Effects of stretching on crystalline phase structure and morphology of hard elastic PVDF fibers

The phase characteristics and morphology of stretched hard elastic poly(vinylidene fluoride) (PVDF) fibers were investigated by X‐ray diffraction (XRD) and wide‐angle and small‐angel X‐ray scattering (WAXS and SAXS). It was indicated that α and β phases coexisted in stretched PVDF fibers, stretching assisted in α to β phase transformation. The β/α ratios of stretched PVDF fibers were affected by stretching temperature, rate, and ratio. The β phase content of stretched PVDF fibers had an abrupt increase when stretched near 70°C, and then it decreased with increasing stretching temperature. Besides, the β/α ratio of PVDF fibers increased with stretching rate and ratio. The total crystallinity of PVDF fibers did not change much even on different stretching conditions. WAXS results indicated that the unstretched and stretched PVDF fibers all exhibited three strong equatorial streaks, with d‐spacing (0.964, 0.488, and 0.439 nm) and (0.946, 0.494, and 0.480 nm), which suggested that PVDF fibers still remained the crystalline reflections of c‐axis orientation even after being stretched. The long periods of stretched PVDF fibers, calculated from SAXS curves, increased from 19.04 to 39.75nm. On the basis of these results, the β transformation mechanism of stretched PVDF fibers was also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2254–2259, 2007     

Structure and thermomechanical properties of stretched cellulose films

Regenerated and stretched cellulose films were investigated for structure and thermomechanical properties as a potential packaging material. Cellulose films were cast from lithium chloride/N, N‐dimethylacetamide and were stretched up to 30% in a dynamic mechanical analyzer sample holder. Wide‐angle X‐ray diffraction analysis indicated that the orientation factor was significantly increased due to stretching. In addition, the stretched films have a higher resistance to the thermal decomposition from thermo gravimetric analysis. The increased orientation of cellulose crystalline structure by the stretching process also increased the storage modulus of cellulose films characterized by dynamic mechanical analysis, which suggest that mechanical properties of cellulose films could be tuned during the stretching process. The α₂ and α₁ relaxations were found at 240 and 300°C, respectively, which are attributed to the micro‐Brownian motion of segments in amorphous region, and activation energies for relaxations were determined with the stretching levels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Extrusion of poly(vinylidene fluoride) filaments: effect of the processing conditions and conductive inner core on the electroactive phase content and mechanical properties

The phase transformation from the α- to the electroactive β-phase of poly(vinylidene fluoride) (PVDF) extruded filaments submitted to different stretching conditions was investigated. Sample filaments of α-PVDF thermoplastic were extruded and stretched uniaxially at different temperatures (80 °C to 120 °C) and stretch ratios (1 to 6). The stretched samples were studied and characterised by x-ray diffraction and quasi-static mechanical experiments. High β-phase contents (~ 80%) are achieved using a stretch ratio of 5 independently of the stretching temperature, between 80 °C and 120 °C. Subsequently, in order to obtain filament geometries and material configurations suitable for application, a two layer filament with coaxial layers was produced by coextrusion. The inner layer consisted of a commercially available grade of a conductive thermoplastic with a polypropylene (PP) matrix. For the outer layer the same grade of PVDF was employed. The double-layer filament was also stretched under the same conditions of the PVDF filaments and the results obtained shows that the inner layer material, acting as an electrode, does not have any influence in the PVDF crystallization process: PVDF crystallizes in the α-phase for stretch ratios of 1 and the α-to β-phase transformation occurs for higher stretch ratios.     

Role of poly(lactic acid) in the phase transition of poly(vinylidene fluoride) under uniaxial stretching

The effect of poly (lactic acid) (PLA) on the crystalline phase transition of poly (vinylidene fluoride) (PVDF) from α‐ to β‐phase under uniaxial stretching for immiscible PVDF/ PLA blends was investigated. The typical sea‐island structure in the blends was found to facilitate the necking of PVDF and the transition from α‐ to β‐phase due to the local stress distribution during stretching. The crystalline phase transition of PVDF in the blends is temperature‐dependent and is affected by the content of PLA. The highest content of β‐phase, F(β), was achieved in the samples stretched at 60°C, while the effect of PLA content on the crystalline phase transition of PVDF is more complex. F(β) increases slightly when the sample with a PLA content no more than 15 wt % is stretched at 60, 80, and 100°C, and decreases sharply for the sample containing 20 wt % PLA; in addition, the sample containing 10 wt % PLA exhibits the highest F(β) no matter what the stretching temperature is. The mechanism of the crystalline phase transition of PVDF during the stretching is interpreted from energy barrier of the transition from α‐ to β‐phase and the morphological structures in the blends. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Crystal structure of uniaxially stretched bio-based polyamide 510 films

The crystal structure changes of PA510 films during uniaxially stretching at 80°C, 110°C, 140°C and 170°C had been investigated as a function of stretching ratio and stretching rate. The stress–strain relationship curves showed that the stress of the PA510 films gradually increased when the stretching ratio increased. The wide-angle X-ray diffraction results verified that only one distinct equator reflection of stretched films was clearly identified at 80°C, 110°C and 140°C, namely γ(100) at 2θ = 20.6°. However, when the stretching temperature reached 170°C, the γ(004), γ(006) and γ(008) crystal form appeared in the meridional direction at λ = 12. Combined with differential scanning calorimeter analysis, it was found that the Xc increased from 7% to 40% as a result of the strain induced crystallization phenomenon and the stretching promoted the appearance of γ crystal form. In addition, the increase in the crystallinity and the molecular chain orientation increased the strength of the PA510 films in the tensile direction. And it also found that the microcracks occurred in the stretched films at high stretching ratio (λ = 12).     

Deformation-mediated superstructures and cavitation of poly (l-lactide): In-situ small-angle X-ray scattering study

Cavitation and superstructure evolution of polymers during stretching play crucial roles to influence the mechanical properties of materials. In this study, we investigated deformation-mediated superstructures and cavitation of poly (l-lactide) (PLA) as well as their dependence on stretching temperatures by in-situ small-angle X-ray (SAXS) analysis coupled with mechanical testing. It is found that the cavitation and crystalline deformation are strongly influenced by stretching stress during deformation, which significantly depends on the stretching temperature. At lower stretching temperature (70 °C), the cavitation is initiated before the yielding and then stimulates the crystallite shearing. At higher stretching temperature (90 °C), however, the crystallites shear firstly and then crystalline deformation promotes the formation of cavities orientated along the stretching direction. High stretching temperature benefits the formation of relatively perfect crystals with high orientation. The results provide the basic knowledge of how to adjust the mechanical properties of polymer materials by controlling their superstructure in the deformation process.     

Effect of annealing temperature on phase composition and tensile properties in isotactic poly(1‐butene)

The influence of annealing temperature on the kinetics of polymorphic changes and mechanical properties within the time in isotactic poly(1‐butene) (PB‐1) has been investigated by wide‐angle X‐ray scattering and tensile testing. Extruded tapes of PB‐1 have been exposed to several annealing temperatures: ?22, +5, +22, +40 and +60°C. The evolution of content of Phase I for various annealing temperatures upon time shows predominantly S‐shaped trend. Annealing temperature considerably affects the overall rate of transformation in PB‐1. On the other hand, the resulting mechanical properties are solely controlled by the polymorphic composition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of the comonomer content on the solid‐state mechanical and viscoelastic properties of poly(propylene‐co‐1‐butene) films

In this study, we quantified the thermal and solid‐state mechanical and viscoelastic properties of isotactic polypropylene (i‐PP) homopolymer and poly(propylene‐1‐butene) copolymer films having a 1‐butene ratio of 8, 12, and 14 wt %, depending on the comonomer content. The uniaxial tensile creep and stress‐relaxation behaviors of the samples were studied in a dynamic mechanical analyzer at different temperatures. The creep behaviors of the samples were modeled with the four‐element Burger equation, and the long‐term creep strains were predicted with the time–temperature superposition method. The short‐term mechanical properties of the samples were also determined with tensile and impact testing at room temperature. We found that the Young's modulus and ultimate strength values of the samples decreased with increasing amount of 1‐butene in the copolymer structure. On the other hand, the strain at break and impact strength values of the samples improved with increasing amount of 1‐butene. Creep analysis showed that i‐PP exhibited a relatively lower creep strain than the poly(propylene‐co‐1‐butene)s at 30 °C. However, interestingly, we discovered that the temperature increase resulted in different effects on the creep behaviors. We also found that short‐chain branching improved the creep resistance of polypropylene at relatively high temperatures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46350.     

Influence of extrusion,stretching and poling on the structural and piezoelectric properties of poly (vinylidene fluoride‐hexafluoropropylene) copolymer films

Three types of poly (vinylidene fluoride‐hexafluoropropylene) (PVDF–HFP) copolymer films were prepared by extrusion, stretching as well as simultaneously stretching and static electric field poling (SSSEP), respectively, and measured by the differential scanning calorimetric, wide angle X‐ray diffraction, fourier transformation infrared‐attenuated total reflection, and Dynamic mechanical analysis. The experimental results showed that the films prepared by stretching and SSSEP have higher crystallinity and β phase than by extrusion. SSSEP improved the chain orientation enormously both in crystalline and amorphous regions, resulting in the highest storage modulus. Because of the lower β phase content, the extruded films exhibited the lowest piezoelectric coefficient d₃₃. For the stretched and SSSEP films, although the β phase content was similar, the d₃₃ was distinct because of the different potential energy for the rotation of the dipoles. In addition, the SSSEP films gave the maximum d₃₃ (24 pC/N), higher than the other PVDF–HFP copolymer films that have been reported. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 858–862, 2007     

Effect of uniaxial stretching on the tensile impact test for poly(ethylene terephthalate)

In order to correlate impact strength with the structure of polymeric materials, a tensile impact test was carried out using a uniaxially stretched poly(ethylene terephthalate) (PET) sheet. The structural factors were the draw ratio (λ) and the cut-out angle (θ) under the conditions of constant impacting speed (10.5 m/sec = 1.8 × 10⁴%/sec) and temperature (20° ± 1°C). The occurrence of structural anisotropy by stretching of isotropic amorphous quench-rolled PET was classified into three drawing stages: λ = ?1.5 or 2.0, ?3.5, and over 3.5. This is related to a deformation mechanism of masses with dimensions a few tenths of a μm and their boundaries. The boundaries are not clear until adiabatic deformation (mechanical impact) is applied. The area supporting the mechanical strength was limited to just a small section. Its character was affected by macroscopic deformation only in the direction parallel or near to the stretching direction, since the mechanical properties were not changed for the range of the cut-out angle θ = 45–90°.     

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     

Effect of hot‐press on electrospun poly(vinylidene fluoride) membranes

Poly(vinylidene fluoride) (PVDF) was electrospun into ultrafine fibrous membranes from its solutions in a mixture of N,N‐dimethylformamide and acetone (9:1, v/v). The electrospun membranes were subsequently treated by continuous hot‐press at elevated temperatures up to 155°C. Changes of morphology, crystallinity, porosity, liquid absorption, and mechanical properties of the membranes after hot‐press were investigated. Results of scanning electron microscopy showed that there were no significant changes in fibrous membrane morphology when the hot‐press temperature varied from room temperature to 130°C, but larger pores were formed because of fibers melting and bonding under higher temperatures. Analyses of X‐ray diffraction and differential scanning calorimeter exhibited that the crystalline form of PVDF could transfer from β‐type to α‐type during hot‐press at temperatures higher than 65°C. Tensile tests suggested that the mechanical properties of the electrospun PVDF membranes were remarkably enhanced from 25 to 130°C, whereas the porosity and the liquid absorption decreased. The hot‐press at 130°C was optimal for the electrospun PVDF membranes. The continuous hot‐press post‐treatment could be a feasible method to produce electrospun membranes, not limited to PVDF, with suitable mechanical properties as well as good porosity and liquid absorption for their applications in high‐quality filtrations or battery separators. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

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.     

Preparation and characterization of biaxially oriented films from polybutylene terephthalate based thermoplastic elastomer block copolymers

Film casting and biaxial stretching of a series of polyester thermoplastic elastomers (TPEs) were studied. Biaxial orientation in the stretched films was characterized by wide‐angle X‐ray diffraction and birefringence measurements. Biaxial orientation factors were determined. The X‐ray diffraction and birefringence clearly indicated the development of planar biaxial orientation in the stretched films with biaxial stretching. The phenyl groups in the stretched PBT and TPE films gradually became more parallel to the film surfaces with increasing biaxial orientation. The lower the PBT content in the stretched TPE films, the lower the planar biaxial orientation achieved. The β form of crystalline PBT was found only in the stretched PBT films, but not in the TPE films.     

Styrene‐assisted grafting of maleic anhydride onto isotactic poly butene‐1

Grafting of maleic anhydride (MAH) onto isotactic poly butene‐1 (iPB‐1) was carried out by thermal decomposition of dicumyl peroxide (DCP) using electron‐donating monomer styrene (St), and were carried out in the molten state in a twin‐screw extruder according to an experimental design in which the content of MAH and St were varied. The calibration curve was constructed from FTIR measurements and titration which can obtain the absolute amounts of grafted MAH according to FTIR data. The proposed mechanism was that when St is added to the iPB‐1/MAH/peroxide grafting system, St reacted first with MAH to form a charge‐transfer complex (CTC). Then CTC react (or copolymerize) with macroradicals. The grafting of MAH onto iPB‐1 (iPB‐1‐MAH) accelerated crystalline transformation rate of form II to I. The contact angle decreased with the increase of grafting degree, which indicated that surface polarity increased. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Investigation of deformation and pore formation in isotactic polypropylene containing active nano‐CaCO3

In order to improve the β‐lamellae distribution and properties of β‐isotactic polypropylene (β‐iPP) membranes, amounts of 5 and 10% active nano‐CaCO₃ were added into β‐iPP. Differential scanning calorimetry, X‐ray diffraction and scanning electron microscopy results show that nano‐CaCO₃ does not reduce the content of β‐crystals, but the thickness, lamellae thickness distribution and stability of β‐lamellae decrease apparently. Tensile testing was conducted at 25 and 90 °C. The results manifest that the second yield point, which has a strong negative correlation with lamellae thickness distribution, is delayed monotonically with addition of nano‐CaCO₃ when stretched at 25 °C, indicating that nano‐CaCO₃ could narrow effectively the lamellae thickness distribution of β‐iPP. Furthermore, when stretched at 90 °C, the subdued yield peak, retarded necking‐down phenomenon and enhanced strain‐hardening modulus demonstrate that the deformation stability improves gradually with introduction of nano‐CaCO₃, which is completely opposite to the trend for β‐lamellae stability. Through further detailed characterization of morphological evolutions during stretching, we found that interfacial debonding between nano‐CaCO₃ and β‐iPP is triggered and abundant microviods can be formed, which can retard the rotation and slip of β‐lamellae and make the β–α transformation slow down in the initial stage of stretching, consequently leading to better isotropic deformation. Moreover, nano‐CaCO₃ could efficiently restrain the formation of coarse fibrils, leading to more uniform pore size distribution within the biaxial stretching microporous membrane. However, excessive nano‐CaCO₃ (10%) would cause aggregation within the β‐iPP cast film and finally result in larger pores and poor pore distribution in the membrane. © 2017 Society of Chemical Industry     

The influence of thermal treatment and processing on the structure and morphology of poly(propylene‐ran‐1‐butene) copolymers

New poly(propylene‐ran‐1‐butene) copolymers were analyzed to study the influence of different processing techniques on their structure and morphology. Wide‐angle X‐ray diffraction allowed determination of the percentage of the γ form and the crystallinity in the samples and also the influence of the percentage of 1‐butene on the cell parameters. Furthermore, it was possible to appraise the contributions of different stacks of lamellae to the small‐angle X‐ray diffraction patterns. © 2001 Society of Chemical Industry     

Silver–polyimide nanocomposite membranes: Macromolecular‐matrix‐mediated metallization of an aromatic,fluorinated polyimide yielding highly reflective films at low metal concentrations

Highly reflective, surface‐metalized, flexible polyimide films were prepared by the incorporation of a soluble silver‐ion complex, (hexafluoroacetylacetonato)silver(I) (AgHFA), into dimethylacetamide solutions of poly(amic acid) prepared from 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane. The thermal curing of solution‐cast silver(I)–poly(amic acid) films to 300°C led to cycloimidization of the amic acid with concomitant silver(I) reduction and the formation of a reflective, air‐side‐silvered surface at very low (2 wt % and 0.3 vol %) silver concentrations. The reflective surface evolved only when the cure temperature reached about 275°C, although X‐ray diffraction showed metallic silver in the hybrid film by 200°C. After a maximum specular reflectivity greater than 80% was achieved for the 2 wt % silver film, the specular reflectivity diminished sharply with further heating at a constant temperature of 300°C. Incorporating the AgHFA complex into the soluble, fully imidized form of poly{(1,3‐dihydro‐1,3‐dioxo‐2H‐isoindole‐2,5‐diyl)[2,2,2‐trifluoro‐1‐(trifluoromethyl)ethylidene](1,3‐dihydro‐1,3‐dioxo‐2H‐isoindole‐5,2‐diyl)‐1,4‐phenyleneoxy‐1,4‐phenylene[2,2,2‐trifluoro‐1‐(trifluoromethyl)ethylidene]‐1,4‐phenyleneoxy‐1,4‐phenylene} gave films that were 25% less reflective than those beginning with poly(amic acid). Though highly reflective, the films were not electrically conductive. The metalized membranes were thermally stable and maintained mechanical properties similar to those of the parent polyimide. Transmission electron microscopy revealed an air‐side, near‐surface layer of silver that was about 40 nm thick; the interior of the film had well‐dispersed metal particles with diameters mostly less than 2 nm. The near‐surface silver layer maintained its integrity because of physical entrapment of the metal nanoparticles beneath a thin layer of polyimide; that is, the practical adhesion of the metal layer was good. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2409–2418, 2007     

Morphology,structure, and properties of poly(lactic acid) microporous films containing poly(butylene terephthalate) fine fibers fabricated by biaxial stretching

The effects of size and shape, i.e., sphere and fiber, of dispersed poly(butylene terephthalate) (PBT) in poly(lactic acid) (PLA) matrix on the morphology and porous structure of the biaxially stretched films are comparatively investigated. Scanning electron microscope results confirm that the PBT fine fibers can be produced by melt‐stretching following by fast quenching. Rheological characterization reveals the random network structure of PBT fibers. Further, the stretched films composed of spherical PBT particles show the ellipsoidal microvoids due to the interfacial debonding, and the void size relates to the particle size of PBT. However, size of PBT droplets does not influence the void content of the stretched films. The void content considerably increases for equibiaxial deformation as compared with planar deformation, particularly at high draw ratio. Additionally, the stretched films containing fibrous dispersion exhibit the nonaffine behavior and the highest void content of 8%, which is probably due to the localized deformation between fibers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41415.