Simulation of mechanical properties of epoxy-based chemically amplified resist by coarse-grained molecular dynamics

The mechanical properties of an epoxy-based chemically amplified resists with various cross-linking ratios were simulated using a newly developed coarse-grained molecular dynamics simulation that employs a bead–spring model. Models with the different cross-linking ratios were created in the molecular dynamics calculation step and uniaxial elongation simulations were performed. The results reveal that the simulated elastic modulus of the resist modeled by the Kremer–Grest model with an extended angle bending potential depends on the cross-linking ratio, its dependency exhibits good agreement with that determined by nanoindentation tests.     

Novel organic-inorganic hybrids prepared from polybenzoxazine and titania using sol-gel process

Novel organic-inorganic hybrids were prepared from polybenzoxazine and titania using sol-gel process by blending titanium isopropoxide as a precursor for titania with a typical benzoxazine monomer, bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane (Ba). Deep red brown and transparent hybrid materials were obtained after thermal cure at 200 °C. DSC indicated that, in the presence of titania precursor, the onset and maximum temperature of the exothermic peak due to the ring opening polymerization of Ba decreased by ca. 30 and 70 °C, respectively. Viscoelastic analyses revealed that the glass transition temperatures (T_g) of the polybenzoxazine-titania hybrids shifted to higher temperature than the neat polybenzoxazine. The storage moduli below T_g for the hybrids increased with the increase of the titania content, and the storage moduli were maintained constant up to higher temperature than the neat resin. TGA results confirmed that the thermal stability and char yield of polybenzoxazine increased by hybridization with titania.     

Morphology and mechanical properties of polyolefinic thermoplastic elastomer I. Characterization of deformation process

The structural origin of rubber elasticity in the polyolefinic thermoplastic elastomers composed of isotactic polypropylene (iPP) matrix and ethylene-propylene-diene rubber (EPDM) domains was investigated using scanning and transmission electron microscopes under uniaxial deformation and the computational analysis by a three dimensional finite element method. The rubber domains were dominantly deformed and elongated by accompanying localized yielding in iPP region between neighboring EPDM domains perpendicular to the stretching direction. The iPP region between adjacent EPDM domains in the stretching direction remained undeformed, suggesting that the undeformed iPP region plays the role in connecting rubber domains.     

Synthesis of porphyrin-end-functionalized poly(p-phenylene) as a leaf-green-colored soluble semiconducting polymer: Control of π–π interactions for visible-light absorption

The synthesis of tetraphenylporphyrin (H₂TPP)-end-functionalized poly(p-phenylene) (H₂TPP-PPP) as a leaf-green-colored soluble semiconducting polymer with a well-controlled and defined polymer chain structure was achieved for the first time. Chloromethyl-end-functionalized poly(1,3-cyclohexadiene) (CM-PCHD) was prepared by the living anionic polymerization of 1,3-cyclohexadiene and the post-polymerization reaction of poly(1,3-cyclohexadienyl)lithium and chloro(chloromethyl)dimethylsilane. H₂TPP-end-functionalized PCHD (H₂TPP-PCHD) was then prepared by the addition of 5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin to CM-PCHD. The dehydrogenation of H₂TPP-PCHD with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was performed under ultrasonic irradiation, and H₂TPP-PPP was obtained as a target polymer in almost quantitative yield. The –Si(CH₃)₂–CH₂–O– bond in H₂TPP-PPP effectively inhibited the coordination of the H₂TPP end-group onto the PPP moiety, and the aggregation of H₂TPP-PPP with the accumulation of the H₂TPP end-group was formed. H₂TPP-PPP exhibited a leaf-green color and had a very broad absorption band overlapping the visible-light region, similar to chlorophyll a.     

Agglomeration Characteristics of Aluminum Particles in AP/AN Composite Propellants

Most solid rockets are powered by ammonium perchlorate (AP) composite propellant including aluminum particles. As aluminized composite propellant burns, aluminum particles agglomerate as large as above 100 μm diameter on the burning surface, which in turn affects propellant combustion characteristics. The development of composite propellants has a long history. Many studies of aluminum particle combustion have been conducted. Optical observations indicate that aluminum particles form agglomerates on the burning surface of aluminized composite propellant. They ignite on leaving the burning surface. Because the temperature gradient in the reaction zone near a burning surface influences the burning rate of a composite propellant, details of aluminum particle agglomeration, agglomerate ignition, and their effects on the temperature gradient must be investigated. In our previous studies, we measured the aluminum particle agglomerate diameter by optical observation and collecting particles. We observed particles on the burning surface, the reaction zone, and the luminous flame zone of an ammonium perchlorate (AP)/ammonium nitrate (AN) composite propellant. We confirmed that agglomeration occurred in the reaction zone and that the agglomerate diameter decreased with increasing the burning rate. In this study, observing aluminum particles in the reaction zone near the burning surface, we investigated the relation between the agglomerates and the burning rate. A decreased burning rate and increased added amount of aluminum particles caused a larger agglomerate diameter. Defining the extent of the distributed aluminum particles before they agglomerate as an agglomerate range, we found that the agglomerate range was constant irrespective of the added amount of aluminum particles. Furthermore, the agglomerate diameter was ascertained from the density of the added amount of aluminum particles in the agglomerate range. We concluded from the heat balance around the burning surface that the product of the agglomerate range and the burning rate was nearly constant irrespective of the added amount of aluminum particles. Moreover, the reduced burning rate increased the agglomerate range.     

Study of prevention of solidification cracking in Al‐Mg‐Si alloy laser welds. CO2 laser welding of Al‐Mg‐Si alloys (1st report)

The choice of weld bead size in the case of welded cruciform joints can be problematic, especially when the sheets forming the joint are of differing thickness. Technological standards generally recommend a weld bead thickness less than the minimum thickness of the sheets to be joined, whereas structural standards do not envisage any dependency between joint static and fatigue strength and weld bead dimensions, unless these are so reduced as to lead to failure starting and propagating in the weld bead itself rather than the base metal plates. The scope of this study is the theoretical and experimental analysis of the change in fatigue strength with varying weld bead thickness and minimum welded plate thickness.     

Effect of satellite bubbles on dynamics of gas absorption from a CO2 bubble into a downward-flowing liquid

The dynamic process of gas absorption from a CO₂ bubble into a liquid is examined in the presence of satellite bubbles. The bubble under consideration is held stationary, except its jittering, by the liquid flowing downward. The mass transfer rate is determined by monitoring the rate of reduction in the equivalent bubble diameter during the initial absorption process. It is found that the interaction with the satellite bubbles generally hampers the dissolution of the primary bubble. The extent of reduction in the dissolution rate increases with the net contacting time during the interaction. When the secondary bubbles interact with the primary bubble mainly outside of its wake, however, the dissolution tends to be enhanced due to induced turbulence in the surrounding liquid flow. A simple theoretical model is developed to simulate the observed results as well as the basic features prevailing in a recently proposed scheme, called the GLAD system, for shallow injection of CO₂ gas into seawater.     

Development of a catalytic combustor for a heavy-duty utility gas turbine

Catalytic combustion is an attractive technology for gas turbine applications where ultra-low emission levels are required. Recent tests of a catalytic reactor in a full scale combustor have demonstrated emissions of 3.3 ppm NO_x, 2.0 ppm CO, and 0.0 ppm UHC. The catalyst system is designed to only convert about half of the natural gas fuel within the catalyst itself, thus limiting the catalyst temperature to a level that is viable for long-term use. The remainder of the combustion occurs downstream from the catalyst to generate the required inlet temperature to the turbine.

Catalyst development is typically done using subscale prototypes in a reactor system designed to simulate the conditions of the full scale application. The validity of such an approach is best determined experimentally by comparing catalyst performance at the two size scales under equivalent reaction conditions. Such a comparison has recently been achieved for catalysts differing in volume by two orders of magnitude. The performance of the full scale catalyst was similar to that of the subscale unit in both emission levels and internal temperatures. This comparison lends credibility to the use of subscale reactors in developing catalytic combustors for gas turbines.     

Structural Change of Maize Starch Granules by Ball-mill Treatment

Effect of ball-mill treatment on physical properties and molecular change of maize starch granule was investigated. Ball-mill treatment was done by rotary type mill, and species of maize starch are normal, waxy and high amylose (amylo). Running time of the treatment is 0–320 h. Starch granules loss smoothness on surface and became rough, even though their changing speed was different among the three species. But, they retained whole figure and size after 320 h treatment in the all cases. Amylase susceptivity and water absorption activity were measured. Structural change of starch components was compared among the three species with X-ray diffraction, DSC and GPC. High Performance An-ion Exchange Chromatography (HPAEC) pattern of debranched sample treated with ball-mill for 320 h showed that formation of very short chain in amylopectin is little. ¹³C solid-NMR spectra suggest that disruption of molecules of amylopectin and amylose with ball-mill might occur at their glycosidic linkage. However, very slight radical was observed by Electron Spin Resonance spectroscopy (ESR) in the case of 320 h sample.     

A predictive model and mechanisms associated with hydrogen production via hydrothermal reactions of sulfide

Hydrogen generation and the concurrent formation of sulfur products from hydrothermal reactions of aqueous sulfide solutions at pH values between 9 and 13 and temperatures between 280 and 330 °C were studied. A hydrogen production model was developed by kinetic and statistical analysis of sulfide consumption rates and the ratio of hydrogen produced to sulfide consumed. Results showed that the amount of hydrogen generated in a given reaction may be predicted by a series of equations incorporating starting conditions such as the initial sulfide concentration, pH and temperature. The data from this study suggested that the overall hydrogen generation reaction mechanism consists of one or more elementary reactions which result in the formation of various sulfur products, such as polysulfides and sulfur oxyanions, depending on the reaction conditions. The possible specific sulfur compounds included pentasulfide (S₅²⁻), thiosulfate (S₂O₃²⁻), trithionate (S₃O₆²⁻) and sulfate (SO₄²⁻). The production rate constants of these products increased with temperature, but were independent of pH. Additionally, it was indicated that increasing the reaction temperature and/or pH resulted in the formation of sulfur products with higher oxidation numbers. This work suggests that the optimal mechanism for hydrogen generation via the sulfur redox cycle, taking into account the requirement for sulfide regeneration, is that which forms trithionate as the sole sulfur product.