School of Chemistry - Research Publications

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    Effect of Bulk Viscosity and Emulsion Droplet Size on the Separation Efficiency of Model Mineral Oil-in-Water (O/W) Emulsions under Ultrasonic Standing Wave Fields: A Theoretical and Experimental Investigation
    Mettu, S ; Yao, S ; Sun, Q ; Lawson, SR ; Scales, PJ ; Martin, GJO ; Ashokkumar, M (American Chemical Society (ACS), 2020-04-22)
    Ultrasound standing waves can be used to separate emulsions. So far, they have been applied to oil-in-water emulsions with low continuous phase viscosity. This technique has the potential to be used for novel applications such as separating lipids from algal biomass; however, this requires the methodology to be optimized to process viscous emulsions. We have addressed this issue by studying the effects of bulk phase viscosity (1–23 mPa·s), emulsion droplet size (4.5–20 μm), power (10–54 W/L), and frequency (1 and 2 MHz) of ultrasound on the separation efficiency of model mineral oil-in-water–glycerol-mixture emulsions. For the small droplet size (4.5 μm) emulsion in water, the maximum separation achieved increased from 36 to 79% when ultrasound power increased from 10 to 54 W/L. However, for the large droplet size (11 μm) emulsion, the maximum separation was greater than 95% and was independent of ultrasound power. The maximum separation efficiency for small droplet size (4.5–6 μm) emulsions decreased from 80 to 14% when the viscosity increased from 1 to 23 mPa·s. However, for the large droplet size (11–20 μm) emulsion, the maximum separation efficiency decreased from 98 to 62% when the viscosity of the bulk phase was increased from 1 to 23 mPa·s. The experimental results were then interpreted using analytical and numerical simulations by calculating the time required for the emulsion droplets to migrate to the nearest pressure antinodal plane under the influence of ultrasound standing waves. Further experiments showed that increasing the ultrasound frequency from 1 to 2 MHz increased the maximum separation from 36 to 86% for fine emulsions and water as the continuous phase.
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    Emulsifying properties of ruptured microalgae cells: Barriers to lipid extraction or promising biosurfactants?
    Law, SQK ; Mettu, S ; Ashokkumar, M ; Scales, PJ ; Martin, GJO (ELSEVIER SCIENCE BV, 2018-10-01)
    A systematic investigation of the emulsifying properties of ruptured algae cells was performed for the first time. The slurry of ruptured algae cells was separated into different biomass fractions, namely the cell debris, the delipidated debris, the serum, and the lipid. The interfacial interactions of these biomass fractions with a nonpolar solvent (e.g. hexane or hexadecane) were characterized using pendant drop tensiometry and interfacial shear rheology. The stability of the different emulsions (formed by the different biomass fractions) was tested using analytical centrifugation. The extracted lipid was an excellent surfactant that reduced the interfacial tension, however, it was not effective at stabilizing the emulsions. The protein-rich serum produced a strong interfacial film that stabilized the emulsions against coalescence during centrifugation. The cell debris stabilized the emulsions to a lesser extent by adsorbing to the droplet surface, presumably via interactions with hydrophobic extracellular polymeric substances (EPS). However, neither the serum nor the cell debris were very effective surfactants, and required the presence of the lipid fraction to produce small emulsion droplets. When present together, the components exhibited competitive interfacial adsorption, which influenced emulsion stability. In particular, the interruption of the protein film by the presence of lipid or cell debris reduced the stability of the emulsions. This study provides a new mechanistic understanding of emulsification during wet lipid extraction from microalgae that will be useful for determining strategies to improve solvent recovery. The results also suggest potential for developing effective bioemulsifiers or biosurfactants from fractionated microalgae biomass for commercial application.
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    Rheological properties of concentrated slurries of harvested, incubated and ruptured Nannochloropsis sp. cells
    Mettu, S ; Yao, S ; Law, SQK ; Sun, Z ; Scales, PJ ; Ashokkumar, M ; Martin, GJO (Springer Science and Business Media LLC, 2019-12)
    Biorefining of microalgae biomass requires processing of high-solids (> 10%) slurries. To date there is little knowledge of how processes for weakening and rupturing microalgae cells affect the rheological properties of these materials. To fill this gap in the literature, the rheological properties of concentrated slurries of marine microalgae Nannochloropsis sp. were investigated as a function of processing and solids concentration (12, 20 and 24% w/w). Freshly harvested, incubated (autolysed), and high-pressure homogenised (HPH) slurries were found to be shear thinning up to a shear rate of approximately 200 s− 1. Viscosity increases were far more prominent for partially processed versus unprocessed algal pastes at the higher concentrations. Slurry viscosity as a function of cell volume fraction could not be fitted to the Krieger-Dougherty model due to a network structure resulting from extracellular polymeric substances (EPS) and the intracellular cell components released during incubation and cell rupture. The 24% slurry, which was near the close packing limit, was much more viscous than the less concentrated slurries when comprising whole cells (i.e. harvested and incubated slurries). Cell rupture by HPH completely altered the characteristics of the slurry, increasing the viscosity of even the less concentrated slurries, and producing irreversible shear thinning behaviour. The magnitude of the increases in viscosities and the irreversible shear thinning behaviour observed in this study, have significant implications for processing and optimising the solids concentration of algal slurries.