Fabrication and characterization of poly(methyl methacrylate)/CaCu3Ti4O12 composites

Composites comprising Poly(Methyl Methacrylate) (PMMA) and CaCu₃Ti₄O₁₂ (CCTO) via melt mixing followed by hot pressing were fabricated. These were characterized using X‐ray diffraction, thermo gravimetric, scanning electron microscopy, and Impedance analyzer for their structural, morphology, and dielectric properties. Composites were found to have better thermal stability than that of pure PMMA. The composite, with 38 Vol % of CCTO (in PMMA), exhibited remarkably low dielectric loss at high frequencies and the low frequency relaxation is attributed to the space charge polarization/MWS effect. Theoretical models were employed to rationalize the dielectric behavior of these composites. At higher temperatures, the relaxation peak shifts to higher frequencies, due to the merging of both β and α relaxations into a single dielectric dispersion peak. The AC conductivity in the high frequency region was attributed to the electronic polarization. POLYM. ENG. SCI., 54:551–558, 2014. © 2013 Society of Plastics Engineers     

High-temperature X-ray structural,thermal and dielectric characteristics of ferroelectric Bi2VO5.5

The X-ray powder diffraction, dielectric and thermal studies of bismuth vanadate (Bi₂VO_5.5) ceramic have been carried out as a function of temperature (300–900 K). The hightemperature X-ray studies, supported by differential scanning calorimetry, clearly demonstrate that Bi₂VO_5.5 undergoes two major phase transitions at 730 and 835 K. It was found that the one at 730 K is associated with both the ferroelectric and the crystallographic transition, while at 835 K, Bi₂VO_5.5 undergoes only the crystallographic transition. Anomalies in both the dielectric constant and specific heat curves have been observed at 730 and 835 K. The total heat, Q, and entropy, S, associated with the transition at 730 K were found to be higher than those at 835 K.     

Dielectric behaviour of dysprosium oxide films

The dielectric properties of vacuum-deposited dysprosium oxide films have been studied in the audio-frequency range (10²–10⁴ Hz) at various temperatures (78–373 K). The dielectric constant (6.7) was independent of film thickness for thicker films (d > 1000 Å). The capacitance was dependent both on temperature and frequency, but became constant for all frequencies at low temperature. Tan δ showed a frequency minimum and its variation with frequency and temperature was in agreement with the model proposed earlier by Goswami and Goswami. The breakdown field (≌10⁶ V cm^-1) followed the Forlani-Minnaja relation. The activation energy and the refractive index of these films were also measured.     

Properties and kinetics of thermally crystallized oriented poly(ethylene terephthalate) (PET). I: Kinetics of crystallization

The crystallization kinetics of previously oriented poly(ethylene terephthalate) (PET) sheets have been studied under unconstrained conditions, as functions of stretch ratio, mode of extension, and crystallization temperature. Isothermal and dynamic crystallization conditions have been utilized for the determination of half-times of crystallization and activation energies, respectively. Results indicate that rates of crystallization of pre-oriented PET increase substantially, with increasing stretch ratios. Half-times of crystallization, at a given isothermal temperature, were found to decrease from a few minutes to fractions of seconds. Similarly, the activation energies of thermal crystallization have been shown to decrease from 75 kcal/mol for unoriented PET, to less than 20 kcal/mol for highly oriented material. These changes are most apparent among samples with low to moderate levels of orientation. Highly oriented samples have proven to be less sensitive, yielding similar extents of thermal crystallization, regardless of specific initial extension ratios. These samples have also shown less sensitivity to temperature of crystallization, exhibiting only slightly higher levels of crystallinity as a result of exposure to increasing temperatures in the range from 100°C to 120°C.     

Spray Drying of Metal Alkoxide Sol for Strontium Titanate Ceramics

Conditions for obtaining a stable sol in an isopropyl alcohol–water medium containing titanium isopropoxide and strontium nitrate, and acetic acid as a modifier, have been described. Spray drying of the sol results in submicrometer spherical agglomerates which on further thermal decomposition yield submicrometer particles of strontium titanate at temperatures as low as 500°C. The thermal decomposition characteristics of the spray-dried precursor and the development of strontium titanate phase have been discussed. Calcined precursor powder possesses a specific surface area of 12m²/g, a comp action density of 57%, and a sintered density of > 98%. The optimum sintering temperature of such a powder was 1450°C, which resulted in a sintered grain size around 1.5 μm. Further, such a sintered sample had a dielectric constant of 260 and a loss factor of 0.008 at 1 kHz. This method appears to be very convenient with respect to handling of stable sols and thus avoids the usual difficulties regarding extended gelation as well as inhomogeneous precipitation.     

Processing of mesocarbon microbeads to high-performance materials: Part III. High-temperature sintering and graphitization

The sintering and graphitization behavior of mesocarbon microbeads (MCMB) at high temperatures (1900-2800 K) is investigated. It is shown that while the low temperature sintering performance of MCMB is unique, at high temperature it appears to be similar to that of conventional materials. In contrast, the obtained activation energy for MCMB high-temperature graphitization is ∼100 kcal/mol, which is smaller than that (∼240 kcal/mol) for typical carbon systems. It is concluded that the combination of such unique properties as excellent compressibility, low temperature sinterability, and rapid graphitization makes MCMB an attractive precursor for manufacturing carbon-based materials.     

Processing of mesocarbon microbeads to high-performance materials: Part II. Reaction bonding by in situ silicon carbide and nitride formation

The processing of carbon-ceramic composites by utilizing the unique sintering ability of mesocarbon microbeads (MCMB) is reported. The ceramic constituents (silicon nitride and silicon carbide) are formed in situ by reactions between MCMB and silicon in different atmospheres. In comparison with direct addition of ceramic (SiC, Si₃N₄) phases, in situ formation shows several appealing features. By inducing the reaction of silicon with MCMB, the sintering ability of the composite is enhanced via reaction bonding mechanisms. Similarly, it is demonstrated that composite porosity is limited owing to silicon reaction with nitrogen. The reactive formation of nanoscale ceramic reinforcements via decomposition of the silicon-containing polymer (e.g. poly-carbomethyl-silane) is also reported. This approach results in formation of uniform nanosized (>100 nm) SiC layers strongly bonded to the surface of the carbon particles. The presented results contribute to the development of carbon-ceramic materials with high-operational properties.     

Novel perovskite-based catalysts for autothermal JP-8 fuel reforming

Autothermal reforming is an attractive method for on-site production of hydrogen for use in proton exchange membrane (PEM) fuel cells. The use of liquid hydrocarbons as feedstock, however, remains a challenge as these fuels cause severe coking of the currently available catalysts. In this work, cerium- and nickel-substituted LaFeO₃ perovskites were investigated as potential low cost coking resistant catalysts for autothermal reforming of a JP-8 fuel surrogate. The high surface area complex oxides were prepared using aqueous (solution) combustion synthesis at fuel-rich conditions and characterized by BET and XRD techniques. The catalysts exhibited excellent stability during autothermal reforming at and 1 atm, with near-equilibrium hydrogen yield even at high GHSV values (). The addition of cerium significantly improved coking resistance, attributed to improved oxygen ion conductivity, resulting in carbon oxidation on the catalyst surface.     

Methacrylate/acrylate terminated derivatives of diglycidyl hexahydrophthalate: Synthesis,structural, and thermal characterization

Mono‐ or di(meth)acrylate‐terminated derivatives of diglycidyl hexahydrophthalate (ER) were prepared by reacting 1 : 1 or 1 : 2M ratio of ER and methacrylic acid or acrylic acid. These vinyl ester (VE) resins were characterized by determining epoxy equivalent weight, acid number, and molecular weight by gel permeation chromatography. Structural characterization was done by FTIR and ¹H NMR spectroscopy. In the ¹H NMR spectra of acrylate‐terminated VE resins, three proton resonance signals were observed in the region 5.8–6.4 ppm due to vinyl group while in methacrylate‐terminated VE resins only two proton resonance signals due to vinylidene protons were observed at 5.6–6.1 ppm. The Brookfield viscosity (room temperature (25 ± 2)°C) of these resins diluted with varying amounts of MMA was determined at 20 rpm. Curing behavior was monitored by determination of gel time and differential scanning calorimetry. An exothermic transition was observed in the DSC scans in the temperature range of (81–150)°C. Isothermal curing of MMA‐diluted VE resins containing AIBN as an initiator was done at 60°C for 2 h in N₂ atmosphere, and then heating for another 2 h in static air atmosphere. Thermal stability of isothermally cured resins in N₂ atmosphere was evaluated by thermogravimetric analysis. All cured resins decomposed above 310°C in single step. Thermal stability of the cured resins having acrylate end caps was marginally higher than the resins having methacrylate end groups. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006