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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Biodegradable Hollow Nanospheres for Drug Delivery
Diabetes is one of most common and widespread diseases. As high as 6% of the world population suffers from diabetes, which, including its complications, is the fourth most important cause of mortality and the main cause of permanent blindness. In the United States alone, 16 million people, nearly one in 17 people, have diabetes. More than 2,000 new cases are diagnosed every day. Most patients require three to four injections of insulin a day. In addition to patient compliance problems, chronic subcutaneous injection may cause side effects, such as lipoatrophy or lipohypertrophy. Oral delivery of insulin has been elusive due to acidic and enzymatic degradation of insulin in the gastrointestinal tract.Oral delivery of insulin is more preferable to subcutaneous injections, because it may provide a better glucose homeostasis and decrease the chances of peripheral hyperinsulinaemia, which is linked to neuropathy and retinoendopathy. Successful oral delivery has not been achieved due to various challenges regarding the sustainability of peptides in the gastrointestinal tract. Typical oral bioavailability of proteins is generally less than 1-2 % because of the numerous physiological barriers in the digestive tract. Ingested proteins become subjected to acidic degradation in the stomach, luminal degradation by enzymes in the intestine, and intracellular degradation. Since proteins are built with peptide linkages, they are susceptible to acidic degradation. It has been shown that some proteins do have some bioavailability when administered directly into the intestine, bypassing the acidic milieu of the stomach.  Various polymer matrices have been designed for enteric coatings with adequate pH-response to protect insulin in the stomach. Polyacrylates Eudragit RS1 and RS2 showed bioavailabilities of 9.3-12.7 % due to their ability to release insulin further down in the gastrointestinal tract at pH 7.5-8.0. Polymer nanospheres have been studied for oral delivery. Accordin
A New Absorption Based Model for Sheet Reheat in Thermoforming
Thermoforming is the process of manufacturing plastic parts by preheating a sheet and then draping it onto a mould. At present, the heater temperature set points for sheet preheat are typically chosen by trial and error. Very little work has been published regarding the control of the sheet surface temperature. Such a control system will improve the quality of the product, reduce scrap and allow for temperature zoning. However, before a suitable control can be successfully designed, an accurate model of the process is required. In this paper, we present such a model of the sheet reheat process which includes the effect of radiation absorption inside the sheet. The inclusion of the radiation absorption effect corrects errors which were found in some previously published controllers. The model presented here is a nonlinear, temperature-dependent multivariable representation of the temperature variation through the sheet thickness.
Advanced Technologies for High Contrast & Color Laser Marking of Plastics
The newest generation of laser material science and hardware/software is driving strong industry demand for indelible, high speed laser marking processes to replace conventional ink printing. This paper presents a “total solutions” methodology for achieving unprecedented marking contrast quality and color laser marking of plastics via concomitant engineering of: 1) laser additive material science, 2) primary molding operations, 3) laser/software technology, and 4) systems integration. The first of its kind laser pigment to receive U.S. Food and Drug Administration (FDA) approval for use in laser processes is introduced as well as techniques to achieve high speed vector marking of alphanumeric text, graphics and product security codes.
The Role of Surfaces on the Impact Response of Polymers
We have evaluated the effect of three decoration methods on the impact response of polymers: automotive paint systems, flexible color films, and molded-in-color pigments. The resulting surface composition and mechanical behavior can differ significantly and was found to affect the impact response of the decorated polymer. Painted surfaces induced fracture on otherwise flexible substrates, while color films could increase, decrease, or have no effect on the dynamic flexural modulus of a decorated polymer. The dynamic flexural modulus and strength of injection-molded polymers varied as a function of thermal aging, due to re-crystallization and oxidation of the molded surface. The trends observed intensified at higher deformation speeds (2.2 m/s) and lower temperatures (-20 to -30 °C).
Can the Nanoindentor Become a Rheological Tool?
The Nanoindentor is a modern version of the hardness tester designed for metals and ceramics. Recently, it has been proposed as a technique to measure rheological properties of soft time-dependant polymeric materials. This technique offers the promise of micron scale spatially resolved rheological information. Additionally, the theoretical foundation and historical development of the working equations for nanoindentation and traditional rheological instrumentation will be presented and discussed. The major difference between nanoindentation and the more classical rheological instrumentation is in the treatment of the instrument-sample interface. To illustrate how the treatment of the instrument-sample interface affects the data a series of measurements was preformed on poly(methyl methacrylate), (PMMA), and poly(dimethyl siloxane) (PDMS) samples.
Constancy of Properties Resulting from Foam Injection-Molding Techniques
Modified injection-molding techniques for foam molding show technical benefits over conventional injection molding, e.g. reduced part warpage and improved dimensional accuracy. However, the density reduction leads to a change in mechanical properties that might even cause premature failure. As long as the specific values for stiffness and strength of the foamed product exhibit small variations - comparable to those in conventional injection molding - one might account for the absolute property change during the design procedure. Accordingly, high property constancy is a technical pre-requisite for load-bearing components and would even allow foam molding of safety relevant parts. The effect of foam molding on the constancy of mechanical properties was investigated and compared to the characteristic performance of conventional injection molding with respect to processing repeatability.
Enzymatic Degradation of Polyurethane-Based Coatings
In order to develop a potentially environmentally safe alternative to conventional paint removal methods we are investigating the enzymatic degradation of liquid polyurethane-based coatings and their films. A simple protocol for degradation has been developed using aqueous buffer solutions at 37 °C and an optimum pH. Two enzymes were selected, namely am esterase from Bacillus sp. and a protease (papain) that could potentially attack ester and urethane linkages. The extent of degradation was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and weight loss. Results indicate higher activity for the papain enzyme depending on the type of paint, enzyme concentration and conditions of application.
Eliminating Surface Melt Fracture Using PPA: The Role of Shear Rate
The efficiency of fluoropolymer processing aids (PPA) in the elimination of surface melt fracture (sharkskin) is determined by several factors, including the PPA domain size, the throughput, and PPA/Polyethylene viscosity ratio. The development of techniques such as frustrated total internal reflectance has allowed for a better understanding of the mechanism of the PPA coating. In this work, the role of shear rate in the elimination of surface melt fracture was investigated. The parameters monitored were die entrance pressure, PPA coating thickness and extrudate appearance. We found that the steady state pressure reduction scaled with increasing shear rate while the final PPA coating thickness was only proportional to droplet size. This is consistent with previously observed polyethylene flow curves.
Extrusion of Microcellular PVC
A novel process for continuous production of microcellular plastics has been developed and applied to make microcellular PVC profiles. The first novel aspect of the process consists of the way in which the blowing agent, or gas, is delivered to the extruder. We pre-saturate the solid PVC pellets with carbon dioxide prior to their delivery into the extruder’s hopper. The second novel aspect of the process is the application of nucleation in solid state to continuous extrusion. When the polymer is saturated with a high-pressure gas, a large number of microvoids get 'charged' with the gas, and act as sites where bubbles will nucleate later when the polymer is heated. As the pellets are crushed and heated in the extruder, a large number of bubbles nucleate as the temperature reaches the Tg of the CO2 plasticized PVC. The melt thus is full of nucleated bubbles that are not able to grow in size due to the pressure that develops in the barrel. When the melt exits at the die, where the pressure is atmospheric, the bubbles have a chance to grow larger and create foam. The process employs effective cooling strategies at the die exit, including lower melt temperatures, to keep the bubbles small.
Numerical Simulation of the Flow Behavior and Breakthrough Phenomenon in Co-Injection Molding
In this work, a three-dimensional finite element flow analysis code is used to study the flow behavior during sequential co-injection molding. Non-Newtonian, non-isothermal flow solutions are obtained by solving the momentum, mass and energy equations. Two additional transport equations are solved for tracking polymer/air and skin/core polymers interfaces. In this paper solutions will be presented for the filling of a spiral-flow mold for which experimental data is available. The numerical approach is shown to predict the experimentally observed core advance stage on which the core flow front catches up on the skin flow front and the core expansion phase during which the flow fronts of core and skin materials advance together without breakthrough. The breakthrough phenomenon is also predicted. The numerical solution is in good agreement with the experiment and predicts correctly the beginning of the core expansion phase and the occurrence of core breakthrough.
Recycling of Butyl Rubber by Ultrasonic Devulcanization
The recycling of butyl rubber based tire-curing bladder was carried out by means of a grooved barrel ultrasonic extruder. Die pressure and ultrasonic power consumption were measured as a function of flow rate and ultrasonic amplitude. Gel fraction and crosslink density of the ultrasonically devulcanized rubber were substantially reduced. The latter caused some reduction in gel fraction and crosslink density in the revulcanized rubber. The mechanical properties of the revulcanized rubber, dependent on processing conditions during devulcanization, were compared with that of the virgin vulcanizate. Good mechanical properties of revulcanized rubber was achieved with 86% and 71% reduction of the tensile strength and the elongation at break respectively, and with modulus increased by 44%. The devulcanized rubber was found to contain tiny gel particles of a wide size distribution with a predominant size of less than 4µm.
Effect of the Compatibilization on the Fluidity of Post Consumer Blends
The blends studied are compound from materials of soft drink and milk post consumer bottles. The materials used were HDPE, PET and two compatibilizers, which are triblock copolymers. The melt flow index test serves to distinguish the qualities of the blends and corroborate the molecular weight effects on density and viscosity. It was obtained viscosity versus blend composition behavior; as PET concentration increases, viscosity decreases. Also were obtained mixing energy curves, and was observed the compatibilizer effect.
Development of Novel Barrier Films using Chaotic Advection ‘Smart Blending’ Device
A Smart Blending Device (SBD) enabled by chaotic advection was used to blend linear low density polyethylene (LLDPE) with 20% and 30% by volume ethylene vinyl alcohol co-polymer (EVOH). Films were extruded to study the relationships of morphology to processing conditions and composition. Morphologies other than droplet, i.e. multilayer, platelet, ribbons and fibers were obtained for each composition. Oxygen barrier, water vapor barrier and mechanical properties were measured. Optimal oxygen barrier and break elongation were obtained with mechanically interlocked single phase continuous laminar-platelet morphology. This blend morphology also eliminated the need for a tie layer. Oxygen ermeation was reduced by 238 and 355 times corresponding to 20% and 30% EVOH. Water vapor permeation was not significantly affected. Tensile strength and ultimate elongation for this morphology were at close to the maximum observed for all blends.
Morphology and Fracture Behavior of Nanoclay-Filled Polypropylene
Polymer nanocomposites are of interest due to improvement in certain material properties relative to virgin polymer or conventional composite materials. For example, compared to conventional materials, Nylon 6/Montmorillonite nanocomposites demonstrate improvements including high strength, high modulus and high heat distortion temperature. Generally speaking, optimal composite properties have been achieved with polar polymer matrixes, which readily disperse polar fillers. A plausible hypothesis proposes that similar improvements could be achieved with non-polar polypropylene (PP)/clay nanocomposites, thus expanding their use in automotive and packaging applications. As a result, both academic and industrials labs have extensively investigated these PP nanocomposites. Consistent with most filler-polymer composite systems, this one demonstrates increased stiffness; however, this improvement is often accompanied by a decrease in toughness. This work examines key factors, which influence the stiffness-toughness balance of PP nanocomposites.
The CIE L*C*h Scan-Color Atlas a Novel Tool for Finding the Right Color
As reported earlier, a preliminary, computer assisted 3D-chromographic representation of all 16.7 million possible RGB colors in the standard CIE L*a*b* (or L*C*h) color space reveals important deviations from well established theoretical concepts. Taking into consideration that the newly defined standard color space appears to have the shape of an anisometric, strongly distorted, RGB cube, we have developed, by binary programming, a complete tridimentional color atlas which, within that space, encompasses all possible colors around a white-to-black lightness axis. The longitudinal distribution of the atlas’ 360 “hue pages” and the latitudinal stacking of its 101 individual “lightness strata” allows the user to pinpoint any one specific color of the thousants that compose the particular CIE h page or CIE L* stratum selected by the user and have it isolated and displayed on screen. A simple mouse click on the chosen color makes a larger sample of that same color appear on screen, accompanied by its correct colorimetric values in all imaginable color spaces and systems. Comparisons between complex 3D-chromographic spectra - which can be fingerprints of anything that shines, glows and spakles in plastics, paints and coatings - become much easier when individual colors composing such spectra can be matched with colors readily identifiable with the novel atlas.
Verification of Blow Molded FEA and Extrusion Blow Molded Bottles
Greater blow molded products can be produced in a shorter time if the promises of finite element analysis programs are true. Reliable and accurate simulation software will allow product designers to make better-informed decisions. Currently in the blow molding industry simulation software is rarely used, because its reliability is unknown.Extrusion blow molded bottles were produced for testing. The bottles were then measured and thicknesses applied to the simulation model. The bottles were tested and compared to results from simulation software. Finite Element Analysis (FEA) was run to simulate loading of the top surface and side loading.
Development of Lubricious Compound for Biomedical Applications Using Hydrophilic Polymers
An attempt was made to develop blends having self-lubricating properties. The approach was to melt blend various base polymers used in the medical industry with hydrophilic polymers known to impart lubricity when applied on the surface as coatings.Different base polymers used were nylon based elastomers and nylons. Hydrophilic polymers used were polyethyl oxazoline and polyvinyl pyrrolidone.These polymers were melt-blended at concentrations of 25% and 50% using a twin-screw extruder. Rheology, coefficient of friction and mechanical properties were studied.
Study of Distributive Mixing Using Polymeric Reactive Tracers in a Co-Rotating Twin Screw Extruder
The distributive mixing profiles were studied during melt-melt blending of two polypropylene melts in a corotating twin screw extruder using the interfacial reaction between two functionalized macromolecular tracers, which were separately blended into each of the polymer melts. The mixing performance is directly related to the conversion of this interfacial reaction. We studied the effect of operating conditions and kneading disk configurations with various combinations of staggering angles (forward 30°, neutral 90°, and reverse 30°) and thicknesses (thick and thin) on distributive mixing.
Comparison of X-Ray Fluorescence Spectrometry to Traditional Analytical Methods for Elemental Determination in Polymeric Materials
The ability to quantitatively identify specific restricted or “hazardous” elements (lead, cadmium, etc.) in polymer matrices is an analytical challenge. Many companies, particularly those in the electrical and electronic manufacturing industry supply chains, are attempting to obtain the necessary data to comply with a variety of customer-driven and/or legislative restricted substance requirements. Two analysis testing approaches being employed are traditional elemental analysis procedures, and x-ray fluorescence spectrometry (XRF).The purpose of this work was to empirically evaluate the effectiveness of XRF quantitative elemental analysis in polymeric matrices and compare this approach to traditional acid digestion – inductively coupled plasma (ICP) measurement techniques. While others are included in this evaluation, the primary elements of interest are lead, cadmium, mercury, and chromium.XRF and Acid Digestion - ICP measurements were conducted on twenty-two polymeric materials, including PVC and polyolefin materials. The polymeric specimens included certified reference materials, custom compounded materials, and others. The data includes measurements performed by four different XRF instrument manufacturers as well as Underwriters Laboratories (UL). Both fundamental parameter and simple “standards” calibration XRF data was collected. The majority of the Acid Digestion - ICP measurements were performed by UL.Although correlation between XRF and Acid Digestion – ICP methods varied widely in some instances, this study’s results suggest promise for the use of XRF as a qualitative screening tool for the material types investigated. Additional work needs to be done, however, to realize the full capability of the XRF analysis approach, particularly using a fundamental parameter or simple calibration approach.
Optimization of the Injection Molding Process Using Design Sensitivity Analysis
Getting the proper combination of different process parameters such as injection speed, melt temperature and mold temperature is important in getting a part that minimizes warpage and has the desired mechanical properties. Very often a successful design in injection molding comes at the end of a long trial and error process. Design Sensitivity Analysis (DSA) can help the processors improve the design and can produce substantial investment savings in both time and money. This paper investigates the ability of the sensitivity analysis to drive an optimization tool in order to improve the quality of the injected part. The paper presents the solution of the filling stage of the injection molding process by a 3D finite element solution algorithm. The sensitivity of the solution with respect to different process parameters is computed by using the continuous sensitivity equation method. Solutions are shown for the non-isothermal filling of a rectangular plate with a polymer melt behaving as a non-Newtonian fluid. Sensitivity of the solution is used to build the surface response of the injection pressure with respect to a given design parameter (the injection speed in the present case). This is then used to determine the conditions corresponding to the minimum injection pressure.
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