Low-temperature isothermal Rankine cycle for desalination

In brackish groundwater desalination, high recovery ratio (of fresh water from saline feed) is desired to minimise concentrate reject. To this effect, previous studies have developed a batch reverse osmosis (RO) desalination system, DesaLink, which proposed to expand steam in a reciprocating piston cylinder and transmit the driving force through a linkage crank mechanism to pressurise batches of saline water (recirculating) in a water piston cylinder unto RO membranes. However, steam is largely disadvantaged at operation from low temperature (< 150oC) thermal sources; and organic working fluids are more viable, though, the obtainable thermal cycle efficiencies are generally low with low temperatures. Consequently, this thesis proposed to investigate the use of organic working fluid Rankine cycle (ORC) with isothermal expansion, to drive the DesaLink machine, at improved thermal efficiency from low temperature thermal sources. Following a review of the methods of achieving isothermal expansion, ‘liquid flooded expansion’ and ‘expansion chamber surface heating’ were identified as potential alternative methods. Preliminary experimental comparative analysis of variants of the heated expansion chamber technique of effecting isothermal expansion favoured a heated plain wall technique, and as such was adopted for further optimisation and development. Further, an optimised isothermal ORC engine was built and tested at < 95oC heat source temperature, with R245fa working fluid – which was selected from 16 working fluids that were analysed for isothermal operation. Upon satisfactory performance of the test engine, a larger (10 times) version was built and coupled to drive the DesaLink system. Operating the integrated ORC-RO DesaLink system, gave freshwater (approximately 500 ppm) production of about 12 litres per hour (from 4000 ppm feed water) at a recovery ratio of about 0.7 and specific energy consumption of 0.34 kWh/m3; and at a thermal efficiency of 7.7%. Theoretical models characterising the operation and performance of the integrated system was developed and utilised to access the potential field performance of the system, when powered by two different thermal energy sources – solar and industrial bakery waste heat – as case studies.

TiN-based coatings on fuel cladding tubes for advanced nuclear reactors

Titanium nitride (TiN) thin films are coated on HT-9 and MA957 fuel cladding tubes and bars to explore their mechanical strength, thermal stability, diffusion barrier properties, and thermal conductivity properties. The ultimate goal is to implement TiN as an effective diffusion barrier to prevent the inter-diffusion between the nuclear fuel and the cladding material, and thus lead to a longer lifetime of the cladding tubes. Mechanical tests including hardness and scratch tests for the samples before and after thermal cycle tests show that the films have a high hardness of 28GPa and excellent adhesion properties despite the thermal treatment. Thermal conductivity measurements demonstrate that the thin TiN films have very minimal impact on the overall thermal conductivity of the MA957 and HT-9 substrates, i.e., the thermal conductivity of the uncoated HT-9 and MA957 substrates was 26.25 and 28.44 W m-1 K-1, and that of the coated ones was 26.21 and 28.38W m-1 K-1, respectively. A preliminary Ce diffusion test on the couple of Ce/TiN/HT-9 suggests that TiN has excellent material compatibility and good diffusion barrier properties.

Effect of cooling rate on intercritically reheated microstructure and toughness in high strength low alloy steel

High strength low alloy steels have been shown to be adversely affected by the existence of regions of poor impact toughness within the heat affected zone (HAZ) produced during multipass welding. One of these regions is the intercritically reheated coarse grained HAZ or intercritical zone. Since this region is generally narrow and discontinuous, of the order of 0.5 mm in width, weld simulators are often employed to produce a larger volume of uniform microstructure suitable for toughness assessment. The steel usedfor this study was a commercial quenched and tempered steel of 450 MN m -2 yield strength. Specimen blanks were subjected to a simulated welding cycle to produce a coarse grained structure of upper bainite during the first thermal cycle, followed by a second thermal cycle where the peak temperature T p2 was controlled. Charpy tests carried out for T p2 values in the range 650-850°C showed low toughness for T p2 values between 760 and 790°C, in the intercritical regime. Microstructural investigation of the development of grain boundary martensite-retained austenite (MA) phase has been coupled with image analysis to measure the volume fraction of MAformed. Most of the MA constituent appears at the prior austenite grain boundaries during intercritical heating, resulting in a 'necklace' appearance. For values of T p2 greater than 790°C the necklace appearance is lost and the second phase areas are observed throughout the structure. Concurrent with this is the development of the fine grained, predominantly ferritic structure that is associated with the improvement in toughness. At this stage the microstructure is transforming from the intercritical regime structure to the supercritically reheated coarse grained HAZ structure. The toughness improvement occurs even though the MA phase is still present, suggesting that the embrittlement is associated with the presence of a connected grain boundary network of the MA phase. The nature of the second phase particles can be controlled by the cooling rate during the second cycle and variesfrom MA phase at high cooling rates to a pearlitic structure at low cooling rates. The lowest toughness of the intercritical zone is observed only when MA phase is present. The reason suggested for this is that only the MA particles debond readily, a number of debonded particles in close proximity providing sufficient stress concentration to initiate local cleavage. © 1993 The Institute of Materials.

Mössbauer spectroscopic study of the thermal spin crossover in [Fe(II)(isoxazole)6](ClO4)2

The Fe Mössbauer spectroscopy of mononuclear [Fe(II)(isoxazole)](ClO) has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S = 0) and high-spin (S = 2) states. Temperaturedependent spin transition curves have been constructed with the least-square fitted data obtained from the Mössbauer spectra measured at various temperatures between 84 and 270 K during a cooling and heating cycle. This compound exhibits an unusual temperature-dependent spin transition behaviour with T(?) = 223 and T(?) = 213 K occurring in the reverse order in comparison to those observed in SQUID observation and many other spin transition compounds. The compound has three high-spin Fe(II) sites at the highest temperature of study of which two undergo spin transitions. The compound seems to undergo a structural phase transition around the spin transition temperature, which plays a significant role in the spin crossover behaviour as well as the magnetic properties of the compound at temperatures below T. The present study reveals an increase in high-spin fraction upon heating in the temperature range below T, and an explanation is provided.

Effect of aspect ratio on thermal convection in open and closed systems

Internally heated fluids are found across the nuclear fuel cycle. In certain situations the motion of the fluid is driven by the decay heat (i.e. corium melt pools in severe accidents, the shutdown of liquid metal reactors, molten salt and the passive control of light water reactors) as well as normal operation (i.e. intermediate waste storage and generation IV reactor designs). This can in the long-term affect reactor vessel integrity or lead to localized hot spots and accumulation of solid wastes that may prompt local increases in activity. Two approaches to the modeling of internally heated convection are presented here. These are based on numerical analysis using codes developed in-house and simulations using widely available computational fluid dynamics solvers. Open and closed fluid layers at around the transition between conduction and convection of various aspect ratios are considered. We determine optimum domain aspect ratio (1:7:7 up to 1:24:24 for open systems and 5:5:1, 1:10:10 and 1:20:20 for closed systems), mesh resolutions and turbulence models required to accurately and efficiently capture the convection structures that evolve when perturbing the conductive state of the fluid layer. Note that the open and closed fluid layers we study here are bounded by a conducting surface over an insulating surface. Conclusions will be drawn on the influence of the periodic boundary conditions on the flow patterns observed. We have also examined the stability of the nonlinear solutions that we found with the aim of identifying the bifurcation sequence of these solutions en route to turbulence.

Study of thermal spin crossover in [Fe(II)(isoxazole)6](BF4)2 with Mössbauer spectroscopy

57Fe Mössbauer spectroscopy of the mononuclear [Fe(II)(isoxazole)6](BF4) 2compound has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S = 0) and high-spin (S = 2) states. A temperature-dependent spin transition curve has been constructed with the least-square fitted data obtained from the Mössbauer spectra measured at various temperatures in the 240-60K range during the cooling and heating cycle. The compound exhibits a temperature-dependent two-step spin transition phenomenon with Tsco (step 1) = 92 and Tsco (step2) = 191K. The compound has three high-spin Fe(II) sites at the highest temperature of study; among them, two have slightly different coordination environments. These two Fe(II) sites are found to undergo a spin transition, while the third Fe(II) site retains the high-spin state over the whole temperature range. Possible reasons for the formation of the two steps in the spin transition curve are discussed. The observations made from the present study are in complete agreement with those envisaged from earlier magnetic and structural studies made on [Fe(II)(isoxazole)6](BF4)2, but highlights the nature of the spin crossover mechanism.

Desalination of brackish water by a batch reverse osmosis desalink system for use with solar thermal energy

For remote, semi-arid areas, brackish groundwater (BW) desalination powered by solar energy may serve as the most technically and economically viable means to alleviate the water stresses. For such systems, high recovery ratio is desired because of the technical and economical difficulties of concentrate management. It has been demonstrated that the current, conventional solar reverse osmosis (RO) desalination can be improved by 40–200 times by eliminating unnecessary energy losses. In this work, a batch-RO system that can be powered by a thermal Rankine cycle has been developed. By directly recycling high pressure concentrates and by using a linkage connection to provide increasing feed pressures, the batch-RO has been shown to achieve a 70% saving in energy consumption compared to a continuous single-stage RO system. Theoretical investigations on the mass transfer phenomena, including dispersion and concentration polarization, have been carried out to complement and to guide experimental efforts. The performance evaluation of the batch-RO system, named DesaLink, has been based on extensive experimental tests performed upon it. Operating DesaLink using compressed air as power supply under laboratory conditions, a freshwater production of approximately 300 litres per day was recorded with a concentration of around 350 ppm, whilst the feed water had a concentration range of 2500–4500 ppm; the corresponding linkage efficiency was around 40%. In the computational aspect, simulation models have been developed and validated for each of the subsystems of DesaLink, upon which an integrated model has been realised for the whole system. The models, both the subsystem ones and the integrated one, have been demonstrated to predict accurately the system performance under specific operational conditions. A simulation case study has been performed using the developed model. Simulation results indicate that the system can be expected to achieve a water production of 200 m3 per year by using a widely available evacuated tube solar collector having an area of only 2 m2. This freshwater production would satisfy the drinking water needs of 163 habitants in the Rajasthan region, the area for which the case study was performed.

Review of low-temperature vapour power cycle engines with quasi-isothermal expansion

External combustion heat cycle engines convert thermal energy into useful work. Thermal energy resources include solar, geothermal, bioenergy, and waste heat. To harness these and maximize work output, there has been a renaissance of interest in the investigation of vapour power cycles for quasi-isothermal (near constant temperature) instead of adiabatic expansion. Quasi-isothermal expansion has the advantage of bringing the cycle efficiency closer to the ideal Carnot efficiency, but it requires heat to be transferred to the working fluid as it expands. This paper reviews various low-temperature vapour power cycle heat engines with quasi-isothermal expansion, including the methods employed to realize the heat transfer. The heat engines take the form of the Rankine cycle with continuous heat addition during the expansion process, or the Stirling cycle with a condensable vapour as working fluid. Compared to more standard Stirling engines using gas, the specific work output is higher. Cryogenic heat engines based on the Rankine cycle have also been enhanced with quasi-isothermal expansion. Liquid flooded expansion and expander surface heating are the two main heat transfer methods employed. Liquid flooded expansion has been applied mainly in rotary expanders, including scroll turbines; whereas surface heating has been applied mainly in reciprocating expanders. © 2014 Elsevier Ltd.

Low-temperature organic Rankine cycle engine with isothermal expansion for use in desalination

Groundwater salinity is a widespread problem that contributes to the freshwater deficit of humanity. Consequently, where conventional energy supply is also lacking, organic Rankine cycle (ORC) engines are being considered as a feasible option to harness readily available low-grade heat (<180°C) to drive the desalination of the saline water via reverse osmosis (RO). However, this application is still not very well developed, and has significantly high specific energy consumption (SEC). Hence, this study explores the isothermal expansion of the ORC working fluid to achieve improved efficiency for driving a batch-RO desalination process, "DesaLink". Here, the working fluid is directly vaporized in the expansion cylinder which is heated externally by heat transfer fluid, thus obviating the need for a separate external boiler and high-pressure piping. Experimental investigations with R245fa have shown cycle efficiency of 8.8%. And it is predicted that the engine could drive DesaLink to produce 256 L of freshwater per 8 h per day, from 4000 ppm saline water, with a thermal and mechanical SEC of 2.5 and 0.36 kWh/m3, respectively, representing a significant improvement on previously reported or predicted SEC values. © 2014 © 2014 Balaban Desalination Publications. All rights reserved.