On the mechanism of compatibilization of polyolefin/liquid crystalline polymer blends with graft copolymers

The compatibilization mechanism of some compatibilizers for blends of polyolefins with a liquid crystalline polymer (LCP) was studied. Polyethylene (PE) and polypropylene (PP) were blended with a semirigid LCP (SBH) in a batch mixer, either with and without compatibilizers. The latter were two commercially available samples of functionalized polyolefins, that is, a PE‐g‐MA (HDM) and a PP‐g‐AA (Polybond 1001) copolymer and some purposely synthesized PE‐g‐LCP and PP‐g‐LCP copolymers. Microtomed films of the binary and the ternary blends were annealed at 240°C on the hot stage of a polarizing microscope and the changes undergone by their morphology were recorded as a function of time. The results indicate that the compatibilizers lower the interfacial tension, thereby providing an improvement of the minor phase dispersion. In addition to this, the rate of the coalescence caused by the high‐temperature treatment is appreciably reduced in the systems compatibilized with the PE–SBH and PP–SBH graft copolymers. Among the commercial compatibilizers, only Polybond 1001 displayed an effect comparable to that of the above copolymers. HDM improved the morphology of the as‐prepared PE blends, but failed to grant sufficient morphological stabilization against annealing‐induced coarsening. The results are discussed with reference to the chemical structure of the different compatibilizers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3027–3034, 2000     

Dielectric spectroscopy using dielectric probes: a new approach to study glass transition dynamics in immiscible apolar polymer blends

Dielectric relaxation spectroscopy using dielectric probes was applied to study the (glass transition) dynamics in binary blends of isotactic PP, PS and LDPE. The blends were prepared by melt-mixing and doped with 0.5% of the dielectric probe 4,4′-(N,N-dibutylamino)-(E)-nitrostilbene (DBANS) (van den Berg O, Sengers WGF, Jager WF, Picken SJ, Wübbenhorst M. Macromolecules 2004;37:2460. [17]). Due to the selective amplification of the dielectric relaxation processes related to the dynamic glass transition of the polymers, accurate relaxation data were obtained, even for the minor phases. No substantial influence of the blend composition and the blend morphology on the glass transition dynamics was found, indicating that both blend constituents behave like homogeneous bulk materials. The normalised relaxation strength of glass transition processes remained constant, regardless of the blend type and blend composition. This indicates that the probe molecule, DBANS, was equally distributed over the two blend components in all three polymer combinations PE-PP, PE-PS and PP-PS.     

Heat capacity of polymer melts from the polymer chain-of-rotators equation of state

Recently, the chain-of-rotators equation of state derived from the rotational partition function was extended to polymers. Values of the three equation of state (EOS) parameters were obtained from fitting with experimental pressure–volume–temperature data and the parameters were correlated with the structure of the polymer repeat unit. In this article, the residual molar heat capacity derived from an EOS is added to the ideal gas heat capacity from Benson's group contribution method to obtain the polymer molar heat capacity at constant pressure, C_p. Predictions from the polymer chain-of-rotators (PCOR) using correlated parameters are compared with those obtained from PCOR, Sanchez–Lacombe, Flory–Orwoll–Vrij, and the perturbed-hard-sphere chain equations of state using parameters fitted from experimental data. Deviations of calculated C_p from the formula of van Krevelen for liquid polymers are likewise presented. With the correlations developed for its parameters, the PCOR offers the advantage of predicting the C_p for polymer melts from just the knowledge of the polymer's structure. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:841–848, 1998     

Reactive compatibilization of blends of polybutyleneterephthalate with epoxide-containing rubber. The effect of the concentrations in reactive functions

The influence of the functional groups concentrations on the reactive compatibilization of polybutylene terephthalate (PBT)/epoxide-containing rubber blends has been investigated by using various PBT and ethene-(methyl acrylate)-(glycidyl methacrylate) terpolymer (E-MA-GMA) grades. The reactivity of the rubber phase was modified using different strategies, including the use of commercial terpolymer grades, modification of E-MA-GMA or diluting E-MA-GMA terpolymers with non-reactive ethene-(methyl acrylate) (E-MA) copolymer. The reactive blends were analyzed amongst others by electron microscopy and fractionation experiments. It was shown that the final particle size is directly related to the amount of copolymer formed in situ at the blend interface, i.e. chain area density Σ. A value of approximately 0.05 chains/nm² for Σ is necessary to suppress dynamic coalescence and to obtain very fine dispersion (<0.2 μm). This requires a sufficiently high concentration in reactive functions at the interface vicinity. In this context, the time required for equilibrium morphology is rather independent of the GMA content in the terpolymer but is, however, intimately related to the PBT chain ends concentration. Investigation of PBT/(E-MA-GMA/E-MA) ternary blends revealed unambiguously that the formation of the copolymer at the interface is not controlled by the diffusion of the reactive chains towards the interface. The performed experiments offer new opportunities for modulating the final morphology and the properties of the PBT/rubber blends.     

Reinforcement of the interface in drawn polymer blends PS/PA‐12

The origin of the reinforcement effect in uniaxially drawn films on the basis of immiscible blends composed of crystalline matrix of polyamide‐12 (PA) and glassy polystyrene (PS) dispersed phase has been investigated. Other conditions being equal, the effect becomes the more pronounced the lager the draw ratio and the finer the PS dispersion. Since the latter factor is itself a strong function of phase viscosity ratio (μ), the following two techniques of adjusting the optimal value of μ ≈ 1 have been adopted. According to the first one, a selective plasticizer, which is a good solvent for the PS minor phase and a nonsolvent for the PA matrix phase, was added to the more viscous PS. According to the second approach, the value of μ was varied by the use of PS samples of different molecular weights. It was shown that significant reinforcement effect appears on drawing regardless of the method of adjusting optimal phase viscosity ratio. These data as well as the results obtained with the help of IR‐dichroism and transmission electron microscopy techniques evidence that the formation of a much more ordered crystalline morphology of the PA matrix located at the PS/PA interfaces and a large interface area are mainly responsible for the discussed reinforcement phenomenon. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1299–1305, 2007     

Effect of polymer-filler surface interactions on the phase separation in polymer blends

For the blends of chlorinated polyethylene and copolymer of ethylene with vinyl acetate, the effect of the introducing filler (fumed silica) on the phase behavior of the blends was investigated. It was found that introducing filler in polymer blends depending on its amount lead either to the increase or to the decrease in the temperature of phase separation. At the filler concentration where both components transit into the state of a border layers, the phase separation temperature increases. This effect was explained by the change of the total thermodynamic interaction parameter in the ternary system polymer-polymer-filler. At lower concentration of a filler, the possible effect is the redistribution of the blend components according to their molecular masses between filler surface (in the border layer) and in the bulk that may diminish the phase separation temperature.Effect of the filler on the phase behavior was explained by the simultaneous action of two mechanisms: by changing the thermodynamics of interaction near the surface due to selective adsorption of one of the components and by the redistribution of components according to their molecular masses between the boundary region (near the surface) and in the matrix.The measurements of the kinetics of phase separation and calculation of the parameters of the activation energy are in agreement with proposed mechanisms.     

Effect of additives on the composition dependent glass transition variation in PS/PP blends

The effect of additives on glass transition behavior in melt processed blends of polystyrene (PS) and polypropylene (PP) was studied. Blends of additive‐free polystyrene and additive‐free polypropylene revealed the known effect of the PS T_g increase in blend compositions where PP surrounds PS. Glass transition behavior in these blends was compared to blends prepared from additive‐free PP and commercial grade PS, which contained lubricant additives. The thermal transitions of PS and PP were measured using modulated DSC. Although the behavior of low PS concentration blends was similar in both systems, the characteristics of the high PS blends differed substantially. These differences and the contrast in the PP T_g behaviors were attributed to the migration of additives from the PS phase across the immiscible interface into the PP phase. Similar T_g variations were observed in blends of commercial grade PS and commercial grade PP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Composition and molecular-weight dependence of the glass transition in polystyrene-poly(2,6-dimethylphenylene ether) blends

The glass transition behaviours of a series of poly(2,6-dimethylphenylene ethers) with various molecular weights and their blends with polystyrene have been studied. The data are analysed according to the Fox-Flory equation (M_n dependence) and the Gordon-Taylor equation (composition dependence). A more rigorous treatment according to the theory developed by Kanig is presented and data of polystyrene-poly(vinyl methyl ether) blends, as well as polystyrene-poly(methyl vinylether) blends which do not obey the Gordon-Taylor equation, are discussed in the framework of this theory. The theory allows the estimation of the energy required to separateA-B contacts.     

Conjugated effects of the compatibilization and the dynamic vulcanization on the phase inversion behavior in poly(butylene terephthalate)/epoxide-containing rubber reactive polymer blends

The conjugated effects of both reactive compatibilization and dynamic vulcanization on the phase inversion behavior of poly(butylene terephthalate) (PBT)/epoxide-containing rubber blends have been studied in detail. Pure ethylene-methyl acrylate random copolymer (E-MA) and ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (E-MA-GMA) were used as non reactive or reactive rubber phase, respectively. Location of the phase inversion region was studied using several techniques, including transmission electron microscopy (TEM) and dynamical mechanical thermal analysis (DMTA). To evaluate the relative influence of the blend compatibilization and the dynamic vulcanization on the phase inversion behavior, the relative kinetics of the two reactions were modified using different PBT and E-MA-GMA grades. The obtained results show unambiguously that the position and the width of the phase inversion region is essentially governed by the kinetic of the dynamic vulcanization process. The effect of the blend compatibilization remains quite limited even in the case of fast interfacial reaction. The crosslinking of the rubber phase induces an important shift of the phase inversion composition to higher rubber content. For blends containing low molecular weight PBT, up to 60 wt% of rubber can be homogeneously dispersed in the PBT matrix at long mixing time. In this case, development of high performance PBT based thermoplastic vulcanisates can be envisioned.     

A study about the structure of vulcanized natural rubber/styrene butadiene rubber blends and the glass transition behavior

A study of the thermal behavior of cured elastomeric blends of natural rubber (NR) and styrene butadiene rubber (SBR) prepared by solution blending in toluene is presented. Binary blends with different compositions of NR/SBR were produced using a conventional cure system based on sulfur and TBBS (n-t-butyl-2-benzothiazole sulfonamide as accelerator. The compounds were vulcanized at 433 K up to an optimum time of cure determined by rheometric tests. From swelling tests, the crosslink densities of the compounds were obtained and compared with those obtained in similar blends prepared by mechanical mixing. The results were analyzed in terms of the disentangling of the chain structures of the SBR and NR phases and the achieved cure state of the blend. Using differential scanning calorimetry, the glass transition temperature T_g of each blend was measured. In most compounds, the value of T_g corresponding to each phase of the blend was determined, but in some blends a single value of T_g was obtained. The variation of T_g with the composition and cure level in each phase was analyzed. On the other hand, a physical mixture of two equal parts of NR and SBR vulcanized was measured and the results were compared to those of the NR50/SBR50 cured blend. Besides, to analyze the influence of the network structure, pure NR and SBR unvulcanized samples were measured. On the basis of all the obtained results, the influence of the interphase formed in the blend between SBR and NR phases is discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A preliminary study of the dynamics of phase separation in oligomeric polystyrene-polybutadiene blends

We report here the preliminary results of a study of the kinetics of spinodal decomposition in an oligomeric blend, polystyrene with polybutadiene using small angle light scattering. The data are compared with the theoretical predictions of Cahn-Hilliard and van-Aartsen. The results corroborate the position of the critical point as determined by the pulse induced critical scattering technique.     

Effects of the dispersion state and aspect ratio of carbon nanotubes on their electrical percolation threshold in a polymer

The electrical percolation threshold of carbon nanotubes (CNTs) is correlated with their dispersion state and aspect ratio through modeling. An analytical percolation model based on excluded volume theory and developed for systems containing two types of fillers is used. CNTs are modeled as two types of fillers: single CNT and m‐CNT bundle, and a variable P representing the dispersion state of CNTs is introduced. An equation showing the effects of the dispersion state and aspect ratio on the electrical percolation threshold of CNTs is established and verified with some of the published experimental data. It is useful for predicting the conductive behavior of polymer/CNT composites and for the design of their processing conditions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphological study of two‐phase polymer blends during compounding in a novel compounder on the basis of elongational flows

A new laboratory‐scale mixing device based on an original concept was built and tested. This device has important technical features such as tightness to liquids and gases, the possibility of direct specimen molding after mixing, and easy handling of reactive systems. In comparison with existing laboratory mixers, the flow in this mixer is characterized by a high contribution from elongational flow. Morphological data on model polystyrene/poly(methyl methacrylate) blend systems have proved the high distributive and dispersive mixing efficiency in comparison with a classical rotational batch mixer. The influence of different experimental parameters such as the flow rate, mixing time, mixing element geometry, and viscosity ratio of blends is characterized and discussed. Much finer dispersions have been obtained with this new device versus those obtained with a conventional mixer with equivalent specific energy input. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A calorimetric study of the interchange reactions in bisphenol a polycarbonate/nylon-6 blends

The interchange reactions in a partially miscible blend composed of bisphenol A polycarbonate and nylon-6 have been studied by the use of a calorimetric technique. It has been found that these reactions affect the thermal transitions of the mixtures. These effects have been interpreted to be a consequence of the progressive formation of copolymers which homogenize the mixture.     

Enhancing the crystallinity and heat resistance of poly(ethylene terephthalate) using ZnCl2-ionized polyamide-66 as a heterogeneous nucleator

To achieve the maximal improvement in the crystallization rate and heat resistance of poly(ethylene terephthalate) (PET), 2.6 mol% of ZnCl₂ ionized polyamide (PA)-66 (PA-66–Zn), with a strong coordination ability, is prepared and used as PET nucleator. This study found that the PA-66–Zn heterogeneously nucleates PET more effectively than the CaCl₂-ionized PA-66 and non-ionized PA-66 by differential scanning calorimetry, crystallization kinetics, X-ray diffraction, and polarized optical microscopy. This is probably a result of the introduction of stronger ion–dipole interactions (IDIs) between the PET esters and the ionized-PA-66 ZnCl₂-coordinating amides, which obviously heightens the PET/PA-66–Zn interfacial compatibility. As shown by scanning electron microscopy, the compatibilization through an appropriate concentration of IDIs promotes the formation of smaller and denser PA-66 crystals with immensely increased nucleator efficiency. Furthermore, the PET/PA-66–Zn with significantly improved crystallinity displays a remarkable increase in heat-resistant temperature, at 21.6 and 55.1°C higher than that of PET/PA-66 and PET, respectively. The results demonstrate that the PA-66–Zn can act as a superior nucleator and as an outstanding heat-resistant agent for PET.     

Effect of the molecular structure of ethene–propene and styrene–butadiene copolymers on their compatibilization efficiency in low‐density polyethylene/polystyrene blends

The effect of the molecular structure of styrene–butadiene (SB) block copolymers and ethene–propene (EPM) random copolymers on the morphology and tensile impact strength of low‐density polyethylene (LDPE)/polystyrene (PS) (75/25) blends has been studied. The molecular characteristics of SB block copolymers markedly influence their distribution in LDPE/PS blends. In all cases, an SB copolymer is present not only at the interface but also in the bulk phases; this depends on its molecular structure. In blends compatibilized with diblock copolymers, compartmentalized PS particles can also be observed. The highest toughness values have been achieved for blends compatibilized with triblock SB copolymers. A study of the compatibilization efficiency of SB copolymers with the same number of blocks has shown that copolymers with shorter PS blocks are more efficient. A comparison of the obtained results with previous results indicates that the compatibilization efficiency of a copolymer strongly depends both on the blend composition and on the properties of the components. The compatibilization efficiency of an EPM/SB mixture is markedly affected by the rheological properties of the copolymers. The addition of an EPM/SB mixture containing EPM with a higher viscosity leads to a higher improvement or at least the same improvement in the tensile impact strength of a compatibilized blend as the same amount of neat SB. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Measurement of the thermal diffusivity and specific heat capacity of polyethylene foams using the transient plane source technique

Thermal diffusivity and specific heat at constant pressure of a collection of crosslinked closed cell polyethylene foams have been measured at room temperature using the transient plane source (TPS) method. A theoretical model to predict the thermal diffusivity has been proposed. The predictions of this model are in good agreement with the observed experimental trends. The theoretical model predicts a dependence of the thermal diffusivity on the density and other foam characteristics such as carbon black content and cell size. Copyright © 2004 Society of Chemical Industry     

A morphological study on the dispersion and selective localization behavior of graphene nanoplatelets in immiscible polymer blends of PC and SAN

In this morphological study the dispersion and localization behavior of 1 wt.% graphene nanoplatelets (GnPs) in melt mixed co-continuous polymer blends of polycarbonate (PC, 59 wt.%) and poly(styrene-acrylonitrile) (SAN, 40 wt.%) were investigated. Through varying the mixing sequence as well as the melt mixing parameters, different states of dispersion and different filler localizations were achieved. Melt mixing in a one-step process resulted in the poorest dispersion of the GnPs in the polymer blend. In this case, the filler could hardly be found localized selectively in one of the polymer components but formed its own component. In two-step mixing processes the GnPs were either premixed in PC or SAN to investigate the assumed filler transfer from the SAN into the PC component. Four different premixtures were prepared which showed that longer mixing time and higher rotation speed resulted in better dispersion of the GnPs in the polymer matrix. If the GnPs were predispersed in PC they could still be found in the PC component after blending with SAN. In the case that the GnPs were premixed in SAN, the filler was detected partially in the SAN or at the blend interface, as well as smaller sized particles were found in the PC component. It could be shown that the size and aspect ratio of the filler play a significant role on the localization of GnPs in melt mixed polymer blends.     

The kinetics of the α relaxation in an amorphous polymer at temperatures close to the glass transition

The kinetics of the α relaxation of a crosslinked copolymer of acrylonitrile and butadiene (T_g = ?7°C) were studied in the temperature range (T_g + 17°C) down to (T_g ? 8°C). The techniques used were shear creep analysed by time-temperature (t-T) superposition and thermal sampling (TS) with correction procedures proposed by McCrum. In this range the kinetics do not follow the compensation rule, as had been proposed in the pioneering TS experiments by Zielinski, Swiderski and Kryszewski and by Lacabanne et al.. The McCrum correction removes a discrepancy between the pioneering TS experiments and the conclusions of classical t-T superposition experiments. The methods of TS and t-T superposition are compared. At low temperatures, below (T_g + 3°C), the TS method is superior: t-T superposition is unreliable due to lack of normalization and to the physical ageing perturbation. At temperatures from (T_g + 3°C) to (T_g + 11°C) t-T superposition is highly reliable since normalization is not required and there is no ageing. At temperatures above (T_g + 11°C) the precision of t-T superposition depends on the validity of the normalization procedure. It has yet to be determined whether or not the compensation rule applies at temperatures below (T_g ? 8°C): the method most likely to settle this important question is TS, mechanical or dielectric variant, with McCrum correction for the distribution of relaxation times.