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.     

Transport properties and their correlation with the morphology of thermally conditioned polypropylene

Time-lag and static sorption experiments were employed to measure permeability, diffusivity and solubility constants of He, A, and CF₄ in polypropylene films cooled at various rates from the melt and subsequently annealed at varying temperatures near the melting point. While solubility constants in films annealed above 90°C showed the normal variation with the amorphous content of the polymer, solubility constants for all unannealed, quenched films were remarkably constant and independent of the rate of cooling. In fact, all quenched films appeared to have the same amorphous content (ca. 41%). The remaining material is believed to be a mixture of monoclinic and hexagonal crystallinity, the volume ratio of the two being a function of the rate of quenching, and changing on annealing, in favor of the more stable, monoclinic form; the transition occurring rather sharply at 90°C. X-ray diffraction provided supporting evidence for the presence of the hexagonal crystals. The diffusion behavior in crystalline polypropylene is normal and Fickian but instead of the usual decline with increasing crystallinity, diffusivities showed definite enhancement in the case of the annealed films, i.e., the expected monotonic decline of D with increasing crystallinity is not observed. This behavior is attributed to a reduction in diffusional impedance through formation of defects in existing crystallites, as the lamellae thicken, in a manner similar to that observed on annealing of polyethylene single crystals. The apparent activation energies of diffusion were essentially constant and independent of thermal history. This suggests that in a highly crystalline polymer diffusion is not so much impeded by the restricted mobility of chain segments but rather by the extremely small dimensions of the available diffusive pathways. In support of the argument that the transport properties of polypropylene are controlled at a level of microstructure well below the characteristic dimensions of spherulities, it was observed that bulk-crystallized polypropylene has a spherulitic structure whose size and texture do not change significantly on annealing.     

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.     

Transport and solubility of fluids into polyphenylene sulfide (PPS)

The solubility and transport of toluene and carbon disulfide into amorphous and crystalline polyphenylene sulfide (PPS) was investigated. The rates of sorption, desorption, and resorption of both fluids were measured as a function of temperature. The sorption of these fluids into amorphous PPS produces a semi‐crystalline material by solvent induced crystallinity (SIC). Although the rate of diffusion of carbon disulfide (CS₂) into crystalline PPS, (produced either thermally or by SIC), is several orders of magnitude slower than that observed in amorphous PPS, the solubility is only slightly reduced, by approximately 10%. The PPS films exhibit highly stressed surface regions that rapidly sorb the penetrant. Thermal annealing at temperatures as high as 100°C (note T_g of PPS is 85°C) has little or no effect on the surface stress, the diffusion process or the solubility of toluene into PPS. In addition to SIC, PPS undergoes cold crystallization at 130°–140°C; however, the degree of crystallinity induced by cold crystallization is approximately 60% of that formed by cooling from the melt. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 615–625, 2003     

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.     

Transport and mechanical properties of iPP–sPP fibers

The drawing behavior of a blend of syndiotactic and isotactic polypropylene (iPP–sPP 50:50 w/w) was investigated at different temperatures and compared to that of pure polymers. The film of pure sPP showed that the presence of iPP allowed the blend to reach a much higher draw ratio. Fibers were obtained by drawing the blend at 110°C. The axial elastic modulus of the fibers was measured as a function of draw ratio up the highest λ = 10. The sorption and diffusion of dichloromethane vapors in the undrawn and drawn samples were studied in order to provide information about the structural organization of the amorphous phase. The elastic modulus of the fibers displayed a more‐than‐linear increase with the draw ratio, suggesting a good interconnection of the amorphous phases. The orientation of the chains with increasing λ determined a decrease of entropy and fractional free volume (FFV) and a tighter packing of the chains along the drawing direction, explaining the strong increase of the elastic modulus. The transport properties, which confirmed the mechanical properties, showed a stiffening of the amorphous phase after λ = 6, evidenced by a dual‐type sorption isotherm for the fibers and a sharp drop in the zero‐concentration diffusion coefficient. As a consequence, the permeability of the fibers was much lower than that of the unoriented sample. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 539–545, 2001     

The mass transport of ethyl acetate in syndiotactic polystyrene

The mass transport of ethyl acetate in syndiotactic polystyrene (sPS) has been studied. Two groups of specimens were prepared using press‐cooling and water‐quenching. The press‐cooled and water‐quenched specimens were identified as crystalline and amorphous structures, respectively, by X‐ray diffraction. The weight gain of ethyl acetate in sPS was monitored at temperatures from 50°C to 70°C. The crystallinity of a press‐cooled specimen prior to solvent sorption was greater than that after solvent sorption. However, solvent‐induced crystallization was observed in the water‐quenched specimen. The transport of ethyl acetate in both press‐cooled and water‐quenched specimens was anomalous and consisted of two stages. Each stage of the sorption curves was well fitted with Harmon's model. Both the diffusion coefficient and velocity component satisfy Arrhenius behavior. For the press‐cooled specimen, fluxes of Case I and Case II transport flow from the outer surface to the center, but for the water‐quenched specimen, the solvent is squeezed out. Pure Case II transport did not appear in the water‐quenched specimen.     

Effects of mechanical drawing on the structure and properties of peek

This study examines the effects of crystallinity and temperature on the mechanical properties of PEEK. Crystallinity in PEEK Increases with annealing temperature up to a maximum of 28 percent with a melting point at 335°C. A minor melting peak also occurs about 10°C above the annealing temperature. In cold drawing the samples exhibited a yield stress and necking followed by homogeneous drawing. The yield stress increases with crystallinity, but there is no change in the modulus. The extension in the necking process also increases with crystallinity, however there is only a slight increase in extension-to-break since necking is compensated by the final amount of homogeneous drawing. The yield stress of PEEK when drawn at T_g (145°C) is significantly lower than at room temperature indicating a reduction in mechanical properties at temperatures approaching T_g. After mechanical drawing the minor melting peak disappears and on heating the material undergoes cold crystallization near the onset of T_g. There is evidence that this minor crystalline component might contribute to the yield stress changes with annealing history. Cold drawing induces crystallization of amorphous PEEK but decreases crystallinity and generates microscopic voids in crystalline PEEK, The various effects of crystallinity on mechanical properties could be important in determining the stress response of PEEK as the matrix in composites.     

Effects of orientation on the penetration,crazing, and dissolution of polystyrene by n-hexane

Extruded, drawn, and quenched samples of polystyrene were subsequently immersed in liquid n-hexane at temperatures between 35° and 55°C for various time intervals. Samples were removed from the immersion bath, quenched and fractured. Subsequent microscopic examination of the cross-sections revealed a distinct boundary between a crazed outer shell and an essentially unpenetrated central core. The time dependence of the depth of penetration of the advancing craze front was measured at various temperatures for several draw ratios. The initial rate of penetration increased monotonically with draw ratio (orientation) and the advance of the penetrant front was completely controlled by diffusion for drawn samples at 55°C. More complex kinetics, involving relaxations at the moving boundary, describe the penetration at lower temperatures; a slight systematic variation in the relative contribution of diffusion and relaxation was observed with increasing draw ratio. An activation energy of 23.7 k cal/g-mole characterized the temperature dependence of the initial penetration rate, independent of sample orientation. Gravimetric swelling experiments were confounded by sample dissolution in the case of the oriented samples. Intriguing swelling patterns, including discernable differences between the pronounced edge effects in the draw and tranverse directions, were apparent. Conversely, diffusion transverse to the orientation direction was accelerated by the orientation resulting in an increasing component of relaxation control in the penetration experiments and increased rates of dissolution in the oriented samples.     

Gas permeability of deformed polyethylene films

Low-density polyethylene films strained up to 35% exhibit an initial increase of diffusivity and permeability which soon reach a maximum and subsequently drop to steadily decreasing values below those of the unstrained starting material. The sorption steadily increases and seems to approach a plateau. The maximum and the subsequent decrease are probably caused by significant, recoverable plastic deformation which seems to depress the tortuosity factor but not the free volume, as one concludes from the opposite trend of diffusion and sorption. Permanently deformed drawn or rolled films on the strain range from 0.5 through 3.0 exhibit a continuous decrease of diffusivity and permeability with an almost constant reduction of sorption. This postulates a decrease in free volume and a steadily decreasing tortuosity factor as a consequence of the gradually increasing fraction of the new, practically impermeable fibrous structure.     

Strain‐induced crystallization in uniaxially drawn PETG plates

The copolyester poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) (PETG) is used industrially as an uncrystallizable polymer, whereas PET is an inherently crystallizable polymer. Nevertheless, a crystalline phase could appear in the material. To create a strain‐induced crystalline phase in an initially amorphous PETG material, plates were placed in the heating chamber of a tensile machine at 100°C and uniaxially drawn to obtain different samples with various draw ratios. During DSC analysis of highly drawn samples, perturbations of the baseline appear above the glass‐transition temperature, consisting of weak exothermic and endothermic phenomena. Comparison of DSC and X‐ray diffraction analysis of drawn PETG and PET shows that a strain‐induced crystalline phase appears in this copolyester. A spherulitic superstructure could also appear after lengthy annealing. Analysis of this semicrystalline material allowed estimation of the degree of crystallinity, about 3% after a drawing at high draw ratio and about 11% for undrawn annealed material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3405–3412, 2001     

Mechanical anisotropy in oriented linear polyethylene of various crystallinities

We have studied the mechanical moduli of oriented linear polyethylene with crystallinities X varying from 0.44 to 0.63 and draw ratios λ = 1–9 by using a dynamic tensile method at 10 Hz and an ultrasonic technique at 10 MHz. Wide-angle X-ray diffraction and birefringence measurements reveal that the chains in the crystalline regions are fully aligned at λ > 4, but the degree of amorphous orientation increases steadily up to the highest draw ratio. From −180°C to the β relaxation region (near 0°C at 10 Hz) the mechanical behavior at all crystallinities is controlled by three factors: molecular orientation, weak c-shear deformation and stiffening effect of taut tie molecules. At low temperature the chain alignment in an oriented sample gives rise to an axial Young's modulus E₀ which is much larger than the transverse Young's modulus E₉₀, with the modulus for the undrawn material lying in-between. However, the results that E₄₅ < E₉₀ and C₄₄ (axial shear modulus) < C₆₆ (transverse shear modulus) imply that a weak c-shear process occurs even at low temperature. At the β relaxation where the amorphous regions are rubbery, the stiffening effect of taut tie molecules becomes prominent and leads to increases in all moduli upon drawing. For the polyethylene with the lowest cyrstallinity a strong c-shear process is activated at the α relaxation (about 50°C at 10 Hz), which gives rise to very low values of C₄₄ and E₄₅. This effect becomes weaker with increasing crystallinity and is hardly observable at X > 0.6.     

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     

Annealing of drawn crystalline polymers

The annealing of drawn samples mobilizes the almost fully extended amorphous tie molecules which try to assume the thermodynamically required random conformations. The sample shrinks if annealed with free ends which permits the crystal blocks on different microfibrils and connected by almost fully extended taut tie molecules to move towards the position they had before plastic deformation. Hence the annealed sample has irretrievably lost most of its high axial elastic modulus which in the sample as drawn was caused by the high fraction of taut tie molecules. With fixed ends no shrinkage is possible so that the partial relaxation of interfibrillar taut tie molecules still lets them connect far away blocks. If their fraction is large enough so that in spite of the high surface to volume ratio which drastically depresses the crystallization temperature they can crystallize they do so after cooling to room temperature. The new axial crystalline bridges restore the high elastic modulus of the material before annealing, partially stabilize the sample against shrinkage during a new annealing, but also cause the dead bend effect which is the consequence of the replacement of flexible taut tie molecules in still amorphous conformation by rigid crystalline bridges. The drawing or extrusion at high temperature produces some annealing effects comparable with those of cold drawn material annealed with fixed ends.     

Effect of the ultradrawing behavior of gel films of ultrahigh‐molecular‐weight polyethylene and low‐molecular‐weight polyethylene blends on their physical properties

This study examined the effect of the ultradrawing behavior of gel film specimens of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and UHMWPE/low‐molecular‐weight polyethylene (LMWPE) blends on their physical properties. The concentration of a gel film approximated its critical concentration at a fixed drawing temperature; its achievable draw ratio was higher than that of other blend specimens with various concentrations. Noticeably, when about 5 wt % LMWPE was added to a UHMWPE/LMWPE gel film specimen, the achievable draw ratio of the gel film increased, and this contributed to an apparent promoting effect on its anticreeping properties and thermal stability. Therefore, when UL_B?0.9 was drawn to a draw ratio of 300, the anticreeping behavior was improved to less than 0.026%/day. Moreover, with respect to the thermal stability, when the same specimen was drawn to a draw ratio of 300, the retention capability of its storage modulus could resist a high temperature of 150°C, which was obviously much higher than the temperature of an undrawn gel film specimen (70°C). To study these interesting behaviors further, this study systematically investigated the gel solution viscosities, anticreeping properties, dynamic mechanical properties, thermal properties, molecular orientations, and mechanical properties of undrawn and drawn UHMWPE/LMWPE gel film specimens. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Structural analysis of oriented poly(ε‐caprolactone) including CaCO3 particles with 13C solid‐state NMR

The results of a study of the relation between the oriented structure and drawn Poly(ε‐caprolactone) specimens including CaCO₃ particles and their dynamic mechanical properties are presented. The loss elasticity, E″, showed almost the same curve for both undrawn sheets and drawn sheets as a function of CaCO₃ content. On the other hand, the storage modulus, E′, of drawn sheets increased nonlinearly with increasing CaCO₃ content, and their curve showed lower E′ values than those of undrawn sheets. By simulation of ¹³C CP NMR spectra of drawn PCL/CaCO₃ sheets, both oriented and unoriented components were observed. The distribution parameter, p, of drawn PCL/CaCO₃ sheets was 13°, which was larger than those (8°) of drawn PCL. Further, the fraction of the unoriented component increased with increasing CaCO₃ content. Thus, adding CaCO₃ particles into the PCL, the arrangement of the oriented component was disturbed and decreased. In addition, from the line shape analyses of ¹³C CP MAS NMR spectra, four peaks were obtained in not only undrawn sheets but also in drawn sheets of both PCL and PCL/CaCO₃ compounds. Besides, structural change occurred at only drawn PCL/CaCO₃ sheets. Therefore, the change in dynamic mechanical properties observed only for drawn PCL/CaCO₃ sheets were strongly dependent on the orientational structure, which was formed under shear stress of the stretching drawn process. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2376–2382, 2001     

Long Spacing in Polyblock Poly(ether ester)s—Origin and Peculiarities

Abstract

Poly(ether ester)s (PEE) based on poly(butylene terephthalate) (PBT) as hard segments and poly(ethylene glycols) (PEG) with different molecular weight as soft segments are studied by means of WAXS and SAXS in the drawn and undrawn state after annealing at various temperatures (T_a ). The repeatedly reported strong increase of the long spacing L with T_a is confirmed once again. In the same time the directly measured by WAXS crystallite size of PBT remains insensitive to T_a and the increase of L with T_a is the stronger, the higher the PEG content. It is concluded therefore that the rise in L is due to the expansion of the amorphous intercrystalline layers rather than to crystal thickening, the latter being the case of semicrystalline homopolymers.

The observed much stronger increase of L with T_a in undrawn samples than in drawn ones is explained by melting of less perfect crystallites at higher T_a and dephasing processes in the amorphous regions. The conclusions drawn seem to be valid for other segmented polyblock copolymers and suggest some specific features of the block copolymers in comparison to homopolymers.     

Eutectic structure from amorphous Al2O3-ZrO2-Y2O3 system by rapid quenching technique for potential hybrid solar cell application

Abstract

Ternary Al₂O₃-ZrO₂-Y₂O₃ samples with a eutectic composition were prepared using the rapid quenching method, with some samples further annealed at 1300°C for 30?min and then slow cooled. The microstructural evolution was observed with XRD, SEM, and TEM. The SEM and TEM observations of the ternary samples agreed with the XRD. The rapid quenched sample was an amorphous phase with a small amount of crystalline phase mixed in. Observations showed that the rapid quenched and annealed sample was completely crystalline with a granular structure and well defined crystals of 40-60?nm in size.     

Determination of intrinsic birefringence of smectic phase in isotactic polypropylene

When isotactic polypropylene is quenched at 0°C from the molten state, a biphasic material, amorphous-smectic, is obtained. The smectic phase has an intermediate order between the amorphous and the crystalline. In this study the intrinsic birefringence of the smectic phase was determined. Tapes with different draw ratio were prepared at room temperature, at which the smectic phase does not transform into the crystalline phase. The amount of the smectic phase was determined with measurements of density and sorption of vapors of dichloromethane. The value of the intrinsic birefringence for the smectic phase is: δ°n_sm = 40 · 10⁻³. This value is in good agreement with the values proposed by Samuels for the intrinsic birefringence of the amorphous and the crystalline phases. © 1996 John Wiley & Sons, Inc.