3rd International Symposium on Food Rheology and Structure

EFFECTS OF DIFFERENT EMULSIFIERS ON RHEOLOGICAL AND PHYSICAL PROPERTIES OF CHOCOLATE

Birgit Schantz, Lothar Linke, Harald Rohm
Institute of Food Technology and Bioprocess Engineering, Dresden University of Technology, D-01062 Dresden, Germany

ABSTRACT
The influence of several commercially available emulsifiers on the flow properties, crystallisation and solidification behaviour as well as on the physical stability of dark and whole milk chocolate was determined. The investigations partly showed a pronounced influence on viscosity and/or yield value of chocolate masses, depending on the type of emulsifier and its concentration, which was varied in a technological relevant range. Besides some effects on the crystallisation behaviour, the physical stability of filled chocolate was clearly influenced by the emulsifier in case of alcoholic aqueous fillings, whereas fat-based fillings were hardly affected by the emulsifier.

potential alternatives and standard lecithin on physical properties of fluid and solid chocolate products.

2 MATERIALS
A dark chocolate mass (D) containing 34 % fat and a whole milk chocolate (WM) with 31 % fat were manufactured without emulsifier addition. Several types of surface-active substances from different manufacturers were added to the base masses. Apart from lecithin (L), we used ammoniumphosphatide (YN), polyglycerol polyricinoleate (PGPR), sorbitan tristearate (STS) and mono- and diglycerides (MD), which are all permitted in Germany. Samples were prepared by adding a defined amount of emulsifier to a fixed quantity of base chocolate mass, followed by a defined manual mixing procedure [3].

1 INTRODUCTION
Emulsifiers added to melted chocolate tend to concentrate at the area between the liquid continuum (cacaobutter) and the solid phase, i.e., particles of sugar, cacao solids, and milk powder. Because of their special molecular structure and their lipophilic and hydrophilic functional groups, they are able to lower the interfacial tension between these components, and are known to affect a number of properties of the suspension, e.g., rheology, the sensitivity to moisture and temperature, and tempering behaviour. Furthermore, the addition of emulsifiers may presumably influence properties such as bloom, the stability against fillings, and oxidisation [1, 2]. However, the main advantage of emulsifier application in chocolate is the improvement of flow parameters, thus allowing to minimise cacaobutter addition and to reduce production costs. The function of lecithin as the most commonly used emulsifier in chocolate technology has been extensively studied. Since 1998, some more surfaceactive components have been approved for the use in chocolate by German legislation. The aim of the current study was to compare the effects of

3 EXPERIMENTAL RESULTS
3.1 Determination of flow curves It is well known that the addition of different types and amounts of emulsifiers leads to chocolate masses showing a wide spectrum of flow properties. Therefore, a method of measurement applicable to all chocolate systems had to be developed. Viscosity measurements were carried out at 40C with a UM rheometer (PHYSICA Messtechnik GmbH, Germany) in a controlled shear rate rotation mode using a Z3 DIN concentric cylinder measuring geometry. After 5 min of pre-shearing -1 -1 at 200 s and 150 s for dark chocolate and whole milk chocolate, respectively, shear rate was -1 reduced to 0.1 s within 10 min in a logarithmic ramp, and the corresponding flow curves were recorded. Due to the largely different shapes of the flow curves, the calculation of equilibrium viscosity and yield stress by a uniform mathematical model did

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not lead to reasonable results. However, reliable results require the equal handling of all data series with a uniform modelling method. Therefore, additional data were collected during 1 min after the pre-shearing period as well as during 1 min at the -1 minimum shear rate of 0.1 s , thus allowing a direct estimation of viscosity and yield stress. In case of masses with a very high viscosity, yield stress was determined from the bending point in the flow curves. Generally, both dark chocolate and whole milk chocolate showed a similar qualitative response with respect to type and concentration of the added emulsifying agent. Quantitative differences between D- and WM-systems, observed for viscosities and yield values, are obviously attributable to the different fat contents and, hence, flow properties of the emulsifier-free base masses.
Viscosity [Pa.s]

reduction of yield stress appeared in masses made by addition with PGPR (90 %), followed by L and YN-masses (60 %), whereas STS and MD showed only minor effects on the yield stress. In case of deoiled lecithin with a higher relative amount of surface-active groups, a significant yield stress minimum was observed at an emulsifier concentration of 0.2 % (results not shown).
Yield Stress [Pa]

40

30

20

10

L YN PGPR MD STS 0.0 0.1 0.2 0.3 0.4 0.5 0.6

Emulsifier concentration [%]

Figure 2: Effects of selected emulsifiers on the yield

3 L YN PGPR MD STS

stress of dark chocolate. L, lecithin; YN, ammoniumphosphatide; PGPR, polyglycerol polyricinoleate; MD, mono- and diglycerides; STS, sorbitan tristearate.

0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 Emulsifier concentration [%]

Figure 1: Effects of selected emulsifiers on the viscosity of dark chocolate. L, lecithin; YN, ammoniumphosphatide; PGPR, polyglycerol polyricinoleate; MD, monoand diglycerides; STS, sorbitan tristearate.

Figures 1 and 2 depict the rheological efficiency of selected emulsifiers in dark chocolate mass. As compared to melted chocolate without emulsifier, the reduction of apparent viscosity was highest after addition of lecithin and YN, followed by PGPR. At an emulsifier concentration of 0.4 %, which is most commonly used in chocolate technology, the relative reduction of viscosity was approx. 40 % for emulsifiers L and YN, 30 % for PGPR and about 10 % for MD and STS. Again based on a 0.4 % concentration level, the highest

3.2 Crystallisation The process of pre-crystallisation and, consequently, the following solidification of chocolate is partly shear-induced and, therefore, affected by the rheological properties of the processed mass [4, 5]. Since emulsifiers heavily influence the flow properties of melted chocolate, it is difficult to distinguish between rheologically caused effects and effects caused by the emulsifier as a substance. To answer the question whether the emulsifier itself affects crystallisation, it is necessary to eliminate shear flow as a factor of influence. Consequently, stationary pre-crystallisation with manual torque adaption was applied by using a RHEOSYST 5000 (Coesfeld GmbH, Germany), defining the torque profile during pre-crystallisation of lecithinated chocolate under fixed mixing and temperature conditions as standard. The investigation was carried out only with alternative emulsifiers (PGPR, YN) that proved to be rheological active at a concentration of 0.4 %. Rotation speed for YN

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and PGPR-chocolate pre-crystallisation was appropriately changed to approach these torque profiles, allowing to compare seed-forming time and complete crystallisation time. In a second trial, the controlled-torque method was applied to determine an optimum re-heating temperature at the end of the pre-crystallisation process. This temperature can be estimated by taking samples of chocolate at several end temperatures, and by visually assessing the solidified product with respect to demoulding, appearance and gloss. Based on visual inspection, the samples were classified in 5 groups: Strongly under-crystallised Under-crystallised Optimum Over-crystallised Strongly over-crystallised Whereas only minor rotation speed corrections were necessary for YN-chocolate, PGPR-masses had to be crystallised with noticeable lower revolution as compared to standard L-masses. This is attributable to the higher viscosity values of chocolate made with PGPR, resulting in a higher torque during mixing. Figure 3 shows the seed-forming and crystallisation times of dark and whole milk chocolate prepared with different emulsifiers. PGPR-chocolate tends towards faster seed-forming, and shorter crystallisation times might be an indicator for enhanced susceptibility to over-crystallisation.
Time [min] 120
Seed-Forming Crystallisation

This behaviour was confirmed by the results of the second trial (Figure 4): higher re-heating temperatures were required for PGPR-chocolate than for lecithin masses to achieve optimum quality. This tendency appears even in chocolates prepared with an 0.2 % / 0.2 % mixture of lecithin and PGPR. Consequently, the influence of the type of emulsifier on the crystallisation behaviour of chocolate is clearly evident [6, 7].

L YN L/PGPR PGPR

L 5 YN L/PGPR PGPR 30 32 34 36 4 3 2 1

38

Re-heating temperature [C]

Figure 4: Re-heating temperature of dark chocolate (upper fgigure) and whole milk chocolate (lower figure). L, lecithin; YN, ammoniumphosphatide; PGPR, polyglycerol polyricinoleate; L/PGPR, mixture of L and PGPR. Classification of results: 1, strongly under-crystallised; 2, under-crystallised; 3, optimum; 3, over-crystallised, 5, stongly over-crystallised.

90

60

30

YN

PGPR

YN

PGPR

Dark chocolate

Whole milk chocolate

Figure 3: Seed-forming time and crystallisation time of chocolate masses as affected by the emulsifier. L, lecithin; YN, ammoniumphosphatide; PGPR, polyglycerol polyricinoleate.

3.3 Physical shelf life Among the reasons for the quality loss of filled chocolate products during storage are interactions at the interface between the chocolate cover and the filling, presumably resulting in deterioration of gloss, stability and taste. It is of high economical interest to know whether emulsifiers are able to improve the resistance of chocolate against the fillings. In our study, we used a standard brandy filling (65 % sugar content, 17,5 % ethanol) and sunflower oil as representative examples for an aqueous alcoholic filling and a fat-based filling, respectively.

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The experiments were performed with D and WM chocolate masses with 0.4 % of the emulsifiers L, YN, PGPR, and a L/PGPR-mixture (0.2 % each). The reverse model method was used to achieve reliable results within a short period of time [8]. Cylindrical samples of chocolate were placed in beakers containing the filling material and stored at 26 C (brandy filling) or 18 C (sunflower oil). The firmness of the chocolate cylinders was measured in intervals of 7 days by means of a penetration method, using a 27 stainless steel cone with a total mass of 22 g.
Penetration depth [mm] 12
L YN L/PGPR PGPR L YN L/PGPR PGPR

Penetration depth [mm] 20

15

10

0 0 10 20 30 40 50 60

L YN L/PGPR PGPR L YN L/PGPR PGPR

70

Storage time [d]

Figure 6: Structure loss of chocolate in sunflower oil as affected by emulsifier type and storage time. Closed symbols, dark chocolate; open symbols, whole milk chocolate. L, lecithin; YN, ammoniumphosphatide; PGPR, polyglycerol polyricinoleate; L/PGPR, mixture of L and PGPR.

0 0 10 20 30 40 50 Storage time [d] 60 70

Figure 5: Structure loss of chocolate in alcoholic fillings as affected by emulsifier type and storage time. Closed symbols, dark chocolate; open symbols, whole milk chocolate. L, lecithin; YN, ammoniumphosphatide; PGPR, polyglycerol polyricinoleate; L/PGPR, mixture of L and PGPR.

Fat based fillings interact with the covering chocolate obviously by another principle as the continuous cacaobutter phase is affected rather than sugar, cacao solids, and milk particles. Figure 6 depicts structure loss of dark and whole milk chocolate as a function of storage time in sunflower oil. Obviously, neither the type of the emulsifier nor the type of chocolate are relevant factors for sample decomposition.

CONCLUSIONS
The efficiency of some commercially available emulsifiers as well as of some mixtures thereof was investigated by using two base chocolate recipes. Different contributions of both type and concentration of the emulsifier to the rheological properties of chocolate masses allow producers to adjust processing parameters to their specific needs. The findings indicate that, if necessary, the commonly used emulsifier lecithin may easily be substituted by alternative products. In addition to the influence on viscosity and yield stress, emulsifiers also show effects on the crystallisation process. Therefore, manufacturers should take into account that pre-crystallisation profiles and, consequently, solidification times are affected by the emulsifying agent. As regards filled chocolate products, physical shelf life expressed

It is obvious from Figure 5 that, for both dark chocolate and whole milk chocolate, the type of emulsifier largely determines the stability against alcoholic fillings. Evidently, masses made with addition of lecithin, showing a more polar molecular structure than YN and PGPR, are less resistant to diffusion of aqueous filling compounds into chocolate, consequently showing an enhanced stability loss than masses made by addition of synthetic emulsifiers such as YN and PGPR. Reduced stability was also observed when using lecithin in combination with PGPR. Additionally, milk components significantly decreased stability losses during storage.

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in terms of stability towards phase exchanges is one of the most important consumer-relevant properties. Differences caused by the type of emulsifier can be explained by interactions between chocolate and filling.

[4]

[5]

ACKNOWLEDGEMENTS
This study was granted by Arbeitsgemeinschaft industrieller Forschungsvereinigungen (AiF) via Forschungskreis der Ernhrungsindustrie (FEI) as AiF-FV 11794. The authors would like to thank Deutsche Forschungsanstalt fr Lebensmittelchemie (DFA, Munich) and the involved companies for supplying material and helpful discussions. [6]

[7]

[8]

REFERENCES
[1] G. Schuster, Emulgatoren in Lebensmitteln. Berlin, Heidelberg: Springer Verlag, Akademie Verlag, 1985. G. L. Hasenhuettl and R. W. Hartel, Food Emulsifiers and Their Applications. New York: Chapmann & Hall, 1997. B. Schantz, L. Linke, A. Setrdle, and P. Khler, Zur Wirkung handelsblicher Emulgatoren auf die rheologischen Eigenschaften flssiger Schokoladenmassen I, II, Zucker- und Swarenwirtschaft, vol. 54, pp. 30-32, 36-38, 2001.

G. Ziegleder, Kristallisation von Kakaobutter und Schokoladenmassen, presented at II. International Congress on Cocoa and Chocolate, Munich, 1991. Y. Zeng, Impf- und Scherkristallisation von Schokoladen, in Institute of Food Science. Zrich: ETH, 2000, pp. 167. B. Schantz and L. Linke, Der Einfluss von Emulgatoren auf das Kristallisationsverhalten, Zucker- und Swarenwirtschaft, vol. 54, pp. 20-22, 2001. B. Schantz and L. Linke, Messmethoden fr Erstarrung und Kontraktion, Zuckerund Swarenwirtschaft, vol. 54, pp. 1517, 2001. I. Tralles, H. Miertsch, L. Linke, and E. Markov, Alkoholgefllte Pralinen-Messmethoden zur Qualittskennzeichnung I, II, Swaren, vol. 40, pp. 68-73, 32-39, 1996.

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