Effect of test method and crack size on the fracture toughness of a chain-silicate glass-ceramic

The fracture toughness of a canasite glass-ceramic with a highly acicular, interlocked grain structure was measured by a number of different methods. The values at room temperature obtained by the chevron-notch, short-bar and notched-beam methods ranged from 4 to 5 M Pa m^–1/2, well above literature values for other glass-ceramics. Similar values of toughness were obtained by the fracture of bars with indentation cracks introduced with loads ranging from 1.96 to 400 N, but only for crack sizes >200 m, with lower values for cracks of smaller size. The toughness values obtained by the direct measurement of the size of the indentation cracks were appreciably lower than the values obtained by all other methods over the total range of indentation loads and corresponding crack size. SEM fractography showed that the surface within the indentation cracks was appreciably smoother than the surrounding fracture surface. The high values of fracture toughness were attributed to the combined mechanisms of crack-deflection and microcrack-toughening due to the stress-enhanced creation of microcracks caused by the residual stresses which arise from the thermal expansion anisotropy of the canasite monoclonic crystal structure. The strong negative temperature dependence of the fracture toughness suggests that at room temperature microcrack toughening represents the primary contributing mechanism to the fracture toughness. The combined effects of crack-deflection and microcrack-toughening can lead to the development of glass-ceramics with greatly improved resistance to crack propagation.     

Environmental Control Symposium

MAN is but a part of the universe; his capabilities make him a significant link, in the cycle of life. To ensure this life, man must live in harmony with his environment. Recently, a disharmony has been discovered which could have grave effects upon the existence of man. It appears that man in his great thrust forward is destroying his own environment. The gravity of this threat to man's own existence carries some intrinsic problems of its own: man must allow his reason rather than his emotion to take command.     

Within-plant variation in concentrations of amino acids,sugar, and sinigrin in phloem sap of black mustard,Brassica nigra (L.) Koch (Cruciferae)

Although within-plant variation in the nutrient and allelochemical composition of phloem sap has been invoked to explain patterns of host use by phloem-feeding insects, little is known about within-plant variation in phloem chemistry. Here I describe a new technique in which I use the green peach aphid,Myzus persicae Sulz., to investigate within-plant variation in the concentrations of chemicals in the phloem sap of black mustard,Brassica nigra (L.) Koch (Cruciferae). Relationships between the concentrations of chemicals in aphid diets and honeydew were established using honeydew from aphids fed on artificial diets with known concentrations of amino acids, sucrose, and sinigrin. These relationships were applied to honeydew from aphids fed on different aged leaves of black mustard to estimate the concentrations of the chemicals in phloem sap. Sinigrin concentration was estimated to be high (>10 mM) in phloem sap in young leaves, calling into question the prevailing opinion that phloem sap contains only low concentrations of allelochemicals. High concentrations may function as defenses against sap-feeding herbivores. Within-plant variation in phloem sap composition was high: (1) young leaves had high concentrations of nutrients (216 mM amino acids, 26% sugar) and sinigrin (>10 mM); (2) mature and presenescent leaves had lower concentrations of nutrients (77–83 mM amino acids, 19–20% sugar) and low concentrations of sinigrin (1–2 mM); and (3) senescing leaves had high concentrations of nutrients (199 mM amino acids, 25% sugar) and low concentrations of sinigrin (3 mM).     

Partial oxidation of methane to methanol-comparison of heterogeneous catalyst and homogeneous gas phase reactions

Potential catalysts for the partial oxidation of methane to methanol have been synthesised and tested in high pressure annular reactors. Uranium oxide and molybdenum oxide catalysts and iron sodalite catalyst have been tested under the conditions reported in the patents and under conditions which allow comparison with reactions carried out in the gas phase. None of the catalysts tested showed an improvement on the gas phase results. It was found that the oxidative nature of the metal oxide catalysts is an inherent feature which reduces the selectivity to methanol.     

Nitrous Oxide Emissions from New Zealand Agriculture – key Sources and Mitigation Strategies

In most countries, nitrous oxide (N₂O) emissions typically contribute less than 10% of the CO₂ equivalent greenhouse gas (GHG) emissions. In New Zealand, however, this gas contributes 17% of the nation’s total GHG emissions due to the dominance of the agricultural sector. New Zealand’s target under the Kyoto Protocol is to reduce GHG emissions to 1990 levels. Currently total GHG emissions are 17% above 1990 levels. The single largest source of N₂O emission in New Zealand is animal excreta deposited during grazing (80% of agricultural N₂O emissions), while N fertilizer use currently contributes only 14% of agricultural emissions. Nitrogen fertilizer use has, however, increased 4-fold since 1990. Mitigation strategies for reducing N₂O emissions in New Zealand focus on (i) reducing the amount of N excreted to pasture, e.g. through diet manipulation; (ii) increasing the N use efficiency of excreta or fertilizer, e.g. through grazing management or use of nitrification inhibitors; or (iii) avoiding soil conditions that favour denitrification e.g. improving drainage and reducing soil compaction. Current estimates suggest that, if fully implemented, these individual measures can reduce agricultural N₂O emissions by 7–20%. The highest reduction potentials are obtained from measures that reduce the amount of excreta N, or increase the N use efficiency of excreta or fertilizer. However, New Zealand’s currently used N₂O inventory methodology will require refinement to ensure that a reduction in N₂O emissions achieved through implementation of any of these mitigation strategies can be fully accounted for. Furthermore, as many of these mitigation strategies also affect other greenhouse gas emissions or other environmental losses, it is crucial that both the economic and total environmental impacts of N₂O mitigation strategies are evaluated at a farm system’s level.     

采用有限元分析法量化不同中空玻璃边缘密封的热位移

间隔条和玻璃板片之间的相对热位移是中空玻璃边缘密封乃至中空玻璃(IGU)本身老化的主要原因之一.作者采用有限元分析法(FEA),建立了发生在大尺寸(1.5 m×2.1 m)的中空玻璃边缘密封的热位移与温差变化之间的模型,这是三种商业化的、不同材质的、不同设计的间隔条,在温度变化为-30～ 60℃范围内的模型.此模型是基于铝间隔条和镀锌钢间隔条与尼龙插角的搭配,不锈钢间隔条和弯曲插角的搭配.尼龙插角假定为实心的并稳固地固定于间隔条上;弯曲插角被建模成实心弯曲的金属插角,并同样稳固地固定于间隔条上.由于实际的弯曲插角是空心的,模型可能高估了这种转角设计的应力.正如预期那样,在低温时,插角会被向内拉,导致弯曲角度大于90°;在高温下,插角会被向外推,导致弯曲角度小于90°.通过检测发生在中空玻璃周边第一道密封的聚异丁烯密封胶厚度的变化,作者发现,到目前为止,不锈钢间隔条对于截面积的变化影响最小;铝制间隔条的影响最大.这个发现与基于间隔条材料与浮法玻璃之间热膨胀系数差异而预期的性能一致.因此,热位移引起的第一道密封的有效扩散横截面变化,可以解释为何具有不同间隔条材料的中空玻璃之间的性能差异.     

Characterisation of the adsorption sites of hydrogen on Pt/C fuel cell catalysts

A key component of a hydrogen fuel cell is a catalyst to dissociate dihydrogen to hydrogen atoms. In the present study, the adsorption of hydrogen on Pt/C fuel cell catalysts has been investigated by inelastic neutron scattering spectroscopy.

Monitoring a clean Pt(50%)/C catalyst with low energy neutron spectroscopy, after exposure to dihydrogen at 20 K, as it was heated to room temperature, showed three distinct temperature regimes: (i) a decrease in intensity from 10 to 60 K, (ii) a rise to a maximum between 60 and 120 K and then (iii) a slow fall-off towards room temperature. We assign the three regions as: (i) desorption of physisorbed dihydrogen, (ii) dissociation of dihydrogen to give an adsorbed layer and (iii) damping of the response by an increasing Debye–Waller factor.

The vibrational INS spectra of a series of Pt/C catalysts prepared under varying conditions were similar indicating that the same types of site are common to all the catalysts, although the relative proportions of each site are sample dependent. Features at 520, 950 and part of the intensity at 1300 cm⁻¹ are assigned to hydrogen on (1 1 1) faces, in good agreement with single crystal data. The mode at 640 cm⁻¹ is assigned as the doubly degenerate asymmetric stretch of Pt(1 0 0) faces with the symmetric stretch near 550 cm⁻¹.

We assign the bending mode of the on-top site to the feature at 470 cm⁻¹. The Pt–H stretch mode was observed at 2079 cm⁻¹. This is a significant result: this is the first time that hydrogen on the on-top sites has been observed on nanosized platinum particles supported on high surface area carbon black. The width of the INS peak is surprisingly large and may give additional information on the type and relative proportions of the crystallographic faces present on the catalyst particles.     

The electrochemical reduction of VO2 in acidic solution at high overpotentials

An investigation has been carried out to attempt to understand the unusually low apparent symmetry factor observed during the reduction of V(5) at higher overpotentials at carbon electrodes (typically <0.13, or >460 mV decade⁻¹). This reaction is of interest because it occurs in vanadium redox-flow batteries (VRBs) during discharge. Polarisation curves were measured using a rotating disk electrode (RDE). The reaction was not solution mass transport controlled, was pH independent (ca from 0 to 1), and the observed Tafel slope was unaffected by V(5) concentration over a range from 0.031 to 280 mM. Electrode double layer capacitance measurements were also carried out in sulphuric acid with and without vanadium. These tests showed that the presence of V(5) caused a suppression of the normal carbon surface quinone pseudocapacitance, as well as the appearance of two new pseudocapacitance peaks, one around 0.175-0.2 V and the other around 0.675-0.725 V versus SCE. The observed results do not appear consistent with a precipitated film causing diffusion limitations or causing IR drop. A model is developed to try to explain the data, which involves electron transfer through an adsorbed layer of vanadium.