RESUMEN
Cocoa pod husks (CPHs) represent an underutilized component of the chocolate manufacturing process. While industry's current focus is understandably on the cocoa beans, the husks make up around 75 wt % of the fruit. Previous studies have been dominated by the carbohydrate polymers present in CPHs, but this work highlights the presence of the biopolymer lignin in this biomass. An optimized organosolv lignin isolation protocol was developed, delivering significant practical improvements. This new protocol may also prove to be useful for agricultural waste-derived biomasses in general. NMR analysis of the high quality lignin led to an improved structural understanding, with evidence provided to support deacetylation of the lignin occurring during the optimized pretreatment. Chemical transformation, using a tosylation, azidation, copper-catalyzed click protocol, delivered a modified lignin oligomer with an organophosphorus motif attached. Thermogravimetric analysis was used to demonstrate the oligomer's potential as a flame-retardant. Preliminary analysis of the other product streams isolated from the CPHs was also carried out.
RESUMEN
The mixing of a powder of 10- to 50-µm primary particles into a liquid to form a dispersion with the highest possible solid content is a common industrial operation. Building on recent advances in the rheology of such "granular dispersions," we study a paradigmatic example of such powder incorporation: the conching of chocolate, in which a homogeneous, flowing suspension is prepared from an inhomogeneous mixture of particulates, triglyceride oil, and dispersants. Studying the rheology of a simplified formulation, we find that the input of mechanical energy and staged addition of surfactants combine to effect a considerable shift in the jamming volume fraction of the system, thus increasing the maximum flowable solid content. We discuss the possible microscopic origins of this shift, and suggest that chocolate conching exemplifies a ubiquitous class of powder-liquid mixing.
RESUMEN
Oral processing of two milk chocolates, identical in composition and viscosity, was investigated to understand the textural behaviour. Previous studies had shown differences in mouthcoating and related attributes such as time of clearance from the oral cavity to be most discriminating between the samples. Properties of panellists' saliva, with regard to protein concentration and profile before and after eating the two chocolates, were included in the analysis but did not reveal any correlation with texture perception. The microstructure of the chocolate samples following oral processing, which resembled an emulsion as the chocolate phase inverts in-mouth, was clearly different and the sample that was found to be more mouthcoating appeared less flocculated after 20 chews. The differences in flocculation behaviour were mirrored in the volume based particle size distributions acquired with a laser diffraction particle size analyser. The less mouthcoating and more flocculated sample showed a clear bimodal size distribution with peaks at around 40 and 500 µm, for 10 and 20 chews, compared to a smaller and then diminishing second peak for the other sample following 10 and 20 chews, respectively. The corresponding mean particle diameters after 20 chews were 184 ± 23 and 141 ± 10 µm for the less and more mouthcoating samples, respectively. Also, more of the mouthcoating sample had melted after both 10 and 20 chews (80 ± 8% compared to 72 ± 10% for 20 chews). Finally, the friction behaviour between a soft and hard surface (elastopolymer/steel) and at in-mouth temperature was investigated using a commercial tribology attachment on a rotational rheometer. Complex material behaviour was revealed. Observations included an unusual increase in friction coefficient at very low sliding speeds, initially overlapping for both samples, to a threefold higher value for the more mouthcoating sample. This was followed by a commonly observed decrease in friction coefficient with increasing sliding speed (mixed and elasto-hydrodynamic regime), steeper in the case of the more mouthcoating sample until the differences between the two samples became negligible at a sliding speed of ≈0.2 mm s(-1). The stark differences in the tribological behaviour in these regimes begin to allow correlation of data from sensory and physical measurements based on insight into the underlying material behaviour. The complex picture also included comparable behaviour of both samples in the late stages of the elasto-hydrodynamic regime and the early stages of the hydrodynamic regime, until a change of slope was observed and then, at higher sliding speeds, the less mouthcoating sample showed higher friction coefficients. In conclusion, this research uncovered novel correlations of a complex food composite between the sensory behaviour and the physical material properties relating to melting and friction behaviour.
