PET/PEN blends of industrial interest as barrier materials. Part I. Many-scale molecular modeling of PET/PEN blends

Mesoscale molecular simulations, based on parameters obtained through atomistic molecular dynamics and Monte Carlo calculations, have been used for modeling and predicting the behavior of PET/PEN blends. Different simulations have been performed in order to study and compare pure homopolymer blends with blends characterized by the presence of PET/PEN block copolymers acting as compatibilizer. A many-scale molecular modeling strategy was devised to evaluate PET/PEN blend characteristics, simulate phase segregation in pure PET/PEN blends, and demonstrate the improvement of miscibility due to the presence of the transesterification reaction products. The behavior of distribution densities and order parameters of the compatibilized blends demonstrates that mixing properties improve significantly, in agreement with experimental evidences. Barrier properties such as oxygen diffusivity and permeability have also been evaluated by finite element simulations. Accordingly, many-scale modeling seems to be a successful way to estimate PET/PEN blend properties and behavior upon different concentrations and processing conditions.     

Crystallization Study of Glassy PET/PEN Blends by Means of Real Time X-ray Scattering

Abstract

The crystallization of several blends of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6 naphthalene dicarboxylate) (PEN) has been investigated by wide angle- (WAXS) and small angle X-ray scattering (SAXS) using synchrotron radiation. The role of transesterification reactions, giving rise to a fully amorphous non-crystal-lizable material (copolyester) is brought up. For the blends rich in PET, crystallization temperatures (T_c ) of 105 and 117°C were used. For blends rich in PEN, crystaffization was performed at T_c =150 and 165°C, respectively. The time variation of the degree of crystallinity was fitted into an Avrami equation considering the induction time prior to the beginning of crystallization. The Avrami parameters, the half times of crystallization, as well as the nanostructure development (SAXS invariant and long period) for the blends, are discussed in relation to blend composition and are compared to the parameters observed for the homopolymers PET and PEN.     

耐热瓶级PEN／PET合金材料研制和开发应用

针对PEN与PET的合金化及PEN／PET于耐热中空包装容器上的应用进行探索研究。研究表明：PEN与PET的酯交换反应主要由反应时间和温度决定。研究确定了适合应用要求的相容程度（即酯交换率）。本文通过控制螺杆挤出工艺条件,使PEN、PET成为适度相容的耐热瓶级PEN／PET合金材料,该材料在PET基础上,提高了阻气性和耐热性,同时具有与现行注吹设备的设备兼容性、工艺可行性和易为市场接受的经济性。本研究采用国产二步法机器和通用聚酯瓶的成型工艺加工成型耐85℃以上湿度的果汁、茶饮料等热封装瓶,填补了耐热瓶塑料材料和耐热瓶制品的国内空白。     

Study on phase separation of PET/PEN blends by dynamic rheology

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) were processed into biaxially drawn films, and samples taken from the bi‐oriented films were then investigated by dynamic rheology experiments in the melt state. Storage modulus G′ and loss modulus G″ were determined in the frequency range of 10^?2–10² rad/s at temperatures between 260 and 300°C. Although the time–temperature superposition (TTS) principle was found to hold in the high frequency regime, a breakdown of TTS was observed at low frequencies, and the terminal behavior of the storage modulus G′ of the blends departs drastically from the terminal behavior observed for the blend components. This is caused by interfacial surface tension effects. The results indicate that despite the effect of transesterification reactions, the PET/PEN blend systems investigated consist of a microseparate phase of PEN platelets in a matrix of PET. This morphology is produced when the blends are processed into biaxially oriented PET/PEN films, and droplets of PEN are deformed into a lamellar structure consisting of parallel and extended, separate layers. The large interfacial surface area of the bi‐oriented PET/PEN blends leads to remarkably strong interfacial tension effects in dynamic rheology measurements. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nanostructural features of a spider dragline silk as revealed by electron and X-ray diffraction studies

Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to examine the nanostructure of a natural polymer—a spider dragline silk—that has potential applications as an engineering material. The silk studied was collected from the cob-web weaving spider Latrodectus hesperus. Single crystal and polycrystalline electron diffraction patterns indicate the presence of crystals with a bimodal size distribution, in the range of 2 nm and 40-120 nm. The chain axis of the smaller crystals is more strictly aligned with the fiber axis than that of the larger crystals. Lattice parameters for the orthogonal unit cell are: a=9.4 Å (interchain), b=7.0 Å (dipeptide, fiber axis) and c=10.8 Å (intersheet). A fine structure in single crystal electron diffraction patterns indicates possible composition-dependent lattice strains. Results of tensile tests of the spider dragline silk are reported, and a simple model is presented linking the observed nanostructural features to the force-elongation response of this material.     

Formation and transformation of hierarchical structure of β-nucleated polypropylene characterized by X-ray diffraction, differential scanning calorimetry and scanning electron microscopy

Commercial grade isotactic polypropylene has been modified with a specific β-nucleant (N,N′-dicyclohexylnaphthalene-2,6-dicarboxamide) in two concentrations (0.03 and 0.10 wt%). Specimens for structural characterization have been prepared by injection moulding, subsequent melting and re-crystallization or solid-state drawing at 100 °C. Individual levels of hierarchical structure, including molecular orientation, have been characterized by a combination of wide angle X-ray scattering (WAXS), differential scanning calorimetry and scanning electron microscopy. Based on the analysis of the azimuthal reflections (110) and (300), the Hermans orientation functions have been calculated separately for the crystalline phases α and β. Besides the longitudinal orientation along the injection-moulding direction, β-crystallites tilted to the injection-moulding direction have been found. Upon thermal treatment the fraction of the crystalline β-phase has decreased and molecular alignment within the crystalline regions has improved. During solid-state drawing the fraction of the crystalline β-phase was markedly decreasing with increasing draw ratio, while the overall crystallinity has not changed but slightly. The experiments have also revealed a disruption of molecular alignment at the beginning of the drawing process and subsequent distinct improvement of molecular orientation along the draw direction in crystallites α and β. The Hermans orientation functions provided by the WAXS analysis have been compared with recently published data obtained with similar specimens by polarized photoacoustic spectroscopy.     

Mesoscale pore structure of a high-performance concrete by coupling focused ion beam/scanning electron microscopy and small angle X-ray scattering

This contribution couples (a) Small angle X-ray scattering (SAXS) experiments of a high-performance concrete (HPC) at the millimetric scale, and (b) Focused ion beam/scanning electron microscopy (FIB/SEM) of the cement paste of the HPC, with 10-20 nm voxel size. The aim is to improve the understanding of the 3D pore network of the HPC at the mesoscale (tens of nm), which is relevant for fluid transport. The mature HPC is an industrial concrete, based on pure Portland CEMI cement, and planned for use as structural elements for deep underground nuclear waste storage. Small angle X-ray scattering patterns are computed from the 3D pore images given by FIB/SEM (volumes of 61-118 μm³). They are positively correlated with SAXS measurements (volumes of 5 mm³). Aside from correlations with FIB/SEM data, experimental SAXS allows to investigate a wider range of effects on the pore structure. These are mainly the HPC drying state, the presence of aggregates (by analyzing data on cement paste alone), and the use of Poly Methyl MethAcrylate resin impregnation.     

Segregation morphology of poly(3-hydroxybutyrate)/poly(vinyl acetate) and poly(3-hydroxybutyrate-co-10% 3-hydroxyvalerate)/poly(vinyl acetate) blends as studied via small angle X-ray scattering

Segregation morphology of poly(3-hydroxybutyrate) (PHB)/poly(vinyl acetate) (PVAc) and poly(3-hydroxybutyrate-co-10% 3-hydroxyvalerate) (P(HB-co-10% HV)/PVAc blends crystallized at 70 °C have been investigated by means of small angle X-ray scattering (SAXS). Morphological parameters including the crystal thickness (l_c) and the amorphous layer thickness (l_a) were deduced from the one-dimensional correlation function (γ(z)). Blending with PVAc thickened the PHB crystals but not the P(HB-co-10% HV) crystals. On the basis of the composition variation of l_a, and the volume fraction of lamellar stacks (?_s) revealed that PHB/PVAc blends created the interlamellar segregation morphology when the weight fraction of PVAc (w_PVAc)≤0.2 and the interlamellar and interfibrillar segregation coexisted when w_PVAc>0.2, while P(HB-co-10% HV)/PVAc blends yielded the interfibrillar segregation morphology at all blend compositions. For both PHB/PVAc and P(HB-co-10% HV)/PVAc blends, the distance of PVAc segregation was promoted by increasing PVAc composition and the distance of PVAc segregation in P(HB-co-10% HV)/PVAc blends was greater than in PHB/PVAc at a given PVAc composition. The crystal growth rate played a key role in controlling the segregation of PVAc.     

The effect of cation ordering and domain boundaries on low loss Ba(BI1/3BII2/3)O3 perovskite dielectrics revealed by high-angle annular dark-field scanning transmission electron microscopy (HAADF STEM)

High quality ceramics of Ba((Co_0.7Zn_0.3)_1/3Nb_2/3)O₃ (BCZN), Ba(Mg_1/3Nb_2/3)O₃ (BMN) and Ba(Mg_1/3Ta_2/3)O₃ (BMT) were prepared by the mixed oxide route using sintering temperatures up to 1620 °C. Products with a high degree of cation ordering exhibited dielectric Q × f values from 83,000 GHz (BCZN) to 360,000 GHz (BMT). High Resolution TEM and aberration-corrected scanning transmission electron microscopy (STEM) revealed ordering domains and type I, II and III boundary structures. High-Angle Angular Dark Field (HAADF) STEM images provided direct evidence of 1:2 ordering and stacking sequences, and the presence of disordered regions within domain boundaries. The exceptionally high Q × f values for BMT are associated with a high degree of B-site ordering and the removal of domain boundaries in large, single domain grains. The catastrophic degradation of Q × f values in BMN after prolonged sintering is associated with formation of a lossy ferroelectric secondary phase (Ba₃Nb₂O₈), and changes to composition and stoichiometry of BMN grains.     

The effect of high pressure processing on the morphology of polyethylene films tested by differential scanning calorimetry and X‐ray diffraction and its influence on the permeability of the polymer

This study investigated the influence of high‐pressure processing on the morphology and permeability of low‐density polyethylene (LDPE) films used for food packaging. This was done by monitoring the crystallinity, melting temperature (T_m), and oxygen transmission rate (OTR) of the materials before and after the pressure treatments. A first set of pouches made from the LDPE films were filled with 95% ethanol then pressured at 200, 400, 600, and 800 MPa for 5 and 10 min at 25 and 75°C. The crystallinity and T_m of the films were measured using differential scanning calorimetry (DSC). X‐ray diffraction (XRD) was also used to determine the crystallinity. A second set of LDPE pouches were similarly made but a half of them were filled with 95% ethanol and the other half filled with distilled water. These second set of pouches were pressured at 200, 600, and 800 MPa then their OTR tested. Results of the DSC experiments showed that the T_m increased with increasing pressure intensity but the crystallinity changes were not detectible. The XRD method on the other hand, showed significant (P < 0.05) crystallinity increases with increasing pressure treatments. The gas permeability analyses showed decreasing OTR's with increasing high‐pressure intensity treatments. The OTR in the pouches filled with the 95% ethanol was slightly lower than that of the pouches filled with water. These findings allowed us to better anticipate the behavior of LDPE films used to package high‐pressure processed foods. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Elongation-induced phase separation of poly(vinyl alcohol)/poly(acrylic-acid) blends as studied by C CP/MAS NMR and wide-angle X-ray diffraction

The membrane samples of poly(vinyl alcohol)/poly(acrylic-acid) (PVA/PAA) blend with different draw ratios were studied by both ¹³C CP/MAS NMR and wide-angle X-ray diffraction (WAXD) measurements. Phase separation induced by elongation of the sample was observed and the change of the phase structure with draw ratio was found to be dependent on the composition of the blend samples.     

Proton‐exchange membranes via the grafting of styrene and acrylic acid onto fluorinated ethylene propylene copolymer by a preirradiation technique. IV. Dynamic mechanical analysis,X‐ray diffraction,and scanning electron microscopy studies of grafted and sulfonated membranes

The grafting of styrene and acrylic acid onto fluorinated ethylene propylene copolymer was carried out by a preirradiation technique. The resulting membranes were sulfonated with concentrated sulfuric acid. The effects of the degree of grafting and sulfonation on the structure of the membranes were studied by X‐ray diffraction and scanning electron microscopy. The crystallinity percentage decreased with increasing grafting. Scanning electron microscopy studies confirmed that grafting took place by a front mechanism, by which grafting started at the surface and slowly proceeded inwards. The dynamic mechanical properties of the membranes and their sulfonated derivatives were also investigated. The storage modulus at room temperature increased with grafting and increased further with sulfonation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1426–1431, 2005