Analysis of the structure and mass transport properties of clay nanocomposites based on amorphous PET

The aim of this work is to characterize the rheological and permeability behavior of nanocomposites based on amorphous poly(ethylene terephthalate) (PETg) and organically modified montmorillonites (omMMT), obtained by melt intercalation. The use of PETg instead of semicrystalline PET is believed to reduce the risks associated to organic modifier degradation during processing at high temperatures. X‐ray and transmission electron microscopy analysis performed on the PETg nanocomposites showed that processing for long time at temperatures lower than melting of semicrystalline PET allowed to obtain a partially intercalated structure with some degree of exfoliation. The rheological behavior of PETg nanocomposites was studied as a function of shear rate in a cone–plate rheometer in order to correlate the viscosity with the aggregation state of omMMT. A simple model accounting for an apparent increase of rheological units size, associated with the intercalation of PETg macromolecules into omMMT galleries, is proposed. The glass transition temperature, T_g, as a function of the volume fraction of omMMT content of the nanocomposite, was measured using differential scanning calorimetry. Finally, the water vapour permeability of PETg nanocomposites was correlated to the volume fraction of the impermeable inorganic part of the omMMT. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphology and properties of poly(ethylene terephthalate) and thermoplastic polyester elastomer blends modified in the melt by a diisocyanate chain extender and filled with a short glass fiber

The structural features and rheological, mechanical, and relaxation properties of poly(ethylene terephthalate) (PET) blends with 7–50 wt % polyester thermoplastic polyester elastomer (TPEE), a block copolymer of poly(butylene terephthalate) and poly(tetramethylene oxide), chemically modified by a diisocyanate chain extender (CE) and reinforced with 30% glass fibers (GF) were studied. The composites were obtained by reactive extrusion with a twin‐screw reactor–mixer with a unidirectional rotation of screws. The molecular–structural changes in the materials were judged against data provided by differential scanning calorimetry, scanning electron microscopy, relaxation spectrometry, and rheological analysis of the melts. Regardless of the TPEE concentration in the blends with GF‐reinforced PET, the addition of CE resulted in the growth of the indices of the mechanical properties at straining, bending, and impact loading and an increase in the melt viscosity. In addition, an increase in the average length of short GFs in the composites and an intensification of interphase adhesion in the polyester binder–GF surface system were observed. The introduction of CE promoted a slowdown in PET crystallization in the composites and intensified the interphase adhesion in the binder–GF system at temperatures higher and lower than the PET glass‐transition temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45711.     

Ultraviolet‐induced chain extension of poly(ethylene terephthalate) based on radical reaction with the aid of trimethylolpropane triacrylate and glycidyl methacrylate during extrusion

In order to improve the processing properties of poly(ethylene terephthalate) (PET), carbon–carbon double bonds were end‐capped onto the chain end of PET by reacting with glycidyl methacrylate (GMA) and then the product was reacted with trimethylolpropane triacrylate (TMPTA) based on a free radical reaction initiated by ultraviolet light to form long‐chain branching structures. The reaction was demonstrated by intrinsic viscosity measurements, carboxyl content analysis, Fourier transform infrared spectroscopy and size exclusion chromatography. Then the rheological and thermal properties of PET were investigated with various TMPTA and GMA contents. Chain extended PET displayed higher complex viscosity than pristine PET and pronounced shear‐thinning behavior. Moreover, the relaxation time spectrum revealed that the modified PET displayed a longer relaxation time during the relaxation process, which was attributed to the higher degree of entanglements resulting from long‐chain branching. Besides, its crystallization temperature and melt temperature shifted to lower temperatures, and the glass transition temperature shifted to higher temperature, indicating that the thermal properties of the modified PET had also been improved. Thus this method can be used to improve the overall properties of PET. © 2020 Society of Chemical Industry     

Thermal characteristics of poly(ethylene terephthalate) fiber grafted with poly(vinyl acetate) and poly(vinyl alcohol)

Poly(ethylene terephthalate) (PET) fibers were grafted with poly(vinyl acetate) (PVAc) and poly(vinyl alcohol) (PVA). The effects of graft copolymers PVAc and PVA on morphological properties of PET were evaluated by differential thermal analysis, differential scanning calorimetry, and thermogravimetric analysis. Melting temperature, heat of fusion, and mass fractional crystallinity of PET was not affected by graft PVAc and PVA. No individual glass transition and melting points corresponding to the graft PVAc and PVA were observed, indicating thereby that graft copolymer mainly exists in the form of free chains inside the PET matrix. Poly(vinyl alcohol) graft copolymer degraded at much lower temperatures than poly(vinyl alcohol) in powder form. Thermal stability of PET fiber was not affected by graft PVAc, where as PET–g–PVA showed an additional degradation point at 360°C.     

Static and dynamic mechanical properties of flame‐retardant copolyester/nano‐ZnCO3 Composites

Novel phosphorus‐containing copolyester nanocomposites were synthesized by in situ polymerization with 2‐carboxyethyl(phenylphosphinic) acid (CEPPA) and nano‐ZnCO₃. The flame retardancy and static and dynamic mechanical properties of poly(ethylene terephthalate) (PET)/nano‐ZnCO₃ composites and phosphorus‐containing copolyester/nano‐ZnCO₃ composites were evaluated with limiting oxygen index measurements, vertical burning testing (UL‐94), a universal tensile machine, and a dynamic mechanical analysis thermal analyzer. The phosphorus‐containing copolyester nanocomposites had higher limiting oxygen indices (ca. 32%) and a V0 rating according to the UL‐94 test; this indicated that nano‐ZnCO₃ and CEPPA greatly improved the flame retardancy of PET. The static mechanical test results showed that the breaking strength, modulus, and yield stress of the composites tended to increase with increasing nano‐ZnCO₃ content; when 3 wt % nano‐ZnCO₃ was added to PET and the phosphorus‐containing copolyester, the breaking strength of the composites was higher than that of pure PET. Dynamic mechanical analysis indicated that the dynamic storage modulus and loss modulus of the PET composites increased markedly in comparison with those of pure PET. However, the glass‐transition temperatures associated with the peaks of the storage modulus, mechanical loss factor, and loss modulus significantly decreased with the addition of ZnCO₃ and CEPPA. The morphologies of the composites were also investigated with scanning electron microscopy, which revealed that nano‐ZnCO₃ was dispersed homogeneously in the PET and copolyester matrix without the formation of large aggregates. In addition, the interfacial adhesion of nano‐ZnCO₃ and the matrix was perfect, and this might have significantly affected the mechanical properties of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reactive blending as a tool for obtaining poly(ethylene terephthalate)-based engineering materials with tailored properties

The structure and properties of blends of poly(ethylene terephthalate) (PET) with poly(trimethylene terephthalate) (PTT) at PTT concentration ≤30 wt.%, obtained with three different methods: from solution, melt extrusion, and direct spinning, are investigated. Relationships between the method of preparation and properties of blends are established. All blends show glass transition temperature at values determined by composition, and crystallization properties also dependent on the preparation method. Blends obtained from solution show separated melting of components. For blends obtained from the melt only PET crystallizes. The melting temperature decreases with the residence time of the melt at high temperatures, due to occurrence of ester exchange reactions. It is shown that reactive blending of PET/PTT mixtures occurring during preparation is a versatile route for obtainment of engineering materials with good mechanical properties, high crystallinity, glass transition temperature lower than that of PET, and melting temperature that may be controlled by the processing conditions.     

Interrelationship of thermal and mechanical properties of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate)/graphene nanocomposites

In the present work, attempts were made to investigate the thermal and mechanical properties of melt‐processed poly(ethylene terephthalate) (PET)/poly(ethylene 2,6‐naphthalate) (PEN) blends and its nanocomposites containing graphene by using differential scanning calorimetry and tensile test experimenting. The results showed that crystallinity, which depends on a blend ratio, completely disappeared in a composition of 50/50. By introducing graphene to PET, even in low concentrations, the crystallinity of samples increased, while the nanocomposite of PEN indicated reverse behavior, and the crystallinity was reduced by adding graphene. In the case of PET‐rich (75/25) nanocomposite blends, by increasing the nano content in the blend, the crystallinity of the samples was enhanced. This behavior was attributed to the nucleating effect of graphene particles in the samples. From the results of mechanical experiments, it was found in PET‐rich blends that by increasing the PEN/PET ratio, the modulus of samples decreased, whereas in the case of PEN‐rich blends, a slight increment of modulus is seen as a result of the increment of the PEN/PET ratio. The two contradicting behaviors were attributed to the reduction of crystallinity of PET‐rich blends by enhancement of PEN/PET ratio and the rigid structure of PEN chains in PEN‐rich blends. Unlike the different modulus change of PET‐rich and PEN‐rich blends, the nanocomposites of these blends similarly indicated an increment of modulus and characteristics of rigid materials by increasing the nano content. Furthermore, the same behavior was detected in nanocomposites of each polymer (PET and PEN nanocomposites). The alteration from ductile to rigid conduction was related to the impedance in the role of graphene plates against the flexibility of polymer chains and high values of graphene modulus. J. VINYL ADDIT. TECHNOL., 23:210–218, 2017. © 2015 Society of Plastics Engineers     

Effect of nanoclay type on dyeability of polyethylene terephthalate/clay nanocomposites

Polyethylene terephthalate (PET)-based nanocomposites containing three differently modified clays were prepared by melt compounding. The influence of type of clay on disperseability, thermal, and dyeing properties of the resultant nanocomposite was investigated by various analytic techniques, namely, X-ray diffraction, optical microscopy (OPM), differential scanning calorimetry, thermal gravimetric analysis, dynamical mechanical thermal analysis, contact angle measurement (CAM), reflectance spectroscopy, and light fastness. OPM images illustrated formation of large-sized spherulites in pure PET, while only small-sized crystals appeared in PET/clay nanocomposites. Decreased glass transition temperatures for all PET/clay nanocomposites indicate that the amorphous regions of such composites become mobile at lower temperatures than those in pure PET. CAMs on the resultant PET composites demonstrated that the wettability of such composites depends on hydrophilicity of the nanoclay particles. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of hydrostatic pressure and temperature on the mechanical loss properties of polymers: 3. PET, PVAC and vinyl chloride/vinyl acetate copolymers

A torsion pendulum (1 Hz) has been used to determine the pressure dependence of the glass transition temperatures of poly(ethylene terephthalate) (PET), poly(vinyl acetate) (PVAC) and some vinyl chloride/vinyl acetate copolymers. Their glass transition temperatures are shifted upwards by amounts varying between 11 and 18°C/1000 atmospheres. In the case of PVAC it has proved possible to compare the results with theory and the observed shift is found to be much less than the predicted value. A study of poly(methyl methacrylate) (PMMA) shows the β relaxation to be displaced to a higher temperature at the rate of 4°C/1000 atm. Results are also presented for the temperature dependence of shear modulus, G′, and loss tangent, tan δ for a reinforced crosslinked polymer, Bakelite P17404, at different pressures.     

Mechanical properties and structures of dicyanate–clay nanocomposites

Dicyanate–clay nanocomposites comprising a dicyanate resin and a type of organically modified clay were prepared and characterized, and their thermomechanical properties were investigated. The organically modified clay had silicate layers of nanometer size intercalated with an organic modifier, which improved the compatibility between the clay and organic materials, such as dicyanate resins. Dynamic mechanical analysis was performed to investigate the thermomechanical properties of the dicyanate–clay nanocomposites containing various amounts of the clay. The storage modulus of the nanocomposites below their glass‐transition temperatures slightly increased with increasing clay content. The glass‐transition temperature of the dicyanate–clay nanocomposites increased with increasing clay content. The nanostructures of the dicyanate–clay nanocomposites were characterized by transmission electron microscopy and X‐ray diffraction analysis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2629–2633, 2003     

Characterisation of melt‐processed poly(ethylene terephthalate)/synthetic mica nanocomposite sheet and its biaxial deformation behaviour

BACKGROUND: Poly(ethylene terephthalate) (PET) is widely used in the packaging industry. In order to enhance the mechanical and barrier properties, nanoscale fillers are added to PET matrices to form nanocomposites. In the work reported here, a melt‐processed PET/synthetic mica nanocomposite sheet was characterised to determine the effect of the incorporation of synthetic mica on the sheet properties and also to see if these properties are an indicator of subsequent performance under high‐speed, high‐temperature biaxial deformation, typical of processes such as stretch blow moulding. RESULTS: The incorporation of synthetic mica was found to enhance the modulus, particularly above the glass transition temperature, and barrier properties of the extruded sheet and it significantly altered the deformation behaviour of PET under biaxial deformation. The plastic flow of PET during biaxial deformation was found to diminish for the nanocomposites, and strain hardening occurred earlier. CONCLUSION: The modulus and barrier properties of PET were enhanced by the incorporation of synthetic mica. Clay loading also altered the biaxial deformation behaviour of PET. Copyright © 2009 Society of Chemical Industry     

Effect of organoclay in an immiscible poly(ethylene terephtalate) waste/poly(methyl methacrylate) blend

Blends of organically modified montmorillonite (OMMT) with poly(ethylene terephtalate) (PET) waste and poly(methyl methacrylate) (PMMA) were prepared by melt mixing. The morphology of PET/PMMA nanocomposites with different OMMT contents was characterized by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The nonisothermal crystallization temperatures of nanocomposites were also examined by DSC. TEM observations and XRD patterns revealed that silicate layers were intercalated and well dispersed in the blend. Nanocomposites displayed better mechanical properties when compared with the unfilled blend. DMA analyses also showed efficient mixing of the two immiscible polymers and changes in glass transition temperature with the presence of OMMT. DSC analysis showed an enhancement in crystallization rate of nanocomposites and a decrease in cristallinity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Reduced graphene oxide reinforced PET/PBT nanocomposites: Compatibilization and characterization

This research work focused on the effects of different compatibilizers on the properties of reduced graphene oxide (rGO) reinforced poly(ethylene terephthalate) (PET)/poly(butylene terephthalate) (PBT) nanocomposites. The samples were prepared via melt compounding and injection molding methods. The Joncryl and glycidyl isooctyl polyhedral oligomeric silsesquioxane (GPOSS) were used as compatibilizers at different loading levels (0.5%-4%). The structural, thermal, mechanical, morphological, and electrical properties of the nanocomposites were investigated. The Fourier transform infrared analysis results revealed that no significant interaction was observed when GPOSS was added. On the other hand, there were more obvious changes in the peaks of the nanocomposite containing Joncryl. The thermal results showed that the compatibilizer addition caused small changes while rGO addition did not considerably affect the thermal stability of blend. The glass transition temperature of the nanocomposite significantly decreased with the addition of GPOSS. The tensile test indicated that compatibilizers improved the mechanical performance of PET/PBT/rGO nanocomposite.     

Aging characteristics of oriented ply(ethylene terephthalate)

The physical aging characteristics of oriented poly(ethylene terephthalate) (PET), have been studied ad functions of storage time and temperature below the glass transition temperature (T_g) of PET. The free volume relaxation, associated with aging, has been characterized by the enthalpy at T_g, as measured by differential scanning calorimetry. The effects of the free volume relaxation on mechanical properties and the mode of failure have been investigated. It has been determined that a correlation exists between the enthalpy of relaxation and the ductile-to-brittle failure transition. Molecular orientation reduces significantly the enthalpy of relaxation, resulting in the disappearance of the ductile-to-brittle transition when highly oriented samples are aged over time. It has been established that a minimum amount of orientation is required to reduce or eliminate the effects of PET aging. Molecular orientation has also been found to reduce craze formation when oriented PET is exposed to a stress-cracking medium at constant stress.     

Radiation‐induced crosslinking of acetylene‐impregnated polyesters. II. Effects of preirradiation crystallinity,molecular structure,and postirradiation crosslinking on mechanical properties

Electron beam‐irradiated crosslinking has been studied in a series of acetylene‐impregnated polyesters and amorphous copolyesters, including poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(cyclohexane dimethylene terephthalate) (PCDT), and poly(cyclohexane dimethylene terephthalate‐co‐ethylene terephthalate) (P(CDT‐co‐ET)) having 29 and 60 wt % ethylene terephthalate (ET). The extent of crosslinking was observed by gel fraction measurements and was found to be significantly influenced by the aliphatic chain content of the polyesters (PET < PBT < PCDT). In addition, as the preirradiation crystallinity of the polyesters was reduced, the extent of acetylene‐enhanced crosslinking was greatly raised. Decreases in the postirradiation crystalline melting temperature and degree of crystallinity were observed in all the polyesters, using differential scanning calorimetry measurements. Particularly significant findings have been the shift in the glass‐transition temperatures (Tg) to higher temperatures and the decrease in loss tangents at higher temperatures, both of which confirm that crosslinking has taken place. The storage moduli (E′) in the rubbery plateau region of PCDT and P(CDT‐co‐ET) were significantly affected by irradiation dose. Increased network tightness in postirradiated PBT and PCDT films was also inferred from melt‐rheology measurements, in which stress relaxed more slowly following a stepped strain. Improvements in the mechanical properties of the irradiated polyesters and copolyesters were clearly evidenced by the increased modulus at higher temperatures, observed using dynamic mechanical thermal analysis and melt‐rheology methods. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4476–4490, 2006     

DSC and DMTA study of annealed cold-drawn PET: a three phase model interpretation

Cold-drawn poly(ethylene terephthalate) (PET) samples annealed at different undercoolings are studied by means of differential scanning calorimetry and dynamic mechanical thermal analysis. When heating from room temperature, the onset of the glass transition region in cold-drawn, un-annealed samples is found to be significantly lower than in the case of un-oriented PET. On the contrary, the presence of crystalline lamellae in oriented PET cause a shift (and spread out) of the glass transition region towards higher temperatures. The crystal thickening process caused by heating above the annealing temperature, is suggested to take place after a rigid amorphous phase linked to the basal surface of the lamellae has softened. It is found that the low-temperature (between 100 and 140 °C) annealed samples have a glass dispersion region ranging significantly above the annealing temperature itself. This circumstance leads to envisage vitrification as a possible mechanism able to limit lamellar thickening during the annealing process at these low temperatures.     

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.     

Morphology,barrier, and mechanical properties of biaxially deformed poly(ethylene terephthalate)‐mica nanocomposites

Nanocomposites of poly(ethylene terephthalate) PET with a partially synthetic fluoromica were prepared by melt mixing and extruded into sheet and subjected to large‐scale biaxial stretching. Transmission electron microscopy (TEM) analysis of the mica tactoids showed that biaxial stretching had caused the tactoids to be more orientated and with improved exfoliation. The moduli of the nanocomposites were enhanced with increasing mica loading and the reinforcement effect was higher when the stretch ratio was 2 or 2.5, accommodated by having more aligned tactoids and reduced agglomeration. Enhancement in modulus was less pronounced for a stretch ratio of 3. Storage modulus was enhanced more significantly above the glass transition temperature. The barrier properties were enhanced by addition of mica before and after stretching. The Halpin‐Tsai theory underpredicted the relative modulus of the PET nanocomposites, whereas the Nielsen model over‐predicted the relative permeability. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Supercritical carbon dioxide (scCO2) dispersion of poly(ethylene terephthalate)/clay nanocomposites: Structural,mechanical, thermal,and barrier properties

Dispersed poly(ethylene terephthalate) (PET)/clay nanocomposites can lead to materials with superior barrier and mechanical properties. PET/clay nanocomposites were prepared by melting extrusion of PET with as‐received or supercritical carbon dioxide (scCO₂) predispersed Cloisite^® 30B (30B). The predispersion of 30B was assessed by WAXD, SEM, and TGA, and results indicated that scCO₂ processing could predisperse 30B and the surface modification of the clay was preserved after processing. The structure of PET/30B nanocomposites was investigated by WAXD and TEM confirming that PET has penetrated into the clays inter‐galleries and the predispersed clays lead to improved interfacial interaction and homogenous clay dispersion. Both tensile strength and Young's modulus were improved by 12.1% and 24.9% respectively, as incorporating of 3 wt % of scCO₂ processed clay. Differential scanning calorimetry (DSC) results indicated that clay particles served as nucleation agent could increase the crystallinity whereas had no impact on melting process. In addition, with the addition of 1 wt % of predispersed clay, a significant reduction of oxygen permeation (～33%) was achieved at 23 °C and the maximum reduction (44%) was achieved by adding 3 wt % processed clay. Moreover, we confirmed the effect of temperature on the permeation of PET/30B nanocomposites depended both on the Arrhenius behavior of the organic phases and tortuous path effects, where improved clay dispersion resulted in a higher effective activation energy. Moreover, the transparency of PET matrix was preserved for all nanocomposites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44779.