Poly(ethylene terephthalate) nanocomposites by in situ interlayer polymerization: the thermo-mechanical properties and morphology of the hybrid fibers

Nanocomposites of poly(ethylene terephthalate) (PET) with C₁₂PPh-MMT as an organoclay were synthesized by using the in situ interlayer polymerization approach. The PET nanocomposites were melt-spun at different organoclay contents and different draw ratios to produce monofilaments. The thermo-mechanical properties and the morphologies of the PET nanocomposites were examined by using a differential scanning calorimeter, a thermogravimetric analyzer, a wide angle X-ray diffactometer, scanning and transmission electron microscopes, and a universal tensile machine. Some of the clay particles were well dispersed in the PET matrix, and some of them were agglomerated at a size level of greater than approximately 10 nm. The thermal stability and the tensile mechanical properties of the PET hybrid fibers increased with increasing clay content at a DR=1. However, the values of the ultimate tensile strength and the initial modulus of the hybrid fibers decreased markedly with increasing DR from 1 to 16.     

Polyester nanocomposite fibers: comparison of their properties with poly(ethylene terephthalate) and poly(trimethylene terephthalate) (II)

Summary Two polyester nanocomposites were synthesized, one with poly(ethylene terephthalate) (PET) and the other with poly(trimethylene terephthalate) (PTT), by using organoclay. The in-situ interlayer polymerization method was used to disperse the organoclay in polyesters at different organoclay contents and at different draw ratios to produce monofilaments. The thermal stability and tensile mechanical properties increased with increasing organoclay content at a DR=1 . However, the values of the tensile mechanical properties of the hybrid fibers decreased with increasing DR. The reinforcing effects of the organoclay of the PET hybrid fibers were higher than those of the PTT hybrid fibers.     

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     

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     

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.     

Comparison of Thermomechanical Properties and Morphologies of Polyester Nanocomposite Fibers: PBT,PET, and PTT

Nanocomposites of three different polyesters with dodecyltriphenyl-phosphonium-montmorillonite (C₁₂PPh-MMT) organoclay are compared with respect to their thermal properties, mechanical properties, and morphologies. Poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET), and poly(trimethylene terephthalate) (PTT) were used as matrix polymers in the fabrication of polyester nanocomposite fibers. The variations in their properties with respect to both the organoclay content in the polymer matrix and the draw ratio (DR) are discussed. Transmission electron microscopy (TEM) micrographs show that some of the clay layers are dispersed homogeneously within the polymer matrix on the nanoscale, although some clay particles are agglomerated. The results additionally show that the addition of only a small amount of organoclay is enough to improve the thermal stabilities and mechanical properties of the polyester nanocomposite fibers.     

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.     

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     

Poly(ethylene terephthalate)/clay nanocomposites with trisilanolphenyl polyhedral oligomeric silsesquioxane as dispersant: simultaneously enhanced reinforcing and stabilizing effects

This paper presents a new approach for the preparation of poly(ethylene terephthalate) (PET)/clay nanocomposites using surfactant‐free clay (sodium montmorillonite, Na‐MMT) with trisilanolphenyl polyhedral oligomeric silsesquioxane (Tsp‐POSS) as dispersant. The dispersion of clay in the PET/Na‐MMT/Tsp‐POSS nanocomposites is enhanced over that in PET/Na‐MMT by using a very small amount of Tsp‐POSS, which acts as functional spacer to keep clay platelets apart and pull monomers in, and, at the same time, acts as a PET chain extender. As a result, thermomechanical properties and thermo‐oxidative stability of PET/Na‐MMT/Tsp‐POSS are improved simultaneously compared with those of PET/organoclay nanocomposites. © 2013 Society of Chemical Industry     

Preparation of PET/clay nanocomposites via in situ polymerization in the presence of monomer‐activated organoclay

Various polyethylene terephthalate (PET)/clay nanocomposites containing a commercial organoclay (organophilic montmorillonite nanoclay [OMMT]) and a monomer‐activated OMMT (remodified OMMT) were prepared via in situ interlayer polycondensation of dimethyl terephthalate and ethylene glycol. In order to remodify the commercial OMMT nanoparticles, a diacid chloride monomer was applied. The prepared nanocomposites were characterized by diverse methods, including X‐ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and intrinsic viscosity measurements. The results of the study revealed that the PET/(remodified OMMT) nanocomposites possess a better state of clay dispersion as well as significantly better thermal properties as compared with the PET/OMMT nanocomposites. Moreover, the PET/(remodified OMMT) nanocomposites showed higher crystallization temperature, degree of crystallinity, maximum degradation temperature, and lower half‐time of crystallization than that of the PET/OMMT nanocomposites. It was found that the remodification process for OMMT led to less of a foaming problem during in situ polymerization. J. VINYL ADDIT. TECHNOL., 21:70–78, 2015. © 2014 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     

Reactive extrusion of poly(ethylene terephthalate)–(ethylene/methyl acrylate/glycidyl methacrylate)–organoclay nanocomposites

This study was conducted to investigate the effects of component concentrations and addition order of the components on the final properties of ternary nanocomposites composed of poly(ethylene terephthalate), organoclay, and an ethylene–methyl acrylate–glycidyl methacrylate (E‐MA‐GMA) terpolymer acting as an impact modifier for PET. In this context, first, the optimum amount of the impact modifier was determined by melt compounding binary PET‐terpolymer blends in a corotating twin‐screw extruder. The amount of the impact modifier (5 wt%) resulting in the highest Young's modulus and moderate elongation at break was selected owing to its balanced mechanical properties. Thereafter, by using 5 wt% terpolymer content, the effects of organically modified clay concentration and addition order of the components on the properties of ternary nanocomposites were systematically investigated. Mechanical testing revealed that different addition orders of the materials significantly affected the mechanical properties. Among the investigated addition orders, the best sequence of component addition (PI‐C) was the one in which poly(ethylene terephthalate) was first compounded with E‐MA‐GMA. Later, this mixture was compounded with the organoclay in the subsequent run. In X‐ray diffraction analysis, extensive layer separation associated with delamination of the original clay structure occurred in PI‐C and CI‐P (Clay + Impact Modifier followed by PET) sequences with both 1 and 3 wt% clay contents. X‐ray diffraction patterns showed that at these conditions exfoliated structures resulted as indicated by the disappearance of any peaks due to the diffraction within the consecutive clay layers. POLYM. COMPOS., 28:251–258, 2007. © Society of Plastic Engineers     

Poly(butylene terephthalate)/organoclay nanocomposites prepared by in situ interlayer polymerization and its fiber (II)

Intercalated nanocomposites with poly(butylene terephthalate) (PBT) incorporated between the montmorillonite layers were synthesized from dimethyl terephthalate and 1,4-butane diol by using an in situ interlayer polymerization. The PBT nanocomposites were melt-spun at different organoclay contents to produce monofilaments. The samples were characterized by using wide angle X-ray diffraction, electron microscopy, thermal analysis, and tensile testing. The extent of the clay layer in the PBT was confirmed by using X-ray diffraction and electron microscopy, and the clay layer was found to be highly dispersed on a nanometer scale. The addition of only a small amount of organoclay was enough to improve the thermo-mechanical properties of the PBT hybrid fibers. The hybrids were extruded with various draw ratios (DRs) to examine the tensile mechanical property of the fibers. At DR=1, the ultimate tensile strength of the hybrid fibers increased with the addition of clay up to a critical content and then decreased. However, the initial modulus monotonically increased with increasing amount of organoclay in the PBT matrix. When the DR was increased from 1 to 6, for example, the strength and the initial modulus values of the hybrids containing 3 wt% organoclay decreased linearly.     

Morphology and thermomechanical properties of recycled PET–organoclay nanocomposites

Recycled PET/organoclay nanocomposites were prepared by melt intercalation process with several amounts (1, 3, and 5 wt %) of clay modified with quaternary ammonium salt (DELLITE 67G) dispersed in a recycled poly(ethylene terephthalate) (rPET) matrix. The resultant mechanical properties (modulus and yield strength) of the nanocomposites were found to be different from those of rPET. Wide angle X‐ray scattering (WAXS) and Transmission Electron Microscopy (TEM) measurements have shown that although complete exfoliation was not achieved, delaminated clay platelets could be observed. Thermal analysis did not show significant changes in the thermal properties from those of recycled PET. Mechanical testing showed that nanocomposite properties were superior to the recycled PET in terms of strength and elasticity modulus. This improvement was attributed to nanoscale effects and strong interaction between the rPET matrix and the clay interface, as revealed by WAXS and TEM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1839–1844, 2007     

Poly(ethylene terephthalate)/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate)/clay nanocomposites: Mechanical properties,optical transparency,and barrier properties

Poly(ethylene terephthalate) (PET)/clay, PET/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate) (PETG), and PET/PETG/clay nanocomposites were fabricated using the twin‐screw extrusion technique. The spherulitic morphologies, thermomechanical, mechanical, and gas‐barrier properties, as well as the effect of clay on the transparency of the resulting nanocomposites were identified. The clay induced the heterogeneous nucleation of the nanocomposites during the cold crystallization process, thereby increasing the crystallinities and melting temperatures of the resulting nanocomposites. The incorporation of clay increased the storage moduli, Young's moduli, impact strengths, and barrier properties of the PET, PETG, and PET/PETG blend. Regarding the optical transparency, the inclusion of clay can make the crystallizable PET matrix crystalline opaque. However, the amorphous PETG maintained its transparency. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39869.     

Physical and dyeing properties of poly(ethylene terephthalate)/montmorillonite nanocomposite filament yarns

This research paper describes the generation of poly(ethylene terephthalate) (PET)/organoclay nanocomposite filaments by melt‐spinning method and investigation of their physical and dyeing properties. Two montmorillonite types of clay were modified using an intercalating agent synthesized and PET/organoclay (85/15 wt/wt) master batches were prepared using a corotating intermeshing twin screw extruder. Afterward, nanocomposite filaments containing different amounts of organoclay (0.5–5 wt%) were produced and dyed with two disperse dyes at atmospheric and high temperature dyeing conditions. Increased clay concentration led to reduced mechanical properties. Nonetheless, PET/organoclay nanocomposite filaments showed enhanced dyeability. POLYM. ENG. SCI., 2013. © Society of Plastics Engineers     

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     

Effect of water‐assisted extrusion and solid‐state polymerization on the microstructure of PET/Clay nanocomposites

An melt‐mixing process has been used to prepare Poly(ethylene terephthalate) (PET)/clay nanocomposites with high degree of clay delamination. In this method, steam was fed into a twin‐screw extruder (TSE) to reduce the PET molecular weight and to facilitate their diffusion into the gallery spacing of organoclays. Subsequently, the molecular weight (M_W) reduction of the PET matrix due to hydrolysis by water was compensated by solid‐state polymerization (SSP). The effect of the thermodynamic compatibility of PET and organoclays on the exfoliated microstructure of the nanocomposites was also examined by using three different nanoclays. The dispersion of Cloisite 30B (C30B) in PET was found to be better than that of Nanomer I.28E (I28E) and Cloisite Na⁺. The effect of feeding rate and consequently residence time on the properties of PET nanocomposites was also investigated. The results reveal more delamination of organoclay platelets in PET‐C30B nanocomposites processed at low feeding rate compared to those processed at high feeding rate. Enhanced mechanical and barrier properties were observed in PET nanocomposites after SSP compared to the nanocomposites prepared by conventional melt‐mixing. POLYM. ENG. SCI., 54:1723–1736, 2014. © 2013 Society of Plastics Engineers     

Poly(trimethylene terephthalate) nanocomposite fibers by in situ intercalation polymerization: thermo-mechanical properties and morphology (I)

A series of poly(trimethylene terephthalate) (PTT) nanocomposites, containing an organically modified montmorillonite (C₁₂PPh-MMT), were prepared by in situ intercalation polymerization of dimethyl terephthalate (DMT) and 1,3-propanediol (PDO). The PTT nanocomposites were melt-spun at different organoclay contents and different draw ratios (DRs) to produce monofilaments. The nanocomposites were characterized by X-ray diffraction, electron microscopy, universal tensile testing, differential scanning calorimetry and thermogravimetric analysis. Some of the clay particles appeared well dispersed within the PTT matrix, while others were found to agglomerate with a size greater than 10 nm. The addition of a small amount of C₁₂PPh-MMT was sufficient to improve the thermo-mechanical properties of the PTT hybrid fibers. Both the thermal stability and the tensile strength increased with increasing clay content at DR=1. As the DR was increased from 1 to 9, the ultimate tensile strength of the hybrid fibers decreased, while the initial modulus remained constant.     

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