Polymer Crystallization Induced by Biaxial Stretching During Film Manufacture

Abstract

In the manufacture of semicrystalline polymer films, orientation is commonly introduced. This orientation may be uniaxial, unbalanced biaxial, or balanced biaxial. Machine-direction and transverse stretching may be concurrent or sequential; each orienting process is characterized by a trajectory on the biaxial stress plane and the biaxial extension plane. The presence of uniaxial or biaxial tensile stress strongly affects the process of polymer crystallization, influencing the crystal-amorphous equilibrium, crystallization kinetics, and the resulting polymer morphology. Post-solidification alterations in morphology can be imposed by drawing or heat-setting under biaxial tension, below the crystalline melting point.

The machine-direction and transverse properties of a semicrystalline polymer film depend strongly on the crystalline morphology, and hence on the processing history. The dependence of film properties on processing conditions are well recognized and widely exploited; but the morphology of biaxially oriented films and the structure-property relationships involved are only partly understood.     

Studies on the biaxial stretching of polypropylene film. XI. Type II orientation during [2-2FI]-type stretching and its change by subsequent thermal contraction

In order to study the deformation mechanism of type II stretching, the change in orientation during the restretching and subsequent thermal contraction was investigated by x-ray diffraction method. When a uniaxially oriented film is restretched, the lamellae which are stacked in the stretching direction by the stretching rotate as a whole toward the restretching axis. They rotate backward nearly reversibly during the thermal contraction, unless the restretching exceeds a balancing state, where the orientation in the film plane are equal in all directions. However, when the restretching degree is so high and the film orientation exceeds the balancing state, the lamellar rotation is accompanied by a complex phenomenon. It is considered from the wide-angle and small-angle x-ray diffraction patterns that the lamellar surface becomes indented because of slippage between microfibrils composing the lamellae, and the microfibrils themselves bend at the boundary between the amorphous and crystalline regions within which the tilting of c-axis also occurs. Upon contracting of the film; these changes recover, but even in the last stage of contraction the orientation approaches the symmetrical biaxial orientation but not the uniaxial orientation from which the biaxial orientation is started. These orientation and disorientation behaviors are not affected basically by a slight change in the restretching temperature and the degree of stretching.     

双轴取向聚乙烯薄膜晶体取向的二维X光衍射分析

聚乙烯膜的晶体取向决定着薄膜的多种力学性能和热力学性能。因此,针对薄膜晶体取向的表征显得非常重要,尤其是具有双轴取向的聚乙烯薄膜。通过二维广角衍射研究了单轴和双轴高取向聚乙烯薄膜的取向度。建立表征取向度的三种方法,包括Herman取向分析法、局部积分法和环向积分法。结果发现,上述方法均适用于所有的双轴取向的高分子薄膜,包括非晶态高分子薄膜。Herman取向分析法可以通过取向因子定量计算简单取向材料取向度;局部积分的方法能分析出衍射较弱方向晶体信息,更适用于取向度较复杂的样品;环向积分法能更直观地分析薄膜的取向特点、取向强度。     

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.     

Biaxial orientation in HDPE films: comparison of infrared spectroscopy, X-ray pole figures and birefringence techniques

In this study, high-density polyethylene films (HDPE) were produced using different processes (film blowing and biaxial orientation) and processing conditions. The orientation of the films was characterized in terms of their biaxial crystalline, amorphous and global orientation factors using birefringence, Fourier transform infrared spectroscopy (FTIR) using a tilted incidence technique and X-ray pole figures. Evaluation of a simplified FTIR procedure without using the tilted method for the determination of crystalline orientation factors proposed in the literature is also evaluated and assessed. The results indicate that FTIR overestimate the crystalline orientation factors, particularly for the crystalline a-axis. Significant discrepancies are also observed for the b-axis orientation, which may be due to an overlap of the amorphous contribution and/or saturation of FTIR bands. Those differences are larger for films with low orientation, such as blown films. Amorphous phase orientation from FTIR depends on the band used and is not necessarily in agreement with that determined from combination of X-ray and birefringence.     

Mechanical properties,stress‐relaxation,and orientation of double bubble biaxially oriented polyethylene films

Biaxially oriented linear low density polyethylene (LLDPE) films were produced using the double bubble process with different machine direction (MD) orientation levels and the same transverse direction (TD) blow‐up ratio. Their mechanical behavior was characterized in terms of the tensile strength and tear resistance. The viscoelastic behavior of oriented films was studied using dynamic‐mechanical thermal analysis (DMTA). The microstructure and orientation were characterized using microscopy, X‐ray diffraction pole figures, and birefringence. The results indicate that MD ultimate tensile strength increases and the TD one decreases with MD stretching ratio. Tear propagation resistance, in general, remained mainly constant in TD and decreased in MD, as the draw ratio was increased. The morphology analyses exhibit a typical biaxial lamellar structure for all samples with different lamellar dimensions. Orientation of c‐axis in crystalline phase, molecular chain in amorphous phase along MD increased with draw ratio. In most crystals, a‐axis was located in the normal direction (ND) and the b‐axis in the ND–TD plane. A good correlation was observed between c‐axis orientation factor and MD mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3545–3553, 2006     

Characterization of the physical and molecular structure of thermally elongating poly(ethylene terephthalate) fibers

The mechanism of thermally induced elongation in poly(ethylene terephthalate) fiber spun at 3500 m min⁻¹ has been examined. This partially oriented fiber has a crystalline content of about 25% and a high degree of orientation. The effect of time and tension during heat treatment was examined, and it was found that yarns that were allowed to relax during an initial brief heat treatment at 130°C subsequently elongated by up to 5% during a long heat treatment at the same temperature. Yarns that were not allowed to relax during the brief heat treatment did not elongate on subsequent heating. The morphological and mechanical changes associated with these processes have been studied using differential scanning calorimetry, X-ray diffraction (XRD), birefringence measurement, microscopy, and tensile testing. A large increase in crystallinity was observed during the brief heat treatment, but a much smaller increase took place during the long heat treatment. XRD indicated that substantial crystal reorganization occurred during both heat treatments, but c-axis growth was most significant in those materials that elongated during long heat treatment. It is proposed that it is this c-axis growth, in conjunction with conversion of disordered amorphous material into oriented crystalline material, that is responsible for the observed elongation. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 989–995, 1997     

Characterization of biaxial strain of poly(l‐lactide) tubes

Poly(l ‐lactide) in its l ‐form has promising mechanical properties. Being a semicrystalline polymer, it can be subjected to strain‐induced crystallization at temperatures above T_g and can thereby become oriented. Following a simultaneous (SIM) biaxial strain process or a sequential (SEQ) biaxial strain process, the mechanical properties of biaxially strained tubes can be further improved. This study investigated these properties in relation to their morphology and crystal orientation. Both processes yield the same mechanical strength and modulus, yet exhibit different crystal orientation. Through further wide angle X‐ray scattering analysis it was found that the SEQ biaxial strain yields larger interplanar spacing and distorted crystals and looser packing of chains. However, this does not influence the mechanical properties negatively. A loss of orientation in SEQ biaxially strained samples at high degrees of strain was detected, but was not seen for SIM biaxial strain and did not correlate with mechanical performance in either case. However, post‐annealing reduced the orientation to the same level in both cases, and the modulus and strength decreased for both SIM and SEQ biaxial strain. It is therefore concluded that mechanical properties after biaxial strain are related to strain‐induced amorphous orientation and the packing of crystals, rather than strain‐induced crystallinity. © 2015 Society of Chemical Industry     

Characterization of molecular orientation in injection-molded thermoplastics by transmission and reflection infrared spectroscopy

Orientation in injection moldings of polypropylene (PP), polyethylene (PE), polyamide 6 (PA-6), and polystyrene (PS) was investigated by transmission and reflection infrared spectroscopy. Orientation of the surface was measured by the reflection method, the depth profiles of orientation and of the fraction of the crystalline phase were measured by the transmission spectroscopy of microtome sections. The maximum of orientation of PP lies in the subsurface layer (ca. 250 μm); the crystalline phase is oriented more than the amorphous one. The maximum of the depth profile of orientation corresponds to the minimum of the fraction of the crystalline phase in PP. The profile of orientation of PE Is similar; at the beginning (to a depth of about 500 μm) the parallel orientation of the c axis of the crystalline phase is the most distinct one, towards the center the orientation of the a axis passes from the perpendicular to the parallel one. Under the described molding conditions PA-6 is not significantly oriented, the fraction of the crystalline phase increases towards the center of the molding. Unoriented PA-6, the surface layer of which was removed by milling, has a highly oriented surface due to its mechanical treatment. No pronounced orientation of PS was observed under the molding conditions used.     

Uniaxial roll-drawing of isotactic polypropylene sheet

The process described as “roll-drawing” has been applied to commercial extruded sheets of isotactic polypropylene (M?_n = 70,900). Preheated billets were drawn into thin, clear, transparent sheets in a single pass, producing uniaxial orientation of the polymer molecules in the draw direction. At the maximum draw ratio of 20, the ultimate tensile strength and Young's modulus in the draw direction were 0.5 GPa and 20 GPa respectively. The mechanical properties transverse to the draw direction were virtually unchanged. The theory of fiber reinforcement for unidirectional anisotropic plates was applied to interpret the orientation dependence of the stress-strain behavior of the drawn sheets. From these results, it was estimated that the mechanical properties of biaxially laminated polypropylene sheets equaled the performance of aramid and carbon fiber composites, The roll-drawing process appears to be economically attractive for the production of ultra-high modulus crystalline thermoplastics in sheet form having excellent uniaxial or biaxial properties.     

Correlations between processing parameters,morphology, and properties of blown films of linear low‐density polyethylene/low‐density polyethylene blends. I. Crystalline biaxial orientation by IR and mechanical properties

The change of the processing parameters of a blown film operation alters the mechanical and optical properties of the films. This work studied the influence of some of these parameters on the properties of blown films made of blends of linear low‐density polyethylene (LLDPE) and LDPE. Correlations between the crystalline biaxial orientations of these films and the mechanical properties were found. The crystalline biaxial orientation was measured by IR following the Krishnaswamy approach. The a axis of the unit cell was oriented along the machine direction (MD) at all LDPE concentrations, and it was not affected by the blow‐up ratio (BUR). In contrast, the b axis changed its orientation from orthogonal to MD to along the transverse direction (TD), and it was affected by the BUR. Finally, the c axis changed its orientation from equiplanar between the MD and TD to along the thickness of the film, and it was influenced by the BUR. The decrease of the tensile mechanical properties along the MD with the increase in the amount of LDPE in the blends was attributed to the tilting of the c axis toward the film thickness. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3161–3167, 2006     

Solid‐state structural evolution of poly(ethylene terephthalate) during step uniaxial stretching from different initial morphologies: An in situ wide angle x‐ray scattering study

This work reports an in situ wide‐angle X‐ray scattering (WAXS) study of the structural evolution of PET with distinct initial morphologies during step uniaxial stretching in the solid state. Two types of samples were analyzed under synchrotron X‐ray radiation, namely quasi‐amorphous (QA) and semicrystalline (SC) (with 2D and 3D order). Results show that initially different QA morphologies evolve following the same stages: (i) stage I (before neck), at almost constant orientation level the amorphous phase evolves into mesophase; (ii) stage II (neck formation), there is a rapid increase of polymer orientation and the appearance of a periodical mesophase from the highly oriented mesophase; (iii) stage III (necking propagation), there is a leveling off of the average polymer orientation together with partial conversion of the periodical mesophase and mesophase into highly oriented amorphous. The behaviors of the two SC morphologies are completely distinct. A 2D order crystalline morphology evolves with stretching likewise the QA through three stages: (i) at early stages of deformation the polymer orientation remains unchanged while the amorphous phase amount increases slightly, stage I; (ii) in stage II, a fast increase of polymer orientation is accompanied by large formation of mesophase; and (iii) in stage III there is the level off of polymer orientation as the chains approach their finite extensibility and the 3D crystalline order is achieved. Evolution of SC sample with 3D crystalline order mainly features constant orientation increase together with mesophase increment. Structure deformation models are suggested. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Interphases in ethylene–vinyl acetate copolymer/steel sandwiches

The properties of a polymer near an interface with a substrate can be different from the bulk properties. To characterize the interphasial zone, the influence of the thickness of a polymer inserted between two steel sheets is carried out. The chosen polymer is a semi-crystalline ethylene–vinyl acetate copolymer with different amounts of vinyl acetate. Dynamic mechanical spectroscopy measurements were performed directly on the assemblies using a three-point flexure test in order to characterize the mobility of the amorphous phase. The crystalline properties were analyzed by differential scanning calorimetry. The mechanical transition temperature, T_mech, corresponding to the temperature at which the loss factor goes through a maximum was examined. The results show that at high thicknesses T_mech remains constant. However, when the polymer thickness decreases, T_mech increases greatly, indicating a decrease of mobility of the chains. This effect is seen whatever the vinyl acetate content. The crystalline properties are also modified with a higher proportion of small crystals for thin layers. For interfacial energy-minimization reasons, the vinyl acetate groups of the copolymer chains are oriented toward the polar steel surface. These orientation phenomena probably induce some reorganization of the phases, leading to more crystals that constitute physical ties, reducing the mobility of the amorphous phase. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:347–353, 1997     

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

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

Morphological studies on roll extruded,plasticized composites

A study of the morphologies of polymer/carbon black composites, plasticized with small molecule organics, is presented. Four different plasticizers and three different polymers were used. In all cases, the plasticizers depress the T_g of the polymers. Whereas in some cases the organic small molecule was found to be molecularly dispersed in the polymer matrix, phase separation occurred in other cases beyond a certain composition. In the latter instances, the excess plasticizer formed crystalline aggregates and a depression of the melting point of the plasticizer was observed. The samples were prepared by a process similar to roll extrusion, which causes biaxial orientation of the crystalline aggregates.     

Mechanical Fabrication of Thermoplastic Polymers

Abstract

The physical properties and performance of fabricated thermoplastic items depend upon the molecular structure (mainly established during polymerization) and the spatial arrangement of the polymer molecules (established during fabrication). The spatial arrangements can be favorably influenced by controlled molecular orientation (uniaxial, biaxial and “crossed”) and by composites (fiber reinforcement, multi-layer films).     

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.     

High modulus polypropylene fibers. II. Influence of fiber preparation upon structure and morphology

The influence of drawing on the limiting draw ratio upon formation of the morphological structure of fibers spun from binary polypropylene (PP) blends was studied. Fibers were spun from a fiber‐grade CR‐polymer and from the blends of a fiber‐grade CR‐polymer with a molding‐grade polymer in the composition range of 10–50 wt % added. As‐spun fibers were immediately moderately and additionally highly drawn at the temperature of 145°C. The structure and morphology of these fibers were investigated by small‐angle X‐ray scattering, wide‐angle X‐ray scattering, differential scanning calorimetry, scanning electron microscopy, density, birefringence, and sound velocity measurements. It was shown that continuously moderately drawn fibers are suitable precursors for the production of high tenacity PP fibers of very high modulus, because of so called oriented “smectic” structure present in these fibers. With drawing at elevated temperature, the initial metastable structure of low crystallinity was disrupted and a c‐axis orientation of monoclinic crystalline modification was developed. Hot drawing increased the size of crystallites and crystallinity degree, the orientation of crystalline domains, and average orientation of the macromolecular chains and resulted in extensive fibrillation and void formation. It was found that the blend composition has some influence on the structure of discontinuously highly drawn fibers. With increasing the content of the molding‐grade polymer in the blend, the size of crystalline and amorphous domains, density and crystallinity, as well as amorphous orientation decreased. Relationship has been established between the mechanical properties, crystallinity, and orientation of PP fibers. It was confirmed that by blending the fiber‐grade CR‐polymer by a small percentage of the molding‐grade polymer, maximization of elastic modulus is achieved, mainly because of higher orientation of amorphous domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1067–1082, 2006     

Craze behaviour in isotactic polystyrene: 1. Craze-spherulite interaction

The deformation of isotactic polystyrene (i-PS) in uniaxial tension at room temperature has been studied in detail by transmission electron microscopy. Quantitative analysis reveals that crazes in amorphous i-PS are similar to crazes formed in atactic polystyrene (a-PS) under the same conditions, except for a higher stress concentration at the craze tip. Fully spherulitic i-PS films contain crazes with very irregular paths which often nucleate at spherulite triple points. Craze-spherulite interactions have been observed in films which contain spherulites isolated in an amorphous matrix. Lamellae with their c-axis perpendicular to the tensile axis generally yield a higher craze fibril draw ratio than in the amorphous matrix. Lamellae with their c-axis parallel to the tensile axis cause a decrease in both λ and craze width. When the c-axis is in the plane of the film but oblique to the tensile axis, the craze deviates toward the centre of the spherulite. The entanglement network approach applied to crystalline i-PS predicts the correct anisotropic behaviour of λ when neutron scattering data on chain conformation in i-PS crystals are used.     

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.