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PHBV is a promising plastic for replacing conventional petroleum-based plastics in the future. However, the mechanical properties of PHBV are too low for use in high-stress applications and the degradation of the polymer limits possible applications. In this work, the mechanical properties were, therefore, increased using bio-based regenerated cellulose fibers and degradation processes of the PHBV-RCF composites were detected in accelerated aging tests under various environmental conditions. Mechanical, optical, rheological and thermal analysis methods were used for this characterization. The fibers significantly increased the mechanical properties, in particular the impact strength. Different degradation mechanisms were identified. UV radiation caused the test specimens to fade significantly, but no reduction in mechanical properties was observed. After storage in water and in aqueous solutions, the mechanical properties of the compounds were significantly reduced. The reason for this was assumed to be hydrolytic degradation catalyzed by higher temperatures. The hydrolytic degradation of PHBV was mainly caused by erosion from the test specimen surface. By exposing the regenerated cellulose fibers, this effect could now also be visually verified. For the use of regenerated cellulose fiber-reinforced PHBV in more durable applications, the aging mechanisms that occur must be prevented in the future through the use of stabilizers.

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.

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.

3D printing has established itself in the 21st century as the process for producing prototypes and very small series. In the plastics sector, the fused filament fabrication (FFF) process is used in particular. A plastic filament is melted in a nozzle and a component is built up layer by layer. As with all manufacturing processes, there is an interest in continuously optimizing and improving the FFF process. One possibility is based on process simulations, which enable a better understanding of the entire process. Afterwards a validation of the simulation with the real process is always necessary. In the case of FFF, this validation was so far only possible to a limited extent. In this work, a method is presented that enables a non-destructive investigation of the melting behavior during the printing process. For this purpose, a 3D printer nozzle with an extruder was integrated into an X-ray computed tomography system. Thus, a computed tomography scan (CT scan) can be performed during the extrusion process. By using filaments with high absorbent tungsten, a sufficient contrast can be created between the metal nozzle and the plastic filament, which allows an analysis of the melting behavior. This setup allows to distinguish between the solid filament area and the melt area, as well as to determine contact between the filament and the nozzle wall. In this way, the simulations can be validated and nozzle geometries to be improved in the future by means of improved simulation tools.

Abstract 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.

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.

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.

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.

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.

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.

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.

The shape and size of processed materials play a crucial role in the solid conveying characteristics of single-screw extruders. Thus, the increasing amount of plastic regrind leads to new challenges in screw extrusion. This work investigates the conveying behavior of three distinctly different material shapes in an axially as well as a helically grooved solid conveying zone. A uniform virgin polypropylene (PP) granule, an irregularly plate-shaped PP regrind and a powdery polyethylene (PE) are processed at screw speeds up to 1350 rpm. Thereby, frictionally engaged conveying in the grooves is visualized for the utilized powder. Similarly, the virgin granule is subject to forced conveying by interlocking in the grooves. The experimentally determined throughput is furthermore compared to analytical calculations which assume a so-called nut–screw conveying. It is found that these calculations perfectly predict the throughput when processing the virgin granule and the powder in a helically grooved barrel. In contrast, the analytical calculation significantly underestimates the throughput for the regrind. This underestimation is expected to be mainly caused by its plate shape and a difference in bulk density. The actual bulk density in the extruder is probably significantly higher due to both orientation and compaction effects compared to the measured bulk density that is used for the analytical calculation. Additionally, the regrind exhibits a fluctuating throughput due to the non-constant bulk density, which results from an irregular regrind shape and a broad size distribution.

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.

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.

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.

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.

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.

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.

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.

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.

Bone defects introduced by accidents or diseases are very painful for the patient and their treatment leads to high expenses for the healthcare systems. When a bone defect reaches a critical size, the body is not able to restore this defect by itself. In this case a bone graft is required, either an autologous one taken from the patient or an artificial one made of a bioceramic material such as calcium phosphate. In this study β-tricalcium phosphate (β-TCP) was dispersed in a polymer matrix containing poly(lactic acid) (PLA) and poly(ethylene glycole) (PEG). These compounds were extruded to filaments, which were used for 3D printing of cylindrical scaffolds via Fused Deposition of Ceramics (FDC) technique. After shaping, the printed parts were debindered and sintered. The components combined macro- and micropores with a pore size of 1 mm and 0.01 mm, respectively, which are considered beneficial for bone healing. The compressive strength of sintered cylindrical scaffolds exceeded 72 MPa at an open porosity of 35%. The FDC approach seems promising for manufacturing patient specific bioceramic bone grafts.

Short fiber reinforced thermoplastics (SFT) are extensively used due to their excellent mechanical properties and low processing costs. Long fiber reinforced thermoplastics (LFT) show an even more interesting property profile and are increasingly used for structural parts. However, their processing by injection molding is not as simple as for SFT, and their anisotropic properties resulting from the fiber microstructure (fiber orientation, length, and concentration) pose a challenge with regard to the engineering design process. To reliably predict the structural mechanical properties of fiber reinforced thermoplastics by means of micromechanical models, it is also necessary to reliable predict the fiber microstructure. Therefore, it is crucial to calibrate the underlying prediction models, such as the fiber orientation model, within the process simulation. In general, these models may be adjusted manually, but this is usually ineffective and time-consuming. To overcome this challenge, a new calibration method was developed to automatically calibrate the fiber orientation model parameters of the injection molding simulation by means of optimization methods. This optimization routine is based on experimentally determined fiber orientation distributions and leads to optimized parameters for the fiber orientation prediction model within a few minutes. To better understand the influence of the model parameters, different versions of the fiber orientation model, as well as process and material influences on the resulting fiber orientation distribution, were investigated. Finally, the developed approach to calibrate the fiber orientation model was compared with a classical approach, a direct optimization of the whole process simulation. Thereby, the new optimization approach shows a calculation time reduced by the factor 15 with comparable error variance.

Although fiber-reinforced plastics combine high strength and stiffness with being lightweight, major difficulties arise with high volume production and the return of manufactured parts back into the cycle of materials at the end of their lifecycles. In a novel approach, structural parts were produced from recycled material while utilizing the so-called injection molding compounding process. Recycled fibers and recycled polyamide matrix material were used by blending carbon and matrix fibers into a sliver before processing. Injection molding was then used to produce long fiber-reinforced parts through a direct fiber feed system. Recycled matrix granules were incorporated into the injection molding process by means of an injection molding compounder to investigate their influences on the mechanical properties of the parts. The findings show that the recycled fibers and matrix perform well in standardized tests, although fiber length and fiber content vary significantly and remain below expectations.

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.

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.

In this comprehensive study, the influence of (i) material specific properties (e.g., molecular weight, zero shear viscosity, D-content) and (ii) process parameters (e.g., saturation temperature, -time, -pressure, and pressure drop rate) on the expansion behavior during the autoclave foaming process were investigated on linear Polylactide (PLA) grades, to identify and evaluate the foam relevant parameters. Its poor rheological behavior is often stated as a drawback of PLA, that limits its foamability. Therefore, nine PLA grades with different melt strength and zero shear viscosity were systematically chosen to identify whether these are the main factors governing the foam expansion and whether there is a critical value for these rheological parameters to be exceeded, to achieve low density foams with fine cells. With pressure drop induced batch foaming experiments, it could be shown that all of the investigated PLA grades could be foamed without the often used chemical modifications, although with different degrees of expansion. Interestingly, PLAs foaming behavior is rather complex and can be influenced by many other factors due to its special nature. A low molecular weight combined with a high ability to crystallize only lead to intermediate density reduction. In contrast, a higher molecular weight (i.e., increased zero shear viscosity) leads to significant increased expandability independent from the D-content. However, the D-content plays a crucial role in terms of foaming temperature and crystallization. Furthermore, the applied process parameters govern foam expansion, cell size and crystallization.

Polylactide (PLA) is known as one of the most promising biopolymers as it is derived from renewable feedstock and can be biodegraded. During the last two decades, it moved more and more into the focus of scientific research and industrial use. It is even considered as a suitable replacement for standard petroleum-based polymers, such as polystyrene (PS), which can be found in a wide range of applications—amongst others in foams for packaging and insulation applications—but cause strong environmental issues. PLA has comparable mechanical properties to PS. However, the lack of melt strength is often referred to as a drawback for most foaming processes. One way to overcome this issue is the incorporation of chemical modifiers which can induce chain extension, branching, or cross-linking. As such, a wide variety of substances were studied in the literature. This work should give an overview of the most commonly used chemical modifiers and their effects on rheological, thermal, and foaming behavior. Therefore, this review article summarizes the research conducted on neat and chemically modified PLA foamed with the conventional foaming methods (i.e., batch foaming, foam extrusion, foam injection molding, and bead foaming).

Hydrogels are an interesting class of materials used in extrusion-based 3D printing, e.g., for drug delivery or tissue engineering. However, new hydrogel formulations for 3D printing as well as a detailed understanding of crucial formulation properties for 3D printing are needed. In this contribution, hydrogels based on poly(ethylene glycol) diacrylate (PEG-DA) and the charged monomers 3-sulfopropyl acrylate and [2-(acryloyloxy)ethyl]trimethylammonium chloride are formulated for 3D printing, together with Poloxamer 407 (P407). Chemical curing of formulations with PEG-DA and up to 5% (w/w) of the charged monomers was possible without difficulty. Through careful examination of the rheological properties of the non-cured formulations, it was found that flow properties of formulations with a high P407 concentration of 22.5% (w/w) possessed yield stresses well above 100 Pa together with pronounced shear thinning behavior. Thus, those formulations could be processed by 3D printing, as demonstrated by the generation of pyramidal objects. Modelling of the flow profile during 3D printing suggests that a plug-like laminar flow is prevalent inside the printer capillary. Under such circumstances, fast recovery of a high vicosity after material deposition might not be necessary to guarantee shape fidelity because the majority of the 3D printed volume does not face any relevant shear stress during printing.