Paul Munroe

An investigation into the reactions of biochar in soil

Interactions between biochar, soil, microbes, and plant roots may occur within a short period of time after application to the soil. The extent, rates, and implications of these interactions, however, are far from understood. This review describes the properties of biochars and suggests possible reactions that may occur after the addition of biochars to soil. These include dissolution-precipitation, adsorption-desorption, acid-base, and redox reactions. Attention is given to reactions occurring within pores, and to interactions with roots, microorganisms, and soil fauna. Examination of biochars (from chicken litter, greenwaste, and paper mill sludges) weathered for 1 and 2 years in an Australian Ferrosol provides evidence for some of the mechanisms described in this review and offers an insight to reactions at a molecular scale. These interactions are biochar- and site-specific. Therefore, suitable experimental trials—combining biochar types and different pedoclimatic conditions—are needed to determine the extent to which these reactions influence the potential of biochar as a soil amendment and tool for carbon sequestration.

Mesoporous LiFePO4/C nanocomposite cathode materials for high power lithium ion batteries with superior performance

Hexagonally ordered mesoporous LiFePO4/C nanocomposites can be synthesized with LiFePO4 nanoparticles embedded in an interconnected carbon framework. Mesoporous LiFePO4/C nanocomposites exhibit superior electrochemical performance and ultra-high specific power density, which makes this architecture suitable for high power applications such as hybrid electric vehicles (HEVs) and stationary energy storage for smart grids.

Porous Graphene Nanoarchitectures: An Efficient Catalyst for Low Charge-Overpotential, Long Life, and High Capacity Lithium–Oxygen Batteries

The electrochemical performance of lithium-oxygen (Li-O2) batteries awaits dramatic improvement in the design of porous cathode electrodes with sufficient spaces to accommodate the discharge products and discovery of effective cathode catalysts to promote both oxygen reduction reactions and oxygen evolution reactions. Herein, we report the synthesis of porous graphene with different pore size architectures as cathode catalysts for Li-O2 batteries. Porous graphene materials exhibited significantly higher discharge capacities than that of nonporous graphene. Furthermore, porous graphene with pore diameter around 250 nm showed the highest discharge capacity among the porous graphene with the small pores (about 60 nm) and large pores (about 400 nm). Moreover, we discovered that addition of ruthenium (Ru) nanocrystals to porous graphene promotes the oxygen evolution reaction. The Ru nanocrystal-decorated porous graphene exhibited an excellent catalytic activity as cathodes in Li-O2 batteries with a high reversible capacity of 17,700 mA h g(-1), a low charge/discharge overpotential (about 0.355 V), and a long cycle life up to 200 cycles (under the curtaining capacity of 1000 mAh g(-1)). The novel porous graphene architecture inspires the development of high-performance Li-O2 batteries.

Mechanical Deformation in Silicon by Micro-indentation

The mechanical deformation of crystalline silicon induced by micro-indentation has been studied. Indentations were made using a variety of loading conditions. The effects on the final deformation microstructure of the load–unload rates and both spherical and pointed (Berkovich) indenters were investigated at maximum loads of up to 250 mN. The mechanically deformed regions were then examined using cross-sectional transmission electron microscopy (XTEM), Raman spectroscopy, and atomic force microscopy. High-pressure phases (Si-XII and Si-III) and amorphous silicon have been identified in the deformation microstructure of both pointed and spherical indentations. Amorphous Si was observed using XTEM in indentations made by the partial load–unload method, which involves a fast pressure release on final unloading. Loading to the same maximum load using the continuous load cycle, with an approximately four times slower final unloading rate, produced a mixture of Si-XII and Si-III. Slip was observed for all loading conditions, regardless of whether the maximum load exceeded that required to induce “pop-in” and occurs on the {111} planes. Phase transformed material was found in the region directly under the indenter which corresponds to the region of greatest hydrostatic pressure for spherical indentation. Slip is thought to be nucleated from the region of high shear stress under the indenter.

Transmission electron microscopy observation of deformation microstructure under spherical indentation in silicon

Spherical indentation of crystalline silicon has been studied using cross-sectional transmission electron microscopy (XTEM). Indentation loads were chosen below and above the yield point for silicon to investigate the modes of plastic deformation. Slip planes are visible in the XTEM micrographs in both indentation loads studied. A thin layer of polycrystalline material has been identified (indexed as Si-XII from diffraction patterns) on the low-load indentation. The higher-load indentation revealed a large region of amorphous silicon. The sequence of structural deformation by indentation in silicon has been observed with the initial deformation mechanism being slip until phase transformations can take place.

FIB‐induced damage in silicon

The damage created in silicon transmission electron microscope specimens prepared using a focused ion beam miller is assessed using cross‐sections of trenches milled under different beam conditions. Side‐wall damage consists of an amorphous layer formed by direct interaction with the energetic gallium ion beam; a small amount of implanted gallium is also detected. By contrast, bottom‐wall damage layers are more complex and contain both amorphous films and crystalline regions that are richer in implanted gallium. More complex milling sequences show that redeposition of milled material, enriched in gallium, can occur depending on the geometry of the mill employed. The thickness of the damage layers depends strongly on beam energy, but is independent of beam current. Monte Carlo modelling of the damage formed indicates that recoil silicon atoms contribute significantly to the damaged formed in the specimen.

Water extractable organic carbon in untreated and chemical treated biochars.

Biochar, as a soil amendment, can increase concentrations of soil organic matter, especially water-extractable organic carbon (WEOC). This can affect the adsorption-desorption equilibrium between the dissolved solid phases in soil organic matter. Dissolved organic carbon (DOC) represents a small proportion of soil organic matter, but is of significant importance in the soil ecosystem due to its mobility and reactivity. Here, water extracts obtained from twelve non-herbaceous biochars (before, and after, chemical treatment with either H(3)PO(4) or KOH), were tested by Liquid Chromatography - Organic Carbon Detection (LC-OCD) to identify the effects of both pyrolysis conditions and chemical treatments on WEOC content. LC-OCD has the capacity to provide a fingerprint of WEOC, which allows analysis of the various fractions present. WEOC content was affected by both the pyrolysis temperature and the feedstock used. High mineral ash contents deriving from the feedstock can prompt thermochemical reactions of lignocelluloses to produce a relatively high WEOC content, which includes low molecular weight neutrals and humic acids as dominant components. A significant change in WEOC occurred during pyrolysis due to secondary reactions which resulted in a much lower WEOC in the high temperature biochars where fractions of low molecular weight acids and neutrals are dominant. Chemical treatments with H(3)PO(4) or KOH increased WEOC concentration, possibly by promoting hydrolysis reactions on biochar surfaces. These observations assist in assessing the contribution of biochar additions to the soil ecosystem and demonstrate the utility of LC-OCD in providing an understanding of how biochar additions to soil can alter DOC.

Ruthenium nanocrystals as cathode catalysts for lithium-oxygen batteries with a superior performance

The key factor to improve the electrochemical performance of Li-O2 batteries is to find effective cathode catalysts to promote the oxygen reduction and oxygen evolution reactions. Herein, we report the synthesis of an effective cathode catalyst of ruthenium nanocrystals supported on carbon black substrate by a surfactant assisting method. The as-prepared ruthenium nanocrystals exhibited an excellent catalytic activity as cathodes in Li-O2 batteries with a high reversible capacity of about 9,800 mAh g−1, a low charge-discharge over-potential (about 0.37 V), and an outstanding cycle performance up to 150 cycles (with a curtaining capacity of 1,000 mAh g−1). The electrochemical testing shows that ruthenium nanocrystals can significantly reduce the charge potential comparing to carbon black catalysts, which demonstrated that ruthenium based nanomaterials could be effective cathode catalysts for high performance lithium- O2 batteries.

Substitution-induced pinning in MgB2 superconductor doped with SiC nano-particles

By doping MgB2 superconductor with SiC nano-particles, we have successfully introduced pinning sites directly into the crystal lattice of MgB2 grains (intra-grain pinning). It became possible due to the combination of counter-balanced Si and C co-substitution for B, leading to a large number of intra-granular dislocations and the dispersed nano-size impurities induced by the substitution. The magnetic field dependence of the critical current density was significantly improved in a wide temperature range, whereas the transition temperature in the sample MgB2(SiC)x having x = 0.34, the highest doping level prepared, dropped only by 2.6 K.

Indentation-induced damage in GaN epilayers

The mechanical deformation of wurtzite GaN epilayers grown on sapphire substrates is studied by spherical indentation, cross-sectional transmission electron microscopy (XTEM), and scanning cathodoluminescence (CL) monochromatic imaging. CL imaging of indents which exhibit plastic deformation (based on indentation data) shows an observable “footprint” of deformation-produced defects that result in a strong reduction in the intensity of CL emission. Multiple discontinuities are observed during loading when the maximum load is above the elastic-plastic threshold, and such a behavior can be correlated with multiple slip bands revealed by XTEM. No evidence of pressure-induced phase transformations is found from within the mechanically damaged regions using selected-area diffraction patterns. The main deformation mechanism appears to be the nucleation of slip on the basal planes, with dislocations being nucleated on additional planes on further loading. XTEM reveals no cracking or delamination in any of the sam...