Isotope Geochemical Studies on Carbonates of Quaternary Glacio-Lacustrine Lake Sediments as indicators of Paleoenvironment

Selected silty “summer” and argillaceous “winter” layers of profiles of the rhythmically bedded glacio-lacustrine ice-marginal lake sediment of the Dehlitz-Leipzig varved clay (Leipziger Tieflandsbucht, Central Germany) have been examined for isotope composition (¹⁸O/¹⁶O, ¹³C/¹²C) of carbonate and organic fraction. In addition, mineralogical and grain size compositions were determined. The results show 1) a change in source of carbonate sediment (provenance) through time; 2) the oxygen isotope ratios differed between the “summer” and “winter” layers of varves couplets due to different rates of sedimentation; 3) anoxic events occurred in the lake; 4) carbon isotope ratios suggest organics in lake sediments which were derived from land and the primary productivity was low in the lake itself. In the study of cold-climatic lake sediments, isotope investigations can efficiently be used as additional paleosedimentological and facies indicators.     

Effects of molecular geometry on liquid crystalline phase behaviour: isotropic-nematic transition

The effects of range and geometry of a simple attractive square-well on the phase diagram of hard ellipsoids and hard spherocylinders is systematically studied using a simple van der Waals type theory. The orientational single particle distribution function is approximated using the Onsager trial function. The quantitative errors introduced by this are thought to be considerably smaller than the use of the van der Waals approximation, which has been shown to give qualitatively correct phase diagrams for similar models. The phase diagrams obtained for hard ellipsoids and hard spherocylinders of aspect ratios ranging between 3 and 10 with a variety of square-well attractions are found to fall into three general types. The first type shows liquid-vapour coexistence and an isotropic-nematic transition, which meet at a liquid-vapour-nematic triple point. The second type shows a marked widening of the isotropic-nematic biphasic region which pre-empts the liquid-vapour coexistence. The final phase diagram shows a strong destabilization of the nematic phase with respect to the isotropic, which results in a shift of the phase transition to higher densities and pressures as the temperature is lowered.     

Crystalline Morphology and Nonisothermal Crystallization Behaviors of iPP/PcBR Blends

Isotactic polypropylene/poly(cis‐butadiene) rubber (iPP/PcBR) blends were prepared by melt mixing. The influence of PcBR content on crystalline morphology and nonisothermal crystallization behaviors of iPP was investigated by polarized optical microscopy (POM), small angle light scattering (SALS), and differential scanning calorimetry (DSC). The POM showed that an increase of PcBR ranging from 10 vol% to 40 vol% led to less perfection of spherulites, vaguer boundaries between spherulites, and smaller spherulite size, which was quantitatively validated by SALS. The presence of PcBR also remarkably affected the nonisothermal crystallization behaviors of iPP. An addition of PcBR caused higher crystallization peak temperature and a faster crystallization rate, meaning a heterogeneous nucleation effect of PcBR upon crystallization of iPP. For the same sample, the crystallization peak temperature moved to lower temperature and the crystallization rate increased as the cooling rate increased. The Ozawa and combined Avrami and Ozawa equations were used to describe the nonisothermal crystallization process of iPP and blends. The combined Avrami and Ozawa equation was more appropriate for the crystallization of the blends. Crystallization activation energy of iPP and blends was calculated by the Kissinger equation; the result showed that crystallization activation energy decreased as the content of PcBR increased from 30 vol% to 40 vol%.     

Investigation of Carbon Black Network in Natural Rubber with Different Bound Rubber Contents

A new method was applied to modify the surface activity of virginal carbon black (VCB). LA‐57, one kind of hindered amine light stabilizer, was adsorbed onto the carbon black surface through a strong shear force induced by the screws of a HAAKE internal mixer. The modified carbon black (MCB) was characterized by FT‐IR and thermogravimetric analysis (TGA). The bound rubber content of the natural rubber (NR) compounded with MCB and VCB varied with the fraction of LA‐57 on the MCB surface. The nonlinear effect at small strains, generally referred as the Payne effect, was investigated in the rubber compounds based on the different bound rubber contents. The NR compound containing the lowest bound rubber content had an obvious Payne effect. Based on the bound rubber content, the types of filler network varied from direct contact mode to the joint rubber shell mechanism.     

Dynamic Rebound Behavior of Silica/Natural Rubber Composites: Fly Ash Particles and Precipitated Silica

This article investigated the elastic response of natural rubber (NR) compounds filled with silica from fly ash particles (FASi) and commercial precipitated silica (PSi), through a dynamic rebound test. The effects of silica content and initial drop‐height on the height and number of rebounds, dynamic stiffness, and the energy loss were of interest. The results suggested that the unfilled NR vulcanizates exhibited a greater elastic response than the FASi and PSi‐filled vulcanized composites. For given silica contents, the NR compounds with FASi had better elastic response than those with PSi, where the elastic response decreased with an increase in silica content. The greater the silica contents, the higher the dynamic stiffness of the composites. The initial drop‐height had no effects on the elastic response change for the unfilled NR compound, but resulted in an increase in the energy loss for the silica‐filled NR composites. The differences in the elastic responses for the NR compounds filled with silica from FASi and PSi were associated with the differences in crosslink density and the filler–filler interaction influenced by content of bis(3‐triethoxysilylpropyl) tetrasulfane (designated as Si69) used.     

A Comparative Study on the Reinforcing Effect of Aramide and PET Short Fibers in a Natural Rubber-Based Composite

Four types of chopped fibers have been studied as reinforcement additives in a standard natural rubber based, carbon black filled formulation. The fibers studied were aramide (2 types) and polyester (2 types). The chopped fibers were added on top of the carbon black filled rubber compound at 2, 4, and 8 phr levels. The extra reinforcing effect in the modulus, especially at low elongation, the increase in hardness, the anisotropic properties, and the stiffening effects have been studied together with the evaluation of the mechanical hysteresis in strain and in compression. The permanent set of the resulting rubber compounds have been evaluated as well. The best compromise in performances and price was found for a certain type of polyester fiber.     

Performance and Mechanism of Epoxy Resin for Reinforcement of Styrene–Butadiene Rubber

Styrene–butadiene rubber (SBR) vulcanizates reinforced by epoxy resin (EP) have been synthesized by an in-situ vulcanization and curing process. The influences of synthetic parameters, such as the contents of EP, carbon black, and types of compatilizers, on the microstructures, vulcanization, and mechanical properties of SBR have been investigated. It was found that EP in SBR exists in the form of a fibrillar interpenetrating network, which is important for the enhancement of mechanical properties of SBR. The experimental results showed that when the percentage of EP was in the range of 10–20%, the composite materials had the best comprehensive performance. In comparison with pure SBR, the tear strength and the tensile stress at 300% elongation of SBR-EP composite were increased significantly. The method can be applicable for other rubber vulcanizates to improve their mechanical properties.     

Influence of Mixing Technique on Microstructure and Impact Properties of Isotactic Polypropylene/ Poly(Cis-Butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR vol%: 80/20) blends were prepared by melt mixing with various mixing rotation speeds. The effect of mixing technique on microstructure and impact property of blends was studied. Phase structure of the blends was analyzed by scanning electron microscopy (SEM). All of the blends had a heterogeneous morphology. The spherical particles attributed to the PcBR-rich phase were uniformly dispersed in the continuous iPP matrix. With increase of the mixing rotation speed, the dispersed phase particle's diameter distribution became broader and the average diameter of the separated particles increased. The spherulitic morphology of the blends was observed by small angle light scattering (SALS). Higher mixing rotation speed led to a more imperfect spherulitic morphology and smaller spherulites. Crystalline structure of the blends was measured by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). The introduction of 20 vol% PcBR induced the formation of iPPβ crystals. Higher rotation speed led to a decrease in microcrystal dimensions. However, the addition of PcBR and the increase of mixing rotation speed did not affect the interplanar distance. The long period values were the same within experimental error as PcBR was added or the mixing rotation speed quickened. The normalized relative degree of crystallinity of the blends slightly increased under lower rotation speeds (30 and 45 rpm) and decreased under higher rotation speeds. The notched Izod impact strength of the blends was enhanced as a result of the increase of mixing rotation speed.     

Radiation Processed Styrene-Butadiene Rubber/Ethylene-Propylene Diene Rubber/Multiple-Walled Carbon Nanotubes Nanocomposites: Effect of MWNT Addition on Solvent Permeability Behavior

Different compositions of SBR/EPDM 50:50 blends containing multiple-walled carbon nanotubes (MWNT) as nanoparticulate fillers (0.5%–10%) were evaluated for radiation sensitivity and solvent permeability. The efficiency of radiation ***cross-linking was analyzed by gel-content and Charlesby–Pinner parameter measurements. ***Gamma-radiation-induced cross-linking extent was found to increase with radiation dose and MWNT concentration, which was reflected in different extents of swelling. Rigorous analysis of swelling and diffusion data, on the basis of the transport exponent (n) values and diffusion/relaxation rate indicated anomalous diffusion behavior for most of the nanocomposites. The swelling extent in different solvents was found to be a function of polymer-solvent interaction as well as stearic hindrance due to the structure/size of the solvent molecules. Polymer-filler interaction investigated by a Kraus plot indicated high reinforcement of the SBR/EPDM matrix on MWNT addition. There was no significant change in surface energy or hydrophilicity of the SBR/EPDM matrix on introduction of MWNT into it.     

Properties of Natural Rubber Vulcanizates/Nanosilica Composites Prepared Based on the Method of In-situ Generation and Coagulation

Using the characteristics of silica sol dispersing well in water and easy formation of silica gel when the silica sol is heated, by mixing a system of concentrated natural rubber latex and silica sol, the silica sol can in-situ generate SiO₂ particles when heated. After coagulation of the mixed system, natural rubber/nanosilica composites C(NR/nSiO₂) were obtained. The composites C(NR/nSiO₂) and their vulcanizates were studied using a rubber processing analyzer (RPA), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The influence of silica contents on the C(NR/nSiO₂) vulcanizates mechanical properties, cross-linking degree, Payne effect, dissipation factor (tanδ), and the particle size and dispersion of SiO₂ in NR were investigated. The results obtained were compared with the NR/SiO₂ composites based on traditional dry mixing of bale natural rubber and precipitated silica (white carbon black). The results showed that when using a sulfur curing system with a silica coupling agent (Si69) in C(NR/nSiO₂), the vulcanizate had better mechanical properties, higher wet resistance, and lower rolling resistance than those without Si69. In the composites C(NR/nSiO₂) and their vulcanizates, the SiO₂ particles’ average grain diameter was 60 nm, and the good-dispersion of the in-situ generated SiO₂ in the rubber matrix were a significant contribution to the satisfactory properties of C(NR/nSiO₂) composites and their vulcanizates.