Dechlorination behaviour of flexible poly(vinyl chloride) in NaOH/EG solution

Flexible poly(vinyl chloride) (PVC) was found to be dechlorinated in NaOH/ethylene glycol (EG) solution at moderate temperature and at atmospheric pressure. The degree of dechlorination increased over time with all particle sizes and with decreasing particle size. Decreased particle size resulted in an increased effective surface area, increasing the contact between the material and OH⁻ in the NaOH/EG solution, which contributed to the high degree of dechlorination. The dechlorination of flexible PVC in NaOH/EG solution was expressed as a first-order reaction and proceeded under chemical reaction control. Diisononyl-phthalate (DINP) in the flexible PVC powder decomposed readily into phthalic acid and isononyl alcohol in a short time. For the dechlorination of the flexible PVC, the substitution (S_N2) of chloride by the hydroxyl group was considered to be preferential to the elimination (E2) of hydrogen chloride.     

Solvation structure of Li+ in concentrated LiPF6-propylene carbonate solutions

Time-of-flight neutron diffraction measurements were carried out for 6Li/7Li isotopically substituted 10 mol % LiPF6-propylene carbonate-d6 (PC-d6) solutions, in order to obtain structural information on the first solvation shell of Li+. Structural parameters concerning the nearest neighbor Li+...PC and Li+...PF6- interactions were determined through least-squares fitting analysis of the observed difference function, DeltaLi(Q). It has been revealed that the first solvation shell of Li+ consists in average of 4.5(1) PC molecules with an intermolecular Li+...O(PC) distance of 2.04(1) A. The angle Li+...O=C bond angle has been determined to be 138(2) degrees.     

Nuclear moments of neutron-rich aluminum isotopes

Ground-state magnetic-dipole moments (μ) of ^30-32Al and electric quadrupole moments (Q) of ^31,32Al have been measured with the β-NMR method using spin-polarized radioactive-isotope beams produced in projectile-fragmentation reactions. Beams of ^30-32Al were obtained by using RIKEN projectile-fragment separator RIPS after the fragmentation of ⁴⁰Ar projectiles at an energy of E = 95A MeV on a ⁹³Nb target. The obtained μ_exp[^30-32Al] and values agree well with shell-model calculations within the sd shell using the USD interaction. Also, Q_exp[³¹Al] was found to be small. Thus, we can conclude that these aluminum isotopes are located outside the island of inversion.     

Mobile effect of hydrogen on intergranular decohesion of iron: first-principles calculations

Atomistic mechanisms of hydrogen-induced cracking along a bcc Fe Σ3(111) symmetrical tilt grain boundary (GB) have been studied by first-principles calculations. The mobile and immobile effects of hydrogen on the GB decohesion are analyzed by calculating the dependence of hydrogen segregation energy on the coverage relevant to the repulsive interaction among segregated hydrogen atoms at the GB and on its fracture surfaces, together with generalizing McLean's formula. It was found that the segregation of combined mobile and immobile hydrogen atoms from the bulk and/or GB on the fracture surfaces causes much stronger reduction (70–80%) in the GB cohesive energy. It can occur even at a very low bulk hydrogen content of about 10^?9 atomic fraction during slow cracking. This is in contrast to only 10–20% decohesion induced by immobile hydrogen at much higher hydrogen content during fast cracking. The mobile effect of hydrogen, giving rise to a profound reduction in the GB cohesive energy, is a key factor controlling the mechanism of hydrogen-induced GB cracking.     

Synthesis of Hydrotalcite using Magnesium from Seawater and Dolomite

Abstract

Three methods of synthesizing hydrotalcite(HT) have been developed using magnesium from seawater and dolomite(MgCa(CO₃)₂). In the first process, 1.0M Na₂CO₃solution was added to calcium ion free artificial seawater containing AlCl₃ with an initial Mg/Al molar ratio of 2.0～3.7 until a pH of 10 was obtained. The solution was then continuously stirred for Ih at 60°C. CO₃ ^2--HT was precipitated as a single phase, and the initial Mg/Al molar ratio, which each recovery of Mg²⁺and Al³⁺ from the solution was above 98%, was 2.0–2.3. In the second process, a Ca(OH)₂ slurry was added to artificial seawater containing AlCl₃ with an initial Mg/Al molar ratio of 1.0～5.0 until a pH of 10.5 was obtained, and then was stirred for Ih at 60°C. HT was also precipitated as a single phase with initial Mg/Al molar ratio 2.0～4.0. The initial Mg/Al molar ratio, which each recovery of Mg²⁺ and Al³⁺ from the solution was above 98%, was 2.2～3.3, but SO₄ ^2- and Cl^? were contained in the precipitated HT. When HT was produced using initial Mg/Al molar ratio of 3.0 at 25°C, SO₄ ^2- and Cl^?in the HT were ion-exchanged with CO₃ ^2- in a 0.05M Na₂CO₃solution for 24h at 25°C, and SO₄ ^2- and Cl^? content of the HT were decreased to 0.5 and 0.05wt%, respectively. In the third process, dolomite calcined at 1000°C was added to an AlCl₃ solution with an initial Mg/Al molar ratio of 1.0～2.0, and the solution was stirred for 1～4h at 25～90°C. HT was precipitated with the smallest amount of MgO and Mg(OH)₂ when the initial Mg/Al molar ratio was 1.5 and the solution was stirred for 4h at 90°C.     

Chemical modification of poly(vinyl chloride) by nucleophilic substitution

The reaction of poly(vinyl chloride) (PVC) in nucleophile (Nu)/ethylene glycol (EG) or Nu/N,N-dimethylformamide (DMF) solution was found to result in the substitution of Cl in PVC with Nu from solution, in addition to the straight elimination of HCl, both of which led to the dechlorination of PVC. Examined Nu⁻ were I⁻, SCN⁻, OH⁻, N₃⁻, and the phthalimide anion. For the Nu/EG solution, elimination was favoured over substitution for all Nu⁻. The ratio of substitution to dechlorination was notable, descending in the order OH⁻ > SCN⁻ = N₃⁻ > phthalimide anion > I⁻. For the Nu/DMF solution, the ratio of substitution to dechlorination was high, in the order SCN⁻ > N₃⁻ > I⁻ > phthalimide anion. In both cases, the orders of the ratios were similar to those of the nucleophilic reactivity constant, I⁻ > SCN⁻ > N₃⁻ > phthalimide anion, except for I⁻. The low ratio for I⁻ was attributable to the elimination of HI after the substitution of Cl in PVC with I in solution, because I⁻ is a strong nucleophile, as well as an excellent leaving group. Comparing the effect of EG and DMF on the substitution of Cl in PVC with Nu in solution, the ratio of substitution to dechlorination was higher for I⁻, SCN⁻, N₃⁻, and the phthalimide anion in DMF than in EG. The substitution of Cl in PVC with Nu in solution was found to occur preferentially in DMF versus EG.     

Determination of airborne particle-associated benz[a]anthracene-7,12-quinone using high-performance liquid chromatography with in-line reduction and fluorescence detection

A simple and sensitive method for measuring airborne particle-associated benz[a]anthracene-7,12-quinone (BaAQ) based on two-dimensional high-performance liquid chromatography (HPLC) with fluorescence detection was established. The system involves an ODS column for sample clean up, a 6-port switching valve, an ODS column for trapping the fraction containing BaAQ, an ODS column for sample separation, and a Pt-Rh catalytic column for reduction of BaAQ to a corresponding fluorescent compound. The accuracy of the assay, as applied to airborne particulate sample extracts spiked with known amounts of BaAQ was 94–108%. The detection limit was 97 fmol per injection (signal-to-noise ratio = 3), and the calibration range was from 1 to 100 pmol with excellent proportionality (R² = 0.9995). BaAQ in airborne particles collected in Osaka, Japan every 3 h was successfully measured using the established analytical method with simple sample preparation steps: ultrasonic extraction in organic solvent and concentration under reduced pressure and/or nitrogen stream.     

Electric quadrupole moment of the neutron-rich 33Al

The nuclear electric quadrupole moment (Q moment) of the neutron-rich nucleus ³³Al (I = 5/2 , T _1/2 = 41 ms) has been measured by the $ \beta$ -ray detected nuclear quadrupole resonance ( $ \beta$ -NQR) method for the first time. The ³³Al nucleus is considered to be on the border of the island of inversion within which a significant intrusion of the pf orbits occurs across the N = 20 shell gap and the intrusion causes an anomalous enhancement of the Q moment. Polarized ³³Al nuclei were produced from ³⁶S (77.5MeV/u beams through the fragmentation process and separated by LISE fragment separator at GANIL. The ³³Al nuclei were implanted into a Al₂O₃ single-crystal plate and the $ \beta$ -NQR spectrum was successfully obtained.     

Nitrogen nanobubbles and butane nanodroplets at Si(1 0 0)

Nanobubbles and nanodroplets were spontaneously formed at Si(1 0 0) in contact with nitrogen and butane saturated water, respectively. The topographic images obtained by tapping mode AFM were similar truncated nanospheres, but the phase images suggested that the nanobubbles were harder than the nanodroplets. The tip–sphere interactions showed the nanodroplets were much viscoelastic than the nanobubbles. The surface and three-phase contact line energies were estimated by analysis of the topographic images. The nanodroplet was stable, but the nanobubble was unstable in spite of the experimental long life. The two-dimensional spatial distribution indicated an attractive interaction between the nanodroplets, but no interaction was observed between the nanobubbles.