Viscoelastic behavior of polypropylene/nitrile rubber thermoplastic elastomer blends: Application of Kerner's models for reactively compatibilized and dynamically vulcanized systems

The viscoelastic properties of binary blends of nitrile rubber (NBR) and isotactic polypropylene (PP) of different compositions have been calculated with mean‐field theories developed by Kerner. The phase morphology and geometry have been assumed, and experimental data for the component polymers over a wide temperature range have been used. Hashin's elastic–viscoelastic analogy principle is used in applying Kerner's theory of elastic systems for viscoelastic materials, namely, polymer blends. The two theoretical models used are the discrete particle model (which assumes one component as dispersed inclusions in the matrix of the other) and the polyaggregate model (in which no matrix phase but a cocontinuous structure of the two is postulated). A solution method for the coupled equations of the polyaggregate model, considering Poisson's ratio as a complex parameter, is deduced. The viscoelastic properties are determined in terms of the small‐strain dynamic storage modulus and loss tangent with a Rheovibron DDV viscoelastometer for the blends and the component polymers. Theoretical calculations are compared with the experimental small‐strain dynamic mechanical properties of the blends and their morphological characterizations. Predictions are also compared with the experimental mechanical properties of compatibilized and dynamically cured 70/30 PP/NBR blends. The results computed with the discrete particle model with PP as the matrix compare well with the experimental results for 30/70, 70/30, and 50/50 PP/NBR blends. For 70/30 and 50/50 blends, these predictions are supported by scanning electron microscopy (SEM) investigations. However, for 30/70 blends, the predictions are not in agreement with SEM results, which reveal a cocontinuous blend of the two. Predictions of the discrete particle model are poor with NBR as the matrix for all three volume fractions. A closer agreement of the predicted results for a 70/30 PP/NBR blend and the properties of a 1% maleic anhydride modified PP or 3% phenolic‐modified PP compatibilized 70/30 PP/NBR blend in the lower temperature zone has been observed. This may be explained by improved interfacial adhesion and stable phase morphology. A mixed‐cure dynamically vulcanized system gave a better agreement with the predictions with PP as the matrix than the peroxide, sulfur, and unvulcanized systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1417–1432, 2004     

Thermogravimetric and dynamic mechanical thermal analysis of pineapple fibre reinforced polyethylene composites

The thermal behaviour of pineapple leaf fibre (PALF) reinforced polyethylene composites was studied by thermogravimetric and dynamic mechanical thermal analysis. Fibre treatment was carried out using isocyanate, silane and peroxide to improve the interfacial adhesion between fibre and matrix. The effects of fibre loading and surface modification on the thermal properties were evaluated. It was found that at high temperature PALF degrades before the polyethylene matrix. The storage modulus increased with increase of fibre loading and decreased with increase of temperature. The treated fibre composites impart better properties compared to untreated system. Tan δ showed a distinct peak at low temperature ascribed to the glass transition temperature of polyethylene but no peak was observed for PALF fibre. The relative damping increased with fibre loading. Cole-Cole analysis was made to understand the phase behaviour of the composite samples.     

Distereoselective one-pot synthesis of pyrimidopyrimidines using sulfated tin oxide as a reusable catalyst： An extension of Biginelli-type reaction

The Biginelli-type compounds 4,5,8a-triarylhexahydropyrimido[4,5-d]pyrimidine-2,7（1H,3H）-diones were synthesized by a one-pot three-component reaction using sulfated tin oxide as a reusable catalyst. This method has the advantages of high yields, short reaction time, simple starting materials and reusability of catalyst for several times.     

Dynamic mechanical behavior of acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) blends

The dynamic mechanical behavior of uncrosslinked (thermoplastic) and crosslinked (thermosetting) acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) (NBR/EVA) blends was studied with reference to the effect of blend ratio, crosslinking systems, frequency, and temperature. Different crosslinked systems were prepared using peroxide (DCP), sulfur, and mixed crosslink systems. The glass‐transition behavior of the blends was affected by the blend ratio, the nature of crosslinking, and frequency. sThe damping properties of the blends increased with NBR content. The variations in tan δ_max were in accordance with morphology changes in the blends. From tan δ values of peroxide‐cured NBR, EVA, and blends the crosslinking effect of DCP was more predominant in NBR. The morphology of the uncrosslinked blends was examined using scanning electron and optical microscopes. Cocontinuous morphology was observed between 40 and 60 wt % of NBR. The particle size distribution curve of the blends was also drawn. The Arrhenius relationship was used to calculate the activation energy for the glass transition of the blends, and it decreased with an increase in the NBR content. Various theoretical models were used to predict the modulus of the blends. From wide‐angle X‐ray scattering studies, the degree of crystallinity of the blends decreased with an increasing NBR content. The thermal behavior of the uncrosslinked and crosslinked systems of NBR/EVA blends was analyzed using a differential scanning calorimeter. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1556–1570, 2002     

Preparation and characterization of some stereochemically rigid seven-coordinate η-cyclopentadienyltris(N,N-dialkyldithiocarbamato)hafnium(IV) complexes

Summary N,N-Dialkyldithiocarbametohafnium(IV) complexes of the type -CpHf(S₂CNR₂)₃, (R = Me or Et) have been prepared in nonaqueous media by reacting dichlorodicyclopentadienylhafnium(IV) with sodium salts of substituted dithiocarbamic acids. Conductance and i.r. studies show that these complexes are nonelectrolytes in which all of the dithiocarbamate ligands are bidentate. A coordination number of seven may be assigned to hafnium(IV) in these complexes, 'H n.m.r. spectra of the complexes in CDCI₃ at ambient temperature (30°) indicate that the metal centered rearrangement and the S₂C N bond rotation are both slow on the n.m.r. time scale. A capped octahedron configuration is suggested for these complexes.Author to whore all correspondence should be addressed.     

η-Methylcyclopentadienyltris(N,N-dimethyldithiocarbamato)-titanium(IV); a stereochemically rigid heptacoordinate chelate

Summary (-Methylcyclopentadienyltris(N,N-dimethyldithiocarbam-ato)titanium(IV), MeC₅H₄Ti(S₂CNMe₂)₃ has been prepared from (MeC₅H₄)₂TiCl₂ and sodiumN,N-dimethyl-dithiocarbamate solution. On the basis of the i.r. spectrum a coordination number of seven is assigned to the complex whilst the¹H n.m.r. spectrum indicates that it is a stereochemically rigid chelate. A pentagonal bipyramidal structure is suggested.On study leave from S. D. College, Muzaffar Nagar, U.P., India.     

Density functional theory studies of interactions of graphene with its environment: Substrate,gate dielectric and edge effects

This paper reviews the theoretical work undertaken using density functional theory (DFT) to explore graphene's interactions with its surroundings. We look at the impact of substrates, gate dielectrics and edge effects on the properties of graphene. In particular, we focus on graphene-on-quartz and graphene-on-alumina systems, exploring their energy spectrum and charge distribution. Silicon-terminated quartz is found to not perturb the linear graphene spectrum. On the other hand, oxygen-terminated quartz and both terminations of alumina bond with graphene, leading to the opening of a band gap. Significant charge transfer is seen between the graphene layer and the oxide in the latter cases. Additionally, we review the work of others regarding the effect of various substrates on the electronic properties of graphene. Confining graphene to form nanoribbons also results in the opening of a band gap. The value of the gap is dependent on the edge properties as well as width of the nanoribbon.     

Reconstruction of thermally quenched glow curves in quartz

The experimentally measured thermoluminescence (TL) glow curves of quartz samples are influenced by the presence of the thermal quenching effect, which involves a variation of the luminescence efficiency as a function of temperature. The real shape of the thermally unquenched TL glow curves is completely unknown. In the present work an attempt is made to reconstruct these unquenched glow curves from the quenched experimental data, and for two different types of quartz samples. The reconstruction is based on the values of the thermal quenching parameter W (activation energy) and C (a dimensionless constant), which are known from recent experimental work on these two samples. A computerized glow-curve deconvolution (CGCD) analysis was performed twice for both the reconstructed and the experimental TL glow curves. Special attention was paid to check for consistency between the results of these two independent CGCD analyses. The investigation showed that the reconstruction attempt was successful, and it is concluded that the analysis of reconstructed TL glow curves can provide improved values of the kinetic parameters E, s for the glow peaks of quartz. This also leads to a better evaluation of the half-lives of electron trapping levels used for dosimetry and luminescence dating.     

Processability characteristics and physico-mechanical properties of natural rubber modified with cashewnut shell liquid and cashewnut shell liquid-formaldehyde resin

Natural rubber (NR) has been modified with 5-15 phr each of cashewnut shell liquid (CNSL) and cashewnut shell liquid-formaldehyde (CNSLF) resin with a view to studying the processability characteristics of the mixes and physicomechanical properties of their vulcanizates. The plasticizing effect of these additives in NR was shown by the reduction in melt viscosity and power consumption during mixing in a Brabender Plasticorder compared to that of unmodified NR. Despite the reduction in chemical crosslink density, the vulcanizates containing 15 phr of CNSL and 5-10 phr of CNSLF showed higher tensile and tear strengths and elongation at break. The higher values of activation energy for thermal decomposition of the vulcanizates containing 15 phr each of CNSL (301 kJ/mol) and CNSLF (372 kJ/mol) than that of the unmodified NR vulcanizate (177 kJ/mol) indicate improvement in thermal stability of NR vulcanizates in presence of the modifiers.     

Transport properties of crosslinked acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) blends

The diffusion and transport of organic solvents through crosslinked nitrile rubber/poly(ethylene‐co‐vinyl acetate) (NBR/EVA) blends have been studied. The diffusion of cyclohexanone through these blends was studied with special reference to blend composition, crosslinking systems, fillers, filler loading, and temperature. At room temperature the mechanism of diffusion was found to be Fickian for cyclohexanone–NBR/EVA blend systems. However, a deviation from the Fickian mode of diffusion is observed at higher temperature. The transport coefficients, namely, intrinsic diffusion coefficient (D*), sorption coefficient (S), and permeation coefficient (P) increase with the increase in NBR content. The sorption data have been used to estimate the activation energies for permeation and diffusion. The van't Hoff relationship was used to determine the thermodynamic parameters. The affine and phantom models for chemical crosslinks were used to predict the nature of crosslinks. The experimental results were compared with the theoretical predictions. The influence of penetrants transport was studied using dichloromethane, chloroform, and carbon tetrachloride. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1815–1831, 1999