RESUMO
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.
RESUMO
The current study presents the effect of the backbone as an important binder component on the mechanical, rheological, and thermal properties of Aluminium (Al) alloy feedstocks. A thermoplastic elastomer (TPE) main binder component was blended with either polypropylene (PP), grafted-maleic anhydride-PP (PPMA), or grafted-maleic anhydride-PPwax (PPMAwax) plus PP, as the backbone. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) tests were performed to investigate the thermal properties of binder systems and feedstocks. Fourier-transform infrared (FTIR) spectroscopy was used to study the chemical interaction between the binder and the Al alloy. After making feedstock filaments, tensile tests, scanning electron microscopy (SEM), and fused filament fabrication (FFF) printing were done. The results showed that although the PP printability was acceptable, the best mechanical properties and printed quality can be achieved by PPMA. TGA test showed that all binder systems in the feedstocks could be removed completely around 500 °C. From FTIR, the possibility of chemical reactions between Al alloy particles and maleic anhydride groups on the grafted PP backbone could explain the better dispersion of the mixture and higher mechanical properties. Tensile strength in PP samples was 3.4 MPa which was improved 1.8 times using PPMA as the backbone.
RESUMO
Measuring the shear viscosity of polymeric melts is an extensive effort frequently performed in high-pressure capillary rheometers, where the pressures required to push the melt through a capillary at various temperatures and volumetric flow rates are recorded. Then, the viscosity values are obtained through Bagley and Weissenberg-Rabinowitsch corrections involving parameter fitting. However, uncertainties in those conversions due to pressure variations and measurement inaccuracies (random errors) affect the accuracy of the consequently calculated viscosities. This paper proposes quantifying them through a propagation of uncertainties calculation. This has been experimentally demonstrated for a polycarbonate melt. In addition, the derived viscosity uncertainties were used for the weighted residual sum of squares parameter estimation of the Cross-WLF viscosity model and compared with the coefficients obtained using the standard residual sum of squares minimization approach. The motivation was that, by comparison, individual poorly measured viscosity values should have a less negative impact on the overall fit quality of the former. For validation, the rheometer measurements were numerically simulated with both fits. The simulations based on the Cross-WLF fit, including the derived viscosity uncertainties, matched the measured pressures ~16% more closely for shear rates below 1500 1/s. Considering the uncertainties led to more precise coefficients. However, both fits showed substantial deviations at higher shear rates, probably due to substantial non-isothermal flow conditions that prevailed during these measurements. A capillary rheometer experiment was also simulated using arbitrarily chosen Cross-WLF parameters to exclude such systematic errors. A normally distributed error was then applied to the simulated pressures before re-fitting the parameters. Again, taking advantage of the derived viscosity uncertainties, the fit could recover the initial parameters better.
RESUMO
The good interaction between the ceramic powder and the binder system is vital for ceramic injection molding and prevents the phase separation during processing. Due to the non-polar structure of polyolefins such as high-density polyethylene (HDPE) and the polar surface of ceramics such as zirconia, there is not appropriate adhesion between them. In this study, the effect of adding high-density polyethylene grafted with acrylic acid (AAHDPE), with high polarity and strong adhesion to the powder, on the rheological, thermal and chemical properties of polymer composites highly filled with zirconia and feedstocks was evaluated. To gain a deeper understanding of the effect of each component, formulations containing different amounts of HDPE and or AAHDPE, zirconia and paraffin wax (PW) were prepared. Attenuated total reflection spectroscopy (ATR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and rotational and capillary rheology were used for the characterization of the different formulations. The ATR analysis revealed the formation of hydrogen bonds between the hydroxyl groups on the zirconia surface and AAHDPE. The improved powder-binder adhesion in the formulations with more AAHDPE resulted in a better powder dispersion and homogeneous mixtures, as observed by SEM. DSC results revealed that the addition of AAHDPE, PW and zirconia effect the melting and crystallization temperature and crystallinity of the binder, the polymer-filled system and feedstocks. The better powder--binder adhesion and powder dispersion effectively decreased the viscosity of the highly filled polymer composites and feedstocks with AAHDPE; this showed the potential of grafted polymers as binders for ceramic injection molding.
RESUMO
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.
RESUMO
To achieve future recycling targets and CO2 and waste reduction, the transfer of plastic contained in mixed waste from thermal recovery to mechanical recycling is a promising option. This requires extensive knowledge of the necessary processing depth of mixed wastes to enrich plastics and their processability in polymer processing machines. Also, the selection of a suitable processing method and product application area requires appropriate material behaviour. This paper investigates these aspects for a commercial processed, mixed waste, and two different mixed polyolefin fractions. The wastes are processed at different depths (e.g., washed/not washed, sorted into polyethylene, polypropylene, polyethylene terephthalate, polystyrene/unsorted) and then either homogenised in the extruder in advance or processed heterogeneously in the compression moulding process into plates. The produced recyclates in plate form are then subjected to mechanical, thermal, and rheological characterisation. Most investigated materials could be processed with simple compression moulding. The results show that an upstream washing process improves the achievable material properties, but homogenisation does not necessarily lead to an improvement. It was also found that a higher treatment depth (recovery of plastic types) is not necessary. The investigations show that plastic waste recovery with simple treatment from mixed, contaminated wastes into at least downcycling products is possible.
RESUMO
Epoxy-anhydride vitrimers are covalent adaptable networks, which undergo associative bond exchange reactions at elevated temperature. Their service temperature is influenced by the glass transition temperature (Tg) as well as the topology freezing transition temperature (Tv), at which the covalent bond exchange reactions become significantly fast. The present work highlights the design of high-Tg epoxy-anhydride vitrimers that comprise an efficient stress relaxation at elevated temperature. Networks are prepared by thermally curing aminoglycidyl monomers with glutaric anhydride in different stoichiometric ratios. The tertiary amine groups present in the structure of the aminoglycidyl derivatives not only accelerate the curing reaction but also catalyse the transesterification reaction above Tv, as shown in stress relaxation measurements. The topology rearrangements render the networks recyclable, which is demonstrated by reprocessing a grinded powder of the cured materials in a hot press. The epoxy-anhydride vitrimers are characterised by a high Tg (up to 140 °C) and an adequate storage modulus at 25 °C (~2.5 GPa), which makes them interesting candidates for structural applications operating at high service temperature.