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

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.This research was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)—project number 426052763.Deutsche Forschungsgemeinschaft (DFG, German Research Foundation

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.Deutsche Forschungsgemeinschaf

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.Bundesministerium für Bildung und Forschun

Analysis of melting and flow in the hot-end of a material extrusion 3D printer using X-ray computed tomography

This paper presents in-situ X-ray computed tomography (CT) experiments used to study the flow behavior within a conventional hot-end of a fused filament fabrication printer. Three types of experiments were performed to better understand the melt and flow behavior. In one experiment, 360{\deg} CT scans were conducted, focusing on the air gap between the filament and the nozzle wall. In a second experiment, the flow profile inside the nozzle was studied using radiography. To provide a good contrast to the surrounding nozzle material, filament was prepared containing small amounts of tungsten powder as a contrast agent. During a third test, the extruder forces were measured and compared with the X-ray results and the predictions of a numerical simulation. The CT scans showed that at higher filament speeds, less area of the nozzle wall is in contact with the melt. This means that a larger part of the barrel section is occupied by an air gap between the solid filament and the nozzle wall. In contrast to the filament speed, the influence of the heater temperature shows no discernible effect on the part of the nozzle filled with melt. Radiographic evaluation of the velocity profile revealed a parabolic distribution under the studied conditions, closely matching numerical simulations modeling the flow as isothermal and non-Newtonian. The study's findings offer potential for improving nozzle design. Furthermore, the presented experimental method can serve as a valuable tool for future validation of more complex numerical simulations

Evaluation of the Zero Shear Viscosity, the D-Content and Processing Conditions as Foam Relevant Parameters for Autoclave Foaming of Standard Polylactide (PLA)

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.Deutsche Forschungsgemeinschaf

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

Degradation of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) reinforced with regenerated cellulose fibers

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.This research was funded by the Federal Ministry of Food and Agriculture (BMEL) and the Fachagentur Nachwachsende Rohstoffe e.V. (FNR): 2220NR089M.Federal Ministry of Food and Agriculture (BMEL)Fachagentur Nachwachsende Rohstoffe e.V. (FNR