Relating scratch resistance to injection molding‐induced morphology of polypropylene

The relationship between the scratch resistance and the injection molding‐induced morphology of polypropylene (PP) was investigated. The crystal structure near the surface was controlled by the mold temperature and the doping of a nucleating agent (NA). Although α‐ and β‐NA were used to improve the scratch resistance of PP that was molded at a mold temperature of 40°C, both of the NAs only slightly affected the scratch resistance due to low crystallinity at the surface. When the mold temperature was increased, the skin layer became thin and a β‐form crystal formed. Plastic deformation under the scratch was limited in the frozen layer. Consequently, the thickness of the frozen layer (which had low crystallinity) had the predominant effect on the scratch resistance in comparison to the polymorphism differences. The crystal morphology was analyzed with synchrotron micro‐beam wide angle X‐ray diffraction and Fourier transform infrared spectroscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Theoretical and experimental studies of anisotropic shrinkage in injection moldings of various polyesters

A novel approach to predict anisotropic shrinkage of slow crystallizing polymers in injection moldings was proposed, using the flow‐induced crystallization, frozen‐in molecular orientation, elastic recovery, and PVT equation of state. In the present study, three different polyesters, polyethylene terephthalate, polybutylene terephthalate, and polyethylene‐2,6‐naphthalate (PEN), are used. The anisotropic thermal expansion and compressibility affected by the frozen‐in orientation function and the elastic recovery that was not frozen during moldings were introduced to obtain the in‐plane anisotropic shrinkages. The frozen‐in orientation function was calculated from the amorphous contribution based on the frozen‐in and intrinsic amorphous birefringence and crystalline contribution based on the crystalline orientation function determined from the elastic recovery and intrinsic crystalline birefringence. To model the elastic recovery and frozen‐in stresses related to birefringence during molding process, a nonlinear viscoelastic constitutive equation was used with the temperature‐dependent viscosity and relaxation time. Occurrence of the flow‐induced crystallization was introduced through the elevation of melting temperature affected by entropy production during flow of the viscoelastic melt. Kinetics of the crystallization was modeled using Nakamura and Hoffman‐Lauritzen equations with the rate constant affected by the elevated melting temperature. Numerous injection molding runs were carried out by varying the packing time, packing pressure, flow rate, melt and mold temperature, and anisotropic shrinkage of moldings were measured. The experimental results were compared with the simulated data and found in a fair agreement. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3526–3544, 2006     

Theoretical and experimental studies of anisotropic shrinkage in injection moldings of semicrystalline polymers

A novel approach to predict anisotropic shrinkage of semicrystalline polymers in injection moldings was proposed using flow‐induced crystallization, frozen‐in molecular orientation, elastic recovery, and PVT equation of state. The anisotropic thermal expansion and compressibility affected by the frozen‐in orientation function and the elastic recovery that was not frozen during moldings were introduced to obtain the in‐plane anisotropic shrinkages. The frozen‐in orientation function was calculated from amorphous and crystalline contributions. The amorphous contribution was based on the frozen‐in and intrinsic amorphous birefringence, whereas the crystalline contribution was based on the crystalline orientation function, which was determined from the elastic recovery and intrinsic crystalline birefringence. To model the elastic recovery and frozen‐in stresses related to birefringence during molding process, a nonlinear viscoelastic constitutive equation was used with temperature‐ and crystallinity‐dependent viscosity and relaxation time. Occurrence of the flow‐induced crystallization was introduced through the elevation of melting temperature affected by entropy production during flow of the viscoelastic melt. Kinetics of the crystallization was modeled using Nakamura and Hoffman‐Lauritzen equations with the rate constant affected by the elevated melting temperature. Numerous injection molding runs on polypropylene of various molecular weights were carried out by varying the packing time, flow rate, melt temperature, and mold temperature. The anisotropic shrinkage of the moldings was measured. Comparison of the experimental and simulated results indicated a good predictive capability of the proposed approach. POLYM. ENG. SCI., 46:712–728, 2006. © 2006 Society of Plastics Engineers     

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.     

Numerical prediction of residual stresses and birefringence in injection/compression molded center‐gated disk. Part I: Basic modeling and results for injection molding

The present study attempted to numerically predict both the flow‐induced and thermally‐induced residual stresses and birefringence in injection or injection/compression molded center‐gated disks. A numerical analysis system has been developed to simulate the entire process based on a physical modeling including a nonlinear viscoelastic fluid model, stress‐optical law, a linear viscoelastic solid model, free volume theory for density relaxation phenomena and a photoviscoelasticity and so on. Part I presents physical modeling and typical numerical analysis results of residual stresses and birefringence in the injection molded center‐gated disk. Typical distribution of thermal residual stresses indicates a tensile stress in the core and a compressive stress near the surface. However, depending on the processing condition and material properties, the residual stress sometimes becomes tensile on the surface, especially when fast cooling takes place near the mold surface, preventing the shrinkage from occurring. The birefringence distribution shows a double‐hump profile across the thickness with nonzero value at the center: the nonzero birefringence is found to be thermally induced, the outer peak due to the shear flow and subsequent stress relaxation during the filling stage and the inner peak due to the additional shear flow and stress relaxation during the packing stage. The combination of the flow‐induced and thermally‐induced birefringence makes the shape of predicted birefringence distribution quite similar to the experimental one.     

Numerical prediction of residual stresses and birefringence in injection/compression molded center‐gated disk. Part II: Effects of processing conditions

The accompanying paper, Part I, has presented the physical modeling and basic numerical analysis results of the entire injection molding process, in particular with regard to both flow‐induced and thermally‐induced residual stress and birefringence in an injection molded center‐gated disk. The present paper, Part II, investigates the effects of various processing conditions of injection/compression molding process on the residual stress and birefringence. The birefringence is significantly affected by injection melt temperature, packing pressure and packing time. However, the thermally‐induced birefringence in the core region is insignificantly affected by most of the processing conditions. On the other hand, packing pressure, packing time and mold wall temperature affect the thermally‐induced residual stress rather significantly in the shell layer, but insignificantly in the core region. The residual stress in the shell layer is usually compressive, but could be tensile if the packing time is long, packing pressure is large, and the mold temperature is low. The lateral constraint type turns out to play an important role in determining the residual stress in the shell layer. Injection/compression molding has been found to reduce flow‐induced birefringence in comparison with the conventional injection molding process. In particular, mold closing velocity and initial opening thickness for the compression stage of injection/compression molding have significant effects on the flow‐induced birefringence, but not on the thermal residual stress and the thermally‐induced birefringence.     

Evaluation of mechanical properties of adjacent flow weldline

Weldlines occur at the interface of two adjacent flows of material behind an obstructive pin in a cavity in injection molding (meldline or hot weldline). Tensile strength of such “adjacent flow weldline” in injection molded polystyrene plates was evaluated by a mechanical step‐by‐step milling technique. The strength when the milling depth was 1/5 of the thickness from each surface was about the same and independent of the distance from the pin. In contrast, the strength without milling decreased once and then increased along the flow direction. This demonstrates that the strength of a weldline is predominantly dependent on the properties of the surface layer of the weldline. The depth of the surface layer was defined as the depth of the weld, D_w. D_w reduced monotonously along the flow direction and faded away with the V‐notch, resulting in an increase of strength along the direction. On the other hand, it was considered that the farther from the pin, the flow‐induced molecular orientation in the surface layer is greater. It caused a decrease of the strength along the flow direction. The sequence of decrease and increase in tensile strength of adjacent flow weldline is due to the complex effect of these two contradictory factors. POLYM. ENG. SCI., 45:1180–1186, 2005. © 2005 Society of Plastics Engineers     

Weldline morphology of injection molded modified poly(phenylene‐oxide)/polyamide‐6 blends

The weldline morphology of modified‐poly(phenylene‐oxide)/polyamide‐6 blends has been investigated. A distinct contacting layer consisting of fine spherical particles was observed from the V‐notch at the surface to the center of the molded part for the low viscosity ratio blend. In contrast, such small particles were not found and a slight deformation was observed near the part's surface for the high viscosity ratio blend. The weldline morphology was found to be dominated by the deformation, the breakup, and the relaxation of the dispersed modified‐poly(phenyleneoxide) phase. The effect of injection conditions on the weldline morphology has also been investigated. The morphology of the meldline was quite complicated. Distorted multi‐layered structures were observed. It was found that those structures arise from the subsequent flow after merging of the two flow fronts. Weldlines and meldlines have been studied separately, and their formation mechanisms were found to be basically similar.     

Toward a viscoelastic modeling of anisotropic shrinkage in injection molding of amorphous polymers

A novel approach to predict anisotropic shrinkage of amorphous polymers in injection moldings was proposed using the PVT equation of state, frozen‐in molecular orientation, and elastic recovery that was not frozen during the process. The anisotropic thermal expansion and compressibility affected by frozen‐in molecular orientation were introduced to determine the anisotropy of the length and width shrinkages. Molecular orientation calculations were based on the frozen‐in birefringence determined from frozen‐in stresses by using the stress‐optical rule. To model frozen‐in stresses during the molding process, a nonlinear viscoelastic constitutive equation was used with the temperature‐ and pressure‐dependent relaxation time and viscosity. Contribution of elastic recovery that was not frozen during the molding process and calculated from the constitutive equation was used to determine anisotropic shrinkage. Anisotropic shrinkages in moldings were measured at various packing pressures, packing times, melt temperatures, and injection speeds. The experimental results of frozen‐in birefringence and anisotropic shrinkage were compared with the simulated data. Experimental and calculated results indicate that shrinkage is highest in the thickness direction, lowest in the width direction, and intermediate in the flow direction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2300–2313, 2005     

Preparation and properties of polyurethane‐coated talcum/polypropylene composite materials

In order to improve the toughness of polypropylene (PP) and expand its applications, a layer of polyurethane (PU) elastomer was coated on the surface of ultrafine talcum powder by an in‐situ synthesis method. In this way, an organic‐inorganic composite particle was formed. Then the surface‐treated talcum powder was mixed with melted PP to prepare PP composite materials through extrusion, granulation, and injection molding. Infrared spectral characterization and energy‐dispersive X‐ray analysis showed that there was a layer of PU elastomer on the surface of the talcum powder. Impact fracture analysis indicated that there was good compatibility between the talcum powder and the PP matrix. With the incorporation of PU elastomer coated on the surface of talcum powder, the toughness of PP was significantly improved, while the tensile strength decreased slightly. The optimum properties of the composite material were obtained when the weight fraction of talcum powder was 20% and the PU coating coverage was 25%. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Crystallization of polypropylene near the surface in injection‐molded plaques: A comparison of morphology and a numerical analysis

Skin morphology formation on injection‐molded isotactic polypropylene (PP) was investigated using micro‐beam synchrotron wide‐angle X‐ray diffraction and numerical simulation. The 1–20 μm depth range was characterized with an X‐ray beam of 0.273 μm χ 0.389 μm in size. From an evaluation of doping nucleating agents (NA) in PP, the NAs did not work at a depth of 1 μm. α‐specified NA affected crystallization within a 5‐μm depth. β‐specified PP showed α‐form crystallinity at the 5–20 μm depth. The mesomorphic crystal near the surface showed extremely high orientation. From viscoelastic flow simulation, PP molecules near the surface were oriented in the flow direction by extensional flow in the flow front, but freezing occurred faster than flow‐induced crystallization. It was estimated that the delay of crystallization occurred during the transient temperature. The deformation rate did not cause a difference in crystal morphology near the surface, but the cooling rate did. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Birefringence in injection‐compression molding of amorphous polymers: Simulation and experiment

The influence of the processing variables on the residual birefringence was analyzed for polystyrene and polycarbonate disks obtained by injection‐compression molding under various processing conditions. The processing variables studied were melt and mold temperatures, compression stroke, and switchover time. The modeling of flow‐induced residual stresses and birefringence of amorphous polymers in injection‐compression molded center‐gated disks was carried out using a numerical scheme based on a hybrid finite element/finite difference/control volume method. A nonlinear viscoelastic constitutive equation and stress‐optical rule were used to model frozen‐in flow stresses in moldings. The filling, compression, packing, and cooling stages were considered. Thermally‐induced residual birefringence was calculated using the linear viscoelastic and photoviscoelastic constitutive equations combined with the first‐order rate equation for volume relaxation and the master curves for the Young's relaxation modulus and strain‐optical coefficient functions. The residual birefringence in injection‐compression moldings was measured. The effects of various processing conditions on the measured and simulated birefringence distribution Δn and average transverse birefringence <n_rr?n_θθ> were elucidated. Comparison of the birefringence in disks manufactured by the injection molding and injection‐compression molding was made. The predicted and measured birefringence is found to be in fair agreement. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Birefringence and interface in sequential co‐injection molding of amorphous polymers: Simulation and experiment

Modelings of the interface distribution and flow‐induced residual stresses and birefringence in the sequential co‐injection molding (CIM) of a center‐gated disk were carried out using a numerical scheme based on a hybrid finite element/finite difference/control volume method. A nonlinear viscoelastic constitutive equation and stress‐optical rule were used to model the frozen‐in flow stresses in disks. The compressibility of melts is included in modeling of the packing and cooling stages and not in the filling stage. The thermally induced residual birefringence was calculated using the linear viscoelastic and photoviscoelastic constitutive equations combined with the first‐order rate equation for volume relaxation and the master curves for the relaxation modulus and strain‐optical coefficient functions of each polymer. The influence of the processing variables including melt and mold temperatures and volume of skin melt on the birefringence and interface distribution was analyzed for multilayered PS‐PC‐PS, PS‐PMMA‐PS, and PMMA–PC–PMMA molded disks obtained by CIM. The interface distribution and residual birefringence in the molded disks were measured. The measured interface distributions and the gapwise birefringence distributions in CIM disks were found to be in a fair agreement with the predicted interface distributions and the total residual birefringence obtained by the summation of the predicted frozen‐in flow and thermal birefringence. POLYM. ENG. SCI., 55:88–106, 2015. © 2014 Society of Plastics Engineers     

Deformation velocity dependence on tensile fracture characteristics of polypropylene injection molding parts

To clarify the mechanism of the deformation and fracture in a low‐velocity impact test on the isotactic polypropylene (i‐PP) sheet made by injection molding, the change of the style of fracture and the form of deformation was examined while changing the speed of the striker in a low‐velocity impact test. In the injection molding sheet, an oriented skin layer of some thickness is formed on the surface of the sample sheet. By the stress perpendicular to the orientation direction of the skin layer, crazes were formed easily in parallel with the orientation direction in this layer, and cracks were formed from there. Because these cracks bring the sample sheet a strong restraint of strain, a high stress concentration occurs at the end of this crack even if the formation of the oriented layer is limited on the surface of the sample sheet only, and the low‐velocity impact test leads the sample sheet to a brittle fracture. As a result, the injection molding sheet that forms oriented structure on its surface causes the ductility‐brittleness transform at a lower velocity of deformation compared with the nonoriented sheet. POLYM. ENG. SCI., 53:2659–2665, 2013. © 2013 Society of Plastics Engineers     

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     

Thermal degradation behavior of low‐halogen flame retardant PC/PPFBS/PDMS

Flame retardant polycarbonate (FRPC) with 0.2 wt % additives of potassium perfluorbutane sulfonate and polydimethylsiloxane was found to achieve V‐0 rate at 1.6 mm thickness without significantly affecting the mechanical properties of PC. Condensed aromatic bonds with a small amount of Si? O bonds were found in the UL‐94 burning residues tested by FTIR spectra. A compact char layer with cavities inside was formed on the surface of the sample during the rapid decomposition of FRPC, and the concentration of Si was found to be much higher inside the surface of the char layer than that outside the surface analyzed by SEM‐EDX, which was related to the synergistic effects of the two flame retardants of PPFBS and PDMS. A schematic diagram was designed to describe the mechanism of the FRPC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modeling and experimental study of birefringence in injection molding of semicrystalline polymers

The prediction of birefringence developed in injection moldings is very important in order to satisfy required specification of molded products. A novel approach for the numerical simulation of the flow-induced crystallization and frozen-in birefringence in moldings of semicrystalline polymers was proposed. The approach was based on the calculation of elastic recovery that becomes frozen when the flow-induced crystallization occurred. The flow effect on the equilibrium melting temperature elevation due to the entropy reduction between the oriented and unoriented melts was incorporated to model crystallization. To find the entropy reduction and the frozen-in elastic recovery during crystallization, a non-linear viscoelastic constitutive equation was used. From the ultimate elastic recovery the crystalline orientation function was calculated. The crystalline and amorphous contributions to the overall birefringence were obtained from the crystalline orientation function and the flow birefringence, respectively. The birefringence profiles were measured and predicted in moldings of polypropylenes of different molecular weights obtained at various melt temperatures, injection speeds, holding times and mold temperatures. The resulting predictions were in fair agreement with corresponding experimental data.     

No‐flow temperature in injection molding simulation

Most injection molding simulation packages use the no‐flow temperature (NFT) as a means of determining whether the polymer flows or is solid. The NFT is not well defined, and a standard method for measuring it does not exist. A sensitivity analysis of the filling stage has been carried out with two different packages [VISI Flow (Vero Software Limited, Gloucestershire, UK) and Moldflow (Autodesk, Inc., San Rafael, CA)] to estimate the influence of the NFT on the main processing parameters. The NFT has a large influence on the thickness of the frozen layer, but it does not appreciably affect the filling pressure. Because the NFT affects the frozen layer, an effect on the estimation of shrinkage and warpage is expected. Software packages have also been compared, and similar simulations have been found to produce contrasting results. A simple correlation for NFT estimation, derived from the Cross–Williams–Landel–Ferry equation, is proposed for both amorphous and semicrystalline polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

注射速度对高透光性PMMA制件光学性能的影响

以某平板类仪表板模具为例,以聚甲基丙烯酸甲酯(PMMA)为实验材料,通过单因子实验研究了注射速度对高透光性制件的应力双折射、雾度和透光率的影响。结果表明,随着注射速度(螺杆速度)由25 mm/s至55 mm/s逐步提高,相同点位处制品的应力双折射率呈准线型逐渐下降的趋势,雾度呈倒"V"趋势变化,且在注射速度为30 mm/s时达到极大值,而透光率则与雾度变化趋势相反,同样在注射速度为30 mm/s时达极小值。在注射速度一定的条件下,随着测量点距离进浇位置的增大,应力双折射率会在浇口前方出现一个峰值,并以该峰值为中心呈下降趋势,雾度逐渐升高,透光率总体呈下降趋势。     

Development of a rheo‐dielectric sensor for online shear stress measurement during the injection molding process

This study presents the development of a novel rheo‐dielectric sensing technique, based on dielectrostriction measurement, for online injection molding process monitoring. Dielectrostriction, defined as a variation of dielectric properties of material under deformation, detects evolution of molecular orientation during injection molding and enables online shear stress measurement. The dielectrostriction effect resembles the well‐known birefringence phenomenon. As birefringence in polymers is described by the stress‐optical relationship (Fuller, Optical Rheometry of Complex Fluids, Oxford University Press, New York (1995); Janeschitz‐Kriegl, Polymer Melt Rheology and Flow Birefringence, Springer, Berlin (1983); Saiz and Rainde, Dipole Moments and Birefringence of Polymers, Prentice‐Hall, New Jersey (1992)), a stress‐dielectric relationship exists for and is applicable to dielectrostriction. In addition,dielectrostriction measurements can be performed on both transparent and opaque materials with a much simpler data acquisition technique. To demonstrate the feasibility of the dieletrostriction measurement, a planar capacitor sensor rosette has been developed and attached to the surface of an injection mold to obtain the dielectrostriction signal under various processing conditions. The calculated shear stresses of polymer melts based on dielectrostriction signals were validated by agreement with simulation predictions. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers