The SPE Library contains thousands of papers, presentations, journal briefs and recorded webinars from the best minds in the Plastics Industry. Spanning almost two decades, this collection of published research and development work in polymer science and plastics technology is a wealth of knowledge and information for anyone involved in plastics.
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Flexible Polyolefins and Low Density Polyethylene Blends for Film Extrusion Applications
Polyethylene/i-PP(isotactic/crystalline) blends have been studied for years. However, these blends indicate a phase separation that detracts from compatibility and alters properties. It is expected that a combination of a novel less-crystalline polypropylene (FPO) with LDPE will allow for greater compatibility over a wide composition range. The LDPE/FPO blends appear semicompatible. Specifically, film extrusion processability increases, blocking decreases, along with better film appearance, and improvements in tensile strength without a decrease in flexibility. Alternatively, toughness, elongation and impact resistance increase. These enhanced properties may lend the blends to potential packaging applications.
Foamed Polymer Sandwich Composites Reinforced with Three-Dimensional Filler
Open-pore flexible polyurethane (PUR) foam with various pore sizes (1 - 8 mm) was used as filler to reinforce low-density closed-cell PUR flexible foam. The final composite has a sandwich structure, where the core zone has foam-in-foam" structure and skin zones are unreinforced PUR foams. Compared to the regular non-sandwich one-layer PUR flexible foam the sandwich composite exhibits improved mechanical properties: the support factor can be increased up to 65 percent and the compressive force deflection value can be increased almost 100 percent while the density of the composite increases only 25 percent."
ANSI Standards Combined with European Hazard Ranking Methods Provide Plastic Web Processors with Powerful Tools for Enhancing Workplace Safety
A set of four safety standards for film, sheet, coating & laminating, and plastic web winding machinery has been developed under the sponsorship of SPI, and accepted as consensus standards by ANSI. The author reviews some of the more significant requirements of these standards. The standards represent an excellent tool against which to audit existing processing lines to identify hazards to personnel. The European Community has evolved a standard (EN 1050)*1 methodology for identifying and ranking the hazards in processing plants. This methodology is outlined in detail. By utilizing both of these approaches in tandem, hazards can be identified by the auditing against the appropriate ANSI standards, the identified hazards ranked for probable degree of harm to personnel, then safeguarding actions prioritized to obtain the most benefit from the minimum effort.
Continuous Polymerization of Polycaprolactone in a Modular Co-Rotating Twin Screw Extruder
Bulk polymerization of e-caprolactone (CL) has been carried out in a modular intermeshing co-rotating twin screw extruder using aluminum isopropoxide as a coordination-insertion" initiator under a range of processing condition including temperature profiles throughput and screw speed. This homo-polymerization was investigated for various ratios of monomer to initiator. GPC analysis demonstrated that significant quantities of oligomers were produced together with high molecular weight polymer under different reaction temperatures. For continuous polymerization at 130°C using a modular co-rotating twin screw extruder high molecular weight up to 200000 were produced without substantial oligomers by increasing the ratio of monomer to initiator."
Surface Delamination of an Injection Molded Medical Device Using Flexible PVC
An autoclavable medical device was designed using flexible PVC. The device was injection molded and subsequently was exposed to steam autoclaving. Surface delamination was observed in the adjacent area of the gate. Investigations on material properties, pigment dispersion, and residual stresses were conducted. It appeared that by simply controlling the molded-in stresses, the defect could be minimized. In a Design of Experiment (DOE) study, the key molding parameters were identified.
Rheology of Randomly Branched Polymers
The molecular structure of randomly branched polymers is understood using percolation theory. Once the chain length between branch points and the extent of reaction relative to the gel point are specified by synthesis, both the molecular structure and the linear viscoelastic response can be determined using simple models. We demonstrate these ideas using randomly branched polymers with known chain lengths between branch points. Then we exploit this finding to characterize the chain length between branch points for polyethylenes from knowledge of their weight-average molecular weight and zero-shear-rate viscosity.
Analysis of the Flow Front Profile by In-Line Visualization of the Filling Stage
Using a special tool designed with the purpose to visualize the melt flow across the thickness dimension of the mold cavity [l], an experimental investigation was made to assess the polymer melt behavior in specific processing conditions. The aim of the work is to visualize some unexpected flow front behaviors in the selected injection molding conditions. The design of the mold enables to adjust the location of a special glass window along the material flow path. The mold feed is based on a hot runner system. The results presented are direct visualization images of the melt front.
Fracture and Fatigue Properties of Injection-Molded Short Glass Fiber-Reinforced Poly(cyclohexylene-dimethylene-terephthalates)s (PCT) as a Function of Molding Conditions
Summary The static fracture toughness (Kc) and fatigue crack propagation (FCP) behavior of injection-molded short glass fiber (GF) reinforced poly(cyclohexylene-dimethylene- terephthalate) (PCT) composites were determined as a function of material parameters (with and without flame retardant) and molding conditions (injection speed and plaque thickness were varied). The anisotropy in the fracture mechanical response of GF-PCT, determined on compact tension (CT) specimens notched along and transverse to the mold filling direction (L- and T-notching, respectively) was interpreted by considering the molding-induced microstructure (GF layering and alignment). It was established that the effect of injection molding speed is negligible at the same specimen thickness. By contrast, increasing thickness strongly affected the GF structuring and thus the related fracture mechanical response.
Toughening of Epoxy Resins by Partially Decomposed Polyurethane Waste
Hygrothermally decomposed polyurethane (HD-PUR) of polyester type has been used as a cost-efficient impact modifier in tri- and tetrafunctional epoxy (EP) resins. The PUR modifier was added between 5 and 80 wt.% to the EP prior its crosslinking with a diamine compound (Diaminodiphenylsulphone, DDS). The fracture toughness (Kc) and -energy (Gc) of the modified resins were determined on static loaded compact tension (CT) specimens at ambient temperature. The mean molecular weight between crosslinks (Mc) was determined from the rubbery plateau modulus of dynamic mechanical thermal analysis (DMTA) spectra. The change in the Kc and Gc as a function of Mc followed the prediction of the rubber elasticity theory. The efficiency of the PUR modifier was compared with that of a carbonyl terminated liquid nitrile rubber (CTBN). DMTA and fractographic inspection revealed that the PUR modifier was not only present in a dispersed phase of the EP matrix but participated in the build-up of the EP crosslinked network structure. Thus HD-PUR works as active diluent and phase separating additive at the same time. As HD-PUR can be regarded as an amine-functionalized rubber, it was used as hardener alone (by replacing DDS) in some EP formulations.
Thermoplastic Elastomers of Poly(ethylene terephthalate) and Grafted Rubber Blends
Thermoplastic elastomers containing 50 wt.% poly(ethylene terephthalate) (PET) and 50 wt.% rubber with and without glycidyl methacrylate (GMA) functionalization were produced by melt blending. In some cases the method of dynamic curing was also adopted. The static tensile properties and dynamic-mechanical thermal analysis (DMTA) response of the systems were studied. The phase morphology of the blends was of interpenetrating network (IPN) type according to fractographic and DMTA results. It was established that the best mechanical performance exhibited those blends which contained a GMA-grafted nitrile rubber (NBR-g-GMA). The effect of dynamic dynamic curing, for which a two-step procedure was developed, was marginal. Cost reduction opportunities of the recipes by using high-volume polyolefins have also been explored.
Structure/Process/Part Quality Relationship for BMC Injection Molding
Thanks to its qualities and performances, BMC injection molding has nowadays reached a satisfactory maturity level. But nevertheless, this technology remains complex. Thus, the aim of the present study is to determine the technological parameters capable of improving the surface quality of the molded parts. The experiments are performed with a semi-industrial mold for rectangular plate. A first Taguchi Design Of Experiments was used in order to quantify the effect of the feeding, filling, holding and curing parameters on the surface quality. It was completed by a second hybrid DOE, the aim of which was to estimate more precisely the incidence of the main key factors (mold surface temperature, injection flow rate and holding pressure) previously identified. These results have been then confirmed with a different gate location and a modified geometry.
Optimization of Cooling Systems in Injection Molds by an Easily Applicable Analytical Model
The production rate of injection-molded articles is determined by the cooling time of the polymer melt in the mold. By using state-of-the-art numerical software the mold design can be optimized in order to achieve fast cooling. However, the efforts required to apply this software do not always justify its use in dealing with the daily design problems. Taking the changing mold wall temperature into account a straightforward analytical procedure for optimizing the cooling channel lay-out for a thermoplastic resin has been developed. The equations in the model can be easily solved by means of a hand-held calculator, thus enabling quick estimates of the effect of relevant parameters on mold design. Results of numerous simulations and a worked-out example illustrate the application of the model which has led to good results in the practice.
Nucleation in Foam Extrusion
Nucleation results are presented for polyethylene sheet extrusion while using volatile carbon dioxide without any nucleating agent to study homogeneous nucleation. Since the extrusion pressure has to exceed the system pressure, mechanical superheat was calculated from the processing pressure. The experimental results show a different distribution from the conventional nucleation predictions, based on either chemical superheat or mechanical superheat. Also noted was the shear energy dependence. Various nucleation mechanisms are discussed to address the energy role played by shear in foam extrusion.
Modeling Flow-Induced Crystallization in Film Blowing
A mathematical model was developed for the simulation of film blowing including the effects of flow-induced crystallization, viscoelasticity, and film cooling. The microstructural model is based on the formulation of Doufas et al. Our model predicts the location of the freezeline naturally as a result of crystallization and the stresses at the frost line, which are closely related to the mechanical and physical film properties. Depending on the processing conditions, our model predicts uniaxial or biaxial film stretching.
Thermorheological Investigation of Entangled Branch Polybutadienes Having Different Architectures and Arm Lengths
Rheological behavior of entangled six-arm and eight-arm 1,4-polybutadiene melts of the types A3-A-A3 and A3-A- A2-A-A3 is investigated using low amplitude oscillatory shear and viscosity measurements. Experiments covered a time (frequency) and temperature range broad enough to characterize the complete relaxation spectrum. In oscillatory shear, three separate relaxation modes are identified. At high frequencies a maximum in the loss modulus is linked with segmental relaxation. At intermediate frequencies a new relaxation mode characteristic of the arms is observed. Finally, at low frequencies a terminal relaxation process is identified. This process is characterized by a lower plateau" modulus and is thought to reflect cross-bar reptation in an enlarged tube."
Prediction of Degradation of Polyethylene during Rotational Molding
During rotational molding the plastic is subjected to relatively high temperatures for long periods of time. This often causes degradation of the polymer at the inner surface of the molded article. The resulting degraded layer is responsible for the deterioration of the mechanical properties of the part. In practice, the optimum processing temperature and/or heating time must be obtained by means of an extensive molding and testing program. Moreover, as the degradability of polyethylene depends on many factors, such as the molecular structure of the material, the type and concentration of stabilizers and the thermal history experienced during processing, an optimization program that takes into account all these variables is very expensive and time consuming. In this work the degradation of polyethylene is studied using a technique widely used in the assessment of degradation resistance in the pipe industry - Oxygen Induction Time (OIT). The method enables the onset temperature of degradation to be identified using only a few milligrams of material. The data obtained from simple and quick experiments was used to produce an empirical model to predict the optimum inner air temperature for rotational molding of the materials. It is shown that whilst the maximum internal air temperature experienced during rotational molding is a good quality control parameter, there are many other important factors, such as the heating rate of the mold, the thickness of the mold material, etc.
Mixing Characteristics and Mechanical Properties of Polypropylene-Clay Composites
Polypropylene(PP)-clay composites were prepared by melt mixing in an intensive mixer. Three grades of PP's having different melt viscosities were employed to investigate the mixing characteristics of the composites with various clays which belong to organically modified montmorillonite(org-MMT). Depending on the matrix viscosity and nature of the organic layer in MMT, significant variations in the phase structure of the composites were found. In addition to the simple combination of PP and clay, modified PP's having various content of maleic anhydride were also incorporated. Major interest was focused on the effect of varying thermodynamic affinity between the components on the phase evolution and mechanical properties of the composites. Requirements for the effective dispersion of clay in the PP matrix are discussed in terms of both rheological effect and thermodynamic interaction.
Orientation Measurements Online
Orientation of polymers enhances many of their properties, particularly mechanical, impact, barrier and optical etc.. Orientation processes all involve extrusion prior to deformation and can generally be classified into three categories: fibers, films, and parts (sheets, bottles, rods, ...). The knowledge of the polymer orientation produced by the different processes is critical for establishing the process conditions and the final properties of the oriented polymer. There is a long history of investigations of orientation in polymers, mainly from off-line measurements, involving techniques such as birefringence, infrared spectroscopy, X-ray scattering, Raman, NMR, fluorescence, ultrasonic etc. In this presentation, we will focus on techniques which are or could be used for on-line monitoring of orientation processes. These include birefringence, spectroscopy, fluorescence and ultrasonic.
Process Monitoring Using UV-VIS Spectroscopy
The paper describes process monitoring applications by spectroscopic methods for polymer/additive analysis, polymer melt analysis, additive quantitation, QA/QC purposes, on-line compositional polymer analysis, in-situ reaction monitoring (cure kinetics, polymerisation, color designation, molecular interactions, monitoring of extrusion processes, real-time measurements and use of fiber optics. In particular, the current status of on-line multicomponent additive analysis in the polymer melt by means of UV-VIS spectroscopy will be illustrated.
Color Stable, Glass Filled Thermoplastic Polyesters
Color stability is a general term which can be manifest in several ways, for example, color consistency over the course of a run, color stability on UV exposure, color stability on processing, chemical exposure or color stability of the final article at elevated temperature. Materials with enhanced capability of the latter type are positioned in applications where sustained high temperatures would rapidly discolor conventional thermoplastics or thermosets. This paper will discuss the variables that control heat aged color stability in ignition resistant and non-ignition resistant glass filled thermoplastic polyesters.
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