Josélio Batista Vieira

Tracking Structural Changes in Lipid-based Multicomponent Food Materials due to Oil Migration by Microfocus Small-Angle X-ray Scattering

One of the major problems in the confectionery industry is chocolate fat blooming, that is, the formation of white defects on the chocolate surface due to fat crystals. Nevertheless, the mechanism responsible for the formation of chocolate fat blooming is not fully understood yet. Chocolate blooming is often related to the migration of lipids to the surface followed by subsequent recrystallization. Here, the migration pathway of oil into a cocoa butter matrix with different dispersed particles was investigated by employing microfocus small-angle X-ray scattering and contact angle measurements. Our results showed that the chocolate powders get wet by the oil during the migration process and that the oil is migrating into the pores within seconds. Subsequently, cocoa butter is dissolved by the oil, and thus, its characteristic crystalline structure is lost. The chemical process provoked by the dissolution is also reflected by microscopical changes of the surface morphology of chocolate model samples after several hours from the addition of oil to the sample. Finally, the surface morphology was investigated before and after oil droplet exposure and compared to that of water exposure, whereby water seems to physically migrate through the particles, namely cocoa powder, sucrose, and milk powder, which dissolve in the presence of water.

Changes in contact angle providing evidence for surface alteration in multi-component solid foods

Chocolate blooming, one of the major problems in the confectionery industry, is the formation of visible white spots or a greyish haze on the surface of chocolate products due to large sugar or fat crystals on the surface. This leads to aesthetic changes and deterioration of taste and thus large sales losses for the confectionery industry due to consumer complaints. Chocolate blooming is often related to migration of lipids or sugar molecules to the chocolate surface, where they recrystallize with an associated polymorphic change of crystal structure on the surface. The wetting behaviour from contact angle measurements gives further insight into surface properties and is needed to determine surface energies and to evaluate possible migration mechanisms and preferred pathways. Therefore, an equilibrium contact angle is needed which is not directly accessible and is influenced by surface texture and interaction between solid and test liquid. In this study, the surface of cocoa butter and conventional chocolates was characterized by measuring the contact angle with the sessile drop protocol. The influence of roughness, test liquid and pre-crystallization of the samples as well as the storage temperature were investigated. In case of no pre-crystallization, a change in surface properties due to storage at 20 °C was detected, whereas samples stored at 30 °C showed the same wetting behaviour as fresh samples. This is associated with polymorphic transformation from thermodynamically less stable crystals to more stable configurations.

Fast field cycling NMR relaxometry studies of molten and cooled cocoa butter

ABSTRACT Due to its relevance in the confectionery industry, cocoa butter (CB) has been extensively studied. However, most studies focus on its crystallisation properties, whilst studies of its liquid state are lacking. Here, and for the first time, a study of the self-diffusion of CB at different temperatures is presented, using fast field cycling (FFC) nuclear magnetic resonance (NMR) further validated using pulsed field gradient stimulated echo (PGSTE) NMR. Measurements were performed upon heating CB to either 50°C or 100°C and cooling it to 22°C. No hysteresis was found between the different thermal treatments. However, the activation energy (28.7 kJ/mol) estimated from the cooling protocol of the 100°C treatment, was the closest to that reported in the literature for similar systems. This suggests that measurements using a wider range of temperatures, and starting with a liquid material are advisable. Additionally, samples were measured during isothermal crystallisation at 22°C, showing that the region below 1 MHz is the most sensitive to phase changes. GRAPHICAL ABSTRACT

Synchrotron x-ray microtomography of the interior microstructure of chocolate

The structure of chocolate, a multicomponent food product, was analyzed using microtomography. Chocolate consists of a semi-solid cocoa butter matrix and a dense network of suspended particles. A detailed analysis of the microstructure is needed to understand mass transport phenomena. Transport of lipids from e.g. a filling or liquid cocoa butter is responsible for major problems in the confectionery industry such as formation of chocolate bloom, which is the formation of visible white spots or a grayish haze on the chocolate surface and leads to consumer rejections and thus large sales losses for the confectionery industry. In this study it was possible to visualize the inner structure of chocolate and clearly distinguish the particles from the continuous phase by taking advantage of the high density contrast of synchrotron radiation. Consequently, particle arrangement and cracks within the sample were made visible. The cracks are several micrometers thick and propagate throughout the entire sample. Images of pure cocoa butter, chocolate without any particles, did not show any cracks and thus confirmed that cracks are a result of embedded particles. They arise during the manufacturing process. Thus, the solidification process, a critical manufacturing step, was simulated with finite element methods in order to understand crack formation during this step. The simulation showed that cracks arise because of significant contraction of cocoa butter, the matrix phase, without any major change of volume of the suspended particles. Tempering of the chocolate mass prior to solidification is another critical step for a good product quality. We found that samples which solidified in an uncontrolled manner are less homogeneous than tempered samples. In summary, our study visualized for the first time the inner microstructure of tempered and untempered cocoa butter as well as chocolate without sample destruction and revealed cracks, which might act as transport pathways.

Rheological Modification of Reduced Fat Chocolate Induced by the Addition of Limonene

The objective of this study is to understand how the addition of limonene, a low molecular weight hydrophobic compound, to chocolate, leads to a decrease in the viscosity of molten chocolate. Chocolate is a fat (cocoa butter) based dispersion of solids (sugar, cocoa and milk solids). We showed that, by mixing with cocoa butter, limonene decreases the viscosity of chocolate by decreasing the viscosity of its continuous phase, liquid cocoa butter. To understand the functionality of limonene in decreasing the viscosity of cocoa butter (triacylglyceride melt), additional mixtures of cocoa butter and limonene were prepared and their viscosity was measured. The dependence of the viscosity on the ratio of cocoa butter to limonene analyzed using Kays equation seems to indicate that limonene mixes with and within the cocoa butter triacylglycerides, diluting the fat and leading to a decrease in the overall fat viscosity.