An Investigation towards Coupling Molecular Dynamics with Computational Fluid Dynamics for Modelling Polymer Pyrolysis

Building polymers implemented into building panels and exterior façades have been determined as the major contributor to severe fire incidents, including the 2017 Grenfell Tower fire incident. To gain a deeper understanding of the pyrolysis process of these polymer composites, this work proposes a multi-scale modelling framework comprising of applying the kinetics parameters and detailed pyrolysis gas volatiles (parent combustion fuel and key precursor species) extracted from Molecular Dynamics models to a macro-scale Computational Fluid Dynamics fire model. The modelling framework was tested for pure and flame-retardant polyethylene systems. Based on the modelling results, the chemical distribution of the fully decomposed chemical compounds was realised for the selected polymers. Subsequently, the identified gas volatiles from solid to gas phases were applied as the parent fuel in the detailed chemical kinetics combustion model for enhanced predictions of toxic gas, charring, and smoke particulate predictions. The results demonstrate the potential application of the developed model in the simulation of different polymer materials without substantial prior knowledge of the thermal degradation properties from costly experiments.

Stability of pyrolysis condensates during their high-temperature treatment

As part of a project dealing with the material use of waste plastics processed by pyrolysis, a method for the purification of primary pyrolysis gas at temperatures above the dew point of condensing components was proposed. In order to avoid the loss of liquid products, two procedures have been proposed to study this issue. The first procedure consists in separating the pyrolysis condensate from permanent gases and its subsequent evaporation and introduction into a high-temperature reactor where the purification takes place. The second procedure used the same equipment, but the pyrolyser was connected in series with a high temperature reactor by a heated tube. The function of the device is demonstrated on a pair of pure polymers, namely highdensity polyethylene and polypropylene. In practice, however, the device is used for testing waste plastics. The mass balance of liquid, gaseous and solid products of pyrolysis and subsequent vapour phase conduction through a high-tem-perature reactor was supplemented by data from chromatographic analysis. Experiments have shown that the separation of pyrolysis and subsequent evaporation of the condensate in an independent reactor causes the formation of an undesirable amount of fine aerosol (mist). Pyrolysis without any subsequent high-temperature step produced 85–90 % condensate. The inclusion of a separate high-temperature reactor reduced the yield of condensate to 44.5–47.5 %, at the expense of the above-mentioned mist. Its conver-sion back to liquid is difficult and makes the process inefficient for industry. In tests with the series-connected pyrolyser and the high-temperature reactor, the situation was significantly better. 68.5–73.5 % of condensate was obtained in this case. In addition to the formation of mist, the conduction of steam of condensing components through the high-temperature reactor also caused a slight change in the composition of the liquids obtained. There was a decrease in the proportion of C21–C29 hydrocarbons in products and, conversely, an increase in the concentration of C5–C15 hydrocarbons. Besides verifying a suitable approach to the high-temperature processing of pyrolysis products, the experiments showed that changing a single subparameter (in this case the separation of the two reactors) significantly altered the results of the experiments. During laboratory simulation of industrial processes, it is important not to approach simplifications, but to copy all conditions as much as possible.

Material Analysis and a Visual Guide of Degradation Phenomena in Historical Synthetic Polymers as Tools to Follow Ageing Processes in Industrial Heritage Collections

Identifying the most vulnerable plastics and monitoring their deterioration is one of the main problems within heritage collections with historical synthetic polymers. Gathering and interpreting data about material and degradation phenomena in a collection reveals its conservation needs. A systematic survey of the collection can help towards this purpose. Surveys aiming at inspecting and documenting damages rely on several tools in order to fulfill their purpose. Firstly, objective descriptions of the damages that may appear, and secondly, the means of acquiring and interpreting material information. To address these needs, this article presents (a) a visual damage catalogue of degradation phenomena in plastic and rubber materials, and (b) the implementation of Fourier-transform infrared spectroscopy (FTIR) and pyrolysis–gas chromatography–mass spectrometry (py-GCMS) for the identification of analytically challenging rubber materials and of blooming phenomena. The damage catalogue is based solely on visual and olfactory signs, so that the assessment is independent of possible causes of damages and underlying processes, with the purpose of allowing objectivity to prime over interpretation. The limitations of the use of FTIR in the identification of heavily compounded rubbers in museum surveys is highlighted, and examples are presented. The use of py-GCMS on these cases conveniently allowed the identification of the constituting monomers of several rubber materials where FTIR could not provide a univocal classification of the material present. The study of several cases of blooming allowed the identification of diverse compositions and origins, showing that the description of a degradation phenomenon is only the first step towards its understanding. Unveiling the nature of a particular case of blooming is particularly critical when conservation treatments, such as the removal of a (potentially protecting) layer, are planned. For this purpose, attenuated total reflection-FTIR (ATR-FTIR) as a surface technique was particularly useful.

Microplastic in Water and Sediments at the Confluence of the Elbe and Mulde Rivers in Germany

Accumulation of microplastics in aquatic environments is an issue of emerging concern. Initially, research focused on marine systems. However, recent studies also investigate the abundance of microplastics in freshwater environments. Rivers connect terrestrial with marine ecosystems and contribute a considerable share of macro- and microplastics to the oceans. A previous study found a large amount of micro-spheres in Dessau downstream the river mouth of the Mulde. Therefore, the objective of this research was to examine whether the Mulde river with its highly industrialized catchment contributes to the microplastic pollution of the Elbe. Sediment (Van Veen grab sampler) and water samples (filter cascade with the smallest mesh size 50 μm and nets with the smallest mesh size 150 μm) were taken from the Elbe river up- and downstream the confluence with the Mulde. After extensive sample preparation, we examined the samples under a digital microscope and determined polymer types by pyrolysis Gas Chromatography/Mass Spectrometry (pyr-GC-MS). The amount of primary microplastics increased in sediment and water samples just downstream the confluence. Those microplastics originate probably from the Mulde. We measured larger amounts and different shapes of microplastics in filter cascades that have a smaller mesh size compared to the nets.

A Multi-Analytical Approach for Studying the Effect of New LED Lighting Systems on Modern Paints: Chemical Stability Investigations

This study aims to investigate the chemical stability of some modern paint samples exposed to a new Light Emitting Diode (LED)-lighting system and a halogen lamp by using micro-attenuated total reflectance of Fourier transform infrared spectroscopy (µ-ATR-FTIR), µ-Raman, pyrolysis—gas chromatography/mass spectrometry (Py-GC/MS), and thermally assisted hydrolysis and methylation of GC/MS (THM-GC/MS). Those investigations were performed before and after the exposure of the samples to lightings for 1250, 2400, 3300, and 5000 h. The results obtained with µ-Raman spectroscopy show the high stability of the selected inorganic pigments after the exposure to the lighting systems; while similar to the UV/Vis/NIR results reported in a previous study, µ-ATR-FTIR and THM-GC/MS results evidence greater chemical changes occurring principally on the linseed oil binder-based mock-ups among the acrylic and alkyd-based samples. Moreover, principal component analyses (PCA) and hierarchical cluster analyses (HCA) of THM-GC/MS results highlight that those changes were mostly dependent on the exposure time and on the type of pigment, while being independent of the lighting system used. Finally, semi-quantitative µ-ATR-FTIR results show slight pigment enrichment at the paint surface due to the auto and photo-oxidative degradation of the linseed oil binder.

Analysis of Acrylic and Methacrylic Networks through Pyrolysis-GC/MS

A direct analytical method developed to characterize UV-cured networks based on multi-step pyrolysis-gas chromatography-mass spectroscopy (GC/MS) is presented. Application of the method to characterize (meth)acrylate-based UV-cured networks is discussed. The reversion process of methacrylates is clearly observed during pyrolysis. In contrast, the decomposition of acrylates in high molecular weight degradation products is hardly detected. The potential impact of this technique to elucidate the structural and compositional nature of UV-cured polymeric networks is highlighted.