Enhanced Hydrothermal Resistance of Y‐TZP Ceramics Through Colloidal Processing

Two commercial zirconia powders with 3 mol% of yttria (TZ3YE and TZ3YS, labeled as ZE and ZS, respectively) supplied by Tosoh (Japan) were used for this study. Maximum colloidal stability for ZE was achieved by dispersing the powders in a mixture of water/ethanol of 90:10 (wt/wt) using a sonication probe. The rheological behavior of the suspensions was optimized in terms of solids content ranging from 20 to 33 vol% and sonication time (0–6 min), the best results being obtained after 2 min. ZS samples were prepared to a solids loading of 30 vol% in water dispersing with 2 min‐sonication. Samples obtained by slip casting in plaster molds were used for dynamic sintering studies, and fully dense and nanostructured specimens were obtained at temperatures of 1300°C–1350°C (ZE samples) and 1400°C per 2 h (ZS samples). The Hardness (H) and Young's Modulus (E) properties of the specimens were studied by nanoindentation technique giving 17 and 250 GPa mean values for H and E, respectively. The specimens were then forced to a low‐temperature degradation (LTD) treatment at 130°C for 240 h in steps of 60 h. Raman spectroscopy and nanoindentation results of hydrothermally treated samples showed the absence of transformation from tetragonal to monoclinic phase until 180 h whereas the mechanical properties maintained constant even at the sample surface. After 240 h of LTD, the monoclinic phase was detected on all specimens by Raman peaks centered at 180, 191, and 383 cm^?1. The nanoindentation study revealed an important loss of mechanical features reaching 10 and 175 GPa for H and E, respectively. In the case of the ZS specimens, no monoclinic phase is detected after 240 h of LTD treatment and no decay of E or H is detected. The free defect microstructure reached for the ZS specimen revealed a higher hydrothermal resistance so that it is concluded that the excellent behavior against thermal degradation is possible due to the large uniformity obtained by colloidal processing rather than the particle size of the starting powders.     

Thermal and X-Ray Diffraction Studies on Interpenetrating Polymer Networks of Soybean Oil-Based Polyurethane and Cardanol-Based Dye

The mixed ester polyol (MEP) is obtained from refined soybean oil on treatment with glycerol at 210°C in presence of lithrage. The probable structure of MEP was established by IR spectra. The polyurethane synthesized from MEP and diphenyl methane diisocyanate (DPMDI) with varying NCO:OH ratios were reacted with cardanol-o-aminophenol dye using ethyleneglycol dimethacrylate (EGDM) as a cross-linking agent and benzoyl peroxide as initiator. The PU was thoroughly characterized by IR spectroscopy. The thermal behavior of the Interpenetrating polymer networks was characterized by TG and the Morphology was studied by XRD studies.     

Strain-Free Total Resonant Sextet Benzenoid Hydrocarbons

The importance of strain-free (total) resonant sextet benzenoid hydrocarbons is pointed out. The first computer-aided generation and enumeration of such systems is reported, and the data represent substantial supplements to the previous numbers of strain-free resonant sextet benzenoid isomers. Supplementary depictions of some forms of the systems in question are also provided. Constant-isomer series are delineated for the resonant sextet benzenoids. The numbers associated with these series are found to match exactly the known numbers for corresponding constant-isomer series of strictly pericondensed benzenoids.     

Resistive switching memory characteristics of Ge/GeOx nanowires and evidence of oxygen ion migration

The resistive switching memory of Ge nanowires (NWs) in an IrO_x/Al₂O₃/Ge NWs/SiO₂/p-Si structure is investigated. Ge NWs with an average diameter of approximately 100 nm are grown by the vapor–liquid-solid technique. The core-shell structure of the Ge/GeO_x NWs is confirmed by both scanning electron microscopy and high-resolution transmission electron microscopy. Defects in the Ge/GeO_x NWs are observed by X-ray photoelectron spectroscopy. Broad photoluminescence spectra from 10 to 300 K are observed because of defects in the Ge/GeO_x NWs, which are also useful for nanoscale resistive switching memory. The resistive switching mechanism in an IrO_x/GeO_x/W structure involves migration of oxygen ions under external bias, which is also confirmed by real-time observation of the surface of the device. The porous IrO_x top electrode readily allows the evolved O₂ gas to escape from the device. The annealed device has a low operating voltage (<4 V), low RESET current (approximately 22 μA), large resistance ratio (>10³), long pulse read endurance of >10⁵ cycles, and good data retention of >10⁴ s. Its performance is better than that of the as-deposited device because the GeO_x film in the annealed device contains more oxygen vacancies. Under SET operation, Ge/GeO_x nanofilaments (or NWs) form in the GeO_x film. The diameter of the conducting nanofilament is approximately 40 nm, which is calculated using a new method.     

High-Toughness Silicon Carbide as Armor

Silicon carbide, with single-edge precracked beam (SEPB) toughness greater than 7 MPa·m^1/2, was made by hot-pressing using Al–B–C (ABC) or Al–Y₂O₃ (YAG) as additives. The hardness of SiC processed with a liquid phase was always less than SiC densified without a liquid phase despite having a similar or finer grain size. With increasing Al content, the ABC system changed from trans- to intergranular fracture with a drop in hardness and a two- to threefold increase in SEPB toughness. Strength and Weibull modulus for materials processed with a liquid phase were higher than those of solid-state densified SiC. Ballistic testing, however, did not show any improvement over SiC densified with B and C additives. Depth of penetration was controlled by hardness of the SiC-based materials, while V ₅₀ values for 14.5 mm WC–Co cored projectiles were in the range of 720–750 m/s for all materials tested.     

Phase Constitution During Sintering of Red Mud and Red Mud–Fly Ash Mixtures

The phase constitution during the sintering of pure red mud and red mud–fly ash mixtures was studied in the temperature range of 900°–1250°C. The phases formed at different sintering temperatures were analyzed by X-ray powder diffraction. The phases that are likely to form at equilibrium at any isotherm were predicted using the Gibbs free energy minimization technique and the databases provided in the FactSage software. Although the thermodynamic prediction is in reasonable agreement with the experimental results for the major phases, there is some disagreement regarding the minor phases, especially the more complex phases. The major limitation of the thermodynamic approach presently is the non-availability of thermodynamic data for several complex and multi-component solution phases.     

Measurement of Activity Coefficients from Unsteady State Evaporation and Growth of Microdroplets

Techniques are presented for determination of activity coefficients of binary systems from unsteady state evaporation and growth of single microdroplets in controlled environments. A high-precision light scattering method based on resonances observed in light scattering by microdroplets was used to determine the size and composition of a microdroplet as functions of time. The techniques were validated through data on growth of glycerol microdroplets in slowly developing water vapor concentration fields and evaporation of microdroplets, containing volatile dimethylphthalate (DMP) and nonvolatile dioctylphthalate (DOP), in vapor-free atmospheres. When the water vapor concentration in the surrounding gas changes slowly a glycerol droplet maintains a dynamic equilibrium with the water vapor; thus the activity coefficient of water was determined from knowledge of the droplet composition and the water vapor saturation ratio in the gas phase. The activity coefficients of DMP were determined on the basis that the instantaneous evaporation rate of a DMP-DOP microdroplet in a vapor-free atmosphere is equal to the product of the activity of DMP and the evaporation rate of a pure DMP droplet. The activity coefficient values obtained from microdroplet experiments are highly reproducible and agree with data available in the literature.     

Prediction of Polymer Properties in LDPE Reactors

Summary: A new analysis tool is presented that uses the governing kinetic scheme to predict properties of low‐density polyethylene (LDPE) such as the detailed shape of the molecular weight distribution (MWD). A model that captures mixing details of autoclave reactor operation is used to provide a new criterion for the onset of MWD shouldering. Kinetic effects are shown to govern the existence of MWD shoulders in LDPE reactors, even when operation is far from perfectly‐mixed. MWD shoulders occur when the mean reaction environment has a relatively high radical concentration and has a high polymer content, and is at a low temperature. Such conditions maximize long chain formation by polymer transfer and combination‐termination, while limiting chain scission. For imperfectly‐mixed reactors, the blending of polymer‐distributions produced in different spatial locations has a small effect on the composite MWD. However, for adiabatic LDPE autoclaves, imperfect mixing broadens the stable range of mean reactor conditions, and thereby increases the possibility for MWD shouldering.

Polymer MWD produced in an LDPE autoclave reactor by various kinetic mechanisms.     

Cover Picture: Macromol. Mater. Eng. 8/2005

Summary: Poly(butylene succinate‐co‐adipate) (PBSA) and organically modified montmorillonite (OMMT) nanocomposites of three different compositions were prepared by melt‐extrusion in a batch mixer. The structure of the nanocomposites was studied using X‐ray diffraction (XRD) and transmission electron microscopy (TEM) that revealed a coexistence of exfoliated and intercalated silicate layers dispersed in the PBSA matrix, regardless of the silicate loading. The degree of crystallinity of PBSA decreases with the addition of OMMT platelets. Dynamic mechanical analysis revealed remarkable increase in flexural storage modulus when compared with that of neat PBSA. Tensile property measurements exhibit substantial increase in stiffness with simultaneous increase in elongation at break of nanocomposites as compared to that of neat PBSA. The effect of clay loading on the melt‐state linear viscoelastic behavior of mixed intercalated/exfoliated nanocomposites was also investigated.

Elongation at break of compression molded annealed samples of neat PBSA and various PBSACNs.