Crystallization and melting of polyethylene under high pressure. II. Effect of pressure on melting behavior of various types of crystals

The effect of pressure on the melting point and volume of fusion of polyethylene was studied by high-pressure dilatometry. Starting materials were crystallized slowly from the melt under pressures of 1500, 3500, 5130 kg/cm², and 1 atm. It has been shown that the unusual behavior observed at pressures above 4000 kg/cm² is due to crystallization and melting of two kinds of extended-chain crystals differing in thermal stability. These are designated as ordinary extended-chain and highly extended-chain crystals, respectively. The relation between pressure P and melting temperature T_m of folded-chain, ordinary extended-chain, and highly extended-chain polyethylene was determined precisely. At pressures up to about 3000 kg/cm², plots of P against T_m for the crystal forms have almost the same curvature and then become parallel. But at pressures above 4000 kg/cm², ordinary extended-chain crystals show a linear increase of T_m with a constant slope of about 70 atm/deg. Curve for the highly extended-chain crystals changes in slope from 70 to 50 atm/deg at pressures between 3500 and 4300 kg/cm², and then show a sharp increase of T_m with increasing pressure. Experiments show that the meltingpoint curve of the highly extended-chain crystals overlaps that of the ordinary extended-chain crystals at pressures below 4000 kg/cm². Annealing experiments with folded-chain and ordinary extended-chain crystals have been made under high pressure. It is suggested that the formation of highly extended-chain crystals occurs stepwise through the formation and reorganization of ordinary extended-chain crystals from the original folded-chain crystals by a mechanism of partial melting and recrystallization at pressures above 4000 kg/cm².     

Temperature dependence of local density augmentation for acetophenone N,N,N',N'-tetramethylbenzidine exciplex in supercritical water

Local density augmentation around exciplex between acetophenone and N,N,N',N'-tetramethylbenzidine in supercritical water was measured by observing the peak shift of transient absorption spectrum at temperatures from 380 to 410 degrees C and at pressures from 6 to 37 MPa. Large local density augmentation was observed at lower solvent densities. Local density augmentation was evaluated by the excess density, which was defined as the difference between local density and bulk density, and the density enhancement factor, which was defined by the ratio of the local density to the bulk density. The number of solvating molecules was estimated with a Langmuir adsorption model. The excess density was found to exhibit a maximum at approximately 0.15 g cm(-3), which decreased with increasing temperature. The density enhancement factor was found to decrease with increasing temperature; however, its value was much greater than unity at 410 degrees C, which provides evidence that exciplex-water interactions still exist at these conditions. The temperature dependence of local density augmentation around the exciplex in supercritical water was comparable with that in supercritical carbon dioxide, which suggests that the ratios of the solute-solvent and solvent-solvent interactions are comparable between these two systems.     

Metallic Ni nanoparticles confined in hexagonally ordered mesoporous silica material

Single nanometer-sized metallic Ni particles have been successfully deposited inside a hexagonally ordered mesoporous silica material by using a liquid-phase reductive deposition method.     

Electrochemical typing of blood using affinity membranes

Human blood group substance of the ABO system was immobilized in a mebrane matrix. The membrane-bound blood group substance retained its binding ability against the corresponding antibody (agglutinin) in serum. The transmembrane potential changed drastically with the agglutination of the membrane-bound blood group substance. Electrochemical typing of blood was performed with sera, using a pair of membranes with immobilized A- and B-type blood group substances. The blood type was determined by measuring the transmembrane potential across these membranes before and after the agglutination reaction. A possible re-use of the membrane-bound blood group substance by treatment with galactose is discussed.     

Magnetic field effect on the pairing state competition in quasi-one-dimensional organic superconductors (TMTSF)2X

We study the effect of the magnetic field on the pairing state competition in organic conductors (TMTSF)₂X by applying random phase approximation to a quasi-one-dimensional extended Hubbard model. We show that the singlet pairing, triplet pairing and the Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) superconducting states may compete when charge fluctuations coexist with spin fluctuations. This rises a possibility of a consecutive transition from singlet pairing to FFLO state and further to S_z = 1 triplet pairing upon increasing the magnetic field. We also show that the singlet and S_z = 0 triplet components of the gap function in the FFLO state have “d-wave” and “f-wave” forms, respectively, which are strongly mixed.     

Practical and convenient synthesis of N-heterocycles: stereoselective cyclization of N-alkenylamides with t-BuOI under neutral conditions

[Structure: see text] tert-Butyl hypoiodite (t-BuOI) was found to be a powerful reagent for the cyclization of N-alkenylamides leading to a variety of N-heterocycles under extremely mild conditions. When N-alkenylsulfonamides were employed in the reaction, three- to six-membered saturated N-heterocycles were obtained in good to excellent yields with complete stereoselectivity. The method was applicable to the cyclization of alkenylbenzamide derivatives to afford N-, O- or N-, S-heterocycles.     

Phase behavior of four homologous compounds of 4-n-alkyl-4′-isothiocyanatobiphenyl (nBT) under pressure

The phase behavior of four homologous compounds of 4-n-nonyl-, 4-n-decyl-, 4-n-undecyl-, and 4-n-dodecyl-4′-isothiocyanatobiphenyl (9BT, 10BT, 11BT, and 12BT) was re-investigated to characterize their high-pressure mesophases under pressures up to 150 MPa using a polarizing optical microscope equipped with a high-pressure optical cell and a wide-angle X-ray diffractometer equipped with a high-pressure sample vessel. The pressure-induced mesophases of 9BT and 10BT appearing under pressures above about 60 and 100 MPa, respectively, were identified as nematic (N) and SmA phases, which indicate the reversible Cr–CrE–N–I and Cr–CrE–SmA–I phase transitions under elevated pressure. 11BT and 12BT exhibited the reversible transition of Cr–CrE–SmA–I in the low-pressure regions below about 5 and 23 MPa, respectively. Both the stable CrE phases changed into the monotropic (and metastable) one under higher pressures, in which the Cr–SmA–I and I–SmA–CrE–Cr phase transitions on heating and cooling processes, respectively, were recognized.     

Flame Emission Spectrometry Using Atomic Absorption Apparatus (I) Determination of Sr In Sea Water

Flame emission determination of Sr in sea water is studied using an ordinary atomic absorption apparatus. The analytical line 4607 A is used with background correction at 4616 A. The ionization is found to be negligible in air acetylene flame with sea water, and the interference of H₂SO₄ is elimentated using the higher part of the flame.     

Coexistence of Spin–Lattice Relaxation and Phonon-Bottleneck Processes in GdIII–Phthlocyaninato Triple-Decker Complexes under Highly Diluted Conditions

Gd³⁺ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd³⁺ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd³⁺ complexes, we have investigated the magnetic properties and heat capacities of two Gd³⁺-phthalocyaninato triple-decker complexes, one of which has intramolecular Gd³⁺–Gd³⁺ interactions and the other does not. It was found that the Gd³⁺–Gd³⁺ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd³⁺ complexes into a large amount of diamagnetic Y³⁺ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin–lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes.