Demonstration of the cold sintering process study for the densification and grain growth of ZnO ceramics

With the cold sintering process (CSP), it was found that adding acetic acid to an aqueous solution dramatically changed both the densities and the grain microstructures of the ZnO ceramics. Bulk densities >90% theoretical were realized below 100°C, and the average conductivity of CSP samples at around 300°C was similar to samples conventionally sintered at 1400°C. Frequently, ZnO is also used as a model ceramic system for fundamental studies for sintering. By the same procedure as the grain growth of the conventional sintering, the kinetic grain growth exponent of the CSP samples was determined as N=3, and the calculated activated energy of grain growth was 43 kJ/mol, which is much lower than that reported using conventional sintering. The evidence for grain growth under the CSP is important as it indicates that there is a genuine sintering process being activated at these low temperatures and it is beyond a pressurized densification process.     

Oxidation kinetics strength of Hi‐NicalonTM‐S SiC fiber after oxidation in dry and wet air

Hi‐Nicalon?‐S SiC fiber strengths and Weibull moduli were measured after oxidation for up to 100 hours between 700°C and 1400°C in wet and dry air. SiO₂ scale thickness and crystallization extent were measured by TEM. The effect of furnace environment on trace element levels in the SiO₂ scales was characterized by secondary ion mass spectroscopy. Crystallization kinetics and Deal‐Grove oxidation kinetics for glass and crystalline scale, and the transition between them, were modeled and determined. Crystallization retards oxidation kinetics, and scale that formed in the crystalline state was heavily deformed by the growth stress accompanying SiC oxidation volume expansion. Glass scales formed in dry air slightly increased fiber strength. Glass scales formed in wet air did not increase strength, and in some cases significantly decreased strength. Scales more than 200 nm thick were usually partially or completely crystallized, which degraded fiber strength. Contamination of scales by trace impurities such as Al and Ca during heat treatment inhibited crystallization. The oxidation kinetics and the strengths of oxidized Hi‐Nicalon?‐S fibers are compared with previous studies on SiC fibers, bulk SiC, and single‐crystal SiC. Empirical relationships between oxidation temperature, time, scale thickness, and strength are determined and discussed.     

Structural and Dielectric Properties in (1−x)BaTiO3–xBi(Mg1/2Ti1/2)O3 Ceramics (0.1 ≤ x ≤ 0.5) and Potential for High‐Voltage Multilayer Capacitors

Structural and dielectric properties of (1?x)BaTiO₃–xBi(Mg_1/2Ti_1/2)O₃ (x = 0.1–0.5) were investigated to understand the binary system and utilize it for high‐voltage, high energy density capacitors. The solubility limit for Bi(Mg_1/2Ti_1/2)O₃ in a BaTiO₃ perovskite was between x = 0.4 and x = 0.5. A phase with pseudocubic symmetry was formed for x = 0.1–0.4; a secondary phase developed at x = 0.5. Dielectric measurements showed highly diffusive and dispersive relaxor‐like characteristics from 10 to 40 mol% of Bi(Mg_1/2Ti_1/2)O₃. These compositions also showed high relative permittivity with low‐temperature coefficients of permittivity over a wide range of temperatures ?100°C–600°C. Relaxation behavior was quantitatively investigated using the Vogel–Fulcher model, which revealed the activation energy of 0.17–0.22 eV. Prototyped multilayer capacitors of 18 mm × 17 mm × 4 mm dimensions with a capacitance of 12.5 nF at 1 kHz were successfully constructed and demonstrated multiple charge–discharge characteristics up to 10 kV.     

Incorporating platinum precursors into a NaA-zeolite synthesis mixture promoting the formation of nanosized zeolite

Sodium A-zeolite with different platinum contents were prepared by directly incorporating platinum precursor (Pt(NH₃)₄Cl₂) into the zeolite during synthesis. Pt/KA-zeolite was then obtained by ion-exchange with KCl solution. The effect of platinum concentration on the crystal morphology and platinum dispersion was investigated by hydrogen chemisorption, scanning electron microscopy (SEM), X-ray diffraction (XRD), and time-of-flight secondary ion mass spectrometer (TOF-SIMS). SEM results revealed a bimodal crystal size distribution for NaA-zeolite with low platinum concentration (<1 wt%). Chamfered edges were found for all the larger cubic crystals (～4 μm). Two types of cubic crystals, smooth surface cubes with chamfered edges and rough surface cubes, were observed for the smaller crystals (～400 nm). The proportion of the rough surface nanosized cubes increased as the platinum content increased. At about 4 wt% platinum, only nanosized rough surface cubic crystals were obtained, which were transformed into nanocrystals of KF-zeolite after ion-exchange with KCl, as indicated by X-ray diffraction results. TOF-SIMS data taken before and after sputtering the surface layers revealed that platinum was distributed homogeneously inside of the zeolite, which was supported by hydrogen chemisorption results, indicating that platinum particles were confined in the zeolitic cages for both the microsized and nanosized cubic crystals. A mechanism was proposed to elucidate the role of platinum precursor on the nucleation and growth of nanosized zeolite, which is consistent with all of the characterization results.     

Revisiting metastable immiscibility in SiO2–Al2O3: Structure and phase separation of supercooled liquids and glasses

Understanding and controlling liquid–liquid phase separation in aluminosilicates is crucial for optimizing glass properties. However, the metastable nature of aluminosilicates’ phase separation has made it difficult to study experimentally, and uncertainty persists regarding the compositional and temperature extents of the miscibility gap. Here, we present new experimental evidence that suggests a consolute temperature between 1440 and 1590°C and endmember compositions of 7 and 62 mol.% Al₂O₃ for the phase-separated glasses. Using containerless melt processing, deeply supercooled liquids over the 0–60 mol.% Al₂O₃ range are probed with in situ small- and wide-angle X-ray scattering, which simultaneously reveals changes in nanoscale density heterogeneity and atomic structure. Correlations between phase separation and atomic coordination environments are compared for liquids and glasses. Pair distribution function analysis shows mean O–(Si + Al) coordination increases with Al₂O₃ content and decreases with temperature.     

A dual functional staged hydrogen purifier for an integrated fuel processor–fuel cell power system

This paper describes the operation of a dual functional, membrane/catalytic CO_x methanator, hydrogen purifier that is well-suited for an integrated fuel processor/fuel cell power system. In combination with a pressure swing reformer (PSR) and a PEMFC, the system provides high overall efficiency and portability for distributed power or onboard vehicle use. Gas testing results illustrate the ability of the purifier to produce fuel cell purity hydrogen at peak power flux. The durability of this purifier is shown by its ability to meet target hydrogen purity even with a membrane that permeates >3000 ppm CO. Gas purge streams from both fuel cell electrodes are combined with the membrane retentate and combusted in the PSR combustion cycle to provide heat for the reforming reaction leading to high thermal efficiency. Most significantly, it is shown that staging of this purifier, enables recovery of some fraction of the purified hydrogen at pressures substantially approaching that of the feed hydrogen partial pressure. This creates an onboard source of high pressure hydrogen to be optionally fed to a storage device for use during vehicle startup, or to the fuel cell, either directly or via the storage device, under high power load conditions. The beneficial impact of this two-stage, dual functional purifier on membrane cost, dependability and fuel processor/fuel cell integration, will be discussed.     

Properties and Biotechnological Applications of Acyl‐CoA:diacylglycerol Acyltransferase and Phospholipid:diacylglycerol Acyltransferase from Terrestrial Plants and Microalgae

Triacylglycerol (TAG) is the major storage lipid in most terrestrial plants and microalgae, and has great nutritional and industrial value. Since the demand for vegetable oil is consistently increasing, numerous studies have been focused on improving the TAG content and modifying the fatty‐acid compositions of plant seed oils. In addition, there is a strong research interest in establishing plant vegetative tissues and microalgae as platforms for lipid production. In higher plants and microalgae, TAG biosynthesis occurs via acyl‐CoA‐dependent or acyl‐CoA‐independent pathways. Diacylglycerol acyltransferase (DGAT) catalyzes the last and committed step in the acyl‐CoA‐dependent biosynthesis of TAG, which appears to represent a bottleneck in oil accumulation in some oilseed species. Membrane‐bound and soluble forms of DGAT have been identified with very different amino‐acid sequences and biochemical properties. Alternatively, TAG can be formed through acyl‐CoA‐independent pathways via the catalytic action of membrane‐bound phospholipid:diacylglycerol acyltransferase (PDAT). As the enzymes catalyzing the terminal steps of TAG formation, DGAT and PDAT play crucial roles in determining the flux of carbon into seed TAG and thus have been considered as the key targets for engineering oil production. Here, we summarize the most recent knowledge on DGAT and PDAT in higher plants and microalgae, with the emphasis on their physiological roles, structural features, and regulation. The development of various metabolic engineering strategies to enhance the TAG content and alter the fatty‐acid composition of TAG is also discussed.     

Properties of lysophosphatidylcholine acyltransferase from <Emphasis Type="Italic">Brassica napus</Emphasis> cultures

Acyl-CoA:lysophosphatidylcholine acyltransferase (LPCAT; EC 2.3.1.23) catalyzes the acyl-CoA-dependent acylation of lysophosphatidylcholine (LPC) to produce PC and CoA. LPCAT activity may affect the incorporation of fatty acyl moieties at the sn-2 position of PC where PUFA are formed and may indirectly influence seed TAG composition. LPCAT activity in microsomes prepared from microspore-derived cell suspension cultures of oilseed rape (Brassica napus L. cv Jet Neuf) was assayed using [1-¹⁴C]acyl-CoA as the fatty acyl donor. LPCAT activity was optimal at neutral pH and 35°C, and was inhibited by 50% at a BSA concentration of 3 mg mL⁻¹. At acyl-CoA concentrations above 20 μM, LPCAT activity was more specific for oleoyl (18∶1)-CoA than stearoyl (18∶0)- and palmitoyl (16∶0)-CoA. Lauroyl (12∶0)-CoA, however, was not an effective acyl donor. LPC species containing 12∶0, 16∶0, 18∶0, or 18∶1 as the fatty acyl moiety all served as effective acyl acceptors for LPCAT, although 12∶0-LPC was somewhat less effective as a substrate at lower concentrations. The failure of LPCAT to catalyze the incorporation of a 12∶0 moiety from acyl-CoA into PC is consistent with the tendency of acyltransferases to discriminate against incorporation of this fatty acyl moiety at the sn-2 position of TAG from the seed oil of transgenic B. napus expressing a medium-chain thioesterase.     

Factors enhancing diacylglycerol acyltransferase activity in microsomes from cell-suspension cultures of oilseed rape

Several factors, including an unidentified endogenous component, were found to stimulate microsomal diacylglycerol acyltransferase (DGAT, EC 2.3.1.20) from a microspore-derived cell-suspension culture of oilseed rape (Brassica napus L. cv. Jet Neuf). At a concentration of 25mM, MgSO₄ and MgCl₂ stimulated microsomal DGAT 25- and 10-fold, respectively. AIP and CoA at concentrations of 2 and 1 mM stimulated the enzyme 2.4- and 12-fold, respectively, although the effects were lessened in the presence of higher Mg²⁺ concentrations. Although microsomal DGAT activity was increased only slightly by the addition of exogenous sn-1,2-diacylglycerol to the reaction mixture, it was increased substantially by the addition of exogenous phosphatidate. sn-Glycerol-3-phosphate and other phospholipids tested did not have this stimulatory effect. DGAT activity did not decrease when microsomes were incubated with ATP in the presence of the cytosolic fraction. This fraction, however, contained a small organic compound(s) that stimulated microsomal DGAT activity.