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1.
Structural and morphological behavior under stress–strain of polypropylene/multi‐walled carbon nanotubes (PP/MWCNTs) nanocomposites prepared through ultrasound‐assisted melt extrusion process was studied by means of optical microscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, small angle X‐ray scattering (SAXS), and wide angle X‐ray scattering (WAXS). A high ductile behavior was observed in the PP/MWCNT nanocomposites with low concentration of MWCNTs. This was related to an energy‐dissipating mechanism, achieved by the formation of an ordered PP‐CNTs interphase zone and crystal oriented structure in the undeformed samples. Different strain‐induced‐phase transformations were observed by ex situ SAXS/WAXS, characterizing the different stages of structure development during the deformation of PP and PP/MWCNTs nanocomposites. The high concentration of CNTs reduced the strain behavior of PP due to the agglomeration of nanoparticles. A structural pathway relating the deformation‐induced phase transitions and the dissipation energy mechanism in the PP/MWCNTs nanocomposites at low concentration of nanoparticles was proposed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 475–491  相似文献   

2.
Three stages of elastic behavior were observed during cyclic deformations for poly(ether‐b‐amide) (PEBA) segmented copolymers based on crystalline hard segments of polyamide 12 (PA12) and amorphous soft segments of poly(tetramethylene oxide) (PTMO). The underlying microstructural evolution was characterized by a combination of in situ Fourier transform infrared spectroscopy (FTIR), wide‐angle X‐ray diffraction (WAXD), and small‐angle X‐ray scattering (SAXS) technologies. The γ–α″ phase transition of crystalline PA12 occurred upon stretching, and the orientation of the α″ phase was less reversible under larger strains. PTMO chain orientation cannot be restored to the initial state, contributing to plastic deformation. Driven by the entropy effect, the strain‐induced crystallization of PTMO can fuse during sample retarding, exerting little influence on the residual strain. For PEBA with a shore D hardness of 35 D, the long period (L) can be restored to the initial L after the sample was unloaded until system fibrillation. The tie molecules between adjacent oriented lamellae can be by drawn out high stress in a PEBA material with a shore D hardness of 40 D, and the relaxation led to a second long period. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 855–864  相似文献   

3.
Local deformation of a polymer mixture crosslinked by irradiation with ultraviolet light was in situ monitored by using a Mach‐Zehnder interferometer. In combination with the refractive index data obtained from independent measurements, the deformation in the nanometer scales of the crosslinked blends was calculated by using the difference in optical path length of the blend measured before and after irradiation. Upon varying the crosslink density of the blend by changing the light intensity, it was found that the local deformation well correlates with the crosslink density obtained from the reaction kinetics experiments. Furthermore, the strain relaxation of the blends was also monitored in situ and analyzed after irradiation over different time intervals. The results obtained in this study reveal the possibility of monitoring the nanometer‐scale deformation in polymers during radiation curing. These data also provide important information on the correlations between the irradiation‐induced elastic strain and the resulting morphology of reacting polymer blends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2898–2913, 2005  相似文献   

4.
The evolution in the hard/soft domain microstructure of an elastomeric‐like polyurea during different tensile loading histories was studied using in situ small‐ and wide‐angle X‐ray scattering (SAXS/WAXS). The nonlinear stress–strain behavior is initially stiff with a rollover yield to a more compliant response; unloading is highly nonlinear showing substantial hysteresis while also exhibiting significant recovery. Reloading reveals a substantially more compliant “softened” behavior and dramatically reduced hysteresis. WAXS peaks monitor characteristic dimensions of regular features within the hard domains; the peak location remains unchanged with tensile deformation indicating no separation of the internal structure within a domain, but the peak intensity becomes anisotropic with deformation evolving in a reversible manner consistent with orientation due to stretch. The SAXS profiles provide information between major hard domains. SAXS peaks are found to shift with tensile loading in a relatively affine manner up to a tensile true strain of ~0.4, which, using a Bragg reduction to aid interpretation, reveals an axial increase and a transverse decrease in interdomain spacings; this evolution is reversible for strains less than ~0.4. Increasing axial strain beyond a true strain of ~0.4 is accompanied by a dramatic, progressive, and irreversible reduction in axial Bragg spacing, indicating a breakdown in the hard domain aggregate network structure. A four‐point pattern is seen to develop during stretching. The breakdown in networked structure during a first load cycle gives a new structure for subsequent load cycles, which is seen to evolve in a reversible manner for strains less than or equal to the prior maximum strain. However, for strains exceeding the prior maximum strain excursion, additional breakdown is found. These SAXS results show that a breakdown in the hard domain aggregate network structure is a governing mechanism for the large dissipation (hysteresis) loops of the first load cycle and are also responsible for the softened reloading response. The absence of structure breakdown during subsequent load cycles corresponds to the substantially reduced hysteresis loops as well as the stable softened behavior. DMA data on pristine and previously deformed samples show a more compliant storage modulus in the predeformed sample, supporting the softened cyclic stress–strain data and the structural breakdown observed in the SAXS; the loss modulus was unchanged with deformation, which correlates with the lossy features measured in DMA with time‐dependent viscosity rather than losses due to structural breakdown. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

5.
A unique in situ multiaxial deformation device has been designed and built specifically for simultaneous synchrotron small angle X‐ray scattering (SAXS) and wide angle X‐ray scattering (WAXS) measurements. SAXS and WAXS patterns of high‐density polyethylene (HDPE) and HDPE/clay nanocomposites were measured in real time during in situ multiaxial deformation at room temperature and at 55 °C. It was observed that the morphological evolution of polyethylene is affected by the existence of clay platelets as well as the deformation temperature and strain rate. Martensitic transformation of orthorhombic into monoclinic crystal phases was observed under strain in HDPE, which is delayed and hindered in the presence of clay nanoplatelets. From the SAXS measurements, it was observed that the thickness of the interlamellar amorphous region increased with increasing strain, which is due to elongation of the amorphous chains. The increase in amorphous layer thickness is slightly higher for the nanocomposites compared to the neat polymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

6.
Films of a blend of styrene–isoprene triblock copolymer and mineral oil have been simple-cast and roll-cast from a toluene solution. Their microstructure has been analyzed by transmission electron microscopy and small-angle X-ray scattering. The blend formed polystyrene spheres arranged on a body-centered cubic lattice in a matrix composed of polyisoprene and mineral oil, and the samples display large grain sizes and very long-range order. The roll-cast sample exhibits approximately uniaxial symmetry around the rolling direction, which corresponds to the [111] crystallographic direction of the lattice. The glassy spheres act as physical crosslinks of known crosslinking functionality in the soft rubbery matrix. The high-strain deformation mechanism of this oriented cubic material has been studied by a simultaneous tensile–SAXS experiment, where the sample was stretched up to 300% along the [111] direction. By monitoring the position of the (222) and (11 0) reflections, the deformation of the lattice is shown to be affine with the macroscopic deformation of the sample, and the Poisson's ratio is approximately 0.46. The first zero of the sphere form factor in the SAXS patterns remains also essentially unchanged up to 300% deformation indicating that the reinforcing glassy PS domains retain their spherical shape throughout the deformation. Deformation of the microstructure is totally reversible upon unloading. A model of {hk0} faults is proposed to describe the microstructural changes induced by high-strain deformation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1625–1636, 1998  相似文献   

7.
Simultaneous measurements of microscopic infrared dichroism, mesoscale deformation, and macroscopic stress have been made for a microphase‐separated film of poly(ether‐block‐amide) 4033 during uniaxial stretching at temperatures between 30 and 91 °C, well below the melting point of the hard polyamide‐12 (PA) domains. Before the onset of dramatic microstructural alterations, the true stress–strain relationship on the mesoscale can be described with an interpenetrating network model, and poly(tetramethylene oxide) (PTMO) soft segments undergo affine deformation. Beyond a threshold strain at which stress from the soft network becomes larger than that from the hard network, plastic deformation occurs in the hard PA domains, and this is accompanied by the downward derivations of the true stress and molecular orientation of PTMO blocks from the model predictions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1161–1167, 2005  相似文献   

8.
The effects of annealing semicrystalline polymers in the presence of plasticizing agents is an area of considerable current interest, given the potential to modify the degree and nature of crystallinity. These effects were studied for two semicrystalline polymers, custom‐synthesized methyl‐substituted poly(aryl ether ether ketone) (MePEEK) and industrial‐grade poly(ethylene terephthalate) (PET). Small‐angle X‐ray scattering (SAXS) was used to characterize the microstructure of both amorphous and preannealed materials. Differential scanning calorimetry (DSC), wide‐angle X‐ray scattering, and density measurements were also performed for the PET samples, and reference is made to similar analysis work done for MePEEK. A distinct morphological effect could be identified from SAXS measurements of MePEEK annealed in a stepwise fashion in the presence of high‐pressure CO2 with the polar cosolvent CH3OH. This result was absent in MePEEK similarly annealed in air and supports earlier DSC measurements. A very different morphological effect of pressure alone was observed in PET annealed in pure CO2 (170 and 510 atm) at a temperature of 150 °C, well above the glass transition. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2457–2467, 2000  相似文献   

9.
In this study, the mechanical performance of the different polymorphs of isotactic polypropylene, typically present in iPP crystallized under industrial processing conditions, is assessed. Different preparation strategies were used to obtain samples consisting of almost solely α, β, or γ crystals. X‐Ray measurements were used to validate that the desired phase was obtained. The intrinsic true stress ‐ true strain response of all individual phases was measured in uniaxial compression at several strain rates (deformation kinetics). Moreover, measurements were performed over a wide temperature range, covering the window in between the glass transition and the melting temperature. The relation between obtained yield stress and the strain rate is described with a modification of the Ree‐Eyring model. Differences and similarities in the deformation kinetics of the different phases are presented and discussed. Furthermore, the presence of three deformation processes, acting in parallel, is revealed. The Ree‐Eyring equation enables lifetime prediction for given thermal and mechanical conditions. These predictions were experimentally validated using constant load tests in uniaxial compression. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 729–747  相似文献   

10.
The synthesis of amphiphilic triblock copolymers, poly(di[methylamine]ethyl methacrylate)‐b‐poly(cyclohexyl methacrylate)‐b‐poly(di[methylamine]ethyl methacrylate) PDMAE‐b‐PCH‐b‐PDMAE, has been performed by atom transfer radical polymerisation. Those have been obtained in a well‐controlled manner in terms of molecular weight and polydispersity index. The triblock copolymer characterisation has been made in condensed state and in solution. The existence of microphase separation has been confirmed by differential scanning calorimetry. However, the domains of both inner and outer blocks seem not to be ordered for one another from small‐angle X‐ray scattering (SAXS) measurements using synchrotron radiation. The micelle formation in dilute methanol solutions has been confirmed for all triblock copolymers by dynamic light scattering analyses. The size of these micelles has been demonstrated to be dependent on the molecular weight. Similar observations have been made in concentrate methanol solutions by using SAXS experiments, pointed also out that an increment of the intermicelle interactions is produced as the concentration increases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 85–92, 2008  相似文献   

11.
The crystallization kinetics and morphology of PEN/PET copolyesters were investigated using differential scanning calorimetry (DSC), time‐resolved small‐angle X‐ray scattering (TR‐SAXS), and transmission electron microscopy (TEM). The Avrami exponents obtained using DSC were approximately 3 for homo PEN and 4 for all the copolyesters. The 3‐parameter Avrami model was successfully fitted to the invariants with respect to the time obtained from TR‐SAXS, and the exponent values were similar to those obtained from DSC. Moreover, the Avrami rate constants obtained from TR‐SAXS showed marked temperature‐sensitive decreases in all samples, like those obtained from DSC. This indicates that not only could changes in morphological parameters be obtained from the analysis of TR‐SAXS data but also crystallization kinetics. The changes in the morphological parameters determined from the SAXS data indicate that the minor components, dimethyl terephthalate (DMT) segments, are rejected into the amorphous phase during crystallization. In the TEM study, copolyesters crystallized at temperature above 240 °C grew into both the α‐ and β‐form, although 240 °C is the optimum condition for the β‐form crystal. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 805–816, 2005  相似文献   

12.
Two ABA‐type liquid crystalline oligomers were newly synthesized, where A was a mesogenic group and B was polyolefin whose molecular mass was 2470. The A segment was prepared from p‐hydroxyl benzoic acid and terephalic acid. The elastomeric films, whose moduli at 20% elongation were 0.4–1.0 MPa, were obtained by solution casting of the ABA‐type oligomers. Dynamic mechanical analysis and differential scanning calorimetry measurement showed the glass transition of amorphous polyolefin segments, the melting of mesogenic groups, and the meso‐to‐isotropic transition of liquid crystalline phase. The formation of microphase‐separated structures was confirmed by a small‐angle X‐ray scattering (SAXS) measurement. The presence of hexagonal cylinder domains, which were attributed to the aggregation of mesogenic groups in the polyolefin matrix, was also detected by SAXS. These liquid crystalline oligomers showed anisotropy under the crossed Nicoles, and the textures were observed to be nematic. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2247–2253, 2000  相似文献   

13.
True model linear poly(styrene‐b‐dimethylsiloxane) PS‐b‐PDMS copolymers were synthesized by using sequential addition of monomers and anionic polymerization (high‐vacuum techniques), employing the most recent experimental procedures that allow the controlled polymerization of each monomer to obtain blocks with controlled molar masses. The model diblock copolymers obtained were analyzed by using different techniques, such as size‐exclusion chromatography, 1H NMR, Fourier transform infrared spectroscopy, small angle X‐rays scattering (SAXS), and wide angle X‐rays scattering (WAXS). The PS‐b‐PDMS copolymers obtained showed narrow molar mass distribution and variable PDMS content, ranging from 2 up to 55 wt %. Compacted powder samples were investigated by SAXS to reveal their structure and morphology changes on thermal treatment in the interval from 30 to 200 °C. The sample with the highest PDMS content exhibits a lamellar morphology, whereas two other samples show hexagonally packed cylinders of PDMS in a PS matrix. For the lowest PDMS content samples, the SAXS pattern corresponds to a disordered morphology and did not show any changes on thermal treatment. Detailed information about the morphology of scattering domains was obtained by fitting the SAXS scattering curves. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3119–3127, 2010  相似文献   

14.
The annealing at 373 K of ultrastrong, gel‐spun polyethylene (PE) has been studied. At this temperature, the fibers show no significant shrinkage. Still, a significant decrease in the mechanical properties is observed. The fibers have been analyzed with differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), atomic force microscopy (AFM), and small‐angle X‐ray scattering (SAXS). During the annealing, the glass transition of the intermediate phase is exceeded, as shown by DSC. When split for structure analysis by AFM, the annealed fibers undergo plastic deformation around the base fibrils instead of brittle fracture. The quasi‐isothermal TMDSC experiments are compared to the minor structural changes seen with SAXS and AFM. The loss of performance of the PE fibers at 373 K is suggested to be caused by the oriented intermediate phase, and not by major changes in the structure or morphology. The overall metastable, semicrystalline structure is shown by TMDSC to posses local regions that can melt reversibly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 403–417, 2003  相似文献   

15.
This work is devoted to the study of the deformation mechanisms of a high‐density polyethylene deformed in tension. Specific treatments were applied to synchrotron wide‐angle X‐ray scattering patterns obtained in situ with the aim of quantifying: (i) the evolution of the apparent crystal sizes during the deformation process, (ii) the reorientation dynamics of the fragmented crystals while aligning their chains along the drawing axis during the establishment of the fibrillar morphology, and (iii) the reorientation dynamics of the amorphous chains. In addition, the volume strain evolution was measured using 3D digital image correlation. The cavitation phenomenon was found to mainly occur during the lamellae fragmentation phase. At the end of the deformation process, when the lamellar structure is destroyed, the fragmented crystals have new degrees of freedom and become free to rotate to align their chains along the drawing axis. Crystal fragmentation is then no longer needed to allow material deformation, and there is no further volume strain increase. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1470–1480  相似文献   

16.
Nonelastic deformation of semicrystalline poly(butylene terephtalate) (PBT) was investigated by calorimetric measurements and strain‐recovery tests. Differential scanning calorimetry on PBT specimens deformed both below and above their glass‐transition temperature (Tg ≈ 50 °C) showed the presence of a broad exothermal peak whose area represents the energy released for the nonelastic strain recovery. This energy became more and more pronounced as the strain level increased, and it decreased as the deformation temperature increased, even if a significant contribution was detected on specimens deformed at temperatures much higher than Tg. For two temperature conditions (21 and 100 °C), strain‐recovery master curves were built showing the following two distinct deformation components: one recoverable with time and another one irreversible, this latter one arising from relatively low levels of strain. The recoverable component can be erased by heating the material at temperatures much higher than its Tg, close to the onset of the melting process. On the other hand, the irreversible strain component does not recover even if the material is brought close to the onset of the crystals melting. The shift factor for the strain‐recovery master curves was compared with the shift factor for the construction of the dynamic storage modulus master curve obtained in the linear viscoelastic regime (small strain). © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 236–243, 2002  相似文献   

17.
A functionalized cyclic carbonate monomer containing a cinnamate moiety, 5‐methyl‐5‐cinnamoyloxymethyl‐1,3‐dioxan‐2‐one (MC), was prepared for the first time with 1,1,1‐tri(hydroxymethyl) ethane as a starting material. Subsequent polymerization of the new cyclic carbonate and its copolymerization with L ‐lactide (LA) were successfully performed with diethyl zinc (ZnEt2) as initiator/catalyst. NMR was used for microstructure identification of the obtained monomer and copolymers. Differential scanning calorimetry (DSC) was used to characterize the functionalized poly(ester‐carbonate). The results indicated that the copolymers displayed a single glass transition temperature (Tg) and the Tg decreased with increasing carbonate content and followed the Fox equation, indicative of a random microstructure of the copolymer. The photo‐crosslinking of the cinnamate‐carrying copolymer was also demonstrated. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 161–169, 2009  相似文献   

18.
Small‐angle X‐ray scattering (SAXS), atomic force microscopy (AFM), and other techniques were combined in a study of segmented thermoplastic elastomers (Pebax) containing poly(tetramethylene oxide) soft segments and hard blocks of nylon‐12. AFM was used to provide real‐space resolution of the morphology during tensile elongation and after subsequent relaxation. Nanofibril formation, starting at strains of about 1.5×, was characterized in detail, showing the evolution of the number, orientation, and size of these highly stressed load‐bearing fibrils that dominated the mechanical properties. AFM results were combined with two‐dimensional SAXS data to develop a model considering the breakup of the original ribbonlike nylon‐12 lamellae in combination with progressive reformation and orientation of highly stressed fibrils. The complex changes in the two‐dimensional SAXS images included a distorted arc pattern due to increased spacing of the lamellae in the stretch direction at low strains, with an evolution to completely different patterns dominated mainly by intrafibrillar and interfibrillar scattering contributions. Between stretch ratios of 1.5 and 2.3× original lamellae were progressively broken up, and by 3.2×, all lamellae independent of the initial orientation were broken into smaller crystals with low aspect ratios. The results were combined with differential scanning calorimetry and birefringence data taken on films under strain to obtain insight into the microscopic basis for strain softening and plastic deformation in Pebax and related segmented polymers. Birefringence cycling with strain provided a consistent picture with the other techniques for understanding the redistribution of stress on a nanoscopic scale during deformation and relaxation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1727–1740, 2002  相似文献   

19.
The true electric actuation thickness strain of poly (styrene‐b‐ethylbutylene‐b‐styrene) (SEBS) gel was measured using an in situ synchrotron SAXS. The thermoplastic elastomer SEBS gel was microphase‐separated to form a disordered styrene micelle nanostructure in an oil‐swollen ethylbutylene matrix. The SEBS gel showed reversible cyclic load–unload compression behavior without permanent residual strain. The electromechanical strain of the SEBS gel with carbon paste electrodes could be evaluated by means of a nanostructure dimensional change traced by using the in situ synchrotron SAXS during actuation. The strain measured with SAXS was compared with the strain measured using conventional laser displacement sensor systems. The optical laser sensor method was likely to overestimate the thickness strain due to the bending movement of the dielectric elastomer. To our knowledge, the thickness strain value measured by the synchrotron SAXS is the closest to the true strain ever measured in the field of dielectric elastomer studies, because the nanostructure dimensional change depends on the thickness dimension change, not on the translational movement like the bending motion. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010  相似文献   

20.
Small‐angle X‐ray scattering (SAXS) was performed on a sample of poly(4,4′‐ phthaloimidobenzoyldoeicosamethyleneoxycarbonyl) (PEIM‐22) as a function of temperature. Wide‐angle X‐ray diffraction and differential scanning calorimetry were used to follow the isotropization of the crystalline PEIM‐22. The crystals of PEIM‐22 consist of biphasic layers up to the isotropization temperature. A series of SAXS peaks are observed for the crystals between θ = 0.3 and 3.5°. The width of these peaks indicates the formation of a smectic‐like, crystalline layer structure of a coherently scattering domain size of only 3–4 repeating units. In the isotropic phase, a single, broader peak remained at a spacing of ≈2.6 nm, suggesting even at high temperature the existence of equilibrium, short‐range, local order. The SAXS profiles were calculated based on a model of alternating layers of a linear, paracrystalline lattice. The results were discussed together with similar data on model compounds in the literature, and it is suggested that the short‐range order in the isotropic phase is due to a nanometer‐scale separation of the polar, aromatic phthaloimidobenzoyl from the flexible doeicosamethyleneoxycarbonyl. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 611–621, 2000  相似文献   

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