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Fat Bloom On...O Surface.Pdf Fat bloom on chocolate confectionery systems - From core to surface Dahlenborg, Hanna 2014 Link to publication Citation for published version (APA): Dahlenborg, H. (2014). Fat bloom on chocolate confectionery systems - From core to surface. 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LUND UNIVERSITY PO Box 117 221 00 Lund +46 46-222 00 00 HANNA DAHLENBORG HANNA Fat bloom on chocolate on confectionery bloom Fat systems Fat bloom on chocolate confectionery systems From core to surface Hanna Dahlenborg Department of Food Technology, Engineering and Nutrition 2014 Faculty of Engineering LTH Lund University, Sweden 2014 ISBN 978-91-978122-8-3 Doctoral Thesis Fat bloom on chocolate confectionery systems From core to surface Hanna Dahlenborg Department of Food Technology, Engineering and Nutrition Faculty of Engineering LTH Doctoral Thesis at Lund University Lund, Sweden 2014 Akademisk avhandling som för avläggande av teknologie doktorsexamen vid tekniska fakulteten vid Lunds Universitet, kommer att offentligen försvaras tisdagen den 11 februari 2014, kl. 13:15 i hörsal B, på Kemicentrum, Getingevägen 60, Lund. Fakultetsopponent: Prof. Alejandro G. Marangoni, Department of Food Science, University of Guelph, Canada. Academic thesis, which by due permission of the Faculty of Engineering at Lund University, will be publicly defended on Tuesday 11th of February 2014 at 13:15 p.m. in lecture hall B, at the Centre of Chemistry and Chemical Engineering, Getingevägen 60, Lund, for the degree of Doctor of Philosophy in Engineering. Faculty opponent: Prof. Alejandro G. Marangoni, Department of Food Science, University of Guelph, Canada. Department of Food Technology, Engineering and Nutrition Faculty of Engineering, LTH Lund University P.O. Box 124 SE-221 00 Lund Sweden SP Chemistry, Materials and Surfaces P.O. Box 5607 SE-114 86 Stockholm Sweden ISBN 978-91-978122-8-3 SP Chemistry, Materials and Surfaces Publication A-3219 Copyright © 2014 Hanna Dahlenborg The following papers are printed with permission: Paper I: Copyright © Springer Paper II: Copyright © John Wiley and sons Printed in Sweden by US-AB, Stockholm 2014 ”The best way to keep really good chocolate tasting really nice is not to stash it away in a safe place, but to eat it up in one go” Chokladfabriken, Stockholm Abstract Fat bloom on chocolate is a major problem for the confectionery industry since the unappetising appearance and negative sensory effects lead to rejection by customers. The presence of fat bloom on chocolate confectionery systems is usually connected to migration of liquid fat due to the difference in composition between filling triacylglycerols (TAGs) and cocoa butter TAGs. The filling TAGs migrate into the chocolate shell where they can dissolve cocoa butter crystals. Consequently, cocoa butter TAGs migrate to the surface followed by a re-crystallisation into the most stable polymorph β1VI. Cocoa butter is the main fat in chocolate which can be considered as a composite material consisting of solid particles (i.e. cocoa particles, sugar crystals and in some cases milk solids) in a lipid continuous matrix of cocoa butter. The final quality of the product is highly dependent on the polymorphic forms of the cocoa butter TAGs in the fat phase and the distribution and size of the solid particles. In this thesis the migration of filling oil into model shells of cocoa butter and of chocolate has been investigated as well as the fat bloom development. This was implemented through the development of novel analytical methods, where optical profilometry and confocal Raman microscopy give information regarding the shell microstructure at and below the surface, and energy dispersive X-ray spectroscopy (EDS) provides the opportunity to follow the movement of brominated TAGs from the filling into the shell. By combining these techniques with established methods such as low vacuum scanning electron microscopy (LV SEM) and differential scanning calorimetry (DSC) a toolkit for the investigation of oil migration connected to surface microstructure development has been established. Imperfections, in form of pores and protrusions, at chocolate surfaces have been identified, confirming previous studies reporting these features. These imperfections were characterised using confocal Raman microscopy indicating that some protrusions are filled with fat and some are air-filled in conjunction with a fat shell, while the pores consist of air. These imperfections continued further into the chocolate shell, thus, it is suggested that they could be connected to oil migration and further to fat bloom development. The microstructure of model shells was shown to have a substantial impact on the TAG migration rate which was connected to fat bloom development. By applying seeding as pre-crystallisation technique to the shells the migration rates were decreased as well as the development of fat bloom crystals at the surface. In contrast, model pralines with poorly tempered shells indicated a higher oil migration rate and accelerated development of fat bloom. Furthermore, the presence of non-fat particles was shown to increase the migration rate and the fat bloom development. Additionally, the particle size of the non-fat particles proved to have an impact, where a smaller particle size gave rise to higher migration rates and thus, accelerated fat bloom development. The importance of controlled storage temperature was further demonstrated, where a minor increase in temperature from 20 to 23°C lead to substantially higher migration rates and accelerated fat bloom development. The mechanisms of oil migration in chocolate confectionery systems have mainly been referred to as molecular diffusion or capillary flow in literature. However, through results from the work of this thesis, convective flow is suggested to be an important contribution to the migration of filling oil in addition to molecular diffusion and capillary flow. Sammanfattning Chokladprodukter som utvecklat fettblom är ett centralt problem för konfektyrindustrin då konsumenterna väljer bort dessa produkter på grund av oaptitligt utseende och negativa sensoriska effekter. Förekomsten av fettblom på fyllda chokladprodukter är vanligtvis kopplad till migrering av flytande fett från fyllning till skal vilket sker på grund av skillnader i sammansättning mellan fyllningens triacylglyceroler (TAG) och kakaosmörets TAG. Då fyllningens TAG migrerar in i chokladskalet löser de upp kristaller av kakaosmör, vilket är det huvudsakliga fettet i choklad. Flytande kakaosmör migrerar då till chokladytan där det genomgår en omkristallisation och antar den mest stabila polymorfen β1VI. Choklad kan ses som ett kompositmaterial bestående av partiklar (t.ex. kakaopulver, socker och i vissa fall mjölkpulver) i en lipidkontinuerlig matris av kakaosmör. Kvaliteten hos den slutliga produkten är i hög grad beroende av de polymorfa formerna i fettfasen samt av partiklarnas storlek och fördelning. I denna avhandling har migrering av fyllningsfetter in i modellskal av kakaosmör och av choklad undersökts, liksom utveckling av fettblom. Detta har genomförts via utveckling av nya analysmetoder, där optisk profilometri och konfokal Raman-mikroskopi ger information om skalets mikrostruktur på och under ytan, och där EDS (energy dispersive X-ray spectroscopy) ger möjligheten att följa hur bromerade triacylglyceroler (BrTAG) rör sig från fyllningen in i skalet. Genom att kombinera dessa metoder med redan etablerade metoder, så som LV SEM (low vacuum scanning electron microscopy) och DSC (differential scanning calorimetry), har en verktygslåda tagits fram, som kan ge information om migrering av fyllningsfetter kopplat till mikrostrukturella förändringar på chokladytan. Tidigare forskning har beskrivit ytliga oregelbundenheter på chokladytor, i form av porer och bubblor. Förekomsten av dessa kunde bekräftas i detta arbete. Vidare kunde dessa oregelbundenheter karakteriseras, genom användning av konfokal Raman-mikroskopi, vilket indikerade att vissa bubblor är fyllda med fett och vissa är luftfyllda under ett fettskal, medan porerna består av luft. Dessa oregelbundenheter förefaller fortsätta in i chokladskalet, vilket antyder att de kan ha en koppling till migrering av flytande fett och därigenom till utveckling av fettblom. Mikrostrukturen i modellpralinernas skal visade sig ha en betydande inverkan på migreringshastigheten av BrTAG, vilken i sin tur visades relatera till utvecklingen av fettblom. Genom att tillämpa s.k. seedning på modellskalen kunde man minska migreringshastigheten liksom utvecklingen av fettblomkristaller på ytan. I motsats
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