Effect of the coupling agent's reactivity on the shrinkability of the blends consisting of grafted low‐density polyethylene and ethylene acrylic elastomer

Blends prepared by melt mixing of thermoplastic elastomer have gained considerable attention in recent years from a heat shrinkability point of view. Our present study deals with the measurement of heat shrinkability of the maleic anhydride grafted low‐density polyethylene and ethylene acrylic elastomer. Two samples have been prepared to study the effect of coupling agent's reactivity on the shrinkability of the blends. The coupling agents used are 4,4′‐diamino diphenyl sulphone, and 4,4′‐diamino diphenyl methane. Shrinkability was measured at room temperature, 120 °C, 150 °C, and 180 °C. Shrinkability is found to be greater in high temperature stretched sample rather than that of room temperature stretched sample. It is observed that reactivity as well as heat shrinkability is more when 4,4′‐diamino diphenyl methane is used as a coupling agent. The mechanism of interchain crosslinking reaction has been confirmed by IR spectroscopy. Differential scanning calorimetry was performed to study the thermal stability of the sample. Copyright © 2002 John Wiley & Sons, Ltd.     

Heat shrinkability of electron-beam-modified thermoplastic elastomeric films from blends of ethylene-vinylacetate copolymer and polyethylene

The heat shrinkability of electron-beam-irradiated thermoplastic elastomeric films from blends of ethylene–vinylacetate copolymer (EVA) and low-density polyethylene (LDPE) has been investigated in this paper. The effects of temperature, time and extent of stretching and shrinkage temperature and time have been reported. Based on the above data, the optimized conditions in terms of high heat shrinkage and low amnesia rating have been evaluated. Influence of radiation doses (0–500 kGy), multifunctional sensitizer levels (ditrimethylol propane tetraacrylate, DTMPTA), and blend proportions on heat shrinkability has been explained with the help of gel fraction and X-ray data. With the increase in radiation dose, gel fraction increases, which in turn gives rise to low values of heat shrinkage and amnesia rating. At a constant radiation dose and blend ratio, percent heat shrinkage is found to decrease with increase in DTMPTA level. Gel content increases with the increase in EVA content of the blend at a constant radiation dose and monomer level, giving rise to decrease in heat shrinkability. Heat shrinkage increases with the increase in percent crystallinity, although the amnesia rating follows the reverse trend.     

Effect of Interchain Crosslinking on the Shrinkability of Blends Consisting of Low‐Density Poly(ethylene) and Ethylene Acrylic Rubber

Two samples have been prepared to study the effect of interchain crosslinking on the heat shrinkability of the blends. In the first sample low‐density poly(ethylene) is blended with ethylene acrylic rubber while in the second one glycidyl acrylate‐grafted low‐density poly(ethylene) is blended with ethylene acrylic rubber. It is revealed that interchain crosslinking in the glycidyl acrylate grafted low‐density poly(ethylene) and ethylene acrylic rubber improves the heat shrinkability in the second sample.     

Study of heat treatment on the behaviour towards shrinkage,orientation and molecular order of stretched poly(vinyl chloride) fibres

The behaviour of stretched PVC fibres during thermomechanical treatments between 110–160°C has been studied. As far as shrinkage is concerned, three ranges of temperature have been characterized. Within the range 100–140°C the poly(vinyl chloride) undergoes a plastic deformation and has an elastoplastic behaviour. From 140 up to 170°C a creep phenomenon superimposes the elastic behaviour and then the polymer has a viscoplastic behaviour. As the temperature increases above 170°C there is flowing of polymer chains and the fibres break rapidly. Annealings carried out between 100 and 150°C cause the formation of ordered domains which are responsible for the formation of a temporary physical crosslinking network which hinders the shrinkage to such a temperature lower than their melting temperature. The loss of orientation of the amorphous phase is a rapid process which takes place as the temperature rises above 100°C even if the applied stress counterbalances the overall strain resulting from the potential shrinkage.     

Influence of the annealing conditions on the polarization and electromechanical response of high‐energy‐electron‐irradiated poly(vinylidene fluoride trifluoroethylene) copolymer

In this study, we investigated the influence of annealing conditions before irradiation on the ferroelectric and electromechanical properties of uniaxially stretched high‐energy‐electron‐irradiated poly(vinylidene fluoride trifluoroethylene) (HEEIP) copolymer (68/32 mol %) films. For films annealed at one fixed temperature before the irradiation (one‐step annealing), the highest crystallinity, which was highly desirable for enhancing the electromechanical response, was obtained only for films annealed between 132 and 136 °C. In addition, annealing over 10 h in this temperature window resulted in a large increase in the crystal lamellar thickness, which was required for reducing the polarization hysteresis to a minimum in the HEEIP samples. For improvements in the mechanical qualities of the uniaxially stretched films, a two‐step annealing procedure was investigated; that is, before the irradiation, the films were first annealed at a lower temperature to release the mechanical stress in the films due to the stretching and then were annealed in the high‐temperature window to raise the crystallinity and crystalline size. The experimental results indicated that this approach could produce uniaxially stretched HEEIP films with much improved mechanical qualities. Furthermore, the uniaxially stretched HEEIP films with this two‐step annealing exhibited the same electromechanical response as or an even higher one than that from the one‐step‐annealed HEEIP films. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 797–806, 2003     

Isobaric cure shrinkage behaviors of epoxy molding compound in isothermal state

The warpage of plastic‐encapsulated IC packages after molding is believed to be induced by thermal and cure shrinkage of epoxy molding compound (EMC). To study the warpage behaviors of EMC, the amount of cure‐induced shrinkage needs to be understood. Volume shrinkage behaviors induced by cure reaction of EMC in isothermal and isobaric states were studied with a differential scanning calorimeter (DSC) and a pressure–temperature‐controlled dilatometer. The results show that higher pressure induce more volume shrinkage under fixed temperature but the difference of volume shrinkage under different pressure levels doesn't obey the principle of linearity. It is observed that the amount of chemical volume shrinkage at 145 °C is higher than those under three other temperatures: 160, 175, and 190 °C. The chemical volume shrinkage of EMC is found to be very process dependent. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2392–2398, 2005     

Visualization of structural rearrangements responsible for temperature-induced shrinkage of amorphous polycarbonate after its deformation at different conditions

Structural rearrangements during the temperature-induced shrinkage of amorphous polycarbonate after its tensile drawing below and above the glass transition temperature, rolling at room temperature, and solvent crazing have been studied with the use of the direct microscopic procedure. This evidence demonstrates that the character of structural rearrangements during the temperature-induced shrinkage of the oriented amorphous polymer is primarily controlled by the temperature and mode of deformation. In the case of the polymer sample stretched above the glass transition temperature, the subsequent temperature-induced shrinkage is shown to be homogeneous and proceeds via the simultaneous diffusion of polymer chains within the whole volume of the polymer sample. When polymer deformation is carried out at temperatures below the glass transition temperature, the subsequent temperature-induced shrinkage within the volume of the polymer sample is inhomogeneous and proceeds via the movement of rather large polymer blocks that are separated by the regions of inelastically deformed polymer (shear bands or crazes).     

Determination of free serotonin and its metabolite 5‐HIAA in blood human samples with consideration to pre‐analytical factors

Significant differences have been reported over the years in measuring physiological levels of free circulating serotonin (f5‐HT) in platelet‐poor plasma (PPP). This work shows that there are crucial pre‐analytical factors in sample manipulation that can provoke an artifactual release of 5‐HT from platelets, and that, even when the sample is accurately processed to obtain PPP, f5‐HT levels are approximately 2.8 times higher than those of f5‐HT in blood. An alternative methodology consisting of ex vivo blood microdialysis coupled to high‐performance liquid chromatography–electrochemical detection is proposed and validated. It is considered the most accurate technique to measure physiological circulating f5‐HT and its metabolite 5‐hydroxyindoleacetic acid (f5‐HIAA), owing to its sensitivity (limits of quantification of 0.08 ng/mL) and reliability since there is no sample manipulation. The f5‐HT and f5‐HIAA levels in blood and in PPP were studied in control subjects, hypertensive and end‐stage renal disease patients, who have a deregulated serotonergic system. This work reveals that blood is the best matrix to determine f5‐HT concentrations, and the clinical relevance of the accuracy of f5‐HT determination is discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrospun poly(3‐hexylthiophene)/poly(ethylene oxide)/graphene oxide composite nanofibers: effects of graphene oxide reduction

In this article, we report on the production by electrospinning of P3HT/PEO, P3HT/PEO/GO, and P3HT/PEO/rGO nanofibers in which the filler is homogeneously dispersed and parallel oriented along the fibers axis. The effect of nanofillers' presence inside nanofibers and GO reduction was studied, in order to reveal the influence of the new hierarchical structure on the electrical conductivity and mechanical properties. An in‐depth characterization of the purity and regioregularity of the starting P3HT as well as the morphology and chemical structure of GO and rGO was carried out. The morphology of the electrospun nanofibers was examined by both scanning and transmission electron microscopy. The fibrous nanocomposites are also characterized by differential scanning calorimetry to investigate their chemical structure and polymer chains arrangements. Finally, the electrical conductivity of the electrospun fibers and the elastic modulus of the single fibers are evaluated using a four‐point probe method and atomic force microscopy nanoindentation, respectively. The electrospun materials crystallinity as well as the elastic modulus increase with the addition of the nanofillers while the electrical conductivity is positively influenced by the GO reduction. Copyright © 2016 John Wiley & Sons, Ltd.     

A Kinetic Investigation of Thermal Shrinkage of Aromatic Polymers by Thermomechanical Analysis

The kinetics of thermal shrinkage of the stretched polypyromellitimide (PI) films, Du Pont Kapton H, were investigated by thermomechanical analysis (TMA) at a constant rate of heating. The two-stage model of extended polymers has been applied to analyze the TMA data. The activation energy of the contraction reaction could be obtained from TMA curves at various heating rates. The one-step shrinkage of the 12.5% stretched PI film gives an activation energy of 10 kcal/mole for the first shrinking. From the 30% stretched sample, the second activation of contraction is 25 kcal/mole, and from 40% sample the third one is 33 kcal/mole. These three contraction reactions are observed successively for the TMA curves for highly stretched samples, and correspond to the various kinds of molecular motion of this special rigid polymer structure, which are also observed in the dynamic mechanical and dielectric properties of the same polymer.

Polypyromellitimide (PI) is a typical thermally stable polymer due to the rigid aromatic and heterocyclic ring structures in its backbone chain. This polymer is able to be cold-drawn in the glassy state, and it shrinks markedly on heating. The thermal shrinkage was investigated thermoanalytically by thermomechanical analysis (TMA) at a uniform heating rate. The activation energies of thermal shrinkage in three stages are estimated by this method.     

Thermal and shrinkage behaviour of stretched peroxide-crosslinked high-density polyethylene

The thermal shrinkage of stretched crosslinked high-density polyethylene (HDPE) was investigated with the aim to produce heat shrinkable materials. The heat shrinkable property was achieved by a process of heating-stretching-cooling by aid of tensile machine on crosslinked HDPE obtained by compounding with various amount of peroxide. Effect of stretching ratio and stretching temperature on thermal and shrinkage behaviour at varying peroxide contents was investigated. The results showed that crosslinking hindered the crystallization process by decreasing the melting and crystallization temperatures as well as the total degree of crystallinity. The stretching ratio had no significant effect on shrink temperature but rather on ultimate shrinkage. The stretching temperature had relatively significant influence on the shrink temperature. Crosslinked HDPE stretched at above melting point (140 °C) had higher shrink temperature as compared to those stretched at lower temperature (90 °C). These effects could be reasonably explained by Hoffman theory and changes in crystallites size and total amount of crystallinity.     

Mechanical properties and heat shrinkability of electron beam crosslinked polyethylene–octene copolymer

The mechanical properties and heat shrinkability of electron beam crosslinked polyethylene–octene copolymer were studied. It was found that gel content increases with increased radiation dose. The analysis of results by the Charlesby–Pinner equation revealed that crosslinking was dominant over chain scission upon irradiation. Formation of a crosslinked structure in the electron beam irradiated sample was confirmed by the presence of a plateau of dynamic storage modulus above the melting point of the polymer. Wide-angle X-ray diffraction revealed that there was little change in crystallinity for the irradiated samples, indicating that radiation crosslinking occurs in the amorphous region of the polymer. The tensile modulus increases, whereas the elongation at break decreases with increased radiation dose. The heat shrinkability of the material increased with an increased radiation dose because the radiation-induced crosslinks serve as memory points during the shrinking process.     

Morphological changes of annealed poly‐ε‐caprolactone by enzymatic degradation with lipase

The effects of crystallinity and temperature on enzymatic degradation of poly‐ε‐caprolactone (PCL) films and structural changes after degradation have been studied using weight loss, differential scanning calorimetry, and optical microscopy. The weight loss during the enzymatic degradation of PCL suggested that the extent of biodegradation and the rate of degradation strongly depend on the initial crystallinity. PCL films of lower crystallinity (24%) degraded much faster than films of higher crystallinity (45%). The crystallinity of low‐crystalline PCL films increased with increasing degradation time, whereas the crystallinity of high‐crystalline PCL films decreased with time. The spherulite size increased with increasing degradation time for low‐crystalline samples but decreased with time for high‐crystalline samples. These results revealed that degradation occurs first in the amorphous region where the degradation rate is much higher, and the crystalline region of the PCL film started to degrade simultaneously for those PCL with higher crystallinity. The enzymatic degradation of PCL proceeded from the free amorphous to restricted amorphous followed by lamellar edges, where PCL chains have higher mobility irrespective of hydrolysis temperature. Caproic acid was identified as the primary product formed after degradation and confirmed by proton nuclear magnetic resonance spectroscopy, suggesting that degradation occurs through the depolymerization mechanism. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 202–211, 2010     

Enhanced thermal properties and flame retardancy of unsaturated polyester‐based hybrid materials containing phosphorus and silicon

A phosphorus and silicon containing liquid monomer (9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide–vinyltrimethoxysilane (DOPO–VTS)) was synthesized by the reaction between DOPO and VTS. DOPO–VTS and methacryloxypropyltrimethoxylsilane were introduced into unsaturated polyester resin to prepare flame retardant UPR/SiO₂ (FR‐UPR/SiO₂) hybrid materials by sol–gel method and curing process. DOPO–VTS contributes excellent flame retardancy to UPR matrix, which was confirmed by the limiting oxygen index and microscale combustion calorimeter results. The thermogravimetric analysis (TGA) results indicate that the FR‐UPR/SiO₂ hybrid materials possess higher thermal stability and residual char yields than those of pure UPR at high temperature region. The thermal degradation of materials was investigated by TGA/infrared spectrometry (TG‐IR) and real‐time infrared spectrometry (RT‐IR), providing insight into the thermal degradation mechanism. Moreover, scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS) were used to explore the morphologies and chemical components of the residual char. Copyright © 2013 John Wiley & Sons, Ltd.     

High‐resolution MALDI‐TOF MS study on analysis of low‐molecular‐weight products from photo‐oxidation of poly(3‐hexylthiophene)

High‐resolution matrix‐assisted laser desorption/ionization (MALDI) time‐of‐flight mass spectrometry (TOF MS) was used for the analysis of the low‐molecular‐weight products from the photo‐oxidation of poly(3‐hexylthiophene) (P3HT) in solution and thin film. Eight new peak series were observed in the low‐mass range of the mass spectra of the products degraded in solution, and the formulas of the eight components were determined from the accurate mass. From SEC/MALDI‐TOF MS, two components were identified as the degraded products, and the other six components were derived from the fragmentation of the degraded products during the MALDI process. A mechanism for the formation of these components was proposed on the basis of the results of MALDI‐TOF MS. For the thin film degradation, a part of products in the solution degradation were observed, which supports that the oxidation of P3HT in solution and thin film proceeded in the same mechanism. This study shows that high‐resolution MALDI‐TOF MS is effective for the analysis of the low‐molecular‐weight products from P3HT photo‐oxidation and expected to be feasible for the degradation analyses of other polymers. Copyright © 2015 John Wiley & Sons, Ltd.     

Determination of Fusarium mycotoxins by liquid chromatography/tandem mass spectrometry coupled with immunoaffinity extraction

A method for the simultaneous quantitative determination of deoxynivalenol (DON), T‐2 toxin (T‐2), HT‐2 toxin (HT‐2) and zearalenone (ZEN) in wheat and biscuit by liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI‐MS/MS) coupled with immunoaffinity extraction is described. A clean‐up was carried out using a DZT MS‐PREP® immunoaffinity column (IAC), and the effect of the sample dilution rate and sample loading was investigated. Furthermore, the effects of ion suppression of a multifunctional column (MFC) and the IAC in the clean‐up were compared. The results with the DZT MS‐PREP® IAC showed that it is possible to make the sample dilution rate low, and indicated a higher solvent‐tolerance than usual with an IAC. Sample loading was optimized at 0.25 g. Ion suppression was lowered by purification of the toxins using the DZT MS‐PREP® IAC. Recoveries of each mycotoxin from wheat and biscuit samples spiked at two levels ranged from 78 to 109%. The limits of detection in wheat and biscuit was in the range of 0.03–0.33 ng·g^?1. From these studies, it is suggested that use of an IAC is effective in the clean‐up of each mycotoxin, and, when combined with LC/ESI‐MS/MS, it is good for the determination of mycotoxins in foodstuffs due to its rapidity and high sensitivity. Copyright © 2010 John Wiley & Sons, Ltd.     

Melting behavior of highly stretched isotactic polypropylene film

Isotactic polypropylene film was stretched in poly(ethylene glycol) at 140°C and its melting behavior was investigated by using a differential scanning calorimeter (DSC-1B). The shape of the melting curve depends largely on the stretching ratio, v. A sample stretched to moderate extension (1 < v < 3.5–4) has only a single melting peak (163°C) in the thermogram. When the sample is stretched beyond v = 3.5–4, the thermogram becomes more and more complex with increase of v, and some peaks appear when stretched to 10 < v < 13. The lowest peak which is considered to be the melting peak of the intermolecular crystals produced by the unfolding of chain molecules in the lamellae develops gradually with increase of v. In the thermogram for v = 18 the lowest temperature peak is most pronounced, in contrast to the highest temperature peak which decreases markedly in intensity. The phenomenon shows that large amounts of lamellar crystals are converted to intermolecular crystals in this region. On further stretching (v > 20) a very sharp high temperature peak appears, whose half-width is about 1°C. Qualitatively similar results were obtained for the samples stretched in poly(ethylene glycol) at 150°C and in air at 140 and 150°C.     

Heat Shrinkable Behavior and Mechanical Response of a Low‐Density Polyethylene/Millable Polyurethane/Organoclay Ternary Nanocomposite

Summary: A low‐density polyethylene (LDPE)/millable polyurethane (PU)/organoclay ternary nanocomposite was successfully prepared. The nanocomposites were characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The nanocomposites, as evidenced by XRD, are intercalated. The heat shrinkable behavior of the nanocomposites, as well as their pristine counterparts, was studied. It was observed that heat shrinkability decreases with increased filler content. The tensile strength and the tensile modulus of the nanocomposites are higher than their pristine counterparts.

The heat shrinkability of the unfilled LDPE/millable PU blend is highest and it decreases with increased nanofiller content.     

Strain‐induced crystallization and strength of elastomers. I. cis‐1,4‐polybutadiene

Crosslinked samples of cis‐1,4‐polybutadiene (BR) were crystallized at low temperatures and then slowly melted. From volume changes and differential scanning calorimetry measurements, the degree of crystallization in the unstrained state was estimated to be about 20%, much lower than for natural rubber (NR). Crystallization and melting were followed in stretched samples by corresponding changes in tensile stress. Crystallization was faster at higher strains, and the melting temperature was raised significantly on stretching but less than for NR, and the decrease in stress on crystallizing was smaller. Measurements of tensile strength were made over a wide temperature range and showed a marked drop with heating to temperatures of 40–60 °C, falling to values of only 1–2 MPa. A similar drop in strength occurred in NR vulcanizates at high temperatures and was attributed to failure to crystallize on stretching (A. G. Thomas & J. M. Whittle, Rubber Chem Technol 1970, 43, 222; A. N. Gent, S. Kawahara & J. Zhao, Rubber Chem Technol 1998, 71, 668). At ambient temperatures, where strain‐induced crystallization occurred, the strength of BR samples was only about one‐half of that of similar NR materials. This was attributed to less strain‐induced crystallinity in BR (verified by X‐ray studies), paralleling the lower amount developed at low temperatures. We speculate that the higher density of molecular entanglements in BR than in NR prevents BR from crystallizing to the same degree as NR. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 811–817, 2001     

Plasticity in Aerogels

When gently stressed, aerogels show an elastic response. However it was found that under isostatic pressure aerogels display an irreversible shrinkage which may be attributed to plastic behaviour. As a consequence of this plastic shrinkage it is possible to densify and modify the elastic properties of aerogels at room temperature.The structural evolution is followed by Small Angle X ray Scattering and the increase of the connectivity is revealed by the evolution of the elastic properties of the material.The SAXS data show that the densification mechanism is different from that obtained by sintering at high temperature. The densification mechanism induces a textural change at the periphery of the constitutive clusters but not inside, conversely to a sintering effect. We also show that the elasticity of the material is strongly influenced by this structural transformation. The power law evolution of the elastic modulus as a function of the density, usually observed on as-prepared and sintered aerogels, is not valid for compressed material.