Orientation in injection molded polystyrene

The ultimate properties of injection-molded thermoplastics articles are controlled to a large extent by flow and heat transfer phenomena that take place during the injection-molding process. In fact, the thermo-mechanical history of the melt during the molding process leads to a non-uniform distribution of many of the critical properties of the molding. Birefringence has been employed as an indirect measure of the distribution of frozen stresses or strains in amorphous polymers. The present study employs birefringence to study the development of frozen stresses in injection-molded polystyrene. In general, orientation in the flow direction is much greater than the orientation in the transverse direction of the moldings. In the vicinity, of the gate, where mold filling is characterized by spreading radial flow of the melt, the hoop stresses (planar deformation) at the melt front give rise to high orientation in the transverse direction. It appears that relaxation phenomena are not very important during the filling stage; however, they become more, important in the packing and pressure holding stages. With the aid of the appropriate rheo-optical relationship, it is shown that the distribution of frozen-in orientation in injection-molded polystyrene may be estimated on the basis of data relating to pressure variations during the filling stage.     

Unlimited flex life in the molded-in hinge in polypropylene: A structural hypothesis

Injection molded hinges of polypropylene possess uniquely unlimited flex life. Polypropylene when crystallized from the melt under extensional flow (as in injection, molded hinges), shows a unique morphology characterized by a planar row structure of lamellae accompanied by a bimodal distribution of the unit cells having the alpha crystal phase. This bimodal orientation consists of two apparently independent orientations of the unit cells with respect to the flow direction: one with the c-(chain) axis parallel to and one with the a′-axis parallel to the flow direction. (The a′-axis is a vector normal to (100) and thus parallel to a* in reciprocal space.) Experimental data on the morphology of polypropylene crystallized under extensional flow are interpreted in terms of two components. The c-axis component corresponds to those molecules in the planar row structure. The a′-component is attributed to secondary crystallization in which small crystallites are finely dispersed between the lamellae of the row structure. These small crystallites act as a “morphological plasticizer” protecting the load-bearing row structure from destructive stress during flexure.     

A new route to high modulus polyethylene by lamellar structures nucleated onto fibrous substrates with general implications for crystallization behaviour

In the case of recent experiments with polyethylene involving nucleation of lamellar crystals along flow induced fibrous substrates unexpectedly high modulus (up to 10¹¹ N/m²) filaments were obtained in spite of the fact that the samples consisted predominantly of lamellar material. This finding has led to reconsideration of the requirements for high moduli in general providing explanation for our observation and indicating new routes for the attainment of high moduli. In brief, the principle is that high modulus need not require complete chain extension and can be generated by lamellar crystals. We identify the following conditions as necessary: (1) the lamellae are all parallel; (2) the plane normals are along the tensile direction; (3) the straight chain segments within the lamellae are also parallel to the tensile direction (hence perpendicular to the lamellar surfaces); (4) the lateral extension of the lamellae in all directions is large compared to the lamellar thickness; (5) there is intimate and strong contact between consecutive lamellae piled onto each other; (6) there is interlocking between lamellae in lateral contact. It is shown how and why these conditions are fulfilled by our lamellar samples of ultra-high modulus while additional reasons for the observed stiffness are being looked for. It is noticeable that samples based on lamellar morphology have advantages over the more usual high modulus material of purely fibrous nature as obtained along more conventional routes. The issue of modulus apart, the lamellae of tapering thickness in our samples (the morphological feature meeting requirement 6) imply the presence of folds of unprecedently short stem lengths which raise new issues in crystallization studies, notably relating to crystallization of chains in confined spaces, and opens up avenues towards the visualization of space filling by lamellae in bulk samples in general.     

Zur struktur von schlauchfolien aus polyäthylen

The crystal orientation and the morphology of a tubular extruded LDPE film and two HDPE films, each of different molecular weight and different blow ratio, were investigated by means of small- and wide-angle X-ray techniques and, after staining, by electron microscopy. Only by combining these methods the structure of the films can be described in detail. In the LDPE film the orientation of the a-axis parallel to the machine direction is dominant. The morphology is more complicated than is usually supposed from X-ray measurements. The lamellae show a variety of orientations. The periodicity of the lamellae is more strongly marked in the machine direction than in all other directions. The morphology of one of the HDPE films consists of biaxially oriented stacked lamellae, their normals preponderantly lying in the plane of the film.In the other HDPE film the normals of the lamellae lie in the film plane, too, but they are oriented preponderantly in the machine direction. The distribution of the crystal orientations as determined from the pole figures corresponds to the electron microscopie results. An essential part of the morphology determining the mechanical properties of the film are the shish-kebabs. They form in the strained melt. The observed greater X-ray periods and radial intensity bridges in the small-angle region of the HDPE-films are due to greater periods along thc shish-kebabs.     

Flow induced crystallization in isotactic polypropylene during and after flow

Using a unique slit flow device and in situ synchrotron X-ray methods, the entire evolution of flow induced crystallization in isotactic polypropylene (iPP) was studied from the start-up of flow up to completion of crystallization. Two WAXD detectors, including the ultrafast Pilatus and the two-dimensional Frelon, were combined to achieve a sufficient time resolution for a fairly short period (during and just after flow) and a sufficient spatial resolution for measuring the kinetics of different crystallites oriented in different directions. The complete evolution of these structures is obtained and this reveals several important issues on crystallization. Firstly, the appearance of crystallites can occur already within a short flow duration of maximum 0.25 s. The specific formation time strongly depends on the flow strength. The formation of crystallites just after flow can be distinguished from that occurring during flow, although both happen on the sub-second time scale. Next, we quantified the subsequent appearance of iPP daughter lamellae and determine the time dependent ratio between parent and daughter lamellae as a function of the flow strength. The average orientation of the initial shish is relatively high while the orientation of parent lamellae decreases with their lateral growth. Finally, at the experimental temperature of 145 °C and depending on the shear strength, iPP β-phase can be induced. The quantitative information provided by this data set is well suited for validation and extension of our models for flow induced crystallization of polymers. Such complete data sets, including the fully specified initial and boundary conditions are not available yet for the (nearly) processing conditions as we applied in this study.     

Plastic deformation of oriented lamellae: 1. Cold rolling of β-phase isotactic polypropylene

Isotactic polypropylene was crystallized by the oriented growth method and the oriented β-phase obtained. This has unidirectional lamellar orientation with the lamellar long axis parallel to the growth direction, the lamellae being twisted along this direction. The sample plates were cold-rolled in three orthogonal directions, and the deformation behaviour of each case was investigated chiefly by wide-angle and small-angle X-ray diffraction methods. It was revealed that deformation takes place by a different mechanism in each case, including rotation of lamellae, interlamellar slip, chain-directional and transversal chain slip. These results are discussed in connection with the anisotropic structure of these samples due to the lamellar orientation.When the β-phase samples are rolled, α-phase crystals appear with c-axis orientation and the proportion increases with draw ratio. For crystallographic reasons it is concluded in this case that by stretching the c-axis orientation is brought about not through block formation of the original β-phase lamellae and incorporation of these blocks into microfibrils, but by melting or unfolding of the original β-phase lamellae and recrystallization to the c-axis-oriented new α-phase.     

Orientation distribution of solids in continuous solid-liquid flow in a vertical tube

During continuous flow of solid-liquid mixtures, the solids may be oriented in a variety of directions relative to the flow axis. The character of the distribution takes on particular importance when materials are processed using electric fields. In this study, solids orientation distributions in continuous, vertical upflow was investigated experimentally combining particle tracking velocimetry. Cylindrical solids showed a more pronounced tendency than cubes to align along the flow direction; this tendency was even greater for elongated cylindrical objects. Solids orientation is influenced by the principal orienting factor (shear flow) and the randomizing factor (orientations of other solids in the mixture). Increasing flow rate tends to drag objects towards their equilibrium (aligned orientation) until they are restricted from further rotation by the presence of other solids. Orientations of cubes were more widely distributed than cylinders, without sharp peaks. The orienting effects of flow rate were also observed for cubes. High solids concentration and larger solids tend to restrict rotation, thus the initial distribution may be maintained through the flow length.     

Cleavage resistance of plastically deformed natural diamonds revealed by dissolved planar features

We describe here diamonds with planar segments of limited lateral extension, some of which have dissolved to form flat etch channels. We have documented such features only in diamonds which show otherwise lamellae of brown or pink color due to plastic deformation along (111) planes, called “colored graining lamellae”. The planar segments are identified as cleavage segments. We suggest that the extension of the etch channels is controlled by the geometry of the pre-existing cleavage segments, as dissolution happens preferentially at sites offering a high available surface. These cleavage segments (indifferently dissolved as flat etch channels or not) are laterally limited by colored graining lamellae along another set of (111) planes. This indicates that plastically deformed diamond is “cleavage resistant”. Further, it reveals that plastic deformation may induce different types of defects–either cleavage or colored graining lamellae–along different sets of octahedral planes in the same crystal.     

Crystallization from a strained melt or solution

The elongation and orientation of randomly coiled macromolecules in a strained melt or solution reduces their entropy and thus increases the crystallization or melting temperature of the ideal lattice. At any given temperature of experiment this enhances nucleation and crystal growth rate. As a rule, linear primary nuclei are formed. They contain more or less extended chains. The existence of row nuclei reduces the local gradient in the liquid to such an extent that further crystallization proceeds by epitaxial overgrowth of folded chain lamellae. Densely packed cylindrites are formed with the ribbon-like lamellae radiating from the central row nucleus. The irregular shish-kebab structure observed in stirred or sonicated solutions seems to be formed by subsequent exial deformation of cylindrites in the flow field. It displaces the lamellae irregularly and thus produces a great many microfibrillar elements parallel to the original row nuclei. The almost completely extended chains in the shish yield a high elastic modulus and tensile strength for exial loading. The shish-kebab morphology in fibers as spun does not affect to a great extent the mechanical properties obtainable by subsequent drawing. The lamellae are transformed into microfibrils in very much the same manner as in spherulitic samples. But the highly regular orientation of lamellae seems to result in a more uniform drawing and hence a stronger fiber. In an extremely high temperature and pressure gradient, the melt extrusion produces hard elastomers where the lamellae of the cylindrites seem to be locally stapled. Upon application of tensile load in the extrusion direction, the intervening sections bend like beams, thus forming thin holes extending in the direction perpendicular to the load. The holes enormously enhance the permeability for gases and liquids. The elastic bending of lamellae yields the high recoverable strain and low tensile modulus.     

Forced assembly by multilayer coextrusion to create oriented graphene reinforced polymer nanocomposites

A potential advantage of platelet-like nanofillers as nanocomposite reinforcements is the possibility of achieving two-dimensional stiffening through planar orientation of the platelets. The ability to achieve improved properties through in-plane orientation of the platelets is a challenge and, here, we present the first results of using forced assembly to orient graphene nanoplatelets in poly(methyl methacrylate)/polystyrene (PMMA/PS) and PMMA/PMMA multilayer films produced through multilayer coextrusion. The films exhibited a multilayer structure made of alternating layers of polymer and polymer containing graphene as evidenced by electron microscopy. Significant single layer reinforcement of 118% at a concentration of 2 wt % graphene was achieved—higher than previously reported reinforcement for randomly dispersed graphene. The large reinforcement is attributed to the planar orientation of the graphene in the individual polymer layers. Anisotropy of the stiffening was also observed and attributed to imperfect planar orientation of the graphene lateral to the extrusion flow.     

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.     

Effect of aspect ratio and fluid elasticity on chain orientation in isothermal film casting process

The characteristics of extensional flow and the chain orientations of the isothermal film casting process utilizing a two-dimensional (2-D) viscoelastic model with finite element methods (FEM) were studied. Steady state and transient solutions were obtained for a relatively large aspect ratio regime by employing successive iterative schemes. In this work, higher aspect ratios of the equipment caused highly oriented molecular structures because the aspect ratio increases as the flow changes from planar to uniaxial extensional flow. Fluid viscoelasticity always alleviated the neckin phenomenon and led to the planar extension regime even if dichotomous behavior was observed for draw resonance in extensional thickening and thinning fluids. Consequently, the change in the characteristic of extensional deformation from uniaxial deformation to the planar extension deteriorated the molecular orientation.     

Enhancing mechanical performance of polylactide by tailoring crystal morphology and lamellae orientation with the aid of nucleating agent

The performance of semicrystalline polymers is significantly dependent on the crystal morphology and lamellae orientation. In this work, the crystal superstructure and mechanical properties of polylactide (PLA) with different amounts of nucleating agent (tetramethylene-dicarboxylic dibenzoyl-hydrazide, TMC-306) were investigated. It was found that TMC-306 can be dissolved in PLA melt and re-crystallize into fibrils upon cooling. These fibrils can serve as nucleation templates to induce the crystallization of PLA on their surface, resulting in a large enhancement in crystallization rate. More importantly, PLA lamellae can grow perpendicular to the long axis of TMC-306 fibrils, inducing the formation of shish-calabash, shish-kebab and needle-like structures, depending on the concentration of TMC-306 used. Taking advantage of shear flow experienced in injection molding, TMC-306 fibrils tend to align in PLA melt along the shear flow direction, inducing the formation of highly orientated PLA lamellae in injection-molded articles. In this way, a simultaneous improvement in impact toughness, tensile strength and elongation at break is achieved. This work provides a good example of using a fibrous nucleating agent as a template to tailor the crystal morphology and lamellae orientation, thus achieving greatly enhanced properties for PLA.     

Higher-order structural analysis of bacterial poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanote] highly oriented films

Bacterial poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] (PHBH) highly oriented films were prepared by the combination of roll and uniaxial drawing processes. The change in the higher-order structure of PHBH films was investigated by wide-angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). Extended films, which show superior mechanical properties and high ductility, have complicated structures. By roll extension, both deformed and undeformed spherulites co-exist, the former inclined to the direction perpendicular to the film surface. The latter were destroyed by further uniaxial extension. The tie-molecules between uniaxially oriented lamellae were extended and transformed to the β-form with a planar zig-zag conformation. Three kinds of structures, c-axis parallel to the uniaxial drawing direction, c-axis inclining to the normal vector of the film surface, and the β-form between lamellae, are intermingled in the film.     

Biaxial deformation of polyamide‐6: Assessment of orientation by means of infrared trichroism

Infrared spectroscopy was used to study the evolution of structure in films of polyamide‐6 drawn on a Cellier tenter frame laboratory tester under conditions of simultaneous equibiaxial stretching and planar uniaxial stretching. The “tilted film” method was used to obtain trichroic spectra corresponding to the machine, transverse, and normal directions, as well the “structural factor” spectrum. From these it was possible to obtain information on the molecular orientation and the evolution of the crystalline structure. The starting films, prepared by melt casting from an extruder on a chilled roll, contained predominantly the mesomorphic β form. The structural factor spectra confirmed that strain‐induced transformation into the α form occurred upon drawing, and that the amount of α form increased with the extent of drawing. The trichroic spectra showed that the molecular orientation was localized mainly, but not exclusively, in the α form. Orientation functions could be determined for both the molecular chain axis and the normal to the hydrogen‐bonded sheets. For both the equibiaxial and planar uniaxial films, these sheets were found to be strongly oriented parallel to the plane of the film, with the degree of orientation increasing with overall draw ratio. For the biaxial samples, the molecular chain orientation was found to be equibiaxial, as expected. Mechanical test results indicated that the chains are evenly distributed in the film plane rather than showing a preference for the two orthogonal draw directions. For the planar uniaxial samples, the chain orientation was predominantly in the draw direction, but some degree of orientation in the transverse direction was also observed. The variation of orientation functions with draw ratio suggested that the α structure evolves in two stages, the first involving chain orientation in the draw direction and the second involving rotation of the sheets into the plane of the film.     

Simulation of planar welding flows: Part 2. Strain history,stress calculation,and experimental comparison

A numerical method is described for calculating the stress a viscoelastic melt exhibits in a flow, based on approximate kinematics. The method assumes that the kinematics are reasonably close to those of a shear-thinning fluid such as the Carreau model. The strain history of a given flow and the resulting stress are calculated via a tracking method from finite element kinematics. Fullfield flow birefringence experiments were done for lowdensity polyethylene and polystyrene flowing past a thin plate divider in a 1.254-mm planar slit die. By digitally analyzing birefringence photographs of the flow field, the birefringence was measured over two dimensions. These birefringence results are in good agreement with birefringence fields calculated from the numerical simulations and the stress-optical law. The flow fields were most highly oriented in a region surrounding the weld interface just downstream of the plate divider. This orientation relaxed farther downstream, with polystyrene relaxing faster than low-density polyethylene.     

Structural characterization of Celgard® microporous membrane precursors: Melt-extruded polyethylene films

“Row nucleated lamellar” structures are formed when highly crystalline polymers are melt-extruded and recrystallized under high stress. Polyethylene (PE) and polypropylene (PP) films with row lamellar structures have been utilized to produce microporous membranes. Birefringence measurements of melt-extruded PE films show that improved film orientation can be achieved by annealing, extruding at higher speed, and using higher molecular weight polymers. Images from scanning tunneling, atomic force, and field emission scanning electron microscopy (STM, AFM, and FESEM) clearly show the lamellar structures in the melt-extruded PE and PP films. Microscopy results also show that surface lamellar textures are more pronounced with thicker lamellae and are better aligned along the extrusion direction after annealing. X-ray diffraction results show that the increase in film orientation can be attributed to increased lamellar perfection and orientation during annealing and also to better crystallite alignment along the machine direction with higher extrusion speed or with higher molecular weight. High-resolution capabilities of STM, AFM, and FESEM prove to be very effective tools in elucidating lamellar structures in polymeric membrane precursors and can be used as an aid in establishing structure–process–property relationships in making microporous membranes. © 1994 John Wiley & Sons, Inc.     

The birefringence and anisotropic planar shrinkage of polycarbonate/organoclay injection moldings

The main objective of the present work was the study of the effect of organoclay on planar shrinkage anisotropy of polymeric injection‐molded products by means of a rheological technique, in conjunction with birefringence measurements, performed on polycarbonate/organoclay samples. Polarized optical microscopy at elevated temperatures revealed that the birefringence due to the ordered‐silicate layers had a negative contribution to the overall birefringence of the samples. The maximum value of the calculated‐order parameter based on these results was found to be near unity, indicating an appreciable degree of flow alignment for the silicate layers. Different states of silicate layer orientation, with some layers aligned parallel to the in‐plane direction at the skin layer or partially tilted from the planar direction at the core region, were observed through the optical analysis along the thickness direction. The anisotropic shrinkage measurements showed that organoclay reduced both in‐flow and cross‐flow shrinkages, resulting in a low extent of planar shrinkage anisotropy. This can be attributed to the flow alignment of clay particles closely parallel to the in‐plane direction. Prolonged relaxation of the flow‐induced molecular orientation combined with faster solidification were also found to play an appreciable role in the decreased shrinkage anisotropy. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Influence of shear processing on morphology orientation and mechanical properties of styrene butadiene triblock copolymers

The influence of ram extrusion on structure and mechanical properties of a triblock copolymer consisting of polystyrene (S) outer blocks and poly(styrene–stat–butadiene) (S/B) middle block is studied for a wide range of shear rates. Structural features on the mesoscale (10–100 nm) are investigated by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Transition Moment Orientation Analysis (TMOA) is applied to quantify the orientation on the molecular (segmental) scale (<1 nm). All extruded samples microphase-separate and show a lamellar morphology with periodicities of about 33 nm. Significant orientation is observed on the mesoscale where the surface normals of the lamellae are preferentially perpendicular to the extrusion direction. The corresponding degree of orientation drops slightly at elevated shear rates of about 600 s⁻¹. Interestingly, Chevron-like pattern with two preferred orientations of the lamellae are observed in cross-sections probably due to shear velocity gradients in the rectangular die. In contrast, significant orientation on the molecular scale is absent for styrene and butadiene units indicating basically random orientation of the chain segments. The mechanical properties are, however, strongly anisotropic. Uniaxial tensile tests performed parallel and perpendicular to the extrusion direction reveal higher E_∥ moduli (1.1 – 0.6 GPa) along with yielding but significantly smaller E_⊥ moduli (100−250 MPa) without pronounced yielding. Main trends in both moduli, E_∥ and E_⊥, can be explained based on mesoscale orientation using the analytical composite model. In general, the results demonstrate that orientation effects on the mesoscale have a strong influence on the mechanical properties and must be considered during the optimization of extruded or injection-molded components made from microphase-separated block polymers.     

Anisotropic shrinkage of injection-molded rubber

The anisotropic characteristics of injection-molded flat rubber sheets were investigated. The shrinkage and mechanical properties were measured in two directions: parallel and perpendicular to the flow direction. The results showed that (1) the shrinkage in the parallel direction is larger than that in the perpendicular direction, (2) such anisotropic shrinkage increases with the increase of vulcanization temperature and flow distance, (3) similar anisotropy was also noticed in 300% modulus, tensile strength, and elongation. Two kinds of orientation, “shear orientation” and “expanded orientation,” were observed. The former occurs by plug flow, and the latter by the expansion of the materials. The shrinkage was independent of the expanded orientation but was strongly associated with the shear orientation, while the mechanical properties were affected by the expanded orientation.