Reprocessing acrylonitrile–butadiene–styrene plastics: Structure–property relationships

Acrylonitrile–butadiene–styrene (ABS) plastics from computer equipment housings have been reprocessed, some under various conditions of temperatures and shearing rates and others for multiple numbers of cycles. Structural changes in these reprocessed materials were investigated by infrared spectroscopy (FTIR), gel permeation chromatography, and dynamic mechanical thermal analysis. Gas chromatography/mass spectrometry was used to analyze extracts from the ABS plastics. These studies were related to measurements of the mechanical properties of the reprocessed materials, and the fracture surfaces were examined using scanning electron microscopy. It was found that impact strength was much more significantly affected than tensile properties by reprocessing. Within the range of reprocessing parameters studied, temperature had a more significant effect than shear rate on mechanical properties. Significant reductions in impact strength and slight increases in stiffness and strength, particularly following reprocessing at the highest temperature of 270°C and multiple reprocessing, were linked to loss of small molecules (including lubricants), degradation (crosslinking and scission) of the rubber phase, and changes in the morphology seen in the fracture surfaces. POLYM. ENG. SCI., 47:120–130, 2007. © 2007 Society of Plastics Engineers     

A rate‐type nonlinear viscoelastic–viscoplastic cyclic constitutive model for polymers: Theory and application

A thermodynamically consistent rate‐type viscoelastic–viscoplastic constitutive model is developed in the framework of isothermal and small deformation to describe the nonlinear and time‐dependent deformation behaviors of polymers, e.g., ratchetting, creep, and stress relaxation. The model is proposed on the base of a one‐dimensional rheological model with several springs and dashpot elements. The strain is divided into viscoelastic and viscoplastic parts, and the stress is also decomposed into two components. Each stress component is further divided into elastic and viscoelastic sub‐components. The viscoelasticity is described by introducing pseudo potentials, and the ratchetting is considered by the viscoplastic flow which is derived by the codirectionality hypotheses. The capability of the proposed model to describe the nonlinear and time‐dependent deformation of polymers is then verified by comparing the simulations with the corresponding experimental results of polycarbonate (PC) polymer. It is shown that the nonlinear and time‐dependent stress–strain responses of the PC can be reasonably predicted by the proposed model. POLYM. ENG. SCI., 56:1375–1381, 2016. © 2016 Society of Plastics Engineers     

Polypropylene/carbon nanotube nanocomposite fibers: Process–morphology–property relationships

This study is focused on aligning carbon nanotubes in polypropylene matrix by melt spinning. Two different weight percentages (0.5% and 1.0%) of nanotubes were used for the synthesis of the nanocomposite fibers. The effect of the nanotubes on the crystallization and mechanical behavior of polypropylene as well as the effect of draw ratio on the nanocomposite morphology and properties is also discussed. Correlation of fiber morphology and nanotube alignment was done using differential scanning calorimetry, wide‐angle X‐ray diffraction, and transmission electron microscopy. Significant improvement in tensile modulus and tensile strength were observed, which is characteristic of a highly aligned nanotube system. A substantial vincrease in the onset of decomposition was observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3844–3850, 2007     

Processing–morphology–property relationships in epoxy resins

An investigation was conducted into processing–morphology–property relationships of a series of epoxy resin formulations. Diglycidyl ether of bisphenol A (DGEBA) epoxy resin was cured with diethylene triamine (DETA) and 2,5-dimethyl 2,5-hexane diamine (DMHDA). The two systems were compared by electron microscopic investigation and thermomechanical and fracture property measurements. Transmission electron microscopy has revealed a difference in the morphology of fracture surfaces. On the other hand, thermomechanical and fracture properties of DETA- and DMHDA-cured formulations were found to be very similar. Three different processing (curing) conditions were used for DMHDA-cured formulations, without an apparent effect on their properties. The previously reported improvement in impact energy of DMHDA-cured formulations is unfounded.     

Processing–morphology–property relationships of polypropylene–graphene nanoplatelets nanocomposites

Polypropylene (PP) nanocomposites reinforced with graphene nanoplatelets (GNPs) were prepared via melt extrusion. A special sheet die containing with two shunt plates was designed. The relationships among the flow field of the special die, exfoliation, and dispersion morphology of the GNPs in PP and the macroscopic properties of the nanocomposites were analyzed. Flow field simulation results show that the die with shunt plates provided a high shear stress, high pressure, and high velocity. The differential scanning calorimetry, X‐ray scattering, and electron microscopy results reveal that the nanocomposites prepared by the die with the shunt plates had higher crystallinity values and higher exfoliation degrees of GNPs. The orientation of the GNPs parallel with the extrusion direction was also observed. The nanocomposites prepared by the die with shunt plates showed a higher electrical volume conductivity, thermal conductivity, and tensile properties. This indicated that the high shear stress exfoliated the GNPs effectively to a thinner layer and then enhanced the electrical, thermal, and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44486.     

Nonlinear load–strain modeling of polypropylene geogrids during constant rate‐of‐strain loading

This article describes a rate‐dependent hyperbolic model that was developed to predict the tensile load–strain behavior of a polypropylene geogrid reinforcement material under monotonic and stepped constant rate‐of‐strain testing. A more general three‐component model previously reported in the literature was also used in the current study but with some modifications to compute model parameters. Details of the trial and error procedure to select three‐component model parameters, not previously reported in the literature, are explained. Both models gave similar good agreement between measured and predicted constant rate‐of‐strain tests. The accuracy of the three‐component model to simulate stepped constant rate‐of‐strain tests was judged to be better, but for practical purposes, the simpler hyperbolic model was judged to be satisfactory. An advantage of the hyperbolic model is that the model parameters are easy to determine, only monotonic constant rate‐of‐strain tests are required, and numerical implementation is simple. However, the hyperbolic model is restricted to monotonic or stepped constant rate‐of‐strain load paths. An advantage of the more complicated three‐component model is that it has been demonstrated in previous studies to be more general and thus can be used for other load paths and other polymeric reinforcement material types that do not have characteristic hyperbolic load–strain behavior. POLYM. ENG. SCI., 55:1617–1627, 2015. © 2014 Society of Plastics Engineers     

Viscosity–temperature relationships for cellulose acetate–acetone solutions

Viscosity measurements were made for dilute solutions of three grades of cellulose acetate (acetyl content 39.8%, molecular weight M?_v 30270 to 46250) in acetone in the temperature t range of 10° to 35°C. The data satisfied the Mark-Houwink equation, [η] = KM?, where [η] = limiting viscosity number and K and α are Mark-Houwink constants. The values of [η] and α decreased with increase in temperature, and straight-line correlations were obtained for ?d[η]/dt versus M?_v and log η versus 1/T (absolute temperature). The results are discussed in terms of solution properties of cellulose acetate in acetone and their possible relevance to reverse osmosis membrane science.     

Structure–property relationships in acrylate/epoxy interpenetrating polymer networks: Effects of the reaction sequence and composition

Interpenetrating polymer networks (IPNs) of poly(ethylene glycol) 200 diacrylate and diglycidyl ether of bisphenol A were formed over a range of compositions and with different reaction sequences. We controlled the reaction sequence by thermally initiating the cationic epoxy polymerization, photoinitiating the free‐radical acrylate polymerization, and changing the processing order. The reaction was monitored by attenuated total reflectance Fourier transform infrared spectroscopy, photo differential scanning calorimetry. and modulated differential scanning calorimetry (mDSC). The glass‐transition temperature was estimated from mDSC. Mechanical and rheological tests provided the strength and hardness of the materials. Morphology and phase separation were explored with optical and scanning electron microscopy. All of the physical properties were dependent on IPN composition. Some properties and the morphology were dependent on the reaction sequence. Significant differences in glass‐transition temperature were observed at the same composition but with different reaction sequences. Even with minimal structure, correlations existed between the morphology and material properties with partially phase‐separated samples exhibiting maximum damping. The rapid reaction allowed minimal phase separation, yet different reaction sequences resulted in significantly different properties. This systematic study indicated that the relationships between phase morphology, processing, and the physical properties of IPNs are complex and not predictable a priori. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 891–901, 2007     

Structure–physical property relationships in peroxide-cured butadiene–styrene copolymers

Structure–physical property relationships in high-vinyl butadiene–styrene copolymers have been determined for samples cured with dicumyl peroxide under the same conditions. Three different structures, butadiene–styrene–butadiene (B–S–B) triblocks, butadiene–styrene (B–S) diblocks, and random butadiene–styrene copolymers, have been examined. Flexural modulus increases with increasing styrene content owing to the inherent stiffness of a polystyrene backbone. Swelling increases whereas hardness and heat distortion temperature decrease with increasing styrene content. This behavior is explained by the decrease in crosslink density with increasing styrene content in all structures. Heat distortion temperatures of the B–S–B and B–S networks are superior to the heat distortion properties of the random structures. The B–S–B structure is the most solvent resistant, followed by the random copolymers, with the B–S structures swelling to the greatest extent. Swelling differences between the B–S–B and random networks decrease with increasing styrene content, while swelling differences between the B–S–B and B–S networks increase with increasing styrene content. These results are explained by the nature of the crosslinking reaction and the number of loose ends present in each network.     

Polymerization of propylene with TiCl3–AlEt2Cl–trilauryltrithiophosphite catalyst

AlEt₃Cl was modified with TLTTP (trilauryltrithiophosphite) in the catalyst system consisting of TiCl₃ and AlEt₂Cl. The effects of TLTTP on the polymerization of propylene were studied in comparison with those of alkyl homologues of TLTTP. The catalytic behavior of the TiCl₃–AlEt₂Cl-TLTTP catalyst system in the polymerization of propylene was also studied in comparison with that of the TiCl₃–AlEt₂Cl catalyst system. In the study of the effect of various alkylthiophosphites added, it is found that the bulkiness of the alkyl group affects the rate of propylene polymerization and the stereoregularity of the resultant polymers. The TiCl₃–AlEt₂Cl–TLTTP catalyst system gave different catalytic behavior in the propylene polymerization from that of the unmodified conventional catalyst system (TiCl₃–AlEt₂Cl). These effects of TLTTP were considered to be due to the bulkiness of the alkyl groups attached to the phosphorous atom and the higher reactivity to TiCl₃ of the modified AlEt₂Cl than of the unmodified AlEt₂Cl.     

Structure–protein adsorption relationships of polyurethanes

A series of hydroxyl‐terminated polybutadiene (HTPB) and 4,4′‐dicyclohexylmethane diisocyanate (H₁₂MDI)‐based polyurethanes (PUs) with different molecular weight, hard‐segment content, or 4‐vinyl pyridine content (4‐VP content) were synthesized by solution polymerization. Protein adsorption ratio of fibrinogen to albumin (F/A molar ratio), which was adopted as the indicator of blood compatibility, was measured. The F/A molar ratio on the film's surface was affected by surface composition. The surface composition was quantified by carbonyl group to butadiene group (C=O/C=C) adsorption ratio on FTIR‐ATR spectra and oxygen to carbon atom (O/C) ratio, which was determined by ESCA. PUs with more hard‐segment content on the surface (i.e., high C=O/C=C ratio) possess more fibrinogen adsorption and less albumin deposition (i.e., high F/A molar ratio). The C=O/C=C ratio, hydrogen‐bonding index (HBI value), frequency shift and difference (Δν), glass transition temperature of soft segment (T_gs) as a measure of homogeneity, average strength of interpolymer hydrogen bonds, and interpenetrating networks (IPNs) were utilized to study the surface composition, intermolecular attraction, and IPN formation of the prepared PUs. The effect of hard‐segment content, molecular weight or 4‐VP content on the F/A molar ratio were investigated. The results of FTIR and ESCA explain well the surface composition, and hence, the F/A molar ratio as well. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 297–305, 1999     

Structure–property relationships of composite films

Coextruded multifilms of varying chemical composition and structure were studied by the dynamic mechanical technique. The films studied were two- and three-ply combinations of a polyimide (Kapton) and fluorinated ethylene–propylene copolymer (FEP) and four other two-ply polyethylene and modified polyethylene composites: low-density polyethylene (LDPE)–ionomer, rubber-modified high-density polyethylene (HDPE)–ionomer; ethylene–vinyl acetate (EVA) copolymer–LDPE, and EVA-modified HDPE–LDPE. The mechanical spectra of individual film components were also obtained at 110 Hz between ?120° and 120°C (220°C for the Kapton–FEP system). Mechanical relaxations were examined to determine the degree of interaction between adjacent films and correlate them with tensile and ultimate properties of the composite.     

Architecture–process relationships in stochastic honeycombs

Stochastic honeycomb sandwich panels are fabricated through a simple process of melt‐stretching molten polymer blanks. This study mapped their internal architecture over a wide domain of material process space, defined by the areal density and melt‐stretch rate. The internal architectures were characterized using both topological and geometric parameters: the node density, the total length of webs, the Euler number , and a characteristic fractal area fraction. The mechanical response of the polymer melt was quantified in terms of peak stress and stiffness, along with apparent elongation viscosity. The observed architectures and polymer melt responses were consistent with a varying activated entanglement density in the melt and illustrate how the fabrication conditions can be tuned to obtain a desired architecture. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42174.     

Skin-core structure–fatigue behavior relationships for injection-molded parts of polypropylene. II. Morphology–fatigue behavior relationships

The flexural fatigue properties were studied for PP injection-molded samples of different molecular weight and well-defined skin-core morphology (see Part I). It can be clearly seen that the crack initiation always occurs in the subskin layer of higher macromolecular orientation, and propagates towards the core. The mechanisms of cracking are discussed on the basis of fatigue kinetic data and analytical measurements on the stressed sections. The important influence of processing conditions, essentially holding pressure on the fatigue behavior is illustrated.     

Crystalline/crystalline polymer blends: Some structure–property relationships

Mechanical properties, morphology, and compatibility of polybutene-1 blended with polypropylene, both crystallizable polymers, are described in the present study. Blends of various compositions were studied using tensile tests, differential scanning calorimetry, wide-angle x-ray diffractometry, and optical microscopy. A discussion on the state of compatibility and structure–property relationships for such blends in presented.     

Processing–formulation–performance relationships of polypropylene/short flax fiber composites

This work is a comprehensive study of the effect of extrusion process parameters and formulation on the properties of polypropylene (PP)/short flax fiber composites. The parameters that were varied during the twin‐screw extrusion process were screw configuration, revolutions per minute (rpm), extrusion temperature, and flow rate. The effect of the feeding zone location of cellulosic fiber was also considered. This study investigates the effect of the formulation, cellulosic fiber content, the presence of a coupling agent, and of a reactive additive on composite performance. The composites were characterized in terms of morphology and microstructure, fiber length, rheological, thermal, and mechanical properties. Sensibility to humidity and recyclability were also considered. When compared with as‐received PP, the tensile strength of injection‐molded parts increased with cellulosic content by up to 40 vol %, and the tensile modulus increased 3.5 times when a combination of coupling and reactive agents was used. Exposed to controlled humidity of 50% during 1 year, these composites exhibited a very low level of humidity uptake around 0.85 wt %. The processability of these materials using a cast film line and the mechanical properties of extruded sheets are also presented. Furthermore, these materials demonstrate a good recyclability using injection molding by keeping the integrality of their mechanical properties after five reprocessing cycles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41528.