Chocolate yield stress as measured by oscillatory rheology

Liquid chocolate exhibits a non-Newtonian flow behavior that is conventionally characterized by a yield stress and plastic viscosity. In general, yield stress is determined by shear rheology experiments and the data are plotted as viscosity as a function of shear stress or shear stress as a function of shear rate. For the shear stress-shear rate plot, a frequently used approach to estimate the yield stress is to fit the data to one of several established models, with the Casson model being the most popular. Even though ICA (former IOCCC) recommendation is not to use the Casson model, it is still frequently applied. With the Casson model, a good fit to the experimental data for the shear rate ranging from 5 s^{− 1} to 60 s^{− 1} is realized. However, this model is unable to resolve real differences between chocolate samples that manifest at shear rate values below 5 s^{− 1}. In this study, oscillatory rheology was applied and the stress at the end of the linear viscoelastic region (LVR) was taken as an estimate for the yield stress. This method was shown to be sensitive to fat content, emulsifier concentration and type of emulsifier. Furthermore, oscillatory rheology was found to be capable to capture differences in yield stress of chocolates that were not differentiated using the Casson model fitting approach.     

Comparison of rheological models for determining dark chocolate viscosity

Parameters in chocolate rheology, namely shear viscosity and yield stress, are important in manufacture and directly influenced by product particle size distribution (PSD) and composition. The Casson model was the standard confectionery industry strategy to quantify rheological properties of molten chocolate until in 2000, the International Confectionery Association recommended the use of interpolation data to describe viscosity. The two strategies are compared and correlated in defining rheological properties of molten dark chocolates prepared using different PSD, fat and lecithin content. Rheological parameters were determined using a shear rate-controlled rheometer and data examined using correlation, regression and principal component analyses to establish their inter-relationships. Correlation and regression analyses showed high correlation ( r  = 0.89–1.00) and regression coefficients ( R ² = 0.84–1.00). The newer International Confectionery Association technique gave higher correlation and regression coefficients than the Casson model, but multivariate principal component analysis showed that the two models were highly related and either could effectively quantify dark chocolate viscosity parameters.     

Flow Characterization of Peach Products During Extrusion

Suitability of Bingham, Herschel-Bulkley, Casson, and Mizrahi-Berk models, to characterize the flow behavior of peach products during extrusion was investigated. The Casson equation sufficiently described the flow of peach extrudates within the 49 to 125 s^-1 shear rate range. As concentration increased, yield stress and consistency coefficients increased. A rheological model was proposed to describe the viscosity of peach extrudates. The model incorporates the effect of shear rate by the Casson equation and the effect of concentration by a linear expression. The model provided good fit to the experimental data for peach extrudates reconstituted from drum-dried peach purees.     

RHEOLOGY OF DIFFERENT FORMULATIONS OF MILK CHOCOLATE AND THE EFFECT ON COATING THICKNESS

This work characterized the flow properties and investigated the effect of grind, emulsifier type and emulsifier level on the coating thickness of milk chocolate. Rheological properties were characterized using a concentric cylinder viscometer according to the method recommended by the International Confectionery Association. The thickness of the chocolate on dip‐coated acrylic plates was obtained by a gravimetric method. A three‐way analysis of variance was performed for the coating thickness. All three factors were significant; the thickness of the chocolate coating was greater for fine grind, soy lecithin for emulsifier and for low concentrations of emulsifier. The thicknesses were well predicted using the model with the Casson model parameters from the rheological characterization.     

Effects of particle size distribution and composition on rheological properties of dark chocolate

Control of chocolate viscosity is vital to its quality and production cost, and directly influenced by solids particle size distribution (PSD) and composition. Effects of PSD and composition on rheological properties of molten dark chocolate were investigated by varying PSD [D₉₀ (90% finer than this size) of 18, 25, 35 and 50 μm], fat 25, 30 and 35% and lecithin (0.3 and 0.5%) using a shear rate-controlled rheometer. PSD, fat and lecithin content significantly affected all rheological parameters, with significant interaction among factors. Increasing particles size gave significant reductions in Casson plastic viscosity, Casson yield value, yield stress, apparent viscosity and thixotropy, with greatest effect with 25% fat and 0.3% lecithin, which reduced with increasing fat and lecithin contents. Statistical analysis revealed that fat exerts the greatest effect on the variability in all the rheological properties followed by PSD and lecithin. PSD, fat and lecithin could be manipulated to control dark chocolate rheology, influencing quality whilst reducing production cost.     

Thermal,structural and rheological characteristics of dark chocolate with different compositions

The effect of different cocoa composition of dark chocolate samples and their ingredients on their thermal, structural and rheological characteristics was investigated. Thermal behavior was evaluated by means of differential scanning calorimetry (DSC), while the crystal morphology was observed by polarized light optical microscopy. The rheological measurements were carried out using both continuous and oscillatory experiments. The formation of more stable polymorphic structures was time and temperature dependent; and it was not affected by either cocoa composition or particle sizes. The kinetics of crystallization was determined by a step crystallization method and modeled by the Avrami equation, it was accelerated by solid particles concentration, lower particle size and lower crystallization temperatures. Negative spherulites with featherlike microstructures defined the time dependent crystal growth and were consistent with Avrami indexes of 3–4. Under continuous shear, cocoa butter was well described by the Bingham rheological model, while Casson and Carreau equations modeled the flow of cocoa liquor and chocolate samples. However the Carreau model was preferred for presenting better fittings and for predicting apparent viscosities at low and at high shear rates. From both, continuous and oscillatory experiments, it was found that composition of chocolate samples in terms of fat and nonfat cocoa solids, and sugar content, affected their rheological behavior. The solid liquid transition of chocolate samples and cocoa liquor was obtained at a yield stress of around 1 Pa from both continuous and oscillatory shear experiments.     

MODELING THE TEMPERATURE EFFECT ON THE FLOW BEHAVIOR OF SWEET POTATO PUREE1

A study was conducted to investigate the effect of temperature on viscosity of sweet potato (SP) puree. Rheological data of the puree were measured using a Bohlin VOR Rheometer. Shear rates employed ranged from 0.01–921 s^?1. Thermal scans were run at 15, 25, 40, 60, 75, and 90C. The puree exhibited “shear thinning” behavior with a yield stress value of 10 Pa at each temperature tested. The characteristic of the flow behavior of the puree was determined by fitting the experimental data to Herschel-Bulkley, Casson and Modified Casson models. The model with the best fit was then used to represent the combined effect of shear rate and temperature on the apparent viscosity of SP puree in a model based upon the Modified Casson model. The model was validated using data for SP puree samples at 50C. Results showed that, within the experimental conditions used in this study, the model could adequately predict apparent viscosities of sweet potato puree processed at different temperatures.     

INTERNATIONAL INTER-LABORATORY TRIALS TO DETERMINE THE FACTORS AFFECTING THE MEASUREMENT OF CHOCOLATE VISCOSITY

The working group of the International Office of Cocoa, Chocolate and Sugar Confectionery (IOCCC) performed a sequence of five ring tests to improve the agreement of the standard method for measuring viscosity of chocolate between laboratories. Reporting shear stress measurements instead of using the Casson equation improved the agreement, as did standardising the method of cleaning the concentric cylinder and calibrating the viscometers. In the revised method, the standard deviation for shear stress measurement at shear rates greater than 5 s⁻¹ from 23 laboratories was less than 8%. However, the Casson yield values had a seven-fold range and the Casson plastic viscosity a two-fold range, which was unacceptably high. A new method (IOCCC 2000) has been published as a result of this work and is available from CAOBISCO in Bruxelles, Belgium.     

Tomographic Techniques for Measuring Fluid Flow Properties

Experimental fluid velocity profiles can be readily obtained by using tomographic techniques. Combining measurements of a fluid velocity profile with a simultaneous pressure drop permits the evaluation of rheological properties. In order to control a process and to assure product quality, it is useful to monitor the rheological properties in‐line or on‐line. Two tomographic techniques, magnetic resonance imaging (MRI) and ultrasonic Doppler velocimetry (UDV), were used to obtain velocity profiles for a 65.7 °Brix corn syrup solution and a 4.3 °Brix tomato juice. The UDV technique provided velocity profiles that compared well with the MRI method. For the corn syrup, the shear viscosity of 1.37 Pa‐s (UDV) and 1.51 Pa‐s (MRI) agreed well with the offline measurement of 1.57 Pa‐s. The tomato juice was best characterized as a Bingham plastic fluid. The yield stress ranged from 4.44 Pa to 4.70 Pa, which matched well with the off‐line value of 4.50 Pa. The strengths and limitations of both techniques are presented.     

YIELD STRESSES IN MOLTEN CHOCOLATES

Yield stress and flow properties of four molten chocolate samples at 40C were measured using coaxial cylinder and vane fixtures. The possibility for slip to occur during measurement was demonstrated by significant differences (p < 0.05) in Gasson parameters when measured between coaxial cylinders of different radius ratios. Significant differences in the Casson flow parameters (p ≤ 0.05) were also found when samples were sheared for 12 min as compared to 30 min. A piecewise regression technique, which fitted the Casson model to the low shear rate ranges and the Bingham model to higher shear rate ranges, could be used to best describe the flow behaviour of chocolate melts. Stress relaxation produced very low o_y values, which were believed to be an artifact of the measuring fixture and instrument. In the case of the single vane method, use of different start-up speeds had a marginal but significant effect (p < 0.05) on o_y values. When the multiple vane method was employed, start-up speeds below 0.23 rpm had no significant effect on o_y. The multiple vane method proved to be simple and more rapid than obtaining the steady shear data and then fitting the Casson flow model, and thus may be more suitable for routine yield stress measurements of molten chocolate for quality assurance purposes.     

RHEOLOGICAL AND TEXTURE STUDIES OF BUTTER3

Four commercial butters (conventional batch and Westfalia, Contimab and Cherry-Burrell continuous churned) were stored at two temperatures and evaluated periodically for rheological and textural properties. Evaluation methods included four mechanical tests (quasistatic shear, quasistatic uniaxial compression, Penetrometer, and extrusion) and sensory ratings of spreadability, firmness, and other texture parameters. The first three mechanical methods produced quasistatic shear yield stress values that had close agreement. For quality control the three tests can be considered equivalent. Shear stress-strain rate data from extrusion testing developed using the Rabinowitch-Mooney equation could be represented well by the Casson model. Casson yield stress values were an order of magnitude lower than the quasistatic values. The power law equation with a yield stress also represented the butter flow well, and all four butters had similar power law exponents (approx. 0.56). The Cherry-Burrell butter had much higher quasistatic and Casson model constants than the other butters. It was also the most temperature sensitive and most stable with storage time. Temperature-shear rate equivalent effects on shear stress were demonstrated by developing shift factors. The quasistatic yield values for the butters best predicted sensory spread-ability and hardness. The changes in flow properties (Casson yield stress and Casson slope) correlated with aging.     

DETERMINATION OF CHOCOLATE VISCOSITY

A critical appraisal of the Casson model for measuring chocolate versus a new proposed method is performed. The new method is validated with both research grade rheometers and factory grade viscometers. This includes elements of measurement uncertainty. In this way, a new reference method is validated for the viscosity of chocolate and related cocoa products using factory grade viscometers. It involves recording: (1) the value of the stress at a shear rate of 5 s ^-1 to represent the yield stress of chocolate, (2) the value of the viscosity at a shear rate of 40 s ^-1 to represent the high shear viscosity, and (3) the difference between the viscosity measured at a shear rate of 40 s ^-1 during the ramp up and down in shear rate to represent thixotropy. Results relate to the solid to liquid glass transition of dispersions under applied stress, and it is shown that they reflect existing theories of stress induced formation and rupture of fractal aggregates, for particle crowded colloidal suspensions with low interaction energy.     

A GENERALIZED RHEOLOGICAL MODEL FOR INELASTIC FLUID FOODS1

A versatile four-parameter model is presented for the rheological characterization of inelastic fluid foods. The model has been shown to accurately represent shear stress versus shear rate, and apparent viscosity versus shear rate relationships for several food materials. By appropriate specification of the four parameters of the model, conventional rheological models used in fluid food analyses (power law, Bingham plastic, Herschel-Bulkley, Casson, Heinz-Casson, and Mizrahi-Berk) can be obtained from the generalized equation.     

Physical characterization of low-calorie chocolate formulations

Development of a high-quality low-calorie chocolate needs the use of the most appropriate ingredients that could substitute sugar without negatively affecting several product properties. In this study, sucrose-reduced chocolates sweetened with sucralose and stevia by using bulking agents were investigated in relation to their rheological, textural and sensory attributes. Dark, milk and white chocolates with different amounts of sweeteners were formulated. The Casson model best fitted to the rheological data. In dark chocolates, partial substitution of sucrose with stevia (DCSSt) gave similar plastic viscosity and yield stress values with control samples (DCS). Hardness measurements also supported these results. DCSSt sample was again found to be very similar to control in tested sensory attributes when assessed by a consumer panel. The data indicated that it was possible to manufacture chocolate by partial replacement of sucrose with stevia without adversely affecting its important rheological, textural properties and sensory acceptance.     

EFFECT OF UNIMODAL PARTICLE SIZE AND PULP CONTENT ON RHEOLOGICAL PROPERTIES OF TOMATO PUREE

The vane method in controlled shear stress mode was used to determine the yield stress and the shear rate—shear stress data of tomato purees containing 10–35% pulp of two different average particle sizes: 0.34 and 0.71 mm. Consistency index and apparent viscosity increased significantly with pulp content and decreased with average particle size. The effect of pulp weight fraction (P) on relative viscosity (η_r) could be described by the single parameter equation: η_r= [1 – (P/A)]⁻², while the effect of particle diameter on η_r could be described using Peclet number. Magnitudes of yield stress determined directly by the vane method were higher than those obtained by using the Casson model, and were proportional to the square of pulp content. Reduced Casson yield stress—P data on purees of both particle sizes followd a single curve. Effects of pulp content and particle size on vane yield stress and apparent viscosity were evident from the correlation forms with high values of R².     

Effect of lecithin concentration on properties of sucrose-free chocolate masses sweetened with isomalt

Rheological properties such as Casson viscosity and yield value strongly affect costs and efficiency of the chocolate making process. The addition of a proper amount of lecithin to the blend of chocolate ingredients results in a decrease of both the aforementioned parameters. However, overdosing of lecithin leads to worse sensory attributes and flow properties of the chocolate mass. Our studies on rheological properties of isomalt-containing dark chocolate masses and sucrose-containing milk chocolate masses revealed that the critical lecithin concentration was 0.9 g/100 g; and the Casson yield value of both the types of chocolate blends was enhanced above this content. The same phenomenon, i.e. chocolate thickening, was observed at lecithin concentrations of 0.4 g/100 g and 0.6 g/100 g for milk chocolate masses sweetened with isomalt, and for dark chocolate masses sweetened with sucrose, respectively.     

Capillary Flow and Rheology Measurements on Chocolate Crumb/Sunflower Oil Mixtures

ABSTRACT: Rates of penetration of sunflower oil into beds of 3 types of chocolate crumb have been measured and the results analyzed using the Washburn-Rideal theory. The data show that the rates are a function of both the specific surface area of the crumb particles and their surface composition. Addition of an emulsifier to the oil reduces the penetration rate into the crumb made with full-cream milk powder, whereas for crumbs containing skimmed-milk powder, rates go through a maximum with increase of emulsifier concentration. Rheological data for dispersions of crumb in oil were fitted to the Casson equation. An inverse correlation was found between penetration rates and Casson yield values.     

In-Line Measurement of Rheological Parameters and Modeling of Apparent Wall Slip in Diced Tomato Suspensions Using Ultrasonics

ABSTRACT: Rheological behavior of a slurry consisting of 1- to 3-mm diced tomatoes suspended in tomato juice was evaluated by an in-line measurement method based upon ultrasonics. This technique permitted the measurements of yield stress, consistency index, and apparent wall slip. The suspension exhibited a yield stress at every flow rate studied, and its value was found to be 0.79 ±0.11 Pa. The shear viscosity at different shear rates was obtained in-line without assuming a specific constitutive equation. A comparison of Herschel-Bulkley, Power Law, Bingham Plastic, and Casson models showed that this suspension was best characterized with the Herschel-Bulkley model. The apparent wall slip region was successfully modeled as a Bingham fluid. This study shows the usefulness of this method for in-line characterization of particulate tomato products.