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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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Conference Proceedings

Molecular Modeling Studies of the Molecular Components of Starch. I. an Atomistic Model of the Double Helical Structure of Amylose and Amylopectin
F.A. Momany, J.L. Willett, May 1999

Starch is made of amylose and highly branched (amylopectin) ?-linked chains of D-anhydroglucose. A detailed atomistic model for the amylose and amylopectin components of starch was simulated using established molecular modeling methods. In particular, attention is paid to the formation of A and B amylose in the double helix configuration, and to the formation of the double helix configuration after the branch point in amylopectin. Molecular dynamics simulations are carried out over extended periods of time, and calculations suggest that the observed crystallographic parameters for the A and B forms of amylose can be reproduced with water molecules either inside the core of the double helix or with the core devoid of water. In both cases the strand repeat distance of ~2.14 nm is found. Models of the amylopectin macroscopic formation are described and speculation as to the molecular details of the amorphous high solvent and crystalline starch structure are made.

Investigation of the Reaction Kinetics within Expandable Mixtures Used for Preparing Injection-Molded Polyolefin Foams
Pierre Moulinié, Caroline Woelfle, May 1999

In this study, expandable polyolefin elastomer mixtures used for preparing cross-linked polyolefin foams were studied by Differential Scanning Calorimetry (DSC) to determine the reaction rate constants for azodicarbonamide (AZDC) decomposition. Activation energies and rate constants were computed from results obtained by variable heating rate DSC experiments. Predictions made from the kinetic equations were compared with results from isothermal aging experiments as well as observations made during injection molding of cross-linked foams.

Use of a Hexafunctional Coupling Agent to Control Free Radical-Induced Molecular Weight Degradation during Reactive Processing of Polypropylene
Kristine N. Ludwig, Robert B. Moore, May 1999

Variable quantities of a hexafunctional coupling agent were reacted with polypropylene (PP) in a twin-screw extruder. An increase in the z-average molecular weight was observed, and attributed to the formation of PP crosslinks through the coupling agent, which tended to offset molecular weight degradation due to ?-scission. The mechanical properties and morphologies of the resultant extrudates were analyzed. Notched Izod impact and tensile strengths were enhanced over those of the control, which lacked added coupling agent. The presence of coupling agent crosslinks resulted in increased nucleation and growth rate during crystallization from the melt.

Fill Length Determination for a Non-Intermeshing Twin-Screw Extruder
D. Tomayko, D. Knoeller, L. Ridzon, R. Mudalamane, D. Bigio, May 1999

This paper describes the effect screw speed and material throughput have on the filled regions in front of restrictive elements on a Non-Intermeshing Twin-Screw Extruder (NITSE). Fill length, operating conditions, material properties, and the pressure over the cylinders are all measured and compared to a model of pressu fill lengths can be predicted for a non-transparent barrel from geometric terms and material properties."re buildup in the screw elements of a NITSE. Experiments are performed over a range of operating conditions in a clear barrel ?0.8 NITSE. By determining the relationship between fill length and pressure across the cylinders

Fill Length Determination for a Non-Intermeshing Twin-Screw Extruder
D. Tomayko, D. Knoeller, L. Ridzon, R. Mudalamane, D. Bigio, May 1999

This paper describes the effect screw speed and material throughput have on the filled regions in front of restrictive elements on a Non-Intermeshing Twin-Screw Extruder (NITSE). Fill length, operating conditions, material properties, and the pressure over the cylinders are all measured and compared to a model of pressure buildup in the screw elements of a NITSE. Experiments are performed over a range of operating conditions in a clear barrel ?0.8 NITSE. By determining the relationship between fill length and pressure across the cylinders fill lengths can be predicted for a non-transparent barrel from geometric terms and material properties."

Amorphous Orientation in Polymers Determined Using Two-Dimensional X-Ray Diffraction Data and its Significance
N.S. Murthy, K. Zero, May 1999

Amorphous orientation in polymers is described in terms of the fraction of the amorphous chain segments which are oriented, and the degree of alignment of the amorphous chain segments. The method for evaluating these two features using two-dimensional x-ray diffraction data is described. Whereas the unoriented amorphous component contributes to an isotropic amorphous halo, the oriented component gives rise to enhanced scattering near the equator. The method is illustrated using the data from PET and nylon 6. The role of amorphous orientation in determining dimensional stability, diffusion behavior and glass transition temperature is discussed.

Compositional Effect on Phase Behavior and Uniaxial Deformation Properties for Polyethylene Naphthalate/Polycarbonate Cast Films
A. Beers, M. Cakmak, K. Min, May 1999

The influence of Polycarbonate on the deformation behavior of PEN at temperatures between the glass transition and cold crystallization was investigated at PEN/PC compositions containing 5-30% Polycarbonate. Deformation studies revealed that the addition of as little as 5% Polycarbonate eliminates the neck formation that occurs in stretching of 100% PEN films at intermediate stretch ratios. This neck formation is responsible for narrowing the processing window of 100% PEN to high stretch ratios where the films become uniform after all the necks are eliminated. This neck formation was attributed to the cooperative reorientation of the naphthalene planes parallel to the film surface that occurs at highly localized regions upon stretching1. In this paper, the effect of PC concentration, processing temperature, deformation mode, and ratios on the dynamics of film formation and the structure and properties.

Advances in Thermoforming through the Use of ESPOR, a Micro-Porous Aluminum Mold Alloy
Russell L. Bowen, May 1999

ESPOR is a new product that uses micro-porous casting technology for the production of tooling for the thermoforming industry. Some unique characteristics of ESPOR are: • The ability to cast off an existing pattern due to the absence of material shrinkage. • The porous microstructure of the material (10-15% air by volume) eliminates the need for drilling vacuum holes through the core or cavity area. In addition to the above, by having metallic cooling properties, excellent machining properties, and castable water lines, all in a package that weighs approximately 36% less than an aluminum mold, ESPOR promises to be a major tooling option in the future thermoforming industry.

Measuring the Diffusivity of Additives in Polymer Films Using In-Situ FTIR-ATR Spectroscopy
Christine A. Gagliardi, Linwood B. Muire, Douglas E. Hirt, May 1999

In many polymer-film applications, additives migrate from the bulk of a film to the film surfaces. For these cases, it is more realistic to measure the additive diffusivity in a diffusion-out mode rather than using a mass-sorption (diffusion-in) experiment. This is particularly true for additives that are solids at the testing temperature. This research focuses on the evaluation of additive diffusivity in a diffusion-out mode via in situ FTIR-ATR spectroscopy, which has the advantage of requiring only small samples of thin films. The technique will be described, including methods to obtain reproducible contacting pressure between a film sample and an ATR crystal and to perform in situ experiments at elevated temperatures. Diffusivity results are presented for the migration of an erucamide slip agent in LLDPE films.

The Use of Morphology Data in the Design of Injection Moulded Flat Products
A.S. Pouzada, N.M. Neves, May 1999

Thermoplastics are one of the first choices that engineers consider for many practical applications. Most of those parts, often used in automotive or appliance products, are required to have high mechanical performance and are mostly made by injection molding. Strength and dimensional stability under stress are common requirements. Moreover, the quick completion of the development and production process before entry in the market is a mandatory specification for many plastic products. The design process of plastic parts follow the general pattern of the engineering design activity, which was partially reorganized for time-delivery shortening by implementing the concept of concurrent or simultaneous engineering [1]. The overall process flow chart can be structured as shown in Figure 1.

Microwave and Optical Applications of Metallic Conductive Polymers
L. Olmedo, P. Buvat, P. Hourquebie, F. Lubrano, May 1999

Recent progress obtained in the synthesis of conductive polymers with a well controlled structure have shown that high levels of conductivity can be achieved with a metal like character. The consequence is a large modification of their dielectric properties, especially in the microwave and optical range. So far, applications such as EMI shielding, microwave absorption or optical modulation have been developed with this class of materials. We are presenting here a survey on these works and we shall show how metallic conductive polymers represent, beyond their pure scientific interest, strong potentialities for microwave and optical applications.

Solubility of HFC-134A, HCFC-142B, and HFC-152A in Polystyrene
Yoshiyuki Sato, Toru Iketani, Shigeki Takishima, Hirokatsu Masuoka, May 1999

The vapor-liquid phase equilibria of HFC-134a, HCFC-142b, and HFC-152a in polystyrene were measured at temperatures from 348 to 473 K and pressures up to 3.2 MPa by using a volumetric method. The solubility of these blowing agents decreased with temperature. Amount of HCFC-142b, HFC-152a, and HFC-134a in polystyrene decreased in that order. The solubilities measured were correlated by the Sanchez-Lacombe equation of state. Agreement between the experimental solubilities and the correlations with a temperature-dependent binary interaction parameter was satisfactory. The interaction parameters linearly varied with temperature.

Evaluation of Additive Concentration Profiles in Multilayer Films
Shilpa Y. Sankhe, Douglas E. Hirt, William P. Roberts, Marvin R. Havens, May 1999

The diffusion of additives in single-layer polymer films has been characterized using FTIR microspectroscopy. This research extends that work to multilayer films. In particular, this investigation focuses on the diffusion characteristics of an erucamide slip agent in press-laminated bilayer and coextruded trilayer LLDPE films. The objective was to monitor the extent of additive partitioning between the various layers and to the outside surfaces of the multilayer films. Results demonstrate the effect of initial additive loading on the spatial distribution of additive and the apparent surface concentration as a function of time.

Proper Utilization of Porous Mold Steel to Solve Venting Problems
Russell Bowen, May 1999

Since its introduction to the North American mold making market, this porous, self-venting mold steel has proven remarkably successful. This porous steel has allowed molders to reduce injection pressure, cycle times, shot size and scrap rates. Additional benefits have included elimination of flow lines, short shots, and material burning and ghosting on edges of textured parts. Design consideration should include: 1. Resins Used 2. Tool size 3. Prevention of Problems 4. Whether to use 3 micron, 7 micron or 20 micron porosity Additional considerations should be given to regular maintenance and cleaning of porous inserts.

Organic Solar Cells - Stabilization by Plastic Encapsulation
R. Schroeder, G. Feistritzer, W. Graupner, G. Meinhardt, D. Berman, P. Preishuber-Pfluegl, F. Stelzer, D. Faiman, G. Leising, May 1999

Due to the simple chemical tuning of the electronic properties of organic molecular semiconductors these materials are investigated in optoelectronic devices, covering the field from laser diodes to solar cells. In all these applications the stability of the active organic layer is crucial. Photo-oxidation is one of the biggest problems when using organic molecules for solar cells. We show how encapsulation affects the lifetime and performance of such devices. We present examples of organic solar cells based on poly (para) phenylene vinylene (PPV) and sexiphenyl (PHP). Its spectral response and electrical characteristics were tested under laboratory conditions and under AM1.5 conditions in the desert.

Thermal Expansion and its Effect on the Normal Force for a Modified Force Rebalance Transducer
Carl R. Schultheisz, Gregory B. McKenna, May 1999

Prior work in this laboratory [Niemiec, et al, J. Rheology, 40, 323-334 (1996)] showed that anomalous normal forces could arise in rotary shear measurements when thermal expansion of the force rebalance transducer (FRT) superimposed a squeezing flow on the shear flow. Transducer heating results from the current to the magnetic coils in the FRT necessary to counteract the applied torque. Partly due to this work, the manufacturer redesigned the transducer by replacing stainless steel components with Invar, an alloy with a very low coefficient of thermal expansion. Tests on the new transducer show that the thermal expansion is significantly reduced. The behavior of the new transducer is described.

A Nonlinear Fluid Standard Reference Material: Progress Report
Carl R. Schultheisz, Gregory B. McKenna, May 1999

A new NIST Standard Reference Material (SRM 2490 - Nonlinear Fluid for Rheological Measurements) demonstrates shear thinning and normal stresses typical of polymeric fluids. SRM 2490 consists of polyisobutylene dissolved in 2,6,10,14-tetramethylpentadecane (pristane), giving a stable fluid with a wide temperature range. NIST will certify the linear viscoelastic behavior and the shear-rate dependence of the viscosity and first normal stress difference between 0 °C and 50 °C. NIST will also use the fluid in a round robin to help the polymer community identify sources of variability in rheological measurements. Here we report progress on the project.

Pressure Flow in the Barrel: The Relationship of Fluid Elements in the Cavity to Original Barrel Locations
Lawrence R. Schmidt, May 1999

Pressure-driven flows dominate the injection molding process. A pressure flow is established in the barrel of the injection molding machine initially when the screw moves forward to inject material into the cavity. The laminar shear flow established by this action exhibits a parabolic velocity profile with the highest velocity in the center of the barrel and zero velocity at the barrel walls (Figure 1). With plastic melts the velocity profile is somewhat “flattened” due the non-Newtonian, i.e. nonlinear, rheological behavior of the melt. Such a velocity profile is not only characteristic of the basic flow in the barrel, but it also applies to the pressure-driven shear flows in the nozzle, runners, gates and cavities. The shear flow in the barrel is unique since the origin of the pressure energy is the screw displacement during injection. In order to maintain the highest velocity in the center of the various flow channels, material needs to be constantly added at the pressure source. This occurs in the barrel in the region closest to the screw. As the screw moves down the barrel, slow moving melt adjacent to the screw tip and near the barrel wall, is forced to the fast-moving center region (Figure 2). This sequence continues until the screw bottoms out or until the injection is stopped. Experiments with colored tracers have verified the laminar flow conditions and the volume-element relationship.

A Study of the Long-Term Crystallization Process in Polypropylene and Acetal
Michael P. Sepe, May 1999

Over the years there has been a great deal of discussion regarding the length of time required for certain semi-crystalline materials to achieve full potential crystallinity. Many suppliers of flexible chain crystalline materials have studied the phenomenon of post mold shrinkage. In addition, many suppliers of these materials recommend an extended conditioning period for molded test specimens before conducting physical property tests. It is supposed that it can take two to three weeks for properties to fully develop. Yet even within supplier organizations there seems to be no consensus on the necessity for this practice and little documentation exists to support either a long-term or a short-term approach to sample conditioning. This study uses tensile stress-strain properties and dynamic mechanical analysis to track the property development of test specimens molded in polypropylene and acetal. Unfilled homopolymers and copolymers were used in both material families.

The Application of New Spectral Birefringence Technique to Characterize the Structural Changes That Take Place in Heat Setting of Preoriented PET and PETG
Toprak F. Serhatkulu, Miko Cakmak, May 1999

With the intent of simulating the heat-setting process of a tenter film stretching process, the birefringence development of PET and PETG films are monitored on-line using spectral birefringence technique. In this technique, a white light source is used on an optical train with a heating chamber equipped with rapid sample insertion capability. The full visible spectrum is utilized and essentially, this technique has no limitations on measurements of retardation to very high values. Spectral birefringence technique also enables one to detect the changes in the trend in birefringence (such as decrease as a result of relaxation, or increase as a result of crystallization) and to investigate changes that occur very rapidly in the order of seconds. The effects of stretch ratio on the kinetics of the structural changes in PET and PETG films are investigated. It is found that heat setting at temperatures where crystallization rates are slow results in partial relaxation followed by a rapid rise in birefringence, particularly for samples with low stretch ratios. In this paper, only the results for PETG films are presented due to the limited space. However the presentation will cover the results for both PET as well as PETG films.










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