Solid state sintering of nano-crystalline indium tin oxide

The sintering of single phase nano-crystalline In₂O₃ and ITO (In_1.9Sn_0.1O_3.05) powders is reported and discussed with particular focus on the underlying mass transport mechanisms. The mass transport in the initial stage of sintering was surface diffusion, resulting in necking and coarsening, and grain boundary diffusion, accompanied by grain growth. Lattice diffusion caused significant densification at higher temperatures, leading to densities higher than 95%. The onset of densification and the maximum densification rate were shifted significantly to higher temperatures for ITO compared to In₂O₃. The reduced sintering rate of ITO was related to the higher valence state of Sn⁴⁺ relative to In³⁺, and due to precipitation of SnO₂(s). The volatile sub-oxides In₂O(g) and SnO(g) caused significant weight losses at high temperatures, particularly in the case of ITO and inert conditions. The sintering at intermediate temperatures is discussed with focus on heat treatment of ITO thin films.     

Preparation and sintering of nanocrystalline ITO powders with different SnO2 content

The effect of SnO₂ content on the sintering behavior of nanocrystalline indium tin oxide (ITO) ceramics was examined. Nanocrystalline ITO powders with different SnO₂ content from 0 to 12 at.% were prepared by a coprecipitation method. The particle size of the ITO powders was in the range of 20–26 nm. The temperature that showed maximum densification increased as the content of SnO₂ increased. Since the solubility limit of SnO₂ in In₂O₃ is known to be about 6–8 at.%, the samples with 8 and 12 at.% Sn showed second phases after sintering. Various phase development processes of the second phases were observed, i.e., In₂SnO₅, which was observed at a low temperature, decomposed into In₂O₃ and SnO₂ at over 1000 °C, then synthesized again into In₄Sn₃O₁₂ at over 1300 °C. The densification behavior with respect to the SnO₂ content was explained from a viewpoint of the second phase development at different sintering temperatures.     

Direct electroreduction of oxides in molten fluoride salts

A new kind of electrolyte composed of molten fluorides has been evaluated in order to perform a feasibility study of the direct electroreduction reaction. The direct reduction of SnO₂ and Fe₃O₄ was realised in LiF–NaF at 750 °C and in LiF–CaF₂ at 850 °C for TiO₂ and TiO. The electrochemical behaviour of these oxides was studied by linear sweep voltammetry: a current corresponding to the oxide reduction was evidenced for TiO₂, SnO₂ and Fe₃O₄. After galvanostatic electrolyses, a complete conversion was obtained for all oxides, except TiO, and the structure of reduced Ti and Fe samples had a typical coral-like structure while dense drops of Sn were recovered (Sn is liquid at operating temperature). After TiO electrolysis, a thin external metallic titanium layer was detected, acting as a barrier for the oxide ion diffusion and no complete reduction can be achieved. This could be explained by a Pilling–Bedworth ratio around 1 for Ti/TiO.     

Effect of TiO2 addition on the sintering densification and mechanical properties of MgAl2O4–CaAl4O7–CaAl12O19 composite

Materials designed in the high-alumina region of Al₂O₃–MgO–CaO system have been widely used in many technological fields. However, their further applications are limited by the high sintering temperatures necessary to achieve densification due to the poor sintering ability of calcium hexaluminate (CaAl₁₂O₁₉) and spinel (MgAl₂O₄). Considering this aspect, the present work investigated the effect of TiO₂ addition on the sintering densification and mechanical properties of MgAl₂O₄–CaAl₄O₇–CaAl₁₂O₁₉ composite by solid state reaction sintering. The results showed that the CA₆ grains presented a more equiaxed morphology instead of platelet structure by incorporating Ti⁴⁺ into its structure, which greatly improved the densification after heating at 1600 °C. The flexural strength was greatly enhanced with increasing addition of TiO₂ due to the significant decrease in porosity and improvement in uniformity of grain size as well as the absence of microcracks in the presence of Al₂TiO₅. The increased content of TiO₂ also played an active role in toughening this composite attributed to the increase in resistance to crack initiation and propagation.     

Crack Healing in Ti2Al0.5Sn0.5C–Al2O3 Composites

Oxidation induced crack healing of Al₂O₃ composites loaded with a MAX phase based repair filler (Ti₂Al_0.5Sn_0.5C) was examined. The fracture strength of 20 vol% repair filler loaded composites containing artificial indent cracks recovered fully to the level of the virgin material upon isothermal annealing in air atmosphere after 48 h at 700°C and 0.5 h at 900°C. SEM‐EBSD analysis of crack microstructure indicates two different oxidation reaction regimes to govern the crack filling: near the surface SnO₂, TiO₂, and Al₂O₃ were formed whereas deeply inside the cracks Al₂O₃ and TiO₂ and metallic Sn were detected. The presence of elemental Sn was attributed to partial oxidation of aluminum and titanium which lowered the local oxygen concentration below a threshold value required for Sn oxidation to SnO₂. Thus, Ti₂Al_0.5Sn_0.5C may represent an efficient repair filler system to trigger oxidation induced crack healing in ceramic composites at temperatures below 1000°C.     

Effect of dual liquid phase sintering aids on the densification and microstructure of low temperature sintered alumina ceramics

Alumina ceramics was prepared by pressureless sintering technology in which a CuO–TiO₂–Bi₂O₃ mixture (0–4.0 wt% Bi₂O₃ and 4.0 wt% CuO and TiO₂) was added as dual liquid phase sintering aids. The phase compositions, microstructural feature, and sintering behaviour of the alumina ceramics were analyzed. The results showed that adding 2.5 wt% Bi₂O₃ to alumina ceramics can increase the contribution rate of initial stage of sintering to the sintering process. The relative density of the sample reached 97.63% after sintering at 1200 °C for 90 min. Measurements from differential scanning calorimetry, with the addition of CuO–TiO₂–Bi₂O_3, demonstrated the formation of two liquid phase points, 827.4 and 936.8 °C. Notably, the solid solution temperature of TiO₂ and Al₂O₃ ceramics diminished thanks to the dual liquid phase sintering aids, and at the same time the activation energy required also dropped from 368.96 to 137.31 kJ/mol. Research indicates that the combined action of dual liquid phase sintering and solid-state reaction sintering has promoted the densification of alumina ceramics during the sintering process while at the same time inhibiting the growth of abnormal grains so that a homogeneous microstructure can be formed.     

Preparation of Ti/Pt/SnO2–Sb2O4 electrodes for anodic oxidation of pharmaceutical drugs

Ti/Pt/SnO₂–Sb₂O₄ electrodes were prepared by alternating Sn and Sb electrodepositions, repeated 4 or 16 times, onto a platinized titanium foil by a thermo-electrochemical method. Chemical, electrochemical, and structural tests have been used for the characterization of Ti/Pt/SnO₂–Sb₂O₄ electrodes. Anodic oxidation of the aqueous solution contaminated by amoxicillin, clofibric acid, diclofenac, and ibuprofen having a concentration of 100 mg L^?1 and 0.035 M of Na₂SO₄ have been applied using Ti/Pt/SnO₂–Sb₂O₄ electrodes at a current density of 10 and 30 mA cm^?2. The chemical oxygen demand removals increased with current density and except for diclofenac, the Ti/Pt/SnO₂–Sb₂O₄ electrode with 4 electrodeposition repetitions gave the best results. The combustion efficiencies for diclofenac and ibuprofen were higher than those obtained with similar electrode material, prepared without platinization, especially in the assay run with Ti/Pt/SnO₂–Sb₂O₄ (16 electrodeposition repetitions).     

TiO2 as a sintering additive for KNbO3 ceramics

Improved densification during the conventional sintering of KNbO₃ ceramics was achieved by using small additions of TiO₂. This improved densification can be explained on the basis of high-temperature chemical reactions in the system. X-ray diffractometry and electron microscopy were used in combination with diffusion-couple experiments in order to elucidate the chemical reactions between KNbO₃ and TiO₂. TiO₂ reacts with KNbO₃ forming KNbTiO₅, and a low concentration of Ti incorporates in the KNbO₃ structure resulting in the formation of oxygen vacancies and, consequently, in an improvement in the densification. At ∼1037 °C eutectic melting between the KNbO₃ and the KNbTiO₅ further improves the densification of the KNbO₃ ceramics.     

Preparation of Ti/SnO2-Sb2O4 photoanode by electrodeposition and dip coating for PEC oxidations

Thin films of antimony-doped SnO₂ on titanium substrate with a doping range of 1.5-8 mol% were prepared by an electrodeposition and dip coating method. The prepared Ti/SnO₂-Sb₂O₄ thin films were tested as a photoanode in the photoelectrocatalytic(PEC) experiments to degrade phenol in aqueous solution in order to evaluate their PEC performance. The photocatalytic (PC), electrocatalytic (EC) and PEC activity of Ti/SnO₂-Sb₂O₄ thin films was compared in the degradation processes. And the effect of annealing temperature on their PEC activity was also investigated. The experimental results confirmed that the Sb-doped Ti/SnO₂ thin films enhanced the phenol degradation and the Ti/SnO₂-Sb₂O₄ film containing 6 mol% of Sb calcinated at 450 °C achieved the best performance for phenol degradation. The degradation experiments also demonstrated that the Ti/SnO₂-Sb₂O₄ film achieved faster degradation of phenol in the PEC process than in the PC and EC processes. Compared with Ti/TiO₂ and Ti/SnO₂ photoanodes, the Ti/SnO₂-Sb₂O₄ photoanode showed higher activity.     

Enhanced mechanical and sintering properties of MgO-TiO2 ceramic composite via digital light processing

In this work, MgO was applied to modify the titania ceramic slurry, which could realize the high-quality DLP printing of titania ceramic by promoting the grain growth during sintering. Combining the phase and element analysis, it was revealed that the reduced stress concentration and improved mechanical property were attributed to the formation of MgTi₂O₅ in solid-state reaction between MgO and TiO₂. When MgO content increased beyond 10 wt.%, the microstructure pinning effects showed a negative impact on ceramic grain growth. Among all the samples, 5%MgO/TiO₂ has exhibited the best bending strength of 71.9 MPa and the densification of 85%, while its sintering temperature reduced by 200 °C. Meanwhile, the compressive property of representing porous TiO₂ samples reached 18.2 MPa, which was similar to those of porous ceramics produced by conventional manufacturing routes. Overall, MgO-TiO₂ composite ceramic prepared in this study have potential application in field of monolithic catalysts and tissue engineering scaffold.     

Sintering densification behavior of ZnO–SnO2 binary ceramic targets

In this work, high-performance ZnO–SnO₂ binary ceramic targets for magnetron sputtering of transparent conductive oxide (TCO) films were prepared by pressureless oxygen atmosphere sintering. The sintering behavior and densification mechanism of the ZnO–SnO₂ binary targets were analyzed by systematically studying the oxide powder state, formation process of the solid reaction phase, and evolution of the target microstructure. The data revealed that the ZnO–SnO₂ powder treatment improved the sintering activity and the powder dispersion; furthermore, it promoted a mutual reaction between the different components during sintering and the homogeneity of the target composition. The densification of the pure SnO₂ ceramic target was difficult to achieve, and the addition of ZnO led to a continuous interaction between the ZnO and SnO₂ components. The Zn₂SnO₄ phase started to form, and a temporary shrinkage of the target occurred above 800°C. After formation of the stable Zn₂SnO₄ and SnO₂ phases, the target shrunk rapidly with increasing temperature, densification occurred during growth, and the two phases started to interact. The sintering temperature provided the driving force for the target densification, with the densification activation energy of the ZnO–SnO₂ binary ceramic target estimated to be 580 kJ/mol based on the master sintering curve. A binary ceramic target with a high density (99.78% relative density), a fine grain size, and a homogeneous phase structure was achieved at a temperature of 1600°C. These findings are promising for the further improvement and performance enhancement of SnO₂-based materials.     

Oxidation Behavior of MAX Phase Ti2Al(1−x)SnxC Solid Solution

MAX phase Ti₂Al_(1?x)Sn_xC solid solution with x = 0, 0.32, 0.57, 0.82, and 1 was synthesized by pressureless sintering of uniaxially pressed Ti, Al, Sn, and TiC powder mixtures. Annealing in air atmosphere at 200°C–1000°C triggered a sequence of oxidation reactions which reveal a distinct influence of solid solution composition on the oxidation process. With decreasing Al/Sn ratio, the characteristic temperature of accelerated oxidation reaction of A‐element was reduced from 900°C (x = 0) to 460°C (x = 1). SnO₂ was formed at temperatures significantly lower than TiO₂ (rutile) and Al₂O₃. Substitution of A‐element in MAX phase solid solution by low‐melting elements such as Sn may offer potential for reducing oxidation‐induced crack healing temperatures.     

Effect of ZnO and TiO2 doping on the sintering behavior of Y2O3 ceramics

Full densification of Y₂O₃ is challenging and requires a very high sintering temperature (above 1700 °C). In this study, the effect of ZnO and TiO₂ dopants on its densification was investigated, showing that both dopants lowered the sintering temperature and improved the process. Moreover, ZnO promoted the grain growth, while TiO₂ inhibited it; hence, the ZnOTiO₂ co-doping and the change in the ZnO/TiO₂ ratio allowed the control of the sintered body microstructure while maintaining high densification. Since Y₂O₃ has a higher plasma erosion resistance than conventional Si-based materials, the plasma dry etching resistance of the sintered Y₂O₃ was also evaluated and found superior due to the improved densification and controlled grain size of the doped samples.     

Fabrication of submicron Li-rich Li2(Ti,Zr)O3 solid solution ceramics with sluggish grain growth rate

Doping and forming solid solution is an effective approach to tailor densification and grain growth. In this study, submicron Li₂(Ti,Zr)O₃ solid solution ceramics was successfully fabricated by a modified solid-state route for the first time. The use of appropriate starting powders can greatly reduce the synthesis temperature, and the preparation of Li₂(Ti,Zr)O₃ with submicron grain size is possible. The substitution of Ti by Zr will inhibit the phase transition from cubic to monoclinic structure, as well as the grain growth and pore removal. By doping 10-at.% Zr, the grain size was significantly decreased from several μm to 400 nm at 900°C, which contributes to a high conductivity eight times that of pure Li₂TiO₃. Moreover, after being heated at 900°C for 10 days, the grain size of Li₂(Ti,Zr)O₃ only increases to 5 μm; however, the grains of Li₂TiO₃ grows up to 16 μm with abnormal grain growth. The compositions of Li₂(Ti,Zr)O₃ are high uniform with no element segregation, indicating the sluggish grain growth rate is caused by the slow diffusion of Zr rather than segregation-induced solute drag. By adding excess Li and two-step sintering, the Li-rich Li₂(Ti,Zr)O₃ ceramic pebbles with high crush load of 50–60 N and small grain size of 300–500 nm were successfully fabricated. This work demonstrates a simple method for the synthesis of Li₂(Ti,Zr)O₃, which makes this material more widely accessible for exploration and also help accelerate its engineering application to be an advanced solid breeder.     

Development and evolution of a novel (Zr1-xSnx)O2 toughened alumina-mullite slip cast refractory: Effect of SnO2

Zr_1-xSn_xO₂ reinforced alumina-mullite refractory was manufactured by slip cast methods using SnO₂ as a sintering agent. SnO₂ had considerable influence in the enhanced reaction kinetics of zircon dissociation and subsequent reaction sintering of alumina and zircon. Presence of pro-eutectic transient Al₂O₃-SnO₂ liquid and SnO₂-SiO₂-ZrO₂ amorphous phases, enhanced densification and mullitisation through liquid phase sintering and, mitigated SnO₂ volatilisation by (Zr_1-xSn_x)O₂ solid-solution formation. Based on their morphology and aspect ratios, three types of mullite crystals, MI, MII and MIII, were evolved across the matrix microstructure. Characterization of the evolved microstructure revealed coalescence and grain growth of matrix alumina grains including the presence of an acicular tertiary MIII mullite which acts as both a reinforcement and bridging network of matrix to aggregate grains. SnO₂ had the effect of lowering the monoclinic – tetragonal phase transformation temperature. Hot flexural strength values remained nearly unchanged (±2%) compared with the AZS composition without SnO₂ doping.     

Ultrafine-grained β-Sialon fabricated by two-stage sintering and study on diffusion toughening of Ti–22Al–25Nb

The ultrafine-grained β-Sialon ceramics were fabricated by spark plasma sintering at different temperatures with inorganic Al₂O₃–Y₂O₃ and Ti–22Al–25Nb intermetallic powder as composite additives. The research showed that β-Sialon ceramics achieve two-stage sintering densification. Al₂O₃–Y₂O₃ inorganic additives promoted the synthesis and densification of β-Sialon ceramics at 1125–1215°C. Ti–22Al–25Nb intermetallic powder diffused Ti and Nb elements at 1240–1425°C, thereby improving the fracture toughness of β-Sialon ceramics. The maximum fracture toughness (∼9.69 MPa m^1/2) under 19.6 N was obtained for β-Sialon ceramics sintered at 1600°C.     

Effect of addition of TiO2 on reaction sintered MgO–Al2O3 spinels

Three different spinel compositions with MgO:Al₂O₃ molar ratios 2:1, 1:1 and 1:2 were studied using TiO₂ as an additive up to 2 wt.%. Solid state reaction sintering technique was employed for all the compositions in the temperature range of 1550–1650°C. Attrition milling was done for the reduction of particle size. Sintered products were characterised in terms of densification and shrinkage studies, phase analysis, strength evaluation both at ambient temperature and at elevated temperature, strength retention after different number of thermal cycles at 1000°C, quantitative elemental analysis and microstructural studies.     

Sintering kinetics of ZrO2 nanopowders modified by group IV elements

The sintering behavior of tetragonal zirconia nanopowders modified by the group IV elements at the initial sintering stage was investigated. It was found that different additives SiO₂, SnO₂, and GeO₂ have a significant influence on the densification kinetics of 3Y-TZP nanopowders obtained by coprecipitation during sintering as it depends on the amount of additives (0-5 wt%). The shrinkage of zirconia-based specimens during the nonisothermal sintering was analyzed using the dilatometric data. The constant rate of heating technique was applied in order to determine the dominant mass transfer mechanism at the initial stage of sintering in modified zirconia nanopowders. It was found that there was a change in the mass transfer mechanism and diffusion activation energy in 3Y-TZP as a result of the additives. The dominant sintering mechanism in 3Y-TZP changed from the volume diffusion to the grain boundary diffusion due to the addition of SiO₂ and SnO₂ and the sintering activation energy increased in these cases. However, GeO₂ additive activated the viscous flow mechanism in sintering process of 3Y-TZP nanopowders which led to acceleration of the densification due to the decrease in the diffusion activation energy.     

Solvothermal fabrication of three-dimensionally sphere-stacking Sb–SnO2 electrode based on TiO2 nanotube arrays

TiO₂-NTs-based Sb–SnO₂ electrode with three-dimensionally sphere-stacking structure was successfully fabricated by the solvothermal method, followed by annealing at 500 °C for 1 h. The physico-chemical properties of electrodes were characterized through scanning electron spectroscopy (SEM), X-ray diffraction (XRD) and electrochemical measurements. SEM result showed that TiO₂-NTs/Sb–SnO₂ electrode has morphology of vertically sphere-stacking coralline. Compared with Ti/Sb–SnO₂, TiO₂-NTs/Sb–SnO₂ electrode has smaller grain size and greater specific surface area which can provide with more active sites. Compared with Ti/Sb–SnO₂ electrode, TiO₂-NTs/Sb–SnO₂ has a higher oxygen evolution potential and stronger phenol oxidation peak, indicating an improved catalytic activity for phenol degradation. The kinetic analysis of electrochemical phenol degradation showed that the first-order kinetics rate constant on TiO₂-NTs/Sb–SnO₂ electrode is 1.33 times as much as that on Ti/Sb–SnO₂, confirming that the sphere-stacking Sb–SnO₂ based on TiO₂ nanotube has a good electrocatalytic activity.     

Conduction and sintering mechanism of high electrical conductivity Magnéli phase Ti4O7

In this paper, the crystal structure and electronic structure of Ti₄O₇ were calculated based on density functional theory, and Magnéli phase Ti₄O₇ bulks were successfully prepared by spark plasma sintering (SPS). Results indicated that the contribution of Ti 3d to Fermi level increased due to the lack of oxygen atom in lattice, and the energy band gap of Ti₄O₇ was reduced compared with that of TiO₂. By calculating the relationship between the densification rate and effective stress in the process of SPS, it can be known that the densification mechanism of Ti₄O₇ powders was controlled by diffusion. Based on this, under the conditions of sintering temperature of 1000 °C, holding time of 10 min and sintering pressure of 30 MPa, Ti₄O₇ bulks with the optimal electrical conductivity (961.5 S cm⁻¹) could be obtained, which was more than 30% higher than the graphite material reported in literature. The results reveals that Ti₄O₇ will be one of the most promising electrode materials in the electrochemical field.