Morphology and mechanical properties of heterophasic PP–EP/EVA/organoclay nanocomposites

The effect of vinyl acetat (VA) on the morphological, thermal stability, and mechanical properties of heterophasic polypropylene–(ethylene‐propylene) copolymer (PP–EP)/poly(ethylene vinyl acetate) (EVA)/organoclay nanocomposites was studied. Tailored organoclay C20A was selected to enhance the exfoliation of the clay platelets. Depending on the VA content, there were two morphological organoclay populations in the systems. Both populations were directly observed by scanning transmission electron microscopy and measured by wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The content of VA in EVA originated spherical and elongated morphologies in the resultant nanocomposites. High‐VA content led to a better intercalation of the organoclay platelets. Measurement of thermal properties suggested that higher VA decreases thermal stability in samples both with and without organoclay, although nanocomposites had higher thermal stability than samples without clay. The storage modulus increased both with nanoclay and VA content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphological and mechanical properties of polypropylene [PP]/poly(ethylene vinyl acetate) [EVA] blends. II: Polypropylene‐(ethylene‐propylene) heterophasic copolymer [PP‐EP]/EVA systems

Morphological characteristics and mechanical properties of PP‐EP/EVA blends were studied and compared to those of PP/EVA previously reported. For the PPEP/EVA blends, interfacial interactions in amorphous zones, which were associated with shifts in T_g, were well defined compared to those of PP/EVA blends, although the nature of crystalline zones was similar for both systems. At EVA concentrations up to 20%, the elongation at break and impact strength slightly increased in both systems. However, PP‐EP/EVA displayed higher values of these properties compared with PP/EVA. At high EVA concentrations (above 20%), the indicated properties were enhanced in both polymeric systems, and the same proportional behavior was maintained. The decrease in tensile strength of PP‐EP/EVA was not as marked as in PP/EVA with the addition of EVA, and it remained below PP/EVA at high EVA concentrations. The improvement in properties of PP‐EP/EVA was attributed to favorable interactions between the ethylene groups contained in both copolymers. These interactions rendered a high degree of compatibility between the PP‐EP and EVA components.     

Morphology and chain mobility of reactive blend nanocomposites of PP‐EVA/Clay

Polypropylene (PP)‐ethylene vinyl acetate (EVA)/clay nanocomposites were prepared via reactive blending using dicumyl peroxide (DCP) as an initiator with the goal of enhancing the interaction between both phases and modified nanoclay. The effect of the reactive blending and clay incorporation strategies (direct and masterbatch) on the blend and nanostructure morphology, and chain mobility of nanocomposites were studied. The chemical analysis showed the chemical bonding of PP‐EVA, which helped to enhance the interaction in the nanocomposites. The nanocomposites obtained from the direct clay strategy presented a co‐continuous morphology of bordering intercalated and agglomerated nanoclay sheets, while the nanocomposites obtained from the masterbatch strategy showed that blend morphology change from droplet to co‐continuous with the increase of EVA concentration, with intercalated/exfoliated nanoclay sheets located in the EVA domains and at the interface. The dynamic mechanical and creep‐recovery results showed different behavior for the both strategies in terms of chain mobility and relaxation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40897.     

Effect of heterophasic or random PP copolymer on the compatibility mechanism between EVA and PP copolymers

Compatibility mechanisms between EVA and PP copolymers (C‐PP) blends have been studied as a function of the type of copolymer, using a heterophasic PP copolymer (PP‐EP) and a random PP copolymer (PP‐r‐EP), with similar ethylene content. The morphology and thermal and mechanical properties of PP/EVA blends with different levels of EVA containing 28% vinyl acetate (VA) were determined. The obtained results indicated compatibility for both systems showing interactions at the amorphous interfaces; however, this interaction was higher for the PP‐r‐EP/EVA, which showed a single glass transition temperature and changes in the PP crystalline fraction (changes in the fusion temperature and in the diffraction patterns). The evolution of the morphology from isolated spherical domains (20% EVA) to elongated shapes (40% EVA) was related to the observed changes in thermal and mechanical properties. The impact strength and deformation properties showed significant improvement with increasing EVA content above 40% where the highest values of elongation for the PP‐r‐EPand of impact strength for the PP‐EP were obtained. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Tuning the nano/micro‐structure and properties of melt‐processed ternary composites of polypropylene/ethylene vinyl acetate blend and nanoclay: The influence of kinetic and thermodynamic parameters

The present study reports the dependence of the nano/micro‐structure and properties of polypropylene (PP)/ethylene vinyl acetate (EVA)/nanoclay ternary composites on the kinetics and thermodynamics of the melt‐mixing process. The size of dispersed EVA particles in the blends increased in the presence of the nanoclay particles, whereas in the ternary blend composites the size of the EVA dispersions decreased with increasing processing time. Intercalation and exfoliation were achieved more efficiently in ternary composites prepared with a longer EVA processing time. Moreover, the incorporation of the nanoclay particles within the EVA phase and interphase, as well as a long processing time stabilized the morphology. The degree of crystallinity, melting behavior, and crystallization temperature of PP in the ternary composites were not influenced by the presence of the nanoclay particles or by the duration of the melt‐mixing process. The thermal stability of the ternary composites improved with increasing melt‐mixing time. The rheological and thermomechanical properties were found to be dependent on the processing time and on the resulting structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45585.     

Mechanical,thermal and dynamic‐mechanical behavior of banana fiber reinforced polypropylene nanocomposites

Natural fiber‐reinforced nanocomposites based on polypropylene/nanoclay/banana fibers were fabricated by melt mixing in a twin‐screw extruder followed by compression molding in this current study. Maleic anhydride polypropylene copolymer (MA‐g‐PP) was used as a compatibilizer to increase the compatibility between the PP matrix, clay, and banana fiber to enhance exfoliation of organoclay and dispersion of fibers into the polymer matrix. Variation in mechanical, thermal, and physico‐mechanical properties with the addition of banana fiber into the PP nanocomposites was investigated. It was observed that 3 wt% of nanoclay and 5 wt% of MA‐g‐PP within PP matrix resulted in an increase in tensile and flexural strength by 41.3% and 45.6% as compared with virgin PP. Further, incorporation of 30 wt% banana fiber in PP nanocomposites system increases the tensile and flexural strength to the tune of 27.1% and 15.8%, respectively. The morphology of fiber reinforced PP nanocomposites has been examined by using scanning electron microscopy and transmission electron microscopy. Significant enhancement in the thermal stability of nanocomposites was also observed due to the presence of nanoclay under thermogravimetric analysis. Dynamic mechanical analysis tests revealed an increase in storage modulus (E′) and damping factor (tan δ), conforming the strong interaction between nanoclay/banana fiberand MA‐g‐PP in the fiber‐reinforced nanocomposites systems. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Effects of process conditions and mixing protocols on structure of extruded polypropylene nanocomposites

Polymer melt‐direct intercalation or exfoliation is a promising approach for the preparation of nanocomposites. The structure of nanoclay platelets in the nanocomposites depends not only on the properties of polymer matrix and nanoclay, but also on the operating conditions during processing. The objective of the present work is to investigate the effects of clay chemical modifiers, mixing protocols, and operating conditions upon the clay structure in nanocomposites prepared with a corotating twin‐screw extruder. Two mixing methods were used for the nanocomposite preparation: two‐step mixing and one‐step mixing. Experimental results obtained from melt flow index and complex viscosity measurements suggest that nanoclay C15A is more exfoliated than C30B in a polypropylene homopolymer containing a maleic anhydride grafted PP (PB) as compatibilizer. The two‐step mixing method results in better exfoliation for the nanofillers than the one‐step mixing method. A numerical simulation has been carried out to evaluate the mean residence time and shear rate in different screw configurations under various process conditions. X‐ray diffraction experiments indicate that the residence time is a dominant factor in producing satisfactory nanocomposites in extruders. However, high shear rate coupled with long residence time might result in poor exfoliation of clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1891–1899, 2004     

Effect of polymer matrix/montmorillonite compatibility on morphology and melt rheology of polypropylene nanocomposites

In this study, Ca²⁺‐montmorillonite (Ca²⁺‐MMT) and organo‐montmorillonite (OMMT) were modified by three compatibilizers with different degrees of polarity [poly(ethylene glycol) (PEG), alkyl‐PEG, and polypropylene (PP)‐g‐PEG]. PP/MMT nanocomposites were prepared by melt blending and characterized using X‐ray diffraction and transmission electron microscopy. The results showed the degree of dispersion of OMMT in the PP/PP‐g‐PEG/OMMT (PMOM) nanocomposite was considerably higher than those in the PP/PEG/OMMT and PP/alkyl‐PEG/OMMT nanocomposites, which indicated that the dispersion was relative to the compatibility between modified OMMT and PP matrix. Linear viscoelasticity of PP/MMT nanocomposites in melt states was investigated by small amplitude dynamic rheology measurements. With the addition of the modified MMT, the shear viscosities and storage modulus of all the PP/MMT nanocomposites decreased. It can be attributed to the plasticization effect of PEG segments in the three modifiers. This rheological behavior was different from most surfactant modified MMT nanocomposites which typically showed an increase in dynamic modulus and viscosity relative to the polymer matrix. The unusual rheological observations were explained in terms of the compatibility between the polymer matrix and MMT. In addition, the mechanical properties of PP/MMT nanocomposites were improved. A simultaneous increase in the tensile strength and toughness was observed in PP/PMOM nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and Properties of Ethylene Vinyl Acetate (EVA)/Organoclay/Compatibilizer Nanocomposites: Effects of Organoclay Loading and Methyl Ethyl Ketone

Ethylene vinyl acetate (EVA)/organoclay/compatibilizer nanocomposites were produced using a melt compounding technique in an internal mixer, Haake Rheometer, at 120°C and 50 rpm rotor speed. Effects of organoclay loading (from 2 to 10 phr—parts per hundred of resin and methyl ethyl ketone (MEK), used as a compatibilizer, on the processing properties, tensile properties, morphology, thermal degradation, and water absorption behavior of EVA/organoclay nanocomposites were studied. Results indicate that the presence of organoclay increase the processing torque, tensile properties, thermal degradation, and resistance to water absorption. The optimum organoclay loading was achieved at 2 phr. This was caused by the dispersion state of individual silicate layers (intercalation/exfoliation) in EVA matrix. The intercalation/exfoliation structure affects the properties of EVA/organoclay nanocomposites as evidenced from the morphology studies such as x-ray diffraction (XRD) and transmission electron microscopy (TEM) evaluation. The addition of MEK has the ability to improve the tensile properties, thermal degradation, and slightly reduces the resistance of water permeation of EVA/organoclay nanocomposites. The enhanced properties were seen as a result of the better matrix and filler interaction. The EVA/organoclay/MEK nanocomposites shows better intercalation/exfoliation of individual silicate layers in the EVA matrix as indicated by TEM. Moreover, the XRD evaluation shows that intercalation/exfoliation of the organoclay was formed in the EVA matrix.     

Morphological influence on mechanical characterization of ethylene‐vinyl acetate copolymer–clay nanocomposites

Ethylene‐vinyl acetate copolymer (EVA)/montmorillonite (MMT) clay nanocomposites with varying degree of intercalation and exfoliation have been prepared using direct melt blending techniques with various degrees of polarity (9, 18, and 28 wt% vinyl acetate [VA]) and two different types of clay modification. Morphological characterization using wide‐angle X‐ray scattering (WAXS) and transmission electron microscopy (TEM) have indicated/confirmed the presence of intercalation and/or a combination of intercalation and exfoliation existing in the nanocomposites. The effects of these (simple intercalation or mixed intercalation/exfoliation) states and the effect of changing matrix polarity (by changing VA wt% content) on the nanocomposite mechanical behavior were studied. There is sufficient evidence from the mechanical studies that 1) the presence of nanoclay can simultaneously improve modulus and strength of the nanocomposites, and 2) the mechanical properties are a combined function of the clay concentration and the nanocomposite morphology (due to the VA wt% and presence of clay). It is shown here that interrelation between the VA wt% content and the clay exfoliation affects the mechanical properties in a way that has a positive and increasing slope with increasing loading of clay. It is shown that a clear understanding of the nanocomposite mechanical properties can be obtained from its morphological analysis. POLYM. ENG. SCI., 45:889–897, 2005. © 2005 Society of Plastics Engineers     

Reinforcement of polyurethane/epoxy interpenetrating network nanocomposites with an organically modified palygorskite

An organophilic palygorskite (o‐PGS) prepared by the treatment of natural palygorskite with hexadecyl trimethyl ammonium bromide was incorporated into interpenetrating polymer networks (IPNs) of polyurethane (PU) and epoxy resin (EP), and a series of PU/EP/clay nanocomposites were obtained by a sequential polymeric technique and compression‐molding method. X‐ray diffraction and scanning electron microscopy analysis showed that adding nanosize o‐PGS could promote the compatibility and phase structure of PU/EP IPN matrices. Tensile testing and thermal analysis proved that the mechanical and thermal properties of the PU/EP IPN nanocomposites were superior to those of the pure PU/EP IPN. This was attributed to the special fibrillar structure of palygorskite and the synergistic effect between o‐PGS and the IPN matrices. In addition, the swelling behavior studies indicated that the crosslink density of PU/EP IPN gradually increased with increasing o‐PGS content. The reason may be that o‐PGS made the chains more rigid and dense. As for the flame retardancy, the PU/EP nanocomposites had a higher limiting oxygen index than the pure PU. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Quantification of organoclay dispersion and lamellar morphology in poly(propylene)-clay nanocomposites with small angle X-ray scattering

Intensity profiles of small angle X-ray scattering (SAXS) curves were analyzed to simultaneously gain quantitative information on nanoclay dispersion as well as lamellar ordering in polypropylene-clay nanocomposites. Different types of PP nanocomposites prepared with PP homopolymer (HPP), random propylene-ethylene copolymer (RCP) and a high impact polypropylene-ethylene propylene rubber (ICP) were analyzed. Various one-dimensional models for stacked structures were applied on Lorentz corrected SAXS spectra to derive long period, thicknesses of alternating high and low electron density layers and their distributions, and the number of stacks for both nanoclay and PP lamellae. We applied a mixed thickness distribution model comprising combined Gaussian and exponential for a simple stack of finite thickness, which was found to explain the experimental data better for both nanoclay tactoids and lamellar stacks, compared to simple Gaussian and exponential thickness distributions. Long period X and number of stacks N were derived as important parameters signifying changes in levels of nanoclay exfoliation in PP. Among the three types of polypropylenes studied, better nanoclay exfoliation was obtained for the high impact ICP grade compared to HPP and RCP. Complete exfoliation of nanoclay was achieved in ICP matrix, employing a masterbatch processing route. Moreover, role of nanoclay as a γ nucleating agent was evident from small and wide angle X-ray analyses, and was seen strongly in RCP. Changes in lamellar structure of PP as a result of nanoclay incorporation, double population consisting of both α and γ polytypes in the nanocomposites from that of a primarily α population in neat polymer matrices, were also analyzed in detail with the mixed thickness distribution model, thereby demonstrating its usefulness.     

Effects of direct melt compounding and masterbatch dilution on the structure and properties of nanoclay‐filled polyolefins

The differences that direct melt compounding and masterbatch dilution cause in the properties of melt compounded polypropylene (PP) and high density polyethylene‐based (PE‐HD) nanocomposites are presented. The results include comparison of properties and morphology of directly melt processed organoclay nanocomposites with similar compounds diluted from commercial and in‐house‐made masterbatches to clay concentrations of 1, 3, 6, and 8 wt%. The compounds were prepared with a co‐rotating Brabender twin‐screw extruder. The degree of exfoliation and the dispersion of the nanoclay were verified with transmission electron microscopy and X‐ray diffraction. Thermal stability of the materials was examined with thermogravimetric analysis and the mechanical properties of the compounded materials were also determined. The most promising results regarding mechanical behavior were achieved with the in‐house‐made masterbatch in the form of a notable increase in Young's modulus in both matrices. There was also a distinct increase in impact strength when masterbatch was used. Changes were more pronounced in case of PP. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Effect of organoclay structure characteristics on properties of ternary PP‐EP/EVA/nanoclay blend systems

In this study, the effect on the degree of organoclay exfoliation in polypropylene‐ethylene (PP‐EP)/Ethylene vinyl acetate (EVA)/organoclay blend system was studied while varying organoclay structural characteristics. Cloisite 6A, Cloisite 15A, Cloisite 20A, Cloisite 25A, Cloisite 30B, Cloisite 93A, and Cloisite 10A were used because they have different type of modifier. Ternary PP‐EP/EVA/organoclay system was obtained with each type of clay and results were organized to analyze the effect of type of clay chemical modification (C20A, C15A, and C6A), steric effect caused by surfactant structure (C15A and C10A), length of substitute groups on the surfactant (C20 and C25A), and surfactant polarity (C30B and C93A). Samples were characterized by: wide angle X‐ray diffraction, scanning transmission electron microscopy (STEM), dynamic mechanical analysis, and capillary rheometry. Results showed that clay galleries can be saturated with chemical modifier complicating the polymer chain intercalation into the clay galleries. Some clay modifier substituent groups could cause certain steric effect promoting less exfoliated platelets structures. Finally, longer chains in the modifier substituent group can promote a better intercalated–exfoliated structure. Among all the studied organoclays, best results were obtained in the ternary system when using C20A, which modifier has two hydrogenated tallows. In this case, interlayer spacing was increased more noticeable after ternary system was formed. This was corroborated with the obtained increase in viscosity and the intercalated–exfoliated structure observed by STEM. POLYM. COMPOS., 35:2241–2250, 2014. © 2014 Society of Plastics Engineers     

Effect of vinyl acetate content on the mechanical and thermal properties of ethylene vinyl acetate/MgAl layered double hydroxide nanocomposites

Ethylene vinyl acetate (EVA)/Mg‐Al layered double hydroxide (LDH) nanocomposites using EVA of different vinyl acetate contents (EVA‐18 and EVA‐45) have been prepared by solution blending method. X‐ray diffraction and transmission electron microscopic studies of nanocomposites clearly indicate the formation of exfoliated/intercalated structure for EVA‐18 and completely delaminated structure for EVA‐45. Though EVA‐18 nanocomposites do not show significant improvement in mechanical properties, EVA‐45 nanocomposites with 5 wt % DS‐LDH content results in tensile strength and elongation at break to be 25% and 7.5% higher compared to neat EVA‐45. The data from thermogravimetric analysis show that the nanocomposites of EVA‐18 and EVA‐45 have ≈10°C higher thermal decomposition temperature compared to neat EVA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nanoclay effect on transport properties of thermoplastic polyurethane/polypropylene (TPU/PP) blends

In this paper the diffusion of water through the nanoclay filled TPU/PP blends was investigated at various temperatures. The effect of blend ratio, compatibilisation and nanoclay addition on the transport properties was studied in detail. Special attention has been given to study the mechanism of diffusion. Thermodynamics and Arrhenius parameters were evaluated from the diffusion data. The various parameters such as diffusion coefficient (D), permeation coefficient (P), sorption coefficients (S) were evaluated at different diffusion conditions. Attempts were made to correlate the observed morphology of the blends with transport properties. Addition of PP into TPU decreases water sorption of the system due to the decrease in overall polarity of the system and further reduced by addition of compatibiliser and nanoclay into the system. Compared to the ether-TPU based blend nanocomposites, the ester-TPU blends show better compatibility as confirmed by analysis.     

Studies on preparation of immersion‐type polypropylene fragrant fiber. I. Formation of matrix fiber in the melt‐spinning process and its technique of immersion essential oil

Polypropylene/ethylene vinyl acetate (PP/EVA) blends were prepared in a plastic extruder with a static mixer. The thermodynamic compatibility, morphology, crystal form, and rheological behavior of PP/EVA blends were investigated by SEM, DSC, and rheology instruments. The results showed that PP and EVA were thermodynamically incompatible, the viscosity of the PP/EVA blends decreased with increase of shear rate in a range of temperature, the PP/EVA blends had a sea‐islands structure, and the crystalline zones remained in their original state and could not form mixed crystals in the PP/EVA blends. The PP/EVA blends were melt spun to prepare matrix fibers and the spinning conditions such as EVA content, the matching factor between pump delivery and winding velocity, and the melt‐spinning temperature were also determined. The sorption process of a matrix fiber for essential oils, adsorbed under various sorption conditions such as sorption time, sorption temperature, and EVA content, was also studied. The results revealed that the composite isotherm of the adsorption of matrix fiber for essential oil was characteristic of a U model. Through adsorbing essential oil, the immersion‐type PP fragrant fibers could be prepared with the matrix fiber. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1970–1979, 2003     

A novel intumescent flame‐retardant system for flame‐retarded LLDPE/EVA composites

A new intumescent flame retardant (IFR) system consisting of ammonium polyphosphate (APP) and charing‐foaming agent (CFA) and a little organic montmorillonite (OMMT) was used in low‐density polyethylene (LLDPE)/ethylene‐vinyl acetate (EVA) composite. According to limiting oxygen index (LOI) value and UL‐94 rating obtained from this work, the reasonable mass ratio of APP to CFA was 3 : 1, and OMMT could obviously enhance the flame retardancy of the composites. Cone calorimeter (CONE) and thermogravimetric analysis (TGA) were applied to evaluate the burning behavior and thermal stability of IFR‐LLDPE/EVA (LLDPE/EVA) composites. The results of cone calorimeter showed that heat release rate peak (HRR‐peak) and smoke production rate peak (SPR‐peak) and time to ignition (TTI) of IFR‐LLDPE/EVA composites decreased clearly compared with the pure blend. TGA data showed that IFR could enhance the thermal stability of the composites at high temperature and effectively increase the char residue. The morphological structures of the composites observed by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) demonstrated that OMMT could well disperse in the composites without exfoliation, and obviously improve the compatibility of components of IFR in LLDPE/EVA blend. The morphological structures of char layer obtained from Cone indicated that OMMT make the char layer structure be more homogenous and more stable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚丙烯/环氧树脂复合材料的制备及其性能研究

在聚丙烯(PP)基体中加入环氧树脂(EP)、固化剂、马来酸酐接枝聚丙烯(PP-g-MAH),通过动态固化制备了PP/EP复合材料,并对其相容性、力学性能、结晶性能等进行了研究。结果表明:PP/EP为不相容体系,PP-g-MAH作为反应性增容剂对体系的刚性和模量影响较大;通过EP和PP-g-MAH的接枝反应,增强了两相间的界面作用力,降低了EP分散相的尺寸,改善了PP/EP复合材料的力学性能。力学性能测试结果表明,EP与PP-g-MAH的最佳配比为1:1;等温结晶的偏光照片和DSC数据表明,EP阻碍了PP的结晶,使其球晶微细化、结晶度降低。     

Ethylene vinyl acetate/Mg‐Al LDH nanocomposites by solution blending

Partially exfoliated ethylene vinyl acetate (EVA‐40, 40% vinyl acetate content)/layered double hydroxide (LDH) nanocomposites using organically modified layered double hydroxide (DS‐LDH) have been synthesized by solution intercalation method. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) studies of nanocomposites shows the formation of exfoliated LDH nanolayers in EVA‐40 matrix at lower DS‐LDH contents and partially intercalated/exfoliated EVA‐40/MgAl LDH nanocomposites at higher DS‐LDH contents. These EVA‐40/MgAl LDH nanocomposites demonstrate a significant improvement in tensile strength and elongation at break for 3 wt% of DS‐LDH filler loading compare to neat EVA‐40 matrix. Thermogravimetric analysis also shows that the thermal stability of the nanocomposites increases with DS‐LDH content in EVA‐40. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers