Ultrasonic velocity and attenuation of polymeric solids under oscillatory deformation. II: High density and linear low density polyethylene and their blends

In order to understand the viscoelastic non-linearities in polyethylene, dynamic ultrasonic properties of high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and their blends were studied. In the case of HDPE and HDPE-rich films, for which the nonlinearity is high, the dynamic attenuation coefficient increased with the dynamic strain amplitude. The increase in the attenuation coefficient can be ascribed to plastic deformations such as defect- and/or void-formation in the spherulites. On the other hand, in LLDPE and LLDPE-rich blends for which the nonlinearity is low, the attenuation coefficient decreased with strain. The decrease in the attenuation coefficient can be ascribed to the orientation of lamellae. Thus, it was concluded that the viscoelastic nonlinearity of polyethylene is caused by plastic deformation. This conclusion was also deduced from other dynamic ultrasonic quantities such as the dynamic viscosity and dynamic density.     

Photodegradation of partially oriented and drawn polypropylene filaments

The effects of fiber structure on the process of photodegradation are controversial in the field. We tested polypropylene fibers of various form for their effects on photodegradation. Fiber grade polypropylene granules were spun into partially oriented multifilament yarns at a spinning speed of 2000 m min^?1. The yarns were drawn using a draw‐twist unit. Yarns were exposed to ultra‐violet radiations in a covered open air chamber for different periods of time under two different sources of emissions (UVA; λ > 300 nm and UVC; λ = 254 nm). The samples were examined by Fourier transform infrared spectroscopy, mechanical testing, differential scanning calorimetry, microscopy, and density measurements. In photodegradation process, the drawn filaments had a longer induction time than undrawn ones. The mechanical properties of the undrawn yarns deteriorate faster than the drawn yarns. During the early periods of degradation helical content increases considerably, while the density fluctuates and increases. The degradation rate under UVC radiation was faster than under UVA radiation because of the higher energy of the UVC radiation. The upper photostability of the drawn yarns compared to the undrawn ones was due to the higher crystalline fraction and greater molecular orientation in the drawn yarn. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45716.     

Mechanical properties of films of poly(vinyl alcohol) derived from vinyl trifluoroacetate

In order to study the influence of the stereoreguralities of polymer chains on the mechanical properties of films of poly(vinyl alcohol) (PVA)_(VTFA) derived from vinyl trifluoroacetate, the strength of the film was measured. In the case of undrawn PVA_(VTFA) films, Young's modulus and strength at break were the smallest at the annealing temperature of about 100°C. It is considered to be due to the melt of small microcrystals and the increase in mobility of chains in amorphous parts. Young's moduli of undrawn PVA_(VTFA) films were in the range of 1.50–3.75 GPs and the values were higher than that (0.17–0.36 GPa) of undrawn film of commercial PVA with the low concentration of syndiotacticity and the high concentration of head-to-head bounds. In the case of drawn, annealed PVA_(VTFA) films, the maximum Young's modulus was about 20 GPa.     

The effect of orientation on radiation-induced degradation in high density polyethylene

The oxidative degradation of cold drawn highly oriented high density polyethylene is studied by IR spectroscopy. Both gamma and ultraviolet radiation sources are used. It is found that under gamma radiation the oxidative degradation, as determined from carbonyl formation, is reduced very significantly but that the trans-vinylene unsaturation in the polymer increases with draw ratio. Similar results are obtained for samples irradiated in vacuum or when the polymer is stabilized with a radical quencher. Annealing (with free-ends) of the samples restores the rate of carbonyl formation over and above that of the undrawn polymer although restoration after annealing with fixed-ends is not complete. There, is further increase in trans-vinylene development after annealing. In stabilized samples, the effect of annealing on carbonyl and trans-vinylene development appears to depend on draw ratio. Under ultra-violet radiation, the oxidative degradation of drawn and unannealed samples is also reduced with increasing draw ratio. The same effect is observed in stabilized samples. Annealing, once again, restores the rate of oxidative degradation to that of the undrawn polymer. The main unsaturation product during ultraviolet irradiation is the vinyl end group and its development is suppressed with drawing. During ultraviolet irradiation of unannealed drawn samples, cracks, generally perpendicular to the draw direction (intrafibrillar cracks) appear on the sample and with further irradiation they penetrate into the sample. In the case of stabilized and unannealed drawn samples, cracks parallel to the draw direction (interfibrillar cracks) appear first and continued irradiation results in the appearance of intrafibrillar cracks. These observations may have significance in modelling the fibrous structures obtained by drawing semicrystalline polymers.     

Surface structure,topology, and liquid wetting behavior in oriented polymers

The structure and the properties of oriented polymer surfaces were studied for three series of uniaxially oriented films of polypropylene (PP), polystyrene (PS), and poly(ethylene terephthalate) (PET). The surface structure was characterized in terms of relative crystallinity and molecular orientation along with topology and roughness by using FT-IR-ATR dichroism technique, optical microscopy and surface profilometer. In all three polymers, the surface orientation function increases with draw ratio. The relative surface crystallinity and the trans con-former also increases for PP and PET, respectively. In uniaxially drawn PP, the surface becomes rough with increasing draw ratio and the roughness is anisotropic with peaks and valleys elongated along the draw direction. For drawn PP, the equilibrium contact angles for four different liquids all exhibit anisotropy with higher values in perpendicular direction than that in parallel to the draw direction. In contrast, both drawn PET and PS films show smooth surfaces, and the equilibrium contact angles were all isotropic. When roughness is removed from the drawn PP by polishing without altering the molecular orientation, the anisotropy becomes negligible and the contact angles approach the value for undrawn PP. When surface roughness was created deliberately on undrawn PET and PS films, the contact angle anisotropy was clearly observed. Therefore, the anisotropy in surface topology rather than the molecular orientation seems to play a dominant role in developing anisotropic wetting behavior. The equilibrium contact angles for smooth surfaces have been calculated using the experimentally obtained roughness and anisotropic contact angle data from the rough surface. These values are in reasonable agreement with the measured contact angles for smooth surfaces, suggesting that the observed contact angle anisotropy can be attributed entirely to the roughness anisotropy rather than to the molecular orientation.     

Morphological analysis of linear low density polyethylene films by atomic force microscopy

Atomic force microscopy has been used to investigate the morphology of hexene linear low density polyethylene (LLDPE) blown film in the undrawn and drawn states. The morphology of the undrawn film, which is biaxially oriented due to the nature of the extrusion process, is composed of crystallites, which consist of aggregates of lamellae. Elongation of the film caused these crystallites to undergo deformation, resulting in the gradual formation of a fibrillar structure in the draw direction. The transformation of these crystallites into fibrils corresponded with an initial increase in the surface roughness, until 250% elongation. Further extension of the film to 450% caused the surface roughness to reach a plateau. The changes observed in the surface roughness and morphology indicate that drawing of the film caused the crystallites to tilt and slip, rupturing crystalline blocks, which then develop into a fibrillar structure. Further extension of these initial fibrillar structures resulted in a more oriented fibrillar morphology. Wide‐angle x‐ray scattering clearly showed the orientation of the crystals with respect to the draw direction throughout the film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 777–784, 2002     

Ultradrawing behavior of one- and two-stage drawn gel films of ultrahigh molecular weight polyethylene and low molecular weight polyethylene blends

The ultradrawing behavior of gel films of plain ultrahigh molecular weight polyethylene (UHMWPE) and UHMWPE/low molecular weight polyethylene (LMWPE) blends was investigated using one- and two-stage drawing processes. The drawability of these gel films were found to depend significantly on the temperatures used in the one- and two-stage drawing processes. The critical draw ratio (λ_c) of each gel film prepared near its critical concentration was found to approach a maximum value, when the gel film was drawn at an “optimum” temperature ranging from 95 to 105°C. At each drawing temperature, the one-stage drawn gel films exhibited an abrupt change in their birefringence and thermal properties as their draw ratios reached about 40. In contrast, the critical draw ratios of the two-stage drawn gel films can be further improved to be higher than those of the corresponding single-stage drawn gel films, in which the two-stage drawn gel films were drawn at another “optimum” temperature in the second drawing stage after they had been drawn at 95°C to a draw ratio of 40 in the first drawing stage. These interesting phenomena were investigated in terms of the reduced viscosities of the solutions, thermal analysis, birefringence, and tensile properties of the drawn and undrawn gel films. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 149–159, 1998     

Wetting of oriented and etched ultrahigh molecular weight polyethylene

Highly oriented gel‐spun ultrahigh molecular weight polyethylene (UHMWPE) fibers possess many outstanding properties desirable for composite materials but their adhesion to such matrices as epoxy is poor. This article describes the combined effects of drawing and surface modification on the bulk and surface properties of gel‐cast UHMWPE films emphasizing the effects of etching on both undrawn and drawn films. Drawing the films yields a fibrillar structural hierarchy similar to UHMWPE fibers and a significant increase in orientation, melting point, modulus, and strength. The effects of drawing on bulk properties were more significant than those of etching. The poor adhesion of epoxy to the smooth, fibrillar, and relatively nonpolar drawn film surface improves significantly with oxidization and roughening on etching. The interlaminar shear failure occurred cohesively in the UHMWPE, and thus the interlaminar shear failure strength was greater for the drawn UHMWPE with its greater tensile strength. Nitrogen plasma etching yielded the best results, both removing any low molecular weight surface layer and etching the UHMWPE beneath. Oxygen plasma etching enhanced wetting but was too harsh, causing extensive surface degradation and a significant reduction in mechanical properties. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 405–418, 1999     

The effect of additives and drawing temperature on gamma- or ultraviolet-radiation induced oxidative degradation of drawn high density polyethylene

The effects of drawing temperature and the presence of various types of additives on gamma and ultraviolet radiation induced oxidative degradation of high density polyethylene have been studied. Uniaxial drawing of the polymer was conducted at 60, 80, and 100°C. The additives were an antioxidant, light stabilizer, and carbon black, used in various combinations, Oxidative degradation was followed from carbonyl formation by IR spectroscopy. It is found that at a given draw ratio, the oxidative degradation is retarded when the drawing temperature is increased, irrespective of whether or not the polymer contains any additives in any combination. This is due to the decrease of the surface and/or bulk microcracks formed during the drawing process at high temperature. Carbon black/antioxidant mixtures were shown to be antagonistic, while a carbon black/light stabilizer mixture resulted in a synergetic effect in drawn or undrawn materials.     

Effect of uniaxial drawing of soy protein isolate biopolymer film on structure and mechanical properties

The effect of uniaxial drawing of biodegradable soy protein isolate (SPI) polymer film on mechanical properties was investigated to accelerate the efforts to develop SPI films with improved properties. The films containing 0–30 wt% glycerol were drawn uniaxially up to a draw ratio of 2.5. The mechanical properties of the SPI film increased significantly after uniaxial drawing. The tensile strength of the undrawn film (49.7 MPa) was approximately doubled by subjecting the film to uniaxial drawing to a D.R. of 2.5. Wide‐angle X‐ray diffraction and differential scanning calorimetry measurements did not show evidence of generation of a crystal phase in the drawn SPI films. ATR‐FTIR revealed that the protein film contained mainly α‐helix and β‐sheets secondary structures. Microwave molecular orientation analysis showed that birefringence increased with increasing draw ratios. Mechanical anisotropy of the SPI film via orientation of α‐helix and β‐sheets structure is thought to be responsible for the enhancement of mechanical properties with uniaxial drawing of the SPI films. POLYM. ENG. SCI., 47:374–380, 2007. © 2007 Society of Plastics Engineers.     

Structure and properties of poly(ethylene terephthalate) crystallized by annealing in the highly oriented state. 3. Dynamic- and static-mechanical properties

Commercial undrawn and cold drawn (5 × ) poly(ethylene terephthalate) (PETP) fibers and bristles have been annealed with fixed ends for 6 h in vacuum at different temperatures between 60 and 260°C. With these samples static- and dynamicmechanical measurements have been carried out. It has been found that the α-and β-processes as well as the moduli depend on the annealing temperature (T_a) in different way, for undrawn and drawn material. The temperature position of the β-peak evaluated from tg δ and loss modulus as well as the step height of α- and β-processes are unsensitive to the T_a for the undrawn material in contrast to the drawn one for which maxima are observed. The appearance of these maxima is explained by the dominating role at the corresponding crystallization temperature of one of the two concurrent processes - crystallization and disorientation, reflected in the change of the effective density of amorphous regions. The dynamic and static measured moduli as well as the stress at break for drawn PETP decrease with the increase of annealing temperature as generally observed. The predominating significance of orientation and the state of amorphous phase in comparison with crystallinity is demonstrated. An extremely high deformation ability at room temperature (up to 200%) of previously drawn and annealed at 255 or 260°C bristles is observed. This originates from the solid state postcondensation and premelting phenomena taking place during annealing in vacuum.     

Electrical and third-order nonlinear optical properties of poly(2-fluoro-1,4-phenylenevinylene) and its copolymers

Summary Poly(2-fluoro-1,4-phenylenevinylene), PFPV, and its copolymers have been synthesized via water soluble precursor route and their electrical and optical propreties were measured. It seems that electron-withdrawing fluorine substituent on phenylene ring increases the band-gap of PFPV and it affects electrical and optical properties. The conductivity values of FeCl₃-doped drawn polymer films ranged from 10^-1 to 10¹ Scm^-1 depending on their composition, and were 10 times larger than those of undrawn ones. The ⁽³⁾ value for undrawn PFPV, using THG technique at 1907nm fundamental wavelength, was 4.76x10^-12 esu.     

Effects of polymer concentration and zone drawing on the physical properties of poly(N‐vinylcarbazole) thick film

To check the possibility of zone‐drawn poly(N‐vinylcarbazole) (PVK) thick films as base materials of photorefractive polymers, the effects of the initial polymer concentration and zone drawing on the physical properties of PVK film were investigated. PVK films were prepared from 1,1,2,2‐tetrachloroethane (TCE) solutions with different initial concentrations. To investigate the drawing behavior of the PVK films with different solution concentrations, the films were drawn under various zone‐drawing conditions. Through a series of experiments, it turned out that the initial concentration of the PVK solution in TCE caused significant changes in the draw ratio of the PVK film, that is, the zone draw ratios of the film at an initial concentration of 9.8 g/dL exhibited their maximum values and gradually decreased at higher or lower concentrations. Thus, it was determined that the initial concentration of 9.8 g/dL is the optimum polymer concentration to produce the maximum draw ratio in this work. The lightness (whiteness) of the zone‐drawn PVK film was much higher than that of the hot‐drawn PVK film, resulting from diminishing microcrystallite formation, crystallization, and back‐folding of molecular chains by zone drawing. Moreover, the mechanical properties of the PVK film were dominantly improved by introducing a zone‐drawing technique, maintaining lightness of the zone‐drawn film to a similar degree as that of the undrawn film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1297–1304, 2001     

The crystalline phase transformation of poly(vinylidene fluoride)/poly(vinyl fluoride) blend films

Poly(vinylidene fluoride) (PVDF), poly(vinyl fluoride) (PVF), and their blends were prepared by solution casting, followed by quenching in ice water after melting to obtain an α-crystalline phase. The films were drawn by solid state extrusion at two different drawing temperatures, 50°C and 110°C. The crystalline phases were analyzed by DSC and FTIR. In the undrawn films, the content of β-crystalline phase in the blend of PVDF/PVF 88.5/11.5 was higher than in the PVDF homopolymer, but it was lower than in the PVDF film with a draw ratio higher than 4. The α-crystalline phase in PVDF/PVF blends was mostly transformed into the β-crystalline phase beyond a draw ratio of 4, regardless of the draw temperature and PVF content. The α-crystalline phase of PVDF systematically transformed into the β-crystalline phase with increasing draw ratio. The crystallinity of PVDF/PVF blend films drawn at 110°C was higher than those drawn at 50°C. In the drawn blend films, characteristic IR bands of the α form were shifted to those of the β form and completely changed into those of β form at draw ratio of 4, regardless of the draw temperature and PVF content.     

Quality assessment of polyester chips and yarn by TMS-2

Penetration in polyester chips of different manufacturers and yarn (undrawn and drawn) was studied between 323 and 423 K on a thermomechanical system (TMS-2) using a penetration kit. It was observed that the penetration of the probe varied in the case of chips from manufacturer to manufacturer. The undrawn and drawn yarns from different batches and also within the same batch showed a clear variation in penetration curve, which may be attributed to the degree of crystallization. The same technique can be utilized for an assessment of the quality of yarn in continuous production and for differentiating the manufacturing process of polyester chips.     

The effect of bromination and inherent vinyl unsaturation on the drawing behavior of high-density polyethylene

Various high-density polyethylenes were brominated in order to eliminate the inherent vinyl Unsaturation in the polymer. They were then drawn uniaxially at three different temperatures, and the resulting fibrous materials were studied under a scanning electron microscope. It was found that the brominated samples yielded transparent fibrous materials that had more regular fibrillar structure and fewer surface overgrowths, cracks, and voids compared with the unbrominated polymers drawn under identical conditions. Bromination also appeared to improve the mechanical properties of the drawn and the undrawn polymer. High-density polyethylene that had no inherent vinyl Unsaturation also yielded transparent fibrous material with fibrillar structure similar to that of brominated polymers.     

Einfluß des Verstreckens und Temperns auf das Dehnungs- und Bruchverhalten von Polyäthylenterephthalat

The stress-strain diagrams of undrawn and drawn polyethylene terephthalate were measured at room temperature and above the glass transition temperature. Before the stress-strain measurements the undrawn samples had been crystallized at various temperatures, whereas the drawn samples had been crystallized in the undrawn state, then were drawn at various temperatures and finally were crystallized again. The influence of the temperature of crystallization and the temperature of drawing on the Young's modulus, the tensile strength, and the fracture strain were of special interest. The fracture strain as a function of the crystallization temperature shows a minimum at room temperature. This minimum disappears above the glass transition temperature. Young's modulus and tensile strength generally are found the higher, the higher the degree of orientation in the sample. Crystallization of the undrawn samples therefore does not change these values significantly. But a drawing of the samples leads to a significant increase which is still more pronounced if the sample is crystallized after the drawing. Crystallization before drawing of a sample leads to a decrease of Young's modulus and tensile strength because in this case apparently the formation of a sufficient orientation during the drawing cannot take place. An increase of the drawing temperature above the glass transition temperature also leads to a decrease in the mentioned values.     

Contribution of interferometry in evaluating structural parameters for drawn textile fibres

Two‐beam and multiple‐beam interferometric techniques were used to determine the refractive indices, birefringence and isotropic refractive index of nylon 6 and polyethylene fibres drawn to different draw ratios. These optical parameters contributed in solving the density problem of the drawn fibres in terms of the density of the undrawn fibre. Related parameters such as, crystallinity, number of monomer units per unit volume, polarizability of monomer unit, molar refractivity and certain other parameters were then calculated. In addition, mechanical parameters, such as shrinkage stress, strain and stress optical coefficients, were also calculated. Moreover, the optical orientation function and orientation angle were evaluated. Microinterferograms and relationships between the parameters obtained are given for illustration. Copyright © 2004 Society of Chemical Industry     

Environmental stress cracking of polyethylene

Deformation of polyethylene in environmental stress cracking (ESC) agents results in changes in both the mechanism of deformation and structure of the resulting drawn material. Stress-cracked failure surfaces are highly fibrillar, the fibrils having less elastic recovery than those in samples drawn in air. In thin films drawn in ESC agents, small blocks of the lamellae remain undrawn and attached to the fibrils drawn across micronecks. The ESC agents are suggested to weaken the cohesion between the fibrils in samples drawn beyond yield as well as the cohesion between mosaic blocks or similar structural elements in the original lamellae as they are being reoriented to form the fibrils. The stress is thus supported by a number of independent, nonuniform fibrils rather than a coherent structure; the weakest of these fibrils fail in turn as the crack propagates through the sample.     

Lewis acid-base complexation of polyamide 66 to control hydrogen bonding, extensibility and crystallinity

Polyamide 66 (PA66) has been complexed with the Lewis acid GaCl₃ for the purpose of disrupting the interchain hydrogen bonded network. FTIR and ¹³C-NMR observations indicate that Ga metal cations form a 1:1 complex with the carbonyl oxygens of the PA66 amide groups. PA66-GaCl₃ films are amorphous and rubbery with a single relaxation, attributable to the glass transition temperature, at ∼−32 °C and a structure that appears by X-ray diffraction to be thermally stable to at least 200 °C. The complexed films could be drawn at room temperature to draw ratios (DR) up to ∼30, and could then be decomplexed, or regenerated, by soaking in water. GaCl₃ complexation and subsequent regeneration of PA66 was accomplished without changing its molecular weight, and all but ∼5 mol% of the amide groups in the regenerated PA66 were uncomplexed. The undrawn regenerated films regain levels of crystallinity much lower than possessed by the uncomplexed PA66 reference film. However, up to a DR of 8, drawing prior to regeneration increases the crystallinity, reaching crystallinity levels that are high for PA66, that has not been heat treated, and that are almost twice higher than in the uncomplexed (undrawn) reference film. It is intriguing that, in this DR regime, crystallinity increases quite sharply as the film is extended, despite the fact that molecular orientation does not appear to be increasing. For DR>8, the crystallinity decreases, but remains above that of the reference film. The level of crystallinity in PA66 can be controlled over a much wider range by the complexation-drawing-regeneration process than by conventional drawing processes.