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International Symposium on Food Rheology and Structure
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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 emulsi-
fiers on the flow properties, crystallisation and solidifi-
cation 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, de-
pending 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 in-
fluenced by the emulsifier in case of alcoholic aqueous
fillings, whereas fat-based fillings were hardly affected
by the emulsifier.
1 INTRODUCTION
Emulsifiers added to melted chocolate tend to
concentrate at the area between the liquid contin-
uum (cacaobutter) and the solid phase, i.e., parti-
cles of sugar, cacao solids, and milk powder. Be-
cause 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 temper-
ature, 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 appli-
cation 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 ex-
tensively studied. Since 1998, some more surface-
active components have been approved for the
use in chocolate by German legislation. The aim
of the current study was to compare the effects of
potential alternatives and standard lecithin on phy-
sical properties of fluid and solid chocolate prod-
ucts.
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 ammon-
iumphosphatide (YN), polyglycerol polyricinoleate
(PGPR), sorbitan tristearate (STS) and mono- and
diglycerides (MD), which are all permitted in Ger-
many. Samples were prepared by adding a de-
fined amount of emulsifier to a fixed quantity of
base chocolate mass, followed by a defined man-
ual mixing procedure [3].
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 proper-
ties. Therefore, a method of measurement appli-
cable to all chocolate systems had to be devel-
oped.
Viscosity measurements were carried out at 40C
with a UM rheometer (PHYSICA Messtechnik
GmbH, Germany) in a controlled shear rate rota-
tion mode using a Z3 DIN concentric cylinder
measuring geometry. After 5 min of pre-shearing
at 200 s
-1
and 150 s
-1
for dark chocolate and
whole milk chocolate, respectively, shear rate was
reduced to 0.1 s
-1
within 10 min in a logarithmic
ramp, and the corresponding flow curves were re-
corded.
Due to the largely different shapes of the flow cur-
ves, 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, addi-
tional data were collected during 1 min after the
pre-shearing period as well as during 1 min at the
minimum shear rate of 0.1 s
-1
, 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 ad-
ded emulsifying agent. Quantitative differences
between D- and WM-systems, observed for visco-
sities and yield values, are obviously attributable to
the different fat contents and, hence, flow
properties of the emulsifier-free base masses.

Figure 1: Effects of selected emulsifiers on the viscosity
of dark chocolate. L, lecithin; YN, ammoniumphospha-
tide; PGPR, polyglycerol polyricinoleate; MD, mono-
and 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 tech-
nology, 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
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 emulsi-
fier concentration of 0.2 % (results not shown).
Figure 2: Effects of selected emulsifiers on the yield
stress of dark chocolate. L, lecithin; YN, ammonium-
phosphatide; PGPR, polyglycerol polyricinoleate; MD,
mono- and diglycerides; STS, sorbitan tristearate.

3.2 Crystallisation
The process of pre-crystallisation and, consequen-
tly, 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 elim-
inate shear flow as a factor of influence. Conse-
quently, stationary pre-crystallisation with manual
torque adaption was applied by using a RHEO-
SYST 5000 (Coesfeld GmbH, Germany), defining
the torque profile during pre-crystallisation of leci-
thinated chocolate under fixed mixing and temper-
ature 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
0
1
2
3
4
Viscosity [Pa.s]
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Emulsifier concentration [%]
L
YN
PGPR
MD
STS
0
10
20
30
40
Yield Stress [Pa]
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Emulsifier concentration [%]
L
YN
PGPR
MD
STS
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and PGPR-chocolate pre-crystallisation was ap-
propriately changed to approach these torque pro-
files, 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 tem-
peratures, and by visually assessing the solidified
product with respect to demoulding, appearance
and gloss. Based on visual inspection, the sam-
ples 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 revolu-
tion as compared to standard L-masses. This is
attributable to the higher viscosity values of choco-
late made with PGPR, resulting in a higher torque
during mixing.
Figure 3 shows the seed-forming and crystallisa-
tion times of dark and whole milk chocolate prepa-
red with different emulsifiers. PGPR-chocolate
tends towards faster seed-forming, and shorter
crystallisation times might be an indicator for en-
hanced susceptibility to over-crystallisation.
Figure 3: Seed-forming time and crystallisation time of
chocolate masses as affected by the emulsifier. L,
lecithin; YN, ammoniumphosphatide; PGPR, polyglyce-
rol polyricinoleate.
This behaviour was confirmed by the results of the
second trial (Figure 4): higher re-heating tempera-
tures 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 cho-
colate is clearly evident [6, 7].
Figure 4: Re-heating temperature of dark chocolate
(upper fgigure) and whole milk chocolate (lower figure).
L, lecithin; YN, ammoniumphosphatide; PGPR, polygly-
cerol 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.
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.
0
30
60
90
120
Time [min]
L YN PGPR L YN PGPR
Dark chocolate Whole milk chocolate
Seed-Forming
Crystallisation
L
YN
L/PGPR
PGPR
30 32 34 36 38
Re-heating temperature [C]
L
YN
L/PGPR
PGPR
5
4
3
2
1
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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.
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.
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 molecu-
lar structure than YN and PGPR, are less resistant
to diffusion of aqueous filling compounds into cho-
colate, consequently showing an enhanced stabi-
lity 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.
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.
Fat based fillings interact with the covering choco-
late obviously by another principle as the contin-
uous cacaobutter phase is affected rather than
sugar, cacao solids, and milk particles. Figure 6
depicts structure loss of dark and whole milk cho-
colate 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 sam-
ple 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 cry-
stallisation 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
0
3
6
9
12
Penetration depth [mm]
0 10 20 30 40 50 60 70
Storage time [d]
L
YN
L/PGPR
PGPR
L
YN
L/PGPR
PGPR
0
5
10
15
20
Penetration depth [mm]
0 10 20 30 40 50 60 70
Storage time [d]
L
YN
L/PGPR
PGPR
L
YN
L/PGPR
PGPR
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in terms of stability towards phase exchanges is
one of the most important consumer-relevant pro-
perties. Differences caused by the type of emulsi-
fier can be explained by interactions between cho-
colate and filling.
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 Lebensmittel-
chemie (DFA, Munich) and the involved
companies for supplying material and helpful
discussions.
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