Extending fragment-based free energy calculations with library Monte Carlo simulation: Annealing in interaction space

Pre-calculated libraries of molecular fragment configurations have previously been used as a basis for both equilibrium sampling (via "library-based Monte Carlo") and for obtaining absolute free energies using a polymer-growth formalism. Here, we combine the two approaches to extend the size of systems for which free energies can be calculated. We study a series of all-atom poly-alanine systems in a simple dielectric "solvent" and find that precise free energies can be obtained rapidly. For instance, for 12 residues, less than an hour of single-processor is required. The combined approach is formally equivalent to the "annealed importance sampling" algorithm; instead of annealing by decreasing temperature, however, interactions among fragments are gradually added as the molecule is "grown." We discuss implications for future binding affinity calculations in which a ligand is grown into a binding site

Life cycle assessment of nanocellulose-reinforced advanced fibre composites

The research and development of nanocellulose-reinforced polymer composites have dramatically increased in the recent years due to the possibility of exploiting the high tensile stiffness and strength of nanocellulose. In the work, the environmental impacts of bacterial cellulose (BC)- and nanofibrillated cellulose (NFC)-reinforced epoxy composites were evaluated using life cycle assessment (LCA). Neat polylactide (PLA) and 30% randomly oriented glass fibre-reinforced polypropylene (GF/PP) composites were used as benchmark materials for comparison. Our cradle-to-gate LCA showed that BC- and NFC-reinforced epoxy composites have higher global warming potential (GWP) and abiotic depletion potential of fossil fuels (ADf) compared to neat PLA and GF/PP even though the specific tensile moduli of the nanocellulose-reinforced epoxy composites were higher than neat PLA and GF/PP. However, when the use phase and the end-of-life of nanocellulose-reinforced epoxy composites were considered, the “green credentials” of nanocellulose-reinforced epoxy composites were comparable to that of neat PLA and GF/PP composites. Our life cycle scenario analysis showed that the cradle-to-grave GWP and ADf of BC- and NFC-reinforced epoxy composites could be lower than neat PLA when the composites contains more than 60 vol.-% nanocellulose. Our LCA model suggests that nanocellulose-reinforced epoxy composites with high nanocellulose loading is desired to produce materials with “greener credentials” than the best performing commercially available bio-derived polymer

Social hotspots life cycle assessment: A case study on social risks of an antimicrobial keyboard cover

This article explores the application of social life cycle assessment (S-LCA) to products or technologies in their earliest developing phase. Indeed, it would be beneficial to have an overview of the social risks generated by novel products and understand what their potential supply chain would be like. To this end, this study presents a S-LCA study for identifying hotspots linked to a novel product: an antimicrobial keyboard cover integrating gold nanoparticles. Firstly, countries which could supply Europe with the input materials required in the system were identified, then by following the S-LCA methodology working hours and working functional hours were estimated. Ultimately, social risks were calculated by combining working functional hours with social risk levels and weights, concerning the relative importance of each category and sub-category. The analysis helped to determine which countries could supply the materials needed and hence become part of the potential supply chain of antimicrobial keyboard covers integrating gold nanoparticles. Furthermore, it led to the identification of main social hotspots linked to each material used. In general, results show that the stakeholders most at risk of adverse social impacts across different sectors and countries are workers. Indeed, they may be affected on both their rights and work conditions, health and safety. The process of gold mining highlights the difference in terms of social risks between more developed countries, such as Australia and Sweden, and developing countries, such as South Africa. The production of chemicals presents a homogeneity in terms of risk hours associated to the considered European countries

The relevance of surface impurities on the effect of temperature on powder flow behavior

Cohesive interparticle forces may have a relevant role in several industrial process operations involving particulate materials, such as fluidization, granulation and drying, as well as storage and solids handling units. Several of these operations require process conditions which involve high temperatures which, in turn, may affect the intensity of interparticle forces such as van der Waals, capillary and electrostatic forces. The mean by which the system temperature can affect all these forces is the change of particle hardness, the generation of liquid phases, which determines the formation of liquid bridges, and the modification of the particle dielectric properties. A direct measure of interparticle forces is possible but can be affected by large fluctuations and require a great number of repetitions. Interparticle forces, instead, play in averaged ensembles in bulk properties such as powder cohesion. It is of interest, therefore, to have the possibility to measure powder cohesion at the process temperature and to observe possible changes due to temperature variations to infer possible changes at the particle level. Powder shear testing is one of the available methods able to measure powder cohesion and it has the great advantage of measuring well established physical properties and of being able to produce highly repeatable results. It has to be remarked, however that to date no established procedure exists to relate powder cohesion measured at the bulk level to powder fluidization properties. In this paper a systematic study on the effect of the process conditions on the fluidization quality of ceramic powders is presented. Tests were carried out on powders of industrial interests, characterized by different particle size distributions and by different amounts of surface impurities, ranging from easy-flowing to cohesive flow behaviour.Two different experimental facilities were used: a modified ring shear tester available at the University of Salerno and aX-ray high temperature fluidization facility available at University College of London. The first apparatus was used to characterize powder cohesion at different temperatures between ambient and 500°C. Experimental results have been interpreted in terms of possible changes in interparticle forces as a function of temperature. The powder samples without impurities show an increase of cohesion with temperature as a result of an increase of interparticle van der Waals forces. A larger increase of cohesion was observed in the case of the powder samples with chemical impurities. The behaviour can be explained only by considering a cooperative effect of both van der Waals and capillary forces. It is noteworthy that the amount of surface impurities that is able to determine significant changes of powder flow properties is still so small that no evidence of phase transition could be detected by means of sample thermal analysis.The same powders have been characterized in terms of fluidization quality by using the x-ray fluidization facility available at University College of London under the same temperature range. Moreover the changes by temperature on the flow properties of the bulk solid evaluated with the shear cell and the behaviour of particles under fluidization conditions are analysed and discussed. Though a direct quantification of the particle-particle interactions in fluidized beds and of their changes under process conditions is very difficult, this paper suggests a method by which powder rheology can be used to indirectly evaluate the effects of the interparticle forces on fluidization

The effect of temperature on the minimum fluidization conditions of industrial cohesive particles

In order to understand the factors responsible for changes in the fluidization behaviour of industrial particles at high temperatures, an experimental campaign was performed using a 140 × 1000 mm heated gas fluidized bed. Five powder cuts sieved out of the same mother powder covering Group B, A and C of Geldart's classification were investigated over a range of temperatures from ambient to 500 °C. The results show that the mean size distribution affects significantly the fluidization behaviour of the materials investigated. In particular, significant differences were observed in the fluidization behaviour of the coarsest samples (Group B-A) and finest samples (Group A-C). The minimum fluidization conditions were compared with the prediction of the Ergun equation. The comparison was satisfactory only when accounting for the experimental values of the bed voidage. In fact, the non-monotonic trend of the minim velocity for fluidization with increasing temperature cannot be explained only with the effects of temperature on the bed fluid dynamics. But several others are the observed effects on the fluidization behaviour due to the temperature rise that can be ascribed to the enhanced interparticle forces: 1) the increase of the peak of pressure drops, close to the minimum for fluidization, in the fluidization curve at increasing gas velocities; 2) the increase for the finest samples of the hysteresis in the fluidization curves, considering the fluidization and defluidization branches of the curve; 3) a greater tendency of the bed to expand homogeneously; 4) the increasing difference between the parameters of the Richardson-Zaki equation found with a fitting procedure on the experiments and those found using the Richardson-Zaki correlations and the theoretical terminal velocity. Furthermore, in the cases where larger interparticle forces were expected, the X-Ray facility allowed to identify different internal structures within the bed. Mostly vertical channels but also, in the case of the finest powder tested, horizontal channels

Can the use of captured CO2 lower the environmental impacts of formate production?

The majority of bulk chemicals (e.g. olefins and alcohols) are organic compounds that are almost exclusively produced from fossil feedstocks such as natural gas. Utilisation of carbon dioxide captured from anthropogenic sources, which are both inexpensive and abundantly available, represents an alternative pathway that is drawing increasing attention, mainly for its potential to decreasing emissions of greenhouse gases and resource depletion of chemicals production. Notably, carbon utilisation does not represent an approach to CO2 mitigation because it only delays its emissions rather than removing it over a long timescale; hence, the relevant question that we aim to address is: "Can captured CO2 be used as feedstock to reduce the environmental impacts of chemicals' production?". As a case study, this work focuses on the production of formate and presents a prospective comparative life cycle assessment (LCA) between the conventional fossil-based pathway and an innovative, CO2-based process, that involves the electro-catalytic reduction of CO2 using an ionic liquid as solvent. CO2 is assumed to originate from a natural gas-fired power plant and captured after combustion, through a conventional monoethanolamine absorption system. Ionic liquids are used to enanche the reduction of CO2 and its conversion to formate. The study adopts a cradle-to-gate perspective and analyses multiple impact categories including, but not limited to, global warming and resources depletion

The life-cycle environmental performance of producing formate via electrochemical reduction of CO_{2} in ionic liquid

Carbon capture and utilisation provide a means to mitigate climate change caused by anthropogenic greenhouse gas emissions by delaying carbon emissions via temporary storage in goods. This article presents a comprehensive Life Cycle Assessment (LCA) study of a novel process that generates formate via electrochemical reduction of CO_{2} in ionic liquid. We performed a scenario analysis, covering uncertain parameters like the recycling rate of unreacted reagents and the market price of CO_{2}, and compared the environmental performance of the carbon utilisation system with that of the conventional process, which relies on fossil sources. Inventory data is obtained from a mix of literature sources and commercial LCA databases. Our analysis indicates that (i) the system needs to attain a 99.9% recycling rate to be competitive with the conventional process; (ii) a future negative market price of CO_{2} would substantially reduce the environmental impacts associated with formate; (iii) there are significant environmental trade-offs between the carbon utilisation system and the conventional process, with the former outperforming the latter in 6/8 out of the 14 impact categories investigated. It should be noted that our results are conservative because inventory data for the electrochemical reduction process is obtained from laboratory experiments

Detection and estimation of capillary interparticle forces in the material of a fluidized bed reactor at high temperature by powder flow characterization

Two ceramic powder samples having different compositions of surface impurities and particle size distributions were considered. These two samples resulted from a high temperature fluidized bed reactor which in its operation showed changes of working condition that might be attributed to the onset of strong interparticle forces. The flow behaviour of these powders was characterized by the High Temperature Annular Shear Cell (HT-ASC), between ambient temperature and 500 °C. Furthermore, a model is developed to relate the change of the powder flowability to the formation of a liquid phase due to the melting of particle impurities present on the particle surface. In particular, the model is used to predict, on the base of the salt composition, the intensity of the interparticle forces at different temperatures. The interparticle forces predicted by the model can be compared with those that can be inferred from the powder flow properties measured with the HT-ASC. Therefore, it is demonstrated that it is possible to derive a theoretical model to predict interparticle forces in a particulate material relevant to fluidized bed reactor, on the basis of the impurities composition. Furthermore, it is demonstrated the possibility to correctly estimate the intensity of average interparticle forces in the same kind of material by the interpretations of bulk flow properties measured with a shear tester, even in the case in which capillary forces take the place of the much weaker van der Walls forces. More in general, the paper suggests a method by which powder rheology can be used to indirectly evaluate the effects of the interparticle forces on fluidization processes even in case in which strong capillary interaction occur

Application of acoustic techniques to fluid-particle systems – A review

Acoustic methods applied to opaque systems have attracted the attention of researchers in fluid mechanics. In particular, owing to their ability to characterise in real-time, non-transparent and highly concentrated fluid-particle systems, they have been applied to the study of complex multiphase flows such as fluidised beds. This paper gives an overview of the physical principles and typical challenges of ultrasound and acoustic emission AE methods when applied to fluid-particle systems. The principles of ultrasound imaging are explained first. The measurement techniques and signal processing methodologies for obtaining velocity profiles, size distribution of the dispersed phases, and solid volume fraction are then discussed. The techniques are based on the measurement of attenuation, sound speed, frequency shift, and transit time of the propagated sound wave. A description of the acoustic emission technique and applications to fluid-particle systems are then discussed. Finally, extensions and future opportunities of the acoustic techniques are presented