External pressure in the hardening of phosphate in tribofilm on iron surfaces

Purpose: In the present work we consider our (in progress) spectroscopy study of zinc and iron phosphates under the influence external high pressure to determine zinc ion change coordination from tetrahedral to octahedral (or hexahedral) structure.----- Design/methodology/approach: The standard equipment is the optical high pressure cell with diamond (DAC). The DAC is assembled and then vibrational or electronic spectra are collected by mounting the cell in an infrared, Raman, EXAFS or UV-visible spectrometer.----- Findings: Mechanism by which zinc and iron methaphosphate material is transformed to glassy meta-phosphate is enhancing mechanical properties of tribofilm. The two decades of intensive study demonstrates that Zn (II) and Fe (III) ions participate to cross-link network under friction, hardening the phosphate.----- Research limitations/implications: Transition metal atoms with d orbital have flexible coordination numbers, for example zinc acts as a cross-linking agent increasing hardness, by changing coordination from tetrahedral to octahedral. Perhaps the external pressure effect on the [Zn–(O-P-)4 ] complex causes a transformation to an [Zn –(O-P-)6] grouping.----- Originality/value: This paper analyses high-pressure spectroscopy which has been applied for the investigation of 3D transition metal ions in solids. When studying pressure effects on coordination compounds structure, we can expect changes in ground electronic state (spin-crossovers), electronic spectra due to structural distortions (piezochromism), and changes in the ligand field causing shifts in the electronic transitions.

Thin film deposition and characterization of pure and iron-doped electron-beam evaporated tungsten oxide for gas sensors

Pure Tungsten Oxide (WO3) and Iron-doped (10 at%) Tungsten Oxide (WO3:Fe) nanostructured thin films were prepared using a dual crucible Electron Beam Evaporation techniques. The films were deposited at room temperature in high vacuum condition on glass substrate and post-heat treated at 300 oC for 1 hour. From the study of X-ray diffraction and Raman the characteristics of the as-deposited WO3 and WO3:Fe films indicated non-crystalline nature. The surface roughness of all the films showed in the order of 2.5 nm as observed using Atomic Force Microscopy (AFM). X-Ray Photoelectron Spectroscopy (XPS) analysis revealed tungsten oxide films with stoichiometry close to WO3. The addition of Fe to WO3 produced a smaller particle size and lower porosity as observed using Transmission Electron Microscopy (TEM). A slight difference in optical band gap energies of 3.22 eV and 3.12 eV were found between the as-deposited WO3 and WO3:Fe films, respectively. However, the difference in the band gap energies of the annealed films were significantly higher having values of 3.12 eV and 2.61 eV for the WO3 and WO3:Fe films, respectively. The heat treated samples were investigated for gas sensing applications using noise spectroscopy and doping of Fe to WO3 reduced the sensitivity to certain gasses. Detailed study of the WO3 and WO3:Fe films gas sensing properties is the subject of another paper.

The rate-limiting mechanism for the heterogeneous burning of cylindrical iron rods

This paper presents the findings of an investigation into the rate-limiting mechanism for the heterogeneous burning in oxygen under normal gravity and microgravity of cylindrical iron rods. The original objective of the work was to determine why the observed melting rate for burning 3.2-mm diameter iron rods is significantly higher in microgravity than in normal gravity. This work, however, also provided fundamental insight into the rate-limiting mechanism for heterogeneous burning. The paper includes a summary of normal-gravity and microgravity experimental results, heat transfer analysis and post-test microanalysis of quenched samples. These results are then used to show that heat transfer across the solid/liquid interface is the rate-limiting mechanism for melting and burning, limited by the interfacial surface area between the molten drop and solid rod. In normal gravity, the work improves the understanding of trends reported during standard flammability testing for metallic materials, such as variations in melting rates between test specimens with the same cross-sectional area but different crosssectional shape. The work also provides insight into the effects of configuration and orientation, leading to an improved application of standard test results in the design of oxygen system components. For microgravity applications, the work enables the development of improved methods for lower cost metallic material flammability testing programs. In these ways, the work provides fundamental insight into the heterogeneous burning process and contributes to improved fire safety for oxygen systems in applications involving both normal-gravity and microgravity environments.

Iron burning in pressurised oxygen under microgravity conditions

An investigation of cylindrical iron rods burning in pressurised oxygen under microgravity conditions is presented. It has been shown that, under similar experimental conditions, the melting rate of a burning, cylindrical iron rod is higher in microgravity than in normal gravity by a factor of 1.8 ± 0.3. This paper presents microanalysis of quenched samples obtained in a microgravity environment in a 2.0 s duration drop tower facility in Brisbane, Australia. These images indicate that the solid/liquid interface is highly convex in reduced gravity, compared to the planar geometry typically observed in normal gravity, which increases the contact area between liquid and solid phases by a factor of 1.7 ± 0.1. Thus, there is good agreement between the proportional increase in solid/liquid interface surface area and melting rate in microgravity. This indicates that the cause of the increased melting rates for cylindrical iron rods burning in microgravity is altered interfacial geometry at the solid/liquid interface.

Exposure of pipe insulation to high temperatures from domestic pumped storage (split) solar water heating systems in Australia and New Zealand

Pipe insulation between the collector and storage tank on pumped storage (commonly called split), solar water heaters can be subject to high temperatures, with a maximum equal to the collector stagnation temperature. The frequency of occurrence of these temperatures is dependent on many factors including climate, hot water demand, system size and efficiency. This paper outlines the findings of a computer modelling study to quantify the frequency of occurrence of pipe temperatures of 80 degrees Celsius or greater at the outlet of the collectors for these systems. This study will help insulation suppliers determine the suitability of their materials for this application. The TRNSYS program was used to model the performance of a common size of domestic split solar system, using both flat plate and evacuated tube, selective surface collectors. Each system was modelled at a representative city in each of the 6 climate zones for Australia and New Zealand, according to AS/NZS4234 - Heat Water Systems - Calculation of energy consumption, and the ORER RECs calculation method. TRNSYS was used to predict the frequency of occurrence of the temperatures that the pipe insulation would be exposed to over an average year, for hot water consumption patterns specified in AS/NZS4234, and for worst case conditions in each of the climate zones. The results show; * For selectively surfaced, flat plate collectors in the hottest location (Alice Sprints) with a medium size hot water demand according to AS/NZS2434, the annual frequency of occurrence of temperatures at and above 80 degrees Celsius was 33 hours. The frequency of temperatures at and above 140 degrees Celsius was insignificant. * For evacuated tube collectors in the hottest location (Alice Springs), the annual frequency of temperatures at and above 80 degrees Celsius was 50 hours. Temperatures at and above 140 degrees Celsius were significant and were estimated to occur for more than 21 hours per year in this climate zone. Even in Melbourne, temperatures at and above 80 degrees can occur for 12 hours per year and at and above 140 degrees for 5 hours per year. * The worst case identified was for evacuated tube collectors in Alice Springs, with mostly afternoon loads in January. Under these conditions, the frequency of temperatures at and above 80 degrees Celsius was 10 hours for this month only. Temperatures at and above 140 degrees Celsius were predicted to occur for 5 hours in January.

Energy and cost savings from pipe insulation on domestic, pumped storage (split), solar water heating systems in Australia and New Zealand

Appropriate pipe insulation on domestic, pumped storage (split), solar water heating systems forms an integral part of energy conservation measures of well engineered systems. However, its importance over the life of the system is often overlooked. This study outlines the findings of computer modelling to quantify the energy and cost savings by using pipe insulation between the collector and storage tank. System sizes of 270 Litre storage tank, together with either selectively surfaced, flat plate collectors (4m2 area), or 30 evacuated tube collectors, were used. Insulation thicknesses of 13mm and 15mm, pipe runs both ways of 10, 15 and 20 metres and both electric and gas boosting of systems were all considered. The TRNSYS program was used to model the system performance at a representative city in each of the 6 climate zones for Australia and New Zealand, according to AS/NZS4234 – Heat Water Systems – Calculation of energy consumption and the ORER RECs calculation method. The results show:  Energy savings from pipe insulation are very significant, even in mild climates such as Rockhampton. Across all climates zones, savings ranged from 0.16 to 3.5GJ per system per year, or about 2 to 23 percent of the annual load.  There is very little advantage in increasing the insulation thickness from 13 to 15mm. For electricity at 19c/kWh and gas at 2 c/MJ, cost savings of between $27 and $100 per year are achieved across the climate zones. Both energy and cost savings would increase in colder climates with increased system size, solar contribution and water temperatures.  The pipe insulation substantially improves the solar contribution (or fraction) and Renewable Energy Certificates (RECs), as well as giving small savings in circulating pump running costs in milder climates. Solar contribution increased by up to 23 percent points and RECs by over 7 in some cases.  The study highlights the need to install and maintain the integrity of appropriate pipe insulation on solar water heaters over their life time in Australia and New Zealand.