Molecular orientation in film extrusion of high-density polyethylene

Molecular orientation in film extrusion has been studied using an extrusion-grade commercial polyethylene resin. First quad (take-up) speed was varied over the range 50 to 120 m/min, Web crystallinities were found to be in the range 0.60 to 0.65 as determined by differential scanning calorimetry. Web crystalline orientation function f_c was slightly negative below a takeup speed of 50 m/min and rose to a value of 0.4 at 120 m/min at a quench bath temperature of 37.8°C and a melt temperature of 251°C for one of the resins used. (Perfect orientation along the machine direction implies f_c equal to 1.0). Amorphous orientation function f_a remained below 0.1 and was almost constant with takeup speed. This behavior was modified in a minor way by changes in quench bath and melt temperature as well as resin lot. A qualitative model was proposed for this without definite proof. The major mechanism at work in the film-forming process is macromolecular network structure deformation in elongational flow. Die gap variation at uniform extrusion rate has a secondary effect on web orientation. With the present state of knowledge, it is not possible to quantitatively separate the amorphous orientation function into its various conformational contributions. It was also noted that high take up speeds and low air gaps tend to freeze the web at greater widths.     

Analysis of zone-drawing process in preoriented polypropylene

Preoriented isotactic polypropylene was used to clarify the molecular process in zone-drawing with which the necking part is confined in a thin heating zone during uniaxial drawing. The process was analyzed on the basis of rate process, the mechanical properties of zone-drawn samples, and the superstructural change during zone-drawing. The values of activation energy for deformation, ΔH^*, and the activation volume, ΔV^*, were affected by the deformation mechanisms preferentially taking place during the zone-drawing. The attainable maximum modulus of zone-drawn sample at θ = 45° was larger than those at θ = 0° and 90°. The highest strength was also obtained at θ = 45°. The values of modulus and strength strongly depended on both the orientation function of the crystal c-axis and the orientation function of amorphous chains. In the region of a very high zone-drawing rate, in which microcracks are preferentially formed, both modulus and strength decreased, whereas they increased with increasing the zone-drawing rate below this region, giving the optimum condition for achieving the maxima in the modulus and strength.     

Structure and property development of aromatic copolysulfonamide fibers during wet spinning process

The structure and performance changes of aromatic copolysulfonamide (co‐PSA) fibers that occurred during wet spinning process have been studied. While using different length scale characterization, including scan electron microscopy (SEM), wide‐angle X‐ray scattering (WAXS), and small‐angle X‐ray scattering (SAXS), it was found that the molecular chains of co‐PSA formed an isotropic network during coagulation which further lead to extension and orientation of these chains during the subsequent stretching. As a result, only after heat stretching and heat setting the molecular chains tended to pack into crystal lattice in the fibrils. This gave rise to a much denser structure along the spinning line and the glass transition temperature of co‐PSA fibers increased a little after heat setting. Before heat stretching, the co‐PSA fibers were in amorphous state, and only the amorphous orientation was observed within the fibers. After heat stretching at the temperature higher than T_g, the fraction of amorphous region decreased, and the crystal structure formed in the fibers, which became more perfect during heat setting. The structure development during spinning process contributed toward the improvement of thermo‐mechanical stability, tenacity and modulus of the co‐PSA fibers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42343.     

Young's modulus and adhesion coefficient of amorphous Ni–P coatings on a metal substrate

In the present paper the Young's modulus and adhesion coefficient of amorphous Ni–P coatings obtained from aqueous solutions were determined. The measurements were carried out using a vibrating reed apparatus. In the temperature range 550–590 K, crystallization of Ni and formation of nickel phosphide Ni₃P were observed. The Young's modulus of Ni–P amorphous layers on stainless steel at room temperature was found to be about 112 GPa. The adhesion coefficient γ of the examined layers depends on the layer thickness a _f and strongly decreases for a _f > 8 μm. This dependence corresponds to the change of the relative adhesion coefficient of about 40% for 8 μm < a _f < 15 μm. It was also shown that the adhesion coefficient does not depend on the temperature, at least in the range 300–550 K.     

The effect of stretching on monofilament polypropylene sutures

The effect of cold drawing on monofilament Polypropylene sutures PP at room temperature 24 °C were studied interferometrically. The changes in the molecular orientation were evaluated to obtain optical and mechanical orientation factors f ₂(θ), f ₄(θ), f ₆(θ), P ₂(cosθ), P ₄(cosθ), crystalline and amorphous orientation functions F _c and F _a, respectively. The shrinkage factors, the reduced stress and the number of chains between cross links per unit volume were determined. Calculation of the cross link density (N ₀) and the chain entanglement density (N _c) with the aid of Moony–Rivlin equation constants were given. Also, other various different opto-mechanical parameters were calculated. Relations between the optical and mechanical parameters were given. The present study demonstrates changes in the different orientation factors and structural parameters. Illustrations were given using curves and microinterferograms.     

Thermal conductivity of ramie fiber drawn in water in low temperature

To understand the effect of extension of molecular chain in amorphous region in polymer fibers to thermal conductivity, the thermal conductivity, tensile modulus and crystal orientation angle of ramie fibers and those drawn by the stress of 17.4 kg/mm² (water treatment) in the water were investigated. The tensile modulus of ramie fiber in fiber direction increased from 61 to 130 GPa by drawing in the water. The crystal orientation angles of ramie fiber with and without water treatment were measured by X‐ray diffraction. The orientation degrees of ramie fibers without and with water treatment were estimated as 92.9 and 93.6%, respectively. Therefore, the tensile modulus increases two times as that of blank ramie by water treatment although crystal orientation angle does not change distinctly. The increasing of tensile modulus of ramie fiber by water treatment was explained by extension of the molecular chains in the amorphous region. Thermal conductivities of ramie fibers with and without water treatment were measured in the fiber direction in the temperature range from 10 to 150 K. Thermal conductivity of ramie fiber in the fiber direction increased by water treatment. The increasing ratio of thermal conductivity by water treatment agreed to that of sound velocity induced by increasing tensile modulus. Those results suggest that thermal conductivity of polymer fiber increase by the extension of molecular chains in the amorphous region. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2196–2202, 2006     

Structure of oriented polystyrene monofilaments and its relationship to brittle-to-ductile transition

Oriented atactic polystyrene monofilaments show brittle-to-ductile transition in the vicinity of a degree of birefringence Δn = ?2 × 10^?3 (at a temperature of 20°C and at the stretching rate of 100%/min) independently of the various spinning conditions. The amorphous orientation of a cylindrically symmetric system was investigated by wide-angle x-ray scattering experiments. The orientation of polystyrene monofilaments in real space is denoted by P₂(cos α) within the precision of measurement. The coefficient D₂(r) of the second term in an expansion of cylindrical distribution function in spherical harmonics has two main peaks, near r = 1.6 Å and r = 4 ～ 5 Å. The negative peak near r = 1.6 Å indicates orientation of phenyl groups in a plane perpendicular to the fiber axis. The positive peak near r = 5 Å (brittle region) or near r = 4 Å (ductile region) indicates the piling up of phenyl groups for the direction of the fiber axis. It is most probable that the amorphous state of atactic polystyrene consists of an appropriate cohesion of planar zigzag chains of syndiotactic polystyrene. The lower spacing (r = 4 Å) of the positive second peak in ductile region suggests that there are interchain phenyl groups near r = 5 ～ 6 Å in a plane perpendicular to the fiber axis and that the molecular chains are extended parallel to the direction of the fiber axis. This parallel packing of chain segments along the fiber axis suppresses the formation and growth of cracks of polystyrene monofilaments resulting in ductile fracture.     

Crystalline and amorphous orientations in injection molded polyethylene

The techniques of density, birefringence, and wide X-ray diffraction were employed to characterize the microstructure of injection molded polyethylene parts. Generally, maximum crystallinity (density) occurs at the center of the molding, while the minimum crystallinity occurs near the surface. Higher densities are observed near the gate. Raising the injection temperature tends to cause a marginal increase in the crystallinity throughout the molding. Birefringence measurements suggest that the maximum orientation occurs near the surface and that the relative orientation distribution is independent of the injection temperature. X-ray diffraction indicates that the crystallographic a-axis tends to orient in the flow direction while the b and c axes vary symmetrically about that direction. Increasing the injection temperature creates c-axis orientation near the surface, while towards the core region a-axis orientation is observed. Generally, near the surface it is the amorphous phase that makes the major contribution to the total orientation as measured by birefringence. Increasing the injection temperature tends to decrease the amorphous phase orientation near the surface. The crystalline phase contribution to the total orientation increases as distance from the surface increases, regardless of injection temperature.     

Opto-thermal properties of fibers. XI. The effect of thermal annealing of drawing behavior for Egyptian polyester fibers on the crystallinity and some optical parameters

The structure developed of annealed Egyptain poly(ethyleneterephthalate) (PET) fibers is studied interferometerically due to the drawing process. Using a two-beam Pluta polarizing interference microscope connected to a device to dynamically study the draw ratio with the birefringence changes, the relations of drawing changes with some optical parameters are given. The evaluation of density, the mean square density fluctuation η², crystallinity, amorphous orientation, crystalline orientation functions, number of chains per unit volume N_c, and number of random links between the network junction points N has been found. The results obtained clarify the effect of annealing time and temperature with different draw ratios on the structure of PET fibers. Empirical formula is suggested to correlate the changes in f_θ, θ, Δn_a, and A with the draw ratio. Microinterferograms and curves are given for illustration. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68: 1371–1386, 1998     

Autooxidation of Oriented Polyolefins

Abstract

The effect of the chemical structure of the polymer on its reactivity in the oriented state is studied, and causes of the effect of orientation drawing of polyolefins on the oxidation kinetics are identified.

The orientation drawing of the polymer is shown to be dependent on the nature of the latter which can either delay or accelerate the oxidation process. The effect of a delayed rate of oxidation for the samples of one drawing degree is determined by the nature of the side substitute in the monomeric link of the polymer.

The effect of the orientation drawing of the polymer on the change of parameters of oxidation (k ₂ k ₆ ^?0.5 [RH]), a decrease of the coefficients of solubility and diffusion of oxygen as well as the change in the polymer structure depending on its nature are considered.

Analysis of structural changes in the polymers due to orientation has shown that drawing of the polymer can result in localization of oxidation in defected zones of amorphous areas isolated from each other by transition chains in extremely straightened conformation. In this case, the oxidation kinetics of oriented polyolefins can be described with the use of postulates of the “zone” model developed by Yu. A. Shlyapnikov. Evaluation of the kinetic parameters of oxidation (k _2eff, k _6eff, θ) with the use of this model is made.

It is shown that the effect of the nature of the polymer is due to a change in activity of the C?H bonds participating in the oxidation process, peculiar features of changes in the structure and physical properties of the polymer in the process of orientation drawing, in terms of the “zone” model, to the rate of the expansion of the oxidation center, that is, the nature of the polymer determines the parameters k _2eff, k _6eff, θ in the oriented sample.     

Contribution of interferometry and mechanical parameters in evaluating molecular orientation for drawn polyester

Mechanical and structural parameters related to the optical properties of polyester (PET) (woollen type) fibres drawn at room temperature have been investigated. The changes in the strain were evaluated to obtain the molecular orientation factors 〈P₂(cos θ)〉 and 〈P₄(cos θ)〉. From the optical orientation, the values of f₂(θ), f₄(θ) and f₆(θ) orientation parameters were calculated. The structure and properties of oriented PET have been studied in the light of the rubber elasticity theory. The dielectric constant, magnetic susceptibility, number N′ of chains between crosslinks per unit volume, optical configuration parameter and the segment anisotropy, were among the calculated parameters. The results of the extension were used to calculate the shrinkage factor. Relationships between the calculated parameters and the draw ratios, together with micro-interferograms, are given for illustration. The present study throws light on how the applied stress changes the molecular orientation factors and the structural parameters. © 1999 Society of Chemical Industry     

A rheo-infrared-dichroism study of sheared molten polystyrene fractions

The development of orientation in molten narrow molar mass fractions of polystyrene during shear flow in the non-Newtonian shear rate range (11–24 s^?1) at temperatures between 225 and 275°C has been assessed by measurement of the infrared dichroism. Deviation from linearity between shear stress and orientation was found at high shear stresses in the steady state region. A sudden change in the shear rate caused a change in the shear stress that was one to two orders of magnitude-state level of the Hermans orientation function (f_ss) was dependent on temperature, shear rate and molar mass (M): f_ss = C₁–C₂/M (where C₁ and C₂ are constants). The time to reach steady state on the inception of shear was proportional to M^1/2. The recovery of the isotropic state after the cessation of shear followed initially a simple exponential law: f ∝ e^?t/τ, where t is the time and τ is the relaxation time. The relaxation time showed only a weak molar mass dependence (τ ∝ M^0.8), indicating that the decay of orientation was initially governed by processes other than reptation.     

Studies on the stretching of polypropylene film. II. Polyaxial stretching

Polypropylene film was stretched polyaxially at 100–160°C., and the orientation behavior was studied by means of optical and x-ray method. The molecular chains oriented progressively to the film surface with an increase in stretching area v_A in the range 1–16, and the (040) selective uniplanar orientation developed at the extreme stretching. The plot of orientation versus v_A was less steep when the stretching was carried out at higher temperature, but the final degree of orientation was independent of the temperature, because the final v_A increased with temperature. At 160°C. premelting occured to such a degree that the high stretching and, consequently, the high orientation could not be obtained. The orientation of the amorphous chains was always behind that of the crystalline region. In the initial stage the polyaxial stretching was not as effective in attaining high biaxial orientation as the two-step biaxial stretching, but the final orientation was the same in both types of stretching because v_A reached a value of 16 in the polyaxial stretching while it was only 2 in biaxial stretching.     

Proton spin–lattice and spin–spin relaxation times in isotactic polypropylene. II. Effects of stretching ratio and temperature

Proton spin–lattice, T₁, and spin–spin, T₂, relaxation times of uniaxially stretched polypropylene film were measured at 40°C using a wide line pulse spectrometer operating at 19.8 MHz. T_1l, the longer T₁, increases almost linearly with increasing stretching ratio, and T_2a, T₂ of the amorphous region, decreases gradually as the stretching ratio is increased. These results can be interpreted in terms of the increased constraints to molecular motion in the amorphous region. The fraction of the rigid protons in the sample, F_c, increases with increasing stretching ratio, while the crystallinity calculated from the density, X_d, does not change largely. The difference between F_c and X_d, therefore, increases as the stretching ratio is increased. This indicates that the physical structure of the highly stretched sample is far from the ideal two-phase model. The influence of the stretching temperature was also investigated. There are only slight increases in T_1l and in F_c for the samples stretched in a temperature range from 80°C to 150°C, whereas the considerable increase in T_2a occurs. The most notable change introduced at a high temperature stretching is the increase in the chain mobility in the amorphous region.     

An Experimental Study of the Thermodynamics of Rubber in Extension and Torsion

The stress-strain properties of three different rubbers have been measured using two different techniques, in order to evaluate the relative internal energy contribution to the total stress f_e/f and the corresponding value of Me/M over a range of strain and temperatures. Two different experimental techniques have been designed; one is to allow measurement in simple extension of the length of a rubber sample in relation to the temperature at constant force, and the other is to measure the variation of torsional couple M in a cylinder of rubber (subjected to combined torsion about the axis and extension in the axial direction) with temperature. The thermoelastic results obtained for natural rubber and butyl rubber do not contain any surprising features, and are found to be in good agreement with other reported experimental results for these rubbers. Values of f_e/f and Me/M obtained for cis-trans polybutadiene rubber show different trends between the two techniques.     

Heat sealing of semicrystalline polymer films. II. Effect of melting distribution on heat-sealing behavior of polyolefins

Heat sealing of films, i. e., formation of a joint between two films by placing them fleetingly between heated platens, was experimentally investigated for a variety of semicrystalline polyolefins, especially various polyethlenes, to determine how sealing temperature affected seal strength measured at room temperature. Seal strength as a function of sealing temperature, SS(T), is closely related to the melting distribution of the polymer determined by DSC measurements, i. e., to the fraction of amorphous phase as a function of temperature, f_a(T). Seal initiation temperature, the temperature at which a specific, low level of seal strength of polyethylene films is achieved, corresponds to the temperature at which the fraction of amorphous phase equals 77±3%. At higher temperatures, SS(T) increases approximately as f_a(T) increases. At the final melting point of the polymer, i.e., when f_a(T) =1, seal strength reaches an approximately constant value termed the plateau seal strength. The magnitude of the plateau seal strength is determined by the yield stress of the polymer film. Thus, the heat-sealing curve, SS(T), for a polyethylene can be semiquantitatively predicted from the melting distribution and yield stress of the polymer. © 1994 John Wiley & Sons, Inc.     

Microstructure and melting behavior of a solution‐cast polylactide stereocomplex: Effect of annealing

The effect of annealing on the microstructure and melting behavior of a solution‐cast polylactide (PLA) stereocomplex (sc) was systematically investigated by differential scanning calorimetry and small‐angle X‐ray scattering. A preorder state, an intermediate form between the amorphous and crystalline states, was found in the solution‐cast poly(l ‐lactide)–poly(d ‐lactide) blend. When the annealing temperature (T_a) was below 220 °C, a part of the preorder state directly formed thicker sc crystallites; these corresponded to the second melting peak, which appeared around 250 °C during the heating process. Although the rest melted and became the amorphous phase, it formed a thinner lamella under the restriction of the unmelted initial sc crystallites during annealing; the melting process of this lamella was parallel to that of the new melting peak, which appeared around 220 °C. The melting of the initial crystal formed as the solvent volatilized corresponded to the range of the first melting temperature around 230 °C. When T_a was above 220 °C, the preorder state melted completely, and the initial crystal experienced perfection process. Furthermore, the highest melting temperature of PLA sc (254.1 °C, with a fusion enthalpy of 125.5 J/g) was obtained when T_a was 235 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44626.     

Proton magnetic relaxation times of isotactic polypropylene films treated with tetrachloroethylene

Proton spin-lattice (T₁) and spin-spin (T₂) relaxation times of isotactic polypropylene films with different thermal histories, treated with tetrachloroethylene, were measured with pulsed NMR. For the melt-quenched sample T₁₁ (the longer T₁) increases and T_2a (the longest T₂) decreases with increasing treatment temperature. The mass fraction of mobile region (F_a) decreases and the mass fraction of rigid region (F_c) increases with increasing treatment temperature. T₁₁ increases almost linearly with increasing F_c, indicating that the removal of the mobile amorphous region is mainly responsible for the change in T₁₁. For the annealed sample T₁₁ also increases with increasing treatment temperature, although a slight decrease in T₁₁ for the low treatment temperature is observed. There is a large decrease in T_2a when the treatment temperature is raised, suggesting that a comparatively selective extraction occurs for the annealed sample.     

Dynamic mechanical properties of partially oriented polyester (POY) and draw-textured polyester (PTY) yarns

Spinning speed is one of the most important process parameters for change in properties of yarn and efficiency of polyester production. In this paper the effect of spinning speed (3000–6200 ypm) on dynamic mechanical properties is presented, and shows a good qualitative picture on the influence of structure change on the dynamic modulus and the height and position of glass transition peak on POY (partially oriented polyester) and PTY (draw-textured polyester) yarns. The dynamic moduli of POY yarns in a temperature range of 25–160°C are increased with increasing spinning speed. Large glass transition peaks (α peak) are observed for POY yarn spun at 3000 and 2800 ypm at about 98°C. This indicates that the yarns are low oriented with low crystallinity (5–6%). But the T_g of POY spun at 5600 or 6200 ypm is about 125°C and shows about 35% crystallinity with high amorphous orientation. An approximately linear relation was found between the height of the loss peak (tan δ) and the degree of amorphous orientation (f_a) by using these analyses.     

Effect of stretching temperature on proton spin-lattice and spin-spin relaxation times of isotactic polypropylene film

Structural properties of isotactic polypropylene film during stretching were investigated mainly by the measurements of proton spin-lattice, T₁ and spin-spin, T₂, relaxation times. Both T₁ and T_2a, T₂ of the most mobile amorphous regions, of the sample stretched at 150°C are longer than those of the sample stretched at 130°C. These results indicate that in the sample stretched at 150°C the proportion of mobile amorphous region decreases, while the amorphous region achieves enhanced molecular mobility.