Solution copolymerization of methyl methacrylate and alkyl methacrylates in a continuous stirred tank reactor(CSTR)

Continuous solution copolymerization of methyl methacrylate with ethyl methacrylate or n-butyl methacrylate was carried out in a continuous stirred tank reactor. Solvent and initiator used were toluene and benzoyl peroxide, respectively. Reaction volume was 1.2 litters, residence time 3 hours and polymerization temperature 80°C. The copolymerization conversions were analyzed by UV spectrophotometry and confirmed by measuring the solid weights of copolymers obtained after evaporating solvent. The copolymerization of methyl methacrylate and alkyl methacrylates followed the second order kinetics. The simulated conversions and copolymerization rates were compared with the experimental results. The average time to reach dynamic steady-state was three and half times of the residence time.     

Glass transition and mechanical properties of PLLA and PDLLA‐PGA copolymer blends

The change of the glass transition temperatures (T_g) in the blend of poly(L ‐lactic acid) (PLLA) and the copolymers of poly(D,L ‐lactic acid) and poly(glycolic acid) (PDLLA‐PGA) with different D,L ‐lactic acid and glycolic acid composition ratio (50 : 50, 65 : 35, and 75 : 25) was studied by DSC. Dynamic mechanical measurement and tensile testing were performed at various temperatures around T_g of the blend. In the blend of PLLA and PDLLA‐PGA50 (composition ratio of PDLLA and PGA 50 : 50), T_g decreased from that of PLLA (about 58°C) to that of PDLLA‐PGA50 (about 30°C). A single step decrease was observed in the DSC curve around T_g between the weight fraction of PLLA (W(PLLA)) 1.0 and 0.7 (about 52°C) but two‐step changes in the curve are observed between W(PLLA) = 0.6 and 0.3. The T_g change between that of PLLA and that of PDLLA‐PGA and the appearance of two T_gs suggest the existence of PLLA rich amorphous region and PDLLA‐PGA copolymer rich amorphous region in the blend. A single step decrease of E′ occurs at around T_g of the pure PLLA but the two‐step decrease was observed at W(PLLA) = 0.6 and 0.4, supporting the existence of the PLLA rich region and PDLLA‐PGA rich region. Tensile testing for various blends at elevated temperature showed that the extension without yielding occurred above T_g of the blend. Partial miscibility is suggested for PLLA and PDLLA‐PGA copolymer blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2164–2173, 2004     

Damage zone development in PVC under a multiaxial tensile stress state

The irreversible deformation mechanisms of poly(vinyl chloride) with a semicircular notch under slow tensile loading have been studied as a function of sheet thickness. Initially, core yielding was observed in the optical microscope as two families of slip lines growing from the notch surface in the centre of the specimen. The size and shape of the core yielding zone could be described by plasticity analysis. A stress-whitened zone subsequently initiated near the tip of the slip line zone. The stress whitening was caused by 1 m voids that were visible in the scanning electron microscope. The mean stress for stress whitening was calculated to be 43.0±1.5 MPa by a plastic stress analysis of a pressure-dependent yield material. By assuming a constant mean stress along the boundary of the stress-whitened zone, the one-dimensional shift of the elastic stress distribution was obtained. At higher stresses, hinge shear and intersecting shear were observed for thick and thin sheet, respectively.     

Constructing confidence intervals of extreme rainfall quantiles using Bayesian,bootstrap, and profile likelihood approaches

Hydrological risk is highly dependent on the occurrence of extreme rainfalls.This fact has led to a wide range of studies on the estimation and uncertainty analysis of the extremes.In most cases,confidence intervals(CIs)are constructed to represent the uncertainty of the estimates.Since the accuracy of CIs depends on the asymptotic normality of the data and is questionable with limited observations in practice,a Bayesian highest posterior density(HPD)interval,bootstrap percentile interval,and profile likelihood(PL)interval have been introduced to analyze the uncertainty that does not depend on the normality assumption.However,comparison studies to investigate their performances in terms of the accuracy and uncertainty of the estimates are scarce.In addition,the strengths,weakness,and conditions necessary for performing each method also must be investigated.Accordingly,in this study,test experiments with simulations from varying parent distributions and different sample sizes were conducted.Then,applications to the annual maximum rainfall(AMR)time series data in South Korea were performed.Five districts with 38-year(1973–2010)AMR observations were fitted by the three aforementioned methods in the application.From both the experimental and application results,the Bayesian method is found to provide the lowest uncertainty of the design level while the PL estimates generally have the highest accuracy but also the largest uncertainty.The bootstrap estimates are usually inferior to the other two methods,but can perform adequately when the distribution model is not heavy-tailed and the sample size is large.The distribution tail behavior and the sample size are clearly found to affect the estimation accuracy and uncertainty.This study presents a comparative result,which can help researchers make decisions in the context of assessing extreme rainfall uncertainties.     

Spatial distribution of silica fillers in phase-separated rubber blends investigated by three-dimensional elemental mapping

The distribution of nano-sized silica in binary rubber blends is characterized by scanning transmission electron microscopy (STEM) tomography combined with energy dispersive X-ray spectrometry (EDX). 3D distribution of silica is visualized by STEM-EDX tomography with the tilt-series of silicon elemental maps, while the phase-separated morphologies of polyisoprene rubber (IR) and styrene-butadiene rubber (SBR) are visualized by STEM-tomography in high-angle-annular-dark field (HAADF) mode. The combination of STEM-EDX and STEM-HAADF tomography enables us to determine the distribution of silica between the two rubber phases quantitatively even with high contents of silica up to 70 phr (weight parts per hundred rubber). It is found that silica is preferentially distributed in the SBR phase, but it is also distributed in the IR phase when the IR fraction in the total rubber components is higher than 40 wt%. The preferential distribution of silica in the SBR phase improves the dispersion of the IR domains. This is the first use of this technique for a multicomponent polymer system, showing the advantage to characterize the complicated multicomponent polymer composite morphologies.     

Preparation and properties of TiC-Ni cermets using Ni-plated TiC

TiC powders were coated with Ni by a chemical plating technique and the pressed compacts sintered at 1623K. The density of the sintered bodies was 98–99%. Compared with mechanically-mixed powder, Ni-plated TiC powders gave a more uniform microstructure in which TiC particles were well dispersed in the Ni matrix. The cermets exhibited ductile fracture for TiC-70 vol.% Ni and brittle fracture for TiC-30 vol.% Ni. The flexural strength was improved by the homogeneous dispersion of TiC. The thermal expansion coefficient increased with a decrease in Ni content, following a nearly linear law of mixtures on the basis of volume fractions of pure TiC and Ni.     

Properties of Induction Plasma Sprayed Iron Based Nanostructured Alloy Coatings for Metal Based Thermal Barrier Coatings

Metal-based thermal barrier coatings (MBTBCs) have been produced using high frequency induction plasma spraying (IPS) of iron-based nanostructured alloy powders. The study of MBTBCs has been initiated to challenge issues associated with current TBC materials such as difficult prediction of their “in-service” lifetime. Reliability of TBCs is an important aspect besides the economical consideration. Therefore, the study of MBTBCs, which should posses higher toughness than the current TBC materials, has been initiated to challenge the mechanical problems of ceramic-based TBCs (CBTBCs) to create a new generation of TBCs. The thermal diffusivity (TD) (α) properties of the MBTBCs were measured using a laser flash method, and density (ρ) and specific heat (C _p) of the MBTBCs were also measured for their thermal conductivity (k) calculation (k = αρ C _p).     

Superplasticity of fine-grained 7475 Al alloy and a proposed new deformation mechanism

A study has been made to investigate the superplastic deformation mechanisms of 7475 Al alloy in relation to the variation of grain size ranging between 5.5 μm and 13 μm. The strain-rate sensitivity (m) was increased with decreasing grain size in the superplastic deformation regime. Microstructural investigation after tension tests revealed that the dispersoid free zones were produced mostly at the grain boundaries normal to the tensile direction. A new model for describing the deformation behavior of the 7475 Al alloy has been proposed based on the assumption that the grain boundary sliding was accommodated by both diffusional flow and slip. This new model well predicts many aspects of experimental results.     

Separation of oxide inclusions from liquid metal in an applied electrostatic field

It is known that oxide inclusions in liquid metal carry mostly positive charges on their surfaces. In an electrostatic field, therefore, such charged particles suspended in a liquid metal experience forces and accumulate in the region of the negatively charged surface, resulting in the separation of oxide inclusions from the liquid metal. In this study, this principle was experimentally demonstrated for the case of a capacitor cell by the imposition of a d.c. potential on electrodes. The capacitor cell consisted of a dielectric container of Pyrex tube, a high voltage d.c. source, and two electrodes, which were symmetrically attached onto the outer surface of the Pyrex. tube. Experiments were carried out for suspensions of liquid tin/metal oxides, such as SnO₂, WO₃, and PbO under an applied potential of up to 12 kV. All experimental results were in good agreement with the theoretical prediction and showed that the degree of separation was significantly increased with the applied potential.     

Magnesium interlayered diamond coating on silicon

Diamond thin films have been deposited using hot filament chemical vapour deposition technique on manually scratched p-Si(1 0 0) substrate, with and without magnesium interlayer. In spite of magnesium melting point being lower (T_m = 649 °C) than the growth temperature of the substrate (T_s  750 °C) used in these experiments, it was found that high quality diamond films could be grown on Mg covered substrate. A liquid substrate is probably generated during the diamond film growth. Raman spectroscopy analysis exhibited only the triply degenerate, zone centre optical phonon peak at 1333 cm⁻¹ indicating that nearly stress free crystallites were present. Broadening of the Raman peak (11.76 cm⁻¹) indicates that some small crystallites also are present. Scanning electron and atomic force microscopy accompanied by X-ray diffraction analysis where used to compare the details of diamond film growth directly on scratched Si(1 0 0) and Mg interlayered scratched Si(1 0 0) substrates.