SPE Library

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

Rheology beyond One Million Reciprocal Seconds
David W. Riley, May 2001

In the wire and cable industry the speed of the insulated copper wire through the die is very fast. In 1963 a 24 gage wire was coated with plastic with a clearance in the die of only 5 mils (1 mm = 40 mils, i.e., 5 mils = 0.125 mm) at a speed that exceeded 2500 feet/min (almost 1 kilometer/minute). The shear rate calculates to be in excess of one million reciprocal seconds (actually this is 4 x 106 sec-1). Drastic changes were discovered in the molecular structure of the plastic. Shearing the polymer chain causes changes in the molecular structure that can be advantageous or severely detrimental. These running conditions and the effect on the PVC is the concern of this paper.

Re-Inventing the Wheel: Breaking New Ground with Rotary Shuttle Technology
Brian L. Dowler, Rolf Weingardt, May 2001

Long-stroke shuttle machines have developed a well-defined role in the extrusion blow molding of calibrated neck bottles. However, these machines have limitations due to factors such as the long axial length of the stroke and the need for large multiples of tooling, knives, dies, punches and In-Mold Labeling (IML) tooling sets per the number of mold sets. Many of these limitations have been overcome through the incorporation of an indexing rotary motion. The end result is a technologically advanced, small footprint machine that can produce IML bottles with very little cycle time penalty. Further, the multi-layer containers are de-flashed before exiting the machine with positive bottle transfer between stations with a true single-point product discharge. All of this is accomplished using fewer die pins, bushing sets, cut-off knives, trim dies, punches, and IML deployment heads than typically required. This paper discusses the technical hurdles that were overcome to re-invent" the shuttle machine and open up new possibilities in extrusion blow molding."

Effects of Chain Extension/Branching on the Viscoelastic Behavior of Styrene-Maleic Anhydride/Polyol Blends
Goknur Bayram, Ulku Yilmazer, Marino Xanthos, May 2001

Styrene Maleic Anhydride (SMAH) / Polytetramethylene Ether Glycol (PTMEG) blends were produced in a batch mixer in the presence or absence of hydrated zinc acetate catalyst. The oscillatory shear properties in the melt state and the Fourier Transform Infrared Spectra (FTIR) of the blends were studied. The SMAH/PTMEG/zinc acetate blend had higher storage modulus, G', loss modulus, G and complex viscosity ?* than the blend without the catalyst. The distribution of relaxation times was calculated by using the oscillatory shear data and a generalized Maxwell Model. In comparison to pure SMAH for all the blends higher relaxation strengths at longer relaxation times were obtained due to chain extension and branching. The FTIR spectra of the SMAH/PTMEG blend indicated ester formation confirming the existence of chain extension / branching reactions in batch mixing."

The Selection of Mould Design Variables in Direct Stereolithography Injection Mould Tooling
R.A. Harris, P.M. Dickens, May 2001

Models produced by rapid prototyping (RP) allow the validation of a parts design with respect to its geometry. Beyond this, the rapid prototyping technique Stereolithography (SL); when used to manufacture moulding cavities, has shown itself to be capable of rapidly and economically producing low volumes of plastic injection moulded parts prior to commitment to hard tooling. These parts are more complete prototypes, they imitate parts that would be produced by a hard tooling manner with respect to their material, geometry and production process. A major drawback of the SL injection moulding process is that the tools are susceptible to producing only a small number of parts before failure. SL tools may break under the force exerted by part ejection when the friction between a moulding and a core is greater than the tensile strength of the core resulting in tensile failure. Very few justified recommendations exist concerning the choice of mould design variables that can lower the part ejection force experienced and reduce the risk of SL tool failure. This research investigates the ejection forces resulting from injection moulding polypropylene (PP), acrylonitrile-butadiene-styrene (ABS) and polyamide 66 (PA66) parts from SL tools which are identical in all respects except for their build layer thickness (a process variable when generating the SL tooling cavities) and incorporated draft angles (a tooling design variable). This work attempts to identify appropriate evidence for recommendations with respect to these variables and SL injection moulding. The results show that linear adjustment of draft angle results in a fairly minor linear change of part ejection force according to the moulding material. A linear adjustment of the build layer thickness results in a greater change in part ejection force as a more non-linear relationship. In both cases greater ejection forces were experienced by PA66, then ABS and then PP parts, respectively. The results also show that the s

Modeling of Fluted Mixing Elements
Petra Samsonkova, Jiri Vlcek, May 2001

3D simulation helps to have a better understanding of material behavior in complicated flow geometries such as extrusion dies or mixing elements where a 2D simplification fails. In our study, we will simulate the material behavior in a fluted mixing element. The fluted mixing element is one of many used mixing elements. Its specific geometry influences a good or bad mixing performance as well as local heat generation because of the shear dissipation. The study is focused on parametrical study of the influence of mixing element dimensions on the material behavior (generated pressure drop, mixing quality etc.). It is also focused on the determination where and under which conditions the heat generation is occurring, what is the related temperature rise and how this high heating can be prevented.

Blends of Various Proteins with Poly(Hydroxy Ester Ether)
C. Wang, C.J. Carriere, J.L. Willett, May 2001

Blends of poly (hydroxy ester ether) (PHEE), a recently developed bisphenol A ether-based synthetic biodegradable thermoplastic polymer, with a soybean protein isolate and two hydrolyzed wheat glutens were studied. Blends of the proteins with PHEE were produced from 20-70% by weight of protein content. The Young's moduli of the protein/PHEE blends falls in the range of 0.8 - 1.5 GPa with the tensile strengths ranging from 10-30 MPa. Fracture strengths of the blends ranged from 9-2 MPa-m1/2 depending on the amount of protein added. Morphological analysis indicated acceptable adhesion between the protein and PHEE phases in the blends. In general, as the protein content was increased the materials lost ductility and failed in a brittle manner; however, the mechanical properties of several compositions were comparable to current commercial thermoplastics such as polystyrene.

The Shelf Life of Filled Polymeric Material for Medical Device: Accelerated Thermal Aging Experiment and Kinetic Prediction
Xiaoping Guo, Richard E. Stehr, May 2001

In the present study, a kinetic method is suggested to determine the shelf life of a filled polymer material prepared for making medical device, including barium sulfate-filled polyethylene and poly(ether block amide), by using an well-designed accelerated thermal aging experiment. Accordingly, the effects of aging time and elevated temperature on mechanical performance of the material are mathematically defined by thermal aging index, namely the ratio of the elongation-at-break after to that before a period of thermal aging. A general m-order rate kinetics with Arrhenius-type temperature dependence is utilized to describe the deterioration of the mechanical properties during aging. An accelerated thermal aging experiment is performed to statistically measure various aging indices for the samples aged at various elevated temperatures within different short-term aging times. Kinetic parameters are acquired using nonlinear regression to the experiment. By assigning a permissible aging index, the shelf life of the material (or medical device) is kinetically predicted at storage temperature.

Robust Simulation for the Heating Stage in Thermoforming
A. Yousefi, A. Bendada, R. DiRaddo, May 2001

Process simulation traditionally relies on the exact knowledge of parameter inputs, such as material properties, process conditions and heat transfer properties. However, these parameters are never known exactly and a degree of uncertainty exists. This level of uncertainty affects the confidence in the results obtained. One therefore has two options, reduce the level of uncertainty or account for it in the simulation through appropriate sensitivity trials. This work reduces the level of uncertainty through accurate evaluation of the input parameters. Accordingly, the accuracy of the predictions is significantly improved.

Thermomechanical Modelling, Microstructure Development and Part Performance in Stretch Blow Moulding
D. Laroche, R. DiRaddo, J. Brace, May 2001

Blow moulding simulation can be used as a predictive tool for determining the bottle performance as a function of the stretch blow moulding operating conditions. Modelling the successive processing steps is necessary in order to obtain the final bottle geometry and the distribution of polymer microstructure. The container properties are then used to estimate top load resistance. The objective of this work is to integrate microstructure models in process simulation in order to better estimate part performance in service. The models are evaluated for the prediction of top load resistance of PET containers. Experimental validations of the integrated process and performance models were conducted for the one-stage injection stretch blow moulding process.

Dispersion of Nanoparticles in High Performance Polymers Using Thermosetting Resins
Sadhan C. Jana, Sachin Jain, May 2001

A low molecular weight epoxy was used as dispersant of fumed silica in polyether sulphone (PES), a high performance polymer with typical processing temperatures of ~340-380°C. Small amounts of low molecular weight epoxy reduced the processing temperatures of PES by as much as 100°C and, due to polar nature, helped disperse fumed silica particles, which contained active silanol groups. Epoxy molecules were later crosslinked using suitable curing agents. An order of magnitude reduction in the size of dispersed fumed silica particles and significant improvement in HDT were observed.

On the Effects of Migration of Filler Particles on Conductivity and Mechanical Properties
Sadhan C. Jana, Sashishekhar Doni, May 2001

Shear-induced migration of filler particles during molding and extrusion of filled polymer compounds of polypropylene and glass beads and conductive carbon particles was investigated. The high-shear flow conditions were generated in capillary rheometers with length to diameter ratio of 20 and 30 and in injection molding machine. Reduction of both surface and volume conductivities of injection molded samples was observed, especially in the cases of conductive compounds with conductive particle composition in the range of percolation volume fraction. Significant migration of glass beads was observed from the surface to the interior in blends with PP. Maleic anhydride grafted polypropylene (PP-g-MAH), used to promote binding with filler particles, reduced the extent of migration of glass beads, but improvement in conductivity of injection molded samples was not observed.

Are Fundamental Mechanistic Studies Useful? A Novel Study in the Thermal Degradation of PET during its Manufacture and Processing Will Be Discussed to Illustrate the Importance of Mechanistic Studies
Kishan C. Khemani, May 2001

PET polyesters for food packaging comprise one of the fastest growing polymer markets in the world. One of the biggest challenges in the PET industrial R&D sector for the past twenty years has been to find the means to reduce the amount of acetaldehyde (a PET polyester's degradation by-product) generated during PET production and processing. A novel approach for studying the mechanism of thermal degradation of PET polyesters and copolyesters is described in this study, which also suggests precisely the ways to significantly reduce the acetaldehyde content in these polyesters. In this study, the amount of acetaldehyde evolved was measured over time at an elevated constant temperature. We found that there was a gradual decrease in the amount of acetaldehyde generated with time, and that this decline eventually approached a near asymptotic value. A degradation mechanism was proposed which showed that acetaldehyde was generated by three different routes involving, first, the hydroxyl end-groups, second, the vinyl end-groups and finally, the mid-polymer chain-scission. It was further suggested that of these, the hydroxyl and the vinyl end-group based acetaldehyde generation routes depleted with time leaving behind the last, but inexhaustible, chain-scission route. From the data in this study, it was also possible to estimate the rate of acetaldehyde generation by this mid-polymer chain-scission route. This information was then applied together with the (a) amount of residual acetaldehyde in the resin, (b) HO-end group concentration and (c) vinyl- end group concentration, to calculate the amount of acetaldehyde generation possible over a given period of time. This calculated [acetaldehyde] compared very well with the actual observed [acetaldehyde] over the same period of time, thereby validating the proposed mechanisms. In agreement with the thermodynamic principles, a near doubling of the chain-scission acetaldehyde generation rate was also observed when the temperature

Surface Modification of Polymer via Surface-Induced Migration of Copolymer Additives
Hojun Lee, Lynden A. Archer, May 2001

Surface-induced migration of low surface tension block copolymer additives, polystyrene-b-polydimethylsiloxane (PS-b-PDMS) and high surface energy copolymer additives, polystyrene-b-polymethylmethacrylate (PS-b-PMMA) in a polystyrene (PS) host was investigated using a series of matrix PS molecular weight (Mw). Dynamic Contact Angle analysis and Attenuated Total Reflection Fourier Transform Infrared spectroscopy measurements were used to characterize surface properties of polymer/additive blends created by solvent casting, precipitation, and melt annealing processes. For all matrix Mw, selective DMS enrichment of the air/polymer interface was observed due to the strong surface energy difference between additives and matrix. The surface excess concentration of DMS group, ??DMS was also found to depend on host polymer Mw and annealing conditions: ??DMS ~ Mw,PS?, where the scaling exponent a is a function annealing conditions. Whereas entropic-driven surface migrations were observed in PS-b-PMMA/ PS blends. The diffusion of PS-b-PMMA in PS matrix was found to depend on matrix molecular weight even though much high Mw, which is not consistent with reptation theory in molecularly homogeneous linear blends. And also for high molecular weight PS, thermodynamic driving force is revealed to compete with diffusion rate of additives. These findings could be discussed in terms of the matrix Mw dependence of diffusivity, surface tension and configurational entropy of host polymer.

Kinematics of Quasistatic Inflation of a Catheter Balloon Made of Elastomeric Material: Simulation and Experiment
Xiaoping Guo, Michael Bednarek, May 2001

Based upon a nonlinear membrane theory, a theoretical model is proposed for simulating a quasistatic deformation process of a catheter balloon made of an elastomeric material and inflated by the internal pressure acting across the membrane of the balloon. A Lagrangian approach is utilized to describe a material particle's motion during inflation. The deformation field and the system of governing equations are determined in terms of the principal stretches and the Cauchy stresses. With ~, incorporation of the constitutive laws of hyperelasticity and a set of proper boundary conditions, the numerical scheme for calculating the deformation-loading relationship of the balloon under quasistatic equilibrium condition is developed. The inflation experiments are conducted under the assumed quasistatic condition for various angiographic catheter balloons of different designs. Intermediate inflated geometries and inflating pressures at various inflating volumes are measured and compared with the predictions. It is found that the theoretical model can reliably predict the short-term kinematic behavior of balloon inflation. In addition, the effects of various balloon design parameters on the kinematics of inflation are evaluated.

High Performance Decoration with Polyamide Films
Joerg Lohmar, Michael Beyer, May 2001

Over the last decades a large number of new surface decoration and protection processes have been developed using polymer films instead of coatings. Films of polyamide 12 and polyamide 12 elastomers offer the best combination of transparency, mechanical properties, and chemical resistance. Highest quality diffusion printing techniques are applied to create brilliant decorations on i. e. sports articles like snowboards, skis, tennis rackets, or for demanding automotive applications. Most recently two-layered so called lacquer films with brilliant metallic or other effect fillers were introduced into the market to replace conventional multi-step coatings. In the paper we will present mono- and multi-layer structures of decorative and protective polyamide films. Printing and processing techniques will be discussed showing various applications.

Structure of Propylene/1-Pentene Random Copolymers
L. Halász, K. Belina, O. Vorster, I. Tincul, May 2001

Propylene/1-pentene copolymers were prepared, characterized and reported previously. [1-6]. This new family of copolymers form ?-modification during isothermal crystallization. Upon deformation significant changes take place in the crystalline structure of the material. Two extensional deformation methods, (thermoforming and cold stretching) were used and the thermal and crystalline properties of both the deformed and undeformed samples were determined by DSC and WAXD. Thermoforming has no effect on the thermal and crystalline properties of the material. On the other hand, cold stretching changes the crystalline structure of the material. Upon extension, the degree of ?-modification decreased with a corresponding increase in the degree of ?-modification.

In Situ Observation of Fracturing Behavior of Polyethylenes by Transmission Electron Microscopy
Tatsuya Kasahara, Noboru Yamaguchi, May 2001

In situ observation of deformation and fracturing process of polyethylenes was carried out using a transmission electron microscope (TEM). It was found that there are three kinds of fracturing behavior concerning polyethylenes. In case of linear polyethylenes, two kinds of fracturing behavior caused by Crazing" and "Elongation" were observed. On the other hand low-density polyethylenes (LDPEs) having long-chain branches (LCBs) were fractured dominantly by "Interfacial splitting" of spherulites. These results show that the molecular structure of polyethylenes effects the deformation and fracturing behavior."

The Effect of Wall Slip on the Performance of Flat Extrusion Dies
W.A. Gifford, May 2001

Flat extrusion dies are commonly used in a wide variety of film, sheet and coating applications. Although flat dies can be designed to produce an exit flow distribution that is very uniform across most of the width, there will usually be a region along each side where it drops gradually to zero. This often requires trimming the edges of the film or sheet downstream in order to meet product specifications. It is commonly believed that treating the land area of the die with coatings that promote a small amount wall slip will reduce the size of this edge effect and therefore improve die performance. This analysis shows that slip over the entire land region of the die will adversely affect die performance. Better performance is possible but only if the sides of the land are treated.

FFT - An Efficient Process Analytical Tool for Plastics Film and Sheet Processes
Tan Srinivasan, May 2001

Every Plastics Film and Sheet Processor, whether using Calendering, Extrusion or Coating process, strives to manufacture the best quality product with minimal variations. The total variations in a product comprise of Cross Direction (CD) and Machine Direction (MD) variations. The Machine Direction variations can be further broken down into controllable Long-Term drift and uncontrolled Short-Term high frequency variations. Gauging Systems have been available in the Marketplace for quite a few years, which efficiently control the Profile (CD) and Long Term Machine Direction (LTMD) variations. This paper illustrates the capability of Gauging Systems that incorporate Fast Fourier Transform (FFT) feature to provide the plastics film & sheet processors with a timely and detailed analysis of the uncontrolled high frequency variations (Short Term Machine Direction (STMD) and the causes thereof. This efficient process analytical tool enables the processor to take timely action to reduce STMD, thus improving the overall product quality. The economic benefits to the plastics film & sheet processors derived from down-gauging, while meeting the specifications for end-use applications of the product can be substantial. This paper presents a case study of FFT application to a vinyl calendering process.

Optical Haze Properties of Polyethylene Blown Films: Part 1-Surface Versus Bulk Structural Considerations
Garth L. Wilkes, Matthew B. Johnson, Ashish M. Sukhadia, David C. Rohlfing, May 2001

In this paper we report on some recent findings regarding the factors affecting the optical (haze) properties of polyethylene (PE) blown films. The large majority of the contribution to the total haze in these blown films was a result of the surface roughness of the films, with the bulk (internal) contribution being relatively minor. Using several characterization techniques, we found, rather unexpectedly, that the surface roughness in some of these films was a result of the development of distinct spherulitic-like" superstructures formed during the blown film processing. Analysis of the rheological and molecular characteristics led us to conclude that in blown films of LLDPE-type resins the optical haze properties are adversely affected due to enhanced surface roughness caused by the formation of "spherulitic-like" superstructures in polymer melts that possess fast relaxing and low melt elasticity rheological characteristics."

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