Densification and grain growth during sintering of porous Ce0.9Gd0.1O1.95 tape cast layers: A comprehensive study on heuristic methods

The sintering behavior of porous Ce_0.9Gd_0.1O_1.95 (CGO10) tape cast layers was systematically investigated to establish fundamental kinetic parameters associated to densification and grain growth. Densification and grain growth were characterized by a set of different methods to determine the dominant sintering mechanisms and kinetics, both in isothermal and at constant heating rate (iso-rate) conditions. Densification of porous CGO10 tape is thermally activated with typical activation energy which was estimated around 440–470 kJ mol^?1. Grain growth showed similar thermal activation energy of ～427 ± 22 kJ mol^?1 in the temperature range of 1100–1250 °C. Grain-boundary diffusion was identified to be the dominant mechanism in porous CGO10 tapes. Grain growth and densification mechanism were found strictly related in the investigated temperature range. Porosity acts as a grain growth inhibitor and grain boundary mobility in the porous body was estimated around 10^?18–10^?16 m³ N^?1 s^?1 at the investigated temperature range.     

Low toxicity binder systems for tape cast Ce0.9Gd0.1O1.95 laminates

Conventional binder systems for tape casting contain toxic phthalate plasticizers and butanone (MEK) as part of the solvent. The effects of exchanging the phthalate with a non-toxic alternative, and butanone with ethanol, were studied on laminates of high-green density CGO (Ce_0.9Gd_0.1O_1.95) tapes. Samples were prepared with a binder system containing DBP (dibutyl phthalate) plasticizer and MEK solvent, and with a binder system based on a non-toxic non-phthalate plasticizer and ethanol. In both systems, the weight ratio of plasticizer to the PVB (polyvinyl butyral) binder was varied between 0.4 and 0.7. Substitution to the less toxic binder system had no adverse impacts on the microstructure. In fact, denser packing and improved homogeneity were observed with the non-phthalate-based system at ratio 0.5 indicating improved dispersion in this system. The denser packing also coincided with a maximum in z-shrinkage and molecular weight of the binder system, which could be related to the distribution of the binder system.     

Performance of IT‐SOFC with Ce0.9Gd0.1O1.95 Functional Layer at the Interface of Ce0.9Gd0.1O1.95 Electrolyte and Ni‐Ce0.9Gd0.1O1.95 Anode

In this paper we present results for a high power density IT‐SOFC and a method for dispersing nanosized Ce_0.9Gd_0.1O_1.95 (GDC) particles at the GDC electrolyte and Ni‐GDC anode interface. Dispersed nanosized particles were deposited to form an anode functional layer (AFL). Anode supports were prepared by tape casting of large micron‐sized NiO powder and sub micron‐sized GDC powder without pore former. For the cathode a La_0.6Sr_0.4Co_0.2Fe_0.8O_{3 – δ} (LSCF)‐GDC composite was used. Without an AFL the open circuit potential (OCP) and the maximum power density were 0.677 V and 407 mW cm^–2, respectively, at 650 °C using 30 sccm of hydrogen and air flow‐rate. With an AFL the OCP and the maximum power density increased to 0.796 V and 994 mW cm^–2, respectively, at the same temperature. Two point probe impedance measurements revealed that the AFL fabricated by the proposed method not only increased the OCP but also reduced the electrode polarisation by 68%. The effect of gas flow‐rate is also present in this paper. When hydrogen and air flow‐rate is increased to 90 sccm, the sample with AFL obtained 1.57 W cm^–2 at 650 °C.     

水热法合成Ce0.9Gd0.1O1.95及其光催化性质研究

采用水热法合成了花状Ce0.9Gd0.1O1.95纳米粉,通过X射线衍射、红外光谱、场发射扫描电子显微镜测试手段对产物进行了表征,探讨了其生长机制,以亚甲基蓝的光降解为模型反应,研究其光催化性能。结果表明,以甲酸为介质,110℃的水热条件下合成的纳米Ce0.9Gd0.1O1.95颗粒经800℃煅烧后具有萤石结构,平均晶粒尺寸为21.6 nm,花状形貌;由于Gd3+的掺杂,纳米Ce0.9Gd0.1O1.95对亚甲基蓝紫外光催化性能强于未掺杂的CeO2。该合成方法简单易行,对纳米Ce0.9Gd0.1O1.95的形貌控制起到了启示作用,所得的花状纳米Ce0.9Gd0.1O1.95在光催化领域有着重要应用价值。     

Influence of pore former on porosity and mechanical properties of Ce0.9Gd0.1O1.95 electrolytes for flue gas purification

Single layered porous Ce_0.9Gd_0.1O_1.95 electrolytes were fabricated by tape casting using different types, shapes and sizes of pore formers and their respective strength and stiffness were compared. The sintered bodies were characterized by scanning electron microscopy, mercury porosimetry, impulse excitation technique (Young modulus) and flexural strength measurements, to investigate the role of the different pore formers on the properties of the compounds. The compared techniques used to evaluate porosity give consistent results. The ratio between open and total porosities, evaluated from mercury porosimetry, varies depending on the used pore formers. The stiffness and strength of the compounds show an exponential dependency to the total porosity. By considering the open porosity instead (functional porosity), we observe that samples with platelets shaped pore formers have higher in-plane strength than spherical pore formers. An optimum can be found in term of Weibull strength and strain of samples obtained with the various pore formers by considering the dependency on the functional open porosity instead of the total porosity.     

Densification and grain growth of 8YSZ containing NiO

The effects of NiO addition on sintering yttria-stabilized zirconia were systematically studied to understand the role of the additive in the sintering process of the solid electrolyte. Specimens of 8 mol% yttria-stabilized zirconia with NiO contents up to 5.0 mol% were prepared using different Ni precursors and sintered at several dwell temperatures and holding times. Densification and microstructural features were studied by apparent density measurements and scanning electron microscopy observations, respectively. The sintering dynamic study was carried out by following the linear shrinkage of powder compacts containing 0-0.75 mol% NiO. Small (up to 1.0 mol%) NiO addition was found to improve the sinterability of yttria-stabilized zirconia. The activation energy for volume diffusion decreases with increasing NiO content, whereas the grain boundary diffusion seems to be independent on this additive. The grain growth of yttria-stabilized zirconia is found to be enhanced even for small NiO contents.     

Densification and grain growth of nanocrystalline 3Y-TZP during two-step sintering

Two-step sintering (TSS) was applied on nanocrystalline yttria tetragonal stabilized zirconia (3Y-TZP) to control the grain growth during the final stage of sintering. The process involves firing at a high temperature (T1) followed by rapid cooling to a lower temperature (T2) and soaking for a prolonged time (t). It is shown that for nanocrystalline 3Y-TZP (27 nm) the optimum processing condition is T1 = 1300 °C, T2 = 1150 °C and t = 30 h. Firing at T1 for 1 min yields 0.83 fractional density and renders pores unstable, leading to further densification at the lower temperature (T2) without remarkable grain growth. Consequently, full density zirconia ceramic with an average grain size of 110 nm is obtained. XRD analysis indicated that the ceramic is fully stabilized. Single-step sintering of the ceramic compact yields grain size of 275 nm with approximately 3 wt.% monoclinic phase. This observation indicates that at a critical grain size lower than 275 nm, phase stabilization is induced by the ultrafine grain structure.     

Densification and grain growth of Gd2Zr2O7 nanoceramics during pressureless sintering

Gd₂Zr₂O₇ nanoceramics were fabricated using pressureless sintering method, in which the nanopowders were synthesized via solvothermal approach. The effects of starting powders on grain growth and densification during sintering of ceramics were revealed. Two distinct pressureless sintering methods were investigated, including conventional and two-step sintering. The sample grain size increases abruptly as sintering temperature increases during conventional sintering. In contrast, in two-step sintering, abnormal or discontinuous grain growth was suppressed in the second step, leading to Gd₂Zr₂O₇ nanoceramics formation (average grain size 83 nm, relative density ∼93%). Such distinct behaviors may originate from the interplay between kinetic factors such as grain boundary migration and diffusion. Moreover, suppression of grain growth and promotion of densification in the two-step sintering are mainly due to dominant role of grain boundary diffusion during the second-step sintering process.     

Effect of niobium doping on the densification and grain growth in alumina

The effect of niobium doping on the densification and grain growth of nano-sized α-Al₂O₃ powders during sintering has been investigated. The dopant concentration added ranged from 0.1 to 0.5 mol%. It was observed that addition of niobium oxide could improve the densification of the pure alumina with a lower sintering temperature, a shorter sintering time. The effect is strengthened by increasing the amount of dopant. It also demonstrated that niobium dopant significantly promotes the grain growth of alumina during sintering and the grain size of alumina increases with increasing the amount of dopant in the added range.     

Hot pressing of nanocrystalline zinc oxide compacts: Densification and grain growth during sintering

Sintering behavior of nanocrystalline zinc oxide (ZnO) powder compacts using hot pressing method was investigated. The sintering conditions (temperature and total time) and results (density and grain size) of two-step sintering (TSS), conventional sintering (CS) and hot pressing (HP) methods were compared. The HP technique versus CS was shown to be a superior method to obtain higher final density (99%), lower sintering temperature, shorter total sintering time and rather fine grain size. The maximum density achieved via HP, TSS and CS methods were 99%, 98.3% and 97%, respectively. The final grain size of samples obtained by HP was greater than that of TSS method. However, the ultra-prolonged sintering total time and the lower final density (88 ks and 98.3%) are the drawbacks of TSS in comparison with the faster HP (17 ks and 99%) method.     

Densification and grain growth behaviour of high-purity MgO ceramics by hot-pressing

High-purity MgO ceramics with a relative density higher than 99.60% and a mean grain size of 8.1 µm were prepared by hot-pressing at 1450 °C and 35 MPa for 120 min. The MgO ceramic was 130 mm in diameter and 10 mm in height. The densification mechanism and grain growth of MgO powder during the sintering process were investigated based on the principles of general deformation and classical phenomenological kinetic theory. The threshold pressure of plastic deformation at the initial sintering stage was also analysed. The results suggest that plastic deformation is the dominant densification mechanism during the initial period and that an applied pressure of 20 MPa is sufficient for the deformation. During the final period, Mg²⁺ diffusion along the grain boundaries controls the densification process, and the grain growth activation energy at the final stage is estimated as 336.38±2.35 kJ mol⁻¹.     

Synthesis,sintering, and grain growth kinetics of Hf6Ta2O17

A systematic study of the solid-state synthesis, pressureless sintering, and grain growth kinetics of Hf₆Ta₂O₁₇ is presented. The ideal conditions for solids-state synthesis of Hf₆Ta₂O₁₇ powder with minimal particle necking was 1250 °C for 2 h in air. The resultant powder has an average particle size of 210 ± 70 nm. The combined synthesis and ball-milling procedure produces highly sinterable Hf₆Ta₂O₁₇ powder, achieving > 97 % of theoretical density after pressureless sintering at 1600 °C for 2 h in air. The grain growth mechanism was sensitive to processing conditions, appearing to be primarily driven by surface diffusion below 1600 °C and grain boundary diffusion above 1650 °C. The respective activation energies for grain growth were found to be Q_S = 659 ± 79 kJ mol⁻¹ and Q_GB = 478 ± 63 kJ mol⁻¹.     

Densification behavior and microstructure evolution of yttrium-doped ThO2 ceramics

Sintering of Th_1-xY_xO_2-x/2 ceramics (x = 0.01, 0.08, 0.15 and 0.22), planned to be used as solid electrolytes in oxygen sensors for sodium-cooled fast nuclear reactors, was investigated. High densification state (i.e. up to 98% TD) was reached after 4 h of heat treatment at 1600 °C and beyond. In addition, ESEM observations showed a major effect of yttrium on grain size due to solute drag effects. Sintering maps were plotted for all the samples and evidenced different stages driven by densification and grain growth. Grain growth was found to be strongly slowed down for x > 0.01, resulting in high values of relative density correlated to submicrometric grain size. Also, activation energies related to densification and grain growth were evaluated around 450 and 500–650 kJ mol⁻¹, respectively. These results led to deliver guidelines for the formulation and sintering of Th_1-xY_xO_2-x/2 ceramics in prospect of their use as a solid electrolyte.     

Densification and grain growth during solid state sintering of LaPO4

This work is devoted to the kinetic study of densification and grain growth of LaPO₄ ceramics. By sintering at a temperature close to 1500 °C, densification rate can reach up to 98% of the theoretical density and grain growth can be controlled in the range 0.6–4 μm. Isothermal shrinkage measurements carried out by dilatometry revealed that densification occurs by lattice diffusion from the grain boundary to the neck. The activation energy for densification (E_D) is evaluated as 480 ± 4 kJ mol⁻¹. Grain growth is governed by lattice diffusion controlled pore drag and the activation energy (E_G) is found to be 603 ± 2 kJ mol⁻¹. The pore mobility is so low that grain growth only occurs for almost fully dense materials.     

The effect of electric fields on grain growth in MgAl2O4 spinel

The application of electrostatic fields during processing of oxide ceramic microstructures was previously reported to enhance densification and grain growth. In this study effects of the externally applied electrostatic field strength on grain growth in MgAl₂O₄ were investigated. Free sintering of green bodies showed accelerated grain growth by about 20% in the presence of an applied nominal field strength of 0.95?kV/cm. In contrast to previous studies, annealing of dense microstructures in the presence of a nominal electric field strength as high as 2.22?kV/cm revealed no additional grain growth. A machine learning algorithm for grain size analysis enabled grain size distributions including up to 30,000 grains. Due to the resulting counting statistics for microstructure analysis, it was discovered that the applied electrostatic fields caused grain growth predominantly during the early stages of sintering, i.e., at lower green body densities, hence suggesting an enhancement of surface diffusion.     

合成镁白云石中CaO和MgO晶粒生长动力学

应用ＴＰ速率等式和线性截距法研究了经１５００℃至１７００℃烧成的两个合成镁白云石体系中ＣａＯ和ＭｇＯ的晶粒生长，采用回归分析和最小二乘法求得ＣａＯ和ＭｇＯ晶粒的生长指数和晶位生长活化能。结果表明，体系中ＭｇＯ晶粒的生长速率总比ＣａＯ的要大，而加入少量ＣｅＯ２添加剂的合成镁白云石中ＣａＯ和ＭｇＯ晶粒生长速率比无添加剂的要快。     

Sintering and grain growth control of high dense YIG

The densification and grain growth of yttrium iron garnet (YIG) were systematically studied to produce highly densified YIG via conventional solid-state route (CSSR). The percentage of purity and structure of YIG was confirmed by XRD characterization. SEM micrographs revealed that with increasing sintering temperature and time, the grain size and the average pores radius (R_p) increased, while the number of pores per volumes (N_v) decreased. The maximum material density obtained using Archimedes principle was 97.9% of that of theoretical density (ρ_theory). It required approximately 132.55 kJ/mol of energy to produce dense YIG sintered for 6 h at 1420 °C. However, beyond this temperature, a new phase that confirmed the presence of YFe₂O_4-δ phase was found through EDX analysis along the grain boundaries. This occurrence lowered the grain boundary mobility thereby resulting in slight change in density. Therefore, the results suggested that a highly densified YIG (ρ_theory of ≈98%) could be successfully obtained when YIG is sintered at 1420 °C for 6 h.     

Texture in silicon carbide via aqueous suspension material extrusion and seeded grain growth

Textured SiC with anisotropic crystallographic texture is proposed as a material with improved mechanical properties. Textured SiC was created via alignment of platelet seed particles during aqueous suspension material extrusion, also known as direct ink writing, and subsequent pressureless liquid phase sintering and annealing. The microstructure and texture of the SiC fabricated with and without 5 vol% platelet seeds, and with and without annealing at 2050 °C and 2150 °C was explored via SEM, XRD, and EBSD. All samples fabricated had over 95% theoretical density. Annealing leads to the development of large, high aspect ratio plate-shaped grains among a matrix of many finer, low aspect ratio grains. Higher annealing temperatures and addition of platelet seeds both increased the size of the large grains. Samples were found to be textured regardless of having platelet seeds. Via XRD and EBSD, unseeded SiC was found to have texture where the crystallographic direction [0001] had a preferred orientation perpendicular to the normal direction. This occurred for both direct ink written and cast SiC, so the texture development must have occurred during sintering, though the mechanism is unknown. For seeded SiC, platelet seeds aligned in direct ink writing seeded the grain growth to develop crystallographic texture. The texture was mainly influenced by the alignment of platelet seed particles via shear stresses in the print nozzle, causing a one-dimensional texture where [0001] is perpendicular to the printing direction. However, it was found that the texture was not the expected concentric alignment of platelet particles in direct ink writing, so the shear stresses in the nozzle are not solely responsible for the texture developed.     

Microstructural evolution and densification behavior of porous kaolin-based mullite ceramic added with MoO3

Microstructural evolution and densification behavior of porous kaolin-based mullite ceramic added with MoO₃ were investigated. The results indicated that MoO₃ addition not only lowered the secondary mullitization temperature to below 950?°C, but also facilitated effectively the anisotropic growth of mullite grains. Fine mullite whiskers grew and interlocked with one another in the pre-existing pore regions, in-situ forming a stiff 3D skeleton structure of mullite whiskers, which arrested further densification of the sample. On the other hand, due to the great capillary attraction of small pores, the liquid phase tended to spread over small grains, which favored the growth from small mullite grains into whiskers at the expense of the liquid phase. Consequently, competitive mechanisms of sintering and crystal growth of mullite functioned, which further limited the sample densification. As a result, the total linear shrinkage of the sample added with MoO₃ after firing at 1400?°C was only ??2.75%, and its porosity was retained at as high as 67%.     

Synthesis of Porous Submicron Gd0.1Ce0.9O1.95 Particles by Carbon Nanoparticle-Addition Ultrasonic Spray Pyrolysis (CNA-USP) and Nanoparticle Preparation by Ball Milling

A new ultrasonic spray pyrolysis method, called carbon nanoparticle-addition ultrasonic spray pyrolysis (CNA-USP), is developed to synthesize nanoparticles of electrolyte material for solid oxide fuel cell applications. In CNA-USP, carbon nanoparticles are added in a precursor solution. First, Gd_0.1Ce_0.9O_1.95 (GDC) particles were synthesized from an aqueous solution of Ce(NO₃)₃ 6H₂O and Gd(NO₃)₃ 6H₂O by using the CNA-USP method. The resulting synthesized GDC particles were agglomerated, porous, primary particles on the order of 10 nm in diameter. EDX images revealed uniform distributions of Ce, Gd, and O in these porous particles. Then, these agglomerated, porous submicron GDC particles were ground into primary nanoparticles by ball milling for 24 h. The average diameter of the ground GDC nanoparticles was about double of their average crystallite size.

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