The heat capacity of liquid carbon disulfide + acetonitrile, especially near the upper critical solution temperature

The heat capacity Cp of the binary liquid system CS2 + CH3CN has been studied. This system has an upper critical solution temperature To ≈ 323.4 K and a critical mole fraction of CS2xo ≈ 0.5920. Measurements were made both for mixtures close to and far away from the critical region. The heat capacity of the mixture with x = xo exhibits a symmetric logarithmic anomaly around Tc, which is apparently preserved even for compositions in the immediate vicinity of xc. For compositions far away from xc, only a normal rise in Cp over the covered temperature range is observed.

Improved damping capacity and machinability of graphite particle-aluminum alloy composites

The damping capacity of cast graphitic aluminum alloy composites has been measured using a torsion pendulum at a constant strain amplitude. It was found that flake-graphite particles dispersed in the matrix of aluminum alloys increased the damping capacity; the improvement was greater, the higher the amount of graphite dispersed in the matrix. At sufficiently high graphite contents the damping capacity of graphitic aluminum composites approaches that of cast iron. The ratio between the damping capacity and the density of graphitic aluminum alloys is higher than cast iron, making them very attractive as light-weight, high-damping materials for possible aircraft applications. Machinability tests on graphite particle-aluminum composites, conducted at speeds of 315 sfm and 525 sfm, showed that the chip length decreased with the amount of graphite of a given size. When the size of graphite was decreased, at a given machining speed, the chip length decreased. Metallographic examination shows that graphite particles act as chip breakers, and are frequently sheared parallel to the plane of the

Effect of carbon equivalent and inoculation on residual stresses in grey iron castings

It is virtually impossible to produce castings free from internal stresses using conventional methods of founding. Castings with appreciable stresses distort during storage, transportation, machining and service. Though composition and melt treatment are known to affect the magnitude of residual stress in castings, the data on the effect of carbon equivalent and inoculation on the magnitude of residual stress in castings are limited. In the present investigation, an attempt is made to study (i) the effect of carbon equivalent on residual stress in cast iron castings, and (ii) the effect of inoculants such as calcium silicide and ferrosilicon on residual stress in iron castings in the carbon equivalent range 3.0–4.0%. The results of the investigation indicate the following: (i) the residual strains decrease linearly with increase in carbon equivalent in the uninoculated and inoculated irons; (ii) the tensile residual stresses decrease linearly with increase in carbon equivalent value of the uninoculated, calcium silicide-inoculated and ferrosilicon-inoculated cast iron castings; (iii) the ratio of UTS to residual stress increased on inoculating the grid castings. This increase is higher for calcium silicide-inoculated grids than for ferrosilicon-inoculated grid castings. This implies that from the residual stress point of view, inoculation of the iron with calcium silicide is beneficial.

Electron Spectroscopic Studies of Oxygen and Carbon Dioxide Adsorbed on Metal Surfaces

Adsorption of oxygen on Ni, Cu, Pd, Ag, and Au surfaces has been investigated by employing UV and X-ray photoelectron spectrscopy as well as electron energy loss spectroscopy (EELS). Molecularly chemisorbed (singlet) oxygen is found on Ni, Cu, Ag, and Au surfaces showing features such as stabilization of the rB* orbital, destabilization of the .nu orbital, higher O(1s) binding energy than the atomic species, and a band 2-3 eV below the Fermi level due to metal d-O(2p)u* interaction. 0-0 and metal-oxygen stretching frequencies have been observed in EELS. Physical adsorption of O2 is found to occur on Pd and Ni surfaces, only at high exposures in the latter case. Physical adsorption and multilayer condensation of CO, on metal surfaces are distinguished by characteristic relaxation shifts in UPS as well as O(1s) binding energies. Adsorption of CO on a Ni surface covered with presorbed atomic oxygen gives rise to C02.

Studies on electrical conductivity of insulator-conductor composites

The variation of electrical resistivity of an insulator-conductor composite, namely, wax-graphite composite, with parameters such as volume fraction, grain size, and temperature has been studied. A model is proposed to explain the observed variations, which assumes that the texture of the composite consists of insulator granules coated with conducting particles. The resistivity of these materials is controlled mainly by the contact resistance between the conducting particles and the number of contacts each particle has with its neighbors. The variation of resistivity with temperature has also been explained with the help of this model and it is attributed to the change in contact area. Journal of Applied Physics is copyrighted by The American Institute of Physics.

Production of cast aluminium-graphite particle composites using a pellet method

Copper- and nickel-coated graphite particles can be successfully introduced into aluminium-base alloy melts as pellets to produce cast aluminium-graphite particle composites. The pellets were made by pressing mixtures of nickel- or copper-coated graphite particles and aluminium powders together at pressures varying between 2 and 20 kg mm–2. These pellets were dispersed in aluminium alloy melts by plunging and holding them in the melts using a refractory coated mild steel cone, until the pellets disintegrated and the powders were dispersed. The optimum pressure for the preparation of pellets was 2 to 5 kg mm–2 and the optimum size and percentage of aluminium powder were 400 to 1000mgrm and 35 wt% respectively. Under optimum conditions the recovery of the graphite particles in the castings was as high as 96%, these particles being pushed into the last freezing interdendritic regions. The tensile strength and the hardness of the graphite aluminium alloys made using the pellet method are comparable to those of similar composites made using gas injection or the vortex method. The pellet method however has the advantage of greater reproducibility and flexibility. Dispersion of graphite particles in the matrix of cast aluminium alloys using the pellet method increases their resistance to wear.

Mechanical properties of nanodiamond-reinforced polymer-matrix composites

Poly(vinyl alcohol)-matrix reinforced with nanodiamond (ND) particles, with ND content up to 0.6 wt%, were synthesized. Characterization of the composites by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) reveal uniform distribution of the ND particles with no agglomeration in the matrix. Differential scanning calorimetry reveals that the crystallinity of the polymer increases with increasing ND content, indicating a strong interaction between ND and PVA. Nano-indentation technique was employed to assess the mechanical properties of composites. Results show that even small additions of ND lead to significant enhancement in the hardness and elastic modulus of PVA. Possible micromechanisms responsible for the enhancement of the mechanical properties are discussed.

Below-ground processes in meadow soil under elevated ozone and carbon dioxide : - Greenhouse gas fluxes, N cycling and microbial communities

This thesis focuses on how elevated CO2 and/or O3 affect the below-ground processes in semi-natural vegetation, with an emphasis on greenhouse gases, N cycling and microbial communities. Meadow mesocosms mimicking lowland hay meadows in Jokioinen, SW Finland, were enclosed in open-top chambers and exposed to ambient and elevated levels of O3 (40-50 ppb) and/or CO2 (+100 ppm) for three consecutive growing season, while chamberless plots were used as chamber controls. Chemical and microbiological analyses as well as laboratory incubations of the mesocosm soils under different treatments were used to study the effects of O3 and/or CO2. Artificially constructed mesocosms were also compared with natural meadows with regards to GHG fluxes and soil characteristics. In addition to research conducted at the ecosystem level (i.e. the mesocosm study), soil microbial communities were also examined in a pot experiment with monocultures of individual species. By comparing mesocosms with similar natural plant assemblage, it was possible to demonstrate that artificial mesocosms simulated natural habitats, even though some differences were found in the CH4 oxidation rate, soil mineral N, and total C and N concentrations in the soil. After three growing seasons of fumigations, the fluxes of N2O, CH4, and CO2 were decreased in the NF+O3 treatment, and the soil NH4+-N and mineral N concentrations were lower in the NF+O3 treatment than in the NF control treatment. The mesocosm soil microbial communities were affected negatively by the NF+O3 treatment, as the total, bacterial, actinobacterial, and fungal PLFA biomasses as well as the fungal:bacterial biomass ratio decreased under elevated O3. In the pot survey, O3 decreased the total, bacterial, actinobacterial, and mycorrhizal PLFA biomasses in the bulk soil and affected the microbial community structure in the rhizosphere of L. pratensis, whereas the bulk soil and rhizosphere of the other monoculture, A. capillaris, remained unaffected by O3. Elevated CO2 caused only minor and insignificant changes in the GHG fluxes, N cycling, and the microbial community structure. In the present study, the below-ground processes were modified after three years of moderate O3 enhancement. A tentative conclusion is that a decrease in N availability may have feedback effects on plant growth and competition and affect the N cycling of the whole meadow ecosystem. Ecosystem level changes occur slowly, and multiplication of the responses might be expected in the long run.

Carbon sequestration: Evaluating the impact on rural land and valuation approach

This thesis uses semi-structured interviews and documentary analysis to explore the impact of carbon sequestration rights on rural land in Queensland and to determine whether current rural valuation knowledge and practice is equipped to deal with these rights. The carbon right in Queensland is complex and subject to significant individual variation. The nature and form of this right will determine whether it has a positive or negative impact on Queensland rural land. Significant gaps in the knowledge of industry stakeholders, including rural valuers, concerning carbon rights were found, and recommendations for valuation practice were made.

Critical Exponent β and Rectilinear Diameter of the Binary-Liquid System Carbon Disulfide + Nitromethane

The system CS2 + CH3NO2 shows β=0.315±0.004 over 10-6<ε=|T-Tc| / Tc<2-10-1 with no indication of a classical value ½ even far away from Tc. The diameter shows a curvature and is of the form - c+b ε+fε7 / 8exp(-gεh).

Carbon-Supported Pt-TiO2 as a Methanol-Tolerant Oxygen-Reduction Catalyst for DMFCs

Carbon-supported Pt-TiO2 (Pt-TiO2/C) catalysts with varying at. wt ratios of Pt to Ti, namely, 1:1, 2:1, and 3:1, are prepared by the sol-gel method. The electrocatalytic activity of the catalysts toward oxygen reduction reaction (ORR), both in the presence and absence of methanol, is evaluated for application in direct methanol fuel cells (DMFCs). The optimum at. wt ratio of Pt to Ti in Pt-TiO2/C is established by fuel cell polarization, linear sweep voltammetry, and cyclic voltammetry studies. Pt-TiO2/C heattreated at 750 degrees C with Pt and Ti in an at. wt ratio of 2:1 shows enhanced methanol tolerance, while maintaining high catalytic activity toward ORR. The DMFC with a Pt-TiO2/C cathode catalyst exhibits an enhanced peak power density of 180 mW/cm(2) in contrast to the 80 mW/cm(2) achieved from the DMFC with carbon-supported Pt catalyst while operating under identical conditions. Complementary data on the influence of TiO2 on the crystallinity of Pt, surface morphology, and particle size, surface oxidation states of individual constituents, and bulk and surface compositions are also obtained by powder X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, energy dispersive analysis by X-ray, and inductively coupled plasm optical emission spectrometry.

Field-Effect and Frequency Dependent Transport in Semiconductor-Enriched Single-Wall Carbon Nanotube Network Device

The electrical and optical response of a field-effect device comprising a network of semiconductor-enriched single-wall carbon nanotubes, gated with sodium chloride solution is investigated. Field-effect is demonstrated in a device that uses facile fabrication techniques along with a small-ion as the gate electrolyte-and this is accomplished as a result of the semiconductor enhancement of the tubes. The optical transparency and electrical resistance of the device are modulated with gate voltage. A time-response study of the modulation of optical transparency and electrical resistance upon application of gate voltage suggests the percolative charge transport in the network. Also the ac response in the network is investigated as a function of frequency and temperature down to 5 K. An empirical relation between onset frequency and temperature is determined.

High Lithium Storage in Mixed Crystallographic Phase Nanotubes of Titania and Carbon-Titania

Morphology and electrochemical performance of mixed crystallographic phase titania nanotubes for prospective application as anode in rechargeable lithium ion batteries are discussed. Hydrothermally grown nanotubes of titania (TiO2) and carbon-titania (C-TiO2) comprise a mixture of both anatase and TiO2 (B) crystallographic phases. The first cycle capacity (at Current rate = 10 mAg(-1)) for bare TiO2 nanotubes was 355 mAhg(-1) (approximately 1.06 Li), which is higher than both the theoretical capacity (335 mAhg(-1)) and the reported values for pure anatase and TiO2 (B) nanotubes. Higher capacity is attributed to it combination of the presence of mixed crystallographic phases of titania and trivial size effects. The surface area of bare TiO2 nanotubes was very high at 340 m(2) g(-1). C-TiO2 nanotubes showed a slightly lower first-cycle specific capacity of 307 mAhg(-1), but the irreversible capacity loss in the first cycle decreased by half compared to bare TiO2 nanotubes. The C-TiO2 nanotubes also showed a better rate capability, that is, higher capacities compared to bare TiO2 nanotubes in the Current range 0.1-2 Ag-1. Enhanced rate capability in the case of C-TiO2 is attributed to the efficient percolation of electrons as well its to the decrease in the anatase phase.

Studies on the reduction of hematite by carbon

Single pellet experiments have been carried out in a nitrogen atmosphere to study the reduction of hematite by graphite in the temperature range 925 to 1060°C. The effect of variables such as c/Fe2O3 molar ratio, pellet size, and so forth, has been investigated. Gas analysis data show a continuous decrease in CO2/CO ratio during reduction, the values being far away from Fe/FeO equilibrium for wustite reduction by CO. The activation energies associated with different degrees of reduction appear to be widely different suggesting a possible changeover in reaction mechanism during the progress of reduction. X-ray diffraction studies confirm the stepwise nature of hematite reduction.

Aerobic carbon-cycle related microbial communities in boreal peatlands: responses to water-level drawdown

Boreal peatlands represent a considerable portion of the global carbon (C) pool. Water-level drawdown (WLD) causes peatland drying and induces a vegetation change, which affects the decomposition of soil organic matter and the release of greenhouse gases (CO2 and CH4). The objective of this thesis was to study the microbial communities related to the C cycle and their response to WLD in two boreal peatlands. Both sampling depth and site type had a strong impact on all microbial communities. In general, bacteria dominated the deeper layers of the nutrient-rich fen and the wettest surfaces of the nutrient-poor bog sites, whereas fungi seemed more abundant in the drier surfaces of the bog. WLD clearly affected the microbial communities but the effect was dependent on site type. The fungal and methane-oxidizing bacteria (MOB) community composition changed at all sites but the actinobacterial community response was apparent only in the fen after WLD. Microbial communities became more similar among sites after long-term WLD. Litter quality had a large impact on community composition, whereas the effects of site type and WLD were relatively minor. The decomposition rate of fresh organic matter was influenced slightly by actinobacteria, but not at all by fungi. Field respiration measurements in the northern fen indicated that WLD accelerates the decomposition of soil organic matter. In addition, a correlation between activity and certain fungal sequences indicated that community composition affects the decomposition of older organic matter in deeper peat layers. WLD had a negative impact on CH4 oxidation, especially in the oligotrophic fen. Fungal sequences were matched to taxa capable of utilizing a broad range of substrates. Most of the actinobacterial sequences could not be matched to characterized taxa in reference databases. This thesis represents the first investigation of microbial communities and their response to WLD among a variety of boreal peatland habitats. The results indicate that microbial community responses to WLD are complex but dependent on peatland type, litter quality, depth, and variable among microbes.