Phase stability and microstructure evolution of yttria-stabilized zirconia during firing in a reducing atmosphere

The phase transition and microstructure evolution of yttria-stabilized zirconia (YSZ) when firing in a reducing atmosphere are investigated in the present study. As the sintering temperature is lower than 1400 °C, the phase observed for the YSZ specimens is the first tetragonal (t) phase with a grain size of only 0.4 μm in average. When the sintering temperature is increased above 1450 °C, the second tetragonal (t′) phase appears together with a rapid grain growth rate. A surface layer with grains larger than 20 μm is observed for the YSZ specimens sintered at 1600 °C. It is found that the addition of metallic nickel particles has little influence on the phase transition of YSZ; however, the growth of t′-phase grains is reduced with the addition of Ni particles.     

Effects of chemical structure of polyurethane‐based low‐profile additives on the miscibility,curing behavior,volume shrinkage,glass transition temperatures,and mechanical properties for styrene/unsaturated polyester/low‐profile additive ternary systems. I: Miscibility,curing behavior,and volume shrinkage

The effects of chemical structure and molecular weight of three series of thermoplastic polyurethane‐based (PU) low‐profile additives (LPA) on the miscibility of styrene (ST)/unsaturated polyester (UP) resin/LPA ternary systems prior to reaction were investigated by using the Flory‐Huggins theory and group contribution methods. The reaction kinetics during the cure at 110°C and the cured sample morphology were also studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), respectively. The phase‐separation characteristics of ST/UP/LPA systems during the cure, as revealed by the cured‐sample morphology, and the DSC reaction‐rate profile, could be generally predicted by the calculated upper critical solution temperature for the uncured ST/UP/LPA systems. Finally, based on the measurements for volume change and microvoid formation, volume shrinkage characteristics for the cured ST/UP/LPA systems have been explored. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 543–557, 2000     

Photocatalytic oxidation of nitrogen oxide over titania–zeolite composite catalyst to remove nitrogen oxides in the atmosphere

The photooxidation of NO with oxygen over Hycom TiO₂ and zeolite (A and Y form zeolite: TiO₂-AZ and TiO₂-YZ) composite catalysts was studied to remove NO_x in the atmosphere. The photocatalytic oxidation activity of the titania in the composite catalyst in a proportion of AZ:TiO₂=3:7 is about three times larger than that in the bare titania. The adsorption behaviors of NO and NO₂ for the bare titania sample obey Langmuir adsorption equations of NO and NO₂, respectively. In the titania–zeolite composite catalysts, the adsorption data indicate the increase in the amount of NO adsorption on the TiO₂ phase and the decrease in the amount of NO₂ adsorption, compared with the bare titania. The acceleration of NO photooxidation rate, resulting from the increase in the amount of NO adsorbed and the decrease in the amount of NO₂ adsorbed, thus occurs on the TiO₂ phase. IR spectra, when irradiating the catalysts with UV, showed the immediate formation of nitrate and NO₂ species on the catalyst. The results lead to the conclusion that the zeolites promote the photocatalytic oxidation of NO over the titania.     

De‐densification mechanisms of yttria‐doped cerium oxide during sintering in a reducing atmosphere

The presence of residual carbon in oxides in which the valence state can change during sintering may lead to de‐densification or swelling phenomena during the last stage of sintering. This was demonstrated by sintering a Ce_0.85Y_0.15O_2‐x powder compact with or without added graphite carbon in a reducing atmosphere (Ar/5 vol.% H₂) at 1450°C. The shrinkage behavior was studied with a dilatometer combined with an oxygen probe and a gas chromatograph to analyze the composition of the released gases. Oxide reduction during sintering leads to a significant release of oxygen. This oxygen can react with carbon to form gaseous species such as CO. These gases can be released during the second stage of sintering, that is, when the porosity is still open, but they can be trapped in the closing pores during the final stage of sintering. This causes the pressure to increase in the pores, resulting in irreversible swelling, cracking and eventually pellet fracture.     

Thermochromic behavior (400 < T °C < 1200 °C) of barium carbonate/binary metal oxide mixtures

Irreversible thermochromism over a wide temperature range has been observed from the decomposition of a mixture of a barium carbonate and a metal oxide. The control of the reaction temperature can be predicted from the calculation of the Madelung energy of the barium/transition metal mixed oxide formed consecutively with the decarbonatation. Moreover, the Madelung energy of this formed mixed oxide may be predicted from bond valence considerations. This study offers a simple predictive approach to propose temperature indicators with significant optical contrast and a thermochromic temperature varying between 400 and 1200 °C.     

Degradation of Bioactive Polydimethylsiloxane–CaO–SiO2–TiO2 and Poly(tetramethylene oxide)–CaO–TiO2 Hybrids in a Simulated Body Fluid

It has been shown that polydimethylsiloxane (PDMS)–CaO–SiO₂–TiO₂ and poly(tetramethylene oxide) (PTMO)–CaO–TiO₂ hybrids form apatite on their surfaces in a simulated body fluid (SBF) and show mechanical properties similar to those of human cancellous bones. In the present study, changes, caused by soaking in SBF, were measured in the mechanical properties of PDMS–CaO–SiO₂–TiO₂ hybrids with different CaO and TiO₂ contents and PTMO–CaO–TiO₂ hybrids with different CaO contents. Significant decreases in the strength and strain at failure of the hybrids were observed for the PDMS–CaO–SiO₂–TiO₂ hybrids with high CaO or TiO₂ contents and PTMO–CaO–TiO₂ hybrids with a high CaO content after soaking in SBF for 4 w. This indicates that incorporation of a large amount of CaO component into the hybrids should result in the deterioration of the hybrids in the body environment.     

Oxidation resistance up to 2600 K under air plasma of (Zr/Hf)B2 composites containing 20 vol% AlN for hypersonic applications

Fully-dense ZrB₂ and HfB₂ composites were elaborated by Spark Plasma Sintering with 20 vol% AlN to replace SiC or TaSi₂ with the objective to improve the oxidation resistance at very high temperature. This study follows the ones on (Zr/Hf)B₂-SiC and (Zr/Hf)B₂-TaSi₂ systems carried out in the same conditions (Pellegrini et al. 2022a; Pellegrini et al. 2022b). Oxidation behavior of several samples in air plasma conditions, at 1000 Pa total pressure and from 1980 K up to 2600 K, was studied using the MESOX facility implemented at the focus of a solar furnace. The mass variation of the samples during oxidation duration of 300 s on a temperature plateau was measured. The characterization of the oxidized samples was done using SEM, EDS, XRD, XPS and Raman. A better oxidation resistance was obtained with these new compositions as, for example, no mass loss up to 2600 K was measured for the ZrB₂-20 vol% AlN composite due to the protective effect of the aluminum-rich phase formed by oxidation and confirmed by the cross-section analysis.     

On-line H NMR spectroscopic investigation of hydrogen bonding in supercritical and near critical CO2–methanol up to 35 MPa and 403 K

On-line NMR spectroscopy can beneficially be applied to studies of supercritical and near-critical fluids as an alternative to optical spectroscopy. Up to now high pressure NMR experiments are predominantly accomplished using custom made NMR batch reactors. The authors present a novel high pressure cell with displacement plunger for on-line NMR experiments on compressible fluids which can be used in conjunction with commercially available SCF NMR flow probes. The on-line technique offers advantages compared to stopped flow techniques such as enhanced control of mixture composition and reaction parameters as well as the facility of engagement into the reaction. The new apparatus is used for NMR studies on hydrogen bonding of methanol in near critical and supercritical carbon dioxide up to 403 K and 35 MPa for which data on the chemical shift of the hydroxyl group and methyl group are reported and interpreted.     

Thermodynamic evaluation of the Al2O3–H2O binary system at pressures up to 30 MPa

The behaviour of the hydrated phases in the Al₂O₃–H₂O system is of major importance in the chemistry of ceramic materials. In this work, stability and metastability relations in the Al₂O₃–H₂O system have been studied. Gibbs free energy functions of the gibbsite and boehmite phases have been critically revised and new optimized functions have been calculated. The functions obtained have been used to predict the stability and metastability relations by calculating a P–T diagram following the CALPHAD methodology. Comparison with the corresponding available experimental data is discussed.     

Oxidation resistance of Zr- and Hf-diboride composites containing SiC in air plasma up to 2600 K for aerospace applications

Microstructure-controlled and fully-dense ZrB₂ and HfB₂ composites were elaborated by Spark Plasma Sintering with two different amounts of SiC (20 and 30 vol%) added to improve their oxidation resistance using optimized sintering parameters. Oxidation of several samples in air plasma conditions, at 1000 Pa total pressure and from 1800 K up to 2600 K, was carried out. The mass variation of samples during oxidation duration of 300 s on a temperature plateau was followed. A four-step oxidation mechanism, identified by four singular mass variation behaviors depending on the oxidation temperature ranges, was proposed and detailed. The total normal emissivity was measured on pre-oxidized samples and high values around 0.90 were obtained from 1300 to 1900 K due to the presence of the oxide layer formed in air plasma conditions and this high emissivity is interesting for aerospace applications.     

Detonation spraying of TiO2-2.5 vol.% Ag powders in a reducing atmosphere

In the present work, rutile powders containing additions of metallic silver (2.5 vol.%) were detonation sprayed in a reducing atmosphere formed by gaseous detonation products of the C₂H₂ + 1.05O₂ mixture. The initial volume of the C₂H₂ + 1.05O₂ mixture - explosive charge - used for a detonation pulse was computer-controlled as the fraction of the barrel volume filled with the mixture. Using a previously developed model of the detonation process, the particle temperatures and velocities were calculated to explain the observed phase and microstructure development in the coatings. With increasing explosive charge, the temperature of the sprayed particles increased and rutile was partially reduced to oxygen-deficient TiO_2−x and then to Ti₃O₅. When the melting temperature of rutile was not reached, the coatings were porous; semi-molten particles formed denser coatings obtained with higher spraying efficiency. Silver inclusions in the titanium oxide matrix experienced melting and substantial overheating, but remained well preserved in the coatings.     

Structure evolution of nanocrystalline CeO2 and CeLnOx mixed oxides (Ln = Pr, Tb, Lu) in O2 and H2 atmosphere and their catalytic activity in soot combustion

This paper reports results of studies on structure and activity in soot combustion of nanocrystalline CeO₂ and CeLnOx mixed oxides (Ln = Pr, Tb, Lu, Ce/Ln atomic ratios 5/1). Nano-sized (4–5 nm) oxides with narrow size distribution were prepared by a microemulsion method W/O. Microstructure, morphology and reductivity of the oxides annealed up to 950 °C in O₂ and H₂ were analyzed by HRTEM, XRD, FT-IR, Raman spectroscopy and H₂-TPR. Obtained mixed oxides had fluorite structure of CeO₂ and all exhibited improved resistance against crystal growth in O₂, but only CeLuOx behaved better than CeO₂ in hydrogen.

The catalytic activity of CeO₂, CeLnOx and physical mixtures of CeO₂ + Ln₂O₃ in a model soot oxidation by air was studied in “tight contact” mode by using thermogravimetry. Half oxidation temperature T_1/2 for soot oxidation catalysed by nano-sized CeO₂ and CeLnOx was similar and ca. 100 °C lower than non-catalysed oxidation. However, the mixed oxides were much more active during successive catalytic cycles, due to better resistance to sintering. Physical mixtures of nanooxides (CeO₂ + Ln₂O₃) showed exceptionally high initial activity in soot oxidation (decrease in T_1/2 by ca. 200 °C) but degraded strongly in successive oxidation cycles. The high initial activity was due to the synergetic effect of nitrate groups present in highly disordered surface of nanocrystalline Ln₂O₃ and enhanced reductivity of nanocrystalline CeO₂.     

Photocatalytic degradation of gaseous trichloroethene using immobilized ZnO/SnO2 coupled oxide in a flow‐through photocatalytic reactor

The photocatalytic degradation of gaseous trichloroethene (TCE) was investigated on immobilized ZnO/SnO₂ coupled oxide in a flow‐through photocatalytic reactor. It was found that gaseous photocatalysis is an efficient method for volatile organic compounds' abatement and air purification. Degradation of ～100% was found for TCE at the concentrations examined, up to 400 ppmv, in a flow‐through dry synthetic gas stream. In our tested conditions, the flow rate had little influence on the photocatalytic degradation efficiencies of TCE, while the relative humidity had a significant influence on the photocatalytic degradation of TCE. The photocatalytic degradation efficiencies of TCE increased slowly below 20% relative humidity and then decreased as the relative humidity increased further. The deactivation of used immobilized photocatalyst was not observed within the 200 h testing period in the present experiment, although the surface of the photocatalyst changed greatly during the use of the photocatalyst. Copyright © 2004 Society of Chemical Industry     

The effect of [bmim][Br] on the solubility of carbon dioxide and methane in glycols at pressures up to 14 MPa and temperatures ranging from 303 to 423 K

Solubility data of methane in ethylene glycol and 1-4 butylene glycol and carbon dioxide in ethylene glycol and 1-2 propylene glycol in the presence of the ionic liquid 1-butyl-3-methylimidazolium bromide have been measured in the temperature range (303–423) K at pressures up to 14 MPa. Henry's law constant of each solute in the studied solvent at saturation pressure is given. The experiments were performed in an autoclave type phase equilibrium apparatus using the total pressure method. For mixtures containing carbon dioxide and ethylene glycol no influence was observed. For mixtures containing carbon dioxide and 1-2 propylene glycol it was observed salting-out effect at 303.2 K and 323.2 K and salting-in effect at the remaining temperatures. For mixtures containing methane and ethylene glycol or 1-4 butylene glycol salting-in effect was observed.     

Mechanical properties up to 1900 K of Al2O3/Er3Al5O12/ZrO2 eutectic ceramics grown by the laser floating zone method

Directionally solidified Al₂O₃–Er₃Al₅O₁₂–ZrO₂ eutectic rods were processed using the laser floating zone method at growth rates of 25, 350 and 750 mm/h to obtain microstructures with different domain size. The mechanical properties were investigated as a function of the processing rate. The hardness, ∼15.6 GPa, and the fracture toughness, ∼4 MPa m^1/2, obtained from Vickers indentation at room temperature were practically independent of the size of the eutectic phases. However, the flexural strength increased as the domain size decreased, reaching outstanding strength values close to 3 GPa in the samples grown at 750 mm/h. A high retention of the flexural strength was observed up to 1500 K in the materials processed at 25 and 350 mm/h, while superplastic behaviour was observed at 1700 K in the eutectic rods solidified at the highest rate of 750 mm/h.     

Intake of up to 3 Eggs/Day Increases HDL Cholesterol and Plasma Choline While Plasma Trimethylamine-<Emphasis Type="Italic">N</Emphasis>-oxide is Unchanged in a Healthy Population

Eggs are a source of cholesterol and choline and may impact plasma lipids and trimethylamine-N-oxide (TMAO) concentrations, which are biomarkers for cardiovascular disease (CVD) risk. Therefore, the effects of increasing egg intake (0, 1, 2, and 3 eggs/day) on these and other CVD risk biomarkers were evaluated in a young, healthy population. Thirty-eight subjects [19 men/19 women, 24.1 ± 2.2 years, body mass index (BMI) 24.3 ± 2.5 kg/m²] participated in this 14-week crossover intervention. Participants underwent a 2-week washout with no egg consumption, followed by intake of 1, 2, and 3 eggs/day for 4 weeks each. Anthropometric data, blood pressure (BP), dietary records, and plasma biomarkers (lipids, glucose, choline, and TMAO) were measured during each intervention phase. BMI, waist circumference, systolic BP, plasma glucose, and plasma triacylglycerol did not change throughout the intervention. Diastolic BP decreased with egg intake (P < 0.05). Compared to 0 eggs/day, intake of 1 egg/day increased HDL cholesterol (HDL-c) (P < 0.05), and decreased LDL cholesterol (LDL-c) (P < 0.05) and the LDL-c/HDL-c ratio (P < 0.01). With intake of 2–3 eggs/day, these changes were maintained. Plasma choline increased dose-dependently with egg intake (P < 0.0001) while fasting plasma TMAO was unchanged. These results indicate that in a healthy population, consuming up to 3 eggs/day results in an overall beneficial effect on biomarkers associated with CVD risk, as documented by increased HDL-c, a reduced LDL-c/HDL-c ratio, and increased plasma choline in combination with no change in plasma LDL-c or TMAO concentrations.