Investigating the Aging Behavior of High-Density Polyethylene and Polyketone in a Liquid Organic Hydrogen Carrier.

Hydrogen is recognized as a significant potential energy source and energy carrier for the future. On the one hand, storing hydrogen is a challenging task due to its low volumetric density, on the other hand, a particular type of hydrogen in the form of a liquid can be used to store large quantities of hydrogen at ambient conditions in thermoplastic tanks. But storing hydrogen in this form for a long time in polymer tanks affects the physical and chemical properties of the liner. In the current automotive industry, high-density polyethylene (HDPE) has already been used in existing fuel tank applications. However long-term exposure to fuels leads to the permeation of hydrocarbons into the polymers, resulting in a loss of mechanical properties and reducing the efficiency of fuel cells (FC) in automotive applications. Additionally, facing material shortages and a limited supply of resin leads to an increase in the cost of the material. Therefore, an alternative material is being searched for, especially for hydrogen fuel tank applications. In this study, two semi-crystalline thermoplastics, HDPE and polyketone (POK), were compared, which were exposed to a selected liquid organic hydrogen carrier (LOHC) at 25 °C and 60 °C for up to 500 h in an enclosed chamber, to measure their fuel up-take. A short analysis was carried out using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and mechanical testing to understand the influence of the LOHC on the polymer over time. Fuel sorption and tensile properties showed a plasticizing effect on HDPE. The material degradation was more pronounced for the aged samples of HDPE in comparison to POK. As expected, thermal aging was increased at 60 °C. The fuel absorption of POK was lower compared to HDPE. A slight increase in crystallinity was observed in POK due to the aging process that led to changes in mechanical properties. Both HDPE and POK samples did not show any chemical changes during the aging process in the oven at 25 °C and 60 °C.

Impact of Multiple Reprocessing on Properties of Polyhydroxybutyrate and Polypropylene.

Biobased plastics have the potential to be sustainable, but to explore their circularity further, current end-of-life options need to be broadened. Mechanical recycling is one of the most accepted methods to bring back plastics into the loop. Polyhydroxybutyrates (PHBs) are biobased and biodegradable in nature with promising properties and varied applications in the market. This study focuses on their potential for mechanical recycling by multiple extrusion cycles (E1-E5) and multi-faceted characterization of the virgin (V) and reprocessed materials from E1 to E5. The behavior is compared to polypropylene (PP) as a reference with a similar property profile, which has also been reprocessed five times. The thermal properties of both series showed a stable melting point and thermal decomposition temperature from thermal analyses (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)). However, a steady increase in the degree of crystallinity was observed which could counterbalance the decrease in molecular weight due to repeated extrusion measured by gel permeation chromatography and resulted in similar values of tensile strength across the cycles. The strain at break was impacted after the first extrusion, but no significant change was observed thereafter; the same was observed for impact strength. Even in scanning electron microscopy (SEM) images, virgin and E5 samples appeared similar, showing the stability of morphological characteristics. Fourier transform infrared spectroscopy (FTIR) results revealed that no new groups are being formed even on repeated processing. The deviation between the PHB and PP series was more predominant in the melt mass flow rate (MFR) and rheology studies. There was a drastic drop in the MFR values in PHB from virgin to E5, whereas not much difference was observed for PP throughout the cycles. This observation was corroborated by frequency sweeps conducted with the parallel plate method. The viscosity dropped from virgin to E1 and E2, but from E3 to E5 it presented similar values. This was in contrast to PP, where all the samples from virgin to E5 had the same values of viscosity. This paper highlights the possibilities of mechanical recycling of PHB and explains why future work with the addition of virgin material and other additives is an area to be explored.

Process Optimization of Injection Overmolding Structural Electronics with Regard to Film Distortion.

The integration of structural electronics in injection-molded parts is a challenging step. The films-comprising of laminated stacks with electronics-are exposed to shear stresses and elevated temperatures by the molten thermoplastic. Hence, molding settings have a significant impact on the successful, damage-free manufacturing of such parts. In this paper, test films with polycarbonate (PC) sheets as outer and two different thermoplastic polyurethanes (TPUs) as middle layers incorporating conductive tracks on a flexible printed circuit board (flexPCB) are manufactured and overmolded with PC. Parameter studies investigating the influence of the melt temperature, mold temperature, injection speed and used TPU layer were performed. The molded parts were inspected visually and compared with a numerical simulation using injection molding software. A shear distortion factor for the TPU layer was derived based on the simulations that linked the shear stresses with the injection time and the softening (melting) of the TPU. The distortion of the films was found to reduce with higher melt temperature, lower mold temperature and faster injection speed. Films using the TPU with the higher melting temperature yielded significantly better results. Moreover, distortion on the films reduced with the increasing distance to the gate and a larger cavity thickness was found to be beneficial. All those relations could be correlated with the shear distortion factor.

Low-Temperature Fibre Direct Compounding of Cellulose Fibres into PA6.

This study reports on the development of a novel polymer processing approach that combines low-temperature (LT) processing and fibre direct compounding (FDC) to reduce the thermal stress on thermosensitive components that occurs during compounding and subsequent injection moulding (IM). Composites based on polyamide 6 (PA6) and cellulose fibres (CeF) were prepared using an LT-FDC process and in parallel with a conventional approach using a twin-screw extruder and IM. The morphological, optical, thermal, and mechanical properties of the prepared samples were investigated using optical microscopy (OM), differential scanning calorimetry (DSC), colorimetry, dynamic mechanical analysis (DMA) and tensile tests. Composites prepared using LT-FDC exhibited worse fibre dispersion but lower fibre degradation. In comparison to neat PA6, the LT-FDC composites had increased tensile modulus (Et) and storage modulus (E') at 120 °C by up to 32% and 50%, respectively, while the tensile strength (σm) decreased by 20%.

Influence of Viscose Fibre Geometry on the Structure-Property Relationships of High-Density Polyethylene Composites.

This study investigated the influence of viscose fibre (VF) geometry on the microstructures and resulting properties of high-density polyethylene (HDPE) composites. Seven types of viscose fibres varying in cross-section shape, linear density, and length were pelletised, compounded into HDPE with a twin-screw extruder, and injection moulded. The microstructures of the composites were characterised by investigating their cross-sections and by extracting the fibres and measuring their lengths using optical microscopy (OM). The mechanical and thermal properties of the composites were characterised using differential scanning calorimetry (DSC), tensile tests, Charpy impact tests, and dynamic mechanical analysis (DMA). The composites prepared using cylindrical fibres with a linear density of 1.7 dtex exhibited the best fibre dispersion, highest orientation, and lowest fibre-fibre contact area. The decrease in the linear density of the cylindrical fibres resulted in increasingly worse dispersion and orientation, while composites containing non-cylindrical fibres exhibited a comparably larger fibre-fibre contact area. The initial fibre length of about 3 to 10 mm decreased to the mean values of 0.29 mm to 0.41 mm during processing, depending on the initial geometry. In general, cylindrical fibres exhibited a superior reinforcing effect in comparison to non-cylindrical fibres. The composites containing cylindrical fibres with a linear density of 1.7 dtex and a length of 5 mm exhibited the best reinforcing effect with an increase in tensile modulus and strength of 323% and 141%, respectively.

Relationships between the Decomposition Behaviour of Renewable Fibres and Their Reinforcing Effect in Composites Processed at High Temperatures.

Engineering polymers reinforced with renewable fibres (RF) are an attractive class of materials, due to their excellent mechanical performance and low environmental impact. However, the successful preparation of such composites has proven to be challenging due to the low thermal stability of RF. The aim of the present study was to investigate how different RF behaves under increased processing temperatures and correlate the thermal properties of the fibres to the mechanical properties of composites. For this purpose, hemp, flax and Lyocell fibres were compounded into polypropylene (PP) using a co-rotating twin screw extruder and test specimens were injection moulded at temperatures ranging from 180 °C to 260 °C, with 20 K steps. The decomposition behaviour of fibres was characterised using non-isothermal and isothermal simultaneous thermogravimetric analysis/differential scanning calorimetry (TGA/DSC). The prepared composites were investigated using optical microscopy (OM), colorimetry, tensile test, Charpy impact test, dynamic mechanical analysis (DMA) and melt flow rate (MFR). Composites exhibited a decrease in mechanical performance at processing temperatures above 200 °C, with a steep decrease observed at 240 °C. Lyocell fibres exhibited the best reinforcement effect, especially at elevated processing temperatures, followed by flax and hemp fibres. It was found that the retention of the fibre reinforcement effect at elevated temperatures can be well predicted using isothermal TGA measurements.

Influence of the Mold Material on the Injection Molding Cycle Time and Warpage Depending on the Polymer Processed.

The thermal properties of the mold influence the cooling situation in the injection molding process. While there are experimental studies investigating the influence of special mold materials, they are limited to few polymers. In this work, an extensive parameter study with the simulation software Autodesk Moldflow Insight was performed to analyze the influence of the polymer itself on the impact of the mold steel on cycle time and warpage. The investigated part was a box with two thickness variations. A conventional mold steel was compared with a steel grade featuring approximately double the thermal conductivity. Simulations were performed with 18 polymers covering the most common material families. The main finding of this study was that the influence of the higher mold conductivity on cycle time ranged from an almost negligible reduction (3%) up to a strong effect (24%), depending mainly on the used polymers, but also on the part thickness. For the cycle time reduction, a correlation was found, with the melt, mold and ejection temperature being the dominant influencing factors of the polymers. With this correlation, it was possible to estimate the potential of cycle time reduction for other polymers. The simulations also showed a positive influence of the higher mold thermal conductivity on part warpage.

The Relationship between a Defined Microstructure within the Mold Surface and the Corresponding Roughness on the Part: A Systematic Study on Particle Size, Filler-, and Compatibilizer Content.

The perception of a surface and its haptic properties are significantly influenced by roughness and microstructure, respectively, whereby non-negligible parameters include friction, contact area, temperature, and humidity between the human finger and the examined surface. In particular, for a scientific investigation on haptic influences, the production of samples with a defined surface roughness is indispensable. The aim of this study is to analyze the impact of various mold insert roughnesses combined with the influences of particle size, filler-, and compatibilizer content on impression quality. An unfilled high density polyethylene was chosen as a reference for the impression quality investigations, while fillers with significantly different particle sizes and a compatibilizer were used to produce proprietary compounds. Injection molded parts were manufactured utilizing mold inserts with three different line roughness values. To support the obtained results, a multivariate analysis of variance, a simulation of the filling phase as well as a rheological material characterization were conducted. The results revealed that (i) the impression quality can be independent of the applied insert roughness based on the filler particle size that was studied, (ii) an increasing on both filler particle size and compatibilizer content raise the sample roughness as a function of the penetration ability of the filler into the insert valleys, and (iii) with a higher insert roughness, the thermoplastic moldings generally exhibit a significantly smoother topography. An assumed correlation between part roughness and melt viscosity could not be confirmed.

Temperature Profile in Rubber Injection Molding: Application of a Recently Developed Testing Method to Improve the Process Simulation and Calculation of Curing Kinetics.

Injection molding of rubber compounds is an easily conducted yet sophisticated method for rubber processing. Simulation software is used to examine the optimal process conditions, identify failure scenarios, and save resources. Due to the complexity of the entire process, various aspects have to be considered in the numerical approach. This contribution focused on a comparison of process simulations with various definitions of the material's inlet temperature, ranging from a stepwise increase, but constant temperature, to an exact axial mass temperature profile prior to injection. The latter was obtained with a specially designed, unique test stand consisting of a plasticizing cylinder equipped with pressure sensors, a throttle valve for pressure adjustments, and a measurement bar with thermocouples for the determination of the actual state of the mass temperature. For the verification of the theoretical calculations, practical experiments were conducted on a rubber injection molding machine equipped with the mold used in the simulation. The moldings, obtained at different vulcanization time, were characterized mechanically and the results were normalized to a relative degree of cure in order to enable comparison of the real process and the simulation. Considering the actual state of the mass temperature, the simulation showed an excellent correlation of the measured and calculated mass temperatures in the cold runner. Additionally, the relative degree of cure was closer to reality when the mass temperature profile after dosing was applied in the simulation.

Physical Foaming and Crosslinking of Polyethylene with Modified Talcum.

The aim of this study was the investigation of the use of modified talcum for supporting crosslinking and as novel nucleating agent for physical foaming of polyethylene. For the modification of the talcum, a thermal initiator was linked to the talcum surface. During the extrusion process, the initiator decomposes, and gas and radicals are formed. The gas generates the nucleation of cells and the radicals support the crosslinking process between the polymer chains. The modification of the talcum was performed in three steps: The first step was the grafting of alkoxysilanes onto the talcum surface. The second step was the chlorination of the thermal initiator for an easier linkage, and the last step was the linking between the initiator and the silanes grafted onto the talcum surface. For this study, two investigations were carried out. One investigation was the analysis of the crosslinking effect with the modified talcum. For this purpose, polyethylene plates were compression molded and the viscoelastic properties were measured with a parallel plate rheometer. The use of the modified talcum led to a higher crosslinking density. The second investigation was the physical foaming experiment in an extrusion process with nitrogen as blowing agent using both a pure and the modified talcum as nucleating agents. The foamed samples were characterized in terms of density, cell size and cell density, and compared with each other. The blend with the modified nucleating agent indicated a foam structure with a smaller mean cell size and a lower density compared to the use of the pristine nucleating agent.