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.     

Flow Behavior of Milk Chocolate Melt and the Application to Coating Flow

ABSTRACT: The rheological properties of chocolate, especially shear viscosity and yield stress, are important control parameters for enrobing processes in confectionery manufacture. The rheological parameters of molten milk chocolate were measured at 42°C during steady pipe flow using a magnetic resonance imaging (MRI) viscometric method. The experimental method combines shear rate values obtained from an MR velocity image and shear stress values obtained from an independent pressure drop measurement. The experimental factors were emulsifier type and emulsifier level. The rheogram data were fit by the Casson model to yield the Casson yield stress and plastic viscosity. The Casson yield stress ranged from 1.9 to 15.0 Pa; the Casson viscosity ranged from 6.0 to 14.6 Pa s as a function of emulsifier content. The rheological parameters were incorporated into a drainage theory model to predict coating thicknesses in the enrobing process. The model was solved numerically and yielded good approximations to the experimental values that were between 1.1 to 2.7 mm.     

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.     

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.     

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.     

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.     

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.     

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.     

RHEOLOGICAL BEHAVIOR AND PHYSICOCHEMICAL CHARACTERISTICS OF GOLDENBERRY (PHYSALIS PERUVIANA) JUICE AS AFFECTED BY ENZYMATIC TREATMENT

Goldenberry (Physalis peruviana) juice was prepared and enzymatically treated with two dosages (300 and 600 ppm) of Pectinex Ultra SP‐L, then, the juice was concentrated to 30 and 40°Brix. Rheological properties of juices were studied at a wide range of temperatures (5 to 100C) and shear rate range from 0.3 to 100/s using Brookfield Digital Viscometer. The Herschel–Bulkley, Casson and Bingham rheological models were applied to describe the rheological properties of different juices. These properties are key parameters required to solve food industry problems in numerous areas such as quality control, evaluation of consumer acceptance and texture. The results indicated that juice concentrates behave as non‐Newtonian fluids (pseudoplastic) and have a definite yield stress. The Bingham and Casson, plastic viscosity, yield stress, consistency index and flow index decreased with increasing enzyme dosage and temperature. The effect of temperature on the viscosity described by means of an Arrhenius‐type equation. The activation energy for viscous flow depends on the total soluble solids. Moreover, sensory evaluation for juices was carried out. In consideration of industrial utilization, detailed knowledge on the rheological and physicochemical characteristics of cape gooseberry juice is of major importance.     

COMPARISON OF IN-LINE CONSISTENCY MEASUREMENT OF TOMATO CONCENTRATES USING ULTRASONICS AND CAPILLARY METHODS

This study focuses on the development of a noninvasive, in‐line rheometer using ultrasonics and its comparison with data from a traditional capillary viscometer. The ultrasonic based pointwise viscosity measurement technique combines a measurement of the velocity profile and the pressure drop to determine the shear rate and the shear stress distributions, respectively in a pipe. The experiments were carried out using tomato concentrates at 8.75%, 12.75%, and 17.10% total solids content. The flow system consisted of a 53.2 mm diameter acrylic tube, a positive displacement pump and two pressure transducers. Multiple shear viscosity‐shear rate data were recorded under actual pipeline conditions from a single combined measurement of the velocity profiles using ultrasonics and the pressure gradient, using the pressure transducers. The samples showed shear thinning behavior and a yield stress. Power law and Casson models were used to fit the data and both obtained R² values higher than 0.99. The yield stress was also directly determined from the velocity profiles. Shear viscosity versus shear rate data of the 12.75% total solids sample were obtained by capillary rheometry at four different flow rates. These showed very‐good agreement with those obtained using the velocity profile technique.     

RHEOLOGICAL BEHAVIOUR OF COCOA DISPERSIONS

The steady-shear viscosities of cocoa mass and cocoa suspensions were measured over a wide range of temperature and cocoa powder content. The effects of gasification, moisture and lecithin contents were also investigated. The viscosity of cocoa mass followed the Quemada or the Casson model. Both viscosity and yield stress decreased with increasing temperature. Degasification also lowered the viscosity and yield stress. The viscosity of concentrated cocoa suspension increased with increasing powder content and exhibited shear-thinning behaviour, and followed the Kreiger and Dougherty model. While the relative intrinsic viscosity was nearly constant, the maximum volume fraction increased with increasing shear stress or shear rate. Addition of moisture in suspension increased the viscosity due to partial gelation of starch; while addition of lecithin decreased the viscosity due to the lesser number of flocs in the suspension.     

AN ADAPTATION OF THE CASSON EQUATION FOR THE RHEOLOGY OF CHOCOLATE

The generalized Casson equation with exponent m was considered. The plastic viscosities and yield values corresponding to different ranges of shear rate D were calculated for different values of exponent m between 0.5 and 1. All the plastic viscosities tend to about the same value at high shear rates, while at low shear rates all the yield values tend to the same value which is supposed to be the "true" yield value. For the exponent m = 0.6, the yield value is least dependent on the shear rate range and the yield value calculated for D > 5 sec⁻¹ is generally much closer to the "true" yield value than the Casson value (m = 0.5). Therefore, choice of the exponent m = 0.6 is proposed.     

FLOW BEHAVIOR of COOKED MAIZE FLOUR SUSPENSIONS and APPLICABILITY of MATHEMATICAL MODELS

The shear-rate/shear-stress data of cooked maize flour suspensions were obtained using a concentric cylinder viscometer in the shear rate range of 3 and 1326 s⁻¹. the effects of concentration of maize flour (2–10%) in the cooked suspensions on yield stress, flow behavior index, consistency index and apparent viscosity, were investigated. Cooked maize flour suspensions were pseudoplastic in nature with yield stress. At flour concentrations above 6%, the experimentally determined yield stresses were lower than those calculated from different rheological models. the shear-rate/shear-stress data were examined using the rheological models: the power law, Bingham plastic, Casson, Costell-Duran, Herschel-Bulkley and Mizrahi-Berk models. the last two models were found to provide the best fit (r ≥ 0.991, p ≥ 0.01).     

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.     

糖对牛奶布丁流变性的影响

奉文采用哈克流变仪研究了不同质量分数下几种糖时鲜奶布丁体系的流变学性质,所用的糖质量分数依次为2%、4%、8%和16%,未著淀耢质量分数为6%. 结果表明:牛奶布丁是-种非宾汉塑性流体,测得的剪切速率和相应的剪切应力的关系符合Casson模型. 随着糖质量分数的提高,牛奶布丁的屈服应力、表观黏度和剪切应力均随糖质量分数的增大而增大.     

RHEOLOGICAL BEHAVIOR OF COCOA DISPERSIONS WITH COCOA BUTTER REPLACERS

The steady shear viscosity and yield stress of cocoa powder dispersed in three cocoa butter replacers (CBRs) are measured over a wide range of powder concentration and temperature. The flow activation energies of the three CBRs are nearly the same, and close to that of cocoa butter. Values of intrinsic viscosity of cocoa powder dispersed in corn oil and Socolate 36–38 are in the range of 4.0–5.0, (similar to that in cocoa butter), suggesting that these two CBRs are good cocoa replacers. A lower value of intrinsic viscosity is found for the powder dispersed in Super YZ-2. Viscosity measurements indicate that all three CBR dispersions exhibit Newtonian behavior at low volume fraction, but non-Newtonian shear thinning characteristics when the volume fraction φ > 0.3 at 60C. The non-Newtonian behavior can be described by the Casson model when φ exceeds a critical value, φ mo , the maximum packing fraction at zero shear. The yield stress can be related to the powder volume fraction using a four-parameter equation originally proposed by Zhou et al. (1995).     

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.     

FLOW BEHAVIOR AND FUNCTIONAL PROPERTIES OF MALT EXTRACT CONCENTRATES

Flow characteristics and functional properties of malt extract concentrates were investigated. Flow behavior was studied using a coaxial viscometer over shear rates of 0.6–145.8 s^-1. The shear rate-shear stress data followed the power law, Casson, Herschel-Bulkley and Bingham plastic models. Herschel-Bulkley values for flow behavior index which ranged from 0.73–0.94, and presence of yield stress indicated the Bingham plastic nature of malt extract concentrates. The activation energy of flow for various concentrates was in the range of 14.8–17.7 kcal/gmole. Magnitudes of Reynold numbers (0.0–49.9) for all concentrates were lower than 2100. Temperature, yield stress and plastic viscosity considerably influenced the flow of concentrates in straight pipes. The pressure drop and power requirements for flow of concentrates in pipes at 50°–60°C were lower than those at 30°C, but negligibly different from those at 80°C. Coefficients of correlation between the Bingham plastic values for pressure drop and yield stress (r = 0.86, P < 0.01), and plastic viscosity (r = 0.97, P < 0.01) were highly significant. Hulled barley and corn concentrates containing high amounts of reducing sugars, showed low viscosities and yield stresses, and required desirably low power for flow in pipes at 50°–60°C. The high protein concentrates of wheat and triticale malts showed high whip volume and good foam stability. Wheat concentrate was superior in fermentability. Hulless barley and finger millet malts produced concentrates with high viscosities which might facilitate their utilization in gums, candies and other such products.     

Food rheological studies using coaxial rotational and capillary extrusion rheometers

Abstract

The rheological constants of commercial sweetened condensed milk, mayonnaise, peanut butter, and tomato paste were obtained using the Hershel‐Bulkley and Casson models. Data using a coaxial rotational rheometer showed that the shear history (shear rate range 0 to 650 s^‐1) affected observed shear stress, and rheological constants. For the shear rate range 0 to 80 s^‐1, the rheological constants, using the capillary extrusion rheometer, were much lower than or similar to those obtained using the coaxial rotational rheometer. Both the Hershel‐Bulkley and the Casson models were equally suitable in predicting the relationships between shear stress and shear rate.