Comparison of structure development in injection molding of isotactic and syndiotactic polypropylenes

A comparative study of the crystallization and orientation development in injection molding isotactic and syndiotactic polypropylenes was made. The injection molded samples were characterized using wide angle X‐ray diffraction (WAXD) techniques and birefringence. The injection molded isotactic polypropylene samples formed well‐defined sublayers (skin, shear and core zones) and exhibited polymorphic crystal structures of the monoclinic α‐form and the hexagonal β‐form. Considerable amounts of β‐form crystal were formed in the shear and core zones, depending on the injection pressure or on the packing pressure. The isotactic polypropylene samples had relatively high frozen‐in orientations in the skin layer and the shear zone. The injection molded syndiotactic polypropylene exhibited the disordered Form I structure, but it did not appear to crystallize during the mold‐filling stage because of its slow crystallization rate and to develop a distinct shear zone. The core zone orientation was greatly increased by application of high packing pressure. The isotactic polypropylene samples exhibited much higher birefringence than the syndiotactic polypropylene samples at the skin and shear layers, whereas both materials exhibited similar levels of crystalline orientation in these layers.     

Polarized internal reflectance spectroscopic studies of oriented poly(ethylene terephthalate)

Polarized internal reflectance spectroscopy (IRS) has been used to evaluate molecular orientation and crystallinity of poly(ethylene terephthalate) film surfaces. Measurements were taken using samples stretched in both uniaxial and biaxial modes. All bands of interest were normalized with a reference band near 1410 cm^?1, resulting from phenylene ring vibrations. Normalization was performed in order to overcome problems with sample contact and effective thickness. Results obtained using bands representing trans and gauche rotational isomers, present, respectively, at 1340 and 1370 cm^?1, have been related to data acquired using density and birefringence techniques. The polarized IRS technique discussed is well suited for investigations of polymer orientation and crystallinity, since it avoids limitations related to sample thickness and clarity imposed by polarized transmission infrared spectroscopy. Parameters such as orientation functions, attenuation indices, dichroic ratios, and structural factors have been determined from data collected in each of the three spatial directions. Results are correlated with corresponding density, birefringence, and refractive index values and are found to give good agreement with these methods. © 1994 John Wiley & Sons, Inc.     

Molecular orientation of polydimethylsiloxane induced by elongational and shearing strains

A study examining the molecular orientation of poly(dimethylsiloxane) for different combinations of elongational and shear strains is presented. Three different cases were studied: (1) pure elongational strain; (2) increasing shear and decreasing elongational strains; (3) increasing shear and increasing elongational strains. The experiments were performed in a converging flow cell (at room temperature), where elongational and shearing strain rates achieved values of 370 s^?1 and 640 s^?1 respectively. Values of the Hermans orientation function were obtained from measurements of birefringence and polarization angles while strain rates were estimated from laser Doppler anemometry velocity measurements. Prospects for predicting molecular orientation from the stress-optical laws and rheological flow models are outlined and commented on.     

Melt viscosity and flow birefringence of polycarbonate

Melt viscosity and flow birefringence of bisphenol A-type polycarbonate were measured and analyzed by the application of rubber-like photoelastic theory. The melt viscosity in the Newtonian flow region increased with the molecular weight to the power of 3.4. In polycarbonate, the shear stress of the Newtonian flow region was to 10⁶ dyn/cm², whereas in PMMA it was at most 3 = 10⁵ dyn/cm². The flow birefringence δn has a linear relation with shear stress S, that is δn = 5.7 × 10^?10 S. The principal polarization difference of flow unit α₁ – α₂ was 1.62 × 10^?23 cm³, which was obtained by the application of the rubber-like elastic theory. In PMMA, it was 3.9 = 10^?25 cm³; about 1/40 of that was polycarbonate. The anisotropy of polarizability of the flow unit of polycarbonate was also about 40 times larger than that of PMMA. So the anisotropy reflected the large flow birefringence of the polycarbonate.     

A study of molecular orientation in one-way drawn poly(ethylene terephthalate) films by means of polarized infra-red spectroscopy and birefringence measurements

Summary Polarized infrared spectroscopy and birefringence measurements have been used to study the changes in molecular orientation which occur on homogeneous hot (T=80°C) and cold (T=20°C) drawing of poly(ethylene terephthalate) (PET) sheets. Excellent agreement was obtained between the infrared orientation functions for absorption bands associated with 1507 cm^–1, 1580 cm^–1 and 1615 cm^–1, C-C stretching mode of the benzene ring, and average orientation functions obtained from optical birefringence. It was confirmed that the Gauche conformer of the ethylene glycol residue in the amorphous phase could be oriented perpendicularly to the draw direction (_p<4). The development of molecular orientation along the specimen axis in the necked sample confirms the entangled nature of the polymer chains in which the natural draw-ratio corresponds to the response of a network stretched up to its maximum of extensibility.     

Shear dependence of thermal conductivity in polyethylene melts

Thermal conductivity measurements with a modified Couette flow cell were obtained as a function of shear rate for two linear polyethylene melts of weight-average molecular weights 27,300 and 56,700, respectively. The lower-molecular-weight polyethylene revealed a maximum decrease in thermal conductivity of 55 percent at 150 s^?1. After shearing at 400 s^?1, approximately 90 minutes was required to recover the value corresponding to the zero shear condition. This was considered consistent with molecular orientation into the flow direction during shear with a subsequent relaxation upon the removal of stress. The higher-molecular-weight polyethylene gave a similar decrease in thermal conductivity at 50 s^?1. Unlike the lower-molecular-weight melt, an increase was observed at higher shear rates. Enhancement of energy transport via cluster flow mechanism was presented as a possible interpretation of these results. A theory of molecular orientation of liquid poly(dimethylsiloxane) (PDMS) under shear flow was previously developed from thermal conductivity and birefringence data of this material. An attempt to clarify the difference in behavior between the two melts examined in this work, and between the polyethylene melts and the PDMS previously studied is presented.     

Molecular orientation in injection molding

A semiquantitative model is proposed to explain the complex molecular orientation distribution, observed in injection moldings of amorphous polymers. The model incorporates flow and heat transfer mechanisms coupled with molecular theories. The orientation in the surface skin is related to steady elongational flow in the advancing front, whereas the orientation in the core is related to the shear flow, behind the front, between two solidyfying layers. Coupled with the elongational and shear-induced orientations, a molecular relaxation process takes place which is determined by the rate of heat transfer. The bead-and-spring macromolecular theory was used to calculate root mean end-to-end distances of macromolecules in the various flow fields, as well as the relaxation process.     

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     

Characterisation and properties of oriented PVC fibres

Drawn PVC fibres were investigated using birefringence, DSC and TMA techniques, and their tenacity was measured. An increase in fibre draw ratio (DR) for heat set samples produced an increase in tenacity, birefringence and X-ray intensity. The linearity of a tenacity/birefringence plot suggested that tenacity was a good indicator of molecular orientation. An ‘undrawn’ filament was substantially amorphous. Drawing without heat setting produced little three dimensional order, and samples relaxed readily on heating. X-ray results for heat set fibres suggested both an increase in the amount of crystallinity, and in crystallite alignment. After heat setting, a minor DSC endotherm was produced; the onset of this endotherm corresponded to the heat setting temperature, as did the onset of shrinkage measured by TMA. For samples with a DR>1.5, maximum shrinkage measured by TMA corresponded to complete elastic recovery.     

Melt flow and fiber properties of copolyesters

The effect of modifying monomer [sodium 3,5-di(carbonethoxy)benzene sulfonate] contents range from 1.5 to 4.5 mol % on the melt flow and fiber properties of copolyesters (COPET) dyeable with basic dyes was investigated. An Instron capillary rheometer was used to obtain data over shear rates ranging from 10 to 10⁴ s^?1 at 265, 275, and 285°C. The COPET's flow properties as a function of temperature, inherent viscosity, melting point, and modifying monomer content were determined. The drawn fibers annealed in oil and air at 80, 110, 130, 150, 175, and 200°C were studied by means of measurements of shrinkage ratio, crystallinity, birefringence, long period, sonic rate, and static state flexibility of molecular chain. All these showed that the large side group, ? SO₃Na in COPET molecular chains causes an increase in chain rigidity and melt viscosity, and a decrease in crystallinity and orientation.     

Evaluation of molecular orientation in injection molded parts with microscale features by Raman spectroscopy

Molecular orientation of polycarbonate (PC) in injection‐molded parts with microscale features was characterized by means of polarized Raman spectroscopy, and the relationship between microstructure and replication was discussed. The microscale feature size of continuous v‐groove was 20 μm in depth and 50 μm in width. PC injection‐molded parts were molded with various molding conditions. The molecular orientation distribution along flow direction on the cross‐section of molding parts were evaluated by the intensity ratio of the bands at 635 to 703 cm^?1 (I₆₃₅/I₇₀₃) in the Raman spectra. Molecular orientation along the flow direction inside the v‐groove was higher than that of the core and the opposite surface region. In particular, the highest molecular orientation was at the surface of the v‐groove. Among the injection molding conditions, the mold temperature showed significant effect on the molecular orientation and replication. Higher mold temperature caused high replication and low molecular orientation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Analysis of molecular orientation and internal stresses in extruded plastic sheets

The development of molecular orientation and internal stresses in extruded sheet made of polypropylene was analyzed, and their correlations to operating conditions such as draw ratio, cooling rate, die temperature, melt temperature, and die gap opening were studied. Measurements of attenuated-total-reflectance infrared dichroic ratio for the surface molecular orientation, birefringence for the orientation stress distribution in the thickness direction, and free shrinkage ratio for the overall frozen-in stresses were carried out to determine the amount of orientation stresses in the extruded samples. As expected, the overall orientation stress depends strongly on draw ratio, while higher melt temperature reduces the overall orientation. It was found that faster cooling rates and lower die temperatures cause surface orientation stresses to increase as the core orientation stresses remain almost unchanged.     

Effects of drawing conditions on the properties of optical fibers made from polystyrene and poly(methyl methacrylate)

Monofilaments possessing various degrees of birefringence were obtained by changing the drawing rate, the molten polymer temperature, and the molecular weight of polystyrene (PS) and poly(methyl methacrylate) (PMMA). The “brittle-toductile” transition point of optically pure PS was found in the range of birefringences of ?0.6 · 10^?3 to ?2.6 · 10^?3. Both the height and position of this point are influenced by M?_w, molecular weight distribution, and polymer melt temperature. The birefringence of PS is higher by two orders of magnitude than that of PMMA in which this transition point has not been observed. The mechanical and optical properties depend not only on the average amount of orientation characterized by the birefringence but on what portion of the relaxation spectrum of the polymer is preferentially oriented. During the drawing of PS and PMMA monofilaments crazes are formed in the centre of the fibers and do not reach the surface.     

Studying deformation behavior of a single spherulite with in-situ infrared microspectroscopic imaging

The deformation behavior of a single spherulite embedded in quenched isotactic polypropylene (iPP) film is studied with in-situ infrared microspectroscopic imaging (FTIRI) with Focal Plane Array (FPA) detector during uniaxial tensile test. Imaging an area of 250 × 250 μm² with 4096 Fourier transform infrared (FTIR) spectra, the absorption distributions of crystalline (998 cm^?1 band) and amorphous (1153 cm^?1 band) phases with radiation polarized parallel and perpendicular to tensile direction are obtained, which are employed to construct the orientation distribution images at different strains. The daughter lamellae in equatorial region are slightly rotated first toward tensile direction, which may postpone the sliding deformation of parent lamellae. The orientation evolution of crystal during tensile deformation suggests that a single spherulite can be divided into three different mechanical zones, corresponding with the crystallinity distribution at different regions of spherulite as estimated through the ratio of 998 cm^?1 to the summation of 998 cm^?1 and 1153 cm^?1. The results may provide a more realistically mechanical model for computer simulation and demonstrate the advantages of FTIRI on the study of structure-property of polymers.     

Intrinsic birefringence of amorphous poly(bisphenol-A carbonate)

The birefringence of uniaxially oriented poly(bisphenol-A carbonate) (PC) samples stretched over a wide range of temperatures has been measured accurately with a combination of the compensator and the wedge methods. The Hermans' orientation function of anisotropic PC was calculated from the measured dichroic ratio of the infrared absorption band at 1364 cm^-1. Measurements using differential scanning calorimetry, X-ray diffraction, or infrared spectroscopy indicated no stress-induced crystallinity in stretched amorphous PC. At each state having a defined molecular orientation, samples stretched below the glass transition temperature (T_g) always exhibited excess birefringence and slightly higher density. This phenomenon is attributed to bond distortion during stretching, a result of the suppression of large-scale segmental motions of polymer chains below the T_g. The birefringence of samples stretched above the T_g arises exclusively from the orientation effect as a result of greater chain mobility. These measured birefringence values are proportional to Hermans' orientation functions, yielding a linear relationship which allows precise determination of the intrinsic birefringence of amorphous PC as 0.192 ± 0.006.     

Fracture and Orientation of Long-Glass-Fiber-Reinforced Polypropylene During Injection Molding

Injection processing parameters directly influence the final fiber length and may have a negative effect on the mechanical properties of a part. The aim of the work is to investigate and quantify the effects of the injection rate (2/10/50 cm³/s) on the fiber length, the distribution, and orientation during injection molding and the mechanical properties of long-glass-fiber-reinforced polypropylene (LGF/PP) by experimental and simulated methods. When the injection rate increases from 2 to 10 cm³/s, the fiber length sharply decreases from the original 11 mm to 3.43 mm at the nozzle and 1.30 mm at the filling end, and almost 88% of the fibers are less than 3 mm when the injection rate is 50 cm³/s. A distinct hierarchical orientation (skin-shear-core) for the fiber distribution in the thickness is obtained via a metallographic microscope, which shows that the shear layer (here the shear stress is larger and the fiber is more inclined to oriented along the flow direction) decreases with increasing injection rate. Moreover, the numerical results of the residual fiber length and orientation at different injection rates are in accord with the trend of the measured results. POLYM. ENG. SCI., 60:13–21, 2020. © 2019 Society of Plastics Engineers     

Morphology and thermal expansion in large HDPE injection moldings

Morphology and linear coefficients of thermal expansion (LCTE) within the wall of a large (10 kg) injection molded container were evaluated. The study employed polarized light microscopic birefringence techniques, differential scanning calorimetry, scanning electron microscopy (SEM), as well as thermal mechanical analysis to determine the LCTE anisotropy in the skin and core of the wall. A difference in crystallinity between skin and core was found, and a region with distinct lamellas was seen under SEM without sample etching. A large variability in anisotropy of the LCTE was found in the relatively thick (~700 μm) skin of the molding. The LCTE differences between skin and core were attributed to molecular orientation related to resin flow. LCTE anisotropy as an important source of residual stress in the transition zone between skin and core was confirmed by fractographic analysis. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47507.     

High temperature zone‐drawing of nylon 66 microfiber prepared by CO2 laser‐thinning

A high temperature zone‐drawing method was applied to a nylon 66 microfiber, obtained by using CO₂ laser‐thinning, to develop its mechanical properties. The microfiber used for the high temperature zone‐drawing was prepared by winding at 150 m min^?1 the microfiber obtained by irradiating the laser at 4.0 W cm^?2 to an original fiber with a diameter of 50 μm, and had a diameter of 9.6 μm and a birefringence of 0.019. The high temperature zone‐drawing was carried out in two steps; the first drawing was carried out at a temperature of 230°C at supplying and winding speeds of 0.266 and 0.797 m min^?1, the second at 250°C at supplying and winding speeds of 0.266 and 0.425 m min^?1, respectively. The diameter of the microfiber decreased, and its birefringence increased stepwise with the processing. The high temperature zone‐drawn microfiber finally obtained had a diameter of 4.2 μm, a birefringence of 0.079, total draw ratio of 4.8, tensile modulus of 12 GPa, and tensile strength of 1.0 GPa. The wide‐angle X‐ray diffraction photograph of the drawn microfiber showed the existence of highly oriented crystallites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 42–47, 2006     

The influence of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers

An investigation was carried out on the effects of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers annealed in an air heated environment at temperatures ranging from 60 to 140°C. Analysis of the equatorial X‐ray diffraction traces showed the presence of a three phase system of amorphous‐smectic‐monoclinic forms and revealed the transformation of the metastable smectic form to the highly stable monoclinic form as the annealing temperature is increased, resulting in an enhanced degree of crystallinity and the crystallite size. The improvements in the degree of crystallinity and the crystallite size became more remarkable above 120°C. Evaluation of the crystallinity was carried out using an analysis of density, infrared spectroscopy, and X‐ray diffraction methods whereas the state of the molecular orientation was evaluated using polarized infrared spectroscopy measurements only. Polarized infra‐red spectroscopy measurements after the curve fitting procedure showed a slight increase of the molecular orientation of the helical chain segments present in the crystalline phase represented by the IR bands at 841 and 998 cm^?1 whereas the amorphous structure represented by the IR band at 974 cm^?1 showed no significant change with increasing annealing temperature. The improvement in the molecular orientation of the crystalline phase became more remarkable above 120°C. Tensile strength of the annealed fibers increased with increasing annealing temperature but the elongation at break and the initial modulus were not affected as much as the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

The solids concentration distribution in the deep cone thickener: A pilot scale test

Cemented backfill or surface deposition of paste tailings is increasingly being considered as a simple and effective means of reducing the hazards of conventional slurry deposition and recovering water for recycle. Although gravity thickening has been widely used in the mineral industry to increase the solids concentration of tailings, the accurate prediction of the concentration distribution in three-dimensions and discontinuous operational state has proven to be difficult. We investigated the axial and radial solids concentration distribution at discontinuous state in a pilot deep cone thickener as a function of bed height and residence time. The feed flux of lead/zinc tailings was 0.254 t·h^?1· m^?2 with a flocculant (high molecular weight anionic polyacrylamide) dose of 20 g/t. The thickened solids bed was sheared by a rotating rake at a rate of 0.2 rpm. The underflow was recirculated at a flux of 0.5 t·h^?1·m^?2, which can introduce additional shear stresses into the bed. The results of the bed density profile showed that, beside the clarification zone, the area below the feedwell could be divided into four zones: the dilution zone caused by free settling and diffusing action, the hindered settling zone in which the concentration was lower than the gel point, the unraked bed zone with a large concentration gradient and, finally, the raking zone with the highest slurry concentration and lower concentration gradient.