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.     

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.     

Relationship between rheological,textural and melting properties of dark chocolate as influenced by particle size distribution and composition

In dark chocolate, rheological properties during processing are influenced by particle size distribution (PSD), fat and lecithin contents with consequential effects on finished texture and melting characteristics. Multivariate regression, correlation and principal component analyses (PCA) were used to explore their interrelationships. A 4 × 3 × 2 factorial experiment was conducted with varying PSD [D ₉₀ (90% finer than this size) of 18, 25, 35 and 50 μm], fat (25, 30 and 35%) and lecithin (0.3 and 0.5%). Rheological properties (yield stress and apparent viscosity), textural properties (firmness, index of viscosity and hardness) and melting index (duration) were respectively measured using shear rate-controlled rheometer, TA.HD Plus texture analyzer and differential scanning calorimetry. The PSD, fat and lecithin contents significantly influenced all rheological, textural properties and some melting characteristics. Increasing particles sizes reduced yield stress, apparent viscosity, firmness, index of viscosity, hardness and melting index of products with greatest influence with 25% fat and 0.3% lecithin, reduced with increasing fat and lecithin contents. There were high correlation (r = 0.78–0.99) and regression coefficients (R ² = 0.59–0.99) among the rheological, textural and melting index indicating their high inter-relationships. In PCA, the rheological, textural and melting index accounted for >95% variance in the data.     

Modelling tempering behaviour of dark chocolates from varying particle size distribution and fat content using response surface methodology

Central Composite Rotatable Design (CCRD) for K = 2 was used to study the combined effects of multi-stage heat exchangers for Stages 1 (14–30 °C) and 2 (12–28 °C) coolant temperatures at constant Stage 3 coolant and holding temperatures during tempering of dark chocolates using laboratory-scale mini-temperer. Quantitative data on chocolate temper index (slope) were obtained for products with varying particle size distribution (PSD) (D₉₀ of 18, 25, 35 and 50 μm) and fat (30% and 35%) content. Regression models generated using stepwise regression analyses were used to plot response surface curves, to study the tempering behaviour of products. The results showed that both Stage 1 and Stage 2 coolant temperatures had significant linear and quadratic effects on the crystallization behaviour causing wide variations in chocolate temper index during tempering of products with variable PSD and fat content. Differences in fat content exerted the greatest variability in temperature settings of the different zones for attaining well-tempered products. At 35% fat content, changes in PSD caused only slight and insignificant effect on tempering behaviour. No unique set of conditions was found to achieve good temper in dark chocolate with a specified tempering unit. Thus, different combinations of temperatures could be employed between the multi-stage heat exchangers to induce nucleation and growth of stable fat crystal polymorphs during tempering. Variations in tempering outcomes of the dark chocolates were dependent more on the fat content than PSD.

Industrial relevance

Tempering consists of shearing chocolate mass at controlled temperatures to promote cocoa butter crystallization in a stable polymorphic form. During industrial processing, multi-stage heat exchangers are used to control temperature adjustments to promote formation of appropriate stable polymorphic crystals to obtain products with good snap, colour, contraction, gloss and shelf life characteristics. The process employs varying time–temperature throughputs of the multi-stage units making it difficult to obtain standard tempering conditions for products with variable particle sizes and fat content, thus prolonging equipment standardization periods with consequential effects on processing times and product quality characteristics. Modelling the tempering behaviour of dark chocolates from varying PSD and fat content would enhance our knowledge and understanding on the optimal temperature conditions for obtaining good tempered products during industrial manufacture, with significance for reducing processing (tempering) times and assurances in quality and shelf characteristics.     

Effects of selected properties of ultrafiltered spray-dried milk powders on some properties of chocolate

The effects of selected properties of spray-dried milk fat powders on chocolate were determined. Milk powders produced from control or ultrafiltered (UF) milks with various levels of fat were blended with skim milk powder to give a standard 26 g fat 100 g⁻¹ powder. Particle size of the chocolate mixes after refining decreased as the fat content and free-fat content of the powders increased. Despite this, increasing fat and free-fat contents of powders reduced the Casson viscosity of the subsequent molten chocolates. Casson viscosities using powders from control or UF milks were similar, but decreased as the particle size of powders increased and particle size after refining the chocolate mix decreased. Casson yield value and hardness decreased as fat content of powders increased. Casson yield value increased with vacuole volume of powders. It is possible to alter important properties of chocolates using milk powders of varying fat contents, free-fat contents and particle sizes.     

Monitoring Tempered Dark Chocolate Using Ultrasonic Spectrometry

Ultrasonic spectrometry was used to distinguish between properly tempered and untempered commercial dark chocolate. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were used to characterize the polymorphic state of tempered and untempered chocolate, results that were correlated to those of ultrasonic spectrometry. Four different kinds of dark chocolate samples with different amounts of sugar (7.5–50 %), fat (30–50 %), and cocoa mass (70–90 %) were subjected to two different tempering protocols. The tempering was achieved using cocoa butter seeds under static cooling from 50 to 14 °C. The ultrasonic generator and analyzer SIA-7 (V.N. Instruments) was used to monitor the crystallization process. The instrument generated a chirp signal with a bandwidth of 0.5 to 3 MHz and was set to work in a four-pathway configuration with two transducers and a center frequency of 2.25 MHz. Spectrometric analysis was carried out with chocolate samples containing 2, 4, and 6 % solid fat content (SFC). The SFC was obtained from DSC measurements. Ultrasonic signals for attenuation, reflection, and velocity were compared between tempered and untempered chocolates. It was shown that seed-tempered chocolate with 30 % sugar and 47.5 % fat attenuated 2.5 MHz of ultrasonic waves by 0.8, 1.7, and 2.0 dB/cm at 2, 4, and 6 % SFC, respectively. On the other hand, untempered chocolate attenuated the ultrasound signal by 3.5, 3.6, and 4.3 dB/cm. Furthermore, it was found that ultrasound reflection signals were stronger and ultrasonic velocity was higher in chocolates with high sugar content.     

Functionality of inulin and polydextrose as sucrose replacers in sugar‐free dark chocolate manufacture – effect of fat content and bulk mixture concentration on rheological,mechanical and melting properties

Inulin and polydextrose are key bulk sugar replacers and have been utilised extensively as functional ingredients due to their fibre and prebiotic claims. This study investigated effects of fat content and bulk mixture concentrations of inulin and polydextrose on rheological properties, mechanical and melting characteristics of sugar‐free dark chocolates sweetened with steviol glycosides. Sucrose was replaced with polydextrose and inulin (0:100, 25:75, 50:50, 75:25, 100:0) at different fat contents (27%, 30% and 33%). Reducing fat content from 33% to 27% had similar effects on the sugar‐free dark chocolates as it did on reference chocolate. Increasing inulin concentrations with simultaneous reduction in polydextrose resulted in consistent increases in Casson plastic viscosity and decreases in Casson yield stress regardless of the fat content. These were explained by microstructural examination of the sugar replacers, which revealed wide variations in network structure. Understanding these factors would help reduce energy load from fat in sugar‐free chocolate confectionery.     

The application of Borneo tallow in dark chocolate shell

Dark chocolate shells, formulated using cocoa butter (CB shell), and fat blends containing 15% Borneo tallow (IP) in cocoa butter (CBIP shell), were filled with truffles formulated using white chocolate (W truffle), milk chocolate (M truffle) and dark chocolate (D truffle). Anhydrous milk fat (AMF) content of the W truffles, M truffle and D truffle were 26·3%, 13·7% and 9·2%, respectively. Degree of tempering was determined using a tempermeter. The chocolates were kept at ambient temperature (25·5±0·5°C) for 3 months. Physical changes of chocolate shells and centres were monitored using DSC and a texture analyser. Results showed that the CBIP shell had to be tempered at 32·5%, ie 1°C higher than the normal CB shell. Physical measurements indicated the occurrence of fat migration. The presence of IP reduced the effect and increased the bloom resistance of the chocolate. © 1998 SCI.     

Partitioning of Printing Ink Solvents on Chocolate

Partitioning (Kp) of printing ink solvents was studied in three types of chocolate with different fat content and degrees of crystallinity. At 25°C, chocolate liquor (48% fat and medium crystallinity) showed a higher Kp than chips (25% fat and higher crystallinity), but cream (29% fat and lowest crystallinity) showed the highest Kp. Order appeared to depend on degree of crystallinity. At 35°C and 45°C as samples became increasingly molten, effect of crystallinity diminished and order of increasing Kp depended on fat content. Kp order of solvents was the same in all chocolates and temperatures: toluene > isopropanol > methyl ethyl ketone > ethyl acetate > hexane in accord with Hildebrand solubility parameter differences.     

Impact of particle size distribution on rheological and textural properties of chocolate models with reduced fat content

ABSTRACT:  With an increasing consumption of lipids nowadays, decreasing the fat content in food products has become a trend. Chocolate is a fat-based suspension that contains about 30%wt fat. Reducing fat content causes an increase in the molten chocolate viscosity. This leads to 2 major issues: difficulties in the process and a loss of eating quality in the final product, reported to have poor in-mouth melting properties, remain hard, and difficult to swallow. Literature shows that optimizing the particle size distribution (PSD), that is, having one with an increased packing fraction, can decrease the viscosity of highly concentrated suspensions. This study focuses on the impact of the PSD and fat content on the rheological properties, melting behavior, and hardness of chocolate models (dispersions of sugar in fat). We show that optimizing the PSD while reducing the fat content to a critical amount (22%wt) can decrease the viscosity of the molten material and reduce the hardness of the crystallized chocolate models. Melting in the mouth, characterized by an in vitro collapse speed, is faster for the samples with an optimized PSD. The decrease in the viscosity by optimizing the PSD in systems with a constant fraction of medium phase is based on the decrease of interparticle contact, reducing the particle aggregates strength, and structure buildup during flow or meltdown. In its crystallized state, the particle network is less interconnected, providing less resistance to breakage and meltdown.     

Ethylcellulose solvent substitution method of preparing heat resistant chocolate

In the present study a structuring technique was developed to produce chocolate which resists deformation at temperatures above 40 °C. It was hypothesized that by adding ethylcellulose (EC) solubilized in ethanol (EtOH) to chocolate and evaporating the EtOH an organogel could be formed in situ with the fat phase of the chocolate. Heat resistant chocolate (HRC) was produced by mixing a 20% EC in EtOH solution with molten chocolate. The EtOH was evaporated and the resulting chocolate was incubated at 40 °C for 2 h and tested for hardness. The effect of various EC viscosities (4, 10, 20, 22, and 45 cP) and concentrations ranging from 1.0 to 2.2% on different types of chocolates was studied. Milk chocolate containing 1.9% EC had a hardness of 26.0 N whereas the control chocolate was too soft to be tested. Further experiments revealed that white and dark chocolates had hardnesses of 29.5 and 10.5 N, respectively. The hardness of the chocolate was dependent on the chocolate formulation and concentration of EC, and independent of EC viscosity. It was observed that the addition and evaporation of EtOH from the compound milk chocolate samples led to an increase in the lightness of the chocolate surface if the EtOH was evaporated at temperatures of 40 °C or higher. Addition of EC to chocolate represents a new strategy for the manufacture of HRC. Future work should focus on determining the mechanism by which heat resistance is achieved in these chocolates.     

Thickening of molten white chocolates during storage

When white chocolates are kept molten in storage tanks, problems can arise due to uncontrolled thickening and solidifying of the chocolate mass. The thickening of molten white chocolate was simulated on a laboratory scale using a rotational rheometer under static conditions, interrupted by short shear periods to measure the increasing viscosity. Several chocolates having different dairy components and fat contents were investigated for their tendency to thicken. In addition, sorption isotherms for white chocolates were obtained using Dynamic Vapour Sorption at different temperatures. The sorption isotherms showed the presence of amorphous lactose in all the chocolates that were manufactured from milk powders. Moisture that is released during the crystallisation of amorphous lactose causes stickiness and agglomeration of the neighbouring particles and starts the thickening process. This process is highly temperature-dependent. On elevating the temperature the lactose crystallisation occurs at lower relative humidities. In order to reduce the tendency of white chocolate to thicken, a high free fat level should be maintained, based on a high total fat content and on the use of high free fat milk powders, preferably roller-dried whole milk powders or the combination of skimmed milk powder and anhydrous milk fat.     

Physical and Sensory Properties of Milk Chocolate Formulated with Anhydrous Milk Fat Fractions

Maximum additions of milk fat that produced temperable milk chocolates were anhydrous milk fat (AMF), middle-melting fraction (MMF) or low-melting fraction (LMF) up to 40 wt % total fat, and high-melting fraction (HMF) up to 35%. The solid fat content (SFC), melting point, melting enthalpy, instrumental and sensory hardness of milk chocolates decreased with increasing milk fat addition. No differences in sensory attributes sweetness, milk powder, chocolate, butter flavor or thickness of melt were observed. Chocolate with 40% MMF or LMF had greater milk flavor than that with 12.2% HMF. Onset of melt correlated (r = 0.96) with melting enthalpy. No differences between types of milk fat (AMF, HMF, MMF, LMF) were observed for any textural attribute assessed.     

Stability and Photochemistry of Vitamin D2 in Model System

Oxidation of vitamin D₂ in a model system of 12% water and 88% acetone in the presence of 15 ppm riboflavin under light and dark was studied by measuring the depleted headspace oxygen. Riboflavin accelerated the oxidation of vitamin D₂ by singlet oxygen under light, but did not affect the vitamin D₂ oxidation under dark. The effect of 0 and 15 ppm riboflavin on the stability of vitamin D₂ during storage at 25 and 60°C was studied by measuring the contents of vitamin D₂ during 48h. Results indicated that photosensitized singlet oxygen oxidation of vitamin D₂ under light was temperature-independent, and triplet oxygen oxidation of vitamin D₂ both under light and in the dark was temperature-dependent.     

Effect of cocoa butter replacement with a β‐glucan‐rich hydrocolloid (C‐trim30) on the rheological and tribological properties of chocolates

BACKGROUND: The food industry has been facing the challenge of developing low‐fat and low‐calorie food products due to rising health awareness of consumers. To meet this consumer demand, an oat β‐glucan‐rich hydrocolloid (C‐trim30) was evaluated as a cocoa butter substitute in chocolates. The effects of C‐trim30 on the rheological, tribological, and textural properties of chocolates were investigated. RESULTS: The viscosity of molten chocolates increased with increasing levels of C‐trim30. Flow behaviors analyzed using the Casson model showed that the Casson viscosity and yield stress increased with increasing concentration of C‐trim30 in the chocolate. Tribological tests on a ball‐on‐flat tribometer showed a reduction in boundary coefficients of friction, with increasing C‐trim30. In addition, hardness of chocolates showed that replacement of cocoa butter with C‐trim30 produced chocolates with softer texture. CONCLUSIONS: The cocoa butter replacement with C‐trim30 up to 10% produced soft chocolates with improved boundary lubrication properties. Also, the chocolate prepared by replacing the cocoa butter with C‐trim30 resulted in a product with a lower caloric value and increased health benefits from the oat β‐glucan. Copyright © 2008 Society of Chemical Industry     

Thickening of molten white chocolates during storage

When white chocolates are kept molten in storage tanks, problems can arise due to uncontrolled thickening and solidifying of the chocolate mass. The thickening of molten white chocolate was simulated on a laboratory scale using a rotational rheometer under static conditions, interrupted by short shear periods to measure the increasing viscosity. Several chocolates having different dairy components and fat contents were investigated for their tendency to thicken. In addition, sorption isotherms for white chocolates were obtained using dynamic vapour sorption at different temperatures. The sorption isotherms showed the presence of amorphous lactose in all the chocolates that were manufactured from milk powders. Moisture that is released during the crystallization of amorphous lactose causes stickiness and agglomeration of the neighbouring particles and starts the thickening process. This process is highly temperature-dependent. On elevating the temperature the lactose crystallization occurs at lower relative humidities. In order to reduce the tendency of white chocolate to thicken, a high free-fat level should be maintained, based on a high total fat content and on the use of high free-fat milk powders, preferably roller-dried whole milk powders or the combination of skimmed milk powder and anhydrous milk fat.     

The role of particle size distribution of suspended solids in defining the flow properties of milk chocolate

The flow characteristics of molten milk chocolate, like most dense suspensions, are a function of the maximum packing fraction ((_m) of the suspended solids. Milk chocolates were prepared from mixtures of two relatively narrow coarse (d_4,3 = 17 μm) and fine (d₄,₃ = 8.5 μm) size distributions of non‐fat solids to contain 0, 25, 50, 75, and 100% of the coarse component. Solids bed density (a measure of maximum packing fraction) correlated with the apparent viscosity of milk chocolates (r = ‐0.98). The highest value for solids bed density and lowest value for apparent viscosity were measured for size distributions with 75% of solids from the coarse fraction. Casson yield value correlated with d_4,3 (r = ‐0.98) and specific surface area (r = 0.93). The maximum packing fraction of binary mixtures of two distinct sizes of non‐fat chocolate solids attained a maximum value for a specific volume ratio of the components. The maximum in _m corresponded with the minimum viscosity in molten chocolate at a given solids volume concentration.     

Structural characteristics of cocoa particles and their effect on the viscosity of reduced fat chocolate

Aimed at the manufacture of reduced fat chocolates, a novel method of trapped fat reduction was assessed: Manipulation of the cocoa ingredient. Cocoa mass was replaced with cocoa powder (11 g/100 g or <1 g/100 g fat) and added ‘free’ cocoa butter. A cocoa solids approach to design reduced fat chocolates with satisfactory flow properties is attractive to industry since it circumvents introduction of ingredients not commonly used in chocolate manufacture. Results showed that the cocoa mass chocolate had a higher viscosity than cocoa powder chocolates of the same total fat content due to the presence of trapped fat globules as identified by confocal laser scanning microscopy. The chocolate prepared with standard defatted cocoa powder containing 11 g/100 g fat had a lower viscosity than the chocolate containing highly defatted cocoa powder (<1 g/100 g) due to particle shape and fat diffusion into the particles as revealed by microscopy analyses. Based on the evidence presented, it can be concluded that standard defatted cocoa powder, as widely used by the industry, is indeed the best compromise in terms of free fat, particle size and morphology attempting to formulate fat reduced chocolate of acceptable molten state viscosity.     

Dark chocolates supplemented with <Emphasis Type="Italic">Lactobacillus</Emphasis> strains

Dark chocolate masses and chocolates were supplemented with viable cells of two bacterial strains Lactobacillus caseii and Lactobacillus paracasei with potential probiotic properties, which were lyophilized in milk. Total number of live bacteria in the lyophilizate was 7.9×10⁹ cfu/g. Sucrose or isomalt and aspartame were used as bulking substances and sweeteners. Sensory attributes of these chocolates were not different from that of traditional chocolates. Calorie value of sucrose-free chocolate was lower by approximately 11.1–14.6% (dependent on their formulation) relative to chocolate sweetened with sucrose. Chocolate, which contains isomalt and aspartame can be consumed by diabetics. Numbers of live L. casei and L. paracasei cells in the examined batches of chocolate were very high and approached 10⁶–10⁷ cfu/g after 12 months of keeping at 4 and 18 °C. Neither the texture nor the total and volatile acidity of chocolate masses were changed by addition of the lyophilized preparation of Lactobacillus cells. Casson yield values of dark sucrose-free chocolate masses supplemented with this lyophilizate were decreased by approximately 3–55% (dependently on fat contents in these masses) as compared to that of analogous chocolate masses sweetened with sucrose.     

EFFECTS OF CONCHING TIME AND INGREDIENTS ON PREFERENCE OF MILK CHOCOLATE

The objective of this study is to determine how the conching time and the quantity of sucrose, lecithin, cocoa butter and whole milk powder affect consumer preference for milk chocolate. Untrained panelists performed a sensory study consisting of acceptability, preference and attribute intensity. Longer conching time produced significantly smoother chocolate with smaller particle size. The longest conche times had the smallest particle size and were the most mouthcoating. There was no change in flavor with conching. The longer conche times were preferred. Panelists preferred higher sucrose levels, and increasing sucrose decreased bitterness and increased chocolate flavor. Increasing lecithin increased smoothness, but less lecithin was preferred, possibly due to off-flavors at high levels of lecithin. Increasing cocoa butter yielded softer chocolate but did not affect bitterness. Panelists preferred 10% over higher levels of cocoa butter. More milk powder produced smoother chocolate with more caramel flavor and was preferred.

PRACTICAL APPLICATIONS

The perceived quality of milk chocolate is affected by conching time, sucrose, lecithin, cocoa butter and whole milk powder. Texture was affected the most by conching, milk powder, lecithin and cocoa butter. Flavor was affected the most by milk powder and sugar. The only variable that did not affect acceptability and preference of milk chocolate was time for underconched samples. While this study did not determine the optimum conditions for milk chocolate, the most preferred and/or acceptable samples were conched for at least 12 h, had 35 to 50% sucrose, 0–0.5% lecithin, 5–10% cocoa butter and 13–30% milk powder.