Numerical simulation analysis for migration-accumulation of oil and water

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Rheology of carbon black suspensions. III. Sol-gel transition system

Linear viscoelastic properties of carbon black (CB) suspensions with various CB volume fractions () in a rosin-modified phenol resin type varnish (Varnish-1) were investigated at various temperatures (T). The CB/Varnish-1 suspensions exhibited a sol-gel transition on an increase in , and the _gel value at the gelation point decreased with increasing T. This T dependence of _gel, being opposite to the dependence seen for usual gelling systems, can be related to a phenol resin type polymeric component included in the Varnish-1. At low T, this polymeric component appeared to be rather well solvated in the Varnish-1 thereby allowing the gelation due to bare attraction between the CB particles at large . In contrast, at high T, the polymeric component appeared to have been less solvated, as evidence from a moderate failure of the time-temperature superposition of pure Varnish-1 and a decrease of its elasticity (in a shifted frequency scale) with increasing T. This less solvated polymeric component would have been adsorbed on the CB particles, thereby allowing the agglomeration of the particles at small _gel at high T.     

Viscoelastic properties of bis(phenyl)fluorene‐based cardo polymers with different chemical structure

Viscoelastic properties of urethane and ester conjugation cardo polymers that contain fluorene group, 9,9‐bis(4‐(2‐hydroxyethoxy)phenyl)fluorene (BPEF), were investigated. As for the urethane‐type cardo polymers containing BPEF in the main chain, it had a high glass‐transition temperature (T_g), which was observed as the α dispersion on viscoelastic measurement, and its temperature depended on the chemical structure of the spacing unit, such as toluene diisocyanate (TDI), 4,4′‐methylene diphenyl diisocyanate (MDI), methylene dicycloexyl diisocyanate (CMDI), and hexamethylene diisocyanate (HDI). Moreover, the T_g of urethane‐type cardo copolymers with various cardo contents increased with an increase of cardo content. Owing to the increase of T_g of cardo polymers, another molecular motion can be measured at the temperature between the α and β dispersion that was assigned to the molecular motion of urethane conjugation unit around 200 K, and it was referred to as the α_sub dispersion. The peak temperature of the α_sub dispersion was influenced by the chemical structure of the spacing unit, but it did not change for the cardo polymer containing the same spacing unit. Consequently, it was deduced that the α_sub dispersion was originated in the subsegmental molecular motions of the cardo polymers. Ester‐type cardo polymer had higher T_g in comparison with noncardo polymer that consisted of dimethyl groups (BPEP) instead of BPEF as well. The α_sub dispersion was also measured at the temperature between the α and β dispersion, which was assigned to the molecular motion of ester conjugation unit, around 220 K. For ester cardo polymer, the γ dispersion was measured in a low‐temperature region around 140 K, and it was due to a small unit motion in the ester‐type cardo polymers, such as ethoxyl unit, ? C₂H₄O? . Moreover, the intensity of the γ dispersion of noncardo polymer was higher than that of cardo polymer, which means the molecular motion was much restricted by the cardo structure of BPEF. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2259–2268, 2005     

Nano-SIMS analysis of Mg, Sr, Ba and U in natural calcium carbonate.

Concentrations of minor (Mg and Sr) and trace (Ba and U) elements in four natural calcium carbonate samples were first analyzed by inductively coupled plasma mass spectrometry (ICP-MS) after chemical dissolution and calibrated against a standard dolomite. Their homogeneities were checked by in situ laser ablation (LA) ICP-MS with 10-20 spots. The carbonate samples were measured by using a high lateral resolution secondary ion mass spectrometer (Nano-SIMS NS50). A approximately 4 nA O- primary beam was used to sputter a 5-6-microm diameter crater on the sample surface, and secondary positive ions were extracted for mass analysis using an accelerating voltage of 8 kV and a Mattauch-Herzog geometry. A multi-collector system was adjusted to detect 26Mg+, 43Ca+, 88Sr+, 138Ba+, 238U16O+ and 238U16O2+ ions at the same time. A resolving power of 2500-5000 at 10% peak height was attained by an entrance slit set at 40 microm, and each exit slit at 50 microm with adequate flat-topped peaks. The observed 26Mg/43Ca, 88Sr/43Ca, 138Ba/43Ca and 238U16O2/43Ca ratios agreed well with those measured by LA-ICP-MS. Foraminifera shells were analyzed at 5-6 microm scale by Nano-SIMS. There was a large variation of the Mg/Ca ratios, up to +/- 38%, even in a single fragment of the shell, suggesting that although the ratios provide a useful paleoceanographic proxy at bulk scale, they may reflect a more complex pattern at < 10 microm scale.     

Synthesis and properties of poly(amic acid)s and polyimides based on 2,2′,6,6′‐biphenyltetracarboxylic dianhydride

Poly(amic acid)s (PAAs) having the high solution stability and transmittance at 365 nm for photosensitive polyimides have been developed. PAAs with a twisted conformation in the main chains were prepared from 2,2′,6,6′‐biphenyltetracarboxylic dianhydride (2,2′,6,6′‐BPDA) and aromatic diamines. Imidization of PAAs was achieved by chemical treatment using trifluoroacetic anhydride. Among them, the PAA derived from 2,2′,6,6′‐BPDA and 4,4′‐(1,3‐phenylenedioxy)dianiline was converted to the polyimide by thermal treatment. The heating at 300 °C under nitrogen did not complete thermal imidization of PAAs having glass‐transition temperatures (T_g)s higher than 300 °C to the corresponding PIs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6385–6393, 2006     

Characteristics of a protein error in determination of serum protein in the presence of inorganic salt.

There is a possibility that the color development of the dye-binding method based on a protein error of a pH indicator is affected by the coexisting inorganic salt. Thus, the author theoretically and experimentally investigated the effect of the inorganic salt on the protein error. In a theoretical analysis, the anion of an inorganic salt, like the dissociated dye and buffer anions, was assumed to react with the protein, forming a colorless anion-protein complex. The calculated results were compared with those obtained by experiments using three pH indicators and various kinds of inorganic salts. The calculated results obtained are as follows: (1) The color development decreases with increasing the concentration of the inorganic salt and the equilibrium constant of the reaction between the inorganic salt and protein; (2) The rate of the absorbance decrease is larger for a lower concentration of the inorganic salt than for a higher one; (3) The larger is the equilibrium constant, the larger is the absorbance decrease. The absorbance decrease was caused by the anion, and was increased by increasing the anion concentration. The magnitude of the effect of the anion was iodide > bromide > chloride, which was associated with their ionic radius. The difference in the effect of the anion was thought to indicate that the equilibrium constant, in other words, the bonding strength of the anion to protein is iodide > bromide > chloride.     

Investigation of individual micrometer-size Kosa particle with on-site combination of electron microscope and synchrotron X-ray microscope.

The Kosa (yellow sand) aerosol affects the global environment as well as human health because it migrates from the interior of China to other areas, absorbing various atmospheric elements. Investigation into individual Kosa aerosol particles, which are submicroscopic to several tens of micrometers in diameter, is required to resolving the issue. We installed a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectrometer (EDX) on a synchrotron radiation (SR) beam line and introduced the SR beam into the SEM chamber for combinatorial application of SEM-EDX and SR X-ray fluorescence (SR-XRF) spectrometry to individual particles. It should be noted that detailed topographic observation by SEM and sensitive elemental analysis by SR-XRF, both crucial for individual particle measurement but which previously had to be carried out separately, were jointly performed inside the SEM chamber in this setup. Here, we show that SR-XRF results, in conjunction with SEM images, contributed toward resolving individual particle dispositions. Atmospheric sulfur primarily adheres to calcium in the aerosol particles and the particle surface roughens as a consequence of the chemical reaction between the two elements.     

Three‐component negative‐type photosensitive polyimide precursor based on poly(amic acid), a crosslinker,and a photoacid generator

A new negative‐working and alkaline‐developable photosensitive polyimide precursor based on poly(amic acid) (PAA), 4,4′‐methylenebis[2,6‐bis(hydroxymethyl)]phenol (MBHP) as a crosslinker, and a photoacid generator (5‐propylsulfonyloxyimino‐5H‐thiophen‐2‐ylidene)‐2‐(methylphenyl)acetonitrile (PTMA) has been developed. PAA was prepared by ring‐opening polymerization of pyromellitic dianhydride with 4,4′‐oxydianiline. The photosensitive polyimide precursor containing PAA (65 wt %), MBHP (25 wt %), and PTMA (10 wt %) showed a clear negative image featuring 10 μm line and space patterns when it was exposed to 436 nm light at 100 mJ·cm^?2, post‐exposure baked at 130 °C for 3 min, followed by developing with a 2.38 wt % aqueous tetramethylammonium hydroxide solution at 25 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 593–599, 2005     

Moment problem of Hamburger,hierarchies of integrable systems,and the positivity of tau-functions

A moment problem of Hamburger is studied to find a parametric Stieltjes measure from given moments. It is shown that if a deformation, or a dynamics, of moments is governed by a hierarchy of a Kac-van Moerbeke system, then the Stieltjes measure can be constructed explicitly by integrating a hierarchy of Moser's nonlinear dynamical system. The positivity of tau-functions is related to the existence of the Stieltjes measure at a deep level.     

Evaluation of an ODS column modified with zwitterionic/nonionic mixed surfactants and its application to direct injection determination of inorganic anions.

An octadecylsilica (ODS) column modified with zwitterionic/nonionic mixed surfactants was evaluated for the direct injection determination of inorganic anions in biological fluids by ion chromatography. A zwitterionic surfactant (sulfobetaine-type) and a nonionic surfactant (polyoxyethylene-type) were used for a stationary-phase modification. When aqueous electrolyte solutions with concentrations of sub-mM to several mM were used as a mobile phase, the zwitterionic surfactant coated on the ODS surface exhibited unique separation selectivity for ionic species, while the nonionic surfactant coated on the ODS might have formed a hydrophilic network over the ODS surface and restricted matrix proteins from adsorbing on the stationary phase. Consequently, the mixed surfactant-modified column system allowed an efficient ion chromatographic separation of inorganic anions as well as a size-exclusive removal of column-fouling proteins. This separation system was applied to the direct injection determination of UV-absorbing anions in human saliva. The detection limits for nitrite, nitrate, iodide and thiocyanate were 3.1, 2.7, 4.5 and 25 microM, respectively, with UV detection at 210 nm (injection volume; 20 microl), and their relative standard deviations for 5 replicate measurements of saliva samples spiked with 100 microM each of those anions were 1.4, 0.9, 2.2 and 5.5%, respectively.