Evaluation of oriented amorphous regions in polymer films during uniaxial deformation; structural characterization of a poly(vinyl alcohol) film during stretching in boric acid aqueous solutions

We have improved the conventional analytical method of the scattering data obtained with in‐situ synchrotron X‐ray scattering experiments, which is applicable to the structural characterization of the film during stretching. Four components of molecular chains in the film are divided from two‐dimensional wide‐angle X‐ray diffraction patterns. These components are the oriented crystals, the unoriented ones, the oriented amorphous chains, and the unoriented ones, respectively. This method allows to evaluate directly the degree of orientation of the amorphous chains and the amount of the oriented amorphous fraction in addition to each evaluation for the crystalline regions. This method is applied to the structural characterization of the poly(vinyl alcohol) (PVA) film during stretching in boric acid aqueous solutions, suggesting that boric acid accelerates orientation of molecular chains in the amorphous regions, and increases the oriented amorphous fraction by producing the cross‐links between the PVA chains and hindering strain‐induced crystallization. At a film break on stretching in the 3 wt% boric acid solution, the oriented amorphous fraction increases up to 70%, which is much higher compared to that in the film stretched in water, 45%. POLYM. ENG. SCI., 55:513–522, 2015. © 2014 Society of Plastics Engineers     

Evolution of phase behavior and orientation in uniaxially deformed polylactic acid films

The development of crystalline structure and orientation during uniaxial stretching of cast amorphous linear and branched lactic acid films were investigated in the rubbery temperature ranges that spans between glass transition temperature and cold crystallization temperature. This material exhibited almost ideal stress‐strain behavior in the temperature range 65–80°C. Because of its strain crystallizability, films with uniform thickness can be obtained at high deformation levels as a result of self‐leveling. Branching was found to retard this self‐leveling through its slightly detrimental effect on the strain hardening. Upon stretching the material undergoes rapid orientation in the amorphous state and beyond a critical level very sharp and highly oriented β crystalline form chains with ?3/1 helix. If the temperature is at or below Tg, with additional stretching, the films were found to revert to a highly oriented amorphous state through the destruction of the crystalline domains. At higher temperatures, further stretching results in continuation of improvement in crystalline order.     

Uniaxial deformation of overstretched polyethylene: In-situ synchrotron small angle X-ray scattering study

Synchrotron small angle X-ray scattering was used to study the deformation mechanism of high-density polyethylene that was stretched beyond the natural draw ratio. New insight into the cooperative deformational behavior being mediated via slippage of micro-fibrils was gained. The scattering data confirm on the one hand the model proposed by Peterlin on the static structure of oriented polyethylene being composed of oriented fibrils, which are built by bundles of micro-fibrils. On the other hand it was found that deformation is mediated by the slippage of the micro-fibrils and not the slippage of the fibrils. In the micro-fibrils, the polymer chains are highly oriented both in the crystalline and in the amorphous regions. When stretching beyond the natural draw ratio mainly slippage of micro-fibrils past each other takes place. The thickness of the interlamellar amorphous layers increases only slightly. The coupling force between micro-fibrils increases during stretching due to inter-microfibrillar polymer segments being stretched taut thus increasingly impeding further sliding of the micro-fibrils leading finally to slippage of the fibrils.     

Tensile deformation of nylon 6 fibers

Nylon 6 fibers which had been relaxed to different extents by annealing were examined at fixed strains by small angle and wide angle X-ray techniques. It was found that the strain of the long period of the semicrystalline microfibrils is identical to the macroscopic fiber strain. Approximately 1/3 of the tensile deformation results from molecular shear of imperfectly oriented crystalline chains. Virtually no evidence for intercrystalline slip is found; the orientation of the intercrystalline amorphous regions results in a low compliance for the shear of crystals past one another. The majority of the microfibril deformation occurs by stretching these intercrystalline amorphous regions, accompanied by the flow of extrafibrillar amorphous material to maintain constant volume. In highly annealed fibers this “filling” mechanism is less efficient, as the amount of extrafibrillar material has been reduced during shrinkage. This effect leads to a decrease in Poisson's ratio after increasingly severe annealing. A related result of annealing is the dehomogenization of the microstructure, leading to the presence of more stress-induced “microcracks” during the stretching of annealed fibers.     

Microprocesses Accompanying Deformation of Oriented Nylon 6

Abstract

Complex nature of tensile deformation of oriented nylon 6 fibers was investigated by broad-line NMR and IR methods. The first method was used for evaluation of a length distribution function for tie chains in amorphous regions of microfibrils and the second one-for chain scission detection. On the base of these results the stress-strain diagram and the elastic modulus dependence on deformation were calculated theoretically for an idealized model of polymer structure. From comparison between the theoretical curves and experimental ones the conclusion was drawn that deformation of fibers is due not only to stretching of tie chains in amorphous regions but to intermolecular interaction also. High values of modulus at small deformations were explained by existence of a rigid framework caused by interfibrillar interaction. External tensile load will be distributed between tie chains in amorphous regions only after destruction of this framework. Strength of the framework were estimated approximately as 70 MPa.     

Kinetics of structural evolution during crystallization of preoriented PET as followed by dual wavelength photometric birefringence technique

A two-color laser photometric measurement system was used to follow birefringence changes in annealing of prestretched PET films. This technique was shown to be capable of detecting large retardation (and thus birefringence) changes beyond one wavelength of the light. The use of green and red lasers in the photometric system allows the detection of the reversals in birefringence during the course of annealing. Unless critical orienialion/erystallinity levels are developed by stretching the films, heat setting the films at temperatures close to glass transition temper ature results in complete elimination of preferential orientation. At Intermediate stretch ratios, crystalline regions form and Ihe acl as anchor points establishing a network for the orienied amorphous chains. These Dims exhibit partial relaxation followed by rapid increase in birefringence due to the accelerating effect of orientation on crystallization. At high stretch ratios, where substantially oriented and strain crystallized structures are obtained, the initial relaxation stage disappears and birefringence continue to increase throughout the heat setting process even at temperatures very close to glass transition temperature. In these films, however, the total change of birefringence decreases as more of the chains are oriented and crystallized in the stretching stage, leaving a smaller fraction of polymer chains to rearrange during Ihe annealing stage. The kinetics of the structural change exhibit a complex behavior and the largest rates of structural changes were observed in films exhibiting intermidiate birefringence levels.     

Structure variation of tensile-deformed amorphous poly(l-lactic acid): Effects of deformation rate and strain

The present work explored the structure-property correlations for the biopolymer poly(l-lactic acid) (PLA) by studying deformation-mediated molecular orientation and crystallization. The structural and morphological variations of amorphous PLA under different strain rates were investigated. The result showed that strain rate significantly influences its strain-hardening behavior. The crystallinity and orientation as well as cavitation of deformed PLA increase with the increase of strain rates. The structure evolution has been divided into three potential stages: (i) at small strains (<100%), the crystallinity of PLA increases by orientation-induced crystallization; (ii) at intermediate strains (100%–160%), the crystallinity of deformed PLA slightly decreases due to the breakage of existing crystals under stress accompanying with newly formed voids and cavities; (iii) at high strains (>160%), the increasing number of oriented chains in the amorphous regions promotes the crystallization of PLA. Our study suggests that strain rate and stretching strain play important roles on modulating the crystallization and orientation of amorphous PLA.     

Molecular orientation and structural development in vulcanized polyisoprene rubbers during uniaxial deformation by in situ synchrotron X-ray diffraction

Molecular orientation and strain-induced crystallization of vulcanized natural rubbers (by sulfur and peroxide) and synthetic polyisoprene rubber (by sulfur) during uniaxial deformation at 0 °C were studied by in situ synchrotron wide-angle X-ray diffraction. The high intensity of synchrotron X-rays and new image analysis methods made it possible to estimate the mass fractions of strain-induced crystals and amorphous chains in both oriented and unoriented states. Most of the polymer chains (∼75%) were found to be in the random coil state even at large strains (>5.0). Only about 5% the amorphous chains were oriented, whereas the rest of the chains (∼20%) were in the crystalline phase. Sulfur vulcanized and peroxide vulcanized natural rubbers did not exhibit notable differences in structure and property relationships. In contrast, synthetic polyisoprene rubber showed a different behavior of deformation-induced structural changes, which can be attributed to the difference in cross-link topology. Our results indicated that strain induces a network of microfibrillar crystals in both natural and synthetic polyisoprene rubbers due to the inhomogeneity of cross-link distribution that is responsible for their elastic properties.     

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     

The role of interlamellar chain entanglement in deformation-induced structure changes during uniaxial stretching of isotactic polypropylene

In-situ small-angle X-ray scattering (SAXS), and wide-angle X-ray diffraction (WAXD) were carried out to investigate the deformation-induced structure changes of isotactic polypropylene (iPP) films during uniaxial stretching at varying temperatures (room temperature, 60 °C and 160 °C). From the WAXD data, mass fractions of amorphous, mesomorphic and crystal phases were estimated. Results indicate that at room temperature, the dominant structure change is the transformation of folded-chain crystal lamellae (monoclinic α-form) to oriented mesomorphic phase; while at high temperatures (>60 °C); the dominant change is the transformation of amorphous phase to oriented folded-chain crystal lamellae. This behavior may be explained by the relative strength between the interlamellar entangled network of amorphous chains, which probably directly influence the tie chain distribution, and the surrounding crystal lamellae. It appears that during stretching at low temperatures, the interlamellar entanglement network is strong and can cause lamellar fragmentation, resulting in the formation of oriented mesomorphic phase. In contrast, during stretching at high temperatures, the chain disentanglement process dominates, resulting in the relaxation of restrained tie chains and the formation of more folded-chain lamellae.     

Crystallization and orientation behaviors in isotactic polystyrene and poly(2,6-dimethylphenylene oxide) blends

The crystallization and orientation behavior in the miscible iPS/PPO blends were studied aiming at producing oriented materials consisting of iPS crystals and amorphous PPO chains. Oriented films of iPS/PPO blends were prepared by drawing the melt-quenched blend films. The films were heat-treated under constraint at the drawing temperature so as to crystallize the molecular chains of iPS in the oriented state. The crystallinity and the crystal orientation in the drawn annealed films were studied by the wide-angle X-ray diffraction (WAXD), and the orientation behaviors of molecular chains were analyzed by polarized FTIR spectroscopy. WAXD diagrams show the presence of the highly oriented crystalline structure of iPS in the drawn annealed films of pure iPS and iPS/PPO=7/3 blend. The polarized FTIR spectra of drawn annealed films suggest that the molecular orientation of the amorphous chains of PPO and iPS is markedly relaxed by the heat treatment, although the orientation of iPS with 3₁ helical structure was retained during the oriented crystallization. It was concluded that the drawn annealed samples of the iPS/PPO=7/3 blend consist of highly oriented iPS crystals and nearly isotropic amorphous materials. The mechanical properties of the oriented iPS/PPO blends were measured not only in the stretching direction but also perpendicular to the stretching direction. It was shown that the ultimate strength in the perpendicular direction is 4-5 times higher in the drawn annealed film of iPS/PPO=7/3 blend than in the drawn annealed iPS. The improvement in the vertical strength in the blend is discussed in relation to the structural characteristics of the iPS/PPO blend.     

Stress relaxation and hysteresis of nanocomposite gel investigated by SAXS and SANS measurement

The stress relaxation phenomena of nanocomposite gel (NC gels) after uniaxial elongation was investigated by time-resolved small-angle scattering techniques of neutrons and X-rays. Nanocomposite gels consist of clay platelets and poly(N-isopropylacrylamide). It was found that clay oriented instantly and polymer chains were elongated along the stretching direction by elongation, followed by gradual process of peeling-off of adsorbed polymer chains on the clay platelets. When the specimen was held in the deformed state, stress relaxation was observed. This was mainly ascribed to peeling-off of polymer chains. When the strain of the specimen was removed, the polymer chains tended to be adsorbed again to the surface of the clay platelets. The deformation mechanism of NC gels is discussed on the emphasis of the peeling-off and peeling-on process of polymer chains.     

Structure of the Amorphous Phase in Oriented Flexible-Chain Polymers

The effect of the cross-section of crystals and thickness of the amorphous phase in fibre-forming oriented polymers on transfer chains, kinks, and “cilia” in them for different values of the forces that stretch the macromolecules in crystallization was investigated by the Monte Carlo method. It was found that the fractions of transfer chains and kinds in the polymer increase and the proportion of “cilia” decrease with an increase in the cross-section of the crystals. The increase in stretching of the macromolecules in crystallization increases the proportion of transfer chains and decreases the proportion of kinks. The average number of segments in the kink and transfer chain decreases with an increase in stretching of the macromolecules. The increase in the thickness of the amorphous region between crystals along the direction of the axes of the molecules in the crystals causes an increase in the proportion of kinks and a decrease in the proportion of transfer chains. Moscow State Textile University. Translated fromKhimicheskie Volokna, No. 6, pp. 54–58, November–December, 2000.     

Orientation in amorphous polymers I. Preparation and testing of oriented samples

Orientation effects in amorphous polystyrene are studied using a uniaxial stretching experiment. The rheological properties of the polymer are determined from an analysis of creep data obtained from the tensile apparatus, and oriented polymer samples are prepared at different extension ratios and rates of stretching. From birefringence and tensile strength measurements on oriented samples of polystyrene, it is shown that the tensile strength is not a unique function of the birefringence. It is proposed that the tensile strength may depend not only on the average orientation, as reflected by the birefringence, but on which portion of the relaxation spectrum is preferentially oriented.     

Relationship of polymorphic crystalline phase texture to strain recovery and stiffness of a propylene‐based elastomer

A stretching process to enhance the stiffness of an elastomeric propylene‐ethylene copolymer through orientation was examined. The tensile extension was performed at various temperatures within the unusually broad melting range of the copolymer. Stretching transformed the unmelted lamellar crystals into shish‐kebab fibers that acted as a scaffold for an elastomeric matrix of entangled, amorphous chains. Density measurements indicated that the process did not significantly affect the amount of crystallinity, which was about 23%. If the specimen was recrystallized by cooling after it recovered from the stretched state, the amount of orientation decreased with increasing stretching temperature. However, if recrystallization occurred in the stretched state, it led to the formation of a second crystalline network that prevented contraction of the oriented crystalline structure during strain recovery. It was suggested that the second network was anchored by α′‐PP daughter lamellae that crystallized epitaxially on the α‐PP mother crystals of the extended fibrils. Although the manner in which the films were stretched and recrystallized strongly affected the modulus, good elasticity of the stretched films revealed the persistence of an elastomeric network. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

半晶态聚乙烯变形机理的分子动力学模拟

采用相间蒙特卡罗方法,建立半晶态聚乙烯模型。在温度350 K,x、y方向压力为0.1 MPa下进行拉伸,探究聚乙烯的拉伸机理和拉伸过程中微观结构的变化。在拉伸过程中,在弹性变形阶段,键长随着应变的增加而增加,键角和二面角也有少量的增加,且键长率先增长。过了屈服极限后,键长、键角和二面角不再增加,有一定量的减小,然后逐渐趋于稳定。变形区域主要发生在非晶区,拉伸时,分子链会发生取向,随着拉伸的进行,分子链发生滑移,最后会出现空穴现象。     

Micro-drawing of glassy polybenzoxazole rigid rods and the molecular interactions with carbon nanotubes

The high-temperature (T_g > 650°) wholly aromatic polybenzoxazoles (PBO) polymer chains in thin films underwent elastic energy release via local deformation of crazing when stretched beyond a critical strain around 0.5%. The strain localization in the ultra-rigid polymer was quickly superseded by craze fibril breakdown, triggering catastrophic fracture at low extensions below ～3%. Although the drawing stress of craze fibrillation, determined to be ～3 GPa, was insufficient to separate chains in PBO crystallites, it forced the chains in the amorphous regions to flow into large molecular deformations (～300% strain) at room temperature. The poor craze fibril stability of the rigid-rod chains was enhanced dramatically when surface-functionalized single-walled carbon nanotubes (SWCNTs) were dispersed into the polymer. No toughening effects were observed, however, for multi-walled carbon nanotubes (MWCNTs) although the elastic enhancement leading to increase of strain delocalization was still operative. The toughening selectivity was attributed to the PBO/CNT load transfer coupling during nanoplastic flows in which only the CNTs of compatible bending moments permitting fibril drawing were allowed to participate.     

On the Theory of NMR Line Shapes in Amorphous Regions of Uniaxially Oriented Polymers

Abstract

A theory of NMR of protons belonging to highly-stretched polymer chains with fixed ends, e.g. tie molecules of amorphous regions of oriented semicrystalline polymers, is presented. Analysis is carried out in terms of the model of freely-jointed chains. All contributions to the line shape from the intramolecular dipole-dipole interactions (DDI) are taken into account. Expressions are derived for the residual time independent component of DDI and the second moments of the fluctuating DDI. The NMR spectra are described in terms of the Anderson-Weiss approximation. A number of spectra are calculated for polyethylene. It is shown that the linewidth of high lemperature spectrum rapidly grows with stretching and approaches that of crystallite polymer. It is demonstrated that the distribution function of tie molecules can, in principle, be obtained from the dependence of the spectra on the stretching ratio.     

Structure and property development of aromatic copolysulfonamide fibers during wet spinning process

The structure and performance changes of aromatic copolysulfonamide (co‐PSA) fibers that occurred during wet spinning process have been studied. While using different length scale characterization, including scan electron microscopy (SEM), wide‐angle X‐ray scattering (WAXS), and small‐angle X‐ray scattering (SAXS), it was found that the molecular chains of co‐PSA formed an isotropic network during coagulation which further lead to extension and orientation of these chains during the subsequent stretching. As a result, only after heat stretching and heat setting the molecular chains tended to pack into crystal lattice in the fibrils. This gave rise to a much denser structure along the spinning line and the glass transition temperature of co‐PSA fibers increased a little after heat setting. Before heat stretching, the co‐PSA fibers were in amorphous state, and only the amorphous orientation was observed within the fibers. After heat stretching at the temperature higher than T_g, the fraction of amorphous region decreased, and the crystal structure formed in the fibers, which became more perfect during heat setting. The structure development during spinning process contributed toward the improvement of thermo‐mechanical stability, tenacity and modulus of the co‐PSA fibers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42343.     

Crystallization,structure, and enhanced mechanical property of ethylene-octene elastomer crosslinked with dicumyl peroxide

Crosslinking of polyolefin elastomer (POE, ENGAGE™ 8480) with Dicumyl Peroxide (DCP) can have effects on its crystallization dynamics, crystal structure, and properties. The POE crosslinked uniformly has significantly lower crystalline ability than the one with only amorphous phase crosslinked, which, in turn, has weaker crystalline ability than neat POE. The crystallinity and melting point depend on how the POE is crosslinked. The neat POE and POE crosslinked in amorphous phase only, are investigated with DSC and in-situ tensile/synchrotron radiation (WAXD/SAXS). In situ tensile/synchrotron X-ray during a uniaxial stretching process indicates that severe crystal fragmentation is observed at a strain around 45%, and with further increase in strain. The stress in the crosslinked POE is significantly larger than neat POE. For both samples, crystal orientation increases sharply within the strain range up to 88% where orientation-induced new crystals aligned in stretching direction are observed. The long period increases more in stretching direction for the crosslinked POE, consistent with larger stress in this sample, and the stress difference is more pronounced at large strains (27.3 vs. 10.9 MPa at a strain 435%). Permanent set of the crosslinked POE is smaller, consistent with less oriented crystals observed after the test for permanent set.