Growth regime map for liquid-bound granules: further development and experimental validation

An attempt was made to quantify the boundaries and validate the granule growth regime map for liquid-bound granules recently proposed by Iveson and Litster (AlChE J. 44 (1998) 1510). This regime map postulates that the type of granule growth behaviour is a function of only two dimensionless groups: the amount of granule deformation during collision (characterised by a Stokes deformation number, St(def)) and the maximum granule pore saturation, s(max). The results of experiments performed with a range of materials (glass ballotini, iron ore fines, copper chalcopyrite powder and a sodium sulphate and cellulose mixture) using both drum and high shear mixer granulators were examined. The drum granulation results gave good agreement with the proposed regime map. The boundary between crumb and steady growth occurs at St(def) of order 0.1 and the boundary between steady and induction growth occurs at St(def) of order 0.001. The nucleation only boundary occurs at pore saturations that increase from 70% to 80% with decreasing St(def). However, the high shear mixer results all had St(def) numbers which were too large. This is most likely to be because the chopper tip-speed is an over-estimate of the average impact velocity granules experience and possibly also due to the dynamic yield strength of the materials being significantly greater than the yield strengths measured at low strain rates. Hence, the map is only a useful tool for comparing the granulation behaviour of different materials in the same device. Until we have a better understanding of the flow patterns and impact velocities in granulators, it cannot be used to compare different types of equipment. Theoretical considerations also revealed that several of the regime boundaries are also functions of additional parameters not explicitly contained on the map, such as binder viscosity. (C) 2001 Elsevier Science B.V. All rights reserved.

Liquid phase sintering of aluminium alloys

The principle that alloys are designed to accommodate the manufacture of goods made from them as much as the properties required of them in service has not been widely applied to pressed and sintered P/M aluminium alloys. Most commercial alloys made from mixed elemental blends are identical to standard wrought alloys. Alternatively, alloys can be designed systematically using the phase diagram characteristics of ideal liquid phase sintering systems. This requires consideration of the solubilities of the alloying elements in aluminium, the melting points of the elements, the eutectics they form with aluminium and the nature of the liquid phase. The relative diffusivities are also important. Here we show that Al-Sn, which closely follows these ideal characteristics, has a much stronger sintering response than either Al-Cu or Al-Zn, both of which have at least one non-ideal characteristic. (C) 2001 Elsevier Science B.V. All rights reserved.

Evaluation of liquid Bacillus thuringiensis var. israelensis products for control of Australian Aedes arbovirus vectors

Laboratory bioassay studies were conducted in southeast Queensland, Australia,: on the efficacy of Teknar (R), VectoBac (R) 12AS, and Cybate (R) (active ingredient: 1,200 international toxic units Bacillus thuringiensis var, israelensis [Bti]) against 3rd instars of the arbovirus vectors Aedes aegypti. Ae. notoscriptus, Ae. vigilax, and Ae. camptorhynchus. Probit analyses were then used to determine LD,, (median lethal dose), LD95, and lethal dose ratios (LDR). Aedes aegypti and Ae. notoscriptus, both container-habitat species, tolerated the highest Bti concentrations compared with saltmarsh Ae. vigilax and Ae. camptorhynchus. For example, the LDR for Ae. vigilax versus Ae. notoscriptus exposed to Cybate was 0.14 (95% confidence limit [CL] 0.03-0.61). Similarly, the Cybate LDR for Ae. camptorhynchus versus Ae. notoscriptus was 0.22 (95% CL 0.07-0.70). Teknar produced similar results with an LDR of 0.21 (95% CL 0.04-1.10) for Aedes vigilax versus Aedes notoscriptus. Differences in product efficacy were found when tested against the 2 container-breeding species. Cybate was less effective than Teknar with LDRs of 1.55 (95% CL 0.65-3.67) and 1.87 (95% CL 0.68-5.15) for Aedes aegypti and Ae. notoscriptus, respectively. The significant differences in susceptibility between mosquito species and varying efficacy between products highlight the importance of evaluating concentration-response data prior to contracting with distributors of mosquito control products. This information is crucial to resistance management strategies.

Transient mesenteric ischaemic episodes tracked by continuous jejunal PCO2 monitoring during liquid feeding

Objective: To test the effect of liquid feeds on the responses to splanchnic ischaemia of a continuous rapid response PCO2 sensor inserted in the jejunum. Design: Prospective experimental animal study in a university research laboratory. Subjects: Adult male Wistar rats. Interventions: Adult male Wistar rats (285-425 g) were anaethetised with sodium pentobarbitone 60 mg/ kg i.p. and ventilated with 100 % oxygen and isoflurane via tracheostomy to a PaCO2 of 30-40 mmHg. A sensor was inserted into the mid-jejunum to record PCO2 every second. Distal aortic pressure was transduced. Four control rats received no feeds whilst in another four rats liquid feed was infused into the proximal jejunum at 3 ml/h. In each rat five episodes of splanchnic ischaemia were induced by 2-min elevations of an aortic sling to a mean distal aortic pressure of 30 mmHg. Measurements and main results: PCO2 elevations were always detectable, usually less than a minute from the onset of splanchnic ischaemia in both fed and unfed rats, with no difference in mean times to detectable response. In the fed rats there was a small but significant increase in the time to peak sensor response (196 +/- 16 vs. 180 +/- 12 s) and a trend towards an elevated mean baseline luminal PCO2 (67 +/- 9 vs. 55 +/- 4 mmHg). Conclusions: Brief episodes of splanchnic ischaemia were tracked successfully by a rapid response jejunal continuous PCO2 sensor during the infusion of a proprietary liquid feed preparation despite minor changes in PCO2 response characteristics and a possible elevation in baseline luminal PCO2.

The IWA Anaerobic Digestion Model No 1 (ADM1)

The IWA Anaerobic Digestion Modelling Task Group was established in 1997 at the 8th World Congress on,Anaerobic Digestion (Sendai, Japan) with the goal of developing a generalised anaerobic digestion model. The structured model includes multiple steps describing biochemical as well as physicochemical processes. The biochemical steps include disintegration from homogeneous particulates to carbohydrates, proteins and lipids; extracellular hydrolysis of these particulate substrates to sugars, amino acids, and long chain fatty acids (LCFA), respectively; acidogenesis from sugars and amino acids to volatile fatty acids (VFAs) and hydrogen; acetogenesis of LCFA and VFAs to acetate; and separate methanogenesis steps from acetate and hydrogen/CO2. The physico-chemical equations describe ion association and dissociation, and gas-liquid transfer. Implemented as a differential and algebraic equation (DAE) set, there are 26 dynamic state concentration variables, and 8 implicit algebraic variables per reactor vessel or element. Implemented as differential equations (DE) only, there are 32 dynamic concentration state variables.

Quantification of sulfur and sulfur-containing compounds in wastewaters by means of a combination of liquid chromatographic methods

Low-micromolar concentrations of sulfite, thiosulfate and sulfide, present in synthetic wastewater or anaerobic digester effluent, were quantified by means of derivatization with monobromobimane, followed by HPLC separation with fluorescence detection. The concentration of elemental sulfur was determined, after its extraction with chloroform from the derivatized sample, by HPLC with UV detection. Recoveries of sulfide (both matrices), and of thiosulfate and sulfite (synthetic wastewater) were between 98 and 103%. The in-run RSDs on separate derivatizations were 13 and 19% for sulfite (two tests), between 1.5 and 6.6% for thiosulfate (two tests) and between 4.1 and 7.7% for sulfide (three tests). Response factors for derivatives of sulfide and thiosulfate, but not sulfite, were steady over a 13-month period during which 730 samples were analysed. Dithionate and tetrathionate did not seem to be detectable with this method. The distinctness of the elemental sulfur and the derivatizing-agent peaks was improved considerably by detecting elution at 297 instead of 263 nm. (C) 2002 Elsevier Science B.V. All rights reserved.

Gas permeation in silicon-oxide/polymer (SiOx/PET) barrier films: role of the oxide lattice, nano-defects and macro-defects

We propose a model for permeation in oxide coated gas barrier films. The model accounts for diffusion through the amorphous oxide lattice, nano-defects within the lattice, and macro-defects. The presence of nano-defects indicate the oxide layer is more similar to a nano-porous solid (such as zeolite) than silica glass with respect to permeation properties. This explains why the permeability of oxide coated polymers is much greater, and the activation energy of permeation much lower, than values expected for polymers coated with glass. We have used the model to interpret permeability and activation energies measured for the inert gases (He, Ne and Ar) in evaporated SiOx films of varying thickness (13-70 nm) coated on a polymer substrate. Atomic force and scanning electron microscopy were used to study the structure of the oxide layer. Although no defects could be detected by microscopy, the permeation data indicate that macro-defects (>1 nm), nano-defects (0.3-0.4 nm) and the lattice interstices (<0.3 nm) all contribute to the total permeation. (C) 2002 Elsevier Science B.V. All rights reserved.

Development of a novel titration and off-gas analysis (TOGA) sensor for study of biological processes in wastewater treatment systems

The development of the new TOGA (titration and off-gas analysis) sensor for the detailed study of biological processes in wastewater treatment systems is outlined. The main innovation of the sensor is the amalgamation of titrimetric and off-gas measurement techniques. The resulting measured signals are: hydrogen ion production rate (HPR), oxygen transfer rate (OTR), nitrogen transfer rate (NTR), and carbon dioxide transfer rate (CTR). While OTR and NTR are applicable to aerobic and anoxic conditions, respectively, HPR and CTR are useful signals under all of the conditions found in biological wastewater treatment systems, namely, aerobic, anoxic and anaerobic. The sensor is therefore a powerful tool for studying the key biological processes under all these conditions. A major benefit from the integration of the titrimetric and off-gas analysis methods is that the acid/base buffering systems, in particular the bicarbonate system, are properly accounted for. Experimental data resulting from the TOGA sensor in aerobic, anoxic, and anaerobic conditions demonstrates the strength of the new sensor. In the aerobic environment, carbon oxidation (using acetate as an example carbon source) and nitrification are studied. Both the carbon and ammonia removal rates measured by the sensor compare very well with those obtained from off-line chemical analysis. Further, the aerobic acetate removal process is examined at a fundamental level using the metabolic pathway and stoichiometry established in the literature, whereby the rate of formation of storage products is identified. Under anoxic conditions, the denitrification process is monitored and, again, the measured rate of nitrogen gas transfer (NTR) matches well with the removal of the oxidised nitrogen compounds (measured chemically). In the anaerobic environment, the enhanced biological phosphorus process was investigated. In this case, the measured sensor signals (HPR and CTR) resulting from acetate uptake were used to determine the ratio of the rates of carbon dioxide production by competing groups of microorganisms, which consequently is a measure of the activity of these organisms. The sensor involves the use of expensive equipment such as a mass spectrometer and requires special gases to operate, thus incurring significant capital and operational costs. This makes the sensor more an advanced laboratory tool than an on-line sensor. (C) 2003 Wiley Periodicals, Inc.

Quantification and stability of everolimus (SDZ RAD) in human blood by high-performance liquid chromatography-electrospray tandem mass spectrometry

We report here a validated method for the quantification of a new immunosuppressant drug, everolimus (SDZ RAD), using HPLC-tandem mass spectrometry. Whole blood samples (500 mul) were prepared by protein precipitation, followed by C-18 solid-phase extraction. Mass spectrometric detection was by selected reaction monitoring with an electrospray interface operating in positive ionization mode. The assay was linear from 0.5 to 100 mug/l (r(2) > 0.996, n = 9). The analytical recovery and inter-day imprecision, determined using whole blood quality control samples (n = 5) at 0.5, 1.2, 20.0, and 75.0 mug/l, was 100.3-105.4% and less than or equal to7.6%, respectively. The assay had a mean relative recovery of 94.8 +/- 3.8%. Extracted samples were stable for up to 24 h. Fortified everolimus blood samples were stable at -80 degreesC for at least 8 months and everolimus was found to be stable in blood when taken through at least three freeze-thaw cycles. The reported method provides accurate, precise and specific measurement of everolimus in blood over a wide analytical range and is currently supporting phase 11 and III clinical trials. (C) 2002 Elsevier Science B.V. All rights reserved.

Shock standoff on hypersonic blunt bodies in nonequilibrium gas flows

This paper presents a new theory of hypersonic blunt-nose shock standoff, based on a compressibility coordinate transformation for inviscid flow. It embraces a wide range of nonequilibrium shock-layer chemistry and gas mixtures including ionization and freestream dissociation. An extended binary scaling property of the analysis is also demonstrated. Specific application is made here to the family of arbitrarily diluted dissociating diatomic gases, with parametric study results presented for the scaled shock standoff distance as a function of an appropriate blunt-nose region Damkohler number. Comparisons with other theories and data in the case of nitrogen are also given and discussed.

The mechanism of protection of molten magnesium by cover gas mixtures containing sulphur hexafluoride

Experimental studies have been undertaken, involving in situ observations of the interaction between cover gas mixtures and molten magnesium. It has been shown that, in the presence of sulphur hexafluoride (SF6), the contact angle between solid MgO and molten magnesium is reduced, resulting in the wetting of MgO by magnesium metal. In contrast, it was observed that the absence of SF6 results in a large contact angle, poor wetting of the MgO by magnesium metal and a non-adherent surface film. It is proposed that the formation of an adherent, protective surface film under a cover gas mixture containing SF6 is due to capillary forces acting within the film.

Scale-up of mixer granulators for effective liquid distribution

There is considerable anecdotal evidence from industry that poor wetting and liquid distribution can lead to broad granule size distributions in mixer granulators. Current scale-up scenarios lead to poor liquid distribution and a wider product size distribution. There are two issues to consider when scaling up: the size and nature of the spray zone and the powder flow patterns as a function of granulator scale. Short, nucleation-only experiments in a 25L PMA Fielder mixer using lactose powder with water and HPC solutions demonstrated the existence of different nucleation regimes depending on the spray flux Psi(a)-from drop-controlled nucleation to caking. In the drop-controlled regime at low Psi(a) values. each drop forms a single nucleus and the nuclei distribution is controlled by the spray droplet size distribution. As Psi(a) increases, the distribution broadens rapidly as the droplets overlap and coalesce in the spray zone. The results are in excellent agreement with previous experiments and confirm that for drop-controlled nucleation. Psi(a) should be less than 0.1. Granulator flow studies showed that there are two powder flow regimes-bumping and roping. The powder flow goes through a transition from bumping to roping as impeller speed is increased. The roping regime gives good bed turn over and stable flow patterns. This regime is recommended for good liquid distribution and nucleation. Powder surface velocities as a function of impeller speed were measured using high-speed video equipment and MetaMorph image analysis software, Powder surface velocities were 0.2 to 1 ms(-1)-an order of magnitude lower than the impeller tip speed. Assuming geometrically similar granulators, impeller speed should be set to maintain constant Froude number during scale-up rather than constant tip speed to ensure operation in the roping regime. (C) 2002 Published by Elsevier Science B.V.

Unsaturated liquid percolation flow through nonwetted packed beds

The unsaturated flow of liquid through packed beds of large particles was studied using six different liquids, all with contact angles greater than 90degrees on the bed packing (wax spheres of 9, 15 and 19.4 mm diameter). The liquid flow was discrete in nature, as drops for low flow rates and rivulets for high flow rates. For unsaturated liquid flows, the actual percolation velocity, not superficial velocity, should be used to characterize the flow. The percolation velocity did not vary with packed-bed depth, but was a strong function of liquid flow rate, liquid and particle properties. Effects of liquid and particle properties (but not flow rate) are well captured by a simple correlation between the liquid-particle friction factor and Reynolds number based on actual percolation velocities. Liquid dispersion, characterized by the maximum dispersion angle, varies significantly with liquid and particle properties. The tentative correlation suggested here needs further validation for a wider range of conditions.

Electrospray liquid chromatography/mass spectrometry fingerprinting of Acanthophis (death adder) venoms: taxonomic and toxinological implications

Death adders (genus Acanthophis) are unique among elapid snakes in both morphology and venom composition. Despite this genus being among the most divergent of all elapids, the venom has been historically regarded as relatively quite simple. In this study, liquid chromatography/mass spectrometry (LC/MS) analysis has revealed a. much greater diversity in venom composition, including the presence of molecules of novel molecular weights that may represent a new class of venom component. Furthermore, significant variation exists between species and populations,, which allow for the LC/MS fingerprinting of each species. Mass profiling of Acanthophis venoms clearly demonstrates the effectiveness of this technique which underpins fundamental studies ranging from chemotaxonomy to drug design. Copyright (C) 2002 John Wiley Sons, Ltd.