Effect of combining ethylene/methyl acrylate/glycidyl methacrylate terpolymer and an organoclay on the toughening of poly(lactic acid)

Blends of poly(lactic acid) (PLA) and ethylene/methyl acrylate/glycidyl methacrylate terpolymer (EMA‐GMA) with and without the addition of an organoclay were prepared by melt mixing in a twin screw extruder. Mechanical, morphological, structural, and rheological properties of the systems have been investigated as function of its compositions. The impact strength (IS) of PLA increased with the addition of EMA‐GMA. Furthermore, the addition of 2.5 wt% of organoclay to the PLA/EMA‐GMA blend promoted improvements in the mechanical properties, such as IS, tensile strength, and strain‐at‐break. Further addition of organoclay, 5 wt%, led to a formation of a double percolated network, where the clay particles form bridges across EMA‐GMA droplets and glue them together, however, without coalescence. In addition, morphological and wide‐angle X‐ray scattering analyses evidenced that the clay presents a partially exfoliated structure and that remains inside the EMA‐GMA droplets, probably as a consequence of the approach used to produce the systems. POLYM. ENG. SCI., 54:1922–1930, 2014. © 2013 Society of Plastics Engineers     

Synthesis and characterization of poly(ethylene terephthalate) nanocomposites with organoclay

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo‐modified with the intercalation agent cetylpyridinium chloride (CPC). Wide‐angle X‐ray diffraction (XRD) showed that the layers of MMT were intercalated by CPC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt % were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay present. According to the results of differential scanning calorimetry (DSC) analysis, clay behaves as a nucleating agent and enhances the crystallization rate of PET. The maximum enhancement of crystallization rate for the nanocomposites was observed in those containing about 10 wt % organoclay within the studied range of 1–15 wt %. From thermogravimetric analysis (TGA), we found that the thermal stability of the nanocomposites was enhanced by the addition of 1–15 wt % organoclay. These nanocomposites showed high levels of dispersion without agglomeration of particles at low organoclay content (5 wt %). An agglomerated structure did form in the PET matrix at 15 wt % organoclay. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 140–145, 2004     

Poly(ethylene terephthalate) nanocomposite fibers by in situ polymerization: The thermomechanical properties and morphology

A series of nanocomposites of poly(ethylene terephthalate) (PET) with the organoclay dodecyltriphenylphosphonium‐mica (C₁₂PPh‐mica) were synthesized with the in situ polymerization method. PET hybrid fibers with various organoclay concentrations were melt‐spun at various draw ratios (DRs) to produce monofilaments. The thermomechanical properties and morphologies of the PET hybrid fibers were characterized with differential scanning calorimetry, thermogravimetric analysis, wide‐angle X‐ray diffraction, electron microscopy, and universal tensile analysis. The organoclay was intercalated in the polymer matrix at all magnification levels, and some of the agglomerated organoclay layers were greater than 50 nm thick. The thermal stabilities and initial tensile moduli of the hybrid fibers increased with an increasing clay content for DR = 1. For DR = 1, the ultimate tensile strengths of the PET hybrid fibers increased with the addition of clay up to a critical clay loading and then decreased above that critical concentration. However, the tensile mechanical properties of the hybrid fibers did not improve with increasing DR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2009–2016, 2005     

Transparent copolyester/organoclay nanocomposites prepared by in situ intercalation polymerization: Synthesis,characterization, and properties

In this study, amorphous poly(ethylene terephthalate‐co‐1,3/1,4‐cyclohexylenedimethylene terephthalate) (PETG)/organoclay nanocomposites was synthesized by the in situ intercalation polymerization of terephthalic acid, ethylene glycol, 1,3/1,4‐cyclohexanedimethanol, and organoclay. The organoclay was obtained by modifying sodium montmorillonite (clay) with hexadecyl triphenylphosphonium bromide. The thermal, mechanical, optical, and gas barrier properties of these PETG nanocomposites with various organoclay contents (0–3 wt%) were discussed. The differential scanning calorimetry and X‐ray analyses revealed that all of the nanocomposites were amorphous. X‐ray diffraction and transmission electron micrographs showed that the organoclay was well dispersed in the polymer matrix, although some parts of the agglomerated layers remained on the scale of several hundreds of nanometers. The thermal stability and the mechanical property of the nanocomposites increased with organoclay content. The optical transmittances of nanocomposites that contained 0.5, 1, and 3 wt% of organoclay were 86.8%, 84.4%, and 77.4%, respectively. The oxygen transmission rate of the nanocomposite that contained 3 wt% of organoclay was about 50% of the PETG base polymer. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Poly(ethylene terephthalate) nanocomposite fibers with new organomica via in situ intercalation

Poly(ethylene terephthalate) (PET) nanocomposites with a newly synthesized organomica (C₁₆BIMD‐Mica) were obtained by using the in situ interlayer polycondensation of ethylene glycol with dimethylterephthalic acid. The PET hybrids were melt‐spun to produce monofilaments with various organoclay contents and draw ratios. The thermomechanical properties and morphologies of the PET hybrid fibers were determined using differential scanning calorimetry, thermogravimetric analysis, wide angle X‐ray diffraction, electron microscopy (SEM and TEM), and a universal tensile machine. The XRD analyses and TEM micrographs showed that the levels of exfoliation and intercalation could be controlled by varying the clay content. The thermomechanical properties of the PET hybrid fibers were found to be better than those of pure PET fibers. POLYM. ENG. SCI., 47:1820–1826, 2007. © 2007 Society of Plastics Engineers     

Preparation and characterization of low density polyethylene/ethylene methyl acrylate glycidyl methacrylate/organoclay nanocomposites

The effects of organoclay type, compatibilizer, and the addition order of components during melt‐blending process on the morphology and thermal, mechanical, and flow properties of ternary nanocomposites based on low‐density polyethylene (LDPE) were investigated. As a compatibilizer, ethylene/methyl acrylate/glycidyl methacrylate (E‐MA‐GMA), as organoclays Cloisites® 15A, 25A, and 30B were used. All samples were prepared by a corotating twin screw extruder, followed by injection molding. The highest increase of the basal spacing for ternary nanocomposites was obtained in LDPE/E‐MA‐GMA/Cloisite® 30B nanocomposites with interlayer spacing of 59.2 Å. Organoclay and compatibilizer addition did not influence the melting/crystallization behavior of the compositions, and both compatibilizer and organoclays had no significant nucleation activity in LDPE. Among the ternary nanocomposites, the maximum increase in tensile strength and tensile modulus values was observed for nanocomposites containing organoclay Cloisite® 15A. The improvement with respect to neat LDPE was 43% for tensile strength and 44% for tensile modulus. According to the mechanical analysis, the best sequence of component addition was the one in which LDPE, organoclay, and compatibilizer were simultaneously fed to the extruder in the first run, and the product of the first run was extruded once more. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of different types of organoclays and compatibilizers on the properties of polystyrene‐based nanocomposites

Polystyrene/organoclay nanocomposites were prepared by melt intercalation in the presence of elastomeric impact modifiers. Three different types of organically modified montmorillonites; Cloisite® 30B, 15A, and 25A, were used as reinforcement, whereas poly [styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS‐g‐MA) and poly(ethylene‐b‐butyl acrylate‐b‐glycidyl methacrylate) (E‐BA‐GMA) elastomeric materials were introduced to act as impact modifier. Owing to its single aliphatic tail on its modifier and absence of hydroxyl groups, Cloisite® 25A displayed the best dispersion in the polystyrene matrix, and mostly delaminated silicate layers were obtained in the presence of SEBS‐g‐MA. This was attributed to the higher viscosity of SEBS‐g‐MA compared with both E‐BA‐GMA and poly(styrene‐co‐vinyloxazolin) (PS). In addition, the compatibility between SEBS‐g‐MA and PS was found to be better in comparison to the compatibility between E‐BA‐GMA and PS owing to the soluble part of SEBS‐g‐MA in PS. The clay particles were observed to be located mostly in the dispersed phase leading to larger elastomeric domains compared with binary PS/elastomer blends. The enlargement of the elastomeric domains resulted in higher impact strength values in the presence of organoclay. Good dispersion of Cloisite® 25A in PS/SEBS‐g‐MA blends enhanced the tensile properties of this nanocomposite produced. It was observed that the change in the strength and stiffness of the ternary nanocomposites mostly depend on the type of the elastomeric material. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of poly(ethylene terephthalate) nanocomposite fibers incorporating a thermally stable organoclay

Summary A series of poly(ethylene terephthalate) (PET) nanocomposites containing organically-modified mica (HB-Mica) were prepared by in-situ interlayer polymerization of dimethyl terephthalate and ethylene glycol. The PET nanocomposites, which contained organoclay loadings of 0 to 2 wt %, were melt-spun to produce monofilaments with various draw ratios. Some of the clay particles appeared well dispersed within the PET matrix, while others were found to form agglomerates with sizes greater than 20 nm. The addition of a small amount of organoclay was sufficient to improve the thermo-mechanical properties of the PET hybrid fibers. Both the thermal stability and the mechanical tensile properties increased with increasing clay content for draw ratios of 1–16.     

Enhanced dyeability of poly(ethylene terephthalate)/organoclay nanocomposite filaments

This study deals with the generation of poly(ethylene terephthalate)/organoclay nanocomposite filaments by the melt‐spinning method and with the investigation of their morphological and dyeing properties. Different montmorillonite types of clay (Resadiye and Rockwood) were modified using different intercalating agents, and poly(ethylene terephthalate) nanocomposite filaments containing 0.5 and 1 wt% organoclays were prepared. Afterwards, the filaments were dyed with two disperse dyes (Setapers Red P2G and Setapers Blue TFBL‐NEW) at different temperatures (100, 110, and 120 °C) in the absence/presence of a carrier. Organoclays and poly(ethylene terephthalate)/organoclay nanocomposites showed an increased d‐spacing between clay layers. Irrespective of clay and surfactant type, poly(ethylene terephthalate)/organoclay nanocomposite filaments dyed at 120 °C in the presence of only a very small amount of carrier showed appreciable dyeability in comparison with neat poly(ethylene terephthalate). The dyeability of the organoclay‐containing poly(ethylene terephthalate) samples was found to be better in spite of having increased degrees of crystallinity. Moreover, the colour fastness properties of the clay‐containing samples were not affected adversely.     

Preparation and properties of styrene–ethylene–butylene–styrene block copolymer/clay nanocomposites: I. Effect of clay content and compatibilizer types

BACKGROUND: Polymer/clay (silicate) systems exhibit great promise for industrial applications due to their ability to display synergistically advanced properties with relatively small amounts of clay loads. The effects of various compatibilizers on styrene–ethylene–butylene–styrene block copolymer (SEBS)/clay nanocomposites with various amounts of clay using a melt mixing process are investigated. RESULTS: SEBS/clay nanocomposites were prepared via melt mixing. Two types of maleated compatibilizers, styrene–ethylene–butylene–styrene block copolymer grafted maleic anhydride (SEBS‐g‐MA) and polypropylene grafted maleic anhydride (PP‐g‐MA), were incorporated to improve the dispersion of various amounts of commercial organoclay (denoted as 20A). Experimental samples were analyzed using X‐ray diffraction and transmission electron microscopy. Thermal stability was enhanced through the addition of clay with or without compatibilizers. The dynamic mechanical properties and rheological properties indicated enhanced interaction for the compatibilized nanocomposites. In particular, the PP‐g‐MA compatibilized system conferred higher tensile strength or Young's modulus than the SEBS‐g‐MA compatibilized system, although SEBS‐g‐MA seemed to further expand the interlayer spacing of the clay compared with PP‐g‐MA. CONCLUSION: These unusual results suggest that the matrix properties and compatibilizer types are crucial factors in attaining the best mechanical property performance at a specific clay content. Copyright © 2007 Society of Chemical Industry     

Preparation and properties of styrene–ethylene/butylene–styrene (SEBS)–clay hybrids

Styrene–ethylene/butylene–styrene triblock copolymer (SEBS)–clay hybrids were prepared by melt blending SEBS and organoclay using an internal mixer. Maleic anhydride modified SEBS (SEBS–MA) was used as a compatibilizer. X‐ray diffraction and transmission electron microscopy revealed that silicate layers of the clay were partially exfoliated and dispersed at a nanometer scale in the polymer matrix. Enhanced mechanical properties of these hybrids were observed from tensile and dynamic mechanical tests. Thermal degradation temperature of the hybrids was increased compared with pristine SEBS. Copyright © 2004 Society of Chemical Industry     

Polyamide 6/maleated ethylene–propylene–diene rubber/organoclay composites with or without glycidyl methacrylate as a compatibilizer

Polyamide 6 (PA6)/maleated ethylene–propylene–diene rubber (EPDM‐g‐MA)/organoclay (OMMT) composites were melt‐compounded through two blending sequences. Glycidyl methacrylate (GMA) was used as a compatibilizer for the ternary composites. The composite prepared through via the premixing of PA6 with OMMT and then further melt blending with EPDM‐g‐MA exhibited higher impact strength than the composite prepared through the simultaneous blending of all the components. However, satisfactorily balanced mechanical properties could be achieved by the addition of GMA through a one‐step blending sequence. The addition of GMA improved the compatibility between PA6 and EPDM‐g‐MA, and this was due to the reactions between PA6, EPDM‐g‐MA, and GMA, as proved by Fourier transform infrared analysis and solubility (Molau) testing. In addition, OMMT acted as a compatibilizer for PA6/EPDM‐g‐MA blends at low contents, but it weakened the interfacial interactions between PA6 and EPDM‐g‐MA at high contents. Both OMMT and GMA retarded the crystallization of PA6. The complex viscosity, storage modulus, and loss modulus of the composites were obviously affected by the addition of OMMT and GMA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of thermally stable phosphonium organoclays and their use in poly(ethylene terephthalate) nanocomposites

Purification of montmorillonite rich bentonite followed by surface modification using organic salts was performed. The bentonite was purified by sedimentation and then surface modified by ion exchange using alkyl‐ and aryl‐based phosphonium salts. The thermal stability, morphology, melt flow, and mechanical properties of the poly(ethylene terephthalate) (PET) nanocomposites prepared with these organoclays were studied with and without using a reactive elastomeric compatibilizer. TEM results showed that the alkyl based organoclay exhibited better dispersion and thus, higher tensile strength and elongation at break in the PET/organoclay/elastomer ternary nanocomposites than the aryl‐based organoclay did. The notched Charpy impact strength of PET increased from 2.9 to 4.7 kJ m^?2 and 3.4 kJ m^?2 for alkyl and aryl phosphonium organoclay‐based ternary nanocomposites, respectively. Upon compounding PET with alkyl and aryl phosphonium organoclays, the onset decomposition temperature of PET increased from 413°C to 420°C and 424°C, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Impact modified polyamide‐6/organoclay nanocomposites: Processing and characterization

The effects of melt state compounding of ethylene‐butyl acrylate‐maleic anhydride (E‐BA‐MAH) terpolymer and/or three types of organoclays (Cloisite® 15A, 25A, and 30B) on thermal and mechanical properties and morphology of polyamide‐6 are investigated. E‐BA‐MAH formed spherical domains in the materials to which it is added, and increased the impact strength, whereas the organoclays decreased the impact strength. In general, the organoclays increased the tensile strength (except for Cloisite 15A), Young's modulus and elongation at break, but the addition of E‐BA‐MAH had the opposite effect. XRD patterns showed that the interlayer spacing for the organoclays Cloisite 25A and Cloisite 30B increased in both polyamide‐6/organoclay binary nanocomposites and in polyamide‐6/organoclay/impact modifier ternary systems. TEM analysis showed that exfoliated‐intercalated nanocomposites were formed. The crystallinities of polyamide‐6/organoclay nanocomposites were in general lower than that of polyamide‐6 (except for Cloisite 15A). In ternary nanocomposites, crystallinities generally were lower than those of polyamide‐6/organoclay nanocomposites. Cloisite 15A containing ternary nanocomposites had higher tensile and impact strengths and Young's modulus than the ternary nanocomposites prepared with Cloisite 25A and Cloisite 30B, owing to its surface hydrophobicity and compatibility with the impact modifier. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Characteristics of impact modified polystyrene/organoclay nanocomposites

The poor impact resistance of Polystyrene (PS) was enhanced by the addition of elastomeric material, SEBS‐g‐MA. To prevent the reduction in strength and stiffness, organoclay Cloisite® 25A was used as filler and introduced into the matrix by a corotating twin screw extruder. Throughout the study, the clay content was kept at 2 wt%, whereas the content of SEBS‐g‐MA was varied between 5 and 40 wt%. It was found that Cloisite® 25A displays well dispersion in the ternary nanocomposites and the degree of dispersion increases with the elastomer content. The elastomeric phase has a greater viscosity than pure PS. Thus, as expected, at low elastomer contents, it forms the dispersed phase in the matrix as droplets. Transmission electron microscopy results show that the clay layers reside at the interphase between PS and elastomer and also inside the elastomeric phase. Owing to the location of the clay particles, the average elastomer domain size in ternary nanocomposites are found to be greater than that in the relative binary blends of PS‐(SEBS‐g‐MA). Moreover, with the organoclay addition, phase inversion point shifts to lower elastomer contents. The mechanical test results showed that the nanocomposites containing 15 and 20 wt% SEBS‐g‐MA have the optimum average domain size that results in high‐impact strength values without deteriorating the tensile properties. POLYM. COMPOS., 31:1853–1861, 2010. © 2010 Society of Plastics Engineers.     

Toughening of PA6 nanocomposites by reactive acrylonitrile–butadiene–styrene core–shell rubber particles

The effect of addition of organoclay and the reactive ABS‐g‐MA core‐shell particles on the mechanical properties and morphology of blends of polyamide (PA6) were reported. The reactive rubber particles with core‐shell structure were selected as modifier instead of conventional reactive bulk rubber. The microstructure of the ternary nanocomposites was characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). Impact strength and stress–strain behavior of blends were measured as a function of organoclay content and core/shell ratio of ABS‐g‐MA. The organoclay plates affected the interfacial adhesion between polyamide and the core‐shell particles because of a shielding effect of organclay on the interacting of amine end groups of PA6 with the MA groups of ABS‐g‐MA. The poor dispersion behavior of ternary nanocomposites was observed when the core/shell ratio is 80/20, and with an increase of organoclay content, the core/shell dispersed phase size increased. Blends based on the maleated elastomer with the core/shell ratio 60/40 gave a more beneficial balance of toughness versus stiffness. POLYM. COMPOS., 35:864–871, 2014. © 2013 Society of Plastics Engineers     

Nanocomposite fibers of poly(ethylene terephthalate) with montmorillonite and mica: thermomechanical properties and morphology

The thermal stabilities, mechanical properties, and morphologies of nanocomposites of poly(ethylene terephthalate) (PET) with two different organoclays are compared. Dodecyltriphenylphosphonium‐montmorillonite (C₁₂PPh‐MMT) and dodecyltriphenylphosphonium‐mica (C₁₂PPh‐Mica) were used as reinforcing fillers in the fabrication of PET hybrid fibers. The variations of their properties with organoclay content in the polymer matrix and draw ratio (DR) are discussed. Transmission electron microscopy micrographs show that some of the clay layers are dispersed homogeneously within the polymer matrix on the nanoscale, although some clay particles are agglomerated. It was also found that the addition of only a small amount of organoclay is enough to improve the thermal stabilities and mechanical properties of the PET hybrid fibers. Even polymers with low organoclay contents (1–5 wt%) were found to exhibit much higher strength and modulus values than pure PET. In the case of C₁₂PPh‐MMT/PET, the values of the tensile mechanical properties of the hybrid fibers were found to decrease linearly with increases in DR from 1 to 16. However, the tensile mechanical properties of the C₁₂PPh‐Mica hybrid fibers were found to be independent of DR. Copyright © 2006 Society of Chemical Industry     

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     

Impact,thermal, and morphological properties of functionalized rubber toughened‐poly(ethylene terephthalate) nanocomposites

In this study, poly(ethylene terephthalate)/organo‐montmorillonite (PET/OMMT) nanocomposites were melt‐compounded using twin screw extruder followed by injection molding. Maleic anhydride grafted styrene‐ethylene/butylene‐styrene (SEBS‐g‐MAH) was used to improve the impact properties of the PET/OMMT nanocomposites. The notched and un‐notched impact strength of PET/OMMT nanocomposites increased at about 2.5 times and 5.5 times by the addition of 5 wt % of SEBS‐g‐MAH. Atomic force microscopy (AFM) scans were taken from the polished surface of both PET/OMMT and SEBS‐g‐MAH toughened PET/OMMT nanocomposites. The addition of SEBS‐g‐MAH altered the phase structure and clay dispersion in PET matrix. It was found that some of the OMMT silicate layers were encapsulated by SEBS‐g‐MAH. Further, the addition of SEBS‐g‐MAH decreased the degree of crystallinity of the PET/OMMT nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The Nucleating Effect of Montmorillonite on Crystallization of PET/Montmorillonite Nanocomposite

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo-modified with intercalation agent of cetyltrimetylammonium chloride (CMC). XRD showed that the layers of MMT were intercalated by CMC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt% were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay. The nucleating effect of organoclay is investigated using differential scanning calorimetry (DSC) analysis. Clay behaves as a nucleating agent and enhances the crystallization rate of PET. Maximum enhancement in crystallization rate for the nanocomposites was observed in blends containing ca. 10 wt% of clay in the range of 1–15 wt%. According to transmission electron microscopy (TEM), the organoclay particle was highly dispersed in the PET matrix without a large agglomeration of particles for low organoclay content (5 wt%). Agglomerated structure did form in the PET matrix at 15 wt% organoclay content.