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.     

Poly(trimethylene terephthalate) nanocomposite fibers comprising different organoclays: Thermomechanical properties and morphology

Poly(trimethylene terephthalate) (PTT) nano composites were synthesized by in situ polymerization at high temperature with two thermally stable organoclays: 1,2‐dimethylhexadecylimidazolium‐montmorillonite (IMD‐MMT) and dodecyltriphenyl phosphonium‐MMT (C₁₂PPh‐MMT). PTT hybrid fibers with various organoclay contents were melt‐spun at various draw ratios (DRs) to produce monofilaments. The thermomechanical properties and morphologies of the PTT hybrid fibers were characterized using differential scanning calorimetry, thermogravimetric analysis, wide‐angle X‐ray diffraction, electron microscopy, and mechanical tensile properties analysis. The nanostructure of the hybrid fibers was observed by both scanning and transmission electron microscopy, which showed that the clay layers were well dispersed into the matrix polymer, although some clusters or agglomerated particles were also detected. Unlike the hybrids containing IMD‐MMT, the clay layers of the C₁₂PPh‐MMT hybrid fiber were more dispersed into the matrix polymer. The thermal stability and tensile properties of the hybrid fibers increased with increasing clay content for DR = 1. However, as DR increased from 1 to 9 the ultimate strength and initial modulus of the hybrid fibers with IMD‐MMT increased slightly whereas those of C₁₂PPh‐MMT hybrid fibers decreased slightly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4535–4545, 2006     

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) 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     

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.     

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.     

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.     

Synthesis and characterization of poly(butylene terephthalate) nanocomposite fibers: Thermo‐mechanical properties and morphology

Nanocomposites of poly(butylene terephthalate) (PBT) with the organoclay C₁₂PPh‐MMT were prepared using in situ intercalation polymerization. Hybrids with various organoclay contents were processed for fiber spinning to examine their thermal behavior, tensile mechanical properties, and morphologies for various draw ratios (DRs). The thermal properties (T_g, T_m, and T_Dⁱ) of the hybrid fibers were found to be better than those of pure PBT fibers and were unchanged by variation of the organoclay loading up to 2 wt %. However, these thermal properties remained unchanged for DRs ranging from 1 to 18. Most clay layers were dispersed homogeneously in the matrix polymer, although some clusters were also detected. The tensile properties of the hybrid fibers increased gradually with increasing C₁₂PPh‐MMT content at DR = 1. However, the ultimate strengths and initial moduli of the hybrid fibers decreased markedly with increasing DR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1247–1254, 2006     

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.     

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(vinyl alcohol) nanocomposites with different clays: Pristine clays and organoclays

Poly(vinyl alcohol) (PVA)/clay nanocomposites were synthesized using the solution intercalation method. Na ion‐exchanged clays [Na⁺–saponite (SPT) and Na⁺–montmorillonite (MMT)] and alkyl ammonium ion‐exchanged clays (C₁₂–MMT and C₁₂OOH–MMT) were used for the PVA nanocomposites. From the morphological studies, the Na ion‐exchanged clay is more easily dispersed in a PVA matrix than is the alkyl ammonium ion‐exchanged clay. Attempts were also made to improve both the thermal stabilities and the tensile properties of PVA/clay nanocomposite films, and it was found that the addition of only a small amount of clay was sufficient for that purpose. Both the ultimate tensile strength and the initial modulus for the nanocomposites increased gradually with clay loading up to 8 wt %. In C₁₂OOH–MMT, the maximum enhancement of the ultimate tensile strength and the initial modulus for the nanocomposites was observed for blends containing 6 wt % organoclay. Na ion‐exchanged clays have higher tensile strengths than those of organic alkyl‐exchanged clays in PVA nanocomposites films. On the other hand, organic alkyl‐exchanged clays have initial moduli that are better than those of Na ion‐exchanged clays. Overall, the content of clay particles in the polymer matrix affect both the thermal stability and the tensile properties of the polymer/clay nanocomposites. However, a change in thermal stability with clay was not significant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3208–3214, 2003     

Mechanical properties and rheological behavior of poly(butylene terephthalate)/clay nanocomposites with different organoclays

Poly(butylene terephthalate)–clay nanocomposites with three different organically modified clays were prepared via melt blending in a twin‐screw extruder. Decyl triphenylphosphonium bromide, hexadecyl triphenylphosphonium bromide, and cetyl pyridinium chloride were used to modify the naturally occurring montmorillonite clay. The organically modified clays were characterized with X‐ray diffraction for the d₀₀₁‐spacing and with thermogravimetric analysis to determine the thermal stability. The prepared nanocomposites were injection‐molded and examined for the dispersion quality of the clay, the mechanical properties, and the rheological behavior. The tensile strength of the nanocomposites increased with a 1% addition of clay; however, more clay decreased the tensile strength. Nanocomposites with finely dispersed clay platelets and nanocomposites with poorly dispersed clay platelets showed very different rheological behaviors. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reinforcing properties of poly(trimethyleneterephthalate) by a thermotropic liquid crystal polymer

A thermotropic liquid crystalline copolymer (TLCP) having a trimethylene terephthalate (TT) unit and a triad terephthaloyl mesogenic unit was synthesized and its blends with poly(trimethylene terephthalate) (PTT) were prepared for TLCP‐reinforced fiber spinning. The TLCP, PTT, and their blends were characterized in terms of their thermal, mechanical, and morphological properties. In the hot‐drawn fibers of 20 wt % TLCP/PTT blend, the well‐oriented fibrils were observed at higher temperature (>T_m) than the PTT melt by polarizing optical microscope. With scanning electron microscopy images of cryogenically fractured surfaces of the blends, the TLCP were well dispersed in 0.3 to 0.5 µm in domain size. Interfacial adhesion between the TLCP and PTT seemed fairly good. The TLCP acted effectively as a reinforcing material in PTT matrix, it led to an increase of initial modulus and tensile strength of the blend fibers as TLCP's content increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41408.     

Poly(trimethylene terephthalate‐block‐tetramethylene oxide) elastomer/single‐walled carbon nanotubes nanocomposites: Synthesis,structure, and properties

Nanocomposites based on poly(trimethylene terephthalate)‐block‐poly(tetramethylene oxide) (PTT‐PTMO)‐segmented copolymer and COOH‐functionalized single‐walled carbon nanotubes (SWCNTs) were prepared by in situ polymerization method. The obtained nanocomposites were characterized by thermogravimetric analysis, scanning electron microscopy, differential scanning calorimetry (DSC), DMTA, wide‐angle x‐ray scattering (WAXS), small‐angle X‐ray scattering, and tensile testing. The nanocomposites with low SWCNTs loading (<0.5 wt %) shows uniform dispersion of CNT in polymer matrix. As the SWCNTs loading in the nanocomposites increase, the significant improvement of thermo‐oxidative stability was observed. It was found that the nanocomposites have slightly higher degree of crystallinity (determined by DSC and WAXS) of poly(trimethylene terephthalate) (PTT) hard phase than neat PTT‐PTMO copolymer. The melting point of PTT hard phase and glass transition temperature of poly(tetramethylene oxide)‐rich phase were not affected by the presence of CNTs in polymer matrix. The SWCNTs played a role as nucleating agent in PTT‐PTMO matrix, which led to increase in the crystallization rate. Tensile tests showed that the tensile strength of the nanocomposites with 0.05–0.3 wt % loading of SWCNTs have improved tensile strength in comparison to the neat PTT‐PTMO copolymer without reduction elongation at break. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure–property evolution of poly(ethylene terephthalate)/poly(trimethylene terephthalate) side-by-side self-crimp filament

To investigate the microstructure and mechanical properties of self-crimping two-component side-by-side bicomponent filament, this paper focuses on systematically investigating the structure–property evolution of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) side-by-side bicomponent filament prepared via melt spinning with various component ratios, drawing and heating treatment. The investigation was operated upon the combination of morphology analysis, thermal analysis, crystallization, and orientation analysis. The variation of cross section and curl-morphology, crystallization, and microstructures mainly containing lamellar and microfibrillar crystals as well as their effects on the mechanical and self-crimping properties were discussed. As the draft ratio (DR) increases, the crystallinity, sonic orientation factor, tensile strength, and crimp-recovery rate of the filaments were increased. The sonic orientation factor in the crystalline region decreases from 0.923 to 0.777 but increases from 0.677 to 0.903 in the amorphous region. In contrast to the variation of the DR, heating temperature has a limited effect on the tensile strength of the PET/PTT hybrid filaments. Crimp-recovery rate, however, first increases to 11.8 and then decreases to 9.8 with an increasing heating temperature from 144 to 168°C. Most of these behaviors have been attributed to changes in the ratio of contractile stress for both PTT and PET components, originating from microstructural evolution in hybrid filaments, including crystal growth, breakage, deflection, and deformation of chains along the axial direction. As a summary, an interpretive diagrammatic sketch has been proposed to clarify the structure–property relationships of the commercial PET/PTT filaments.     

Nanocomposites of poly(trimethylene terephthalate) with organoclay

Two different kinds of clay were organomodified with cetylpyridinium chloride (CPC) as an intercalation agent. Poly(trimethylene terephthalate) (PTT)/organoclay nanocomposites were prepared by the solution intercalation method. Wide‐angle X‐ray diffraction (WAXD) indicated that the layers of clay were intercalated by CPC and the interlayer spacing was a function of the cationic exchange capacity (CEC) of the clay: the higher the CEC, the larger the interlayer spacing is. The WAXD studies showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay. From the results of differential scanning calorimetry analysis it was found that clay behaves as a nucleating agent and enhances the crystallization rate of PTT. The maximum enhancement of the crystallization rate for the nanocomposites was observed in nanocomposites containing about 5 wt % organoclay with a range of 1–15 wt %. The thermal stability of the nanocomposites was enhanced by the addition of 1–10 wt % organoclay as found from thermogravimetric analysis. The thermal stability of the PTT/organoclay nanocomposites was related to the organoclay content and the dispersion in the PTT matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3315–3322, 2003     

Preparation and characterization of polyimide nanocomposites with different organo‐montmorillonites

Poly(amic acid) nanocomposites were synthesized from a dimethylacetamide (DMAc) solution with two organophilic montmorillonites (organo‐MMTs). It was then heated at various temperatures under vacuum, yielding 15–20 um thick films of polyimide/organo‐MMT hybrid with different clay contents (1–8 wt%). Dodecy‐lamine (C₁₂‐) and hexadecylamine (C₁₆‐) were used as aliphatic alkylamines in organo‐MMT. The ultimate strength monotonically increased with increasing clay content in the polymer matrix. Maximum enhancement in the initial modulus was observed for the blends containing 2 wt% clay with two kinds of organo‐clays, and values did not alter significantly with further increases in clay content. Additions of only 2 wt% C₁₂‐ and C₁₆‐MMT to the polyimide were shown to cause 94%‐95% reduction in oxygen gas permeability. This is caused by the barrier properties of the clay layers dispersed in the composite. In general, C₁₆‐MMT is more effective than C₁₂‐MMT in increasing both the tensile property and the gas barrier in a polyimide matrix. Intercalations of the polymer chains in clay were examined through wide‐angle X‐ray diffraction (XRD) and electron microscopies (SEM and TEM).     

Effect of Inorganic Filler on the Crystallization,Mechanical Properties and Rheological Behavior of Poly(trimethylene terephthalate)

Poly(trimethylene terephthalate) filled with nano-CaCO₃ and ultra-fine talc was prepared by melt blending using a co-rotating twin screw extruder. The effect of these two inorganic filler on the crystallization and melting behavior, mechanical properties and rheological behavior of PTT were characterized. The DSC results indicated that both nano-CaCO₃ and ultra-fine talc exhibited heterogeneous nucleation effect on the crystallization of PTT, and more significant nucleation effect were observed in PTT/nano-CaCO₃ composite due to the smaller size and better dispersion of nano-CaCO₃ in PTT matrix. Mechanical properties study suggested that the incorporation of nano-CaCO₃ and ultra-fine talc greatly improved the tensile and flexural properties of PTT. Ultra-fine talc tends to lower the impact properties, while nano-CaCO₃ tend to increase the impact strength of the PTT/nano-CaCO₃ composite. When 2 wt.% of nano-CaCO₃ was added, the impact strength increased by one time. Rheological behavior study indicated nano-CaCO₃ exhibited plasticization effect on PTT melt and decreased the viscosity of PTT, while ultra-fine talc increased the viscosity of PTT due to the hindrance of the layer structure of talc.     

Electrical conductivity and transparency of polymer hybrid nanocomposites based on poly(trimethylene terephthalate) containing single walled carbon nanotubes and expanded graphite

Single‐walled carbon nanotubes (SWCNT)/expanded graphite (EG)/poly(trimethylene terephthalate) (PTT) hybrid nanocomposites were prepared via in situ polymerization. Raman spectroscopy and scanning electron microscopy (SEM) were employed to determine both, purity and morphology of the nanofillers and the dispersion of nanotubes and nanosheets. The electrical and optical properties of thin polymer films based on both “single” nanocomposites and hybrid nanocomposites were studied. For PTT/SWCNT nanocomposites, results confirmed that films optical transmittance decreases as the concentration of SWCNT increases, attaining almost no optical transmittance for 0.3 wt % of nanofiller. Conversely, the electrical conductivity of nanocomposites was found to increase by increasing the nanofiller amount and the σ_dc values indicate that percolation occurs at a very low SWCNT content (around 0.05 wt %). In the case of PTT/SWCNT + EG nanocomposites, when the content of SWCNT is 0.05%, the hybrid system presents lower conductivity than that corresponding to the “single” nanocomposite. The incorporation of additional EG to the PTT/SWCNT nanocomposite has a small effect on the electrical conductivity but inhibits the transparency of the system. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44370.     

Synthesis and characterization of poly(trimethylene terephthalate)/polyhedral oligomeric silsesquixanes nanocomposites

This article reports the preparation of poly(trimethylene terephthalate) (PTT)– polyhedral oligomeric silsesquioxanes (POSS) nanocomposites through in situ polymerization. The chemical structure of the PTT–POSS nanocomposites was characterized with Fourier‐transform infrared and nuclear magnetic resonance spectroscopies and the presence of POSS was further confirmed by the elemental analysis. The crystal structures as well as the position of POSS in the nanocomposites were ascertained by the X‐ray diffraction (XRD) studies. Thermal characterization studies showed the gradual decrease in the glass transition and melt crystallization temperatures. Though the thermal stability of the PTT was not affected by the incorporation of POSS, the amount of residues obtained from thermal degradation process was increased with an increase in the content of POSS. The tensile studies showed that the values of initial modulus and breaking strength were dramatically decreased with an increase in the content of POSS. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers