Structures and properties of injection moldings of crystallization nucleator-added polypropylenes. II. Distribution of higher-order structures

Flexural test specimens were injection-molded from polypropylenes added with 0.5 wt % calcium carbonate, talc, p-tert-dibutyl-benzoic acid monohydroxy aluminum, or p-dimethyl-benzylidene sorbitol under cylinder temperatures of 200–320°C. Distributions in the flow direction of higher-order structures such as a^*-axis-oriented component fraction [A^*] and crystalline orientation functions and distributions in the thickness direction of higher-order structures such as crystallinity, β-crystal content, the degree of b-axis orientation to the thickness direction, [A^*], and crystalline orientation functions were studied. These higher-order structures are inhomogeneous in the flow and thickness directions, which strongly influences the product properties such as mechanical and thermal properties.     

Distribution of higher-order structures in injection-molded polypropylenes

Flexural test specimens were injection-molded from six homoisotactic polypropylenes with MFI = 0.49-25.1 dg/min under cylinder temperatures of 200-320°C. Distributions in the flow direction of higher-order structures such as crystallinity X_c, thickness of skin layer, a*-axis-oriented component fraction [A*], and crystalline orientation functions and distributions in the thickness direction of higher-order structures such as X_c, β-crystal contents, [A*], and crystalline orientation functions were studied. These higher-order structures are inhomogeneous in the flow and thickness directions, which strongly influences the product properties such as mechanical and thermal properties. Molecular orientation process in injection molding was theoretically analyzed from a viewpoint of growth of recoverable shear strain at the gate and its relaxation in the cavity, which could considerably well explain the variations in the flow and thickness directions of the quantities such as thickness of the skin layer and crystalline orientation functions which express the degree of molecular orientation.     

Crystallinity and microstructure in injection moldings of isotactic polypropylenes. Part II: Simulation and experiment

The injection moldings of isotactic polypropylenes with various molecular weights were simulated using finite difference method. In the simulations, the unified crystallization model proposed in our previous paper was applied. The prediction of crystallinity and microstructure development in the moldings was based upon the crystallization kinetics and the “competing mechanisms” for introducing various microstructure layers in the moldings. Extensive injection molding experiments were carried out. The pressure traces during the molding experiments were recorded. The crystallinity distribution in the moldings was determined using differential scanning calorimetry. The measurements on the microstructure embedded in the moldings were performed, including the thickness of the highly oriented skin layer and the gapwise distribution of the spherulite sizes. The measured data for the crystallinity and microstructure in the moldings were compared with the simulated results. The effects of molecular weight and processing conditions on the development of crystallinity and microstructure in the moldings were elucidated. Theoretical predictions were found to be in a good agreement with experimental measurements.     

Structures and properties of injection moldings of crystallization nucleator-added polypropylenes. I. Structure–property relationships

Flexural test specimens were injection-molded from polypropylenes added with 0.5 wt % of calcium carbonate, talc, p-tert- dibutyl-benzoic acid monohydroxy aluminum, or p-di-methyl-benzylidene sorbitol under cylinder temperatures of 200–;320°C. Properties such as flexural modulus, flexural strength, heat distortion temperature, Izod impact strength, hardness, and mold shrinkage and higher-order structures such as crystalline texture, crystallinity, a^*-axis-oriented component fraction, and degree of crystalline orientation were measured and structure–property relationships were studied. By the addition of crystallization nucleators, the flexural modulus, flexural strength, heat distortion temperature, hardness, and mold shrinkage were increased and Izod impact strength was decreased. The degrees of crystalline orientation such as the orientation fraction OF and c-axis orientation function f_c were increased by the addition of nucleators. The degree of the increase was higher as the crystallization temperature was higher. Close relationships were observed between some properties and the degrees of crystalline orientation.     

Determination of different morphological structures in PC/ABS open spiral injection moldings

The internal structure of injection molded polymer blends are complex and greatly affect the mechanical properties. In this work, the microstructure development was observed for a Polycarbonate (PC)/Acrylonitrile‐Butadiene‐Styrene (ABS) blend (60/40 wt% blend ratio) that was injection molded using an open spiral mold. The ABS‐rich phase was chemically etched out, leaving behind cavities of different shapes and sizes. With increasing depth, different morphological structures were observed due to the variation of temperature and shear profiles. The changes in morphology can be abrupt, especially at the regions closest to the external surface of the specimen, while a more gradual transition was observed with increasing specimen depth. Thus, a methodology is developed to segregate these structures into different and distinctive layers (skin, shear, intermediate, and core layers) corresponding to the state of shear flow, cavity pressure and distance from the gate. The thickness of these layers and the characteristics of the cavities (i.e. shapes and sizes) are believed to have a direct impact on the final mechanical properties of the moldings. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Generation of large residual stresses in injection moldings

Large residual stresses have been generated in injection molded bars by ejecting them prematurely and completing the cooling process by quenching into ice water or liquid nitrogen. The stress distribution formed under these conditions was found to be much closer to parabolic than is the case when the moldings cool conventionally. Limited testing on moldings made in this way indicated significant property enhancement and improved resistance to ultraviolet degradation.     

Young's modulus variation within polystyrene injection moldings

Young's modulus distributions in the depth direction within injection moldings made from polystyrene have been investigated by empolying two independent techniques. Both methods show that the material close to the surface exhibits relatively high stiffness, whereas at all other depths a lower uniform stiffness exists. The depth dependency of other material characteristics, such as tan δ peaks in the dynamic mechanical thermal analysis spectra and molecular orientation, have been investigated in an attempt to correlate them with the stiffness distributions. It appears that the thermomechanical history of the different regions within the moldings, particularly the stresses acting during flow and the temperature gradients set up during cooling, are primarily responsible for the Young's modulus distributions presented here. © 1993 John Wiley & Sons, Inc.     

The V-notch at weld lines in polystyrene injection moldings

A major factor that weakens the weld line in injection moldings is the V-notch structure. Though the existence of a V-notch is well known, its depth variation with molding conditions has not been detailed. The aim of this paper is to clarify the V-notch structure and its effect on the strength of general purpose polystyrene injection moldings. A dog bone type tensile specimen with a weld line was molded under several molding conditions. The surface of the weld line was partially eliminated by cutting with a milling machine to seven levels of cut depth (D_c). As a result, the weld strength increased with D_c to about 50%. The relationship between the weld strength and D_c made it possible to determine the V-notch depth, which vas defined as the “depth of the weld line.” From these results, a hypothesis is proposed that the V-notch has a structure with a fine groove on the surface and a poorly bonded inner layer. This study considered the relationships among the weld strength, the depth of the weld line, and molding conditions.     

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.     

Processing–mechanical property relationships in injection moldings of polybutylene

Two unfilled nonpigmented extrusion grades of polybutylene have been injection-molded into a tensile bar mold under a wide range of barrel and mold temperatures. The overall structure of the moldings has been determined and correlated with processing conditions. The short term tensile mechanical properties of the moldings have been ascertained and correlated with molding structure. For low mold temperatures, the Young's modulus and tensile strength of injection moldings of polybutylene are controlled by the extent of and structure within the highly oriented skin. Low barrel temperatures can give rise to highly crystalline thick skins that treble the Young's modulus and fracture stress, when compared to high barrel temperature moldings. Increasing the mold temperature introduces a brittle response in polybutylene injection moldings. Modulus is controlled, at the high mold temperatures, by the skin thickness and by the crystallinity of the material comprising the core of the molding.     

The thermomechanical environment and the mechanical properties of injection moldings

Axisymmetric specimens were injection molded in a propylene copolymer with systematic variations of the melt and mold temperatures and the injection flow rate, in a total of 15 different processing conditions. From computer simulations of the mold filling stage using commercially available software packages, two thermomechanical indices were calculated. They aim at evaluating the level of orientation of the skin and the degree of crystallinity of the core layers. Assuming that these morphological features determine the mechanical response of the moldings, the thermomechanical indices were weighted by the relative thickness of the skin and core layers. The tensile behavior of the moldings was assessed at two velocities of 3.3 × 10^?5 (2 mm/min) and 3 m/s. The mechanical properties studied were the initial modulus, the yield stress and the strain at break. The relationships between the weighted thermomechanical indices and these mechanical properties were analyzed from 3D response surfaces obtained by polynomial fittings. Globally, a marked effect of the strain rate on the mechanical response along with a distinct sensitivity on the weighted thermomechanical indices was found. At high strain rates the microstructural differences were enhanced. The dependence of the yield stress on the thermomechanical indices was not significantly affected by the strain‐rate. However, the strain‐rate dependence of the other mechanical properties was strongly influenced by the initial microstructural state. Furthermore, the maximization of different mechanical properties could not be made simultaneously due to their distinct microstructural dependences. The concept of the thermomechanical indices is evidenced as a simple, valid and valuable tool to establish straightforward relationships between the processing and the mechanical behavior. Polym. Eng. Sci. 44:1522–1533, 2004. © 2004 Society of Plastics Engineers.     

Effect of water absorption and temperature gradients on polycarbonate injection moldings

Polycarbonate injection moldings have been conditioned for various times in (i) hot water (40, 60, 80, and 100°C) or (ii) in a temperature gradient (with hot surface/cold surface temperatures 80/25, 100/25, 120/35, and 140/60°C). Water absorption occurred in hot water and caused the formation of disc-shaped flaws, which were located at all depths within the bars and at all orientations. The presence of the flaws caused severe embrittlement and cracks were nucleated by them during uniaxial tensile testing. Residual stress levels were found to be diminished by hot water conditioning more than those in bars conditioned at the same temperatures in air. The sense of the residual stresses reversed in a bar that was allowed to cool slowly in the water bath, an observation attributed to desorption. It was generally found that the flaws near the surface healed on allowing the bars to stand in air at room temperature. Temperature gradient conditioning caused reversal of the sense of the residual stresses near to the hot surface at the two higher temperatures used and significant reduction in magnitude at the lower temperatures. Fracture nucleated at this surface during uniaxial tensile testing.     

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     

Fracture behavior of glass bead-filled poly(oxymethylene) injection moldings

The mechanical properties of glass bead filled poly(oxymethylene) were investigated as a function of glass bead content and glass bead diameter using injection molded test pieces. Fracture toughness measurements were made using single edge-notched tension and single edge-notched bend specimens. The effect of notch orientation with respect to the mold fill direction on fracture toughness was studied using single gate and double gate moldings. Tensile strength and flexural modulus were measured using standard test pieces. It was found that; (i) fracture toughness of the filled and unfilled polymer was relatively independent of notch orientation, (ii) the presence of weldlines in the molded test pieces did not affect the fracture toughness of unfilled polymer or its composites, (iii) fracture toughness of filled polymer was always considerably lower than that of the unfilled polymer; fracture toughness decreased sharply with increasing bead concentration, (iv) fracture toughness was not a sensitive function of glass bead diameter; it decreased slightly as bead diameter increased, (v) strain energy release rate as measured under impact decreased with increasing bead concentration, (vi) tensile strength decreased linearly with increasing glass bead concentration and was inversely proportional to the square root of the bead diameter, (vii) weldlines did not affect the tensile strength of the polymer or its composities, (viii) flexural modulus increased linearly with increasing glass bead concentration according to the Einstein equation.     

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.     

Polyamide 6—long glass fiber injection moldings

The injection molding ability of long glass fiber reinforced polyamide pellets was studied. The injection moldable materials were produced by a melt impregnation process of continuous fiber rovings. The rovings were chopped to pellets of 9 mm length. Chopped pellets with a variation in the degree of impregnation and fiber concentration were studied. The injection molded samples were analyzed for fiber concentration, fiber length, and fiber orientation. Dumbbell-shaped tensile bars were made to evaluate the mechanical properties. The fibers in the tensile bars had a high orientation in the flow direction and minor fiber concentration gradients were observed. The fiber lengths decreased with fiber concentration from 1.6 mm for a 2 vol% to 0.6 mm for a 25 vol% system. The tensile and impact properties increased considerably with fiber concentration. A low degree of impregnation in the pellets of the fibers resulted in somewhat lower tensile and impact properties.     

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     

Structure and properties of injection moldings of polypropylene/polystyrene blends

A homoisotactic polypropylene (PP) was melt blended with 0–30 wt % of three kinds of polystyrene (PS) with melt flow indexes lower than, similar to, and higher than that of PP. The blends were injection molded at cylinder temperatures of 200–280°C, and the structure and properties of the injection moldings were studied. With PS blending, although the PP molding whitened, no surface defect such as layer peeling and pearl-like appearance occurred. The rigidity and dimensional accuracy of the molding improved without much deterioration in impact strength and heat resistance. At the same time the fluidity also improved. The injection moldings of PP/PS blends did not show clear skin/core structure under a polarizing microscope. The degrees of crystallinity and crystalline c-axis orientation decreased with PS blending. PS particles were the smallest when the ratio of the viscosity of the PS to that of PP at molding shear rate was slightly lower than unity. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1015–1027, 1997     

Flexural properties of moldings of rigid polyurethane made by reaction injection molding

Flexural properties of moldings made by Reaction Injection Molding (RIM), which are structural foams consisting of high density skin and low density core, were investigated by three-point bending tests. Two failure modes were observed in bending tests of the moldings made by RIM, and they are classified as follows according to the density ratio of skin layer to core layer: the opposite side of the skin layer to which load was subjected failed by tensile stress: and the same side of the skin layer to which load was subjected failed by compressive stress, causing wrinkling or buckling. Then the conventional composite beam theory was applied to the former failure mode and Hoff s buckling theory to the latter, and equations were derived to predict the flexural properties of the structural foams, which involved buckling from the flexural properties of solid construction. In addition, it has been shown that there exists a density distribution that maximizes the flexural strength of the moldings made by RIM with a given overall density. The results obtained here should be useful to the optimum structural design of moldings made by RIM.