Effect of uniaxial stretching on thermal,oxygen barrier,and mechanical properties of polyamide 6 and poly(m‐xylene adipamide) nanocomposite films

In this study, the effect of uniaxial stretching on the thermal, oxygen barrier and mechanical properties of aliphatic polyamide 6 (PA6) and aromatic Poly(m‐xylene adipamide) (MXD6) nylon films as well as their in‐situ polymerized nanocomposites with 4 wt% clay were studied. Cast films were prepared by extrusion process and rapidly cooled using an air knife. The precursor films were uniaxially stretched at 110°C with draw ratios varying from 1.5 to 5. DSC results showed that the cold crystallization temperature (T_cc) of the uniaxially stretched MXD6 and MXD6/clay films drastically shifted to the lower temperatures when draw ratio increased. The aromatic nylon films had lower oxygen permeability than those of the aliphatic films, due to more rigidity and chain packing. However, the oxygen permeability of the stretched films increased with draw ratio (DR) up to a critical value for each sample, while further stretching resulted in a reduction in the oxygen permeation. This phenomenon was related to the changes in free volume upon uniaxial stretching. The ability of different geometrical models to describe the experimental relative permeability data was investigated. The Bharadwaj model that took into account clay orientation was the most successful one to predict the oxygen barrier characteristics of the stretched nanocomposites at high draw ratios. The Young's modulus and tensile strength of the aliphatic and aromatic nylons increased with uniaxial deformation, while the flexibility and elongation at break of the former decreased with increasing DR. A larger increase in the Young's modulus of the uniaxially stretched nanocomposite films compared with the neat samples was observed and could be related to the improvement in the clay orientation as well as a better alignment of the crystalline phase due to incorporating the clay platelets in the polymer matrix. In contrast, the flexibility of the stretched MXD6 improved remarkably (ca., 25 times) compared with the precursor film (DR = 1) when the draw ratio increased to 1.5. This could be related to the effect of hot stretching on the enhancement of polymer chains relaxation and mobility at low draw ratios. POLYM. ENG. SCI., 55:1113–1127, 2015. © 2014 Society of Plastics Engineers     

Improving the dielectric performance of poly(vinylidene fluoride)/polyaniline nanorod composites by stretch‐induced crystal transition

The introduction of conductive polyaniline (PANI) can significantly improve the dielectric constant of polymer‐based materials. However, there is a drawback of high dielectric loss. Herein, a simple and efficient stretching process was applied to improve the dielectric performance of poly(vinylidene fluoride)/PANI (PVDF/PANI) nanorod films through the stretch‐induced crystal transition from non‐polar α‐crystal to polar β‐crystal in PVDF and the oriented distribution of PANI nanorods. XRD, DSC and Fourier transform IR analyses indicate that the stretched PVDF and stretched PVDF/PANI films possess a high content of β‐crystal at the stretching temperature of 135 °C under a stretching ratio of 200%–400%. Furthermore, the stretched PVDF/PANI film with 10 wt% PANI displays a high dielectric constant of 338 at 100 Hz, which is increased by 20% compared to non‐stretched PVDF/PANI film (281). More importantly, the corresponding dielectric loss is reduced from 0.31 for the non‐stretched film to 0.17 for the stretched film. © 2018 Society of Chemical Industry     

Microstructure and properties of porous nanocomposite films: effects of composition and process parameters

Porous nanocomposite films based on polypropylene (PP) and titanium dioxide (TiO₂) nanoparticles were prepared by melt extrusion followed by uniaxial stretching. The effects of drawing temperature, extension rate, stretching ratio and composition of the base films on the final properties and microstructure of the stretched films were studied. Water vapor permeability (WVP) results showed a significant decrease in permeability of the films stretched at temperatures higher than 60 °C. Porosity, pore size and water vapor transmission rate in the porous nanocomposite films had a direct relation with nanoparticle content, extension rate and stretching ratio. Study of the morphology of the stretched films, using SEM, revealed that the pores form due to PP/TiO₂ interfacial debonding at low stretching ratios. Higher stretching ratios cause an enlargement of the pores and the formation of a PP fibril structure parallel to the stretching direction. Quantification of dye adsorption revealed that the quantity of adsorbed dye increased with porosity and surface area of the pores. © 2014 Society of Chemical Industry     

γ→β Phase transformation induced in poly(vinylidene fluoride) by stretching

The purpose of this work was to show in a conclusive way the γ→β phase transformation induced by uniaxial stretching in poly(vinylidene fluoride). Poly(vinylidene fluoride) films were melted and crystallized at 163°C for 36 h. Under these conditions, a mixture of α and γ phases was formed, with a predominance of the latter. These films were uniaxially stretched at 130°C at a draw ratio of 4. Fourier transform infrared and differential scanning calorimetry analyses showed a γ→β phase transition in the solid state, whereas orientation of the α phase without any transition was observed. Optical microscopy analysis permitted the observation of the transformation of spherulitic structures into oriented lamellae during stretching. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Doubly oriented β-form films of poly(vinylidene fluoride)

PVDF sheets, rapidly quenched, were (1) two-step transversely stretched at various temperatures and (2) stretched at various temperatures, rolled at room temperature and then annealed. The orientation patterns of the β-form crystal (which contains the polar b-axis) in these films were analysed on the basis of X-ray diffraction photographs taken with flat and cylindrical cameras. In the case of (1), when both of the two-step transversely stretching temperatures were below 100°C, a doubly oriented film with the plar b-axis oriented parallel to the film surface was obtained. In the case of (2), when the stretching temperature was below 100°C, the sheets then rolled without annealing, another doubly oriented film with the polar b-axis preferentially oriented at 30° to the film surface was obtained. On the other hand, when these films were annealed above 100°C, or the stretching temperatures were above 100°C, orientation patterns in which the polar b-axis was partially rotated through 60° were obtained. The orientation mechanisms of these films are discussed using the measurements of the lattice spacings of the β-form crystal.     

Effects of the biaxial orientation on the mechanical and optical properties and shrinkage of polyamide 6-66–montmorillonite–nanosilica nanocomposite films

Polyamide 6–66 (PA6-66)–montmorillonite (MMT)–nanosilica (NS) nanocomposite films were fabricated through a cast film process and then biaxially stretched on a laboratory stretcher. Uniaxial or biaxial stretching induced the elongated conformation of MMT and NS. The b axis of the α crystals and the amorphous phase were revealed to align along the machine direction (MD) after stretching, with the uniaxial orientation playing a more significant role. Furthermore, the crystallinity of PA6-66 stretching increased with the stretching ratio. Uniaxial stretching gave rise to a significantly enhanced tensile strength along the MD, whereas it slightly decreased the mechanical properties along the transverse direction (TD). In contrast, the films subjected to biaxial stretching exhibited more balanced mechanical properties. Uniaxial and biaxial stretching led to decreased transmittance and increased haze in the PA6-66–MMT–NS films; this could have been due to the elongated nanostructure of the two nanofillers, which inhibited the transmission and facilitated the scattering of visible light. The thermal shrinkage of the films increased with increasing stretching ratio, and the biaxially oriented films presented nearly equal shrinkage in the MD and TD. The addition of nanofillers decreased the shrinkage attributed to the mobility inhibition of the polymer chains during heating. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47504.     

High strength poly(vinyl alcohol) films obtained by drying and then stretching freeze/thaw cycled gel

The mechanical properties of stretched poly(vinyl alcohol) (PVA), which is formed by stretching a film prepared from a freeze/thaw cycled gel, were investigated as a function of the stretching ratio. The tensile strength and Young's modulus of 800% stretched PVA annealed at 130°C were 3.4 and 119 GPa, respectively. These values were much higher than those for a PVA film prepared without freeze/thaw cycling. For a film stretched more than 600% before annealing, two melting peaks, assignable to folded and extended chain crystals, were observed around 220°C and 230°C, respectively. This indicates that a shish‐kebab structure is formed as the stretching ratio increases. After annealing at 130°C, the folded‐chain crystal transformed to an extended‐chain crystal if an extended‐chain crystal was present in the stretched film before annealing. High tensile strength and Young's modulus after annealing were due to the formation of extended‐chain crystal. Therefore, the presence of extended‐chain crystal for annealing is important to provide good mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41318.     

Real‐time monitoring of fluorescence anisotropy and temperature during processing of biaxially stretched polypropylene film

An optical sensor based on fiber optics has been developed to measure fluorescence anisotropy and temperature during processing of biaxially stretched polypropylene films. The sensor, containing optical fibers, polarizing elements and lenses, was mounted above the polypropylene film as it was processed in a tenter frame oven stretching machine. Fluorescence observations were made using the fluorescent dye, bis (di‐tert butylphenyl) perylenedicarboximide (BTBP), which was doped into the resin at very low concentrations. To monitor biaxial stretching, fluorescence anisotropy measurements were carried out with light polarized in the machine and the transverse directions corresponding to the directions of biaxial stretching. Fluorescence based temperature measurements were obtained from the ratio of fluorescence intensities at 544 nm and 577 nm. A matrix of experiments involving three levels of stretch ratio in both the machine and transverse directions was undertaken. We observed significant differences between anisotropy in the machine and transverse directions that we attributed to the sequential stretching operation, i.e., the film was stretched in the machine direction first, followed by stretching in the transverse direction, and to film temperature and strain rate for each stretching operation. The result was uniformly higher anisotropies in the machine direction. Film temperature obtained from fluorescence corresponded to oven thermocouple measurements within 2°C. Polym. Eng. Sci. 44:805–813, 2004. © 2004 Society of Plastics Engineers.     

Untersuchung der ursachen für das auftreten mehrerer schmelzpeaks in den DSC-thermogrammen von hochverstreckten und getemperten folien aus isotaktischem polypropylen

Isotactic polypropylen films were highly stretched and annealed during 20 s under stretching tension at temperatures up to 206°C at maximum. The melting behaviour of these films was investigated by using a differential scanning calorimeter (DSC — 1 B). Two melting peaks at about 165 and 174°C respectively, were observed. The heat of fusion of the former peak predominates, if the film temperature during annealing exceeds 190°C. Its position is independent of the stretching ratio. This melting peak is assigned to crystalline domains, which show a long identity period of 140 to 160 Å and corresponds to an amorphous orientation factor of 0 to ?0.2. The higher melting peak appears during stretching. This peak is assigned to crystalline domains, which show a long identity period longer than 200 Å and corresponds to an amorphous orientation factor of 0.4 to 0.5. This fraction refers obviously to the paracrystalline building blocks of the microfibrils, which are transformed at a film temperature higher than 190°C to a greater part into smaller lamellaforming paracrystallites. The transformation of the fibrillar into a lamellar texture was visualised by transmission electronmicroscopy.     

Time and temperature effects on the tensile yield properties of polypropylene

Tensile tests were made on polypropylene films as a function of aging temperature from 80 to 130°C at a strain rate of 5 cm min^-1. Polypropylene films aged at 60 and 100°C and at time intervals up to 180 min were also stretched at the same strain rate. The yield stress and initial modulus were found to be linear functions of temperature, extrapolating to a zero value close to the thermodynamic melting point of the polymer (170°C). The work of yield, the plastic and yield strains also decreased with increase in aging temperature but the elastic strain increased. The plastic strain, yield strain, yield stress, and initial modulus for the 60°C aged film had larger values than the corresponding values for the 100°C aged film at equivalent time intervals and all properties decreased with increasing log time of aging. These decreases in properties were explained in terms of decrease in the density (crystallinity) of aged PP films. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 625–633, 1997     

Structure evolution of polyamide (11)’s crystalline phase under uniaxial stretching and increasing temperature

Thermal processing of polyamide influences the internal crystalline structure and thereafter the post product mechanical performance. In this article, the crystalline transition of polyamide-11 (PA11) plate under uniaxial stretching and increasing temperature was investigated systematically using in-situ synchrotron X-ray technique. It was discovered that the lamellar slippage, fragmentation and recrystallization occurred in sequence under increasing temperature. In detail, the crystal of PA11 plate was stretched with a transition from triclinic α-form to mesomorphic phase at 25 °C. For the thermally activated γ-form crystals, crystal transition was inhibited when temperature was increased up to 160 °C. The melt-recrystallization was inclined to take place at large tensile strains. This work enhances the research significance of the thermal processing of polyamide and provides a theoretical method to improve the high performance of polyamide products.     

Stretching induced phase transformations in melt extruded poly(vinylidene fluoride) cast films: Effect of cast roll temperature and speed

Melt extruded poly(vinylidene fluoride) cast films were prepared at different cast roll temperatures and speeds to study the effect of casting temperature and preorientation of the melt on the α‐ to β‐phase transformation in these films after uniaxial stretching. X‐ray and fourier transform infrared spectroscopy were used to identify the crystalline phases. The unstretched films were characterized using small angle light scattering (SALS). The films were stretched to a stretch ratio of 4.2 and at 80°C. Birefringence of the films and the fraction of β‐phase [F(β)] formed after uniaxial stretching increased with stretch ratio. The films showed increased crystallinity after stretching. For the films prepared at different cast roll temperatures, there was little change in F(β) in the films having a cast roll temperature between 75 and 120°C, but for the film with a cast roll temperature of 130°C F(β) decreased considerably. For the films prepared at different cast roll speeds, the F(β) increased with stretch ratio as well as with cast roll speed for a fixed stretch ratio. The primary effect of changing both the parameters is a change in the average spherulitic radius (R), in the unstretched films measured using SALS. The F(β) obtained correlated well with R and lower spherulitic radii resulted in the higher conversion to the β‐phase. POLYM. ENG. SCI., 47:1992–2004, 2007. © 2007 Society of Plastics Engineers     

Processing characteristics,structure development,and properties of uni and biaxially stretched poly(ethylene 2,6 naphthalate) (PEN) films

Poly(ethylene 2,6, naphthalene dicarboxilate), PEN, is very similar to poly(ethylene terephthalate), PET, in its chemical structure and was, therefore, expected to exhibit similar processing characteristics. We, however, observed a few problems during stretching of PEN, the most important of which was necking behavior at 145°C, which is between T_g (117°C) and T^cc (195°C). This is usually observed in PET only when it is stretched close to or below T_g. At temperatures between T_g and T_cc (cold crystallization temperature) PET stretches rather uniformly. The temperature window for film stretching appears to be rather wide, but our results indicate that this is not the case. Films stretched to high stretch ratios become uniform due to propagation and final disappearance of necks as a result of stress hardening. Our attempts at stretching these films at higher temperatures indicated that necking is eliminated, but so is stress induced crystallization, which causes stress hardening (unless high stretching rates are employed). The presence of stress hardening is essential for obtaining high quality, uniform films of these polymers. In addition, at high temperatures thermally activated crystallization which starts dominating the structure development, detrimentally affects the general appearance of the films. In brief, the PEN films we investigated have a narrower processing window than was anticipated based on their thermal behavior alone. At elevated temperatures the films are sensitive to the rate of stretching even more than typical PET processed at comparable conditions. The uniformity of the films depends on the stretch ratio, stretching mode, ratio(s) and rates and temperature. WAXS studies on the films indicate that the macromolecules packed into the low temperature crystal modification. In addition, WAXS pole figure studies suggest that naphthalene planes preferentially orient parallel to the film surface during biaxial stretching. The biaxially stretched films were observed to exhibit a bimodal chain orientation as evidenced by pole figure analysis of the (010) planes.     

Structure and properties of bio‐based polyamide 109 treated with superheated water

The structure and properties of bio‐based polyamide 109 (PA109) after treatment with superheated water (140 °C ≤ T ≤ 280 °C) were investigated and characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, wide‐angle X‐ray diffraction, scanning electron microscopy and small‐angle X‐ray scattering. Below 170 °C, the hydrothermal treatment was considered to be a physical process, which exerted an annealing effect on PA109. It led to an increase in melting temperature, lamellar thickness and crystallinity, while the macromolecular structure, crystal structure and the order of crystalline regions were not affected. Above 170 °C, complete melting/dissolution of PA109 occurred with partial hydrolysis. Due to the high temperature and long reaction time, the hydrolysis reaction became more and more prominent, and the resin was completely hydrolyzed into oligomers at 280 °C. Also, above 170 °C, the hydrothermal treatment was accompanied by a chemical process and the melting temperature and molecular weight decreased progressively. Notably, the crystal structure was not altered, but the degree of perfection of crystals and the order of crystalline regions were broken, especially above 200 °C. The hydrolytic degradation reaction was significantly affected by temperature, while both time and the water to polyamide ratio were secondary factors which influenced it to a minor extent. The process could be considered as a typical nucleophilic substitution reaction which takes place step by step inducing the molecular weight to decrease gradually. Overall, this study provides a ‘green’ route for the processing, recycling and treatment of environmentally friendly polyamides based on hydrothermal treatment technology. © 2019 Society of Chemical Industry     

Study of the microstructure formation mechanisms of poly(ether-ether-ketone) monofilaments via melt spinning

The microstructure formation mechanism of melt-spun Poly(ether-ether-ketone) monofilaments during poststretching was investigated using in-situ wide-angle X-ray diffraction in combination with polarizing microscopy, differential scanning calorimetry and universal testing machine. As PEEK monofilaments were stretched at 210°C, the crystallinity and microcrystal size first increased during the insulation state (Is-S), then decreased during the poststretching state (Ps-S), and further increased during the postcooling state (Pc-S), at last were observed to selective orientation. At 210°C, the anisotropically aligned molecular chains reach a meritocratic orientation in the stress direction under 4.0 times drawing conditions, resulting in the highest tensile strength and modulus. As the stretching ratio increases, the crystallinity and microcrystal size first increase during Pc-S and then decrease due to the effect of the stretched molecular chains on crystal growth and the degree of tearing in the crystalline region. The molecular chains of PEEK monofilaments stretched by uniaxial stress are aligned more flatly and uniformly along the fiber axis. We hope that this work will provide advice and guidance for the industrial production of high-performance fibers.     

Morphological characterization of branched PP under stretching

An effective approach to achieve high-melt strength polymer is to add long chain branches onto backbone species using gamma radiation. Grafting and branching result from macroradicals combinations during the irradiation process. Polypropylene films were prepared starting with irradiation process of the pellets with a ⁶⁰Co source at doses of 5, 12.5, and 20 kGy under acetylene to improve melt strength and drawability. After irradiation, polypropylene films were obtained by compression molding, at 190 °C and pressure of 80 bar, and dive into a water tank at 23 °C, which generally favors the formation of an amorphous phase. The thin films were stretched at 170 °C using a universal testing machine. Film surface morphology and the thermal properties, were analyzed, using atomic force microscopy, scanning electron microscopy and differential scanning calorimetry. We had a different molecular structure that requested the study of their micro and nanostructure. The results showed some evidence of fibrillar structures containing crystallites and gel formation. Fibrils oriented along the stretching direction were observed.     

Morphology and texture development of uniaxially stretched poly(ethylene naphthalene‐2,6‐dicarboxylate)

The texture development of PEN films with different semicrystalline morphologies have been studied by X‐ray diffraction. These different structures have been obtained by uniaxially stretching PEN amorphous films at 100 and 160°C (below and above T_g) at different drawing ratios. Samples have also been characterized by DSC to determine the crystallinity ratios, the crystallization, and melting temperatures. To define the orientation of crystallites in the oriented samples, pole figures have been constructed, as a function of temperature and drawing ratio (DR) in the range 1.5–4. In the range from DR = 2 to 4 the orientation is clearly uniplanar‐axial. At T_draw = 100°C the crystallinity shown by DSC analysis is higher than the sample stretched at 160°C. The orientation is also higher when samples are stretched at 100°C. The naphthalene rings mainly stay in the plane of the film with a lower fraction perpendicular to the plane of the film. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 395–401, 2007     

Structural Evolution of UHMWPE Fibers during Prestretching Far and Near Melting Temperature: An In Situ Synchrotron Radiation Small‐ and Wide‐Angle X‐Ray Scattering Study

Combining a homemade extension apparatus and the in situ synchrotron radiation small‐ and wide‐angle X‐ray scattering methods for measurement, the structural evolutions of gel‐spun ultrahigh molecular weight polyethylene (UHMWPE) fibers during prestretching at temperatures of 25 and 100 °C are investigated, respectively. Lamellar rotation toward the stretching direction occurs before strain hardening, while the folded‐chain crystal destruction and extended‐chain fibril formation processes occur in the strain hardening zone at 25 °C. While at 100 °C, stretching induced crystal melting before the stress plateau region and formation of fibrous crystals at the onset of the stress plateau are observed. Further stretching results in shear displacement of crystal blocks and, finally, destruction of the folded‐chain crystals and formation of extended‐chain fibrils. Prestretching UHMWPE fibers at 100 °C within a certain strain range can produce highly oriented fibrous crystals, which may provide an ideal precursor structure for the poststretching process.     

Texture and morphology of biaxially stretched poly(ethylene naphthalene‐2,6‐dicarboxylate)

The orientation of poly(ethylene naphthalene‐2,6‐dicarboxylate) (PEN) films with different morphologies were studied by wide‐angle X‐ray diffraction. Different structures were obtained by thermally treating biaxially stretched PEN samples. Virgin and thermally treated (1 h at 240, 250, and 260°C) samples of PEN bioriented films were characterized by DSC to determine the glass‐transition temperature and the crystallinity ratio. To define the orientation of crystallites in the 25 μm thick bioriented samples, pole figures were recorded for various PEN samples, as a function of their position in the transverse drawing direction. The significant result is that there is a dominant crystal population, whose c‐axis direction varies from +45° at one sample edge to ?45° at the other edge, the orientation at the center being parallel to the transverse direction. There is also a secondary population, which can be seen only near the center. DSC studies also showed that by increasing the annealing temperature the crystallinity ratio was increased and pole figures showed that the texture was modified, probably because of disorientation mainly from an annealing temperature of 260°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2224–2232, 2003     

Structural evolution of β – iPP during uniaxial stretching studied by in–situ WAXS and SAXS

Polymorphism and crystal transition are of great significance for property mediation in polymer materials. Isotactic polypropylene (iPP) with β – crystal has been widely utilized for the preparation of high performance plastics or films. In the present work, the structural evolution of initially isotropic β – nucleated iPP (β – iPP) during uniaxial stretching at different temperatures was investigated by in–situ X – ray scattering using synchrotron radiation. The wide – angle X – ray scattering (WAXS) results confirmed that the β – crystal transformed either to the mesophase at lower temperature (30 °C) or to the α – crystal at higher temperature (60, 100 and 120 °C) during stretching. An interesting orientation of β – crystal with molecular chains perpendicular to the tensile direction was identified. As revealed by small – angle X – ray scattering (SAXS), cavitation took place in β – iPP stretched at temperatures lower than 120 °C. The size and shape of the cavities were observed by scanning electron microscope. A deformation mechanism of β – iPP combining the crystal transition, cavitation and orientation was proposed.