School of Chemical Engineering
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The department has a strong research team that is focused on solving problems and providing answers for industry and the wider community. Our work is principally in the areas of:
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School of Chemical Engineering
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Item Metadata only Deformation and metamorphism of massive sulphides at Sulitjelma, Norway(Mineralogical Society, 1993) Cook, N.J.The copper-bearing stratabound pyritic massive sulphide bodies contained in metamorphosed basic eruptives of Ordovician age at Sulitjelma in Nordland County, Norway, form one of the important fields of sulphide mineralisation within the Köli Nappe Complex. The sulphide bodies and their enclosing rocks were subject to successive stages of penetrative deformation and recrystallisation during the cycle of metamorphism and tectonic transport caused by the Scandian Orogeny. Textures within the ores and the immediate envelope of schists show that strain was focused along the mineralised horizons. The marked contrast in competence between the massive pyritic sulphides and their envelopes of alteration composed dominantly of phyllosilicates, and the metasediments of the overlying Furulund Group, led to the formation of macroscale fold and shear structures. On the mesoto microscale, a variety of textures have been formed within the pyrite-pyrrhotite-chalcopyrite-sphalerite sulphide rocks as a result of strain and recrystallisation. Variations in pyrite:pyrrhotite ratios and in the texture and proportions of associated gangue minerals evidently governed the strength and ductility of the sulphide rocks so that the same sulphide mineral can behave differently, displaying different textures in different matrices. In massive pyritic samples there is evidence of evolution towards textural equilibrium by recrystallisation, grain growth and annealment during the prograde part of the metamorphic cycle. Later, brittle deformation was superimposed on these early fabrics and the textural evidence is clearly preserved. By comparing published data on the brittle-ductile transformation boundaries of sulphide minerals with the conditions governing metamorphism at Sulitjelma, it is concluded that most of the brittle deformation in the sulphides took place during or after D3 under retrograde greenschist conditions. Grain growth of pyrite in matrices of more ductile sulphides during the prograde and early retrograde stages of metamorphism produced the coarse metablastic textures for which Sulitjelma is well-known. In some zones of high resolved shear stress, pyrite shows ductile behaviour which could be explained by a dislocation flow mechanism operating at conditions close to the metamorphic peak. In those horizons in which pyrrhotite is the dominant iron sulphide, the contrast in ductility between silicates, pyrite and pyrrhotite has led to the development of spectacular tectonoclastic textures in which fragments of wall rock have been broken, deformed, rolled and rotated within the ductile pyrrhotite matrix.Item Metadata only FTIR and NMR studies on crosslinking reaction between chlorosulfonated polyethylene and epoxidized natural rubber(American Chemical Society, 1993) Roychoudhury, A.; De, P.P.; Dutta, N.; Roy Choudhury, N.; Haider, B.; Vidal, A.A blend of chlorosulfonated polyethylene and epoxidized natural rubber undergoes a self-crosslinking reaction at elevated temperatures. Sulfonyl chloride groups of chlorosulfonated polyethylene react with epoxy groups of epoxidized natural rubber to give ether crosslinks between the two polymers. In addition to the self-crosslinking reaction, these two polymers undergo a number of side reactions as evidenced by spectroscopic studies.Item Metadata only More efficient use of energy in industrial processing(Australian Institute of Energy, 1995) Headon, Kylie A.; School of Chemical EngineeringItem Metadata only Experimental and model studies of the combined effect of temperature and pH on the thermal sterilisation of vegetative bacteria in liquid(Hemisphere Pubishing, 1995) Davey, K.; Hall, R.; Thomas, C.Item Metadata only Laboratory projects: Should students do them or design them?(American Society for Engineering Education, 1995) Middelberg, A.Item Metadata only Cell disruption(1995) Middelberg, A.Item Metadata only Analysis of an improved aqua-ammonia absorption refrigeration cycle employing evaporator blowdown to provide rectifier reflux(Applied Science Publishers, 1995) White, S. D.; O'Neill, Brian K.; School of Chemical EngineeringItem Metadata only A method for automated heat exchanger network synthesis using block decomposition and non-linear optimisation(I. Chem. E., 1995) Zhu, X. X.; O'Neill, Brian K.; Roach, John Robert C.; Wood, R. M.; School of Chemical EngineeringItem Metadata only Studies of collisional energy transfer using pressure-dependent Very Low-Pressure Pyrolysis (VLPP)(J.A.I. Press, 1995) King, K.Item Metadata only The importance of accounting for bioprocess interactions(AUSTRALIAN BIOTECHNOLOGY ASSOC LTD, 1995) Middelberg, A.Item Metadata only Comparison of singlet methylene removal rates by Group IV Hydrides(Wiley & Sons, 1995) Gutsche, G.; Staker, W.; King, K.AbstractThe technique of laser flash photolysis/laser absorption has been used to obtain an absolute removal rate constant of (3.85 ± 0.18) × 10−10 cm3 molecule−1 s−1 for singlet methylene, 1CH2 (ã1A1), with germane (GeH4) at ambient temperature. The removal rate constant is compared with the values for methane (CH4) and silane (SiH4) which have been determined previously. © 1995 John Wiley & Sons, Inc.Item Metadata only Process-scale disruption of microorganisms(PERGAMON-ELSEVIER SCIENCE LTD, 1995) Middelberg, A.Common hosts for the large-scale manufacture of biological products, such as Escherichia coli and Saccharomyces cerevisiae, do not excrete products to the medium. Effective techniques for cell disruption are therefore required. These include physical, chemical, enzymatic and mechanical methods. Mechanical methods such as bead milling, high-pressure homogenization, and microfluidization are preferred. However, gentler, specific methods are receiving increasing attention particularly when used in combination to synergistically exploit their different specificities. Benefits can also be derived by integrating product release and recovery. In all cases it is essential to consider the interaction of the disruption operation with downstream units and to clearly demonstrate the cost benefits of alternative strategies.Item Metadata only Size analysis of poly(3-hydroxybutyrate) granules produced in recombinant Escherichia coli(Chapman & Hall, 1995) Middelberg, A.; Lee, S.; Martin, J.; Williams, D.; Chang, H.Size distributions of PHB granules synthesized in recombinant Escherichia coli are determined by photosedimentation. Mean granule Stokes diameters are in the range 1.13-1.25 μm, which is larger than reported values for wild type microorganisms. Treatment with 1.5% hypochlorite and mild centrifugation did not affect granule size distribution. Treatment with 10% hypochlorite led to a significant reduction in mean diameter and total PHB. © 1995 Chapman & Hall.Item Metadata only Influence of broth dilution on the disruption of Escherichia coli(SPRINGER, 1995) Kleinig, A.; Mansell, C.; Nguyen, Q.; Badalyan, A.; Middelberg, A.The effect of cell concentration (5 to 150 g/L wet wt after broth dilution) on homogenizer disruption efficiency and homogenate viscosity is reported for E. coli. Broth dilution increases homogenizer efficiency and decreases feed and homogenate viscosity. However, this increase in disruption efficiency is not sufficient to warrant dilution of the broth prior to homogenization. The optimal feed concentration is the maximum possible that does not lead to practical handling difficulties due to high viscosity. © 1995 Chapman & Hall.Item Metadata only Thermal deactivation affects disruption of Escherichia coli(CHAPMAN HALL LTD, 1995) Collis, M.; O'Neill, B.; Middelberg, A.The effect of thermal deactivation on disruption efficiency and cell-debris size has been investigated for E. coli. Disruption for thermally-deactivated cells was substantially lower than for stationary cells. Cell-debris size was also larger. Thermal deactivation has a significant impact on subsequent downstream operations such as homogenisation and centrifugation. © 1995 Chapman & Hall.Item Open Access Vibrational energy transfer in shock-heated norbornene(American Institute of Physics, 1995) Barker, J.; King, K.Recently, Kiefer et al. [J. H. Kiefer, S. S. Kumaran, and S. Sundaram, J. Chem. Phys. 99, 3531 (1993)] studied shock-heated norbornene (NB) in krypton bath gas using the laser-schlieren technique and observed vibrational relaxation, unimolecular dissociation (to 1,3-cyclopentadiene and ethylene), and dissociation incubation times. Other workers have obtained an extensive body of high-pressure limit unimolecular reaction rate data at lower temperatures using conventional static and flow reactors. In the present work, we have developed a vibrational energy transfer-unimolecular reaction model based on steady-state RRKM calculations and time-dependent master equation calculations to satisfactorily describe all of the NB data (incubation times, vibrational relaxation times, and unimolecular rate coefficients). The results cover the temperature range from ∼300 to 1500 K and the excitation energy range from ∼1 000 to 18 000 cm−1. Three different models (based on the exponential step-size distribution) for the average downward energy transferred per collision, 〈ΔE〉down were investigated. The experimental data are too limited to enable the identification of a preferred model and it was not possible to determine whether the average 〈ΔE〉down is temperature dependent. However, all three 〈ΔE〉down models depend linearly on vibrational energy and it is concluded that standard unimolecular reaction rate codes must be revised to include energy-dependent microcanonical energy transfer parameters. The choice of energy transfer model affects the deduced reaction critical energy by more than 2 kcal mol−1, however, which shows the importance of energy transfer in determining thermochemistry from unimolecular reaction fall-off data. It is shown that a single set of Arrhenius parameters gives a good fit of all the low temperature data and the shock-tube data extrapolated to the high pressure limit, obviating the need to invoke a change in reaction mechanism from concerted to diradical for high temperature conditions. Some possible future experiments are suggested.Item Metadata only Removal rate constants for singlet methylene with oxygen-containing species(American Chemical Society, 1995) Gutsche, G.; Lawrance, W.; Staker, W.; King, K.The technique of laser flash photolysis/laser absorption has been used to obtain absolute removal rate constants for singlet methylene, 1CH2 (ã 1A1), with various oxygen-containing organic species. Removal rate constants for some 27 alcohols, ethers, ketones, aldehydes, carboxylic acids, and esters are reported for the first time. The removal rate constants for H2O and CH3OH have been remeasured and found to be in excellent agreement with values determined by other researchers. Improved removal rate constants for C2H5OH, n-C3H7OH, CH3OCH3, CH3CHO, CH3COCH3, CH3COOH, HCOOCH3, and CH3OCOOCH3 are also presented. In all cases the removal rate constants are large, indicating that reaction is the dominant process leading to loss of 1CH2. Comparisons are drawn between the reactivities of the various functional groups and between them and their hydrocarbon analogues. Because of the large data base provided by these measurements, mechanistic information can be inferred in a number of instances. © 1995 American Chemical Society.Item Metadata only Primary reaction channels and kinetics of the thermal decomposition of phenylsilane(American Chemical Society, 1995) O'Neal, H.; Ring, M.; Kim, D.; King, K.The thermally induced decomposition of phenylsilane has been investigated by three different experimental methods: a static method, a comparative rate-single pulse shock tube (CR-SPST) method, and a very low-pressure pyrolysis (VLPP) method. Decomposition is mainly heterogeneous under static conditions but appears homogeneous in the other two systems. Homogeneous dissociations occur by two channels with yields, PhSiH3 →1 H2 + PhSiH, φ1 ∼ 0.84 ± 0.04; PhSiH3 →2 PhH + SiH2, φ2 ∼ 0.16 ± 0.04. Coupling of CR-SPST and homogeneous static reactor data spanning temperatures from 693 to 1236 K for the benzene formation channel and adjusting for falloff by RRKM methods gives high-pressure Arrhenius parameters of A1 = 1014.0±0.4, E1= 59.3 ± 2.1 and A2 = 1013.9±0.2, E2 = 62.0 ± 0.9 (A in s-1 and E in kcal/mol) for the two primary dissociation channels. These parameters yield RRKM calculated rate constants under VLPP conditions which agree within the errors with experimental rate constants. © 1995 American Chemical Society.Item Metadata only Studies into the scale-up of a process to produce biosynthetic insulin-like growth factor(Institution of Chemical Engineers, 1995) Kotlarski, N.; Yeates, R.; Milner, S.; Francis, G.; O'Neill, B.; Middelberg, A.A recombinant insulin-like growth factor analog (Long-R3–IGF-I, 19921) is currently produced for industrial use as a component in mammalian cell culture media. Gradually expanding markets require that the existing production process be modified to allow increased throughput. The process is therefore examined and the key bottleneck identified as the ion-exchange recovery of refolded peptide. Theoretically, process throughput can be significantly increased with minimum expense by increasing the refolding concentration and by concentrating the refolded peptide prior to ion-exchange recovery. Experimental studies into the effect of refolding concentration on peptide yield are described and the results fitted to a model of competing first– and second-order reactions. An increase in the refolding concentration is presently uneconomical, due to a reduction in the yield of correctly refolded protein. However, concentrating the refolded peptide by ultrafiltration proved feasible. Using this result, the outline of a semi-continuous de-bottlenecked process is described which is capable of increasing the throughput ten-fold without major purchase of new equipment.Item Metadata only Time-resolved infrared fluorescence studies of the collisional deactivation of CO2(00°1) by large polyatomic molecules(Elsevier, 1995) Poel, K.; Alwahabi, Z.; King, K.The time-resolved infrared fluorescence (IRF) technique has been used to study the vibrational deactivation of CO2(0001) by large polyatomic molecules at ambient temperature (295 ± 2 K).The excited CO2 molecules were prepared by direct pumping with the P(21) line of a pulsed CO2 laser at 10.6 μm. The bimolecular rate constant for deactivation by CO2 was determined to be (0.353 ± 0.026) × 103 Torr-1 s-1, in excellent agreement with previous work. The rate constants for deactivation by the large polyatomic molecules, c-C6H10, c-C6H12, C6H6, C6D6, C7H8, C7D8, C6H5 F, p-C6H4F2, C6HF5 and C6F6, were found to be (143 ± 18), (150 ± 12), (120 ± 4), (238 ± 9), (140 ± 5), (234 ± 15), (121 ± 7), (132 ± 23), (132 ± 12), and (94 ± 5) × 103 Torr-1 s-1, respectively. Experimental deactivation probabilities and average energies removed per collision are calculated and compared. There is little difference in deactivation probabilities between the acyclic ring compounds and their aromatic analogues but the perfluorinated compound, C6F6 is clearly less efficient than its hydrocarbon analogue, C6H6. The perdeuterated species, C6D6 and C7D8 show considerably enhanced deactivation relative to the other species, probably as a result of near-resonant intermolecular V-V energy transfer. © 1995.