Search

We report the results of modelling the transport of n-octane and n-hexadecane and their mixtures through carbonaceous nanopores at high-pressure conditions. Pores are modelled as smooth slit sheets with perturbations added as ridges and steps and a version of the Statistical Associating Fluid Theory (SAFT-γ Mie) is used both as equation of state and as a coarse-grained force field to account for fluid-fluid and fluid-solid molecular interactions. Molecular simulation allowed the description of transport diffusivities in terms of molecular flow, using boundary driven non-equilibrium molecular dynamics (BD-NEMD). Transport diffusivities are also independently calculated using equilibrium and external force non-equilibrium molecular dynamics (EF-NEMD) simulations, after accounting for the adsorption on the pores. We show consistency between the approaches for quantifying transport in terms of permeabilities (Darcy flows) and transport diffusivities. We find that smooth slit carbon pore models, which are commonly employed in literature as surrogates for kerogen regions in shale, are an inadequate representation of ultra-confined natural pores. For slit pores, the flow patterns are characterized by a fully-mutualized plug-like flow and fast transport. However, by incorporating even a small amount of rugosity (roughness) to the solid walls, the diffusion coefficients decrease dramatically with surface roughness significantly affecting the characteristic transport and velocity profiles inside the pores. In all cases, it is seen that there are important cross-correlation effects, influencing the way components of the mixture flow together. Calculated self-diffusivities are orders of magnitude smaller than the observed transport diffusivities for liquid mixtures. This work has a direct impact on the understanding and modelling of unconventional hydrocarbon recovery and flow in organic shale rocks.

The thermal runaway of Lithium-ion batteries (LIBs) is a fire hazard. The Accelerating Rate Calorimetry (ARC) device is commonly used to investigate thermal runaway parameters of LIBs by assuming adiabatic conditions. However, this assumption ignores internal heat transfer within the cell and external heat transfer at the cell surface. In this work, we conducted ARC experiments using prismatic LiCoO2 cells of 50 mm in side to study the effect of heat transfer limitations. Results show that the external temperature difference between this cell surface and ARC walls varies between 0 and 1.5 ℃ before thermal runaway and increases from 10 to 130 ℃ while thermal runaway occurs. Ignoring external heat transfer causes the heat of reaction of the cell to be underestimated by 12%. To study the internal heat transfer, two models are developed and show that heat transfer causes an internal temperature difference that causes an error of kinetics estimation, and the error grows with cell size. Ignoring heat transfer leads to errors on the thermal runaway parameters quantified by ARC, and these errors could propagate to battery safety design and predictions. This study contributes to designing better ARC experiments and a better understanding of battery safety.

Borehole breakout initiation, progression, and stabilization are modeled using a semi-analytical method based on Melentiev’s graphical conformal mapping procedure, and Kolosov–Muskhelishvili complex stress potentials. The only input data required are the elastic moduli of the rock, the Coulomb strength parameters (cohesion and angle of internal friction), and the far-field stresses. The stresses around the borehole wall are computed, the region in which the rock has failed is then “removed”, creating a new borehole shape. This process is iterated until a shape is obtained for which the breakout will progress no further, and a stable state has been reached. This modeling shows that stresses around the flank of the breakout evolve so as to reduce the propensity for shear failure, which helps to explain why the breakout width remains relatively constant throughout the process, even as the breakout region deepens radially. The failed area around the borehole becomes smaller and more localized, as the breakout tip sharpens and deepens. Using the Mogi–Coulomb failure criterion, a good match is obtained between the modeled breakout geometry and the geometry observed by Herrick and Haimson in laboratory experiments on an Alabama limestone. The new method leads to a correlation between breakout geometry, rock strength properties, and in situ stress. The paper ends with a critical discussion of the possibility of inferring the in situ stress state from observed breakout geometries.

The stabilisation of slopes with rows of discrete vertical piles is a commonly adopted method for both cuttings and embankment slopes. The majority of existing design procedures consider the pile only as an additional force or moment acting on the critical slip surface of the unstabilised slope. Based on simplified models, existing design methodologies effectively ignore any interaction of the pile with the evolution of the failure mechanism, while they do not consider important aspects of soil behaviour for slope stability relating to a strain-softening response. This paper presents a numerical investigation that challenges the above-mentioned simplifications, demonstrating the importance of the soil/pile interaction. Two-dimensional plane-strain hydro-mechanically coupled finite-element analyses were performed to simulate the excavation of a slope, considering materials with both a strain-softening and non-softening response. The impact of pile position and time of pile construction on the stability of a cutting were parametrically examined, comparing and contrasting the findings for the different material types. The results suggest that an oversimplification during design regarding the soil/pile interaction could entirely miss the critical failure mechanism.

Making reliable estimates of gas adsorption in shale remains a challenge because the variability in their mineralogy and thermal maturity results in a broad distribution of pore-scale properties, including size, morphology and surface chemistry. Here, we demonstrate the development and application of a hybrid pore-scale model that uses surrogate surfaces to describe supercritical gas adsorption in shale. The model is based on the lattice Density Functional Theory (DFT) and considers both slits and cylindrical pores to mimic the texture of shale. Inorganic and organic surfaces associated with these pores are accounted for by using two distinct adsorbate-adsorbent interaction energies. The model is parameterised upon calibration against experimental adsorption data acquired on adsorbents featuring either pure clay or pure carbon surfaces. Therefore, in its application to shale, the hybrid lattice DFT model only requires knowledge of the shale-specific organic and clay content. We verify the reliability of the model predictions by comparison against high-pressure CO2 and CH4 adsorption isotherms measured at 40 ◦C in the pressure range 0.01–30 MPa on four samples from three distinct plays, namely the Bowland (UK), Longmaxi (China) and Marcellus shale 1 (USA). Because it uses only the relevant pore-scale properties, the proposed model can be applied to the analysis of other shales, minimising the heavy experimental burden associated with high pressure experiments. Moreover, the proposed development has general applicability meaning that the hybrid lattice DFT can be used to the characterisation of any adsorbent featuring morphologically and chemically heterogeneous surfaces.

This study focuses on computational fluid dynamics (CFD) modelling of the air entrainment phenomena in water columns which are commonly used in processing plants. The CFD model is first validated against experimental data. Then, a comprehensive set of CFD simulations are conducted to understand the effect of inlet jet velocity, nozzle diameter, tank diameter, and tank height on the bubble formation. Three main patterns are identified: dispersed bubbles, medium air pockets (MAP) and large air pockets (LAP). For the dispersed bubble case, the initially formed air pockets break into smaller bubbles and hence the water level rises linearly. For the MAP case, the size of the air pockets remains larger than for the dispersed bubble case, though, with time they burst at the surface. Finally, for the LAP case, the inkling jet interacts violently with the wall and hence large air pockets are trapped within the column, causing the overflow of the fluid. The flows are further analysed using non-dimensionless Reynolds and Froude numbers, providing an acceptable range of operating parameters that ensure the fluid does not overflow.

Solution equilibrium calculations were performed in this study to understand the impact of contaminant metal ions on the precipitation efficiency of selected rare earth elements (Ce3+, Nd3+, and Y3+) using oxalic acid as a precipitant. Trivalent metal ions, Al3+ and Fe3+, were found to considerably affect the precipitation efficiency of REEs. When Al3+ and Fe3+ concentrations were increased by 1 × 10−4 mol/L, in order to achieve an acceptable cerium recovery of 93% from solutions containing 1 × 10−4 mol/L Ce3+, oxalate dosage needed to increase by 1.2 × 10−4 and 1.68 × 10−4 mol/L, respectively. Such great impacts on the required oxalate dosage were also observed for Nd3+ and Y3+, which indicates that oxalic acid consumption and cost will be largely increased when the trivalent metal ions exist in REE-concentrated solutions. Effects of the divalent metal ions on the oxalate dosage is minimal. Furthermore, solution equilibrium calculation results showed that the precipitation of Fe3+ and Ca2+ (e.g., hematite and Ca(C2O4)∙H2O(s)) likely occurs during the oxalate precipitation of REEs at relatively high pH (e.g., pH 2.5), which will reduce rare earth oxalate product purity. In addition to the metal ions, anionic species, especially SO42−, were also found to negatively affect the precipitation recovery of REEs. For example, when 0.1 mol/L SO42− occurs in a solution containing 1 × 10−4 mol/L Ce3+ and 4 × 10−4 mol/L oxalate, the pH needed to be elevated from 2.0 to 3.3 to achieve the acceptable recovery. Overall, findings from this study provide guidance for the obtainment of high-purity rare earth products from solutions containing a considerable amount of contaminant metal ions by means of oxalic acid precipitation. Accepted version

The threat of accidental hydrocarbon explosions is of major concern to industrial operations; in particular, there is a need for design tools to assess and quantify the effects of potential deflagration events. Here we present a design methodology based on analytical models that allow assessing the loading and structural response of objects exposed to pressure waves generated by deflagration events. The models allow determining: i) the importance of Fluid-Structure Interaction (FSI) effects; ii) the transient pressure histories on box-like or circular cylindrical objects, including the effects of pressure clearing; iii) the dynamic response of structural components that can be idealised as fully clamped beams. We illustrate by three case studies the complete design methodology and validate the analytical models by comparing their predictions to those of detailed CFD and FE simulations. We employ the validated analytical models to perform Monte Carlo analyses to quantify, for box-like structures, how the uncertainty in input design variables propagates through to the expected maximum force and impulse. We present this information in the form of non-dimensional uncertainty maps.

The depletion of high-grade ore deposits, as well as the generation of large quantities of tailings by mining and metallurgical activities, necessitates an urgent search for not only more cost-effective, but also more eco-friendly methods of recovering minerals from low-grade deposits and secondary resources. Research in the bioflotation process appears to be an answer to this search, thanks to the contribution of the microbial world. This study constitutes the first systematic and the most comprehensive review on bioflotation. The bioflotation studies in the literature were examined in a certain chronological order and by classifying the reagents in terms of both their origin and their use in flotation. Aside from the benefits of bioreagents to the mining industry, the review attempted to reveal the issues that prevent the transition to industrial application. This review aims to raise awareness of future research opportunities for mining and biology researchers while also presenting current bioflotation studies.

In the last couple of decades, researchers have been working on Ruddlesden-Popper phases to realise them as components of solid oxide cells. Ruddlesden-Popper phase materials have been particularly proposed as materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). As such a sizeable literature was produced on Ruddlesden-Popper phases and in this short review we look at these studies with a particular focus on the structural chemistry, oxygen transport and electrical conductivity, electrochemical performance, and stability of these materials under operating conditions. More specifically, the materials have been studied for cathodes and, therefore, we believe a review dedicated to cathode applications of these materials will be beneficial for the community. A brief outlook on the future directions in the field will also be provided.

This paper describes research into the poorly understood axial behaviour of piles driven in chalk. Comprehensive dynamic and monotonic axial testing on 27, mostly instrumented, piles undertaken for the ALPACA joint industry projects is reported and interpreted covering: diameters between 139 mm and 1·8 m; lengths from 3 to 18 m; different pile material types; tip and groundwater conditions; and ages after driving. The experiments show the factors that influence resistance most strongly are: (a) pile end conditions; (b) slenderness ratio and flexibility; (c) shaft material; (d) age after driving; (e) relative water table depth; and (f) whether loading is compressive or tensile. Varying the factors systematically identified a remarkable average long-term shaft resistance range from below 11 kPa to more than 200 kPa for piles driven at the same low- to medium-density chalk test site in Kent (UK). Dynamic and static analyses demonstrate that soil resistances to driving were generally well predicted by the Chalk ICP-18 short-term formulation. Considering the piles’ long-term behaviour, the Chalk ICP-18 approach over-predicted capacity, while the widely used CIRIA approach proved over-conservative for most cases. The research enabled the development of a revised ‘ALPACA-SNW’ long-term capacity assessment method that matches the test outcomes far more faithfully.

Ni-Mn-Ga based alloys are widely studied due to their potential for practical applications, making use of their martensitic transformations. However, hysteresis is a long-standing drawback that reduces the chance of transferring these alloys from the laboratory to industry. In this work, we studied a Cr-doped Ni2.15Mn0.70Cr0.15Ga alloy. We arrived at this composition by integrating data obtained from the previous phase and hysteresis diagrams taken from the literature. The compound presents a magnetostructural transition at room temperature, with a ferromagnetic martensite phase, and moderate thermal hysteresis of approximately 4 K. The magnetocaloric and ferromagnetic shape memory effects were explored, showing a reversible entropy change of approximately 9 Jkg-1K-1 under 0–5 T field change, and a cyclical magnetic-field-induced deformation close to 0.81% under 0–9 T, an advance towards high reversibility for this family alloys.

Fault reactivation and associated microseismicity pose a potential threat to industrial processes involving fluid injection into the subsurface. In this research, fracture criticality, defined as the gradient of critical fluid pressure change to trigger seismicity (Δpc/h), is proposed as a novel reservoir depth-independent metric of fault slip susceptibility. Based on statistics of the fracture criticality, a probabilistic evaluation framework for susceptibility to injection-induced seismicity was developed by integrating seismic observations and hydrogeological modelling of fluid injection operations for faulted reservoirs. The proposed seismic susceptibility evaluation method considers the injection-driven fluid pressure increase, the variability of fracture criticality, and regional fracture density. Utilising this methodology, the probabilistic distribution of fracture criticality was obtained to evaluate the potential for injection-induced seismicity in both fault and off-fault zones at the Hellisheiði geothermal site, Iceland. It has been found that the fracture criticality within both fault and off-fault zones shows natural variability (mostly ranging between 0.001 and 2.0 bar/km), and that fault zones tend to be characterised by larger fracture criticality values than the off-faut zones. Fracture criticality values estimated within each zone roughly follow a Gaussian distribution. Fault zones around five geothermal fluid re-injection wells at the site were estimated to have relatively high probability of seismic event occurrence, and these regions experienced high levels of induced seismicity over the microseismic monitoring period. The seismotectonic state estimated for each zone is generally consistent with the forecasted susceptibility to seismicity based on statistics of fracture criticality.

This study investigated the important role of agitation in obtaining consistent and reproducible results when moving from preliminary qualitative screenings for protein crystallisation to quantitative batch crystallisation experiments. Lysozyme-thaumatin binary protein mixture was used as the model protein system in this study. Poor reproducibility between batches were observed for non-agitated crystallisation conditions even if the same sampling timing and frequency applied. With agitation, from 0 to 200 rpm investigated in this study, improved reproducibility of protein crystallisation was observed with increased agitation. Additionally, agitation also had impacts on supersaturation exhaustion rate, yield and crystal size. Moreover, in agitated batch crystallisation, it was found that target protein crystallisation process was decelerated in the presence of protein impurity. In conclusion, we emphasised the essential role of agitation in protein crystallisation experiments else misleading conclusions with inconsistency might be drawn from non-agitated systems.

Thermo-active structures are underground facilities that enable the exchange of thermal energy between the ground and the overlying buildings, thus providing renewable means of space heating and cooling. Although this technology is becoming increasingly popular, the behaviour of geotechnical structures under additional thermal loading is still not fully understood. This paper focuses on the use of underground tunnels as thermo-active structures and explains their behaviour through a series of finite-element analyses based on an existing case study of isothermal tunnels in London Clay. The bespoke finite-element code adopted – the Imperial College Finite Element Program (ICFEP) – is capable of simulating the fully coupled thermo-hydro-mechanical behaviour of porous materials. The complex coupled interactions between the tunnel and the surrounding soil are explored by comparing results from selected types of coupled and uncoupled simulations. It is demonstrated that: (a) the thermally induced deformation of the tunnel and the ground are more critical design aspects than the thermally induced forces in the tunnel lining, and (b) the modelling approach in terms of the type of analysis, as well as the assumed permeability of the tunnel lining, has a significant effect on the computed tunnel response and, hence, must be chosen carefully.

Research indicates that users of thermally modified wood lack information regarding the improved performance and any variations that may exist for the “same” product when manufactured by different companies. The goal of this study was to evaluate the variability in mechanical properties of three thermally modified hardwoods and determine the variability between three different manufacturers. To determine the hardness, bending (modulus of elasticity and module of rupture) and shrinkage values, testing was conducted following ASTM standard D143. The samples were conditioned at 20 °C and a relative humidity of 65% until they reached an equilibrium moisture content before testing. Analysis of variance was used to determine the variability within and between the different processes used by each company. Seven out of 18 (39%) tests indicated that there were statistical differences regarding the mechanical performances of the wood samples. Yellow poplar had the least variation between companies (only difference in equilibrium moisture content, EMC) and red maple had the most (hardness, tangential shrinkage, and EMC). While the means for these properties were statistically different, the differences in application for hardness and EMC are slight. For example, the largest difference between processes in hardness was 83.6 kg, for tangential shrinkage, 0.45% and 1.37% for EMC. These differences are suggested to be inconsequential when compared to the values that exist between different species of untreated wood. Published version

A probabilistic risk assessment framework was developed to mathematically represent the complex engineering phenomena of rock bursts and gas outbursts for a heterogeneous coal seam. An innovative object-based non-conditional simulation approach was used to distribute lithological heterogeneity present in the coal seam to respect their geological origin. The changing mining conditions during longwall top coal caving mining (LTCC) were extracted from a coupled numerical model to provide statistically sufficient data for probabilistic analysis. The complex interdependencies among abutment stress, pore pressure, the volume of total gas emission and incremental energy release rate, their stochastic variations and uncertainty were realistically implemented in the GoldSim software, and 100,000 equally likely scenarios were simulated using the Monte Carlo method to determine the probability of rock bursts and gas outbursts. The results obtained from the analysis incorporate the variability in mechanical, elastic and reservoir properties of coal due to lithological heterogeneity and result in the probability of the occurrence of rock bursts, coal and gas outbursts, and safe mining conditions. The framework realistically represents the complex mining environment, is resilient and results are reliable. The framework is generic and can be suitably modified to be used in different underground mining scenarios, overcoming the limitations of earlier empirical indices used.

Long-term exploration of the Groningen gas field in the Netherlands led to induced seismicity. Over the past nine years, an increasingly sophisticated Ground Motion Model (GMM) has been developed to assess the site response and the related seismic hazard. The GMM output strongly depends on the shear-wave velocity (V S ), among other input parameters. To date, V S model data from soil profiles (Kruiver et al., Bulletin of Earthquake Engineering, 15(9): 3555–3580, 2017; Netherlands Journal of Geosciences, 96(5): s215–s233, 2017) have been used in the GMM. Recently, new V S profiles above the Groningen gas field were constructed using ambient noise surface wave tomography. These so-called field V S data, even though spatially limited, provide an independent source of V S to check whether the level of spatial variability in the GMM is sufficient. Here, we compared amplification factors (AF) for two sites (Borgsweer and Loppersum) calculated with the model V S and the field V S (Chmiel et al., Geophysical Journal International, 218(3), 1781–1795, 2019 and new data). Our AF results over periods relevant for seismic risk (0.01–1.0 s) show that model and field V S profiles agree within the uncertainty range generally accepted in geo-engineering. In addition, we compared modelled spectral accelerations using either field V S or model V S in Loppersum to the recordings of an earthquake that occurred during the monitoring period (ML 3.4 Zeerijp on 8 January 2018). The modelled spectral accelerations at the surface for both field V S and model V S are coherent with the earthquake data for the resonance periods representative of most buildings in Groningen (T = 0.2 and 0.3 s). These results confirm that the currently used V S model in the GMM captures spatial variability in the site response and represents reliable input for the site response calculations.

Background The severe plastic deformation approach and its well-known cyclic extrusion compression (CEC) method have been established as a powerful tool for fabricating bulk ultrafine-grained metals and alloys with improved properties. Objective This study focused on the microstructure evolution, hardness behavior, and corrosion properties of the CEC-processed Al5052 up to four passes compared to the initial annealed state. Methods The initial and CEC-processed Al5052 samples at different pass numbers were examined experimentally by EBSD analyses, hardness measurements, and corrosion resistance. Results Substantial grain refinement was attained from ~23 μm for the annealed sample to ~0.8 μm in the four passes sample. In addition, the hardness values considerably increased up to 75.7% after four passes from the initial value of 80 HV. In addition, the increment of pass numbers led to a more uniform dispersion of hardness values. Furthermore, the production of more stable protective oxide layers on the UFG structure of the CEC-processed sample led to the improvement in electrochemical response with a corrosion rate reduction from 1.49 to 1.02 mpy, respectively, in the annealed and final pass CEC-processed samples. In fact, the annealed sample manifested more large-sized and deeper pits than the CECed samples due to the increment of potential values and electrochemical attack of chlorine ions that finally deteriorates the corrosion performance. Conclusions CEC is an efficient method to improve the mechanical properties of materials due to substantial microstructural changes along with enhancement of electrochemical behavior because of the presence of small-sized and shallow pits.

In the present paper, we present a method for solving the population balance equation (PBE) with the complete range of kinetic processes included: namely aggregation, fragmentation, nucleation and growth. The method is based on the finite volume scheme and features guaranteed conservation of the first moment by construction, accurate prediction of the size distribution, applicability to an arbitrary non-uniform grid, robustness and computational efficiency which is instrumental for coupling with computational fluid dynamics (CFD). The treatment of aggregation is based on the previous work by Liu and Rigopoulos (2019). An analysis of the aggregation terms in the PBE is made, and the source of conservation error in finite element/volume methods is elucidated. It is subsequently shown how this error is overcome in the present method via a coordinate transformation applied to the aggregation birth double integral resulting from the application of the finite volume method. The contributions to the birth term are delineated and their corresponding death fluxes identified. An aggregation map is then constructed for mapping birth and death fluxes, thus allowing the finite volume method to operate in terms of fluxes and achieve conservation of mass. The method is then extended to fragmentation, for which a map is also constructed to represent the birth and death fluxes. In the implementation, the aggregation and fragmentation maps are pre-tabulated to allow fast computation. It is also shown how the method can be coupled with a total variation diminishing (TVD) scheme for the treatment of growth with minimal numerical diffusion. The method is validated with a number of test cases including analytical solutions and numerical solutions of the discrete PBE for aggregation (theoretical and free molecule/Brownian kernels), fragmentation, aggregation-fragmentation and aggregation-growth. In all cases, the method produces very accurate results, while also being computationally efficient due to the pre-tabulation of the maps and the simplicity of the algorithm carried out per time step.

Coupled numerical models considering fluid flow and particle movement enable fundamental analyses of a variety of phenomena in geomechanics including seepage-induced instabilities. Amongst the various CFD (Computational Fluid Dynamics)-DEM (Discrete Element Method) coupled frameworks which have been proposed, Pore Network Models (PNMs) have the potential to simulate fluid flow in granular materials accurately with a low computational cost to enable simulations on Representative Volume Elements (RVEs). However, the current models of the local conductance between the connected pores are very simple, limiting the accuracy of PNMs. This study develops novel local conductance models by detailed analysis of existing analytical studies of fluid flow through different 3D lattice packings of uniform spheres. The performance of these new models relative to existing, simpler models is demonstrated using CFD simulations in which the flow in the pore space of random assemblies of polydisperse spheres is accurately resolved. The analyses show that the new models proposed here can more accurately predict the local and global permeabilities of specimens with a wide range of void ratios and polydispersities. These models do not require any optimisation via merging pores so that they can efficiently simulate systems with an evolving pore space topology.

The behaviour of gap-graded granular materials – that is, mixtures of coarse and cohesionless finer grains with measurable differences in particle size – does not always conform to established frameworks of sand behaviour. Prior research has revealed that the role of the finer particles on the stress–strain response, liquefaction resistance and internal stability of non-cohesive gap-graded soils is significant and complex, and highly dependent on both the volumetric proportion of finer particles in the material and the size ratio of coarse particles to finer particles. Quantifying the participation of the finer particles in stress transmission and overall behaviour is central to understanding the behaviour of these materials. No experimental technique for directly quantifying the contribution of finer particles to the overall behaviour, however, has hitherto been proposed. This paper explores to what extent the participation of finer particles can be assessed using laboratory geophysics, recognising that granular materials act as a filter to remove the high-frequency components of applied seismic/sound waves. Discrete-element method simulations are performed to understand the link between particle-scale stress transmission and the overall response observed during shear wave propagation. When the proportion of finer particles is increased systematically, both the shear wave velocity (VS) and low-pass frequency (flp) increase sharply once a significant amount of the applied stress has been transferred by way of the finer particles. This trend is also observed in equivalent laboratory experiments. Consequently, the flp–VS relationship can provide useful insights to assess whether the finer particles contribute to stress transmission and hence the mechanical behaviour of gap-graded materials.

Vanillin (VAN) is widely used in medicine, food and optoelectronics, but its low solubility leads to the decrease of bioavailability and increase of application costs. Three APIs-nicotinamide (NIC), isonicotinamide (INM) and isoniazid (INH) were chosen to form cocrystals with VAN, aiming at improving the solubility of VAN and APIs simultaneously. Two cocrystals (VAN-NIC, VAN-INM) were obtained through cocrystallization while VAN reacted with INH to form one novel compound (VAN-INH). The crystal structures were characterized by single-crystal X-ray diffraction (SCXRD), Powder X-ray diffraction (PXRD), Fourier-Transform Infrared Spectroscopy (FT-IR) and Differential Scanning Calorimetry (DSC). The melting temperatures of VAN-NIC and VAN-INM cocrystals are between this of VAN and APIs. Compared with pure VAN and APIs, the solubility and dissolution rate of VAN-NIC and VAN-INM are significantly increased. The melting temperature of VAN-INH is greater than that of VAN and INH, and the solubility and dissolution rate is not increased significantly. The intermolecular energy between VAN and APIs as well as lattice energies of cocrystals/novel compound were computed to elucidate the formation mechanism and stability. The present investigation opens a new pathway for the development of natural product-drug cocrystals to improve solubility and dissolution rate of natural product.

Modeling of ionic diffusion in natural crystals has been developed over the last three decades to calculate timescales of geological processes. As the number of studies and the size of data sets have expanded, improvements in the precision of the general technique are needed to resolve temporal patterns that would otherwise be masked by large uncertainties. This contribution examines fundamental aspects of timescale calculation uncertainty using Mg-Fe zonation in olivine crystals from a Piton de la Fournaise oceanite erupted in 2002 CE. First, we quantitatively consider the role of geometric uncertainty in data sets from the perspectives of sectioning angle, crystal shape, and crystal agglomeration. Second, we assess how crystal growth and changing boundary conditions during diffusion pose problems for simplistic, 1D, diffusion-only modeling. An initial database of 104 timescales (7–45 days) was generated using typical, 1D, isothermal diffusion-only methods for profiles taken from 30 compositionally and texturally zoned crystals of olivine. This simplistic modeling yields poor model fits and imprecise timescales; prior to this work, we would have rejected >60% of these data. Universal-stage measurements of crystal boundary angles and three-dimensional (3D) X-ray microcomputed tomography observations of crystal shape address geometric uncertainties. U-stage measurements show that, contrary to expectations of random sectioning, most boundaries modeled initially were close to the ideal sectioning plane. Assessment of crystal morphology from 2D thin sections suggests olivine crystals are dominantly euhedral; however, 3D imaging reveals that they are significantly subhedral and often exist as agglomerates, an observation that underscores both the potential for diverse crystal interactions through time in the magma (Wieser et al. 2019) and out-of-plane effects capable of influencing calculations of diffusion profiles. Refinements to timescale determination can be made using a dynamic 1D modeling code to resolve growth and changing boundary effects simultaneous with diffusion. We incorporated temperature-dependent crystal growth rates (both linear growth and quadratically increasing, with a peak growth rate ~1.9 ×10–11 ms–1) and temperature-dependent boundary conditions (controlled using a cooling rate of −0.5 ± 0.1 °C/h) to remodel 13 timescales, resulting in significantly improved fits of the diffusion model to the initial data, better agreement between different faces of the same crystal, and less scatter within the whole data set. The use of 3D imaging and the inclusion of changing boundary conditions and crystal growth for diffusion calculations will enable more robust conclusions to be drawn from similar data in the future. Accurately retrieving timescale information from these crystals expands the pool of data available and reduces sampling bias toward “well-behaved” crystals.

One primordial consideration in residential ventilation standards is the comfort of provided to people living in those habitations. This is highly dependent on the thermal and fluid flow conditions, the space geometry and so on. Efficient designs may reduce the energy usage, making the buildings more sustainable over a longer period of time. This study aims to investigate the impact of whole day thermal conditions on the fluid flow structure and heat transfer phenomena, mainly natural convection, inside a partitioned attic-shaped configuration. The Finite Volume Method is applied to solve the governing equations. Sinusoidal thermal boundary condition is applied on the sloping walls to illustrate the characteristics of primary flow through daily cycles. A highly thermal conductive partition was placed vertically at the middle of the cavity. Note that through the partition, only heat could freely transfer between two fluid zones. Results show that, during day time, a stratified fluid flow structure is obtained, which originates from the prevailing conduction heat transfer mechanism, while, for the night-time it changed into a strong convection mechanism which significantly affects the flow structure. These results are particularly important for understanding the fluid dynamics inside the attic shaped building and also designing new residential building.

Despite the large quantity of works dedicated to the analysis and modelling of deposition in single-phase flows, very few models have been proposed for deposition of solids in two-phase pipe flows of gas and liquid. A comprehensive mechanistic model for transient, multiphase pipe flow with phase change is proposed, which takes into account effects of deposition by mass diffusion, ageing, and shearing of the deposit layer. Validation is performed with an exhaustive database of experimental data from the literature, for steady and transient flows without deposition, and deposit thickness measurements for single-phase, slug and stratified flows. Most of the predictions are within a 20% error band from the experimental data, with slightly worse performance in the case of deposition in slug flows. A surrogate model is also developed based on active-learning sampling of the simulator results, demonstrating a technique that could be used for optimization or design of engineering devices.

Ultrasonic treatment is effective in deagglomerating and dispersing nanoparticles in various liquids. However, the exact deagglomeration mechanisms vary for different nanoparticle clusters, owing to different particle geometries and inter-particle adhesion forces. Here, the deagglomeration mechanisms and the influence of sonotrode amplitude during ultrasonication of multiwall carbon nanotubes in de-ionized water were studied by a combination of high-speed imaging and numerical modeling. Particle image velocimetry was applied to images with a higher field of view to calculate the average streaming speeds distribution. These data allowed direct comparison with modeling results. For images captured at higher frame rates and magnification, different patterns of deagglomeration were identified and categorized based on different stages of cavitation zone development and for regions inside or outside the cavitation zone. The results obtained and discussed in this paper can also be relevant to a wide range of carbonaceous and other high aspect ratio nanomaterials.

Seawalls are constructed by covering and protecting the sloping seashore ground with concrete plates or blocks. Their purpose is to sustain high waves induced by strong winds and prevent ground erosion, but they often collapse, mobilising different modes of failure, including that of the ground. Nevertheless, limited research has been conducted on ground failure caused by high waves. In this study, a series of novel centrifuge model tests was first conducted to investigate the failure mechanisms of seawalls due to wave propagation, focusing on the failure of the ground. Finite-element analyses were subsequently conducted to explore the failures observed in the model tests and to provide further insight as to the state of the ground leading to failure. Two failure modes were demonstrated to prevail: floating of the covering panel and sliding failure of the ground. In addition, of the possible causes of failure, the following three were identified in the current study: increased unit weight and reduced suction from wetting; enhanced seepage force under the panel and around the toe block during backwash; water pressure on the back of the panel and the landward side of the toe block during backwash.

In unresolved flow CFD-DEM simulations, the porosity values for each CFD cell are determined using a coarse-graining algorithm. While this approach enables coupled simulations of representative numbers of particles, the influence of the porosity local to the particles on the fluid-particle interaction force is not captured. This contribution considers a two-grid coarse-graining method that determines a local porosity for each particle using a radical Voronoi tessellation of the system. A relatively fine, regular point cloud is used to map these local porosity data to the CFD cells. The method is evaluated using two different cases considering both disperse and tightly packed particles. The data show that the method conserves porosity data, is reasonably grid-independent and can generate a relatively smooth porosity field. The new method can more accurately predict the fluid-particle interactive force for polydisperse particle system than alternative methods that have been implemented in unresolved CFD-DEM codes., 22 pages, 21 figures. Article published in Powder Technology (see https://doi.org/10.1016/j.powtec.2021.02.025)

Installation of granular columns is a cost-effective and versatile in situ technique to improve the shear strength, settlement, and drainage behaviour of weak soils. It involves backfilling vertical boreholes in the ground with granular materials stiffer than the native soil, such as stone or compacted sand. However, the massive use and overexploitation of sand and natural aggregates have depleted their reserves in recent decades, causing damage to the environment, creating sand shortages and skyrocketing their price. Hence, it is essential to develop a sustainable alternative to natural aggregates to construct granular columns. The ever-increasing stockpiles of waste glass could be a potential replacement for natural sand in several geotechnical construction applications, noting that both materials have a similar chemical composition. Using crushed waste glass (CWG) as an alternative to traditional natural and manufactured (quarried) sands in granular columns could offer a multi75 pronged benefit by recycling non-biodegradable waste (glass) and by conserving a depleting natural resource (sand). Using a large direct shear (LDS) machine, this study investigated the shear strength behaviour of kaolin (to represent a typical weak soil) reinforced with a central granular column. Three different materials were separately used to backfill the column, including natural sand (NS), manufactured sand (MS) and CWG. The results revealed that the geocomposites containing the CWG column have the highest peak friction angle and relatively greater shear strength under high normal stresses, favouring the potential use of CWG as a green alternative to traditional sands in backfilling granular columns, ultimately supporting resource conservation, waste recycling and the paradigm shift towards a circular economy.

The use of hydrogen enriched fuel blends, e.g. syngas, offers great potential in the decarbonisation of gas turbine technologies by substitution and expansion of the lean operating limit. Studies assessing explosion risks or laminar flame properties of such fuels are common. However, there is a lack of experimental data that quantifies the impact of hydrogen addition on turbulent flame parameters including burning velocities and scalar fluxes. Such properties are here determined for aerodynamically stabilised flames in a back-to-burnt opposed jet configuration featuring fractal grid generated multi-scale turbulence ( Re t = 314 ± 19 ) using binary H 2 / C H 4 and H 2 /CO fuel blends. The binary H 2 / C H 4 fuel blend is varied from α = X H 2 / ( X H 2 + X F ) = 0.0, 0.2 and 0.4–1.0, in steps on 0.1, and the binary H 2 /CO fuel blend from α = 0.3 − 1 . 0 also in steps of 0.1. The equivalence ratio is adjusted between the mixture specific lower limit of local flame extinction and the upper limit of flashback. The flames are characterised using PIV measurements combined with a flame front detection algorithm. The study quantifies the impact of hydrogen enrichment on (i) turbulent burning velocity ( S T ), (ii) turbulent transport and (iii) the rate of strain acting on flame fronts. Scaling relations (iv) that correlate S T with laminar flame properties are evaluated and (v) flow field data that permits validation of computational models is provided. It is shown that C H 4 results in a stronger inhibiting effect on the reaction chemistry of H 2 compared to CO, that turbulent transport and burning velocities are strongly correlated with the rate of compressive strain and that scaling relationships can provide reasonable agreement with experiments.

This paper describes the results obtained from a field testing campaign on laterally loaded monopiles conducted at Cowden, UK, where the soil consists principally of a heavily overconsolidated glacial till. These tests formed part of the PISA project on the development of improved design methods for monopile foundations for offshore wind turbines. Results obtained for monotonic loading tests on piles of three different diameters (0·273 m, 0·762 m and 2·0 m) are presented. The piles had length-to-diameter ratios (L/D) of between 3 and 10. The tests included the application of monotonic loading incorporating periods of constant load to investigate creep effects, and investigations on the influence of loading rate. Data are presented on measured bending moments and inclinations induced in the piles. Inferred data on lateral displacements of the embedded section of the piles are determined using an optimised structural model. These field data support the development of a new one-dimensional modelling approach for the design of monopile foundations for offshore wind turbines. They also form a unique database of field measurements in an overconsolidated clay, from lateral loading of piles at a vertical distance above the ground surface.

The PISA Joint Industry Research Project was concerned with the development of improved design methods for monopile foundations in offshore wind applications. PISA involved large-scale pile tests in overconsolidated glacial till at Cowden, north-east England, and in dense, normally consolidated marine sand at Dunkirk, northern France. This paper describes the experimental set-up for pile testing, with unique features of load-application mechanisms and built-in fibre optic strain gauges. New procedures are described for the interpretation of pile loading data, and specifically for providing precise interpretation of pile displacements.

The complexity of advanced constitutive models often dictates that their capabilities are only demonstrated in the context of model testing under controlled conditions. In the case of earthquake engineering and liquefaction in particular, this restriction is magnified by the difficulties in measuring field behaviour under seismic loading. In this paper, the well-documented case of the Canterbury earthquake sequence in New Zealand, for which extensive field and laboratory data are available, is utilised to demonstrate the accuracy of a bounding surface plasticity model in fully coupled finite-element analyses. A strong motion station with manifestation of liquefaction and the second highest peak vertical ground acceleration during the 22 February 2011 Mw 6·2 seismic event is modelled. An empirical assessment predicted no liquefaction for this station, making this an interesting case for rigorous numerical modelling. The calibration of the model aims at capturing both the laboratory tests and the field measurements in a consistent manner. The characterisation of the ground conditions is presented, while, to specify the bedrock motion, the records of two stations without liquefaction are de-convolved and scaled to account for wave attenuation with distance. The numerical predictions are compared to both the horizontal and vertical acceleration records and other field observations, showing a remarkable agreement, also demonstrating that the high vertical accelerations can be attributed to compressional resonance. The results provide further insights into the underperformance of the simplified procedure.

Knowledge regarding microseismic characteristics associated with longwall coal mining is crucial in evaluating the potential for underground mining hazards. Although microseismicity is induced by mining activities, it still remains uncertain as to what extent mining activities influence the spatial, temporal, and magnitude characteristics of microseismicity. To establish a thorough understanding of the relationship between microseismic characteristics and mining activities, a 27-month long microseismic monitoring campaign was conducted around a highly stressed coal zone and eight producing longwall panels at Coal Mine Velenje in Slovenia. Each microseismic event was classified to be associated with the producing longwall panel that triggered it, and the microseismic response to multi-panel longwall top coal caving face advance was analysed. Monitoring data have shown that locations of microseismic events coincided with stress concentrated regions. It was established that both seismic count and energy-intensive regions associated with coal mining in different panels are spatially connected, but they do not fully overlap with mined-out or stress concentrated areas. In addition, microseismic event counts frequency was found to be well correlated with mining intensity, while seismic energy magnitude and spatial distribution are poorly correlated with the same. Therefore, microseismic characteristics could not be explained solely by the mining-induced stress transfer and mining intensity, but are believed to be dominated by pre-existing natural fractures throughout the coal seam. Analyses of these observations helped the development of a conceptual seismic-generation model, which provides new insights into the causes of microseismicity in coal mining.

In siliciclastic and carbonate reservoirs, depositional facies are often described as being organized in cyclic successions that are overprinted by diagenesis. Most reservoir modelling workflows are not able to reproduce stochastically such patterns. Herein, a novel geostatistical method is developed to model depositional facies architectures that are rhythmic and cyclic, together with superimposed diagenetic facies. The method uses truncated Pluri-Gaussian random functions constrained by transiograms. Cyclicity is defined as an asymmetric ordering between facies, and its direction is given by a three-dimensional vector, called shift. This method is illustrated on two case studies. Outcrop data of the Triassic Latemar carbonate platform, northern Italy, are used to model shallowing-upward facies cycles in the vertical direction. A satellite image of the modern Bermuda platform interior is used to model facies cycles in the windward-to-leeward lateral direction. As depositional facies architectures are modelled using two Gaussian random functions, a third Gaussian random function is added to model diagenesis. Thereby, depositional and diagenetic facies can exhibit spatial asymmetric relations. The method is applied in two regions of the Latemar carbonate platform that experience two different types of diagenetic transformation: syn-depositional dolomite formation, and post-depositional fracture-related diagenesis. The method can also incorporate proportion curves to model non-stationary facies proportions. This is illustrated in Cretaceous shallow-marine sandstones and mudstones, Book Cliffs, Utah, for which cyclic facies and diagenetic patterns are constrained by embedded transition probabilities.

Glucaric acid is being used increasingly as a food additive, corrosion inhibitor, in deicing, and in detergents, and is also a potential starting material for the production of adipic acid, the key monomer for nylon-66. This work describes a techno-economic analysis of a potential bio-based process for the production of pure glucaric acid from corn stover (biomass). Two alternative routes for oxidation of glucose to glucaric acid are considered: via heterogeneous catalytic oxidation with air, and by homogeneous glucose oxidation using nitric acid. Techno-economic and lifecycle assessments (TEA, LCA) are made for both oxidation routes and cover the entire process from biomass to pure crystalline glucaric acid that can be used as a starting material for the production of valuable chemicals. This is the first TEA of pure glucaric acid production incorporating ion exchange and azeotropic evaporation below 50 °C to avoid lactone formation. The developed process models were simulated in Aspen Plus V9. The techno-economic assessment shows that both production routes are economically viable leading to minimum selling prices of glucaric acid of ∼ $2.53/kg and ∼ $2.91/kg for the heterogeneous catalytic route and the homogeneous glucose oxidation route respectively. It is shown that the heterogeneous catalytic oxidation route is capable of achieving a 22% lower environmental impact than the homogeneous glucose oxidation route. Opportunities for further improvement in sustainable glucaric acid production at industrial scale are identified and discussed.

This paper reports the cyclic behaviour of chalk, which has yet to be studied comprehensively. Multiple undrained high-resolution cyclic triaxial experiments on low- to medium-density intact chalk, along with index and monotonic reference tests, define the conditions under which either thousands of cycles could be applied without any deleterious effect, or failure could be provoked under specified numbers of cycles. Intact chalk's response is shown to differ from that of most saturated soils tested under comparable conditions. While chalk can be reduced to putty by severe two-way displacement-controlled cycling, its behaviour proved stable and nearly linear visco-elastic over much of the one-way, stress-controlled loading space examined, with stiffness improving over thousands of cycles, without loss of undrained shear strength. However, in cases where cyclic failure occurred, the specimens showed little sign of cyclic damage before cracking and movements on discontinuities led to sharp pore pressure reductions, non-uniform displacements and the onset of brittle collapse. Chalk's behaviour resembles the fatigue response of metals, concretes and rocks, where micro-shearing or cracking initiates on imperfections that generate stress concentrations; the experiments identify the key features that must be captured in any representative cyclic loading model.

The paper discusses operation and control of a process for the liquefaction of natural gas in which the refrigeration compressors are driven by electric motors. The aim is to enable the plant to accommodate contingencies in the availability of electrical power and to continue running when there is a shortage of electrical power, avoiding the significant economic impact of a shutdown. The article provides a detailed first principles analysis of the relationships between the electrical power consumption of the process, the production rate of the liquefied natural gas, its exit temperature, and its purity. By doing this, it is possible to ascertain settings for operating the process at various levels of power consumption. The results show that the process can operate with reductions of electrical power of 30 percent or more. Hence, power shortages could be managed by operating the process flexibly to make best use of the available remaining power, rather than by shutting down. The paper also discusses how such a system could be implemented industrially and identifies aspects that require further study.

Low-to-medium density chalk can be de-structured to soft putty by high-pressure compression, dynamic impact or large-strain repetitive shearing. These process all occur during pile driving and affect subsequent static and cyclic load-carrying capacities. This paper reports undrained triaxial experiments on de-structured chalk, which shows distinctly time-dependent behaviour as well as highly non-linear stiffness, well-defined phase transformation (PT) and stable ultimate critical states under monotonic loading. Its response to high-level undrained cyclic loading invokes both contractive and dilative phases that lead to pore pressure build-up, leftward effective stress path drift, permanent strain accumulation, cyclic stiffness losses and increasing damping ratios that resemble those of silts. These outcomes are relatively insensitive to consolidation pressures and are distinctly different to those of the parent intact chalk. The maximum number of cycles that can be sustained under given combinations of mean and cyclic stresses are expressed in an interactive stress diagram which also identifies conditions under which cycling has no deleterious effect. Empirical correlations are proposed to predict the number of cycles to failure and mean effective stress drift trends under the most critical cyclic conditions. Specimens that survive long-term cycling present higher post-cyclic stiffnesses and shear strengths than equivalent ‘virgin’ specimens.

Bubble size distribution (BSD) is a factor that is well known for influencing the performance of many industrial processes, such as froth flotation. The most commonly used method for measuring bubble size consists of processing photographs of the bubbles. However, the source code of the algorithms for performing the image processing has been seldom published. This article addresses the above by presenting a comprehensive open-source software for processing images of bubbles, allowing researchers to quantify BSD. This software - Bubble Analyser - includes a standard image processing algorithm that was tested against manually segmented images, showing errors under 5% in the calculation of the Sauter mean diameter, the most common descriptor of BSD. Additionally, Bubble Analyser has been designed to easily incorporate new segmentation algorithms developed by other researchers, in order to expand the software capabilities, allow for algorithm comparisons, and foster collaboration in research.

Due to the increasing criticality of rare earth elements (REEs), it has become essential to recover REEs from alternative resources. In this study, systematic REEs leaching tests were performed on the calcination product of a coal coarse refuse using hydrochloric acid and different types of organic acid as lixiviants. Experimental results show that the recovery of REEs, especially heavy REEs (HREEs) and scandium (Sc), is improved by using selected organic acids. Citric acid and dl -malic acid afford the best leaching performances; whereas, malonic acid, oxalic acid, and dl -tartaric acid are inferior to hydrochloric acid. Results of zeta potential measurements and solution chemical equilibrium calculations show that malonic acid is more likely adsorbed on the surface of the calcined material compared with citric acid and dl -malic acid. The adsorption may reduce the effective concentration of malonic species in solution and/or increase the amount of REEs adsorbed on the surface, thereby impairing the leaching recovery. Compared with light REEs (LREEs), a stronger adsorption of the HREEs on the surface is observed from electro-kinetic test results. This finding explains why organic acids impose a more positive impact on the leaching recovery of HREEs. By complexing with the HREEs, organic acids can keep the metal ions in solution and improve the leaching recovery. The adsorption of Sc3+ on the surface is the lowest compared with other REEs. Therefore, rather than complexing, the organic anionic species likely play a function of solubilizing Sc from the solid, which is similar to that of hydrogen ions.

Copyright: © 2022 by the authors. Manganese-bearing intermetallic compounds (IMCs) are important for ensuring adequate corrosion performance of magnesium-aluminium alloys and can be deleterious to mechanical performance if they are large and/or form clusters. Here, we explore the formation of Al-Mn IMCs in Mg-9Al-0.7Zn-0.2Mn produced by two industrial casting processes, high-pressure die casting (HPDC) and direct chill (DC) casting. As Al8Mn5 starts forming above the α-Mg liquidus temperature in this alloy, we consider its formation during melt handling as well as during casting and heat treatment. In HPDC, we focus on sludge formation in the holding pot, partial solidification of IMCs in the shot chamber, and Al-Mn IMC solidification in the die cavity. In DC casting, we focus on interactions between Al-Mn IMCs and oxide films in the launder system, Al-Mn IMC solidification in the billet, and the partial transformation of Al8Mn5 into Al11Mn4 during solution heat treatment. The results show that minimising pre-solidification in the shot sleeve of HPDC and controlling pouring and filtration in DC casting are important for ensuring small Al-Mn intermetallic particles in these casting processes. Engineering and Physical Sciences Research Council (EPSRC, UK), grant number EP/N007638/1 (the Future LiME Hub); National Natural Science Foundation of China, grant number 51904352.

Low- to medium-density chalk at St Nicholas at Wade, UK, is characterised by intensive testing to inform the interpretation of axial and lateral tests on driven piles. The chalk destructures when taken to large strains, especially under dynamic loading, leading to remarkably high pore pressures beneath penetrating cone penetration testing and driven pile tips, weak putty annuli around their shafts and degraded responses in full-displacement pressure-meter tests. Laboratory tests on carefully formed specimens explore the chalk's unstable structure and markedly time- and rate-dependent mechanical behaviour. A clear hierarchy is found between profiles of peak strength with depth of Brazilian tension, drained and undrained triaxial and direct simple shear tests conducted from in situ stress conditions. Highly instrumented triaxial tests reveal the chalk's unusual effective stress paths, markedly brittle failure behaviour from small strains and the effects of consolidating to higher than in situ stresses. The chalk's mainly sub-vertical jointing and micro-fissuring lead to properties depending on specimen scale, with in situ mass stiffnesses falling significantly below high-quality laboratory measurements and vertical Young's moduli exceeding horizontal stiffnesses. While compressive strength and stiffness appear relatively insensitive to effective stress levels, consolidation to higher pressures closes micro-fissures, increases stiffness and reduces anisotropy.