The Use of the Indentation Test for Studying the Solidification Behaviour of Different Semicrystalline Polymers during Injection Molding

Summary: An in‐line method for monitoring the solidification process during injection molding of semicrystalline polymers (demonstrated previously in J. Appl. Polym. Sci. 2003 , 89, 3713) is based on a simple device, where an additional ejector pin is pushed on the injection molded part at different times during the solidification phase. The ‘indentation depth profile’, i.e., residual deformation as a function of time, was obtained and allowed to determine the evolution of the solidification front in the mold as a function of the cooling time. The present work shows the reliability and the powerfulness of the aforementioned method for a large variety of different semicrystalline polymers (PET, PBT, polyamide‐6 PA6, isotactic poly(propylene) iPP) characterized also by different molecular weight and/or nucleating agents. The results show that the indentation test may be considered as a ‘predictive’ tool to qualitatively and quantitatively compare the solidification process of different polymers and polymer grades during injection molding.

Comparison of the solid front propagation during injection molding of different materials.     

Evaluation of processing effects in injection‐molded amorphous and crystalline thermoplastics using an excimer laser

The ablation behavior of amorphous [polystyrene (PS), polycarbonate (PC)] and crystalline [PET, glass‐filled poly(butylene terephthalate) (PBT)] polymers by 248‐nm KrF excimer laser irradiation were investigated for different injection‐molding conditions, namely, injection flow rate, injection pressure, and mold temperature, as a possible method for evaluating processing effects in the specimens. For this purpose, dumbbell‐shaped samples were injection‐molded under different sets of processing conditions, and weight loss measurements were carried out for the different injection‐molding conditions. Some of the crystalline (PET) samples were annealed at different annealing times and temperatures. For PET, the weight loss decreased with increasing mold temperature and remained insensitive to injection flow rate. Annealing time and temperature significantly reduced weight loss in PET. For PBT, the weight loss due to laser ablation decreased with increasing material packing due to pressure, and it also showed some sensitivity to flow rate variation. The major effect was seen with glass‐filled PBT samples. The weight loss decreased drastically with increasing glass fiber content. Laser ablation allowed us to observe process‐induced fiber orientation by scanning electron microscopy in PBT samples. For PS and PC, the weight loss increased with increasing injection flow rate and mold temperature and decreased with increasing injection pressure. The position near the gate showed higher ablation than the position at the end for all the conditions. A decrease in the material orientation with injection speed and mold temperature led to an increase in the weight loss, whereas an increase in the injection pressure, and consequently orientation, led to a lower weight loss for PS and PC. Higher residual stress samples showed higher weight losses. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2006     

Effects of filler size and content on shrinkage and gloss of injection molded PBT/PET/talc composites

Effects of filler size and content on the shrinkage of injection molded poly(butylene terephthalate)/poly(ethylene terephthalate)/talc (PBT/PET/talc) composites were investigated. Circular plate specimens were examined by a field emission scanning electron microscope and a numerical analysis code was used for modeling of the injection molding. Orientation effects of polymer molecules and fillers on the shrinkage behavior of PBT/PET/talc composites were illustrated by using schematic diagrams. It was found that the planes of talc particles were aligned parallel to the mold wall due to applied shear stresses and the largest axes of the disk‐like talc particles were oriented along the flow direction. Shrinkage of the PBT/PET/talc composites was decreased more rapidly along the flow direction than along the transverse direction as the talc content was increased. Small‐sized talc was more effective for reduction of the surface shrinkage of PBT/PET composites than titanium dioxide (TiO₂) or large‐sized talc. Although the PBT/PET polymer matrix almost covered the surface of talc particles, surface gloss of the particle filled composites was decreased as the size of mineral filler was increased. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Influence of plasticizers and cryogenic grinding on the high‐cooling‐rate solidification behavior of PBT/PET blends

Two structurally different plasticizers (cyclic and linear) and the effect of cryogenic grinding on the solidification behavior at high cooling rates by a continuous cooling transformation approach of poly(butylene terephthalate)/poly(ethylene terephthalate), PBT/PET, blends are described. The solidification curve (density versus cooling rate) is confirmed as an effective tool to compare the differences in crystallization behavior under conditions mimicking processing. In comparison to the bulky cyclic plasticizer, the linear oligomeric one was found to have a more pronounced influence on the crystallization behavior. A 60/40 by weight PBT/PET blend shows a drop‐off of density at ～50 K/s. In the plasticized sample, the long‐range crystalline order appears up to a cooling rate of ～250K/s, making the blend comparable to pure PBT. Grinding the components before blending further improves crystallizability and synergy to the addition of the plasticizer. The results suggest the important role of local chain mobility in the solidification behavior at high cooling rates. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43083.     

Properties of glass‐filled thermoplastic polyesters

The thermal, mechanical, and rheological properties of glass‐filled poly(propylene terephthalate) (GF PPT) were compared to glass‐filled poly(butylene terephthalate) (GF PBT). The impetus for this study was the recent commercial interest in PPT as a new glass‐reinforced thermoplastic for injection‐molding applications. This article represents the first systematic comparison of the properties of GF PPT and GF PBT in which differences in properties can be attributed solely to differences in the polyester matrices, that is, glass‐fiber size and composition, polymer melt viscosity, nucleant content and composition, polymerization catalyst composition and content, and processing conditions were kept constant. Under these controlled conditions, GF PPT showed marginally higher tensile and flexural properties and significantly lower impact strength compared to GF PBT. The crystallization behavior observed by cooling from the melt at a constant rate showed that GF PBT crystallized significantly faster than did GF PPT. Nucleation of GF PPT with either talc or sodium stearate increased the rate of crystallization, but not to the level of GF PBT. The slower crystallization rate of GF PPT was found to strongly affect thermomechanical properties of injection‐molded specimens. For example, increasing the polymer molecular weight and decreasing the mold temperature significantly increased the modulus drop associated with the glass transition. In contrast, the modulus–temperature response of GF PBT was just marginally influenced by the polymer molecular weight and was essentially independent of the mold temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 889–899, 1999     

Nonisothermal crystallization of poly(ethylene terephthalate) and its blends in the injection-molding process

We investigated the nonisothermal crystallization during the cooling process of injection molding of poly(ethylene terephthalate) (PET), PET/talc, and PET/Surlyn blends. We applied the isothermal crystallization parameters obtained by the Hoffman–Lauritzen theory to the kinetics of nonisothermal crystallization and then calculated the relative crystallinity χ/χ_c as a function of the mold temperature. χ/χ_c were nicely interpreted by calculation without effect of the pressure history on crystallization in PET and PET/talc (1 wt %) blends. In contrast, in the PET/Surlyn (3 wt %) blend, crystallization occurred at a lower mold temperature than predicted by our calculation. The transmission electron micrograph near the surface of the injection-molded PET/Surlyn blend showed deformation and stretching of dispersed Surlyn particles, suggesting that orientation of the PET matrix proceeds with the flow in processing. The orientation of the PET matrix resulted in acceleration of the crystallization in the injection molding. © 1995 John Wiley & Sons, Inc.     

Process‐induced long‐term deformation behavior of semicrystalline PBT

Processing conditions during injection molding always play a major role in influencing the properties of a finished part as it produces a unique structural gradient because of the complex thermorheological history. Therefore it is highly desirable to anticipate the effect of process parameters on the resulting microstructure and mechanical properties of the finished part in the long run. In this work, therefore, the influence of mold temperature, injection flow rate, and holding pressure on the deformation behavior of semicrystalline Polybutylene terepthalate (PBT) has been monitored through creep. The resulting internal structures and stresses due to processing have been determined and the deformation behavior has been analyzed. It has been observed that only the rate of cooling shows a remarkable effect on the long‐term viscoelastic behavior of an injection molded semicrystalline PBT part, as it influences not only the crystalline phase but also the fractional free volume, whereas the different states of frozen‐in orientations and residual stresses have only a negligible effect. A slower cooling rate as well as longer aging time lead to a reduction in free volume and hence reduced tendency to creep. POLYM. ENG. SCI. 46:882–888, 2006. © 2006 Society of Plastics Engineers     

PET的注射成型工艺对制品性能的影响

通过注射成型试验探索聚对苯二甲酸乙二酯(PET)的成型工艺条件,并结合紫外可见光谱和力学性能测试方法,分析注塑成型工艺对PET性能的影响。研究发现:PET适宜的注射成型温度为280℃,模具温度为70℃,注塑压力为50 MPa,冷却时间为20 s。此条件下制得的PET制品不易结晶、透明无缺陷、无翘曲和凹痕、综合力学性能较好,拉伸强度、弯曲强度及弯曲弹性模量较小,断裂伸长率和缺口冲击强度较大。     

Numerical Simulation for Effects of Injection Mold Cooling on Warpage and Residual Stresses

Abstract

The dimensions quality of the injection‐molded parts is the result of a complex combination of material, part, and mold designs and process conditions. In this article, warpage prediction relies on the calculation of residual stresses developed during the molding process. The solidification of a molten thermoplastic between cooled parallel plates is used to model the mechanics of part warp in the injection‐molding process. Flow effects are neglected, and a thermorheologically simple thermoviscoelastic material model is assumed. The warp and residual stresses numerical simulation with finite element method (FEM) is time dependent. At each time step, the material properties can be temperature and pressure dependent. Mold temperature or mold‐cooling rate effects on part warp have been numerically predicted and compared with experimental results. By showing the mold‐cooling effects, it was concluded that mold cooling has a significant effect on part warpage, and mold‐cooling parameters, such as mold temperature, resin temperature, cooling channels, etc., should be set carefully.     

Crystallization of poly(ethylene terephthalate) and poly (butylene terephthalate) modified by diamides

Poly(ethylene terephthalate) (PET) and poly (butylene terephthalate) have been modified by diamide units (0.1–1 mol%) in an extrusion process and the crystallization behavior studied. The diamides used were: for PET, T2T‐dimethyl (N, N′‐bis(p‐carbomethoxybenzoyl)ethanediamine) and for PBT, T4T‐dimethyl (N, N′‐bis(p‐carbomethoxybenzoyl)butanediamine). The above materials were compared to talc (0.5 wt%), this being a standard heterogeneous nucleator, and to diamide modified copolymers obtained by a reactor process. Two PET materials were used: a slowly crystallizing recycled grade obtained from soft drink bottles and a rapidly crystallizing injection molding grade. The crystallization was studied by differential scanning calometry (DSC) and under injection molding conditions using wedge shaped specimens; the thermal properties were studied by dynamic mechanical analysis. T2T‐dimethyl is effective in increasing the crystallization of PET in both of the extrusion compounds as well as in the reactor materials. It was also found that the crystallization temperature of poly(butylene terephthalate) could be slightly increased by the addition of nucleators.     

Compatibilization of a poly(butylene terephthalate)/poly(ethylene octene) copolymer blends with different amounts of an epoxy resin

New toughened poly(butylene terephthalate) (PBT) materials were obtained by melt blending with 20 wt % poly(ethylene octene) (PEO) copolymer and different levels of a difunctional epoxy resin in a twin‐screw extruder followed by injection‐molding. The presence of neither PEO or epoxy influenced either the phase nature of the two amorphous phases of the blends or the crystallization process of PBT, despite the slight reaction of epoxy with PBT as stated by the observed torque increases. The addition of epoxy led to a decrease in the particle size that stopped due to the concomitant viscosity increase. Supertough PBT‐based blends with an impact strength more than 18‐fold that of PBT were obtained without previous chemical modification of any of the blend components at 1.0 wt % epoxy contents. The interparticle distance was the parameter that controlled notched toughness in these PBT/PEO blends. The adhesion at the interphase was the parameter on which the critical interparticle distance appeared to depend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 260–269, 2004     

Engineered poly(lactic acid)‐talc biocomposites for melt processing: Effects of co‐blending with poly(butylene succinate) and poly(butylene terephthalate) on thermal and mechanical behavior

This article deals with the design and manufacturing of a novel class of PLA‐based material specifically engineered for injection molding, suitable for food contact and characterized by a good balance of mechanical properties and thermal resistance. A commercial PLA grade was modified by blending it with microlamellar talc as reinforcing filler, poly(butylene succinate) (PBS), and poly(butylene terephthalate) (PBT) as secondary polymeric phases. Ternary blend/talc biocomposites were achieved. The different constituents of the biocomposites were compatibilized by reactive compounding extrusion using maleic anhydride (MAH) grafted PLA (PLA‐MA). The thermal properties of the compounds prior and after injection molding were characterized by differential scanning calorimetry. The mechanical response of the injection molded materials was evaluated by flat indentation and flexural tests. The mechanical properties of the PLA/talc‐based biocomposites and crystallinity of PLA can be controlled by fine tuning the blend by the addition of PBS and PBT in the formulation. In particular, biocomposites characterized by good strength and toughness can be obtained by injection molding, without affecting thermal stability. Based on the experimental findings, the PLA‐based formulations pose; therefore, solid bases for replacing oil‐based plastics in several markets, specifically in the segment of food and pharmaceutical packaging. POLYM. ENG. SCI., 59:264–273, 2019. © 2018 Society of Plastics Engineers     

Phase behavior of blends containing amorphous poly(resorcinol phthalate‐block‐carbonate) and semicrystalline polyesters

The phase behavior of poly(resorcinol phthalate‐block‐carbonate) (RPC) with engineering polyesters was investigated by using differential scanning calorimeter (DSC) and dynamic mechanical analysis. RPC was found to form miscible blends with poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), and poly(cyclohexylmethylene terephthalate) (PCT), but was partially miscible with poly(1,4‐cyclohexanedimethylene‐1,4‐cyclohexanedicarboxylate) (PCCD) in the melt state and below the melting temperature (T_m). The degree of melting‐point depression indicates that the RPC is most miscible with PCT followed by PET and then PBT. Furthermore, with the help of empirical DSC data and the Nishi–Wang equation, the interaction parameters between RPC and PET, PBT, and PCT were quantified to be ?0.36, ?0.33, and ?0.54, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Phase morphology development during processing of compatibilized and uncompatibilized PBT/ABS blends

The development of the multiphase morphology of uncompatibilized blends of poly(butylene terephthalate) (PBT) and acrylonitrile–butadiene–styrene terpolymer (ABS) and PBT/ABS blends compatibilized with methyl‐methacrylate glycidyl‐methacrylate (MMA‐GMA) reactive copolymers during compounding in a twin‐screw extruder and subsequent injection molding was investigated. Uncompatibilized PBT/ABS 60/40 (wt %) and compatibilized PBT/ABS/MMA‐GMA with 2 and 5 wt % of MMA‐GMA showed refined cocontinuous morphologies at the front end of the extruder, which coarsened towards the extruder outlet. Coarsening in uncompatibilized PBT/ABS blends is much more pronounced than in the compatibilized PBT/ABS/MMA‐GMA equivalents and decreases with increasing amounts of the MMA‐GMA. For both systems, significant refinement on the phase morphology was found to occur after the blends pass through the extruder die. This phenomenon was correlated to the capacity of the die in promoting particles break‐up due to the extra elongational stresses developed at the matrix entrance. Injection molding induces coarsening of the ABS domains in the case of uncompatibilized PBT/ABS blends, while the reactive blend kept its refined phase morphology. Therefore, the compatibilization process of PBT/ABS/MMA‐GMA blends take place progressively leading to a further refinement of the phase morphology in the latter steps, owing to the slow reaction rate relative to epoxide functions and the carboxyl/hydroxyl groups. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 102–110, 2007     

Melting and solidification behavior of blends of high density polyethylene with poly(butylene terephthalate)

This study focuses on the effect of various processing and cooling conditions upon the subsequent melting and solidification behavior of blends of poly(butylene terephthalate) (PBT) and high density polyethylene (HDPE). Differential scanning calorimetry (DSC) measurements have shown that the crystallization of reprocessed PBT is different from the crystallization behavior of virgin samples. Two melting endotherms for PBT were observed for reprocessed PBT and for PBT-PE blends. The nature of each PBT peak is discussed in relation to processing history, solidification conditions, and composition. The presence of two crystallization peaks for the PE component in blends of PE and PBT are thought to be associated with the restriction of molecular motion of PE in the presence of the second component. The relative magnitudes of the two exotherms of PE vary with composition and cooling rate during solidification.     

Primary structure and physical properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) resin blends

The morphology and properties of blends of poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) that were injection molded under various conditions were studied. Under injection molding conditions that make it possible to secure transparency, blends did not show clear crystallinity at blending ratios of more than 20 mol% in spite of the fact that crystallinity can be observed in the range of PEN content up to 30 mol%. Because both transparency and crystallinity could be secured with a PEN 12 mol% blend, this material was used in injection molding experiments with various injection molding cycles. Whitening occurred with a cycle of 20 sec, and transparency was obtained at 30 sec or more. This was attributed to the fact that transesterification between PET and PEN exceeded 5 mol% and phase solubility (compatibility) between the PET and PEN increased when the injection molding time was 30 sec or longer. However, when the transesterification content exceeded 8 mol%, molecularly oriented crystallization did not occur, even under stretching, and consequently, it was not possible to increase the strength of the material by stretching. PET/PEN blend resins are more easily crystallized by stretch heat‐setting than are PET/PEN copolymer resins. It was understood that this is because residual PET, which has not undergone transesterification, contributes to crystallization. However, because transesterification reduces crystallinity, the heat‐set density of blends did not increase as significantly as that of pure PET, even in high temperature heat‐setting. Gas permeability showed the same tendency as density. Namely, pure PET showed a substantial decrease in oxygen transmission after high temperature heat‐setting, but the decrease in gas permeability in the blend material was small at heat‐set temperatures of 140°C and higher.     

Relationship between processing method and microstructural and mechanical properties of poly(ethylene terephthalate)/short glass fiber composites

Composites of recycled poly(ethylene terephthalate) (PET) reinforced with short glass fiber (GF) (0, 20, 30, and 40 wt %) were compounded in a single‐screw extruder (SSE) and in a intermeshing corotating twin‐screw extruder (TSE). An SSE fitted with a barrier double‐flight screw melting section in between two single‐flight sections and a TSE with a typical screw configuration for this purpose were used. The composites were subsequently injection molded at two different mold temperatures (10 and 120°C), with all other operative molding parameters kept constant. The effects of processing conditions on composite microstructure, PET degree of crystallinity, and composite mechanical properties were evaluated. Appropriate dispersive and distributive mixing of the glass fiber throughout the PET matrix as well as fine composite mechanical and thermal‐mechanical properties were achieved regardless of whether the composites were prepared in the SSE or TSE. The performance of the SSE was attributed to the efficiency of the barrier screw melting section in composite mixing. The mold temperature influenced the mechanical properties of the composites, by controlling of the degree of crystallinity of the PET in the composites. For a good balance of mechanical and thermal‐mechanical properties, high mold temperatures are desirable, typically, 120°C for a mold cooling time of 45 s. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Study of the effect of processing conditions on the co‐injection of PBS/PBAT and PTT/PBT blends for parts with increased bio‐content

This work studies the effect of processing parameters on mechanical properties and material distribution of co‐injected polymer blends within a complex mold shape. A partially bio‐sourced blend of poly(butylene terephthalate) and poly(trimethylene terephthalate) PTT/PBT was used for the core, with a tough biodegradable blend of poly (butylene succinate) and poly (butylene adipate‐co‐terephthalate) PBS/PBAT for the skin. A ½ factorial design of experiments is used to identify significant processing parameters from skin and core melt temperatures, injection speed and pressure, and mold temperature. Interactions between the processing effects are considered, and the resulting statistical data produced accurate linear models indicating that the co‐injection of the two blends can be controlled. Impact strength of the normally brittle PTT/PBT blend is shown to increase significantly with co‐injection and variations in core to skin volume ratios to have a determining role in the overall impact strength. Scanning electron microscope images were taken of co‐injected tensile samples with the PBS/PBAT skin dissolved displaying variations of mechanical interlocking occurring between the two blends. © 2014 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41278.     

Rheological behavior of polyester blend and mechanical properties of the polypropylene–polyester blend fibers

The article deals with method of preparation, rheological properties, phase structure, and morphology of binary blend of poly(ethylene terephthalate) (PET)/poly(butylene terephthalate) (PBT) and ternary blends of polypropylene (PP)/(PET/PBT). The ternary blend of PET/PBT (PES) containing 30 wt % of PP is used as a final polymer additive (FPA) for blending with PP and subsequent spinning. In addition commercial montane (polyester) wax Licowax E (LiE) was used as a compatibilizer for spinning process enhancement. The PP/PES blend fibers containing 8 wt % of polyester as dispersed phase were prepared in a two‐step procedure: preparation of FPA using laboratory twin‐screw extruder and spinning of the PP/PES blend fibers after blending PP and FPA, using a laboratory spinning equipment. DSC analysis was used for investigation of the phase structure of the PES components and selected blends. Finally, the mechanical properties of the blend fibers were analyzed. It has been found that viscosity of the PET/PBT blends is strongly influenced by the presence of the major component. In addition, the major component suppresses crystallinity of the minor component phase up to a concentration of 30 wt %. PBT as major component in dispersed PES phase increases viscosity of the PET/PBT blend melts and increases the tensile strength of the PP/PES blend fibers. The impact of the compatibilizer on the uniformity of phase dispersion of PP/PES blend fibers was demonstrated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4222–4227, 2006     

Modeling and simulation of thermally induced stress and warpage in injection molded thermoplastics

Thermally induced stress and the relevant warpage caused by inappropriate mold design and processing conditions are problems that confound the overall success of injection molding. A visco-elastic phase transformation model, using a standard linear solid for the solidified polymer and a viscous fluid model for the polymer melt, of 2-D finite element scheme with 8 noded overlay isoparametric elements was used to simulate and predict the residual stress and warpage within injection molded articles as induced during the cooling stage of the injection molding cycle. Computed results are in good agreement with published experimental data. The approach proposed here is to examine and simulate the injection molding solidification process with the intent of understanding and resolving more inclusive and realistic problems.