Double yielding in PA6/TPV‐MAH blends: Effect of crosslinking degree of the dispersed phase

Thermoplastic vulcanizates (TPVs) based on PP and EPDM (the ratio is 5:5) with different crosslinking degrees were prepared using different contents of phenolic resins, and then blended with polyamide 6 (PA6). The results indicated that with an increase in crosslinking degree, the double yielding phenomenon in PA6/TPV blends became more distinct, the yield stress of the first yield point and the yield stress difference of the two yield points decreased; however, the yield strain of the first yield point did not change with the increasing crosslinking degree of the TPV, but the yield strain of the second yield point increased, resulting in a more broadened yield region. The SEM results showed that with an increase in the crosslinking degree of TPV, the diameter of TPV increased in the core layer, and the orientation degree of TPV in the skin and subskin layer deceased, accompanying with a decrease of the ratio of length to diameter (L/D) of the droplets. The morphology evolution of the PA6/TPV blend during the tensile test was also studied, and the results agreed well with the model we proposed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 912–922, 2009     

Influence of composition on properties of nylon 6/EVOH blends

In this work, the relationships between composition and properties of Ny6/EVOH system were examined by means of several techniques and the results were interpreted in terms of level of compatibility. Blends of different ratio of Ny6 and EVOH have been processed in a laboratory‐based film blowing extrusion apparatus. Rheological measurements, FTIR and morphological analysis, and thermal and mechanical properties were carried out. Peculiar rheological, thermal, and mechanical behaviors were observed for the blend containing 25% by weight of EVOH. At this composition, FTIR analysis has pointed out that a minimum in molecular motion is achieved as a consequence of a maximum interaction of the polar groups (amide groups of Ny6 and hydroxyl groups of EVOH) involved. Moreover, gas permeability measurements on the blown films have been performed at T = 30°C. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2445–2455, 1999     

Investigation into the morphology,crystallization and melting behaviour of nylon 6,6/LCP blends

Journal of Thermal Analysis and Calorimetry - The morphology, isothermal crystallization and melting behaviour of melt-mixed nylon 6,6/Vectra A950 liquid crystalline polymer (LCP) blends were...     

Influence of processing method and components molecular structure on the phase behaviour of polyethylenes/dye blends

The phase dispersion of terthiophene alkyl derivatives on different polyethylene matrices was investigated. The PE affinity toward dichroic dyes with different structure, the effect of blending process and the influence of a polyolefinic compatibilizer on the homogeneity of host-guest blends were comparatively investigated by calorimetry, DSC and SEM analyses. For these purposes, polyethylenes with different molecular weights and densities and EVAc were used as host matrices. The polymeric compatibilizer was prepared by radical functionalization of a commercial low density polyethylene. The dichroic nature of the guest phase allowed to perform UV-Vis measurements in polarized light on oriented blend film samples. The dyes affinity toward PE is one of the key factor in obtaining oriented polyolefinic films with high optical performances for several applications.     

Dynamic mechanical properties of epoxy resin/epoxidized rubber blends: Effect of phase separated rubber

The dynamic mechanical properties of blends of diglycidyl ether of bisphenol-A-based epoxy resin and internally epoxidized polybutadiene rubber have been studied. It is shown that the influence of the composition of the continuous phase and of the dispersed phase can be studied not only from the variations of the glass transition temperature but also from the changes in the apparent enthalpy of activation associated with this transition. As the initial rubber content increases, the composition of the dispersed phase remains practically constant while more rubber is able to dissolve in the continuous phase. Analysis of the rubbery plateau region reveals that the shear modulus of the blends is not much affected by the presence of dissolved rubber in the continuous phase but strongly depends on the volume fraction of dispersed phase. This volume fraction can be obtained from the relative drop in shear modulus after modeling the results with the Kerner equation. The results compares well with independent measurements by scanning electron microscopy. © 1994 John Wiley & Sons, Inc.     

Thermal behaviour of styrene butadiene rubber/poly(ethylene-co-vinyl acetate) blends

The thermal behaviour of styrene butadiene rubber (SBR)/poly (ethylene-co-vinyl acetate) (EVA) blends was studied by using thermogravimetry (TG) and differential scanning calorimetry (DSC). The effects of blend ratio, cross-linking systems and compatibilization on the thermal stability and phase transition of the blends were analyzed. It was found that the mass loss of the blends at any temperature was lower than that of the components, highlighting the advantage of blending SBR and EVA. The addition of compatibilizer was also found to improve the thermal stability. DSC studies indicated the thermodynamic immiscibility of SBR/EVA system even in the presence of the compatibilizer. This is evident from the presence of two different glass transition temperatures, corresponding to SBR and EVA phases in both compatibilized and uncompatibilized blends.     

Investigation of phase morphology of incompatible polyethylene/nylon 6 blends containing EPDM-based functionalized compatibilizers

Graft copolymer and graft terpolymer were prepared by solution grafting of maleic anhydride (MAH) or acrylonitrile (AN) alone and mixture of MAH and AN on to ethylene–propylene–diene terpolymer (EPDM) using benzoyl peroxide (BPO) as an initiator. The resulting EPDM-g-MAH, EPDM-g-AN and EPDM-g-(MAH-co-AN) have been used to obtain a binary blend of Nylon 6/functionalized EPDM and a ternary blend of polyethylene/Nylon 6/functionalized EPDM by melt blending. The effects of the nature and the amount of the grafted species on the phase morphology, crystallization behavior and mechanical properties of the blends were characterized through scanning electron microscopy, optical microscopy, infrared spectroscopy and using a dynamic mechanical analyzer. From the morphological study, it can clearly be seen that the presence of the functionalized EPDMs in these blends resulted in an improvement of the dispersion degree in incompatible polyethylene/Nylon 6 blends.     

Influence of Fe‐MMT on crosslinking and thermal degradation in silicone rubber/clay nanocomposites

In this article, silicone rubber (SR)/clay nanocomposites were synthesized by a melt‐intercalation process using synthetic Fe‐montmorillonite (Fe‐MMT) and natural Na‐MMT which were modified by cetyltrimethyl ammonium bromide (CTAB). This study has been designed to determine if the presence of structural iron in the matrix can result in radical trapping and then enhance thermal stability, affect the crosslinking degree and elongation. The SR/clay nanocomposites were characterized by X‐ray diffraction (XRD) patterns and transmission electron microscopy (TEM). Exfoliated and intercalated nanocomposites were obtained. Thermo gravimetric analysis (TGA) and mechanical performance were applied to test the properties of the SR/clay nanocomposites. The presence of iron significantly increased the onset temperature of thermal degradation in SR/Fe‐MMT nanocomposites. The thermal stability, gel fraction and mechanical property of SR/Fe‐MMT were different from the SR/Na‐MMT nanocomposites. So the iron not only in thermal degradation but in the vulcanization process acted as an antioxidant and radicals trap. Copyright © 2006 John Wiley & Sons, Ltd.     

Influence of compatibilizer on the structure properties of polylactic acid/natural rubber blends

Polylactic acid (PLA) was toughened by 5–20 wt % of natural rubber (NR). Two different compatibilizers maleated PLA (PLA-g-MA) and maleated NR (NR-g-MA) were used as coupling agent. The blends were prepared using twin screw extruder at varying levels of NR. Mechanical, thermal and morphological analyses were carried out to study the effect of compatibilizer on PLA/NR blends compatibility.     

Coalescence in quiescent polymer blends with a high content of the dispersed phase

Coalescence in molten quiescent polymer blends induced by van der Waals forces is studied theoretically. Interaction between a droplet and its nearest neighbor keeping spherical shape during drainage of the matrix trapped between them is considered. It is assumed that droplets with time dependent radius R or effective droplets with radius R + h_c/2, where h_c is the critical inter-droplet distance for breakup of the matrix trapped between them, are randomly distributed in the blend through the whole course of the coalescence. Various approaches to calculation of the average time of coalescence, t_c (calculation with preaveraged distance between a droplet and its nearest neighbor at the start of coalescence, h₀, direct averaging of t_c and averaging coalescence frequency, 1/t_c) are compared. Calculated dependence of R on the time of coalescence, t, is compared with experimental results for polypropylene/ethylene–propylene rubber (PP/EPR) blends with EPR content from 15 to 30 wt.%. Calculations using average h₀ and direct averaging of t_c lead to more-less linear dependence of R³ on t. Bare averaging of 1/t_c leads to a steeper than linear dependence of R³ on t and to unreasonably high rate of the coalescence; averaging of 1/t_c with exclusion of pairs with elapsed coalescence time leads to decreasing rate of R³ growth but unreasonably low rate of coalescence. Theories based on the concept of effective droplet radius give smaller differences among various methods of calculations of t_c than the theories assuming random distribution of the droplets. Experimental results show decreasing slope of R³ vs. t dependence, especially for a higher content of dispersed EPR. Theories using average h₀ or direct averaging of t_c predict somewhat smaller rate of coalescence than that experimentally determined for PP/EPR blends. Reasons of these differences are discussed.     

Effect of dispersed phase composition on morphological and mechanical properties of PET/EVA/PP ternary blends

Immiscible ternary blends of PET/EVA/PP (PET as the matrix and (PP/EVA) composition ratio = 1/1) were prepared by melt mixing. Scanning electron microscope results showed core‐shell type morphology for this ternary blend. Binary blends of PET/PP and PET/EVA were also prepared as control samples. Two grades of EVA with various viscosities, one higher and the other one lower than that of PP, were used to investigate the effect of components' viscosity on the droplet size of disperse phase. The effect of interfacial tension, elasticity, and viscosity on the disperse phase size of both binary and ternary blends was investigated. Variation of tensile modulus of both binary and ternary blends with dispersed phase content was also studied. Experimental results obtained for modulus of PET/EVA binary blends, showed no significant deviations from Takayanagi model, where considerable deviations were observed for PET/PP binary blends. Here, this model that has been originally proposed for binary blends was improved to become applicable for the prediction of the tensile modulus of ternary blends. The new modified model showed good agreement with the experimental data obtained in this study. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 251–259, 2010     

Influence of electron beam irradiation on the impact properties of polystyrene/EPDM rubber blends

The influence of electron beam (EB) irradiation on the impact properties of compatibilized polystyrene/ethylene-propylene-diene-monomer (PS/EPDM) blends was studied. The change in impact value upon irradiation proved to be strongly dependent on the type of compatibilizer used. Using a polystyrene/polybutadiene (SB) diblock copolymer as a compatibilizer, a twofold increase in Izod value could be achieved upon irradiation. Irradiation of a blend using a polystyrene/ethylene-propylene (SEP) copolymer as a compatibilizer resulted in a decrease in impact strength. These observations can be related to a radiation induced increase in interfacial adhesion in case of the SB copolymer, which does not occur for the SEP copolymer. Due to the abundance of double bonds in the SB copolymer, this copolymer reacts very fast upon irradiation and may co-crosslink with, or graft onto the EPDM phase. For the SEP copolymer crosslinking occurs only at much higher doses and is (partly) overruled by chain scission and consequently the adhesion between matrix and dispersed phase will hardly change. This view is supported by analytical methods as FT-IR and NMR as well as from T_g measurements.     

Shapes of dispersed phase in confined PIB/PDMS blends with different compositions during shear flow

The morphology of immiscible fluid mixtures under confined environment usually displays different scenarios compared with those presented in bulk systems. In this work, the influence of confinement and component ratio on the droplet morphology of immiscible polyisobutylene (PIB)/polydimethylsiloxane (PDMS) blends in confined steady shear flow was investigated. While increasing the degree of confinement, the morphology of dispersed phase experienced a transition from the bulk behavior toward the confined behavior. Increasing the concentration of PIB phases in confined blends resulted in more coarsened structure under low shear rate and generated pearl necklace or string-like structures under a higher shear rate. The maximum aspect ratio of PIB droplets increased while increasing PIB concentration. The width and the aspect ratio of PIB droplets obtained experimentally were compared to the predictions of a single droplet MM model for bulk flow and an M model considering confinement. The experimental droplet width agreed well with the predictions of these two models only in the small droplet zone, large deviations appeared for the degree of confinement up to 0.36 and higher, whereas constant droplet width was found. The M model decreased the deviation between the experimental aspect ratio and the prediction of MM model in the high Ca zone. Good agreement between the prediction of M model and experiment results was found when the orientation angles of the droplets were corrected by using the M model.     

The effect of mesogenic and non-mesogenic crosslinking units on the phase behaviour of side-chain smectic and cholesteric elastomers

Chiral monomer (M₁ ), mesogenic and non-mesogenic crosslinking agents (C₁ and C₂ ), and the corresponding liquid crystalline elastomers (P₁ and P₂ series), have been synthesised. Their chemical structures have been characterised by Fourier transform infrared or ¹H nuclear magnetic resonance and their phase behaviour investigated by differential scanning calorimetry, polarising optical miscoscopy, thermo-gravimetric analysis (TGA) and X-ray diffraction. The effect of the crosslinking unit on the phase behaviour of the elastomers has been studied. M₁ showed a cholesteric oily streak and focal conic texture. C₂ exhibited a nematic enantiotropic thread-like and schlieren texture, and a monotropic fan-shaped texture in the S_A phase. Due to the introduction of the mesogenic crosslinking unit, elastomers, P_2-1 ?P_2-5 , exhibited a cholesteric phase, while elastomers, P_1-1 ?P_1-4 , derived from a non-mesogenic crosslinking unit, exhibit a S_A phase. As the content of the crosslinking unit increased, the T _g of the P₁ series initially decreased and then increased, and the T _i of the series decreased. In the P₂ series the T _g increased, but the T _i initially increased and then decreased. TGA confirmed that all the elastomers had improved thermal stability.     

Radiation effect on properties of carbon black filled NBR/EPDM rubber blends

Rubber blend of acrylonitrile butadiene rubber (NBR) and ethylene-propylene diene monomer (EPDM) rubber (50/50) has been loaded with increasing contents, up to 100 phr, of reinforcing filler, namely, high abrasion furnace (HAF) carbon black. Prepared composites have been subjected to gamma radiation doses up to 250 kGy to induce radiation vulcanization under atmospheric conditions. Mechanical properties, namely, tensile strength (TS), tensile modulus at 100% elongation (M₁₀₀), and hardness have been followed up as a function of irradiation dose and degree of loading with filler. On the other hand, variation of the swelling number as a physical property, as a function of same parameters, however, in car oil as well as brake oil has been undertaken. In addition, the electrical properties of prepared composites, namely, their electrical conductivity, were also evaluated. The thermal behavior of the prepared composites was also investigated. The results obtained indicate that improvement has been attained in different properties of loaded NBR/EPDM composites with respect to unloaded ones.     

Influence of size reduction of crosslinked rubber particles on phase interface in dynamically vulcanized poly (vinylidene fluoride)/silicone rubber blends

In this paper, the influence of rubber particle size on the phase interface in dynamically vulcanized poly(vinylidene fluoride)/silicone rubber (PVDF/SR) blends without any modifier is discussed through the studies of specific surface of crosslinked SR particles, crystallization behavior and crystal morphology of the PVDF phase, interfacial crystallization, melt rheological behavior and mechanical properties of blends. A series of decreased average particle size was successfully obtained by control of rotor rate. It was found that properly high rotor rate helped to achieve a reduced particle size and a narrowing size distribution. The reduced SR particle size enlarged the PVDF/SR interface which has a positive effect on the interfacial crystallization and the melt rheological behavior. At high SR content, the negative effect of the poor interface interactions played the dominate role on determining the mechanical properties. However, the blend exhibited a unique stiffness-toughness balance at the PVDF/SR = 90/10. We hope that the present study could help to lay a scientific foundation for further design of a useful PVDF/SR blend with promoted properties to partly replace the high-cost synthetic fluorosilicone materials.     

A SAXS and swelling study of cured natural rubber/styrene–butadiene rubber blends

A small‐angle X‐ray scattering (SAXS) and swelling study of natural rubber and styrene–butadiene rubber blends (NR/SBR) is presented. To this aim, specimens of NR and SBR and blends with 75/25, 50/50, and 25/75 NR/SBR ratios (in phr) were prepared at a cure temperature of 433 K and the optimum cure time (t₁₀₀). This time was obtained from rheometer torque curves. The system of cure used in the samples was sulfur/n‐t‐butyl‐2‐benzothiazole sulfenamide. From swelling tests of the cured samples, information about the molecular weight of the network chain between chemical crosslinks was obtained. For all cured compounds, in the Lorentz plots built from SAXS scattering curves, a maximum of the scattering vector q around 0.14 Å^?1 was observed. However, the q position shows a linear‐like shift toward lower values when the SBR content in the SBR/NR blend increases. In pure NR or SBR the q values show a different tendency. The results obtained are discussed in terms of the existence of different levels of vulcanization for each single phase forming the blend and the existence of a third level of vulcanization located in the interfacial NR/SBR layer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2320–2327, 2009     

Characterization of multiphase polymer system nylon 6/ABS blends

Seven different ratios of blends from nylon 6 and acrylonitrile — butadiene — styrene (ABS) were prepared by melt blending. Thermal analysis of these blends was carried out by DSC and TG. It has been observed that blend ratios such as 50/50, 40/60, 25/75 and 15/85 of nylon 6/ABS were having more compatibility in comparison with other blends. It is evident from the study of glass transition temperature, melting point, heat of fusion, change of crystallinity and activation energy values. Thermogravimetric analysis shows a decreasing trend of pyrolysis temperature of these blends with the increase in ABS concentration. Melt flow index and density data are found to indicate better physical and flow characteristics in blends compared to pure nylon 6.

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Zusammenfassung Durch Mischschmelzen wurden Gemische aus Nylon 6 und Acrylnitril-Butadien-Styrol (ABS) mit sieben verschiedenen Zusammensetzungen hergestellt. Mittels DSC und TG wurde eine Thermoanalyse dieser Gemische durchgeführt. Es konnte festgestellt werden, daß Gemische mit Nylon 6/ABS Verhältnissen von 50/50, 40/60, 25/75 und 15/85 im Vergleich zu anderen Gemischen eine größere Kompatibilität besitzen, was aus der Betrachtung von Schmelzpunkt, Schmelzwärme und der Veränderung der Kristallinität und der Aktivierungsenergiewerte eindeutig hervorgeht. TG zeigt für die Pyrolysetemperatur dieser Gemische mit zunehmendem ABS-Gehalt eine sinkenden Tendenz an. Der festgestellte Schmelzindex und die gefundenen Dichtewerte weisen im Vergleich zu reinem Nylon 6 auf bessere physische und Fließeigenschaften hin.

     

Influence of structure on the impact behaviour of nylon-rubber blends

Blends of nylon-6 and EPDM rubber were prepared by reaction blending to study the influence of rubber concentration, rubber particle size and interfacial adhesion on the impact strength. Rubber particles induce a sharp brittle-tough transition which is independent of the glass transition of the nylon matrix. Increasing the rubber concentration or decreasing the particle diameter shifts the brittle-tough transition temperature for notched Izod impact tests to lower values. A toughening mechanism is proposed in which the interparticle distance, the rubber modulus and the temperature play crucial roles.     

Studies on phase morphology and thermo-physical properties of nitrile rubber blends

The study deals with the morphological and thermal analysis of binary rubber blends of acrylonitrile-co-butadiene rubber (NBR) with another polymer. Either ethylene propylene diene terpolymer (EPDM), ethylene vinyl acetate (EVA), chlorosulphonated polyethylene (CSM), or polyvinyl chloride (PVC) has been selected for the second phase. Depending on the relative polarity and interaction parameter of the components, the binary blends showed development of a bi-phasic morphology through scanning electron microscopy (SEM). Use of different types of thermal analysis techniques revealed that these blends are generally incompatible excepting one of NBR and PVC. Derivative differential scanning calorimetry (DDSC), in place of conventional DSC, has been used to characterize the compatibility behavior of the blends. NBR–PVC shows appearance of only one glass transition temperature (T _g) averaging the individual T _g’s of the blend components. The partially missible blend of NBR and CSM shows a broadening of T _g interval between the phase components, while the immiscible blends of either NBR–EPDM or NBR–EVA do not show any change in T _g values corresponding to the individual rubbers of their blend. The experimental T _g values were also compared with those calculated theoretically by Fox equation and observed to match closely with each other. Studies have also been made to evaluate the thermal stability of these blends by thermo-gravimetric analysis (TG) and evaluation of activation energy of respective decomposition processes by Flynn and Wall method. Thermo-mechanical analysis (TMA) was found to be effective for comparison of creep recovery and dimensional stability of the blends both at sub-ambient as well as at elevated temperatures.