Morphologies and properties of plasticized starch/polyamide compatibilized blends

A new sodium carboxymethylcellulose (CMC) compatibilized glycerol-plasticized starch/polyamide PA11 blend having improved mechanical properties was realized in a one step extrusion process. Blends were prepared in internal mixer and twin screw extruder. Mechanical properties (stress and strain at break) are improved by adding 1 wt% of CMC. Rheological characterization and scanning electron microscopy show that a co-continuous morphology is observed on a wide range of TPS amount.     

Compatibility effect on the thermal degradation behaviour of polypropylene blends with polyamide 6, ethylene propylene diene copolymer and polyurethane

The morphology and thermal behaviour of polypropylene/polyamide 6 (PP/PA6), polypropylene/copolymer ethylene propylene diene (PP/PEBAX) and polypropylene/rigid polyurethane (PP/PUR) blends compatibilised with polypropylene-graft-maleic anhydride (PP-g-MA) were studied using scanning electron microscopy and thermogravimetric analyses. The study focuses on the influence of different blends obtained by mixing a thermoplastic, thermoplastic elastomer or thermoset with PP, compatibilised with PP-g-MA. The compatibilising effect of PP-g-MA in an immiscible PP/PA6 blend induces a homogeneous dispersion due to interfacial adhesion. For the PP/PEBAX and PP/PUR binary blends studied slight changes in the morphology were observed with a continuous phase but the PEBAX or PUR domains remained in the PP matrix. The deconvolution of the TGA curve permitted an evaluation of the decomposition stage of the undiluted and blend systems. Thermal stability is slightly influenced by the position of the maximum decomposition rate temperature of the first derivative thermogravimetric curve (DTG). However, the DTG curve profile remains consistent. The activation energy of undiluted PP was in the range of 162–169 kJ mol⁻¹ determined by the Ozawa method. The stabilized activation energy value for all blends studied above a 0.4 weight-loss fraction is discussed.     

Nanostructured carbon black filled polypropylene/polystyrene blends containing styrene-butadiene-styrene copolymer: Influence of morphology on electrical resistivity

This paper is part of a comprehensive study on using selective localization of carbon black (CB) at the interface of immiscible polymer blends in order to reduce the percolation threshold concentration and enhance the conductivity of the blends. CB was successfully localized at the interface of polypropylene/polystyrene (PP/PS) blend by introducing styrene-butadiene-styrene (SBS) tri-block copolymer to the blend. In CB-PP/PS/SBS blends, CB has higher affinity for the polybutadiene (PBD) section of the SBS copolymer, whereas in CB-PP/PS blends, CB prefers the PS phase. PP/PS interface is one of the preferred locations for the SBS copolymer in the (PP/PS) blend; at which the PBD section of the SBS copolymer forms a few nanometers thick layer able to accommodate the CB nano-particles. The influence of SBS addition on the morphology and electrical properties of various PP/PS blends filled with 1 vol% CB were studied. SBS influence on the conductivity of PP/PS blends was found to be a function of the PP/PS volume ratio and SBS loading. The most dramatic increase in conductivity was found in the (60/40) and (70/30) PP/PS blends upon the addition of 5 vol% SBS. 5 vol% SBS was found to be the optimum loading for most blends. Using 10 vol% of SBS was reported to deteriorate electrical conductivity of the conductive co-continuous PP/PS blends. For all blends studied, SBS addition was found to compatibilize the blends. Finer morphologies were obtained by increasing SBS loading.     

Films on amorphous polyamide nanocomposites: structure and properties

The ability of a nanoclay to improve the transport and mechanical properties of amorphous polyamide (aPA)‐based films was studied as a function of the draw ratio (DR) and the nanoclay content. The presence of nanoclay did not hinder the drawing ability as the maximum DR of the nanocomposites (NCs) and of the aPA were almost the same (51 for the aPA and from 51 to 55 for the NCs). The high degree of exfoliation and orientation along the drawing direction led to a 30% reduction in the water diffusion coefficient compared with the aPA. Moreover, the already low permeability of the aPA to oxygen was halved. The modulus of elasticity presented unusual increases both in the machine and transverse directions. Both increases of properties were attributed to the planar geometry of the oriented nanoclay sheets. The effects of the presence of nanoclay on the modulus of elasticity in the draw direction in addition to the effects caused by drawing lead to a combined modulus increase of 65% in the highly drawn 6%NC films. The nanoclay also reduced the modulus anisotropy of the films. An increase in either the nanoclay content or the DR causes a decrease in ductility due to both the stress concentrations created by the nanoclay and to the increasing number of chain segments located parallel to the drawing direction. The dimensional stability of the films greatly increased as the addition of 6% nanoclay led to a 70% decrease in creep deformation after 120 h. Copyright © 2012 John Wiley & Sons, Ltd.     

Role of monomer structure and compressibility on the properties of multicomponent polymer blends and solutions

Summary The lattice cluster theory of corrections to Flory-Huggins theory is applied to binary compressible blends (at a pressure of one atmosphere) that are formed by polymers having structured monomers. Calculations are performed in the high molecular weight limit for the dependence of the small angle neutron scattering effective interaction parameter _eff on composition ₁, monomer structure, microscopic interaction energies, and temperature. The limiting high molecular weight _eff (₁) curves have an overall general parabolic behavior with center, curvature, and magnitude that vary significantly with monomer structures and with interaction energies. The latter variation is stronger and occurs even at constant Flory-Huggins interaction parameter _FH ¹² where incompressible blend models cannot describe the strong dependence on the self-polymer-polymer-interactions obtained here. A quasi-athermal limit, in which _eff (₁) is nearly temperature independent, appears for high molecular weights only when _FH ¹² is vanishingly small. Phase diagrams are studied by evaluating the cloud points for coherent scattering from binary blends. Blends with negative _FH ¹² have only a LCST, but ones with positive _FH ¹² may have closed loop phase diagram or both LCST and UCST. However, one of the latter two critical points may be unobservable due to an intervening glass transition or because of thermal degradation.     

Solid-state morphology,structure, and tensile properties of polyethylene/polyamide/nanoclay blends: Effect of clay fraction

The effect of nanoclay fraction on the linear and non-linear tensile properties of a polyethylene/polyamide 12 blend with droplet morphology was investigated. All ternary blends were prepared at a fixed polyamide (PA) weight fraction of 20%, and at clay volume fractions varying from 0.5 to 2.5% relative to PA. Scanning electron microscopy and transmission electron microscopy were used to characterize the morphology of the blends and the clay interphase structure. The nanoclay content was shown to strongly influence both linear and non-linear tensile properties. Young's modulus, elongation at yield, yield strength, tensile strength and elongation at break as a function of clay fraction were studied and discussed in terms of morphological changes and strain-induced structural reorganization of the clay interphase.     

Crystal forms and ferroelectric properties of poly(vinylidene fluoride)/polyamide 11 blends prepared by high‐shear processing

Nanostructured poly(vinylidene fluoride) (PVDF)/polyamide 11 (PA11) blends have been melt‐processed using a high‐shear extruder. Uniaxially oriented blended films were fabricated by hot rolling to prepare ferroelectic films. The effects of rolling temperature and draw ratio on the crystal forms of both PVDF and PA 11 were investigated by means of Fourier transform infrared spectra (FTIR) and wide‐angle X‐ray diffraction (WAXD). It was shown that hot rolling in the range of 25–110 °C results in the crystal form transformation from the nonpolar α‐form into the polar β‐form for PVDF. The content and orientation function of β‐crystallites are strongly dependent upon the rolling temperature and the draw ratio. The highest content of well‐oriented β‐crystallites was achieved with a draw ratio of 4.0 upon rolling at 80 °C. At the same time, the content of the α‐form of PA11 in the blend was also found to decrease by hot rolling. The ferroelectric properties (D‐E hysteresis) of the oriented blended films were measured. The remanent polarization of the PVDF/PA11 = 90/10 blend is as high as 91 mC/m², which is about 1.2 times higher than that of pure PVDF. The D‐E hysteresis curves and the temperature dependence of the piezoelectric stress coefficients of the high‐shear‐processed sample suggested that the formation of nano‐dispersed structures resulted in the improvement of the remanent polarization and thermal characteristics at a temperature higher than 80 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2707–2714, 2007     

Investigations on the cure chemistry and polymer properties of benzoxazine-cyanate ester blends

Thermosetting polymer blends composed of bisphenol A based benzoxazine (BA-a) and cyanate ester (BACY) were prepared via co-curing of benzoxazine with cyanate ester. DSC results manifested a multiple curing pattern with associated heat of reaction implying a co-reaction between oxazine moiety and cyanate group. The catalysis during the co-curing of blend was ascribed to the cycloaddition reaction between the two groups followed by the ring-opening of benzoxazine and cyclotrimerisation of cyanate ester. The spectral and analytical data supported the possibilities of further polymerization through the insertion of the phenolic OH of polybenzoxazine to cyanate group to form the intermediate iminocarbonate, which further induce curing of cyanate ester to form polycyanurate. A co-reacted network composed of triazine ring as a part of polybenzoxazine matrix is postulated. The co-reaction temperature diminished with increase in cyanate ester content in the blend. A single T_g was observed in DMTA of the cured matrix that implied a linked homogeneous matrix containing both triazine and polybenzoxazine. This was substantiated by the TGA, DTA and SEM behavior of the cured polymer. The modulus of the cured blend was higher than those of the component resins of the blend. The co-reaction with cyanate ester enhanced the high temperature stability of polybenzoxazine.     

Mechanical and barrier properties of ternary nanocomposite films based on polycarbonate/amorphous polyamide blends modified with a nanoclay

Ternary polycarbonate (PC)/amorphous polyamide–nanoclay (naPA) nanocomposite (PC/naPA) films were obtained by melt mixing and drawing, and the effects of the naPA content and the draw ratio (DR) on the structure, morphology and mechanical and barrier properties were studied. Despite the presence of nanoclay, the films exhibited a negligible roughness and the excellent optical properties of PC and amorphous polyamide (aPA). The dispersed naPA phase was pure and small, indicating compatibility. The naPA did not hinder the drawing ability of PC. At low DRs the dispersed phase was elongated and oriented along the machine direction (extrusion flow direction), but at high DRs, it fibrillated due to the higher non‐isothermal elongational flow induced by drawing. The laminar structure of the nanoclay allowed the films to be reinforced both in the machine and the transverse directions. The oxygen permeability of PC was reduced by 42% in the nanocomposite with 25% of naPA, and dropped further with the DR, which is attributed to the increased tortuosity of the oxygen path induced by fibrillation. Copyright © 2015 John Wiley & Sons, Ltd.     

Mechanical properties and thermal analysis of low‐density polyethylene + polypropylene blends with dialkyl peroxide

Polypropylene + low density polyethylene (PP + LDPE) blends involving 0, 25, 50, 75 and 100 wt% of PP with dialkyl peroxide (DAP) were prepared by melt blending in a single‐screw extruder. The effects of adding dialkyl peroxide on mechanical and thermal properties of PP + LDPE blends have been studied. It was found that at lower concentrations of peroxide (e.g., 0–0.08 wt% of dialkyl peroxide) LDPE component is cross‐linked and Polypropylene (PP) is degraded in all compositions of PP + LDPE blends. Mechanical properties (Tensile strength at break, at yield and elongation at break), Melt flow index (MFI), hardness, Scanning Electron Microscope (SEM) and thermal analyses (DSC) of these blends were examined. Because of serious degradation or cross‐linking the mechanical properties and the crystallinty (%) of those products were decreased as a result of increasing peroxide content. Copyright © 2009 John Wiley & Sons, Ltd.     

Structure and mechanical properties of talc‐filled blends of polypropylene and styrenic block copolymers

The structure–property relationships of isotactic polypropylene (iPP)/styrenic block copolymer blends filled with talc were examined by optical and scanning electron microscopy, wide‐angle X‐ray diffraction, and tensile‐ and impact strength measurements. The composites were analyzed as a function of the poly(styrene‐b‐ethylene‐co‐propylene) diblock copolymer (SEP) and the poly(styrene‐b‐butadiene‐b‐styrene) triblock copolymer (SBS) content in the range from 0 to 20 vol % as elastomeric components and with 12 vol % of aminosilane surface‐treated talc as a filler. Talc crystals incorporated in the iPP matrix accommodated mostly plane‐parallel to the surface of the samples and strongly affected the crystallization process of the iPP matrix. The SBS block copolymer disoriented plane‐parallel talc crystals more significantly than the SEP block copolymer. The mechanical properties depended on the final phase morphology of the investigated iPP blends and composites and supermolecular structure of the iPP matrix because of the interactivity between their components. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1255–1264, 2004     

Influence of structure on the properties of polypropylene copolymers and terpolymers

Several Ziegler-Natta copolymers of iPP with ethylene or 1-butene, and terpolymers with both counits have been characterized, devoting special attention to the effect of composition and processing conditions on the crystal structure and final properties. DSC and X-ray diffraction were used to study the polymorphism of copolymers and terpolymers. Comonomer insertion interrupts the isotactic sequences, acting as a structural defect, and the formation of γ form is enhanced. Moreover, crystallinity decreases and crystal structure is modified. Comonomer type and concentration determine the extent of these modifications, resulting in important changes in macroscopic properties. In particular, the excellent optical properties of the analyzed terpolymers make them very attractive for applications such as transparent film or packaging.     

Morphology, crystalline structure and thermal properties of PEO/MEEP blends

Poly(ethylene oxide) and poly[bis[2-(2′-methoxyethoxy) ethoxy] phosphazene], PEO/MEEP, polymer blends were investigated by thermal analysis, X-ray diffraction, and atomic force microscopy. MEEP is an amorphous polymer and its semicrystalline blends with PEO showed two distinct glass transitions, whose composition dependence was analysed by the Lodge and McLeish self-concentration model. It appears that an amorphous miscible phase is present in these blends. Excess melting enthalpy was observed for blends with high MEEP concentration. PEO lamellar characteristics exhibited changes as a function of MEEP content, both in X-ray patterns and AFM images that indicated the intercalation of MEEP side chains in the lamellar crystalline structure.     

Structure and properties for biomass-based polyester blends of PLA and PBS

Structure and properties are studied for binary blends composed of poly(lactic acid) (PLA) and poly(butylene succinate) (PBS). The rheological measurements in the molten state reveal that the entanglement molecular weight of PLA is lower than that of PBS. Further, the interfacial tension of the immiscible blend system is evaluated employing a rheological emulsion model and found to be 3.5 [mN/m]. Moreover, thermal analysis directly detects that addition of PBS enhances the crystallization of PLA even though PBS is in a molten state. Further, the cold-crystallization for quenched blends occurs at lower temperature than that for a quenched PLA. This would be attributed to the nucleating ability of PBS, leading to generation of PLA crystallites during the quench operation.     

Evaluating of reinforcing effect of Ceratonia Siliqua for polypropylene: Tensile,flexural and other properties

The aim of this study is to investigate the reinforcing effect of Ceratonia siliqua (CS) powder as a novel natural filler for polypropylene (PP) based composites. CS powder up to 20 wt% was filled into PP matrix by using high speed thermo kinetic mixer. Mechanical and thermal properties of CS filled PP based composites were investigated by tensile and three point bending test, dynamic mechanical analysis, thermogravimetric analysis, differential scanning calorimetry analysis, fourier transform infrared analysis, and thermomechanical analysis. Morphology of the composites was also investigated by scanning electron microscopy. By filling 5% and 10% of CS into PP, tensile strength and flexural strength of PP increased by about 32 and 23%, respectively. This indicates that CS has a great potential to be used as reinforcing filler for PP composites. CS filling into PP led to lower coefficient of thermal expansion values which could help preventing the thermal expansion.     

Thermal properties and structure of electrospun blends of PVDF with a fluorinated copolymer

We report the structure and thermal properties of blends comprising poly(vinylidene fluoride) (PVDF) and a random fluorinated copolymer (FCP) of poly(methyl methacrylate)‐random‐1H,1H,2H,2H‐perfluorodecyl methacrylate, promising membrane materials for oil–water separation. The roles of processing method and copolymer content on structure and properties were studied for fibrous membranes and films with varying compositions. Bead‐free, nonwoven fibrous membranes were obtained by electrospinning. Fiber diameters ranged from 0.4 to 1.9 μm, and thinner fibers were obtained for PVDF content >80%. As copolymer content increased, degree of crystallinity and onset of degradation for each blend decreased. Processing conditions have a greater impact on the crystallographic phase of PVDF than copolymer content. Fibers have polar beta phase; solution‐cast films contain gamma and beta phase; and melt crystallized films form alpha phase. Kwei's model was used to model the glass transition temperatures of the blends. Addition of FCP increases hydrophobicity of the electrospun membranes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 312–322     

The effect of compatibilizers on the crystallisation, melting and polymorphic composition of β-nucleated isotactic polypropylene and polyamide 6 blends

Non-compatibilized and compatibilized blends of isotactic polypropylene (iPP) and polyamide 6 (iPP/PA6) as well as their β-nucleated versions were prepared using maleic anhydride functionalized iPP (MAPP) with different anhydride contents as compatibilizer. Ca-suberate, a highly efficient and selective β-nucleating agent was added to the blends in order to promote the formation of the β-modification of iPP. The melting and crystallisation characteristics, as well as the polymorphic composition of the blends were studied by differential scanning calorimetry (DSC). The supermolecular and phase structure of the blends were studied by polarised light microscopy (PLM). iPP and PA6 form blends with heterogeneous phase structure; the PA6 component is dispersed in the iPP matrix in the concentration range studied. The compatibilizer promotes the dispersion of PA6 resulting in smaller particles than without MAPP. In the non-compatibilized β-nucleated blends, an iPP matrix consisting mainly of the α-modification was formed already at low PA6 content. On the contrary, predominantly β-iPP matrix developed in the presence of MAPP compatibilizers. The formation of α-iPP matrix in the absence of compatibilizer is related to the selective encapsulation of the nucleating agent in the polar PA6 phase. The influence of the blending technique on the polymorphic composition of the matrix supports the hypothesis of selective encapsulation. Compatibilizers, besides their traditional benefits assist the distribution of the β-nucleating agent between both phases of the blends and promote the formation of a matrix rich in β-iPP. In the presence of β-nucleating agent MAPP with low anhydride content and blends of iPP containing maleated polypropylene crystallise predominantly in the β-form.     

Specifics of the structure and mechanical properties of blends of isotactic polypropylene with ethylene-propylene-diene elastomer

The structure of unvulcanized and dynamically vulcanized blends of isotactic PP with ethylene-propylene-diene terpolymer (EPDM) having an EPDM content of 5–85 wt % was studied by means of atomic force microscopy. The systems based on the virgin elastomer and the elastomer plasticized with 50% oligomer were examined. During thermal treatment (molding), the structure of the unvulcanized materials undergoes substantial changes. The morphology of dynamically vulcanized blends containing up to 75 wt % rubber is characterized by a homogeneous distribution of crosslinked rubber particles with a particle size of less than 2 μm in the continuous thermoplastic matrix. During PP blending with the plasticized elastomer, the oligomer diffuses into the thermoplastic phase, with the oligomer being distributed evenly between the blend components. As a result, the stress-strain characteristics of the plasticized systems decline relative to those of the oligomer-free materials. A comparative analysis of the dependence of the elastic modulus on the composition of the blends with the theoretical values obtained in terms of the Kerner, Uemura-Takayanagi, Davies, and Coran-Patel models was performed.     

Flame retardant polypropylene through the joint action of sepiolite and polyamide 6

The influence of the incorporation of polyamide-6 (PA) and natural sepiolite nanoparticles on both the thermal degradation and fire behaviour of polypropylene (PP) matrix has been investigated by thermogravimetric analysis (TGA) and mass loss calorimetry. For that purpose, PP/PA blends and nanocomposites thereof were prepared by melt processing. TGA results evidenced that the use of maleic anhydride grafted-polypropylene (MA-g-PP) as compatibilizer led to a significant improvement in thermal stability under air. Such improvement was linked to the formation of a char layer preventing the thermo-oxidative degradation of PP. Interestingly, the thermal resistance of this char layer was further improved by adding 5 wt% of natural sepiolite leading to important increase of time to ignition and reduction of peak of heat release rate (pHRR) during mass loss calorimeter test.     

Mechanical properties and structure relationships in drawn fibers of elastomer–polyoxymethylene blends

Superdrawn fibers of an elastomer–poly(oxymethylene) (POM) blend have been prepared and investigated in terms of the structure and mechanical properties. The development of the mechanical properties along the fiber axis and the formation of a higher order structure during drawing were slightly retarded by blending, but the loop tenacity increased greatly with the elastomer content. The blend microtextures had an immiscible and phase-separated morphology in which the elastomer was dispersed in the form of streaks between the oriented POM layers, which allowed the fiber to split into smaller filaments on bending. The high loop tenacity of the blend fibers is due to an increase in the radius of curvature resulting from the filament splitting on bending, because the shear stress at the bending corner becomes higher as the radius of curvature increases. © 1997 John Wiley & Sons, Inc.