Free energy functional expansion as the generalized approach to the equation of state of dense fluids

A version of the thermodynamic perturbation theory based on a scaling transformation of the partition function has been applied to the statistical derivation of the equation of state in a highpressure region. Two modifications of the equations of state have been obtained on the basis of the free energy functional perturbation series. The comparative analysis of the experimental PV T- data on the isothermal compression for the supercritical fluids of inert gases has been carried out. © 2012.

Surface:plasma interactions in GaAs subjected to capacitively coupled RF plasmas

Surface compositional changes in GaAs due to RF plasmas of different gases have been investigated by XPS and etch rates were measured using AFM. Angular Resolved XPS (ARXPS) was also employed for depth analysis of the composition of the surface layers. An important role in this study was determination of oxide thickness using XPS data. The study of surface - plasma interaction was undertaken by correlating results of surface analysis with plasma diagnosis. Different experiments were designed to accurately measure the BEs associated with the Ga 3d, Ga 2P3/2 and LMM peaks using XPS analysis and propose identification in terms of the oxides of GaAs. Along with GaAs wafers, some reference compounds such as metallic Ga and Ga2O3 powder were used. A separate study aiming the identification of the GaAs surface oxides formed on the GaAs surface during and after plasma processing was undertaken. Surface compositional changes after plasma treatment, prior to surface analysis are considered, with particular reference to the oxides formed in the air on the activated surface. Samples exposed to ambient air for different periods of time and also to pure oxygen were analysed. Models of surface processes were proposed for explanation of the stoichiometry changes observed with the inert and reactive plasmas used. In order to help with the understanding of the mechanisms responsible for surface effects during plasma treatment, computer simulation using SRIM code was also undertaken. Based on simulation and experimental results, models of surface phenomena are proposed. Discussion of the experimental and simulated results is made in accordance with current theories and published results of different authors. The experimental errors introduced by impurities and also by data acquisition and processing are also evaluated.

Oxidational wear of low alloy steel in gases other than air

A pin on disc wear machine has been used to study the oxidational wear of low alloy steel in a series of experiments which were carried out under dry wear sliding conditions at range of loads from 11.28 to 49.05 N and three sliding speeds of 2 m/s, 3.5 m/s and 5 m/s, in atmosphere of air, Ar, CO2, 100% O2, 20% O2-80% Ar and 2% O2-98% Ar. Also, the experiments were conducted to study frictional force, surface and contact temperatures and surface parameters of the wearing pins. The wear debris was examined using x-ray diffraction technique for the identification of compounds produced by the wear process. Scanning electron microscopy was employed to study the topographical features of worn pins and to measure the thickness of the oxide films. Microhardness tests were carried out to investigate the influence of the sub-surface microhardness in tribological conditions. Under all loads, speeds and atmospheres parabolic oxidation growth was observed on worn surfaces, although such growth is dependent on the concentration of oxygen in the atmospheres employed. These atmospheres are shown to influence wear rate and coefficient of friction with change in applied load. The nature of the atmosphere also has influence on surface and contact temperatures as determined from heat flow analysis. Unlubricated wear debris was found to be a mixture of αFe2O3, Fe3O4 and FeO oxide. A model has been proposed for tribo-oxide growth demonstrating the importance of diffusion rate and oxygen partial pressure, in the oxidation processes and thus in determination of wear rates.

Application of CFD to model fast pyrolysis of biomass

The article deals with the CFD modelling of fast pyrolysis of biomass in an Entrained Flow Reactor (EFR). The Lagrangian approach is adopted for the particle tracking, while the flow of the inert gas is treated with the standard Eulerian method for gases. The model includes the thermal degradation of biomass to char with simultaneous evolution of gases and tars from a discrete biomass particle. The chemical reactions are represented using a two-stage, semi-global model. The radial distribution of the pyrolysis products is predicted as well as their effect on the particle properties. The convective heat transfer to the surface of the particle is computed using the Ranz-Marshall correlation.

CFD modelling of the fast pyrolysis of an in-flight cellulosic particle subjected to convective heat transfer

The pyrolysis of a freely moving cellulosic particle inside a 41.7mgs -1 source continuously fed fluid bed reactor subjected to convective heat transfer is modelled. The Lagrangian approach is adopted for the particle tracking inside the reactor, while the flow of the inert gas is treated with the standard Eulerian method for gases. The model incorporates the thermal degradation of cellulose to char with simultaneous evolution of gases and vapours from discrete cellulosic particles. The reaction kinetics is represented according to the Broido–Shafizadeh scheme. The convective heat transfer to the surface of the particle is solved by two means, namely the Ranz–Marshall correlation and the limit case of infinitely fast external heat transfer rates. The results from both approaches are compared and discussed. The effect of the different heat transfer rates on the discrete phase trajectory is also considered.

Gas-metal reactions and porosity in the inert gas arc welding of copper

A study has been made of the effects of welding and material variables on the occurrence of porosity in tungsten inert gas arc welding of copper. The experiments were based on a statistical design and variables included, welding current, welding speed, arc atmosphere composition, inert gas flow rate, weld preparation, and base material. The extent of weld metal porosity was assessed by density measurement and its morphology by X-ray radiography and metallography. In conjunction with this the copper-steam reaction has been investigated under conditions of controlled atmosphere arc melting. The welding experiments have shown that the extent of steam porosity is increased by increased water vapour content of the arc atmosphere, increased oxygen content of the base material and decreased welding speed. The arc melting experiments have shown that the steam reaction occurs in the body of the weld pool and proceeds to an apparent equi1ibrium state appropriate to to its temperature, the hydrogen and oxygen being supplied by the dissociation of water vapour in the arc atmosphere. It has been shown conclusively that nitrogen porosity can occur in the tungsten inert gas arc welding of copper and that this porosity can be eliminated by using filler wires containing small amounts of aluminum and titanium. Since it has been shown to be much more difficult to produce sound butt welds than melt runs it has been concluded that the porosity associated with joint fit up is due to nitrogen entrained into tho arc atmosphere. Clearly atmospheric entrainment would also, to a much lesser extent, involve water vapour. From a practical welding point of view it has thus been postulated that use of a filler wire containing small amounts of aluminum and/or titanium would eliminate both forms of porosity since these elements are both strongJy deoxidising and denitriding.

Application of space-charge electrostatic precipitator for collection of oil mist from pyrolysis gases

A novel electrostatic precipitator CAROLA® is developed for collection of fine oil mists. It operates on the principle of unipolar particle charging in the corona discharge and particle precipitation under the field of space charge. The pilot precipitator was tested at different gas temperatures. It is shown that the increase of gas temperature changes the characteristics of the corona discharge and particle size distribution, especially for droplets sub-micron droplets. The CAROLA® precipitator was used for collection of oil mist from pyrolysis gases at the HALOCLEAN® plant. The flow rate of biomass in the HALOCLEAN® plant was 15-30 kg/h. The particle mass concentration in the raw gas was over 100 g/Nm. The operation voltage of the precipitator was 10-12 kV and corona current up to 0,1 mA. Single stage electrostatic precipitator ensured mass collection efficiency 97-99,5% for pyrolysis oil mist.

The intermediate pyrolysis of de-inking sludge to produce a sustainable liquid fuel

De-inking sludge is a waste product generated from secondary fibre paper mills who manufacture recycled paper into new paper sheets; it refers directly to the solid residues which evolve during the de-inking stage of the paper pulping process. The current practice for the disposal of this waste is either by land-spreading, land-filling or incineration which are unsustainable. This work has explored the intermediate pyrolysis of pre-conditioned de-inking sludge pellets in a recently patented 20 kg/h intermediate pyrolysis reactor (The Pyroformer). The reactor is essentially two co-axial screws which are configured in such a way as to circulate solids within the reactor and thus facilitate in the cracking of tars. The potential application of using the volatile organic vapours and permanent gases evolved would be to generate both combined heat and power (CHP) located at paper making sites. The results show that de-inking sludge could be successfully pyrolysed and the organic vapours produced were composed of a mixture of aromatic hydrocarbons, phenolic compounds and some fatty acid methyl esters as detected by liquid GC-MS. The calorific value of the oil after condensing was between 36 and 37 MJ/kg and the liquid fuel properties were also determined, permanent gases were detected by a GC-TCD and were composed of approximately 24% CO, 6% CH and 70% CO (v/v%). The solid residue from pyrolysis also contained a small residual calorific value, and was largely composed of mainly calcium based inert metal oxides. The application of applying intermediate pyrolysis to de-inking sludge for both CHP production and waste reduction is in principle a feasible technology which could be applied at secondary fibre paper mills. © 2013 Elsevier B.V. All rights reserved.

Pyrolysis liquids and gases as alternative fuels in internal combustion engines:a review

Liquids and gases produced through biomass pyrolysis have potential as renewable fuels to replace fossil fuels in conventional internal combustion engines. This review compares the properties of pyrolysis fuels, produced from a variety of feedstocks and using different pyrolysis techniques, against those of fossil fuels. High acidity, the presence of solid particles, high water content, high viscosity, storage and thermal instability, and low energy content are typical characteristics of pyrolysis liquids. A survey of combustion, performance and exhaust emission results from the use of pyrolysis liquids (both crude and up-graded) in compression ignition engines is presented. With only a few exceptions, most authors have reported difficulties associated with the adverse properties of pyrolysis liquids, including: corrosion and clogging of the injectors, long ignition delay and short combustion duration, difficulty in engine start-up, unstable operation, coking of the piston and cylinders and subsequent engine seizure. Pyrolysis gas can be used more readily, either in spark ignition or compression ignition engines; however, NO reduction techniques are desirable. Various approaches to improve the properties of pyrolysis liquids are discussed and a comparison of the properties of up-graded vs. crude pyrolysis liquid is included. Further developments in up-gradation techniques, such as hydrocracking and bio-refinery approaches, could lead to the production of green diesel and green gasoline. Modifications required to engines for use with pyrolysis liquids, for example in the fuel supply and injection systems, are discussed. Storage stability and economic issues are also reviewed. Our study presents recent progress and important R&D areas for successful future use of pyrolysis fuels in internal combustion engines.

Passive scene imaging of absorbing gases by narrowband dielectric filter modulation

This paper examines a method for locating within a scene a distribution of an absorbing gas using a passive imaging technique. An oscillatory modulation of the angle of a narrowband dielectric filter located in front of a camera imaging a scene, gives rise to an intensity modulation that differs in regions occupied by the absorbing gas. A preliminary low cost system has been constructed from readily available components which demonstrates how the location of gas within a scene can be implemented. Modelling of the system has been carried out, especially highlighting the transmission effects of the dielectric filter upon different regions of the image.

The intermediate pyrolysis of de-inking sludge to produce a sustainable liquid fuel

De-inking sludge is a waste product generated from secondary fibre paper mills who manufacture recycled paper into new paper sheets; it refers directly to the solid residues which evolve during the de-inking stage of the paper pulping process. The current practice for the disposal of this waste is either by land-spreading, land-filling or incineration which are unsustainable. This work has explored the intermediate pyrolysis of pre-conditioned de-inking sludge pellets in a recently patented 20 kg/h intermediate pyrolysis reactor (The Pyroformer). The reactor is essentially two co-axial screws which are configured in such a way as to circulate solids within the reactor and thus facilitate in the cracking of tars. The potential application of using the volatile organic vapours and permanent gases evolved would be to generate both combined heat and power (CHP) located at paper making sites. The results show that de-inking sludge could be successfully pyrolysed and the organic vapours produced were composed of a mixture of aromatic hydrocarbons, phenolic compounds and some fatty acid methyl esters as detected by liquid GC-MS. The calorific value of the oil after condensing was between 36 and 37 MJ/kg and the liquid fuel properties were also determined, permanent gases were detected by a GC-TCD and were composed of approximately 24% CO, 6% CH and 70% CO (v/v%). The solid residue from pyrolysis also contained a small residual calorific value, and was largely composed of mainly calcium based inert metal oxides. The application of applying intermediate pyrolysis to de-inking sludge for both CHP production and waste reduction is in principle a feasible technology which could be applied at secondary fibre paper mills. © 2013 Elsevier B.V. All rights reserved.

The influence of a coal gasifier atmosphere on fatigue crack growth rates in BS 4360 steel

Fatigue crack growth tests have been carried out in a number of gaseous environments in order to assess their effects on the crack propagation resistance of BS 4360 grade 50EE, a weldable structural steel. Crack growth rates at 25 °C are up to 20 times higher in hydrogen than in air, but there is no effect when hydrogen is present as a 30% constituent of a simplified product gas (SPG). Indeed, crack growth rates in such a mixture are slightly lower than those measured in air, being comparable with those observed in an inert environment. The other gases present in the SPG are CO, CO2 and CH4, and it is probable that the carbon monoxide is responsible for nullifying the embrittling effects of hydrogen, by preferentially adsorbing on to the surface of the steel and thus blocking hydrogen entry. Experimental observations suggest that oxygen has the same effect when small quantities are allowed to diffuse into a non-flowing hydrogen environment around a propagating crack. The results are encouraging in terms of the suitability of conventional structural steels such as BS 4360 for gas plant applications. The gas mixtures present in such an environment would not have the severe detrimental effects on fatigue crack growth resistance which result from the presence of 'pure' hydrogen. © 1993.