Some dynamic mechanical properties of unimodal and bimodal networks of poly(dimethylsiloxane)

Summary Elastomeric networks of polydimethylsiloxane prepared by end-linking chains having molecular weights in the range 18,500 to 220 g mol^-1 were studied from -128 to 50°C using a Rheovibron DDV III Viscoelastometer. In the case of the unimodal networks, the glass transition temperature T_g was generally insensitive to degree of cross-linking. The intensity of the tan δ relaxation, however, increased by over an order of magnitude over the range of cross-link densities investigated. Bimodal networks prepared from mixtures of relatively long and very short PDMS chains also had values of T_g which were insensitive to degree of cross-linking. Finally, as expected, the intensities of the tan δ peak for the bimodal networks could not be explained on the basis of simple additivity of contributions from the relatively long and the very short network chains.     

Ionic elastomer blends of zinc salts of maleated natural rubber and carboxylated nitrile rubber: Effect of grafted maleic anhydride

Zinc neutralized maleated natural rubbers (Zn‐MNR) were prepared by solution grafting and neutralization with zinc acetate in one‐step. It was later used for blending with carboxylated nitrile rubber (XNBR) in the composition of 50/50 parts by weight. The effect of grafted anhydride content (1.2, 1.6, 2.0, and 2.5% wt of NR) on the tensile properties of ionic rubber blends (Zn‐MNR/XNBR) was investigated. The tensile strength of the ionic blends was found to be greater than those of pure rubbers. The modulus, tensile, and tear strength of the blends dramatically increased with increasing levels of grafted anhydride. The ionic rubber blends also possessed superior physical properties compared to those of the corresponding nonionic rubber blends (MNR/XNBR). Dynamic mechanical thermal analysis and scanning electron microscopic studies were performed to verify the process of mixing. Fourier transform infrared spectroscopic studies were carried out to characterize the nature of specific intermolecular interactions between Zn‐MNR and XNBR chain segments. The results indicated that the ion‐ion (Zn⁺ ‐COO^?) interactions between Zn‐MNR and XNBR are formed at the interface, which provides the mean of compatibilization in the ionic rubber blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Crosslink reaction of natural rubber with thiuram sulphur donors in the presence of a thiuram monosulfide

The vulcanization of natural rubber was studied with the sulfurating agents dipentamethylene thiuram tetrasulfide (DPTT) and tetramethylene thiuram disulfide (TMTD) in the presence of tetramethyl thiuram monosulfide (TMTM). This last accelerant affects the rate and efficiency of the vulcanization as well as the structures of crosslinks formed by the two sulphur donors. It may give rise to a polymerization between adjacent double bonds and generate a inhomogeneous crosslink distribution with an adverse effect on physical properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 491–499, 2002     

Rheology of poly(propylene)/clay nanocomposites

The linear and nonlinear shear rheological behaviors of poly(propylene) (PP)/clay (organophilic‐montmorillonite) nanocomposites (PP/org‐MMT) were investigated by an ARES rheometer. The materials were prepared by melt intercalation with maleic anhydride functionalized PP as a compatibilizer. The storage moduli (G′), loss moduli (G″), and dynamic viscosities of polymer/clay nanocomposites (PPCNs) increase monotonically with org‐MMT content. The presence of org‐MMT leads to pseudo‐solid‐like behaviors and slower relaxation behaviors of PPCN melts. For all samples, the dependence of G′ and G″ on ω shows nonterminal behaviors. At lower frequency, the steady shear viscosities of PPCNs increase with org‐MMT content. However, the PPCN melts show a greater shear thinning tendency than pure PP melt because of the preferential orientation of the MMT layers. Therefore, PPCNs have higher moduli but better processibility compared with pure PP.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2427–2434,2004     

Molecular motions of non-crystalline poly(aryl ether-ether-ketone) PEEK and influence of elecron beam irradiation

The dynamic mechanical relaxation of non-crystalline poly(aryl ether-ether-ketone) PEEK and the one irradiated with electron beam were studied. The three distinct γ, β, α′ relaxation maxima were observed in unirradiated PEEK from low to high temperature. It was revealed from the study on the irradiation effects that three different molecular processes are overlapped in γ relaxation peak, i.e., molecular motion of water bound to main chain (peak temperature; at ?100°C), local motion of main chain (at ?80°C), and local mode of the aligned and/or oriented moiety (at ?40°C). The β relaxation connected with the glass transition occurred at 150°C and it shifted to higher temperature by irradiation. The α′ relaxation which can be attributed to rearrangement of molecular chain due to crystallization was observed in unirradiated PEEK ～ 180°C and its magnitude decreased with the increase in irradiation dose. This effect indicates the formation of structures inhibiting crystallization such as crosslinking and/or short branching during irradiation. A new relaxation, β′, appeared in the temperature range of 40° to 100°C by irradiation and its magnitude increased with dose. This relaxation was attributed to rearrangement of molecular chain from loosened packing around chain ends, which were introduced into the non-crystalline region by chain scission under irradiation, to more rigid molecular packing, From these observations, we proposed that deterioration in mechanical properties of non-crystalline PEEK by high energy electron beam was brought about not only by chain scission but structural changes such as crosslinking and/or branching in the main chain.     

Mass transfer from Taylor bubbles rising in single capillaries

Gas-liquid mass transfer from Taylor bubbles rising in 1, 2 and 3 mm diameter capillaries of circular and square cross-sections was investigated for air-water system. The liquid-phase volumetric mass transfer coefficient k_La was obtained from experimental oxygen absorption dynamics. The experimental k_La values are in good agreement with the model developed by van Baten and Krishna (2004. Chemical Engineering Science 59, 2535-2545), with the additional assumption that the dominant mass transfer contribution is to the film surrounding the bubble.     

Dynamic mechanical behavior of high‐density polyethylene/ethylene vinyl acetate copolymer blends: The effects of the blend ratio,reactive compatibilization,and dynamic vulcanization

The effects of the blend ratio, reactive compatibilization, and dynamic vulcanization on the dynamic mechanical properties of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends have been analyzed at different temperatures. The storage modulus of the blend decreases with an increase in the EVA content. The loss factor curve shows two peaks, corresponding to the transitions of HDPE and EVA, indicating the incompatibility of the blend system. Attempts have been made to correlate the observed viscoelastic properties of the blends with the blend morphology. Various composite models have been used to predict the dynamic mechanical data. The experimental values are close to those of the Halpin–Tsai model above 50 wt % EVA and close to those of the Coran model up to 50 wt % EVA in the blend. For the Takayanagi model, the theoretical value is in good agreement with the experimental value for a 70/30 HDPE/EVA blend. The area under the loss modulus/temperature curve (LA) has been analyzed with the integration method from the experimental curve and has been compared with that obtained from group contribution analysis. The LA values calculated with group contribution analysis are lower than those calculated with the integration method. The addition of a maleic‐modified polyethylene compatibilizer increases the storage modulus, loss modulus, and loss factor values of the system, and this is due to the finer dispersion of the EVA domains in the HDPE matrix upon compatibilization. For 70/30 and 50/50 blends, the addition of a maleic‐modified polyethylene compatibilizer shifts the relaxation temperature of both HDPE and EVA to a lower temperature, and this indicates increased interdiffusion of the two phases at the interface upon compatibilization. However, for a 30/70 HDPE/EVA blend, the addition of a compatibilizer does not change the relaxation temperature, and this may be due to the cocontinuous morphology of the blends. The dynamic vulcanization of the EVA phase with dicumyl peroxide results in an increase in both the storage and loss moduli of the blends. A significant increase in the relaxation temperature of EVA and a broadening of the relaxation peaks occur during dynamic vulcanization, and this indicates the increased interaction between the two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2083–2099, 2003     

Influence of polymerization conditions on the structure and properties of polyethylene/polypropylene in‐reactor alloy synthesized in the gas phase with a spherical Ziegler–Natta catalyst

A spherical TiCl₄/MgCl₂‐based catalyst was used in the synthesis of in‐reactor polyethylene/polypropylene alloys by polyethylene homopolymerization and subsequent homopolymerization of propylene in the gas phase. Different conditions in the ethylene homopolymerization stage, such as monomer pressure and polymerization temperature, were investigated, and their influences on the structure and properties of in‐reactor alloys were studied. Raising the polymerization temperature is the most effective way of speeding up polymerization and regulating the ethylene content of polyethylene (PE)/polypropylene (PP) alloys, but it will cause a greater increase in the PE‐b‐PP block copolymer fraction (named fraction D) than in the fraction of PP‐block‐PE in which the PP segments have low or medium isotacticity (named fraction A). Although changing ethylene monomer pressure could influence the ethylene content of PE/PP alloys slightly, it is an effective way of regulating the structural distribution. Reducing the monomer pressure will evidently increase fractions A and D. The mechanical properties of the alloys, including impact strength and flexural modulus, can be regulated in a broad range with changes in polymerization conditions. These properties are highly dependent on the amount, distribution, and chain structure of fractions A and D. The impact strength is affected by both fraction A and fraction D in a complicated way, whereas the flexural modulus is mainly determined by the amount of fraction A. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2136–2143, 2006     

Using maleic anhydride grafted poly(lactic acid) as a compatibilizer in poly(lactic acid)/layered‐silicate nanocomposites

The goal of this work was to prepare exfoliated poly(lactic acid) (PLA)/layered‐silicate nanocomposites with maleic anhydride grafted poly(lactic acid) (PLA–MA) as a compatibilizer. Two different layered silicates were used in the study: bentonite and hectorite. The nanocomposites were prepared by the incorporation of each layered silicate (5 wt %) into PLA via solution casting. X‐ray diffraction of the prepared nanocomposites indicated exfoliation of the silicates. However, micrographs from transmission electron microscopy showed the presence of intercalated and partially exfoliated areas. Tensile testing showed improvements in both the tensile modulus and yield strength for all the prepared nanocomposites. The results from the dynamic mechanical thermal analysis showed an improvement in the storage modulus over the entire temperature range for both layered silicates together with a shift in the tan δ peak to higher temperatures. The effect of using PLA–MA differed between the two layered silicates because of a difference in the organic treatment. The bentonite layered silicate showed a more distinct improvement in exfoliation and an increase in the mechanical properties because of the addition of PLA–MA in comparison with the hectorite layered silicate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1852–1862, 2006     

Water uptake and mechanical characteristics of natural filler–polypropylene composites

Water uptake characteristics and some mechanical properties of polypropylene composites containing three types of natural fillers, purified α‐cellulose, wastepaper fibers, and wood flour were studied. The fiber contents were 15, 25, and 35% by weight. Two percent maleic anhydride polypropylene (MAPP) was also added to the mix, as the compatibilizer agent. Mixing process was performed in a Brabender Plasticorder until a constant torque was reached. Composites made out of these combinations were then pressed in a laboratory press and ASTM standard test specimens were cut out of the sheets. Water absorption and tensile tests were performed on these specimens. The results showed a significant difference between the various filler types regarding water uptake. Water uptake also increased by the increase in filler content. Tensile strength and elongation at break in composites declined when compared with pure polypropylene, but their modulus of elasticity increased. Among the three types of fillers, no significant discrepancies were observed in terms of improving mechanical properties in composites. Filler content increase had no drastic effect regarding strength improvement. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 941–946, 2003