Ab initio theory and modeling of water

Water is of the utmost importance for life and technology. However, a genuinely predictive ab initio model of water has eluded scientists. We demonstrate that a fully ab initio approach, relying on the strongly constrained and appropriately normed (SCAN) density functional, provides such a description of water. SCAN accurately describes the balance among covalent bonds, hydrogen bonds, and van der Waals interactions that dictates the structure and dynamics of liquid water. Notably, SCAN captures the density difference between water and ice I{\it h} at ambient conditions, as well as many important structural, electronic, and dynamic properties of liquid water. These successful predictions of the versatile SCAN functional open the gates to study complex processes in aqueous phase chemistry and the interactions of water with other materials in an efficient, accurate, and predictive, ab initio manner

Probing defects and correlations in the hydrogen-bond network of ab initio water

The hydrogen-bond network of water is characterized by the presence of coordination defects relative to the ideal tetrahedral network of ice, whose fluctuations determine the static and time-dependent properties of the liquid. Because of topological constraints, such defects do not come alone, but are highly correlated coming in a plethora of different pairs. Here we discuss in detail such correlations in the case of ab initio water models and show that they have interesting similarities to regular and defective solid phases of water. Although defect correlations involve deviations from idealized tetrahedrality, they can still be regarded as weaker hydrogen bonds that retain a high degree of directionality. We also investigate how the structure and population of coordination defects is affected by approximations to the inter-atomic potential, finding that in most cases, the qualitative features of the hydrogen bond network are remarkably robust

Optimization and performance of grinding circuits: the case of Buzwagi Gold Mine (BGM)

Buzwagi Gold Mine (BGM) is operated by Acacia Mining and located in the Lake Victoria Goldfields of central Tanzania. The mine commenced its operation since April 2009 and treats a sulphide copper-gold ore to produce gold in form of doré bars and a concentrate containing gold, copper and silver. The BGM comminution circuit includes a primary crushing stage with a gyratory crusher and a two grinding circuits using a Semi-Autogenous Grinding (SAG) mill and a ball mill. The SAG mill circuit also includes a single-deck screen and a cone crusher while the ball mill circuit utilizes hydrocyclones. Currently, the grinding circuits are inefficient in achieving the aspired product fineness of xP,80 = 125 μm even at low to normal throughputs (450-600 t/h). An evaluation and optimization study of the circuit performance was conducted to improve the product fineness through circuit surveys, experimental lab work and simulations. In three full scale sampling campaigns, size distributions and solids contents of the samples were determined at selected points in the circuit. Further, several types of breakage tests were conducted; standard Bond tests to determine ore grindability and work indices, batch grinding tests to determine parameters for breakage and selection functions , and standard ball mill tests for mineral liberation characterization by an automated mineral liberation analyzer (MLA).The tests were conducted in a size range from 0.063 to 2 mm. Then, mass balance of the circuit was calculated and the models for mills, screens and hydrocyclones were employed in MODSIM (version 3.6.24). Firstly, simulations were conducted to optimize the existing plant. Several options were evaluated such as reduction of SAG screen aperture, adjustment of cyclone feed solids content and reduction of vortex finder and apex diameters. Moreover, simulations were also evaluated for a possible modification of the existing circuit and include; partial splitting of the cyclone underflow back to SAG mill, introduction of a second classification stage as well as introduction of a second ball mill. The evaluation of breakage tests and survey data revealed the following; the Bond work index obtained for the current ore ranges between 17.20 - 18.70 kWh/t compared to 14.50 - 16.50 kWh/t which was estimated during plant design.This indicates a change in hardness of the ore during the last 7 years. Harder ore means more energy requirement for an efficient operation, the consequence of which is increased costs. Thus, a periodic review of the ore hardness for ongoing mining operation is recommended. This will help in establishing better blends as well as prediction of appropriate tonnages for the existing ore types, so as to be efficiently treated by the available plant design. The work indices of the ore blends treated during survey were correlated with their quartz content and showed a strong linear relationship (R2= 0.95). Therefore, the work index for the BGM ore could be predicted based on known quartz content of the material. Further, the model could be used as a control tool for monitoring hardness variation of the SAG mill feed. The mineral liberation studies indicated that the valuable phase (pyrite-pyrrhotite) could be liberated at relatively coarser particle sizes (200-400 µm). This implies that, there could be no problem with the efficiency of the gravity circuit for the BGM operation, where the gold contained in pyrite-pyrrhotite could be easily concentrated. However, the efficiency of flotation and cyanidation processes will still require finer feed. In overall, the liberation characteristics of the ore blends treated during survey showed minor differences. The Bond efficiency factors of 48-61 % were obtained for the BGM grinding circuit, indicating an inefficient operation. This suggests that the operation could achieve targets by lowering the throughput. Further, the SAG mill circuit was characterized by fluctuating feed size of between xF,80 =102 to 185 mm. A need for control of the feed size as well as blending ratios was recommended for an efficient operation in terms of throughput and final product size. This could be achieved through closer monitoring of the primary crusher performance and proper control of the ratios for the SAG mill feeders drawing the ore from the stockpile. The ball mill grinding efficiency was poor and could be indicated by the fraction 400 µm in the mill discharge. This was deemed due to poor hydrocyclone performance which was characterized by higher feed solids content, coarser overflow xP,80: >200 µm as well as cut sizes, xT : > 200 µm. An improvement of product fineness up to 327 µm could be achieved during the simulation and optimization of the existing design. This could be achieved by modification of the operating conditions such as reduction of SAG screen aperture from 12 mm to 10 mm, reduction of vortex finder from 280 mm to 270.3 mm, reduction of apex diameter from 150 mm to 145.6 mm as well as adjustment of the cyclone feed solids content from 66.7 to 67.1 %. Based on this result, it was concluded that the current equipment could not achieve the target product quality (i.e. xP,80 = 125 µm ). Further simulations based on flowsheet modification options showed that a second ball mill (series configuration) can help to achieve the desired product fineness as well as an increase of throughput from 618 t/h to 780 t/h. Although the circulating load increases to approximately 500 % in this configuration, it is outweighed by the benefits. Importantly, this option is cost intensive and hence may be considered as a long term solution and especially after cost-benefit analysis. Finally, the results based on optimization of the existing design is recommended as short term solution for improvement of the BGM operation. Although the fineness achieved is still low (i.e. xP,80 = 327 µm) compared to the target (i.e. xP,80 = 125 µm), this gives additional advantage in the sense that, also better hydrocyclone performance is achieved in terms of overflow product (xP,80 = 105 µm vs. > 240 µm) , cut size (xT =133.1 µm vs. > 220 µm) and circulating load (CL =350 %). The improved overflow fineness will contribute to improved efficiency for the downstream processes

Thermomechanical degradation mechanisms of silicon photovoltaic modules

The durability and lifetime of photovoltaic (PV) modules is one of the chief concerns for an industry which is rapidly approaching maturity. Guaranteeing the economic viability of potential PV installations is paramount to fostering growth of the industry. Whilst certification standards have helped to improve the reliability of modules, with a significant reduction in early failures, long-term performance degradation and overall lifetimes are yet to be addressed in a meaningful way. For this, it is necessary to quantify the effects of use-environment and module design. Long-term degradation of the solder bonds in PV modules causes steady power loss and leads to the generation of more devastating, secondary mechanisms such as hot-spots. Whilst solder bond degradation is well-recognised and even tested for in certification protocols, the potential rate of degradation is not well understood, particularly with respect to different environmental conditions and material selection. The complex nature of a standard silicon PV module construction makes it difficult to observe the stresses experienced by the various components during normal operation. This thesis presents the development of a finite-element model which is used to observe the stresses and strains experienced by module components during normal operating conditions and quantifies the degradation of solder bonds under different environmental conditions. First, module operating temperatures are examined across a range of climates and locations to evaluate the thermal profiles experienced by modules. Using finite-element techniques, the thermomechanical behaviour of modules is then simulated using the same thermal profiles and a quantification of solder bond degradation potential in each location is achieved. It is shown that hot climates are responsible for the highest degradation potential, but further to this, hot environments with many ii clear sky days, allowing for large swings in module temperature, are significantly more damaging. A comparison is drawn between indoor accelerated stress procedures and outdoor exposure, such that an equivalence between test duration and location-dependent outdoor exposure can be determined. It is shown that for the most damaging climate studied, 86 standard thermal cycles is appropriate for one-year of outdoor exposure whereas the least damaging environment would require 11 standard thermal cycles. However, these conclusions may only be applicable to the specific module design which was modelled as the material selection and interaction within a device plays a major role in the thermomechanical behaviour and degradation potential. In addition to a study on the influence of use-environment, a study on the influence of the encapsulating material is conducted with a particular focus on the effects of the viscoelastic properties of the materials. It is shown that the degradation of solder bonds can vary depending on the encapsulating material. Furthermore, the intended use-environment could inform the selection of the encapsulating material. The temperature-dependency of the material properties means that some materials will mitigate thermomechanical degradation mechanisms more than others under certain conditions i.e. hotter or colder climates