Vinyl‐type polymerization of norbornene by nickel(II) bisbenzimidazole catalysts

Novel nickel(II) bisbenzimidazole complexes were prepared via a three‐step synthetic procedure consisting of aniline/diacid condensation, ligand N‐alkylation, and metal complexation. The complexes were characterized by X‐ray crystallography and found to possess a pseudotetrahedral geometry. Upon activation with methylaluminoxane, these nickel bisbenzimidazoles did not polymerize simple olefins (e.g., ethylene, propylene, and 1‐butene) but were found to carry out the rapid and efficient polymerization of norbornene. The polynorbornene products were characterized by gel permeation chromatography/light scattering, ¹³C NMR, and IR, and their Mark–Houwink and dn/dc parameters were determined. The molecular weights of the polynorbornenes were very high (weight‐average molecular weight = 587,000–797,000 g/mol). ¹³C NMR suggested that the polymerization occurred via vinyl addition (i.e., a 2,3‐linked polymer); no ring‐opened product was observed. Thermogravimetric analysis indicated that the polynorbornenes were stable up to 400 °C under nitrogen. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2095–2106, 2003     

Role of water vapor and CO2 in the paleoclimatic fluctuations along northwestern and southern Syria, and the adjacent Mediterranean Sea

Microscopic petrified grains were collected from a mafic–ultramafic pipe, NE of Dreikeesh, NW Syria. The grains were identified as anthers/gynoecia in herb/grass flowers. Three of the grains showed evidence of magnetism, two slowly dissolved in concentrated HCl, and three microprobed grains showed a montmorillonitic composition. Iron originating from pyroxene was oxidized to magnetite. Released silica formed the mineral suite agate–chalcedony–opal. Warm/cold paleoclimatic fluctuations, occurring during late Pliocene–Holocene, depended on water vapor, CO₂ production, and cinders in the atmosphere. Most of these were associated with changing volcanic/tectonic events. Fluctuations were controlled by heat reflected from the Earth's surface being absorbed by water vapor and CO₂, which both re-reflected the heat back to the surface, thus, raising the temperature. This cycle was repeated several times during late Pliocene–Holocene.     

A new VOF‐based numerical scheme for the simulation of fluid flow with free surface. Part II: application to the cavity filling and sloshing problems

Finite element analysis of fluid flow with moving free surface has been performed in 2‐D and 3‐D. The new VOF‐based numerical algorithm that has been proposed by the present authors (Int. J. Numer. Meth. Fluids, submitted) was applied to several 2‐D and 3‐D free surface flow problems. The proposed free surface tracking scheme is based on two numerical tools; the orientation vector to represent the free surface orientation in each cell and the baby‐cell to determine the fluid volume flux at each cell boundary. The proposed numerical algorithm has been applied to 2‐D and 3‐D cavity filling and sloshing problems in order to demonstrate the versatility and effectiveness of the scheme. The proposed numerical algorithm resolved successfully the free surfaces interacting with each other. The simulated results demonstrated applicability of the proposed numerical algorithm to the practical problems of large free surface motion. It has been also demonstrated that the proposed free surface tracking scheme can be easily implemented in any irregular non‐uniform grid systems and can be extended to 3‐D free surface flow problems without additional efforts. Copyright © 2003 John Wiley & Sons, Ltd.     

Structure–electrical property study of anisotropic polyaniline films

The relationships of the structure and electrical properties of anisotropic HCl‐doped polyaniline (PANI) films cast from N,N′‐dimethylpropylene urea (DMPU) solutions and stretched to different draw ratios were studied. The anisotropic structure of the stretched PANI films was examined by X‐ray diffraction, near‐infrared wave‐guide coupling, and polarized infrared measurements. The PANI emeraldine base (EB) films cast from DMPU solutions had a single‐phase noncrystalline structure, and stretching of the films did not cause crystallization to occur. The transition moment angles of two weakly absorbing infrared bands were determined, and the Hermans' orientation functions for the PANI EB films were calculated. The PANI films were then doped with HCl, and the electrical properties were determined by impedance spectroscopy. With a specially designed test fixture, the in‐plane and through‐plane impedance was obtained. The conductivity along the stretch direction increased with orientation. The in‐plane conductivity was significantly higher than the through‐plane conductivity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 823–841, 2003     

Thiol–norbornene materials: Approaches to develop high Tg thiol–ene polymers

The ability to prepare high T_g low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (T_g) for several thiol–norbornene materials. Results indicate that T_gs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high T_g materials. In particular, as much as a 70 °C increase in T_g was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007     

Coercivity analysis in R17Fe83−χBχ magnets

We studied the coercivity in magnets of composition R₁₇Fe_83−χB_χ (R = Nd, Pr and χ = 8, 30), using measurements of the coercive field H_c, its angular dependence, and the magnetic viscosity coefficient S_v, for temperatures between 4.2 and 500 K. The results are discussed in relation to a model which does not specifically consider the detailed mechanisms involved in magnetization reversal, but which provides information about the magnetic properties in the activation volume v where magnetization reversal is initiated. It is concluded that the ordering temperature in v tends to be slightly smaller than in the bulk and that the room temperature anisotropy in v is not strongly reduced with respect to the bulk value. Finally, a direct evaluation of the dipolar interactions is in good agreement with results obtained from H_c(T).     

Ferroelectric polarization switching in nylon-11

Cold-drawn Nylon-11 films, which were prepared by stretching the melt-quenched films to a draw ratio of 2.8: 1 at room temperature, were found to exhibit an electric displacement versus electric field hysteresis loop. The results confirmed that the Nylon-11 film exhibited ferroelectric behavior at or below room temperature. The coercive fields were 65, 98, 125, 160, and 215 MV/m at 20, 0, ?20, ?40, and ?60°C and the remanent polarization at ?20°C (where there was considerably less dc conduction) was 56 mC/m². Switching of the polarization was almost completed within 20 ms.