Prediction of the Bubble Growth Behavior by Means of the Time-, Temperature-, Pressure- and Blowing Agent Concentration-Dependent Transient Elongational Viscosity Function of Polymers.

Bubble growth processes are highly complex processes, which are not only dependent on the foaming process parameters (temperature, pressure and blowing agent concentration) but also on the type and structure of the polymer used. Since the elongational viscosity at the bubble wall during bubble growth also depends on these influencing factors, the so-called transient elongational viscosity plays a key role in describing the gas bubble growth behavior in polymer melts. The model-based description of the transient elongational viscosity function is difficult due to its dependence on time, Hencky strain and strain rate. Therefore, representative viscosities or shear viscosity models are usually used in the literature to predict the bubble growth behavior. In this work, the transient equibiaxial elongational viscosity function at the bubble wall during bubble growth is described holistically for the first time. This is achieved by extending the so-called molecular stress function (MSF) model by superposition principles (temperature, pressure and blowing agent concentration) and by using the elongational deformation behavior (Hencky strain and strain rate) at the bubble wall during the initial, and thus viscosity-driven, bubble growth process. Therefore, transient uniaxial elongational viscosity measurements are performed and the non-linear MSF model parameters of the two investigated polymers PS (linear polymer chains) and PLA (long-chain branched polymer chains) are determined. By applying the superposition principles and by changing the strain mode parameter to the equibiaxial case in the MSF model, the transient equibiaxial viscosity master curve is obtained and used to describe the bubble growth process. The results show that the extended MSF model can fully predict the transient equibiaxial elongational viscosity function at the bubble wall during bubble growth processes. The bubble growth behavior over time can then be realistically described using the defined transient equibiaxial elongational viscosity function at the bubble wall. This is not possible, for example, with a representative viscosity and therefore clearly demonstrates the influence and importance of knowing the transient deformation behavior that prevails at the bubble wall during bubble growth processes.

A Novel In-Line Measurement and Analysis Method of Bubble Growth-Dependent Strain and Deformation Rates during Foaming.

Bubble growth processes are highly influenced by the elongational viscosity of the blowing agent-loaded polymer melt. Therefore, the elongational viscosity is an important parameter for the development of new polymers for foaming applications, as well as for the prediction of bubble growth processes. Thus, knowledge of the initial expansion and deformation behavior in dependency on the polymer, the blowing agent concentration, and the process conditions is necessary. This study presents a novel method for the in-line observation and analysis of the initial expansion and deformation behavior within the bead foam extrusion process. For this purpose, nitrogen as the blowing agent was injected into the polymer melt (PS and PLA) during the extrusion process. The in-line observation system consists of a borescope equipped with a camera, which was integrated into the water box of an underwater pelletizer. The camera is controlled by a developed trigger by means of angular step signal analysis of a rotary encoder on the cutter shaft of the underwater pelletizer. Thus, images can be taken at any time during the foaming process depending on the cutter position to the die outlet. It is shown that the developed method provides reliable results and that the differences of the initial expansion and deformation behavior during bubble growth can be analyzed in-line in dependency on real foaming process conditions and the type of polymer used.

Investigation of Auxetic Structural Deformation Behavior of PBAT Polymers Using Process and Finite Element Simulation.

The current work investigates the auxetic tensile deformation behavior of the inversehoneycomb structure with 5 × 5 cells made of biodegradable poly(butylene adipate-coterephthalate) (PBAT). Fused deposition modeling, an additive manufacturing method, was used to produce such specimens. Residual stress (RS) and warpage, more or less, always exist in such specimens due to their layer-by-layer fabrication, i.e., repeated heating and cooling. The RS influences the auxetic deformation behavior, but its measurement is challenging due to its very fine structure. Instead, the finite-element (FE)-based process simulation realized using an ABAQUS plug-in numerically predicts the RS and warpage. The predicted warpage shows a negligibly slight deviation compared to the design topology. This process simulation also provides the temperature evolution of a small-volume material, revealing the effects of local cyclic heating and cooling. The achieved RS serves as the initial condition for the FE model used to investigate the auxetic tensile behavior. With the outcomes from FE calculation without consideration of the RS, the effect of the RS on the deformation behavior is discussed for the global force-displacement curve, the structural Poisson's ratio evolution, the deformed structural status, the stress distribution, and the evolution, where the first three and the warpage are also compared with the experimental results. Furthermore, the FE simulation can easily provide the global stress-strain flow curve with the total stress calculated from the elemental stresses.

Compounding, Rheology and Numerical Simulation of Highly Filled Graphite Compounds for Potential Fuel Cell Applications.

Highly filled plastics may offer a suitable solution within the production process for bipolar plates. However, the compounding of conductive additives and the homogeneous mixing of the plastic melt, as well as the accurate prediction of the material behavior, pose a major challenge for polymer engineers. To support the engineering design process of compounding by twin-screw extruders, this present study offers a method to evaluate the achievable mixing quality based on numerical flow simulations. For this purpose, graphite compounds with a filling content of up to 87 wt.-% were successfully produced and characterized rheologically. Based on a particle tracking method, improved element configurations were found for twin-screw compounding. Furthermore, a method to characterize the wall slip ratios of the compounded material system with different filler content is presented, since highly filled material systems often tend to wall slip during processing, which could have a very large influence on accurate prediction. Numerical simulations of the high capillary rheometer were conducted to predict the pressure loss in the capillary. The simulation results show a good agreement and were experimentally validated. In contrast to the expectation, higher filler grades showed only a lower wall slip than compounds with a low graphite content. Despite occurring wall slip effects, the developed flow simulation for the design of slit dies can provide a good prediction for both low and high filling ratios of the graphite compounds.

Deformation Behavior Investigation of Auxetic Structure Made of Poly(butylene adipate-co-terephthalate) Biopolymers Using Finite Element Method.

Auxetic structures made of biodegradable polymers are favorable for industrial and daily life applications. In this work, poly(butylene adipate-co-terephthalate) (PBAT) is chosen for the study of the deformation behavior of an inverse-honeycomb auxetic structure manufactured using the fused filament fabrication. The study focus is on auxetic behavior. One characteristic of polymer deformation prediction using finite element (FE) simulation is that no sounded FE model exists, due to the significantly different behavior of polymers under loading. The deformation behavior prediction of auxetic structures made of polymers poses more challenges, due to the coupled influences of material and topology on the overall behavior. Our work presents a general process to simulate auxetic structural deformation behavior for various polymers, such as PBAT, PLA (polylactic acid), and their blends. The current report emphasizes the first one. Limited by the state of the art, there is no unified regulation for calculating the Poisson's ratio ν for auxetic structures. Here, three calculation ways of ν are presented based on measured data, one of which is found to be suitable to present the auxetic structural behavior. Still, the influence of the auxetic structural topology on the calculated Poisson's ratio value is also discussed, and a suggestion is presented. The numerically predicted force-displacement curve, Poisson's ratio evolution, and the deformed auxetic structural status match the testing results very well. Furthermore, FE simulation results can easily illustrate the stress distribution both statistically and local-topology particularized, which is very helpful in analyzing in-depth the auxetic behavior.

Experimental and Simulative Analysis of the Pressure Development in a Closed Injection Pultrusion Process with Multiple Chamber Geometries.

The use of innovative higher-performance highly reactive resin systems requires an enhancement of the established method of fiber impregnation (open bath) towards closed resin-injection pultrusion (CIP), due to the short pot life of the resin systems. The result is that the open bath is developed into a closed injection and impregnation chamber ("ii-chamber"). In this study, three parameters-resin viscosity, opening angle and opening factor at the injection point on the ii-chamber-are varied, each in three stages. For each set of parameters, a pultrusion trial is conducted and the process pressures in the ii-chamber and pultrusion die measured. This enables direct feedback via the process conditions of the as yet uncured composite. The data obtained are used to validate a newly developed simulation model. The model is based on Darcy's law, which has been extended to take fiber movement into account and thus represent the resulting pressure increase in the die. The flexible ii-chamber and die concept enhance our understanding of the processes taking place in the die system. The sensitivity of the process pressures can be shown for the three influencing variables. The experiment shows that of the three influencing variables investigated, viscosity has the greatest sensitivity to pressure development. In general, it can be said that over the length of the pultrusion die system, the pressure level increases across the three measuring points.

Codesign of Biobased Cellulose-Filled Filaments and Mesostructures for 4D Printing Humidity Responsive Smart Structures.

Hygromorphic smart structures are advantageous as passively actuated systems for generating movement, with applications ranging from weather-responsive architectural building skins to adaptive wearables and microrobotics. Four-dimensional (4D) printing is a valuable method for multiscale fabrication and physical programming of such structures. However, material limitations in terms of printability, responsiveness, and mechanical properties are major bottlenecks in achieving reliable and repeatable humidity-responsive actuation. We propose a codesign method for 4D printing hygromorphic structures through fused filament fabrication, incorporating parallel development of (1) biobased cellulose-filled filaments with varying stiffness and hygroresponsiveness, and (2) designed mesoscale structuring in printed elements. We first describe the design of a pallet of filaments produced by compounding cellulose powder in mass ratios of 0-30% within two matrix polymers with high and low stiffness. We then present the design, fabrication, and testing of a series of 4D-printed prototypes tuned to change shape, that is, open and close, in response to relative humidity (RH). The structures can fully transform in conditions of 35-90% RH, which corresponds to naturally occurring shifts in RH in daily and seasonal weather cycles. Furthermore, their motion is fast (within the range of minutes), fully reversible, and repeatable in numerous cycles. These results open new opportunities for the utilization of 4D printing and natural resources for the development of functional humidity-responsive smart structures.

Deformation Behavior of 3D Printed Auxetic Structures of Thermoplastic Polymers: PLA, PBAT, and Blends.

Auxetic structures have a negative Poisson's ratio and therefore expand transversely to the direction of loading instead of tapering. This unique behavior is not caused by the materials used, but by the structure, and thus offers completely new functionalities and design possibilities. As a rule, auxetic structures have a very complex geometry, which makes cost-effective production possible only by means of additive manufacturing processes. Due to the high design freedom of the strand deposition method, it makes sense to manufacture auxetic structures using this process. Therefore, in this project, polylactide acid (PLA), polybutylene adipate terephthalate (PBAT), and blends of the two polymers were produced and characterized. Filaments of the two polymers and a blend were extruded, processed into auxetic structures by strand deposition process (SDP), and investigated for their properties, primarily their Poisson's ratio. The Poisson's ratio was determined and the influence of the material on it was identified. A specific number of 5 × 5 unit cells has been found to be ideal for investigation. Dual printed specimens showed a similar auxetic behavior as the specimens made of pure PBAT. Likewise, multiple loading and unloading of the structure is possible. Furthermore, in-situ computed tomography revealed the detailed characterization of the initial state, including the warpage of the structures, damage, and traced auxetic behavior in detail.

Mechanical Properties of 3D-Printed Liquid Crystalline Polymers with Low and High Melting Temperatures.

Additive manufacturing allows for the production of complex components using various types of materials such as plastics, metals and ceramics without the need for molding tools. In the field of high-performance polymers, semi-crystalline polymers such as polyetheretherketone (PEEK) or amorphous polymers such as polyetherimide (PEI) are already successfully applied. Contrary to semi-crystalline and amorphous polymers, thermotropic liquid crystalline polymers (LCPs) do not change into an isotropic liquid during melting. Instead, they possess anisotropic properties in their liquid phase. Within the scope of this work, this special group of polymers was investigated with regard to its suitability for processing by means of fused filament fabrication. Using an LCP with a low melting temperature of around 280 °C is compared to processing an LCP that exhibits a high melting temperature around 330 °C. In doing so, it was revealed that the achievable mechanical properties strongly depend on the process parameters such as the direction of deposition, printing temperature, printing speed and layer height. At a layer height of 0.10 mm, a Young's modulus of 27.3 GPa was achieved. Moreover, by employing an annealing step after the printing process, the tensile strength could be increased up to 406 MPa at a layer height of 0.15 mm. Regarding the general suitability for FFF as well as the achieved uniaxial mechanical properties, the LCP with a low melting temperature was advantageous compared to the LCP with a high melting temperature.

In situ laboratory for plastic degradation in the Red Sea.

Degradation and fragmentation of plastics in the environment are still poorly understood. This is partly caused by the lack of long-term studies and methods that determine weathering duration. We here present a novel study object that preserves information on plastic age: microplastic (MP) resin pellets from the wreck of the SS Hamada, a ship that foundered twenty-nine years ago at the coast of Wadi el Gemal national park, Egypt. Its sinking date enabled us to precisely determine how long MP rested in the wreck and a nearby beach, on which part of the load was washed off. Pellets from both sampling sites were analyzed by microscopy, X-ray tomography, spectroscopy, calorimetry, gel permeation chromatography, and rheology. Most pellets were made of low-density polyethylene, but a minor proportion also consisted of high-density polyethylene. MP from inside the wreck showed no signs of degradation compared to pristine reference samples. Contrary, beached plastics exhibited changes on all structural levels, which sometimes caused fragmentation. These findings provide further evidence that plastic degradation under saltwater conditions is comparatively slow, whereas UV radiation and high temperatures on beaches are major drivers of that process. Future long-term studies should focus on underlying mechanisms and timescales of plastic degradation.

Experimental Investigation of the Solid Conveying Behavior of Smooth and Grooved Single-Screw Extruders at High Screw Speeds.

Single-screw extrusion at high screw speeds is established nowadays since it allows for a high mass throughput at a comparatively small extruder size. Compared to conventional extrusion at low screw speeds, a considerable non-linearity in mass throughput appears by exceeding a certain threshold screw speed. In this study, the solid conveying behavior of different plastic granules with varying geometries was investigated in a smooth, a helically and an axially grooved solid conveying zone for screw speeds up to 1350 rpm. These experimental findings are compared to classical analytical predictions in the literature. It is found for the first time that both the shape and size of the plastic granules play a decisive role in determining the threshold screw speed at which a non-linear mass throughput is observed. It is shown that small and spherical granules exhibit a later onset of non-linear throughput compared to larger lenticular and cylindrical shaped granules. Moreover, it is revealed that the mass throughput equalizes for an axially and a helically grooved solid conveying zone at high screw speeds. This is contrary to the low screw speed range where the axially grooved barrel results in a significantly higher throughput than the helically grooved barrel. Thus, the maximum throughput at high screw speeds is limited by the granule stream provided by the hopper opening and is no longer governed by the groove angle.

Miscibility and Phase Separation in PMMA/SAN Blends Investigated by Nanoscale AFM-IR.

The miscibility and phase separation of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile (SAN) have already been investigated using various methods. However, these methods have limitations that often result in inconsistent characterization. Consequently, the reasons for the dependence of miscibility on composition as well as on processing temperature have not yet been proved. The phase separation of PMMA/SAN blends was therefore investigated for the first time using a novel technique, nanoscale AFM-IR. It couples nanoscale atomic force microscopy (AFM) with infrared (IR) spectroscopy. Therefore, the phase morphology can be chemically identified and precisely classified within the nm-regime. The PMMA/SAN blends, on the other hand, were analyzed of their changes in morphology under different thermal treatments. It was possible to visualize and define the phase separation, as well as dependence of the miscibility on the mixing ratio. In the miscible domain, no two individual phases could be detected down to the nanometer range. It was shown that with increasing temperature, the morphology changes and two different phases are formed, where the phase boundaries can be sharply defined. The onset of these changes could be identified at temperatures of about 100 °C.

Rigid Amorphous Fraction as an Indicator for Polymer-Polymer Interactions in Highly Filled Plastics.

Above a percolation threshold a flow restriction has to be overcome by higher pressure in plastic processing. Besides amount and geometry of fillers, the interactions of polymer and filler are important. By differing the amorphous phase of polymers into a rigid amorphous and a mobile amorphous fraction, predictions about interactions are possible. The objective is the generation of a flow restriction and the combined investigation of polymer-particle interaction. SiO2 was used up to 50 vol.% in different spherical sizes in PLA and PP. A capillary-rheometer was used as a tool to create a yield point and by that investigations into the state of the flow restriction were possible. All produced compounds showed, in plate-plate rheometry, an increase in viscosity for lower shear rates and a significant change in the storage modulus. In DSC, hardly any specific rigid amorphous fraction was detectable, which suggests that there is a minor interaction between macromolecules and filler. This leads to the conclusion that the change in flow behavior is mainly caused by a direct interaction between the particles, even though they are theoretically too far away from each other. First images in the state of the yield point show a displacement of the particles against each other.

Investigation of the Thermal and Hydrolytic Degradation of Polylactide during Autoclave Foaming.

Polylactide (PLA) is one of the most important bioplastics worldwide and thus represents a good potential substitute for bead foams made of the fossil-based Polystyrene (PS). However, foaming of PLA comes with a few challenges. One disadvantage of commercially available PLA is its low melt strength and elongation properties, which play an important role in foaming. As a polyester, PLA is also very sensitive to thermal and hydrolytic degradation. Possibilities to overcome these disadvantages can be found in literature, but improving the properties for foaming of PLA as well as the degradation behavior during foaming have not been investigated yet. In this study, reactive extrusion on a twin-screw extruder is used to modify PLA in order to increase the melt strength and to protect it against thermal degradation and hydrolysis. PLA foams are produced in an already known process from the literature and the influence of the modifiers on the properties is estimated. The results show that it is possible to enhance the foaming properties of PLA and to protect it against hydrolysis at the same time.

Rheological Characterization and Modeling of Thermally Unstable Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV).

Presently, almost every industry uses conventional plastics. Its production from petroleum and extensive plastic pollution cause environmental problems. More sustainable alternatives to plastics include bioplastics such as poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), which is produced by bacteria and is biodegradable even in seawater. High temperature sensitivity as well as massive thermal degradation cause difficulties during the processing of PHBV. The aim of this work is to create a detailed rheological characterization and master curves to gain deeper knowledge about the material and its processing parameters. The rheological characterization was performed with frequency sweeps in the range of 0.1 rad/s to 628 rad/s and time sweeps over 300 s. Creating master curves at the reference temperature of 180 °C with the software IRIS delivers Carreau and Arrhenius parameters. These parameters allow for a calculation of the master curves for all other temperatures by means of the temperature shift factor. Moreover, the rheological measurements reveal a minimum rheological measurement temperature of 178 °C and a surprisingly high activation energy of 241.8 kJ/mol.

Enhanced Processing of Regrind as Recycling Material in Single-Screw Extruders.

Regrind processing poses challenges for single-screw extruders due to the irregularly shaped particles. For grooved feed zones, the output is lessened by the reduction of bulk density in comparison to virgin material. Simultaneously, the melt temperature increases, reducing the extruder's process window. Through experimental investigations on a test stand, a novel feed zone geometry (nominal diameter 35 mm) is developed. It aligns the regrind's specific throughput with that of virgin material. The regrind processing window is essentially increased. As the solids conveying in the novel feed zone cannot be simulated with existing methods, numerical simulations using the discrete element method are performed. Since plastic deformation occurs in the novel feed zone geometry, a new hysteresis contact model is developed. In addition to spheres, the regrind and virgin particles are modeled as superquadrics to better approximate the irregular shape. The new contact model's simulation results show excellent agreement with experimental compression tests. The throughput of the extruder simulations is considerably underestimated when using spheres to represent the real particles than when using irregularly shaped superquadrics. Corresponding advantages can be seen especially for virgin material.

A Novel Modeling Approach for Plastics Melting within a CFD-DEM Framework.

Existing three-dimensional modeling approaches to single-screw extrusion can be classified according to the process sections. The discrete element method (DEM) allows describing solids transport in the feed section. The melt flow in the melt section can be calculated by means of computational fluid dynamics (CFD). However, the current state of the art only allows a separate consideration of the respective sections. A joint examination of the process sections still remains challenging. In this study, a novel modeling approach is presented, allowing a joint consideration of solids and melt transport and, beyond that, the formation of melt. For this purpose, the phase transition from the solid to liquid states is modeled for the first time within the framework CFDEMCoupling®, combining CFD and DEM by a novel melting model implemented in this study. In addition, a melting apparatus for the validation of the novel melting model is set up and put into operation. CFD-DEM simulations are carried out in order to calculate the melting rate and are compared to experimental results. A good agreement between the simulation and experimental results is found. From the findings, it can be assumed that the CFD-DEM simulation of single-screw extruder with a joint consideration of the feed and melt section is feasible.

Direct Joule Heating as a Means to Efficiently and Homogeneously Heat Thermoplastic Prepregs.

Although direct Joule heating is a known technique for heating carbon fiber reinforced plastics, it is a yet unexplored heating method for thermoplastic prepregs before back-injection molding. The knowledge obtained from resistance welding, for example, is not directly transferable because of considerably higher heated volumes and more complex shapes. In this study, the governing parameters and process limits are established for this method. The influences of the contacting, the materials used, and the size of the heated part are investigated with respect to the part temperature and heating efficiency. The findings show that the quality of heating is determined by the shape and size of the electrodes. Larger electrodes lead to a more homogeneous temperature distribution. Parts based on woven fabric can be heated more homogeneously because of the existence of intersections between rovings, generating contact between fibers. An increase in part width results in uneven heating behavior.

Review on the Biological Degradation of Polymers in Various Environments.

Biodegradable plastics can make an important contribution to the struggle against increasing environmental pollution through plastics. However, biodegradability is a material property that is influenced by many factors. This review provides an overview of the main environmental conditions in which biodegradation takes place and then presents the degradability of numerous polymers. Polylactide (PLA), which is already available on an industrial scale, and the polyhydroxyalkanoates polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-valerate (PHBV), which are among the few plastics that have been proven to degrade in seawater, will be discussed in detail, followed by a summary of the degradability of further petroleum-, cellulose-, starch-, protein- and CO2-based biopolymers and some naturally occurring polymers.

Rheology in the Presence of Carbon Dioxide (CO2) to Study the Melt Behavior of Chemically Modified Polylactide (PLA).

For the preparation of polylactide (PLA)-based foams, it is commonly necessary to increase the melt strength of the polymer. Additives such as chain extenders (CE) or peroxides are often used to build up the molecular weight by branching or even crosslinking during reactive extrusion. Furthermore, a blowing agent with a low molecular weight, such as carbon dioxide (CO2), is introduced in the foaming process, which might affect the reactivity during extrusion. Offline rheological tests can help to measure and better understand the kinetics of the reaction, especially the reaction between the polymer and the chemical modifier. However, rheological measurements are mostly done in an inert nitrogen atmosphere without an equivalent gas loading of the polymer melt, like during the corresponding reactive extrusion process. Therefore, the influence of the blowing agent itself is not considered within these standard rheological measurements. Thus, in this study, a rheometer equipped with a pressure cell is used to conduct rheological measurements of neat and chemical-modified polymers in the presence of CO2 at pressures up to 40 bar. The specific effects of CO2 at elevated pressure on the reactivity between the polymer and the chemical modifiers (an organic peroxide and as second choice, an epoxy-based CE) were investigated and compared. It could be shown in the rheological experiments that the reactivity of the chain extender is reduced in the presence of CO2, while the peroxide is less affected. Finally, it was possible to detect the recrystallization temperature Trc of the unmodified and unbranched sample by the torque maximum in the rheometer, representing the tear off of the stamp from the sample. Trc was about 13 K lower in the CO2-loaded sample. Furthermore, it was possible to detect the influences of branching and gas loading simultaneously. Here the influence of the branching on Trc was much higher in comparison to a gas loading.