Equilibrium and crystallographic measurements of the binary tetrahydrofuran and helium clathrate hydrates

Clathrate compounds are crystalline materials formed by a physical interaction between host and relatively light guest molecules. Various types of nano-sized cages surrounded by host frameworks exist in the highly unique crystalline structures and free guest molecules are entrapped in an open host-guest network. Recently, we reported two peculiar phenomena, swapping and tuning, naturally occurring in the hydrate cages. Helium, one of the smallest light guest molecules, must be the challengeable material in the sense of physics and moreover possesses versatile applications in the field of superconductivity technology and thermonuclear industry. In this regard, we attempted for the first time to synthesize helium hydrates at moderate temperature and pressure conditions. According to inclusion phenomena, helium itself normally cannot form clathrate hydrates due to being too small molecularly without the help of hydrate former molecules (sI, sII, and sH formers). In this study, the hydrate equilibria of the binary clathrate hydrate containing tetrahydrofuran, helium, and water were determined at 2, 3, 5.56 THF mol%. Direct volumetric measurements were also carried out to confirm the exact amount of helium captured in the hydrate cages. Finally, the crystalline structure of the formed mixed hydrates was identified by powder X-ray diffraction, resulting in structure II.     

Design of thermophoretic probe for precise particle sampling

We proposed a design methodology for improved thermophoretic probes that can sample particles with high spatial resolution. A bending vibration analysis for the instantaneous motion of a probe has been done together with direct observation of the probe motion and flow disturbance for systematic study of the effect of different designs on particle sampling. Direct observation of the motion of thermophoretic sampling probes revealed that the probe with a low stiffness would result in inaccurate particle sampling. Based on these, the thermophoretic sampling probe was modified to minimize probe vibration and flow disturbance and this modified design was confirmed to sample particles with higher spatial resolution than the original one by examining transmission electron microscope (TEM) images of particles collected in a flame.     

A positive‐working photosensitive polyimide based on thermal cross‐linking and acidolytic cleavage

A novel positive‐working photosensitive polyimide (PSPI) based on a poly(hydroxyimide) (PHI), a crosslinking agent having vinyl ether groups, and a photoacid generator (PAG) was prepared. The PHI as a base resin of the three‐component PSPI was synthesized from 4,4′‐oxydiphthalic anhydride and 2,2′‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane through ring‐opening polymerization and subsequent thermal cyclization. 2,2′‐bis(4‐(2‐(vinyloxy)ethoxy)phenyl)propane (BPA‐DEVE) was used as a vinylether compound and diphenyliodonium 5‐hydroxynaphthalene‐1‐sulfonate was used as a PAG. The phenolic hydroxyl groups of the PHI and the vinyl ether groups of BPA‐DEVE are thermally crosslinked with acetal structures during prebake step, and the crosslinked PHI becomes completely insoluble in an aqueous basic solution. Upon exposure to UV light (365 nm) and subsequent postexposure bake (PEB), a strong acid generated from the PAG cleaves the crosslinked structures, and the exposed area is effectively solubilized in the alkaline developer. The dissolution behavior of the PSPI containing each 11.5 wt % of BPA‐DEVE and of the PAG was studied after UV exposure (365 nm) and PEB. It was found that the difference in dissolution rates between exposed and unexposed areas was enough to get high resolution. A fine positive pattern with a resolution of 5 μm in a 3.7‐μm‐thick film was obtained from the three‐component PSPI. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of aligned polyetherimide fiber by electrospinning

Fifteen to 20 wt % polyetherimide (PEI) solutions with 1-methyl-2-pyrrolidinone (NMP) were prepared. The electrical conductivity and surface tension of the solutions were determined. The fiber spinning technique of electrospinning was optimized in order to prepare unidirectionally aligned, structurally oriented nanofiber tows. The morphology of the PEI fibers was investigated using field emission scanning electron microscopy (FESEM). The well-aligned fibers with diameters between 0.58 and 0.90 μm (FESEM) were collected by electrospinning 20 wt % PEI solutions with NMP in the range of 8–10 kV onto a target rotating with a surface velocity 9.8 m/s. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structure and processability of iodinated poly(vinyl alcohol). IV. Drawability of the films iodinated at solution before casting

The drawability of iodinated at solution before casting (IBC) polyvinyl alcohol films prepared by casting aqueous solutions of 10 wt % PVA containing 15.2, 39.8, 83.2, 117.0, and 140.1% was examined with a tensile tester at 20–60°C. The tensile behavior of IBC films showed that the yield and breaking loads were much lower, and the breaking elongation was even higher than those of the unoriented iodinated after casting (IAC) films as well as the untreated PVA films. The maximum draw ratios of the films with the weight gain of 15.2, 39.8, 83.2, 117, and 140.1% were 4.5, 5.5, 8.5, 8.0, and 7.5, respectively, which were achieved at 20°C in all. The crystallinity of all films increased by the maximum draw, regardless of crystallinity before drawing. The crystalline structure was recovered to the original PVA crystalline lattice by deiodination. Amorphous orientation and initial moduli increased with the maximum draw ratio, while the orientation of crystals was constant. The orientation and moduli increased up to the weight gain of 83.2%, whose highest draw ratio and initial modulus were 8.5 and of 7.1 GPa, respectively, and then decreased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effects of tube rupture modeling and the parameters on the analysis of multiple steam generator tube rupture event progression in APR1400

A multiple steam generator tube rupture (MSGTR) event in APR1400 has been investigated using the best estimate thermal hydraulic system code, MARS1.4. The effects of the parameters such as the number of ruptured tubes, rupture location, affected steam generator on the analysis of the MSGTR event in APR1400 are examined. In particular, tube rupture modeling methods, single tube modeling (STM) and double tube modeling (DTM), are compared. The APR1400 is found to have the capability of allowing more than 30 min to operators for the MSGTR event of five tubes. The effects of rupture location on the MSSV lift time is not significant in the case of STM, but the MSSV lift time for tube-top rupture is found to be 25.3% larger than that for rupture at the hot-leg side tube sheet in the case of DTM. The MSSV lift time for the cases that both steam generators are affected (4C5x, 4C23x) are found to be larger than that of the single steam generator cases (4A5x, 4B5x) due to a bifurcation of the primary leak flow. The discharge coefficient of Cd is found to affect the MSSV lift time only for a smaller value of 0.5. It is found that the most dominant parameter governing the MSSV lift time is the leak flow rate. Whether any modeling method is used, it gives the similar MSSV lift time if the leak flow rate is close, except in the case where both steam generators are affected. Therefore, the system performance and the MSSV lift time of the APR1400 are strongly dependent on the break flow model used in the best estimate system code.     

Epitaxial growth of GaN on (0001) Al<Subscript>2</Subscript>O<Subscript>3</Subscript> via solution-cast seed layer formation process using Ga(mDTC)<Subscript>3</Subscript>

This paper reports an alternative method for the growth of GaN epitaxial layer on (0001) Al₂O₃ substrate by hot-wall vapor phase epitaxy technique. Tris (N,N-dimethyldithiocarbamato)-gallium (III), Ga(mDTC)₃ was introduced as a precursor material for the seed layer formation in the growth of GaN. Optimal growth conditions with seed layers formed by the Ga(mDTC)₃ concentration of 0.047 mol/L were identified: Growth temperature was found to be 850 °C, and optimal distance between the reactant outlet and substrate was determined to be 12.5 cm. Characterization results showed that this growth method produce high-crystallinity GaN epitaxial layers at a relatively lower growth temperature compared to the existing growth techniques and simplify the growth process.     

Synthesis and comparative molecular field analysis (CoMFA) of antitumor 3-arylisoquinoline derivatives

In this study a series of 3-arylisoquinoline derivatives were synthesized and cytotoxicity against human melanoma tumor cell evaluated, and a three dimensional quantitative structure-activity relationship was investigated using the comparative molecular field analysis (CoMFA). The results suggested that the electrostatic, steric and hydrophobic factors of 3-arylisoquinolines were strongly correlated with the antitumor activity. Considerable predictive ability (cross-validated r2 as high as 0.721) was obtained through CoMFA.