Application of an interpenetrating network model to the solid deformation of a quenched isotactic polypropylene film

The molecular orientation and deformation mechanisms of a quenched isotactic polypropylene (iPP) film deformed at temperatures between 303 K and the melting point are studied. At draw temperature T_E less than 400 K where the degree of crystallinity does not change markedly, a linear relationship between molecular orientations of the crystalline and the amorphous phases is revealed and the slope is estimated about 1.82. The interpenetrating network (IPN) model, that takes into account the plastic response of the crystalline (C) network formed by a small portion of crystallites adhered through intercrystalline links and the pseudo-affine deformation of the crystallite enhanced amorphous matrix (CEAM) network, is able to account for inhomogeneous deformation behavior on the mesoscale accompanied with the localized necking in this T_E range. Meanwhile, the initial Young's modulus and the true yield stress exerted by the deformation of the rigid C network exhibit the Arrhenius type of dependence on T_E. The apparent shear modulus of the CEAM network as a function of T_E is discussed in relation to variations in numbers and average molecular weights of the crystalline and the amorphous sequences being manifested by small consecutive endothermic and exothermic peaks in the DSC curve. The IPN model becomes invalid for deformations above T_E=400 K where morphological changes are induced due to melting of crystallites as proved from the DSC measurement.     

Dependence of disperse dye diffusion on the structure and morphology of oriented heat–set polyester fibres

The structural parameters that predominantly influence dye diffusion behaviour in heat–set polyester fibres have been identified. Dye diffusion has been shown to depend on two factors: the volume of the accessible region (amorphous region) and the tortuosity of the dye diffusion path. The accessible region can be represented in terms of the amorphous volume per crystal, and the tortuosity can be expressed quantitatively by combining the orientation of the amorphous phase and the nature of coupling between the amorphous and the crystalline regions. An integrated model has been proposed by combining these parameters, and has been shown to correlate well with dye uptake in polyester fibres heat–set under slack and taut conditions.     

The determination of molecular orientation in oriented polypropylene by wide angle X-ray diffraction,polarized fluorescence and refractive index measurements

Orientation studies have been undertaken in uniaxially oriented drawn tapes of isotactic polypropylene, using the techniques of wide angle X-ray diffraction, polarized fluorescence and optical birefringence. The results have been interpreted on the basis of a simple two-phase model for orientation of the crystalline and noncrystalline regions. The rise in the orientation of the crystalline regions with increasing draw ratio is extremely rapid, even compared with the pseudo-affine deformation scheme. This result, taken in conjunction with the discontinuous change in the long period, supports the view that the plastic deformation involves a complete breakdown of the original lamellar structure and subsequent recrystallization of the highly oriented drawn material. Further support for this conclusion is obtained from the observation that the orientation of the long fluorescent probes, which might be expected to be constrained to the more highly oriented material, is similar to that measured for the crystalline material by X-ray diffraction.     

Hydrostatically extruded glass-fiber-reinforced polyoxymethylene. I: The development of fiber and matrix orientation

This paper describes the determination of fiber and matrix orientation in oriented short-glass-fiber-reinforced polyoxymethylene (POM) composites produced by hydrostatic extrusion. The starting material was random glass fibers (25 wt% and average length 150 μm) in an isotropic POM matrix, and the oriented composites were produced by extrusion through a reducing conical die at 15°C below the polymer melting point: after extrusion the average fiber length was reduced slightly to 133 μm. Fiber orientations were measured using an image analysis method developed at Leeds University, and the matrix orientation was determined using wide angle X-ray diffraction. The development of fiber orientation with extrusion ratio was found to be close to that predicted by the pseudo-affine deformation scheme although the fiber orientation was greater than that predicted by the model at low draw ratios and slightly less at the highest draw ratio. The development of the orientation of the crystalline portion of the matrix was found to be always significantly greater than that predicted by the pseudo-affine scheme.     

Orientierung und Streckmechanismen in amorphen und teilkristallinen Polycarbonatfäden

Heat-stretched fibres of bisphenol-A-polycarbonate may be produced in the fully amorphous as well as in the semi-crystalline state, depending on the choice of the molecular weight of the polymer and the spinning and stretching conditions. Investigations are made as to the influence of the stretching conditions on the orientation of the amorphous regions of the semi-crystalline material and on the orientation of the fully amorphous fibres. The orientation of the fully amorphous fibres is determined by measuring the birefringence, whereas that of the amorphous regions in semi-crystalline material results from the difference in birefringence of the entire structure of the fibres and the birefringence of the crystalline regions. The latter is calculated from the factor of orientation \documentclass{article}\pagestyle{empty}\begin{document}$ \[ \text{f}_\text{k} \text{ = }\frac{1} {2}(3\overline {\cos ^2 } \text{ }\varphi −1) \] $\end{document}, which in turn is measured by wide-angle X-ray scattering. From the polarizabilities of the individual atomic bonds it was possible, on the basis of known interatomic distances and valence angles, to calculate the components of the polarizability tensor for polycarbonate. These values were used to determine the maximum birefringence of amorphous and crystalline polycarbonate. It was shown that the calculated values for birefringence, which were obtained using orientation functions determined by X-ray scattering, agreed very well indeed with those measured from the optical birefringence. Equally good agreement for the oriented filament yarns was obtained between the values for the mean angle existing between chain direction and fibre axis as determined by X-ray examination, and the results calculated from IR-dichroism. In the case of the highly stretched polycarbonate filament yarns, it was observed that, despite the rigid molecule structure, the orientation of the crystalline regions was as high as with, for example, polyethylene-terephthalate fibres. (Mean angle between chain direction and fibre axis approx. 16°). The formation of stretch-induced crystallites with fibres of higher molecular weight polycarbonate can be explained by assuming a heterogeneous stretching mechanism with necking. In the case of low molecular weight polycarbonate fibres consolidated domains of high density cannot be destroyed by heat stretching; instead, they merely slide past each other, with the result that the stretching process takes place homogeneously without initiating any crystallization.     

Application of an interpenetrating network model to the necking in the microcrystalline region in four annealed isotactic polypropylene films subjected to uniaxial stretching at room temperature

The microscopic infrared dichroism, mesoscale deformation and macroscopic stress measurements are made on the microcrystalline region in four annealed isotactic polypropylene (iPP) thin films subjected to uniaxial stretching at room temperature. Results reveal that volume dilatation might occur during stretching and the necking causes the anisotropic shrinkage in the thickness and the width directions. The average orientation function f_av and the true stress as a function of local draw ratio in the samples showing volume dilatation can be respectively overlapped onto those of the sample undergoing constant volume deformation. The pseudo-affine deformation is applicable for molecular orientation at f_av<0.50 and the true stress-strain relationship on the mesoscale can be well described in the same region by the interpenetrating network model previously proposed for necking in the quenched iPP film. This model becomes invalid for deformations above f_av=0.50 due to that plastic deformations in the crystalline phase, depending on the annealing time, start to play a major role.     

Molecular orientation and relaxation in poly(butylene terephthalate)/polycarbonate blends

Rheo-optical Fourier-transform infrared (FTIR) spectroscopy is based on the simultaneous acquisition of stress-strain data and FTIR spectra on-line to the mechanical treatment of polymers and is frequently applied for the characterization of transient structural changes during deformation and stress-relaxation. In the present communication, this technique has been employed in order to investigate the distribution of molecular orientation and its relaxation in uniaxially drawn solution-cast films of semicrystalline partial miscible blends of poly(butylene terephthalate) (PBT) with polycarbonate (PC) containing 10, 30 and 50 wt% PC. The uniaxial deformation of these blend films having a PBT-crystallinity degree ranging from 31 to 12%, in unstretched blends, leads to a appreciable high segmental orientation for the crystalline PBT due to a structural transformation from lamellae to microfibrils. The formation of this fibrillar structure is attributed to non-reversibility of an extended phase with all-trans conformational sequence of the aliphatic segments of PBT, occurring during elongation. The rate of relaxation of this conformational transition, however, increases with increasing amorphous content in the blends. Also it is observed that even with increasing amorphous content in the PBT/PC blends the crystalline PBT shows significant orientation. In such cases, apart from the few lamellae which transform to microfibrils, it is suggested that a stress induced transformation of PBT chains in amorphous PBT-component to irreversible all-trans extended crystalline form also contributes to PBT crystalline orientation. In contrast with this high crystalline orientation, the amorphous PBT located in the interlamellar regions inside the PBT-spherulites show a lower orientation in blends as compared in pure PBT.On the other hand, an overall segmental orientation of PC chains in blends is of lower order which is attributed mainly to low stretching temperature compared to T_g of pure PC. The results are discussed in terms of the resulting spherulitic morphology and the temporary network formed by the elongated PBT and PC chains inside the interlamellar regions, in blends.     

Deformation of Polyether‐Polyester Thermoelastoplastics: Mechanothermal and Structural Characterisation

The complex investigation of copoly(ether‐ester) based on poly(butylene terephthalate) (PBT) and poly(tetramethylene oxide) (PTMO) reveals its microphase separated nanodomain structure. Initial morphology includes the stacks of crystalline blocks of α‐PBT embedded in amorphous matrix with the different degree of continuity of the crystalline network. Two types of amorphous regions can be distinguished, the PTMO‐rich phase and the other one containing the PTMO and PBT segments. Reduction of PBT content and proper decrease of its fragments length results in dramatic change in crystalline ordering, the crystallites became smaller and distorted, and more and more PBT segments are included in the amorphous phase. The initial reversible stage of deformation is controlled mostly by elastic deformation of amorphous phase, highly constrained by the network of crystallites. The further stretching results in plastic deformation and reorganisation of the crystalline blocks of PBT and a new crystalline morphology arises. Moreover, at large deformations the soft blocks of PTMO can crystallise and form very distorted paracrystalline regions. Finally, at high enough stress (≈25–30 MPa) the transition from α to β crystalline form in PBT crystal lattice occurs due to conformational changes in the tetramethylene segments. After large deformation, both the morphology and the polymer conformations are far from the equilibrium state. Annealing of the stretched samples at high temperature results in partial recovery of material properties, however the morphology is still far from the initial one even after such annealing.     

Morphology of cold-drawn high-density polyethylene fibres

Drawn fibres of high-density polyethylene, and their crystalline residues obtained by nitric acid digestion of the amorphous phase, exhibit single- or double-peaked melting endotherms depending on the degree of crystallinity of the fibre, the draw ratio and, in the case of some of the crystalline residues, whether or not they have been melted once or twice. The melting behaviour of the drawn fibres and their crystalline residues has been accounted for in terms of the rupture of a fraction of the original lamellar structure and the growth of a new crystalline structure.     

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     

Puncture deformation and fracture mechanism of oriented polymers

In this study, we investigated the effect of orientation by solid‐state cross‐rolling on the morphology, puncture deformation, and fracture mechanism of an amorphous TROGAMID material and three semicrystalline polymers: high‐density polyethylene (HDPE), polypropylene (PP), and nylon 6/6. In amorphous TROGAMID, it was found that orientation preferentially aligned polymer chains along the rolling deformation direction and reduced the plastic deformation of TROGAMID in a low‐temperature puncture test. The decrease of ductility with orientation changed the fracture mechanism of TROGAMID from ductile hole enlargement failure in the unoriented control to a more brittle delamination failure in TROGAMID cross‐rolled to a 75% thickness reduction. For semicrystalline polymers HDPE, PP, and nylon 6/6, the randomly oriented crystalline lamellae in the controls were first oriented into an oblique angle to the rolling direction (RD) before the lamellae became fragmented and preferentially oriented with the chain axis parallel to the RD. The morphological change resulted in the decrease of ductility in HDPE in the low‐temperature puncture test. In PP and nylon 6/6, the brittle fracture of unoriented controls was changed into ductile failure when they were cross‐rolled to a 50% thickness reduction. This was attributed to the tilted crystal lamellae morphology, which permitted chain slip deformation of crystals with the chain axis parallel to the maximum shear stress direction. With further orientation of PP and nylon 6/6 to a 75% thickness reduction, the failure mechanism changed back to brittle fracture as the morphology transformed into a layered discoid structure with the chain axis of the fragmented crystal blocks parallel to the RD; this prevented chain slip deformation of the crystals. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Modulus development in oriented short-glass-fiber-reinforced polymer composites

The increase in modulus obtained in a short-glass-fiber-reinforced polymer composite as a result of uniaxial deformation may be related to the observed increase in both fiber and matrix orientation. Quantitative measurements of both fiber and matrix orientation are presented for a series of samples of short-glass-fiber-reinforced polyoxymethylene copolymer, processed to various substantial deformation ratios by solid-phase hydrostatic extrusion. The polymer matrix becomes highly oriented at modest deformations, but the glass fibers orient in a slower pseudo-affine manner and dominate the development of modulus in the composite. A simple “law-of-mixtures” model is used to demonstrate that perfect uniaxial orientation of the fibers is not achieved, but a better fit to measured modulus data is obtained by using an “aggregate” model applied to oriented fibers in an oriented matrix. The development of modulus with deformation ratio may be predicted very well if it is assumed that:

• the composite consists of a series-coupled array of sub-units, each containing continuous and fully oriented fibers in a fully oriented matrix; and
• orientation of the sub-units develops with deformation in a pseudo-affine manner.

     

Phenomenological and mathematical analysis of the orientation in biaxially drawn polymeric films

Equations are derived that relate the orientation of “pseudo-affine” reoriented structural units after a biaxial deformation to the degrees and the directions of the effective drawings. The connection between these drawing parameters and those externally applied is analyzed in detail. It is shown how a comparison of these two sets of drawing parameters allows conclusions regarding the distribution throughout the material of the stresses that cause the deformation, the inhomogeneity of the deformation, and the role of non-orienting flow during deformation. In particular, the orientation of biaxially drawn poly(ethylene terephthalate) films is investigated, and it is shown what general information can be obtained on the deformation behavior of this material on the basis of these considerations.     

Morphology of high-density polyethylene pipes stored under hydrostatic pressure at elevated temperature

The morphology of unimodal and bimodal high-density polyethylene (HDPE) pipes during a hydrostatic pressure test was studied in detail using ¹H solid-state NMR. Characterizing the changes of the molecular network during such a test is of key importance for understanding the long-term properties of different HDPE pipe grades. The changes in amount, thickness, and molecular mobility of the crystalline phase, the interface, and the amorphous phase of the two pipe grades with the storage time have been quantified for the first time. The most sensitive microscopic parameter to storage is the molecular mobility of the amorphous phase, with the strongest changes shown by the unimodal HDPE. The density of the tie-molecules is not the main factor controlling the very different behavior of the two pipe grades, but rather it is the density of the entanglements. The NMR results offer unprecedented insights into the changes in the molecular network and support existing deformation models.     

Molecular Orientation and Mechanical Properties of Poly(Vinyl Alcohol) Fibers

Abstract

A number of poly(vinyl alcohol) fibers with different draw ratios was characterized by measuring the birefringence, crystalline orientational order, crystallinity, tensile strength, and modulus. The birefringence, tensile strength and modulus increased with increasing draw ratio whereas the crystallinity and crystalline order parameters remained constant within narrow limits. The increase in birefringence has to be attributed solely to an increase in chain orientation in the amorphous phase of the semicrystalline fiber. The tensile strength and modulus are therefore directly related to the chain orientation in the amorphous phase. With the aid of a simple two-phase model it was found that the modulus of the amorphous phase in its disordered conformation was 4.8 GPa. The intrinsic birefringence of the amorphous phase was found to be 79 × 10^?3, i.e. much higher than the value obtained for the crystalline phase (52 × 10^?3). When this value was used in calculations, it was found that the order parameter of the amorphous phase increased from around 0.1 for a draw ratio of 1 to approximately 0.6 for a draw ratio of 5, whereas the order parameter of the crystalline phase was close to 1 for all draw ratios.     

Rheo-optical studies on the deformation mechanism of semicrystalline polymers. 1. Deformation mechanism and recoverability of deformation of tubular extruded polybutene-1 films

Rheo-optical studies (involving small-angle X-ray and light scattering, wide-angle X-ray diffraction, and birefringence studies) have been applied to polybutene-1 films prepared by tubular extrusion (the preparation involving crystallization from oriented melts) to investigate the fundamental orientation and deformation mechanisms of molecules (in the crystalline and amorphous regions) and crystalline supermolecular structure. It is shown that the molecular orientation behaviour can be described by deformation of the ‘row-nucleated’ sheaf-like crystalline superstructure and that the deformation of the interlamellar spacing is quite uniform, the microscopic strain being identical to the strain in bulk specimens. The latter is quite important in understanding apparent ‘springy’ or ‘hard-elastic’ properties of the films observed at temperatures above the glass transition of the films. In relation to the springy properties, recoverabilities of the molecular and supermolecular structures from large extensions have been also studied.     

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.     

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.     

Deformation and damage upon stretching of degradable polymers (PLA and PCL)

Microstructure and plastic behavior of poly(lactic acid), PLA, and poly(ε-caprolactone), PCL, are investigated. The injected molded specimens are analyzed as received. Thermomechanical properties are characterized by DSC and DMA and crystalline structure by WAXS. The results show that PLA samples are weakly crystalline (14 wt%) and that amorphous phase is glassy at room temperature. The PCL samples exhibit higher crystallinity (53 wt%) and contain a rubber-like amorphous phase. Mechanical behavior is investigated by means of novel video-controlled materials testing system specially developed to assess true stress vs. true strain curves and to record the volume changes upon stretching. While tested at 50 °C, PLA undergoes extensive plastic deformation with a dramatic yield softening followed by a progressively increasing strain hardening. Volume strain, which characterizes deformation damage, increases steadily over the whole plastic stage until reaching 0.27 for an axial strain of 1, 4. For its part, PCL exhibits at 23 °C a much progressive plastic response with a soft yield point, no softening, and moderate strain hardening at large strain. Volume change is delayed until axial strain reaches 0.4. Subsequent damage grows very quickly, eventually reaching 0.2 for an ultimate strain of 1, 3. Results are discussed on the basis of microscopic damage mechanisms observed in the stretched state.     

Molecular orientation behaviour of uniaxially stretched poly(vinyl chloride) film: 1. Birefringence: effect of plasticizers and draw ratio above and below Tg

In order to investigate the orientation behaviour of a non-crystalline chain polymer, plasticized and unplasticized poly(vinyl chloride) films (PVC) are chosen for investigation. The following two orientation distribution functions are postulated to calculate the second moment of the molecular orientation: (a) for the unplasticized film drawn below the glass transition temperature the distribution function derived from an affine deformation mechanism is applied; (b) for the all plasticized films or for the films drawn above the glass transition temperature a compound distribution function derived from the affine deformation mechanism and that of a rubber-like chain (Langevin model) proposed by Roe et al is applied. The parameters which are included in the distribution function, viz. the ratio of the affine part to the Langevin part, the ratio of polyene to carbonyl in a heat treated film and the segment number of the Langevin chain, can be evaluated experimentally. The intrinsic birefringences of normal and heat treated unplasticized and plasticized films are estimated theoretically on the basis of additivity of band polarizabilities. The calculated birefringences and orientation distribution functions show good agreement with measured values.