High‐Temperature Deformation Mechanisms in Monolithic 3YTZP and 3YTZP Containing Single‐Walled Carbon Nanotubes

Monolithic 3YTZP and 3YTZP containing 2.5 vol% of single‐walled carbon nanotubes (SWCNT) were fabricated by Spark Plasma Sintering (SPS) at 1250°C. Microstructural characterization of the as‐fabricated 3YTZP/SWCNTs composite shows a homogeneous CNTs dispersion throughout the ceramic matrix. The specimens have been crept at temperatures between 1100°C and 1200°C in order to investigate the influence of the SWCNTs addition on high‐temperature deformation mechanisms in zirconia. Slightly higher stress exponent values are found for 3YTZP/SWCNTs nanocomposites (n~2.5) compared to monolithic 3YTZP (n~2.0). However, the activation energy in 3YTZP (Q = 715 ± 60 kJ/mol) experiences a reduction of about 25% by the addition of 2.5 vol% of SWCNTs (Q = 540 ± 40 kJ/mol). Scanning electron microscopy studies indicate that there is no microstructural evolution in crept specimens, and Raman spectroscopy measurements show that SWCNTs preserved their integrity during the creep tests. All these results seem to indicate that the high‐temperature deformation mechanism is grain‐boundary sliding (GBS) accommodated by grain‐boundary diffusion, which is influenced by yttrium segregation and the presence of SWCNTs at the grain boundary.     

Plasticity of nanocrystalline yttria-stabilized tetragonalzirconia polycrystals

The high-temperature behavior of nanocrystalline yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) with an initial grain size of 120 nm has been studied in uniaxial compression as a function of stress (5–200 MPa) and temperature (1150–1250 °C). The creep parameters, n=2 and Q=630 kJ/mol, were obtained for all experimental conditions. Evaluation of the strain rates showed that the material was more creep resistant than expected for very fine-grained materials. An interface-controlled mechanism is proposed to account for the experimental results.     

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.     

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).     

Sintering and grain growth of CoO-doped CeO2 ceramics

Co-doped CeO₂ powders with atomic ratios equal to 0.25, 1 and 3% were synthesized by the conventional mixed-oxide method. No binary compounds were detected in the CeO₂–CoO system, and the Co element exists as the state of Co²⁺ in the samples sintered above 1000°C. A small amount of Co doping reduces sintering temperatures and promotes grain boundary mobility dramatically. Over 99.0% of relative density (R.D.) can be obtained for 0.25% Co-doped sample sintered at 1300°C for 2 h, compared with ∼ 96% of relative density for pure CeO₂ sintered at 1525°C for 2 h. The results from grain growth kinetics study indicate that grain growth exponent, n, and activation energy, Q, are 3 and 697 ± 37 kJ/mol for pure CeO₂, 4 and 572 ± 57 kJ/mol for 0.25% Co-doped CeO₂, respectively.     

Creep behavior of a zirconium diboride–silicon carbide composite

Flexural creep studies of ZrB₂–20 vol% SiC ultra-high temperature ceramic were conducted over the range of 1400–1820 °C in an argon shielded testing apparatus. A two decade increase in creep rate, between 1500 and 1600 °C, suggests a clear transition between two distinct creep mechanisms. Low temperature deformation (1400–1500 °C) is dominated by ZrB₂ grain or ZrB₂–SiC interphase boundary and ZrB₂ lattice diffusion having an activation energy of 364 ± 93 kJ/mol and a stress exponent of unity. At high temperatures (>1600 °C) the rate-controlling processes include ZrB₂–ZrB₂ and/or ZrB₂–SiC boundary sliding with an activation energy of 639 ± 1 kJ/mol and stress exponents of 1.7 < n < 2.2. In addition, cavitation is found in all specimens above 1600 °C where strain-rate contributions agree with a stress exponent of n = 2.2. Microstructure observations show cavitation may partially accommodate grain boundary sliding, but of most significance, we find evidence of approximately 5% contribution to the accumulated creep strain.     

Microstructure and high temperature 4-point bending creep of sol–gel derived mullite ceramics

Four-point bending creep behavior of mullite ceramics with monomodal and bimodal distribution of grain sizes was studied in the temperature range of 1320–1400 °C under the stresses between 40 and 160 MPa. Mullite ceramic with bimodal grain size distribution was prepared using aluminum nitrate nonahydrate as alumina precursor. When γ-Al₂O₃ or boehmite were used as alumina precursors, mullite grains are equiaxial with mean particle size of 0.6 μm for the former and 1.3 μm for the latter alumina precursor. The highest creep rate exhibited the sample with monomodal morphology and grains in size of 0.6 μm, which is about one order of magnitude greater than that for the monomodal morphology but with grains in size of 1.3 μm. The highest activation energy for creep (Q = 742 ± 33 kJ/mol) exhibits mullite with equiaxial grains of 1.3 μm, whereas for sample with smaller equiaxial grains the activation energy is much smaller and similar to mullite ceramics with bimodal grain morphology. Intergranular fracture is predominant near the tension surface, while transgranular more planar fracture is predominant near the compression surface zone.     

Creep mechanisms of laminated alumina/zirconia-toughened alumina composites

High-temperature plastic deformation of laminar composites containing alternate layers of Al₂O₃ and a mixture of 60 vol.% Al₂O₃ + 40 vol.% 3 mol% Y₂O₃-stabilized tetragonal ZrO₂ (ZTA) produced by tape casting is investigated in isostrain compression testing at temperatures between 1400 and 1500 °C. The stress exponent n and the creep activation energy Q are close to 1 and 700 kJ/mol, respectively. Microstructual observations reveal the lack of differential features in the ZTA layers and a general creep damage of the Al₂O₃ layers, with little microcracking by cavity coalescence even up to strains of 30%. The layer interfaces maintain their initial structural integrity after testing. An isostrain composite creep model predicts correctly the overall mechanical behavior of the laminates, which is dictated by the alumina phase via diffusional creep controlled by oxygen grain boundary diffusion.     

Creep behavior of TiCxN1−x-CoTi cermets synthesized by mechanically induced self-sustaining reaction

The plastic flow of TiC_xN_1−x-CoTi cermets has been investigated by uniaxial compression tests carried out in argon atmosphere at temperatures between 1100 and 1200 °C. Two different cermets, with 5 wt.% W or WC content as sintering additives, have been explored to assess the influence of the sintering additives on creep. The microstructural observations of deformed samples and the mechanical results indicate that the hard phase (ceramic grains) controls the plastic deformation. The stress exponent changes from 1 to 2 with increasing strain rate, suggesting a transition in the deformation mechanism from diffusional creep to grain boundary sliding; both with similar activation energy values of about 400 kJ/mol. This value of activation energy agrees with C diffusion in the carbonitride grains as the strain rate controlling mechanism.     

High-temperature mechanical behavior of Al2O3/graphite composites

Uniaxial compressive creep behaviour of spark-plasma-sintered Al₂O₃/graphite particulate composites has been studied at temperature between 1250 and 1350 °C. Values of stress exponent, n, ranging from 1 to 1.4 and, activation energy, Q, of 600 ± 40 kJ/mol have been determined. With 10 vol% graphite in the composite, the creep deformation of the composite is controlled by the fine-grained Al₂O₃ matrix, where Coble creep has been identified as the dominant creep mechanism.     

Mechanical loss,creep, diffusion and ionic conductivity of ZrO2-8 mol%Y2O3 polycrystals

Polycrystalline ZrO₂-8 mol%Y₂O₃ was investigated by combining several experimental techniques on identical materials sintered out of the same high purity powder. The mechanical loss spectrum (damping and elastic modulus) was measured in a large frequency and temperature range (10⁻²Hz–1.5kHz; −150 to 1400°C). Damping due to point defect relaxation at low temperature and to viscoelastic relaxation at high temperature was revealed. The creep resistance was investigated with four-point bending tests (stress and temperature ranges: 20–75 MPa, 1100–1290°C), indicating Nabarro-Herring creep as the main rate-controlling mechanism. Both viscoelastic deformation and creep seem to be controlled by cation diffusion. Measurements of the ⁹⁶Zr tracer diffusivity by secondary ion mass spectrometry at 1125–1460°C yielded an activation enthalpy of 460 kJ/mol. Close values were obtained for creep (440 kJ/mol) and viscoelastic relaxation (530 kJ/mol). Finally, the ionic DC-conductivity of these electrolytes was measured with high accuracy in the range 300–1250°C.     

Thermal conductivity and mechanical properties of Si3N4 ceramics with binary fluoride sintering additives

Silicon nitride (Si₃N₄) ceramics were fabricated by gas pressure sintering (GPS) using four sintering additives: Y₂O₃–MgO, Y₂O₃–MgF₂, YF₃–MgO, and YF₃–MgF₂. The phase composition, grain growth kinetics, mechanical properties, and thermal conductivities of the Si₃N₄ ceramics were compared. The results indicated that the reduction of YF₃ on SiO₂, induced a high Y₂O₃/SiO₂ secondary phase ratio, which improved the thermal conductivity of the Si₃N₄ ceramics. The depolymerization of F atom reduces the diffusion energy barrier of solute atom and weakens the viscous resistance of anion group, which was beneficial to grain boundary migration. Besides exhibiting a lower grain growth exponent(n = 2.5)and growth activation energy (Q = 587.94 ± 15.35 kJ/mol), samples doped with binary fluorides showed excellent properties, including appreciable thermal conductivity (69 W m⁻¹ K⁻¹), hardness (14.63 ± 0.12 GPa), and fracture toughness (8.75 ± 0.18 MPa m^1/2), as well as desirable bending strength (751 ± 14 MPa).     

Effect of LaB6 addition on compressive creep behavior with simultaneous oxide scale growth of spark plasma sintered ZrB2-SiC composites

A study has been carried out to examine the effect of LaB₆ addition on the compressive creep behavior of ZrB₂-SiC composites at 1300–1400°C under stresses between 47 and 78 MPa in laboratory air. The ZrB₂-20 vol% SiC composites containing LaB₆ (10% in ZSBCL-10 and 14% in ZSBCL-14) besides 5.6% B₄C and 4.8% C as additives were prepared by spark plasma sintering at 1600°C. Due to cleaner interfaces and superior oxidation resistance, the ZSBCL-14 composite has exhibited a lower steady-state creep rate at 1300°C than the ZSBCL-10. The obtained stress exponent (n ∼ 2 ± 0.1) along with cracking at ZrB₂ grain boundaries and ZrB₂-SiC interfaces are considered evidence of grain boundary sliding during creep of the ZSBCL-10 composite. However, the values of n ∼ 1 and apparent activation energy ∼700 kJ/mol obtained for the ZSBCL-14 composite at 1300–1400°C suggest that ZrB₂ grain boundary diffusion is the rate-limiting mechanism of creep. The thickness of the damaged outer layer containing cracks scales with temperature and applied stress, indicating their role in facilitating the ingress of oxygen causing oxide scale growth. Decreasing oxidation-induced defect density with depth to a limit of ∼280 μm, indicates the predominance of creep-based deformation and damage at the inner core of samples.     

Ultra-high creep resistant SiC ceramics prepared by rapid hot pressing

The high-temperature compression creep of additive-free β/α silicon carbide ceramics fabricated by rapid hot pressing (RHP) was investigated. The creep tests were accomplished in vacuum at temperature range 1500 °C–1750 °C and compressive loads of 200 MPa to 400 MPa. Under investigated condition the RHP ceramics possessed the lowest creep rate reported in the literature. The observed strain rates changed from 2.5 × 10^?9 s^?1 at 1500 °C and a lowest load of 275 MPa to 1.05 × 10^?7 s^?1 at 1750 °C and a highest load of 400 MPa. The average creep activation energy and the stress exponent remain essentially constant along the whole range of investigated parameters and were 315 ± 20 kJ?mol^?1, and 2.22 ± 0.17, respectively. The suggested creep mechanism involves GB sliding accommodated by GB diffusion and β?α SiC phase transformation.     

Enthalpy of formation and dehydration of lithium and sodium zeolite beta

Zeolite Li-BEA and Na-BEA with Si/Al = 3–4 were synthesized by alumination and ion exchange, then characterized by XRD, TG–DSC and NMR. The enthalpies of formation and dehydration of Li and Na ion exchanged zeolite beta are investigated by high temperature oxide melt solution calorimetry. For Li-BEA, the formation enthalpies of formation from oxides at 25 °C are 25.6 ± 1.7 kJ/mol TO₂ for the dehydrated zeolite and −8.45 ± 0.94 kJ/mol TO₂ for the fully hydrated zeolite; for Na-BEA they are −2.4 ± 0.6 kJ/mol TO₂ for the dehydrated and −17.8 ± 1.0 kJ/mol TO₂ for the fully hydrated zeolite. The integral dehydration enthalpy at 25 °C is 33.2 ± 1.8 kJ/mol H₂O for Li-BEA and 16.5 ± 1.1 kJ/mol H₂O for Na-BEA. The partial molar dehydration enthalpies of both Li-BEA and Na-BEA are a linear function of water content. Molecular mechanics simulations explore the cation and water molecule positions in the framework at several water contents.     

Compressive creep behavior of spark plasma sintered La2O3–YSZ composite

The present paper describes compressive creep behavior of cubic 8 mol% yttria stabilized zirconia+10 mol% La₂O₃ (fabricated by Spark Plasma Sintering) in the temperature range of 1300–1330 °C at a stress level of 45–78 MPa in vacuum. The pre- and post-creep microstructures, relative magnitudes of the stress exponent (n=1.7–2.1) and the activation energy (540–580 kJ/mol) suggest that grain boundary sliding aided by inter-diffusion of La and Zr leading to the formation of pyrochlore La_1.6Y_0.4Zr₂O₇ phase at the grain boundaries during creep is the active creep mechanism in this composite.     

High-Temperature Compressive Creep of Polycrystalline Mullite

Aluminosilicates of three compositions with mullite as the major phase were synthesized by a sol-gel process and characterized with bulk and microchemical analyses and microstructural observation. An apparatus for measuring the compressive creep up to 1900 K with a sensitivity of ±1 μm was constructed and used to measure the creep of singlephase mullite, mullite with second-phase glass, and mullite with second-phase corundum. Measurements in air at stresses of 15 to 100 MPa and temperatures of 1471 to 1724 K determined that samples with second-phase glass crept more rapidly than single-phase mullite or mullite with secondphase corundum. The apparent creep activation energies determined at 100 MPa were 742 kJ/mol for the mullite containing glass, 819 kJ/mol for the single-phase mullite, and 769 kJ/mol for the mullite with second-phase corundum. The stress exponents determined at 1724 K were 1.6 for the mullite plus glass, 1.5 for the single-phase mullite, and 1.2 for the mullite with α-Al₂O₃. The creep behavior of the aluminosilicates containing glass were consistent with rate control by the viscous flow of the glass and the measured creep rates were in good agreement with creep rates calculated from a model by Dryden. The creep behavior of the completely crystalline aluminosilicates was consistent with rate control by diffusional creep.     

High-performance 0.9Al2O3-0.1TiO2 microwave dielectric ceramics prepared by digital light processing

In this work, the 0.9Al₂O₃-0.1TiO₂ ceramic sample with good microwave dielectric properties and complex structures can be well fabricated by digital light processing (DLP). A relationship between dispersant content and rheological behavior of 0.9Al₂O₃-0.1TiO₂ slurry was explored. When dispersant content was 3.0 wt%, 0.9Al₂O₃-0.1TiO₂ slurry with high solid loading (50 vol%) and low viscosity (2.9 Pa s) could be obtained. 0.9Al₂O₃-0.1TiO₂ ceramic parts with high accuracy were fabricated successfully by adding 3.0 wt% photoinitiator under 600 mJ/cm² exposure energy. With the increase of sintering temperature from 1400 °C to 1600 °C, relative density, dielectric constant (ε_r), and quality factor (Q × f) of 0.9Al₂O₃-0.1TiO₂ ceramic sample increased first and then decreased, and all reached the maximum value at 1550 °C due to the uniformity and densification of microstructures. The temperature coefficient of resonant frequency (τ_f) value showed an almost monotonous increase, changing from negative to positive, and near-zero τ_f value at 1550 °C. In addition, 0.9Al₂O₃-0.1TiO₂ ceramic samples sintered at 1550 °C fabricated by DLP method presented much better microwave dielectric properties: ε_r = 11.30 ± 0.02, Q × f = 35,345 ± 143 GHz (@～12 GHz), τ_f = 2.16 ± 0.21 ppm/°C than that of by dry pressing method: ε_r = 11.16 ± 0.11, Q × f = 30,195 ± 257 GHz (@～12 GHz), τ_f = 4.45 ± 0.13 ppm/°C, especially the Q × f value achieved a 17% increase. Accordingly, DLP technique, which has advantages of producing relatively high properties and complex geometry of microwave dielectric ceramics as well as without extra high-cost mold, greatly satisfies application requirements.     

The rate-determining mechanism in the sintering of undoped nonstoichiometric barium titanate

High-purity undoped nonstoichiometric BaTiO₃ powder of TiO₂-excess and BaO-excess has been pressureless-sintered in the range of 1215–1340°C using conventional tube furnace. Low temperature sintering of the TiO₂-excess composition results in the characteristic plate-like grains grown along the {111} plane. Surface energy anisotropy is proposed to account for the anomalous microstructural development and low final sintered density. The activation enthalpy values (ΔH) deduced from isothermal sintering are 522±130 and 396±16 kJ mol for the TiO₂-excess and BaO-excess composition, respectively. The rate-determining mechanism for the solid-state sintering of the undoped nonstoichiometric BaTiO₃ powder is discussed.