. The influence of thermomechanical cycle on the material properties was investigated. Transmittance, grain size distribution, hardness and fracture toughness of the samples were measured and correlated to the microstructure. This new sintering process has allowed obtaining transparent samples with sub micrometric grain size and high mechanical properties, with relatively short times and low temperature. These first results can be compared to some obtained by SPS or HIP. The technical input of this method is that all the process is here conducted in air atmosphere.     

Synthesis of BaCu(B2O5) Ceramics and their Effect on the Sintering Temperature and Microwave Dielectric Properties of Ba(Zn1/3Nb2/3)O3 Ceramics

BaCu(B₂O₅) ceramics were synthesized and their microwave dielectric properties were investigated. BaCu(B₂O₅) phase was formed at 700°C and melted above 850°C. The BaCu(B₂O₅) ceramic sintered at 810°C had a dielectric constant (ɛ_r) of 7.4, a quality factor ( Q × f ) of 50 000 GHz and a temperature coefficient of resonance frequency (τ_f) of −32 ppm/°C. As the BaCu(B₂O₅) ceramic had a low melting temperature and good microwave dielectric properties, it can be used as a low-temperature sintering aid for microwave dielectric materials for low temperature co-fired ceramic application. When BaCu(B₂O₅) was added to the Ba(Zn_1/3Nb_2/3)O₃ (BZN) ceramic, BZN ceramics were well sintered even at 850°C. BaCu(B₂O₅) existed as a liquid phase during the sintering and assisted the densification of the BZN ceramic. Good microwave dielectric properties of Q × f =16 000 GHz, ɛ_r=35, and τ_f=22.1 ppm/°C were obtained for the BZN+6.0 mol% BaCu(B₂O₅) ceramic sintered at 875°C for 2 h.     

Enhanced microwave-assisted sintering of X7R ceramic dielectrics for use in multilayer capacitors

A hybrid furnace, allowing the simultaneous application of microwave (2.45 GHz) and radiant energy, has been used to investigate the sintering of a commercial X7R powder commonly used in multilayer capacitors. Samples were processed at temperatures in the range 1060–1120 °C. Enhanced sintering has been observed in the form of accelerated densification when a microwave field is applied. At 1090 °C for example, 99.4% dense material was obtained by microwave-assisted heating but only 96.9% density was reached by conventional heating. The relative permittivity of the microwave sintered material was ～2200, typically 10%, higher than for conventionally sintering. The Curie temperature was lower by 5 °C in the microwave heated samples.     

Microwave sintering and grain growth behavior of nano-grained BaTiO3 materials

In this paper, we investigated the effect of microwave sintering parameters on the development of the microstructure of nano-grained BaTiO₃ materials co-doped with Y and Mg species. It is observed that the materials can not only be sintered densely at a lower temperature (1150 °C) and a shorter soaking time (20 min), but also the grain growth can be suppressed by 2.45 GHz microwave heating process. However, the grain growth exhibits a unique tendency in some processing conditions such as microwave sintering for longer intervals (≧60 min) or at higher temperatures (1200 °C). The grain growth behavior after densification was investigated in terms of the phenomenological kinetics, and the activation energy for grain growth using microwave sintering (59.4 kJ/mol) is considerably less than that of the conventionally sintered ones (96.0 kJ/mol), which indicates that microwave sintering process can accelerate the densification rate of the BaTiO₃ materials comparing with the conventional sintering process.     

Evidence for the Microwave Effect During Hybrid Sintering

A microwave/conventional hybrid furnace has been used to sinter three ceramics with different microwave absorption characteristics under pure conventional and a range of microwave/conventional hybrid heating regimes. The precursor powder particle size was also varied for each material. In each case it was ensured that every sample within a series had an identical thermal history in terms of its temperature/time profile. An increase in both the onset of densification and the final density achieved was observed with an increasing fraction of microwave energy used during sintering, the effect being greatest for the materials that absorbed microwaves most readily. Twenty-three percent greater densification was observed for submicron zinc oxide powder, the material with the largest microwave absorption capability, when sintered using hybrid heating involving 1 kW of microwave power compared with pure conventional power under otherwise identical conditions. For the ceramic with the lowest microwave absorption characteristic, alumina, the increase in densification was extremely small; partially stabilized zirconia, a moderate microwave absorber, was intermediate between the two. Temperature gradients within the samples, a potential cause of the effect, were assessed using two different approaches and found to be too small to explain the results. Hence, it is believed that clear evidence has been found to support the existence of a genuine "microwave effect."     

Is direct microwave heating well suited for sintering ceramics?

This paper presents a thorough analysis of direct microwave heating as a sintering process of ceramic materials. It questions why susceptor-assisted microwave heating is used in most experimental works, although direct microwave coupling is preferable for taking advantage of the possible beneficial effects of the microwave field on the sintering phenomena. This issue was investigated by conducting both experiments and numerical simulations. The experiments consisted of sintering alumina and yttria doped zirconia powder samples in a 2.45 GHz resonant cavity with automatic thermal monitoring, whereas the numerical simulations coupled electromagnetics, thermal transfer and sample deformation. Alumina and yttria doped zirconia are widely used materials and they exhibit different microwave field behaviours (transparent and absorbent, respectively), which are representative of most ceramic materials. The influence of the insulating material was discussed by considering different sintering cell designs. The very low coupling capacity of alumina made its direct heating very difficult. It was therefore necessary to apply a strong electric field to heat it. This situation promoted the absorption of microwave energy by other elements such as the insulating material, leading to heating instabilities and degradation of the insulation cell. In the case of zirconia, its coupling properties change abruptly with increasing temperature. It is poorly absorbent at low temperature, highly absorbent at intermediate temperature and it finally becomes reflective at the end of the sintering process. The consequences of this behaviour are (i) a very difficult control of direct heating (ii) a propensity to form damaging hot spots and (iii) the impossibility to reach high temperatures without forming plasma. Therefore, this experimental and numerical study showed that direct microwave heating is not suitable for conducting reliable and homogeneous sintering of classical ceramics. This explains why susceptor-assisted heating is most of time preferred.     

Effect of Li2CO3 Addition on the Sintering Temperature and Microwave Dielectric Properties of Mg2V2O7 Ceramics

Li₂CO₃ was added to Mg₂V₂O₇ ceramics in order to reduce the sintering temperature to below 900°C. At temperatures below 900°C, a liquid phase was formed during sintering, which assisted the densification of the specimens. The addition of Li₂CO₃ changed the crystal structure of Mg₂V₂O₇ ceramics from triclinic to monoclinic. The 6.0 mol% Li₂CO₃-added Mg₂V₂O₇ ceramic was well sintered at 800°C with a high density and good microwave dielectric properties of ɛ _r=8.2, Q × f =70 621 GHz, and τ_f=−35.2 ppm/°C. Silver did not react with the 6.0 mol% Li₂CO₃-added Mg₂V₂O₇ ceramic at 800°C. Therefore, this ceramic is a good candidate material in low-temperature co-fired ceramic multilayer devices.     

Modeling and in-situ evaluation of thermal gradients during sintering of large ceramic balls

During the sintering process of ceramic pieces, temperature gradients may arise inside the piece if the thermal cycle is too fast with regards to the size of the ceramic body. Too large temperature gradients may lead to density gradients, thus to strain gradients which may result in defects or in the fracture of the pieces. This article presents both an experimental setup and the first steps towards a numerical method to evaluate these thermal gradients and their evolutions during sintering, in the case of large zirconia, alumina and zirconia-toughened alumina balls. Finally it discusses the advantages of Rate Controlled Sintering thermal cycles in terms of diminishing the temperature gradients during densification.     

Dielectric Characteristics of Nd(Zn1/2Ti1/2)O3 Ceramics at Microwave Frequencies

The microwave dielectric properties and the microstructures of Nd(Zn_1/2Ti_1/2)O₃ (NZT) ceramics prepared by the conventional solid-state route have been studied. The prepared NZT exhibited a mixture of Zn and Ti showing 1:1 order in the B-site. The dielectric constant values (ɛ_r) saturated at 29.1–31.6. The quality factor ( Q × f ) values of 56 700–170 000 (at 8.5 GHz) can be obtained when the sintering temperatures are in the range of 1300°–1420°C. The temperature coefficient of resonant frequency τ_f was not sensitive to the sintering temperature. The ɛ _r value of 31.6, the Q × f value of 170 000 (at 8.5 GHz), and the τ_f value of −42 ppm/°C were obtained for NZT ceramics sintering at 1330°C for 4 h. For applications of high selective microwave ceramic resonators, filters, and antennas, NZT is proposed as a suitable material candidate.     

Processing of a Silicon-Carbide-Whisker-Reinforced Glass-Ceramic Composite by Microwave Heating

A calcium magnesium aluminosilicate-based glass that contained 10 wt% of silicon carbide whiskers (SiC _w ) as reinforcement was prepared by tape casting, followed by sintering either in a conventional furnace or in a microwave oven. The results were consistent with retardation of glass sintering through whisker bridging. The glass, by itself, was sintered to almost-full density at 750°C for 4 h by conventional furnace sintering; the best sintered composite, with an estimated density of ∼90%, was obtained at 800°C with a dwell time of 4 h. Sintering at a temperature of >800°C did not improve the densification but rather resulted in severe whisker oxidation. A reduced densification rate was observed for the samples that were sintered in nitrogen. By contrast, in the microwave oven, almost-full density for the glass and ∼95% of the theoretical density for the composite were obtainable at 850°C for 15 min, which represented a reduction of ∼10 h of the total processing time and a reduced SiC _w oxidation.     

Sintering of Partially Stabilized Zirconia by Microwave Heating Using ZnO–MnO2–Al2O3 Plates in a Domestic Microwave Oven

Partially stabilized zirconia (PSZ) powders were fully densified by microwave heating using a domestic microwave oven. Pressed powder compacts of PSZ were sandwiched between two ZnO–MnO₂–Al₂O₃ ceramic plates and put into the microwave oven. In the first step, PSZ green pellets were heated by self-heating of ZnO–MnO₂–Al₂O₃ ceramics (1000°C). In the second step, the heated PSZ pellets absorbed microwave energy and self-heated up to a higher temperature (1250°C), leading to densification. The density of PSZ obtained by heating in the microwave oven for 16 min was 5.7 g/cm³, which was approximately equal to the density of bodies sintered at 1300°C for 4 h or 1400°C for 16 min by the conventional method. The average grain size of the sample obtained by this method was larger than the average grain size of samples sintered by the conventional method with a similar heating process.     

Low-Temperature Sintering and Microwave Dielectric Properties of Li2MgSiO4 Ceramics

Development of a low-temperature sintered dielectric material derived from Li₂MgSiO₄ (LMS) for low-temperature cofired ceramic (LTCC) application is discussed in this paper. The LMS ceramics were prepared by the solid-state ceramic route. The calcination and sintering temperatures of LMS were optimized at 850°C/4 h and 1250°C/2 h, respectively, for the best density and dielectric properties. The crystal structure and microstructure of the ceramic were studied by the X-ray diffraction and scanning electron microscopic methods. The microwave dielectric properties of the ceramic were measured by the cavity perturbation method. The LMS sintered at 1250°C/2 h had ɛ_r=5.1 and tan δ=5.2 × 10⁻⁴ at 8 GHz. The sintering temperature of LMS is lowered from 1250°C/2 h to 850°C/2 h by the addition of both lithium borosilicate (LBS) and lithium magnesium zinc borosilicate (LMZBS) glasses. LMS mixed with 1 wt% LBS sintered at 925°C/2 h had ɛ_r=5.5 and tan δ=7 × 10⁻⁵ at 8 GHz. Two weight percent LMZBS mixed with LMS sintered at 875°C/2 h had ɛ_r=5.9 and tan δ=6.7 × 10⁻⁵ at 8 GHz.     

Electric-Field-Controlled Permittivity Ferroelectric Composition for Microwave LTCC Modules

A low-temperature cofired ferroelectric ceramic composition for electrically tunable radio frequency devices is introduced. A sintering temperature of 950°C for BaSrTiO₃–MgO was obtained following the combined addition of B₂O₃ and Li₂CO₃. The effects of these sintering aids on densification, microstructure, and ferroelectric properties were investigated. The permittivity and dissipation factor values were 234 and 0.0010, respectively, measured at 286.3 K, 1 kHz. The electrically tunable ferroelectric structure for microwave measurement was fabricated throughout the tape-casting process. Measured permittivity was 130 at 26 GHz and tunability >15% (4 V/μm).