Kinetic and thermodynamic effects of manganese as a densification aid in yttria-stabilized zirconia

This work demonstrates the role of Mn as an effective sintering aid in Yttria-Stabilized-Zirconia (YSZ) is a result of the concomitant reduction of activation energies and change of interfacial energies caused by Mn segregation. Kissinger analyses of the heat of sintering showed a decrease in activation energy from 219.9 kJ/mol for YSZ to 103.4 kJ/mol for YSZ containing 3-mol% Mn. Direct microcalorimetry analyses showed that the average surface and grain boundary energies of YSZ decreased from 0.94 and 0.71 J/m², respectively, to 0.70 and 0.17 J/m² for 3-mol% Mn doped YSZ. The decrease in the ratio between surface and grain boundary energies indicates an increase in dihedral angle from 137.5° to 166.6°, meaning an increase in sintering stress. Segregation of manganese to grain boundaries was experimentally observed and is discussed to be responsible for both kinetic and thermodynamic changes in the system while suggesting interconnection by the thermodynamic extremal principle.     

Densification mechanisms and microstructural evolution during spark plasma sintering of boron carbide powders

Micron-sized boron carbide (B₄C) powders were subjected to spark plasma sintering (SPS) under temperature ranging from 1700 °C to 2100 °C for a soaking time of 5, 10 and 20 min and their densification kinetics was determined using a creep deformation model. The densification mechanism was interpreted on the basis of the stress exponent n and the apparent activation energy Q_d from Harrenius plots. Results showed that within the temperature range 1700–2000 °C, creep deformation which was controlled by grain-boundary sliding or by interface reaction contributed to the densification mechanism at low effective stress regime (n = 2,Q_d = 459.36 kJ/mol). While at temperature higher than 2000 °C or at high stress regime, the dominant mechanism appears to be the dislocation climb (n = 6.11).     

The effect of slip casting and spark plasma sintering (SPS) temperature on the transparency of MgAl2O4 spinel

MgAl₂O₄ bulk samples were fabricated by two different approaches to investigate the effect of slip casting and sintering temperature on their transparency. Three MgAl₂O₄ samples containing 1 wt% LiF, as the sintering aid, were prepared by the spark plasma sintering process (SPS) at 1400 °C and 1500 °C, under 100 MPa, for 15 min. Also, another MgAl₂O₄ sample was prepared by slip casting followed by SPS under similar conditions. It was observed that utilizing slip casting led to more transparency (10% in the visible region and 20% in the IR region) due to the more homogeneous structure. It was also observed that by reducing the SPS temperature from 1500 °C to 1400 °C, the transparency increased (20% in the IR region) because of the lower grain growth rate at the lower temperature.     

The effect of carbon nanotubes on the sintering behaviour of zirconia

The sintering behaviour and activation energy of Y₂O₃ partially stabilised ZrO₂ and ZrO₂–CNT (0.5 and 2 vol%) composites was determined using spark plasma sintering (SPS) under isothermal conditions. The sintering activation energy for the Y₂O₃ partially stabilised ZrO₂ was found to be 456 kJ/mol. The addition of 2 vol% CNTs reduced the sintering activation energy to 172 kJ/mol. The significant reduction of the activation energy with the addition of only 2 vol% CNTs is attributed to the formation of a percolating network of CNTs providing a lower energy diffusion pathway. The sintering mechanism was found to be grain boundary diffusion for all samples suggesting that the presence of CNTs does not change the sintering mechanism but does lower the activation energy for the rate limiting step in the sintering process.     

Two-stage master sintering curve applied to two-step sintering of oxide ceramics

Tetragonal (3 mol% Y₂O₃) and two cubic zirconia (8 mol% Y₂O₃) as well as alumina green bodies were used for the construction of the Master Sintering Curve (MSC) created from sets of constant-rate-of-heating (CRH) sintering experiments. The activation energies calculated according to the MSC theory were 770 kJ/mol for Al₂O₃, 1270 kJ/mol for t-ZrO₂, 620 kJ/mol and 750 kJ/mol for c-ZrO₂. These values were verified by an alternative approach based on an analysis of the densification rate in the intermediate sintering stage. The MSCs established from the Two-Step Sintering (TSS) experiments showed at high densities a significant deflection from those constructed from the CRH experiments. This deflection was explained by lower sintering activation energy in the closed porosity stage. A new two-stage MSC model was developed to reflect the change in sintering activation energy and to describe TSS. The efficiency of TSS of four materials under investigation was correlated with their activation energies during the final sintering stage.     

Structural characterization of YSZ/Al2O3 nanostructured composite coating fabricated by electrophoretic deposition and reaction bonding

Suspension of YSZ and Al particles in acetone in presence of 1.2 g/l iodine as dispersant was used for electrophoretic deposition of green form YSZ/Al coating. Results revealed that applied voltage of 6 V and deposition time of 3 min were appropriate for deposition of green composite form coating. After deposition, a nanostructured dense YSZ/Al₂O₃ composite coating was fabricated by oxidation of Al particles at 600 °C for 2 h and subsequently sintering heat treatment at 1000 °C for 2 h. Melting and oxidation of Al particles in the green form composite coating not only caused reaction bonding between the particles but also lowered the sintering temperature of the ceramic coating about 200 °C. The EDS maps confirmed that the composition of fabricated coating was uniform and Al₂O₃ particles were dispersed homogenously in YSZ matrix.     

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.     

Microstructure and mechanical properties of ZTA composites fabricated by oscillatory pressure sintering

The influence of sintering temperature on the microstructure and mechanical properties of Al₂O₃?20 wt% ZrO₂ composites fabricated by oscillatory pressure sintering (OPS) was investigated by means of X-ray diffraction, scanning electron microscopy, three-point bending test and Vickers indentation. Results were compared to specimens obtained by conventional hot pressing (HP) under a similar sintering schedule. The optimum oscillatory pressure sintering temperature was found to be 1600 °C; almost fully dense materials (99.94% of theoretical density) with homogeneous microstructure could be achieved. The highest flexural strength, fracture toughness and hardness of such composites reached 1145 MPa, 5.74 MPa m^1/2 and 19.08 GPa when sintered at 1600 °C, respectively. Furthermore, the oscillatory pressure sintering temperature could be decreased by more than 50 °C as compared with the HP method, OPS favouring enhanced grain boundary sliding, plastic deformation and diffusion in the sintering process.     

Microwave dielectric properties of low-temperature sinterable α-MoO3

The α-MoO₃ ceramics were prepared by uniaxial pressing and sintering of MoO₃ powder at 650 °C and their structure, microstructure, densification and sintering and microwave dielectric properties were investigated. The sintering temperature of α-MoO₃ was optimized based on the best densification and microwave dielectric properties. After sintering at 650 °C the relative permittivity was found to be 6.6 and the quality factor was 41,000 GHz at 11.3 GHz. The full-width half-maximum of the A_1g Raman mode of bulk α-MoO₃ at different sintering temperatures correlated well with the Qf values. Moreover, the sintered samples showed a temperature coefficient of the resonant frequency of ?25 ppm/°C in the temperature range from ?40 to 85 °C and they exhibited a very low coefficient of thermal expansion of ±4 ppm/°C. These microwave dielectric properties of α-MoO₃ will be of great benefit in future MoO₃ based materials and their applications.     

Low-temperature-sintered Bi0.5Na0.5TiO3-based lead-free ferroelectric ceramics with good piezoelectric properties

Li₂CO₃ has been used as a sintering aid for fabricating lead-free ferroelectric ceramic 0.93(Bi_0.5Na_0.5TiO₃)-0.07BaTiO₃. A small amount (0.5 wt%) of it can effectively lower the sintering temperature of the ceramic from 1200 °C to 980 °C. Unlike other low temperature-sintered ferroelectric ceramics, the ceramic retains its good dielectric and piezoelectric properties, giving a high dielectric constant (1570), low dielectric loss (4.8%) and large piezoelectric coefficient (180 pC/N). The “depolarization” temperature is also increased to 100 °C and the thermal stability of piezoelectricity is improved. Our results reveal that oxygen vacancies generated from the diffusion of the sintering aid into the lattices are crucial for realizing the low temperature sintering. Owing to the low sintering temperature and good dielectric and piezoelectric properties, the ceramics, especially of multilayered structure, should have great potential for practical applications.     

Sintering behaviour of a glass obtained from MSWI ash

The sintering behaviour of a glass obtained by Municipal Solid Waste Incinerator (MSWI) bottom ash (WG) was investigated and compared with a Na₂O–MgO–CaO–SiO₂ composition (CG). The sintering activation energy, E_sin, and the energy of viscous flow, E_η, were evaluated by dilatomeric measurements at different heating rates. The formation of crystalline phases was evaluated by Differential Thermal Analysis (DTA) and X-Ray Diffraction (XRD), and observed by Scanning Electron Microscopy (SEM) and Transition Electron Microscopy (TEM). In CG, the sintering started at ≈10¹³ dPa s viscosity and E_sin (245 kJ/mol) remains constant in the measured range of shrinkage, up to 9%. In WG the densification started at ≈10¹¹ dPa s, E_sin resulted to be 395 kJ/mol up to 5% shrinkage, 420 kJ/mol at 8% and 485 kJ/mol at 10% shrinkage. The sintering rate decreased due to the beginning of the pyroxene formation and the densification stopped in the temperature range 1073–1123 K after formation of 5 ± 3% and 13 ± 3% crystal phase, at 5 and 20 K/min, respectively. Higher densification and improved mechanical properties were obtained by applying the fast heating rate, i.e. 20 K/min.     

Phase formation and crystallization kinetics in cordierite ceramics prepared from kaolinite and magnesia

In this work, Algerian kaolinite, a naturally occurring clay mineral, was used as low-cost precursor for the synthesis of cordierite ceramics. The kaolinite was mixed with synthetic magnesia, and the mixture was ball milled and reaction sintered in the temperature range 900–1350 °C for 2 h. Thermogravimetry (TG), differential thermal analysis (DTA), dilatometry, high temperature x-ray powder diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM) complementary techniques were used to analyze sintering behavior, characterize phase transformations, and investigate crystallization kinetics. Milling the kaolinite and magnesia mixture for 10 h yielded a homogenous powder, decreased the average particle size, and improved the roundness of particles. Different crystalline phases were present in the samples sintered in the temperature range 900–1150 °C, the cordierite phase started to crystallize at 1200 °C, and the formation of highly dense cordierite (99%) was complete at 1250 °C. The activation energy values for cordierite formation calculated using Kissinger, Boswell, and Ozawa methods were found to be equal to 577, 589, and 573 kJ/mol, respectively. The kinetic parameters n and m had values close to 2. Bulk nucleation with a constant number of nuclei was the dominant mechanism in cordierite crystallization, followed by two-dimensional growth controlled by interface reaction.     

Influence of processing on stability,microstructure and thermoelectric properties of Ca3Co4 − xO9 + δ

Due to high figure of merit, Ca₃Co_4 ? xO_9 + δ (CCO) has potential as p-type material for high-temperature thermoelectrics. Here, the influence of processing including solid state sintering, spark plasma sintering and post-calcination on stability, microstructure and thermoelectric properties is reported. By a new post-calcination approach, single-phase materials were obtained from precursors to final dense ceramics in one step. The highest zT of 0.11 was recorded at 800 °C for CCO with 98 and 72% relative densities. In situ high-temperature X-ray diffraction in air and oxygen revealed a higher stability of CCO in oxygen (～970 °C) than in air (～930 °C), with formation of Ca₃Co₂O₆ which also showed high stability in oxygen, even at 1125 °C. Since achievement of phase pure high density CCO by post-calcination method in air is challenging, the phase stability of CCO in oxygen is important for understanding and further improvement of the method.     

Effects of zinc nitrate as a sintering aid on the electrochemical characteristics of Sr0.92Y0.08TiO3–δ and Sr0.92Y0.08Ti0.6Fe0.4O3–δ anodes

Although Sr_0.92Y_0.08TiO_3–δ (SYT) and Sr_0.92Y_0.08Ti_0.6Fe_0.4O_3–δ (SYTF) have been widely considered as promising materials for solid oxide fuel cell anodes, the poor densification restricts their commercial applications. As a sintering aid, zinc nitrate successfully stimulates the sintering process and improves densification. An investigation of linear shrinkage and scanning electron microscopy images indicated that the sinterability of SYT and SYTF materials was effectively improved by impregnating the green body with 5 mol% of Zn. It was found that the modification with zinc lowered the activation energy of the electrical conduction process and significantly improved the electrical conductivities of SYT and SYTF at all atmospheric conditions. The maximum power densities of the SYT and SYTF anodes were improved from 19.7 and 34.1 mW cm^–2 to 56.9 and 92.3 mW cm^–2 in H₂ and from 10.2 and 19.4 mW cm^–2 to 47.5 and 61.9 mW cm^–2 in CH₄, respectively.     

Decarbonising ceramic manufacturing: A techno-economic analysis of energy efficient sintering technologies in the functional materials sector

The rising cost of energy and concerns about the environmental impact of manufacturing processes have necessitated the need for more efficient and sustainable manufacturing. The ceramic industry is an energy intensive industrial sector and consequently the potential to improve energy efficiency is huge, particularly through the introduction of modern sintering technologies. Although several energy efficient sintering processes have been developed, there is no comprehensive techno-economic analysis which compares and contrasts these techniques. This paper presents a critical review and analysis of a number of sintering techniques and compares them with the recently developed cold sintering process (CSP), including mode of operation, sintering mechanism, typical heating rates, duration of sintering, energy consumption profile and energy saving potential, limitations, key challenges for further development and current research efforts. By using a figure of merit, pounds per tonne of CO₂ saved (£/tCO₂-eq), which links initial capital investment with energy savings, within a framework derived from ranking principles such as marginal abatement cost curves and Pareto optimisation, we have demonstrated that under the scenarios considered for 3 separate functional oxides ZnO, PZT and BaTiO₃, CSP is the most economically attractive sintering option, indicating lower capital costs and best return on investment as well as considerable energy and emission savings. Although the current work establishes the viability of CSP as a competitive and sustainable alternative to other sintering techniques, the transition from laboratory to industry of CSP will require hugely different facilities and instrumentation as well as relevant property/performance validation to realise its full potential.     

Sintering behaviour and microwave dielectric properties of BaAl2−2x(ZnSi)xSi2O8 ceramics

BaAl_2?2x(ZnSi)_xSi₂O₈ (x = 0.2–1.0) ceramics were prepared using the conventional solid-state reaction method. The sintering behaviour, phase composition and microwave dielectric properties of the prepared compositions were then investigated. All compositions showed a single phase except for x = 0.8. By substituting (Zn_0.5Si_0.5)³⁺ for Al³⁺ ions, the optimal sintering temperatures of the compositions decreased from 1475 °C (x = 0) to 1000 °C (x = 0.8), which then slightly increased to 1100 °C (x = 1.0). Moreover, the phase stability of BaAl₂Si₂O₈ was improved. A novel BaZnSi₃O₈ microwave dielectric ceramic was obtained at the sintering temperature of 1100 °C. This ceramic possesses good microwave dielectric properties with ε_r = 6.60, Q × f = 52401 GHz (at 15.4 GHz) and τ_f = ?24.5 ppm/°C.     

Crystallization kinetics of PbTiO3 ferroelectric films: Comparison of microwave irradiation with conventional heating

Lead titanate (PTO) films were deposited onto Pt/Ti/SiO₂/Si substrates by a sol-gel method and annealed by microwave irradiation and conventional heating. In contrast to conventional heating, microwave irradiation can crystallize the PTO films at a low temperature of 450 °C or at 550 °C for only 5 min. The XRD and TEM studies reveal that microwave radiation can reduce the nucleation time, and increase the growth rate of perovskite grains in the crystallization process. Moreover, the results using the Avrami’s model show that the effective activation energy for crystallization process by microwave irradiation is 131 kJ/mol, much lower than that for the PTO films by conventional heating (216 kJ/mol). Therefore, microwave irradiation can reduce the effective activation energy for the nucleation and grain growth of the perovskite phase during the crystallization process, contributing to a low-temperature or a short-time preparation process of ferroelectric films.     

Process-tolerant pressureless-sintered silicon carbide ceramics with alumina-yttria-calcia-strontia

Process-tolerant SiC ceramics were prepared by pressureless sintering at 1850–1950 °C for 2 h in an argon atmosphere with a new quaternary additive (Al₂O₃-Y₂O₃-CaO-SrO). The SiC ceramics can be sintered to a > 94% theoretical density at 1800–1950 °C by pressureless sintering. Toughened microstructures consisting of relatively large platelet grains and small equiaxed grains were obtained when SiC ceramics were sintered at 1850–1950 °C. The presently fabricated SiC ceramics showed little variability of the microstructure and mechanical properties with sintering within the temperature range of 1850–1950 °C, demonstrating process-tolerant behavior. The thermal conductivity of the SiC ceramics increased with increasing sintering temperature from 1800 °C to 1900 °C due to decreases of the lattice oxygen content of the SiC grains and residual porosity. The flexural strength, fracture toughness, and thermal conductivity of the SiC ceramics sintered at 1850–1950 °C were in the ranges of 444–457 MPa, 4.9–5.0 MPa m^1/2, and 76–82 Wm^?1 K^?1, respectively.     

Fabrication of porous Al2O3-based ceramics using ball-shaped powders by preceramic polymer process in N2 atmosphere

Porous Al₂O₃-based ceramics were successfully fabricated using ball-shaped powders by preceramic polymer process in N₂ atmosphere. These results showed that the amorphous Si-O-C ceramics were formed on the surface of ball-shaped Al₂O₃ particles by the pyrolysis of the silicone resin during sintering in N₂ atmosphere, which played a role in connecting the Al₂O₃ particles by forming the sintering necks. When the sintering temperatures increased from 1100 °C to 1600 °C, the formed Si-O-C ceramics still existed in the amorphous state and had no crystallization. Interestingly, the amorphous β-SiC formed at 1300 °C and its amount gradually increased with further increasing temperatures. The linear shrinkage rate of the samples varied from 0.49% to 0.73% and the weight loss rate increased from 2.01% to 10.77%. The apparent porosity remarkably varied with the range of 24.9% and 34.5%, as the bulk-density varied from 2.66 to 2.47 g/cm³. The bending strength gradually increased from 9.36 to 22.51 MPa with increasing temperatures from 1100 °C to 1500 °C, however, the bending strength remarkably decreased at 1600 °C, which was attributed to the comprehensive function of the high porosity, broken Al₂O₃ particles and weak connection between Al₂O₃ particles in the samples.     

Filleted RDRA using novel ceramic dielectric (3G-BST) with stable gain and improved bandwidth for X-band application

In the present communication, a filleted rectangular dielectric resonator antenna (FRDRA) using novel synthesized ceramic dielectric is described. The proposed antenna has dual segment rectangular structure filleted at the edges of its upper surface. Teflon (ε_r = 2.1) occupies lower segment of the structure and liquid phase (3 wt% of PbO-BaO-B₂O₃-SiO₂ glass) sintered Ba_0.5Sr_0.5TiO₃ (BST) namely 3G-BST (Average value of ε_r = 15) with filleted structure is used as upper segment. Liquid phase sintering reduces the manufacturing cost by reducing the sintering temperature of BST from 1250 °C to 950 °C without affecting the structure of ceramic with increasing density. The simulated impedance bandwidth of FRDRA is found to be 4.875 GHz (7.735–12.610 GHz), which is 8.57% greater than conventional dual segment rectangular dielectric resonator antenna (DS-RDRA). The experimental impedance bandwidth of FRDRA is 6.048 GHz (7.0–13.048 GHz). Among different feeding mechanisms, aperture-coupled feed mechanism is opted in the proposed antenna to reduce the spurious response and improve the antenna performance. Proposed FRDRA reduces material requirement and provides wider bandwidth with stable radiation pattern over its entire frequency band. The developed antenna is appropriate for use as primary feed in radar and satellite communication.