Influence of sintering additives on densification kinetics and high‐temperature strength in γ‐Y2Si2O7 ceramics

Pressureless sintering of pure γ‐Y₂Si₂O₇ powders that had been synthesized by a solid‐liquid reaction method using Y₂O₃ and SiO₂ powders with Li₂O, MgO, and Al₂O₃ additives was reported. The sintering kinetics of γ‐Y₂Si₂O₇ powders was analyzed to track details of densification evolution. Apparent activation energies of the densification of γ‐Y₂Si₂O₇ powders were reported for the first time, which was 57.1, 96.6, and 100.2 kJ/mol for the powders with Li₂O, MgO, and Al₂O₃ additives, respectively, indicating that Li₂O could promote the densification behavior effectively. The flexural strengths as a function of temperature for the γ‐Y₂Si₂O₇ ceramics with different additives were also investigated. The degradation of high‐temperature flexural strength was mainly ascribed to the softening of grain‐boundary glassy phase. γ‐Y₂Si₂O₇ specimens fabricated using the powders with MgO or Al₂O₃ additives exhibited better high‐temperature mechanical properties.     

Low-temperature sintering of magnesium aluminate spinel doped with manganese: Thermodynamic and kinetic aspects

This work describes the role of manganese (Mn) as a sintering aid for magnesium aluminate (MgAl₂O₄) nanoparticles. Mn-doped MgAl₂O₄ nanoparticles, synthesized by coprecipitation method, showed increased surface area when contrasted to undoped MgAl₂O₄. Fast firing of compacted-doped nanoparticles achieved high degree of densification at temperatures as low as 1100°C with very moderate grain growth, resulting in average sizes at the nanoscale (~60 nm). Differential scanning calorimetry was used to quantify the exothermic heat effects of sintering, which combined with quantitative microstructural evolution analysis enabled calculation of both surface and grain boundary energies. The results revealed that Mn effectively reduces the surface and grain boundary energies which led to dihedral angle broadening and consequently increased sintering stress. Experimental data also revealed a concomitant decrease in the activation energy of sintering with Mn doping which dropped from 644 kJ/mol for undoped MgAl₂O₄ to 285 kJ/mol, informing Mn acts as a sintering aid in a thermokinetic manner.     

Densification of fine-grained alumina ceramics doped by magnesia,yttria and zirconia evaluated by two different sintering models

The influence of various dopants (500 ppm MgO and Y₂O_3; 250 ppm ZrO₂) on sintering of fine-grained alumina ceramics was evaluated by high-temperature dilatometry. The apparent activation energy of sintering was estimated with the help of Master Sintering Curve and a model proposed by Wang and Raj. The densification kinetics was controlled by at least two mechanisms operating at low (higher activation energy) and high (lower activation energy) densities. Good agreement between the activation energies calculated with both models was observed for low as well as for high densities. The lowest value of activation energy exhibited undoped alumina; the addition of MgO resulted in slight increase of the activation energy. Y₂O₃ and ZrO₂ significantly inhibited the densification, which was reflected in the higher sintering activation energies. The low activation energies in the final sintering step indicates the importance of proper choice of sintering temperature, namely in the two-step sintering process.     

Direct measurement of interface energies of magnesium aluminate spinel and a brief sintering analysis

Surface and grain boundary energies are key parameters for understanding and controlling microstructural evolution. However, reliable thermodynamic data on interfaces of ceramics are relatively scarce, limiting the realization of their relevance in processes such as sintering and grain growth. In this work, the heat of sintering itself was used to quantify both surface and grain boundary energies in MgAl₂O₄ spinel. Nanoparticles were compacted and heated inside a Differential Scanning Calorimeter (DSC) when densification and grain growth were observed. The evolved heat signal was quantitatively attributed to the respective microstructural evolution in terms of interfacial area change, allowing determination of average surface and grain boundary energies for MgAl₂O₄ as 1.49 J m⁻² and 0.57 J m⁻², respectively. The data was then used to interpret the thermodynamics involved in density and grain growth during isothermal sintering of MgAl₂O₄.     

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.     

Doping effect of divalent cations on sintering of polycrystalline yttria

The sintering behavior of Y₂O₃ doped with 1 mol% of Ca²⁺, Mg²⁺, Mn²⁺, Ni²⁺, Sr²⁺ or Zn²⁺ was investigated by pressureless sintering in air at a sintering temperature in the range 900–1600 °C. The sintering temperature required for full densification in Y₂O₃ was reduced by 100–400 °C by the cation doping, while undoped Y₂O₃ was densified at 1600 °C. The most effective dopant among the examined cations was Zn²⁺. The grain growth kinetics of undoped and cation-doped Y₂O₃ was described by the parabolic law. The grain boundary mobility of Y₂O₃ was accelerated by doping of the divalent cations. High-resolution transmission electron microscopy (HRTEM) observations and nano-probe X-ray energy dispersive spectroscopy (EDS) analyses confirmed that the dopant cations tended to segregate along the grain boundaries without forming amorphous layers. The improved sinterability of Y₂O₃ is probably related to the accelerated grain boundary diffusion owing to the grain boundary segregation of the dopant cations.     

Lattice dynamics of yttria: A combined investigation from spectrum measurements and first-principle calculations

C-type Y₂O₃ ceramics (relative density ~94%) were prepared at 1500 °C for 2 hours with 1% wt. ZnO as sintering aid. The cell parameters of Y₂O₃ from Rietveld refinements are a = 10.6113(1) Å, V = 1194.8(1) ų. The vibrational modes / lattice dynamics of Y₂O₃ were investigated using vibrational spectra (Raman and infrared reflection spectra) and first-principle (DFT) calculations. Eight of the 22 predicted first-order Raman modes and 12 of 16 predicted IR modes are observed and reliably assigned. For the observed vibrational modes, an excellent linearity (f_exp = 1.023f_theo, R² = 0.9999) between frequency from calculations (f_theo) and that from measurements (f_exp) is observed. Accordingly, the corrected frequency (f_cor) of vibrational modes, phonon band structure, and density of phonon states (DOPS) of Y₂O₃ are presented, in which, the frequency of phonons of Y₂O₃ is ≤625.2 cm⁻¹ (wavelength ≥16.0 μm) with a gap of 30.6 cm⁻¹ from 486.0 to 516.6 cm⁻¹ (wavelength 20.6 - 19.4 μm) at room temperature. The modes with f_theo ≥292.5 cm⁻¹ (f_cor ≥299.2 cm⁻¹) are dominated by the vibrations of O²⁻ (light atom vibrations) and the vibrational modes with f_theo ≤239.0 cm⁻¹ (f_cor ≤244.5 cm⁻¹) are dominated by the vibrations of both Y³⁺ and O²⁻ (co-vibrations). The three modes T_u⁽⁷⁾ at 301.6 cm⁻¹, T_u⁽¹⁰⁾ at 333.7 cm⁻¹, and T_u⁽¹²⁾ at 369.7 cm⁻¹ of Y-O stretch vibrations dominate the phonon dielectric constant and dielectric loss of Y₂O₃ with more than 85% contributions.     

Tape casting and characterizations of MgO ceramics

We report a high density MgO ceramic substrate produced by the tape casting technology. The tape casting formulation and process produced a uniform tape free of cracking. Y₂O₃ and SiO₂ were used as the sintering aid for the pressureless sintering of the green tape. X-ray diffraction phase identification indicates that MgO is the main phase, while both Y₂O₃ and SiO₂ sintering aids react with MgO to form MgY₄Si₃O₁₃ as the second phase. Liquid phase sintering occurs in the temperature range from 1030°C to ~1500°C, which is confirmed by the simultaneous Thermal Gravitation Analysis/Differential Scanning Calorimeter (TGA/DSC) and the percent linear shrinkage and densification. A 96.5% theoretical density was achieved by presureless sintering at 1650°C for 2 hours, which was further increased to a fully dense structure using hot-isostatic-pressing(HIP) at 1650°C and 207 MPa in argon. Scanning electron microscopy (SEM) and energy dispersive(EDS) spectroscopic analysis on the HIP’ed sample show that MgY₄Si₃O₁₃is located at the MgO grain boundary and the sample has a fully dense structure. The refractive indices and extinction coefficient were measured on the HIP’ed sample along with thermal properties and dielectric properties. Thermal diffusivity and heat capacity were measured to calculate the thermal conductivity.     

Effects of Gd Substitution on Sintering and Optical Properties of Highly Transparent (Y0.95−xGdxEu0.05)2O3 Ceramics

Highly transparent (Y_0.95?xGd_xEu_0.05)₂O₃ (x = 0.15–0.55) ceramics have been fabricated by vacuum sintering at the relatively low temperature of 1700°C for 4 h with the in‐line transmittances of 73.6%–79.5% at the Eu³⁺ emission wavelength of 613 nm (~91.9%–99.3% of the theoretical transmittance of Y_1.34Gd_0.6Eu_0.06O₃ single crystal), whereas the x = 0.65 ceramic undergoes a phase transformation at 1650°C and has a transparency of 53.4% at the lower sintering temperature of 1625°C. The effects of Gd³⁺ substitution for Y³⁺ on the particle characteristics, sintering kinetics, and optical performances of the materials were systematically studied. The results show that (1) calcining the layered rare‐earth hydroxide precursors of the ternary Y–Gd–Eu system yielded rounded oxide particles with greatly reduced hard agglomeration and the particle/crystallite size slightly decreases along with increasing Gd³⁺ incorporation; (2) in the temperature range 1100°C–1480°C, the sintering kinetics of (Y_0.95?xGd_xEu_0.05)₂O₃ is mainly controlled by grain‐boundary diffusion with similar activation energies of ~230 kJ/mol; (3) Gd³⁺ addition promotes grain growth and densification in the temperature range 1100°C–1400°C; (4) the bandgap energies of the (Y_0.95?xGd_xEu_0.05)₂O₃ ceramics generally decrease with increasing x; however, they are much lower than those of the oxide powders; (5) both the oxide powders and the transparent ceramics exhibit the typical red emission of Eu³⁺ at ~613 nm (the ⁵D₀→⁷F₂ transition) under charge transfer (CT) excitation. Gd³⁺ incorporation enhances the photoluminescence and shortens the fluorescence lifetime of Eu³⁺.     

Effect of YF3 on densification behavior and thermal conductivity of AlN ceramics with Y2O3–YF3 additives under reducing atmosphere

The effect of yttrium fluoride (YF₃) on the densification behavior, microstructure, phase composition and thermal conductivity of aluminium nitride (AlN) ceramics with yttrium oxide (Y₂O₃) and YF₃ additives were studied. Since YF₃ provided liquid phases and promoted densification at a lower temperature, the sintering temperature required to reach the full density of AlN samples decreased with the increase in YF₃ content. Appropriate addition of YF₃ could improve the thermal conductivity of AlN ceramics, but the values of thermal conductivity decreased as YF₃ increased further. It is attributed to the ability of YF₃ to react with oxygen impurity was worse than that of Y₂O₃. Moreover, the reducing atmosphere significantly affected the phase composition, and the oxygen content in grain boundary phases decreased at 1750 °C and 1800 °C. Therefore, the proper proportion of Y₂O₃–YF₃ additives could simultaneously improve densification and the thermal conductivity of AlN samples at a low sintering temperature.     

Ionic occupation,structures, and microwave dielectric properties of Y3MgAl3SiO12 garnet‐type ceramics

The Y₃MgAl₃SiO₁₂ ceramics with pure phase were successfully synthesized by solid‐state sintering reaction method for the first time. Their microwave dielectric properties were investigated as a function of sintering temperature. Their microstructure characteristics and ionic occupation sites of tetrahedral and octahedral units were characterized and analyzed by SEM& energy dispersive spectrometer (EDS) and Rietveld refinement of X‐ray powder diffraction data. Crystal structure of Y₃MgAl₃SiO₁₂ is isostructural to Y₃Al₅O₁₂ with a cubic garnet structure and space group of Ia‐3d, which contains YO₈ dodecahedra, (Mg/Al_oct)O₆ octahedral, and (Si/Al_tet)O₄ tetrahedral units. The Qf and ε_r values of different samples are strongly dependent on the distribution of grain sizes, grain sizes, and porosity. The samples sintered at 1550°C exhibit optimized microwave dielectric properties with relative permittivity (?_r) of 10.1, Qf values of 57 340GHz (at 9.5 GHz), and τ_f values of ?32 ppm/°C. Such properties indicate potential application of Y₃MgAl₃SiO₁₂ as microwave substrates.     

Constrained sintering of 8 mol% Y2O3 stabilised zirconia films

Constrained sintering kinetics of 8 mol% Y₂O₃/92 mol% ZrO₂ (8YSZ) films approximately 10–15 μm thick screen-printed on dense YSZ substrates, and the resulting stress induced in the films, were measured in the temperature range 1100–1350 °C. The results are compared with those reported earlier for 3YSZ films.Both materials behave similarly, although there are differences in detail. The constrained densification rate was greatly retarded compared with the unconstrained densification rate due to the effect of the constraint on the developing anisotropic microstructure (3YSZ) and, in the case of 8YSZ, considerable grain growth. The stress generated during constrained sintering was typically a few MPa. The apparent activation energies for free sintering, constrained sintering, creep and grain growth are found to cover a wide range (135–670 kJ mol^?1) despite all probably being mainly controlled by grain boundary cation diffusion.     

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.     

Analysis of reactions during sintering of CuO-doped 3Y-TZP nano-powder composites

3Y-TZP (yttria-doped tetragonal zirconia) and CuO nano powders were prepared by co-precipitation and copper oxalate complexation–precipitation techniques, respectively. During sintering of powder compacts (8 mol% CuO-doped 3Y-TZP) of this two-phase system several solid-state reactions clearly influence densification behaviour. These reactions were analysed by several techniques like XPS, DSC/TGA and high-temperature XRD. A strong dissolution of CuO in the 3Y-TZP matrix occurs below 600 °C, resulting in significant enrichment of CuO in a 3Y-TZP grain-boundary layer with a thickness of several nanometres. This “transient” liquid phase strongly enhances densification. Around 860 °C a solid-state reaction between CuO and yttria as segregated to the 3Y-TZP grain boundaries occurs, forming Y₂Cu₂O₅. This solid-state reaction induces the formation of the thermodynamic stable monoclinic zirconia phase. The formation of this solid phase also retards densification. Using this knowledge of microstructural development during sintering it was possible to obtain a dense nano–nano composite with a grain size of only 120 nm after sintering at 960 °C.     

Sintering kinetics and properties of NiFe2O4-based ceramics inert anodes doped with TiN nanoparticles

Sintering kinetics of NiFe₂O₄-based ceramics inert anodes for aluminum electrolysis doped 7 wt% TiN nanoparticles were conducted to investigate densification and grain growth behaviors. The linear shrinkage increased gradually with the increasing sintering temperature between 1000 and 1450°C, whereas the linear shrinkage rate exhibited a broad peak. The maximum linear shrinkage rate was obtained at 1189.4°C, and the highest densification rate was achieved at the relative density of 75.20%. Based on the pressureless sintering kinetics window, the sintering process was divided into the initial stage, the intermediate stage, and the final stage. The grain growth exponent reduced with increased sintering temperature, whereas the grain growth activation energy decreased by increasing sintering temperature and shortening dwelling time. The grain growth was mainly controlled by atomic diffusion. NiFe₂O₄-based ceramics possessed high-temperature semiconductor essential characteristics. The electrical conductivity of NiFe₂O₄-based ceramics first increased and then decreased with increasing sintering temperature, reached their maximum value (960°C) of 33.45 S/cm under 1300°C, mainly attributed to the relatively dense and uniform microstructure. The thermal shock resistance of NiFe₂O₄-based ceramic was improved by a stronger grain boundary bonding strength and lower coefficient of linear thermal expansion.     

Effect of Y2O3 content on densification,microstructure and mechanical properties of reaction sintered magnesium aluminate spinel

Dense magnesium aluminate (MgAl₂O₄) spinels were developed via single-stage solid-state reaction sintering method at 1550–1650^oC using combinations of varied commercial grade reactants-three different sources of alumina and two different sources of magnesia. The effect of Y₂O₃ doping in the concentration range of 1–4 wt % on different spinel batches was studied. Y₂O₃ addition was found to favour the densification of all the spinels at all dopant concentrations and maximum densification was found for the 2 wt % Y₂O₃ containing spinel batches. Phase analysis of the Y₂O₃ containing batches revealed the presence of yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) at all the sintering temperatures. Owing to similar crystal structure isotropic configuration of YAG (cubic) as that of spinel (cubic), Y₂O₃ doping was found to favour densification of spinel. Microstructural investigation revealed that Y₂O₃ containing batches have a controlled grain structure as compared to the without additive batches. Also, 2 wt % Y₂O₃ containing spinel batches sintered at 1650^oC revealed better mechanical properties such as cold modulus of rupture and strength retainment after thermal shock than that of the undoped spinel batches.     

Improved thermal conductivity of β-Si3N4 ceramics by lowering SiO2/Y2O3 ratio using YH2 as sintering additive

A two-step sintering process was conducted to produce β-Si₃N₄ ceramics with high thermal conductivity. During the first step, native SiO₂ was eliminated, and Y₂O₃ was in situ generated by a metal hydride reduction process, resulting in a high Y₂O₃/SiO₂ ratio. The substitution YH₂ for Y₂O₃ endow Si₃N₄ ceramics with an increase of 29% in thermal conductivity from 95.3 to 123 W m⁻¹ K⁻¹ after sintered at 1900°C for 12 hours despite an inferior sinterability. This was primarily attributed to the purified enlarged grains, devitrified grain boundary phase, and reduced lattice oxygen content in the YH₂-MgO-doped material.     

Densification of liquid phase sintered silicon carbide

The densification and phase formation of liquid phase sintered silicon carbide (LPSSiC) with 10 wt.% additives were investigated. The ratio of the Al₂O₃/Y₂O₃-additives was changed between 4:1 and 1:2. Densification was carried out by hot pressing and gas pressure sintering. The different densification routes result in different major grain boundary phases—aluminates in gas pressure sintered materials and silicates in hot pressed samples. Thermodynamic calculations were carried out to determine the amount of liquid phase during densification and for the interpretation of the results.     

Segregation-controlled densification and grain growth in rare earth-doped Y2O3

Cation doping of Y₂O₃ is an established approach for tailoring densification and grain growth during sintering. However, the segregation of doped cations to the grain boundary and their impact on processing are still not completely understood. Segregation can be driven by electrostatic effects due to charge mismatch with the host lattice or elastic effects induced by ion size mismatch. While segregation is caused by thermodynamics, it impacts diffusion and the kinetics of grain boundaries during densification and microstructure evolution. In this study, we utilize two isovalent dopants (La³⁺ and Gd³⁺), that is we focus on the elastic component of segregation. We investigate the densification as well as the grain growth kinetics of both doped and undoped Y₂O₃ during field-assisted sintering/spark plasma sintering (FAST/SPS). While Gd³⁺ is showing no significant effect on densification, La³⁺ resulted in a strongly reduced sintering activity. Furthermore, the analysis of the grain growth behavior during sintering and on predensified samples revealed a decrease in the grain growth coefficient, with La³⁺ having the strongest impact. The structure and chemistry at the grain boundary were observed by aberration-corrected TEM. While no structural change was caused by doping, the chemical analysis showed a strong segregation of La³⁺ to the grain boundary, which could not be observed for Gd³⁺. The results indicate that segregated La³⁺ causes a drastic decrease in grain boundary migration rates through solute drag as well as much slower sintering kinetics, likely caused by a decrease in the grain boundary self-diffusion due to segregation. This study further underlines the importance of the elastic contribution to cation segregation and establishes a clear relationship to grain growth and sintering kinetics, which are both decreased by segregation.     

Molecular-level composition design for efficient synthesis of SiAlON ceramics

SiAlONs are a class of liquid-phase sintered ceramics with excellent room-temperature strength and toughness, but whose residual grain boundary glass softens at high temperatures, limiting use in extreme environments. For this reason, efforts are made to minimize the volume of the grain boundary glass while still facilitating full densification. This work describes a potential route for the densification of SiAlONs with very low concentrations of liquid-phase sintering additive (e.g., rare-earth oxides such as yttria) by using an organometallic precursor. Solid solution of Al and O in the Si₃N₄ lattice was accomplished through the incorporation of solute atoms via liquid organic precursor aluminum sec-butoxide (ASB). Al₂O₃ powder is conventionally used for this purpose, and the subsequent lattice softening associated with the solid solution helps to facilitate densification. However, a liquid-phase additive is still essential for the full densification of SiAlONs. Higher densities were obtained from SiAlON powder blends utilizing organometallic ASB than those utilizing alumina powder, allowing for greater densification at very low Y₂O₃ concentrations. The thermal decomposition of the organic precursor was investigated by high-temperature scanning electron microscopy, thermogravimetric analysis, and various X-ray diffraction experiments. Immersion density measurements and lattice parameter refinements were performed for samples sintered with varying Y₂O₃ concentrations and/or dwell times. Results indicate that ASB-containing powder blends favor SiAlON formation more strongly than Al₂O₃-containing powder blends and favor densification at very low Y₂O₃ concentration.