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Understanding the Role of Processing and Formulation on RBW Oleogel Microstructure

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Understanding the Role of Processing and Formulation on RBW Oleogel Microstructure Understanding the role of processing and formulation on RBW oleogel microstructure Vincenzo di Bari Presentation outlook 1. World innovation trends for lipids 2. Oil structuring strategies: Ø TAGs: Fats Ø Non-TAGs: Oleogels 3. Formulation of RBW oleogels: Ø Understanding the thermomechanical behaviour Ø Engineering RBW oleogels 4. Key features of wax oleogels research 1. World innovation trends for lipids Trend Driver Reduction in trans- & Nutrition – health saturated (≤10%) fats Reduction in chemically Nutrition – health modified oils Natural Nutrition – health Reduction in animal fats Choices Sustainability Reduction in palm oil and Sustainability fats in general Nutrition – health Increase in PUFA content Nutrition – health Natural 2. Edible oil structuring strategies Molecular Particles mechanisms dispersion Image taken from: Pernetti et al. Soft Matter (2007) 12, 221-231. Molecular mechanisms to structure edible oils Traditional: TAGs Fats Solid structure = f(building blocks) Novel: Non-TAGs Oleogels Fats: complex hierarchical structure of TAGs Image taken from “Structure and functionality of edible fats”, Marangoni et al. Soft Matter, 2012, 8, 1275. Non-TAGs based approach to structure edible oils Non-TAGs: Oleogels* Novel routes to structure edible oils Mechanisms & Functionality = f(building block) *Organogels are called “Oleogels” when structuring to edible oils Bio-based: • plants • insects • marine animals 2 Image taken from: Patel, A, and Dewettinck, K (2015). Comparative evaluation of structured oil systems: Shellac oleogel, HPMC oleogel, and HIPE gel. Eur. J. Lipid Sci. Technol. 117, 000-000. Plant waxes • Natural plant hydrophobic compounds deposited outside the epidermal cells • Complex mixture of fatty alcohols and acids, their esters, hydrocarbons, ketones, etc • Considered to be among the most promising oleogelators6,7 Plant wax based oleogels Wax Oil • Candelilla • Olive • Carnauba • Sunflower • Sunflower • Rice bran • Rice Bran • Rapeseed • Berry • Vegetable • Bee • Salad • Fruit Plant wax based oleogels Wax Oil • Candelilla • Olive • Carnauba • Sunflower • Sunflower • Rice bran • Rice Bran • Rapeseed • Berry • Vegetable • Bee • Salad • Fruit Rice bran wax (RBW) Rice Bran (7.6 x 107 tons/year)1 Extraction / Hexane Crude Rice Bran Oil Degumming Dewaxing RBW (5-8%) ~700,000 tons Neutralisation Bleaching De-odorisation Rice Bran Oil 1: Friedman, M., Rice Brans, Rice Bran Oils, and Rice Hulls: Composition, Food and Industrial Uses, and Bioactivities in Humans, Animals, and Cells. J. Agric. Food Chem. 2013, 61, 10626−10641 Rice bran wax (RBW) • By-product • Available in large volumes • Promising gelling agent • Temperature of phase transition compatible with pasteurisation • In food applications Rice Bran Wax is EU regulated as a food additive E908. RBW: structural levels A Macroscale Mesoscale Nanoscale Molecular Wax ester A Image taken from reference 8: Characterization of the Nanoscale in Triacylglycerol Crystal Networks Formulation of RBW oleogels Oleogel research landscape at UoN Characterisation Functionalisation Application: cakes & SCP (LMWO) Oleogels: Definition •Organic liquid entrapped within a thermo- reversible, three-dimensional gel network3 •Network: Thermo-reversible 3D supramolecular structure formed via self-assembly of small molecules in an organic solvent at low concentration4. RBW Oleogels: preparation Formulation definition Solubilisation Crystallisation Structure Development RBW oleogels: Appearance RBW concentration (%) 0.0% 0.1% 0.2% 0.5% 1.0% 2.0% 3.0% 5.0% RBW oleogels: microstructure RBW oleogels: microstructure Oleogel research landscape at UoN Characterisation Functionalisation Application: cakes & SCP Microstructure functionalisation: Understanding the thermo-mechanical behaviour Formulation [RBW] Processing Additives Cooling Thermodynamic/kinetics rate Temperature Shear 100 µm Microstructure = f([RBW]) 1.0% 1.5% 2.0% 2.5% 3.0% 5.0% RBW oleogels thermal properties Liquid oil 3.0 Oleogel 2.5 /g) 2.0 mW 1.5 1.0 Heat Flux ( Heat 0.5 0.0 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 Temperature (°C) Gel strength = f(Temperature) 100,000 2% RBW ω = 10 rad/s 10,000 1,000 G' (20C) G'' (20C) 100 G' (30C) G'' (30C) G', G'' (Pa) G' (40C) G'' (40C) 10 G' (50C) G'' (50C) G' (55C) G'' (55C) 1 0.001 0.01 0.1 1 10 100 1000 γ (%) Engineering the mechanical behaviour= f([RBW], cooling rate) 0.5 °C/min 50 °C/min 240 200 160 120 80 3% RBW Yield Stress (Pa) Stress Yield 40 200 µm 5% RBW 200 µm 0 0.1 1 10 100 Cooling rate (°C/min) PP50 Sandblasted, ω = 10 rad/s, 40 °C, 0.5 mm gap Engineering the mechanical behaviour= f([RBW], cooling rate) 80% 80% 70% 0.5°C/min 70% 5°C/min 60% 60% 50% 50% 40% 40% 30% 30% % of crystals 20% % of crystals 20% 10% 10% 0% 0% 50 100 150 200 250 >250 50 100 150 >150 Lenght of crystals - classes (µm) Length of crystals - classes (µm) 60% 50% 50°C/min Average number (%) of 40% crystals in each 30% length class after cooling, at % of crystals 20% 27°C (1%RBW) 10% 0% 25 50 >50 Length of crystals - classes (µm) Role of additives on RBW oleogels Control (0% Emulsifier) 200 µm 1% Span 60 1% Span 65 Crystallisation profile of RBW + Additive (Span 65) 1% Sp65/1% RBW Heat flow 0.2 (mW) 0.2 flow Heat 0.5% Sp65/1% RBW 0.1% Sp65/1% RBW 1% RBW 20 30 40 50 60 70 80 90 Temperature (°C) Application Pastry re-formulation Palm oil 20% Replacement with 3% RBW Images taken by Khatija Nawaz Husain (CIM Nottingham) 4. Key features of wax oleogels research Reversible physical Increased modification PUFA of oils Type, origin & recovery Matching strategy fats functionality Health Sustainability Natural Economical value / by- Functionality Delayed products lipolysis valorisation RBW for oleogelation: Key features • Low molecular weight gelators • Unidirectional molecular packing leading to anisotropic platelet shaped crystals with β’ sub-cell structure • Long range intermolecular interactions • Self-arrange to form a dispersion of crystals sintered to form an oil-structuring continuous network • The addition of additives promotes new microstructural arrangement mirrored by different crystallisation profile Many thanks for your attention Any Questions?.
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