A study of sintering of magnesium oxide obtained from sea-water

The process of sintering of magnesium oxide obtained from sea-water is studied. The sample thickening stage in the isothermal sintering is determined to establish the manner of pore elimination in the process. The process of isothermal sintering of magnesium oxide is described mathematically to obtain a better insight into the process, in terms of a function giving the best possible correspondence between theoretical and experimental data.     

Preparation of bulk‐nanostructured UO2 pellets using high‐pressure spark plasma sintering for LWR fuel safety assessment

Nuclear fuel undergoes a significant restructuration during its lifetime in the nuclear reactor. Especially at the rim of the pellet, large UO₂ grains disintegrate into a nanosized material. In this paper, we focus on the preparation of bulk UO₂ with grain sizes below 100 nm to investigate the physico‐chemical properties of this so‐called “high burn up structure” (HBS). Preparation of bulk nanocrystalline materials is a challenge that can be overcome using the high‐pressure spark plasma sintering (HP SPS) technique. In‐house developed HP SPS with 500 MPa applied pressure was used for compaction of 11 nm UO₂ powder obtained by oxalate conversion. The procedure yielded dense (>90%) compacts with grain size as low as 34 nm for samples sintered at 800°C.     

Conventional and field-assisted sintering of nanosized Gd-doped ceria synthesized by co-precipitation

Gadolinium-doped ceria is an attractive electrolyte for potential application in SOFCs operating at intermediate temperature; for such use, the fundamental compositions typically contain 10–20 mol% Gd₂O₃. In this work, we produced nanosized 10 mol% gadolinium-doped ceria powder by co-precipitation, starting from Ce and Gd nitrate solutions and using ammonia solution as precipitating agent. The co-precipitate was characterized by DTA-TG, TEM, XRD and nitrogen adsorption analyses. We studied the behavior of the nanopowder under both conventional and Flash sintering. Very different behavior was seen: the conventional sintering cycle produced a poorly densified material, while Flash sintering allowed production of a perfectly densified material, with uniform sub-micrometric grain size.     

LZS/Al2O3 nanostructured composites obtained by colloidal processing and spark plasma sintering

Li₂O-SiO₂-ZrO₂ (LZS) glass-ceramics have high mechanical strength, hardness, resistance to abrasion and chemical attack, but also a high coefficient of thermal expansion (CTE), which can be reduced adding alumina nanoparticles. The conventional glass-ceramic production is relatively complex and energy consuming, since it requires the melting of the raw materials to form a glass frit and a two-step milling process to obtain particle sizes adequate for compaction. This study describes the preparation of LZS glass-ceramics through a colloidal processing approach from mixtures of SiO₂ and ZrO₂ nanopowders and a Li precursor (lithium acetate obtained by reaction of the carbonate with acetic acid). Concentrated suspensions were freeze-dried to obtain homogeneous mixtures of powders that were pressed (100 MPa) and sintered conventionally and by spark plasma sintering. The effect of the alumina nanoparticles additions on suspensions rheology, sintering behavior and properties such as thermal expansion, thermal conductivity, hardness and Young’s modulus were evaluated.     

Development of solid oxide cells by co-sintering of GDC diffusion barriers with LSCF air electrode

The effects of a Cu-based additive and nano-Gd-doped ceria (GDC) sol on the sintering temperature for the construction of solid oxide cells (SOCs) were investigated. A GDC buffer layer with 0.25–2 mol% CuO as a sintering aid was prepared by reacting GDC powder and a CuN₂O₆ solution, followed by heating at 600 °C. The sintering of the CuO-added GDC powder was optimized by investigating linear shrinkage, microstructure, grain size, ionic conductivity, and activation energy at temperatures ranging from 1000 to 1400 °C. The sintering temperature of the CuO–GDC buffer layer was decreased from 1400 °C to 1100 °C by adding the CuO sintering aid at levels exceeding 0.25 mol%. The ionic conductivity of the CuO–GDC electrolyte was maximized at 0.5 mol% CuO. However, the addition of CuO did not significantly affect the activation energy of the GDC buffer layer. Buffer layers with CuO-added GDC or nano-GDC sol-infiltrated GDC were fabricated and tested in co-sintering (1050 °C, air) with La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF). In addition, SOC tests were performed using button cells (active area: 1 cm²) and five-cell (active area: 30 cm²/cell) stacks. The button cell exhibited the maximum power density of 0.89 W cm⁻² in solid oxide fuel cell (SOFC) mode. The stack demonstrated more than 1000 h of operation stability in solid oxide electrolysis cell (SOEC) mode (decay rate: 0.004%/kh).     

Lowering the sintering temperature of solid oxide fuel cell electrolytes by infiltration

A dense electrolyte with a relative density of over 95% is vital to prevent gas leakage and thus the achievement of high open circuit voltage in solid oxide fuel cells (SOFCs). The densification process of ceria based electrolyte requires high temperatures heat treatment (i.e. 1400–1500 °C). Thus, the minimum co-sintering temperatures of the anode-electrode bilayers are fixed at these values, resulting in coarse anode microstructures and consequently poor performance. The main purpose of this study is to densify gadolinia doped ceria (GDC), a common SOFC electrolyte, at temperatures lower than 1400 °C. By this aim, an approach involving the infiltration of polymeric precursors into porous electrolyte scaffolds, a method commonly used for composite SOFC electrodes, is proposed. By infiltrating polymeric precursors of GDC into porous GDC scaffolds, a reduction in the sintering temperature by at least 200 °C is achieved with no additives that might affect the electrical properties. Energy dispersive x-ray spectroscopy line scan analyses performed on porous GDC scaffolds infiltrated by a marker solution (polymeric FeOx precursor in this case) reveals a homogeneous infiltrated phase distribution, demonstrating the effectiveness of polymeric precursors.     

Synthesis and sintering at low temperature of a new nanostructured beta-Eucryptite dense compact by spark plasma sintering

The solid state reaction between kaolin and Li₂CO₃ with a 1:1 M composition has been studied in the temperature range 380°C-550 °C. The role played by Li₂CO₃ (basic medium) in the thermal transformation of the kaolin has been investigated by X-Ray diffraction, FESEM, TEM, MAS-NMR and XPS techniques. For the first time, a nanostructured high density β- Eucryptite (<10 nm) has been obtained by Spark Plasma Sintering (SPS) at 550 °C in high vacuum. The atmosphere used in sintering treatments has a determinant role in lithium migration and crystallization of β- Eucryptite. In the case of low vacuum treatments, an amorphous LiAlSiO₄ geopolymer type material was obtained. Due to exclusive properties and performances of β- Eucryptite based materials, the results reported in the present investigation open new perspectives for new nanostructured and amorphous functional materials with null thermal expansion, ionic conduction and remarkable mechanical properties.     

Sintering behavior of Ba/Sr celsian precursor obtained from zeolite‐A by ion‐exchange method

(Ba, Sr)‐exchanged zeolite A with composition Ba_0.74Sr_0.22Na_0.04Al₂Si₂O₈ was prepared by cation exchange; a mild thermal treatment converts into an amorphous phase. Successive crystallization and sintering behavior was studied by XRD, DTA, and thermodilatometric analysis. The results point out the activation of viscous flow sintering mechanisms between 900°C and 1050°C. The densification process starts when the amorphous phase reaches its glass transition temperature (897°C) and finishes when the material crystallizes forming hexacelsian. The application of an external pressure in such temperature range allows to achieve an almost complete densification, the material transforming at 1300°C into dense monoclinic celsian much below the typical processing temperature.     

Microstructure and mechanical properties of three-dimensional oxide/oxide composite fabricated by a slurry infiltration and sintering process

Oxide/oxide composites reinforced by two-dimensional fiber fabrics are important structural materials at high temperatures but exhibit low delamination resistance. This study developed a simple slurry infiltration and sintering (SIS) process to fabricate three-dimensional oxide/oxide composites. The results showed that a homogeneous microstructure in three directions was obtained. This composite possessed a weak matrix, which had a porous structure and low elastic modulus. Typical mechanical properties of the composite were not lower than those of two-dimensional oxide/oxide composites since the flexural strength and fracture toughness were 332.4 MPa and 11.6 MPa·m^1/2, respectively. Particularly, the composite had a good interlaminar shear strength of 25.4 MPa and a superior transthickness tensile strength of 5.6 MPa. X-ray computed tomography showed that fiber yarns in the through-thickness direction effectively impeded crack propagation and enhanced delamination resistance. Therefore, the reported SIS process is a very promising method for manufacturing three-dimensional oxide/oxide composites.     

Fabrication of nanostructured non-stoichiometric TiO2-x by spark plasma sintering for enhancing its thermoelectric properties

In this study, nanostructured non-stoichiometric TiO_2-x compacts were prepared by the in-situ reduction of rutile titanium oxide (TiO₂) powder with urea powder via spark plasma sintering (SPS). The crystal structure and particle size of the prepared compacts were examined. The XRD patterns revealed that TiO₂ could be reduced easily by the urea powder to obtain non-stoichiometric TiO_2-x, and the compacts still possessed rutile crystal structures. The average particle sizes of the compacts were less than 250 nm, successfully obtaining the non-stoichiometric TiO_2-x with uniform nanostructures at the sintering temperature of 1073 K. In addition, nanostructured TiO_2-x compacts with Magnéli phase Ti_nO_2n-1 (n = 2, 4, 8) were fabricated by varying the volume fraction of Ti powder in a urea environment via SPS. The results suggested that addition of Ti powder contributed to the formation of Magnéli phases Ti_nO_2n-1, and the value of n decreased with an increase in the volume fraction of the Ti powder. Furthermore, the thermoelectric properties of the compacts sintered with and without Ti powder were both investigated. The TiO₂–U13.3-Ti10 compact displayed the highest power factor of 5.04 μWcm⁻¹K⁻² at 973 K. A lower thermal conductivity was achieved by TiO₂–U13.3-Ti10 compact in the temperature range of 373–973 K, approximately 3 Wm⁻¹K⁻¹, due to the nanostructures and Magnéli phases. The highest ZT value of 0.146 was obtained for the TiO₂–U13.3-Ti10 compact at 973 K, achieving a reasonable enhancement of thermoelectric properties.     

Increasing the tensile strength of oxide ceramic matrix mini-composites by two-step sintering

Adapting conventional sintering (CS) techniques of monolithic ceramics for the production of oxide ceramic matrix composites (Ox-CMCs) comes along with a few drawbacks, such as fiber degradation. Thus, the applicability of two-step sintering (TSS) for the production of Ox-CMCs based on Nextel™ 610 fibers and porous alumina matrix is investigated in this study for the first time. Uniaxial tensile tests were performed to evaluate the performance of mini-composites produced by TSS and compared with those produced by CS. Parameters known for influencing the mechanical behavior of the mini-composites, such as grain size, porosity, shrinkage, as well as matrix properties, were analyzed. Both sintering techniques resulted in similar grain size distributions, whereas TSS showed higher total porosity and lower amount of sintering-induced cracks. As a result, TSS samples showed a higher tensile strength of 230±27 MPa when compared to 133±8 MPa for CS. In general, it was observed that most of the densification happens during the first phase of TSS, while the matrix is slowly strengthened during the second step. Therefore, the reported TSS process is a very promising and easy-to-apply heat treatment for producing Ox-CMCs with controlled microstructure.     

Two-step sintering of aluminum-doped zinc oxide sputtering target by using a submicrometer zinc oxide powder

Aluminum-doped zinc oxide (AZO) is a potential substitute for tin-doped indium oxide due to its versatility. The properties of AZO films are related to those of the AZO sputtering target. To improve the performances of AZO targets, two-step sintering was used to densify a submicrometer zinc oxide (ZnO) powder with a size of 0.4 μm to produce both AZO and ZnO targets.     

In situ characterization of ceramic cold sintering by small-angle scattering

The first in situ characterization of the pore morphology evolution during the cold sintering process (CSP) is presented using small-angle X-ray scattering methods. For practical reasons, measurements have been made on a model system, KH₂PO₄ (KDP). The scattering signal revealed a striking behavior that could be modeled with nanoscale structural features associated with the dissolution and reprecipitation of KDP close to the grain/pore interface during CSP. The prospects for future more quantitative experiments under a range of temperature and pressure conditions, as well as for studies of more technologically important materials such as ZnO are considered.     

Two-step pressure sintering of transparent lutetium oxide by spark plasma sintering

Transparent lutetium oxide (Lu₂O₃) body was prepared by spark plasma sintering using a two-step pressure profile combined with a low heating rate. The effects of pre-load pressures from 10 to 100 MPa and heating rates from 0.03 to 1.67 K s⁻¹ on the microstructures and optical properties were investigated. With increasing pre-load pressures from 10 to 100 MPa, the grains became smaller with a narrower distribution, whereas the transmittance showed maxima at 30 MPa. The average grain size slightly increased from 0.67 to 0.86 μm as the heating rate increased from 0.03 to 1.67 K s⁻¹, while the transmittance decreased. Transmittances of 60% at 550 nm and 79% at 2000 nm were obtained under a pre-load pressure of 30 MPa at a heating rate of 0.17 K s⁻¹.     

Densification mechanisms of UO2 consolidated by spark plasma sintering

Despite the growing interest in the spark plasma sintering (SPS) of uranium dioxide, its sintering mechanisms have yet to be studied in great detail. Herein we propose a direct method to calculate the apparent activation energy for densification, Q_act, and the stress exponent, n, for SPS of nearly stoichiometric UO₂. A set of experiments performed at different heating rates (CHR) and different pressures levels allowed us to calculate Q_act and n, respectively, though we were limited to a theoretical density between 50% to 75 %. The master sintering curve was employed as a complementary method to compare Q_act. The average values were Q_act =96 kJ/mol (CHR), Q_act = 100 kJ/mol (MSC) and n = 1.4. We have therefore proposed grain boundary diffusion coupled with grain boundary sliding as the densification mechanism. The activation energy in SPS tends to be lower compared with that in other processes like conventional sintering (250?450 kJ/mol), creep (350?550 kJ/mol) and hot pressing (222 kJ/mol and 480 kJ/mol).This decrease could be due to the effect of the electric field combined with the higher heating rates, typical of SPS.     

Effect of cold sintering process (CSP) on the electro-chemo-mechanical properties of Gd-doped ceria (GDC)

In this report, the effect of the cold sintering process (CSP) on the electro-chemo-mechanical properties of 10 mol% Gd-doped ceria (GDC) is investigated. High purity nanoscale GDC powder is sintered via a cold sintering process (CSP) in pure water followed by post-annealing at 1000 °C. The resultant ceramics exhibits high relative density (∼90 %) with a fine grain size of ∼100 nm. This sample illustrates comparable electrochemical properties at intermediate-high temperatures and electromechanical properties at room temperature to the material prepared via conventional firing, i.e., sintering in the air at 1450 °C. Moreover, a large creep constant, as well as a low elastic modulus and hardness, are also observed in the CSP sample.     

Effect of temperature and holding time on the densification of alumina obtained by two-step sintering

The two-step sintering technique is a process of controlling the sintering curve, which provides materials with higher density and smaller grain size when compared to conventional sintering. This technique was evaluated by optical dilatometry with three commercial alumina powders of different purity (92, 96 and 99 wt% of Al₂O₃) and particle size (between 0.73 and 2.16 µm). Different sintering conditions in the first (temperature, T1) and second (temperature, T2, and holding time, t2) steps were studied in order to evaluate the effect of these variables on densification and grain growth. Considering T1 as the temperature at which a relative density (D_rel) of 83% was achieved, and for the range of conditions tested, it was found that higher D_rel values and lower grain size of alumina were obtained with higher T2 and lower t2. Alumina with 99 wt% purity sintered at T1 of 1550 °C for 5 min and T2 of 1500 °C for 4 h showed the best relationship between higher densification (~96% relative density) and reduced grain size (0.94±0.15 µm). Thus, this work demonstrated that suppression of grain growth can also be obtained for commercial alumina.     

Influence of processing parameters on thermal conductivity of uranium dioxide pellets prepared by spark plasma sintering

High density uranium dioxide (UO₂) pellets with grain sizes between 0.9 μm and 9 μm were produced by spark plasma sintering (SPS). A systematic study was performed by varying the sintering temperature between 750 °C and 1450 °C and hold time between 0.5 min and 20 min to obtain UO₂ pellets with a range of theoretical densities (TD) and grain sizes. The microstructure development in terms of grain size, density and porosity distribution was investigated. The oxygen/uranium (O/U) ratio of the resulting pellets was found to decrease after SPS. The thermal conductivity of UO₂ pellets increased with the theoretical density but the grain size in the investigated range had no significant influence. The measured thermal conductivity values up to 900 °C were consistent with the reported literature for conventionally sintered UO₂ pellets. The benefits of using SPS over the conventional sintering of UO₂ are summarized.     

Preparation of Na0.5Bi0.5TiO3 ceramics by hydrothermal-assisted cold sintering

A recently proposed novel technique, termed “cold sintering process” (CSP), can provide dense ceramic solids at remarkably low temperatures around 180?°C. In a recent work, we successfully obtained dense Na_0.5Bi_0.5TiO₃ ceramics by this method. Bismuth titanate sodium nanoparticles were prepared as the raw material powder by the hydrothermal synthesis route. A hydrothermal precursor solution was used as the transient solvent for cold sintering. Under the combined action of pressure and temperature, the Na_0.5Bi_0.5TiO₃ green body was densified by dissolution-precipitation, and a preliminary densified ceramic sheet was obtained. The amorphous phase in the ceramic sheet was then transformed into a crystalline phase by annealing. Finally, densified Na_0.5Bi_0.5TiO₃ ceramic sheets were obtained, with density of up to 99%, relative permittivity of 681, and dielectric loss of 0.08 at 10?kHz and room temperature. The piezoelectric coefficient d₃₃ of the sample was 52.5?pC/N. The properties of the prepared ceramics were comparable to those of the conventional sintered ceramics.     

Microwave dielectric properties of mineral sillimanite obtained by conventional and cold sintering process

The sillimanite (Al₂SiO₅) mineral has been sintered by conventional ceramic route and by cold sintering methods. The mineral has very poor sinterability and transformed to mullite on sintering above 1525 °C. The dielectric properties of sillimanite mineral (Al₂SiO₅) are investigated at radio and microwave frequency ranges. The mineral sintered at 1525 °C has low ε_r of 4.71 and tanδ of 0.002 at 1 MHz and at microwave frequency ε_r = 4.43, Q_u × f = 41,800 GHz with τ_f = −17 ppm/°C. The sintering aid used for cold sintering Al₂SiO₅ is sodium chloride (NaCl). The Al₂SiO₅NaCl composite was cold sintered at 120 °C. XRD analysis of the composite revealed that there is no additional phase apart from Al₂SiO₅ and NaCl. The densification of the Al₂SiO₅NaCl composite was confirmed by using microstructure analysis. The Al₂SiO₅NaCl composite has ε_r of 5.37 and tanδ of 0.005 at 1 MHz whereas at microwave frequency it has ε_r = 4.52, Q_u × f = 22,350 GHz with τ_f = −24 ppm/°C. The cold sintered NaCl has ε_r = 5.2, Q_u × f = 12,000 GHz with τ_f = −36 ppm/°C.