In situ WAXS/SAXS structural evolution study during uniaxial stretching of poly(ethylene therephthalate) nanocomposites in solid state: Poly(ethylene therephthalate)/montmorillonite nanocomposites

This work investigates the solid state uniaxial stretching of neat polyethylene therephthalate, PET, and its montmorillonite, MMT, nanocomposites (0.3 wt % of MMT particles with different initial agglomerate sizes) showing intercalated and tactoid morphologies, followed by in situ WAXS and SAXS experiments under an X‐ray synchrotron source. The distinct nanocomposite morphologies were assessed by WAXS and transmission electron microscopy. The in situ WAXS experiments during stretching evaluated the evolution of phase's mass fractions and the average level of molecular orientation upon uniaxial deformation, and the in situ SAXS experiments assessed the evolution of craze‐like structures and void sizes. Multiscale structure evolution models are proposed and compared for neat PET and its nanocomposites. Main global mechanisms are identical although with distinct evolutions of phase mass fractions. Also craze‐like/voids structures evolve with distinct sizes. Intercalated MMT morphology induces an earlier formation of periodical mesophase, a retarded widening of craze‐like structures and the smallest void sizes.© 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and crystallization of poly(ethylene terephthalate)/SiO2 nanocomposites by in‐situ polymerization

Poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were prepared by in situ polymerization. The dispersion and crystallization behaviors of PET/SiO₂ nanocomposites were characterized by means of transmission electron microscope (TEM), differential scanning calorimeter (DSC), and polarizing light microscope (PLM). TEM measurements show that SiO₂ nanoparticles were well dispersed in the PET matrix at a size of 10–20 nm. The results of DSC and PLM, such as melt‐crystalline temperature, half‐time of crystallization and crystallization kinetic constant, suggest that SiO₂ nanoparticles exhibited strong nucleating effects. It was found that SiO₂ nanoparticles could effectively promote the nucleation and crystallization of PET, which may be due to reducing the specific surface free energy for nuclei formation during crystallization and consequently increase the crystallization rate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 655–662, 2006     

Hybrid poly(ethylene terephthalate)/silica nanocomposites prepared by in‐situ polymerization

The nanocomposites, based on hybrid poly(ethylene terephthalate) (PET)/silica nanoparticles, were prepared via in‐situ condensation polymerization of terephthalic acid and ethylene glycol in the presence of silica nanoparticles pretreated with a silane coupling agent. Such a polymerization process ensured that the silica nanoparticles were well dispersed in PET matrix with the size ranging from 40 to 60 nm, which was confirmed by transmission electron microscope (TEM) observation. Attributed to the unique bonding between SiO₂ nanoparticle and PET, the crystallization behavior of PET was improved significantly, at a low temperature in particular. To further explore the effects of silica nanoparticles on crystallization, extensive differential scanning calorimeter (DSC) measurements were performed in an attempt to reveal the impact of the morphology of the dispersed silica nanoparticle (i.e., sphere or gel‐like) on the peak temperature during melting as well as the amount of heat involved in crystallization. The influences of the structure of polyether glycol (PEG) used for PET preparation as well as the addition of glass fibres (GF) were also investigated using DSC. It was concluded that the synergy among silica nanoparticles, modified PEG, and GFs lowers both T_g and T_m of PET, thus facilitating the injection processes in application. POLYM. COMPOS. 28:42–46, 2007. © 2007 Society of Plastics Engineers     

In‐situ synthesis of poly(ethylene terephthalate)/clay nanocomposites using TiO2/SiO2 sol‐intercalated montmorillonite as polycondensation catalyst

A novel organic montmorillonite, which could act as both polycondensation catalyst of poly(ethylene terephthalate) (PET) and filler of PET/clay nanocomposites, was prepared. Original montmorillonite was first treated with different amounts of poly(vinylpyrrolidone) (PVP), and then intercalated by TiO₂/SiO₂ sol to gain polycondensation catalytic activity. The acquired clay possessed excellent thermal stability and would not degrade during the polycondensation step. PET/clay nanocomposites were prepared via in‐situ polymerization using the organo‐clay as polycondensation catalysts. The morphologies of the nanocomposites were characterized by X‐ray diffraction and transmission electron microscope. The results indicated that the amount of PVP and TiO₂/SiO₂ sol strongly affected the dispersion state of the clay, and finally, partially exfoliated PET/clay nanocomposites were obtained. The nanocomposites had better properties than pure PET due to the incorporation of the delaminated clay layers. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Preparation and properties of deep dye fibers from poly(ethylene terephthalate)/SiO2 nanocomposites by in situ polymerization

In this study, poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were synthesized by in situ polymerization and melt‐spun to fibers. The superfine structure and properties of PET/SiO₂ fibers were studied in detail by means of TEM, DSC, SEM, and a universal tensile machine. According to the TEM, SiO₂ nanoparticles were well dispersed in the PET matrix at a size level of 10–20 nm. The DSC results indicated that the SiO₂ nanoparticles might act as a marked nucleating agent promoting the crystallization of the PET matrix from melt but which inhibited the crystallization from the glassy state, owing to the “crosslink” interaction between the PET and SiO₂ nanoparticles. The tensile strength of 5.73 MPa was obtained for the fiber from PET/0.1 wt % SiO₂, which was 17% higher than that of the pure PET. The fibers were treated with aqueous NaOH. SEM photographs showed that more and deeper pits were introduced onto PET fibers, which provided shortcuts for disperse dye and diffused the reflection to a great extent. According to the K/S values, the color strength of the dyeing increased with increasing SiO₂ content. It is found that the deep dyeability of PET fibers was improved greatly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and properties of poly(ethylene terephthalate)/ATO nanocomposites

Antimony doped tin oxide (ATO) nanoparticles modified poly(ethylene terephthalate) (PET) composites used for manufacturing antistatic PET fiber were synthesized by in situ polymerization. The crystallization and multiple melting behavior of the nanocomposites were systemically investigated by means of Differential Scanning Calorimeter (DSC), Fourier Transform Infrared (FTIR), X‐ray Diffraction (XRD) techniques. The degree of crystallinity in nanocomposites increased with increasing ATO content. Smaller and more incomplete crystals are presented in the crystalline regions of the nanocomposites with increasing the content of ATO, which could be attributed to heterogeneous nucleation effects of ATO nanoparticles. Dynamic Mechanical Analysis (DMA) measurements showed that the storage moduli of the nanocomposites increased with increasing the content of ATO, due to formation of immobilized layer between polymer and filler. The interactions between ATO and PET molecules result in high tan δ for the PET/ATO nanocomposites. Percolation threshold of PET/ATO hybrid fibers prepared by the nanocomposites at room temperature was as low as 1.05 wt %, much lower than that of the composites filled with conventional conductive particles. Adding ATO nanoparticles obviously improves the conductivity of PET. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Non-isothermal crystallization kinetics of TiO2 nanoparticle-filled poly(ethylene terephthalate) with structural and chemical properties

The present research work includes non-isothermal crystallization kinetics of poly(ethylene terephthalate) (PET)–titanium dioxide (TiO₂) nanocomposites as well as structural and chemical properties of these nanocomposites. The average grain size of chemically synthesized TiO₂ nanoparticles has been calculated 19.31 nm by TEM and XRD. The morphology and structural analysis of PET–TiO₂ nanocomposites, prepared via solution casting method, has been investigated using SEM and XRD, respectively. The nature of chemical bonds has been discussed on the basis of FTIR spectra. The effect of TiO₂ nanoparticles and cooling rates on non-isothermal crystallization kinetics of PET was examined by differential scanning calorimetry at various heating and cooling rates. It has been observed that TiO₂ nanoparticles accelerate the heterogeneous nucleation in PET matrix. The crystallization kinetics could be explained through Avrami–Ozawa combined theory. TiO₂ nanoparticles cause to make molecular chains of PET easier to crystallize and accelerate the crystallization rates during non-isothermal crystallization process; this conclusion has also been verified by Kissinger model for crystallization activation energy.     

Preparation,crystallization, and spinnability of poly(ethylene terephthalate)/silica nanocomposites

Poly(ethylene terephthalate) (PET)/silica nanocomposites were successfully prepared by in situ polymerization. Silica nanoparticles were uniformly dispersed in the process of polymerization. By means of hot‐stage polarization microscope and DSC, the influence of nanosilica on the crystallization of PET/silica nanocomposites has been clarified. The results show that nanosilica does not behave as a nucleating agent in PET but postpones the appearance of crystallite. This phenomenon is very favor to improve spinnability. The investigation on melt spinning of PET/silica nanocomposites also shows that it is advantageous to spinning with descending the spinning temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2564–2568, 2007     

Interface structure of poly(ethylene terephthalate)/silica nanocomposites

The interface structure of the poly(ethylene terephthalate) (PET)/silica nanocomposites was characterized by Fourier transform infrared and solid-state nuclear magnetic resonance. Our study reveals that PET chains are grafted onto the surface of silica nanoparticles, and they form branched and lightly crosslinking structures during the polycondensation. Gel permeation chromatography measurements indicate that the grafted PET chains have a lower molecular weight and broader distribution. Furthermore, a model has been developed to elucidate the interaction of an entanglement network between silica and PET chains that lead to enhancements of G′, G″ and η* values of PET/2 wt% silica nanocomposites.     

Crystal nucleation and growth in poly(ethylene terephthalate)/alumina‐nanoparticle composites

The effect of nanoparticles on nonisothermal polymer crystallization was investigated using poly(ethylene terephthalate) (PET) nanocomposites with alumina (Al₂O₃) nanoparticles of average size 38 nm. The filler content in the nanocomposites was varied from 0 to 10 wt %. The interparticle spacing was observed to decrease (as expected) with an increase in loading of the nanoparticles. Contrary to previous reports in the literature on semicrystalline polymer‐based composites with micron‐size and macroscale particles, our differential scanning calorimetry, transmission electron microscopy, and X‐ray studies showed that the addition of the nanoparticles did not cause heterogeneous nucleation of PET crystals in nanocomposites containing up to 3 wt % Al₂O₃. This is attributed to the nanoparticle curvature being comparable to the radius of gyration of the polymer. The addition of the nanoparticles was found to disrupt the spherulitic morphology of the PET because of their physical presence and their proximity to one another. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Characterization of PET nanocomposites produced by different melt‐based production methods

Poly(ethylene terephthalate) (PET) based nanocomposites containing 3 wt % of different nanoparticles (MontMorilloniTe–MMT; titanium dioxide–TiO₂; and silica dioxide–SiO₂) were prepared via two independent procedures: mechanical mixing with subsequent direct injection molding (DIM) and mechanical mixing, followed by extrusion blending and injection molding (EIM). The contributions of nanofillers with respect to pure PET were evaluated. The incorporation of nanofillers reduces the intrinsic viscosity of the polymer matrix when processed by DIM and EIM. SAXS results showed that: MMT layers were intercalated for both processing procedures, but slightly higher for EIM; a better dispersion with smaller agglomerates size is achieved for TiO₂ and SiO₂ nanoparticles for EIM than for DIM. According to the results of DSC analysis, all fillers behave as nucleating agents for PET except SiO₂ that acts as inhibitor in case of DIM procedure. The mechanical behavior was assessed in tensile testing. The mechanical test revealed that the addition of nanoparticles have a slight influence on the elastic modulus and yield stress, but a drastic negative influence on the deformation capabilities of the moldings. The measured optical properties of the moldings gloss and haze are also strongly affected by the presence of nanoparticles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Nonisothermal melt crystallization kinetics of poly(ethylene terephthalate)/Barite nanocomposites

Poly(ethylene terephthalate) (PET)/Barite nanocomposites were prepared by direct melt compounding. The nonisothermal melt crystallization kinetics of pure PET and PET/Barite nanocomposites, containing unmodified Barite and surface‐modified Barite (SABarite), was investigated by differential scanning calorimetry (DSC) under different cooling rates. With the addition of barite nanoparticles, the crystallization peak became wider and shifted to higher temperature and the crystallization rate increased. Several analysis methods were used to describe the nonisothermal crystallization behavior of pure PET and its nanocomposites. The Jeziorny modification of the Avrami analysis was only valid for describing the early stage of crystallization but was not able to describe the later stage of PET crystallization. Also, the Ozawa method failed to describe the nonisothermal crystallization behavior of PET. A combined Avrami and Ozawa equation, developed by Liu, was used to more accurately model the nonisothermal crystallization kinetics of PET. The crystallization activation energies calculated by Kissinger, Takhor, and Augis‐Bennett models were comparable. The results reveal that the different interfacial interactions between matrix and nanoparticles are responsible for the disparate effect on the crystallization ability of PET. POLYM. COMPOS., 31:1504–1514, 2010. © 2009 Society of Plastics Engineers     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

Solid‐state structural evolution of poly(ethylene terephthalate) during step uniaxial stretching from different initial morphologies: An in situ wide angle x‐ray scattering study

This work reports an in situ wide‐angle X‐ray scattering (WAXS) study of the structural evolution of PET with distinct initial morphologies during step uniaxial stretching in the solid state. Two types of samples were analyzed under synchrotron X‐ray radiation, namely quasi‐amorphous (QA) and semicrystalline (SC) (with 2D and 3D order). Results show that initially different QA morphologies evolve following the same stages: (i) stage I (before neck), at almost constant orientation level the amorphous phase evolves into mesophase; (ii) stage II (neck formation), there is a rapid increase of polymer orientation and the appearance of a periodical mesophase from the highly oriented mesophase; (iii) stage III (necking propagation), there is a leveling off of the average polymer orientation together with partial conversion of the periodical mesophase and mesophase into highly oriented amorphous. The behaviors of the two SC morphologies are completely distinct. A 2D order crystalline morphology evolves with stretching likewise the QA through three stages: (i) at early stages of deformation the polymer orientation remains unchanged while the amorphous phase amount increases slightly, stage I; (ii) in stage II, a fast increase of polymer orientation is accompanied by large formation of mesophase; and (iii) in stage III there is the level off of polymer orientation as the chains approach their finite extensibility and the 3D crystalline order is achieved. Evolution of SC sample with 3D crystalline order mainly features constant orientation increase together with mesophase increment. Structure deformation models are suggested. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermomechanical and optical properties of biodegradable poly(L‐lactide)/silica nanocomposites by melt compounding

Poly(L ‐lactide) (PLA)/silica (SiO₂) nanocomposites containing 1, 3, 5, 7, and 10 wt % SiO₂ nanoparticles were prepared by melt compounding in a Haake mixer. The phase morphology, thermomechanical properties, and optical transparency were investigated and compared to those of neat PLA. Scanning electron microscopy results show that the SiO₂ nanoparticles were uniformly distributed in the PLA matrix for filler contents below 5 wt %, whereas some aggregates were detected with further increasing filler concentration. Differential scanning calorimetry analysis revealed that the addition of SiO₂ nanoparticles not only remarkably accelerated the crystallization speed but also largely improved the crystallinity of PLA. An initial increase followed by a decrease with higher filler loadings for the storage modulus and glass‐transition temperature were observed according to dynamic mechanical analysis results. Hydrogen bonding interaction involving C?O of PLA with Si? OH of SiO₂ was evidenced by Fourier transform infrared analysis for the first time. From the mechanical tests, we found that the tensile strength and modulus values of the nanocomposites were greatly enhanced by the incorporation of inorganic SiO₂ nanoparticles, and the elongation at break and impact strength were slightly improved. The optical transparency of the nanocomposites was excellent, and it seemed independent of the SiO₂ concentration; this was mainly attributed to the closed refractive indices between the PLA matrix and nanofillers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Improving the transparency of stretched poly(ethylene terephthalate)/polyamide blends

Compatibilized blends of poly(ethylene terephthalate (PET) with an aromatic polyamide such as poly(m‐xylylene adipamide) (MXD6) have good transparency (T) because the constituent refractive indices (RIs) match closely. However, haziness is observed when the blends are stretched. This study demonstrated that stretching imparted a greater RI anisotropy to PET than to the aromatic polyamide. The resulting RI mismatch was responsible for the loss in T. Analysis of the strain‐dependent birefringence revealed that different molecular deformation models described the intrinsic birefringence of the PET and aromatic polyamides. Hydrogen bonding of the polyamide may have been responsible for the difference. On the basis of these results, three approaches for improving T of stretched PET blends were attempted. Blends with a lower molecular weight MXD6 exhibited slightly higher T after stretching; however, they did not compare with stretched PET. Increasing the amount of compatibilizer reduced the particle size; however, the dimension of even the smallest particles exceeded the quarter wavelength after biaxial stretching transformed the spherical particles into platelets. Copolyamides based on MXD6 that incorporated isophthalate were designed to increase the RI of the polyamide and thereby reduce the RI mismatch with stretched PET. Unexpectedly, the poor T of stretched copolyamide blends was attributed to the high glass‐transition temperature of the copolyamide, which hampered the molecular orientation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 225–235, 2006     

Poly(ethylene terephthalate)/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate)/clay nanocomposites: Effects of biaxial stretching

In this study, we fabricated poly(ethylene terephthalate) (PET)/clay, PET/poly(ethylene glycol‐co‐1,3/1,4‐cyclohexanedimethanol terephthalate) (PETG), and PET/PETG/clay nanocomposite plates and biaxially stretched them into films by using a biaxial film stretching machine. The tensile properties, cold crystallization behavior, optical properties, and gas and water vapor barrier properties of the resulting films were estimated. The biaxial stretching process improved the dispersion of clay platelets in both the PETG and PET/PETG matrices, increased the aspect ratio of the platelets, and made the platelets more oriented. Thus, the tensile, optical, and gas‐barrier properties of the composite films were greatly enhanced. Moreover, strain‐induced crystallization occurred in the PET/PETG blend and in the amorphous PETG matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42207.     

Superfine structure,physical properties,and dyeability of alkaline hydrolyzed soly(ethylene terephthalate)/silica nanocomposite fibers prepared by in situ polymerization

In this study, poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites were synthesized by in situ polymerization and melt‐spun to fibers. The superfine structure, physical properties, and dyeability of alkaline hydrolyzed PET/SiO₂ nanocomposite fibers were studied. According to the TEM, SiO₂ nanoparticles were well dispersed in the PET matrix at a size level of 10–20 nm. PET/SiO₂ nanocomposite fibers were treated with aqueous solution of sodium hydroxide and cetyltrimethyl ammonium bromide at 100°C for different time. The differences in the alkaline hydrolysis mechanism between pure PET and PET/SiO₂ nanocomposite fibers were preliminarily investigated, which were evaluated in terms of the weight loss, tensile strength, specific surface area, as well as disperse dye uptake. PET/SiO₂ nanocomposite fibers showed a greater degree of weight loss as compared with that of pure PET fibers. More and tougher superfine structures, such as cracks, craters, and cavities, were introduced, which would facilitate the certain application like deep dyeing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3691–3697, 2006     

Thermo-oxidative stability of poly(methyl methacrylate)/poly(methyl methacrylate)-grafted SiO2 nanocomposites

Thermo-oxidative stability of PMMA-grafted SiO₂ and PMMA/PMMA-grafted SiO₂ nanocomposites was investigated by conventional non-isothermal gravimetric technique. It was interesting to find that PMMA-grafted SiO₂ nanoparticles exhibited higher thermo-oxidative stability than that of PMMA. The apparent activation energy of PMMA-grafted SiO₂ nanoparticles increased with the grafting ratio of PMMA from SiO₂, which was estimated by Kissinger method. This indicates that the strong interactions existing between the grafted chains are responsible for the enhanced thermo-oxidative stability of PMMA-grafted SiO₂ nanoparticles. However, the grafting ratio of PMMA from SiO₂ in nanoparticles has only limited effect on the thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites due to a much lower content of grafted PMMA in the nanoparticles relative to PMMA. The increased thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites is possibly resulted from the increased SiO₂ content in the nanocomposites, in which the grafting ratio of PMMA in PMMA-grafted SiO₂ nanoparticles is kept almost as a constant. The glass transition temperature (T _g) of PMMA/PMMA-grafted SiO₂ nanocomposites is about 25 °C and is higher than that of PMMA. The grafting ratio of PMMA from SiO₂ in the nanoparticles has no qualitative effects on the T _g of the nanocomposites.     

Characterization and non-isothermal crystallization behavior of biodegradable poly(ethylene sebacate)/SiO2 nanocomposites

Poly(ethylene sebacate) (PESeb) and PESeb/silica nanocomposites (PESeb/SiO₂) were prepared by in situ polymerization from the direct esterification of ethylene glycol with sebacic acid in the presence of proper amounts of silica nanoparticles. The non-isothermal crystallization behavior of PESeb/SiO₂ nanocomposites has been studied using different theoretical equations such as Avrami, Ozawa and combined Avrami and Ozawa equations. It is found that the addition of nanoparticles of SiO₂ influenced the mechanism of nucleation and the growth of PESeb crystallites. Also, the nanocomposites show a higher Avrami value than the neat PESeb, implying a more complex crystallization configuration. Moreover, the combined Avrami and Ozawa equation can successfully describe the crystallization model under the non-isothermal crystallization. The crystallization activation energies, E _a, calculated from “Kissinger’s equation” have shown that the synthesized PESeb/SiO₂ nanocomposites have lower energy than the neat PESeb, reflecting the much lower energy barrier for the rapid heterogeneous nucleation.