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ORIGINAL PAPER
Jelena M. Tomić
Received: 1 April 2013 / Revised: 31 July 2013 / Accepted: 19 September 2013 / Published online: 8 October 2013
AOCS 2013
123
40 J Am Oil Chem Soc (2014) 91:39–48
the most stable solid form of cocoa butter in finished Chocolate samples obtained from the chocolate mass
chocolates. The process consists of shearing chocolate containing cocoa butter from Ghana with and without
mass at controlled temperatures to promote crystallization addition of CBE were prepared under laboratory condi-
of triacylglycerols in cocoa butter to effect good setting tions. The cocoa butter from Ghana used belongs to the
characteristics, foam stability, demolding properties, cocoa butter group of moderate hardness and CBE of semi
product snap, contraction, gloss and shelf-life characteris- hard consistency commercial name Illexao 30-61 was
tics. Time–temperature regimes and shearing are employed produced by ‘‘Aarhus Olie’’ (Arhus Karlshamns, Sweden).
to induce nucleation of stable polymorphs with the for- The melting point of cocoa butter from Ghana is
mation of a three-dimensional crystal network structure 36.1 C. The solid fat content of cocoa butter from Ghana
influencing the microstructure, mechanical properties and at different temperature is 84.24 ± 3 %; r = 1.00 (20 C),
appearance of the final product [8]. 76.23 ± 3 %; r = 1.00 (25 C), 44.06 ± 2 %; r = 0.67
The formation of a fat bloom on chocolate is a major (30 C) and 2.28 ± 3 %; r = 1.00 (35 C).
problem in the confectionery industry and adversely affects The melting point of Illexao 30-61 is 32–35 C. The
the appearance and texture of the chocolate [9]. This solid fat content of Illexao 30-61 at different temperature is
physical phenomenon is caused by the dispersion of light 71.0 ± 4 %; r = 1.33 (20 C), 63 ± 3 %; r = 1.00
on the small fat crystals that are formed on the surface of (25 C), 47 ± 4 %; r = 1.33 (30 C) and 4.0 ± 4 %;
and deprives chocolates of a smooth appearance, a bright r = 1.33 (35 C) [16].
color, and gloss [10]. Fat bloom occurs due to poor tem- The samples of chocolate mass were tempered at three
pering, addition of incompatible fats, incorrect cooling different pre-crystallization temperatures (25, 27 and
methods, warm or fluctuating storage temperature, abrasion 29 C) and three different quantities of CBE were added
or finger marking. Bloom formation has been assessed by (10, 15 and 20 % calculated on the total fat content), so the
color techniques using colorimeters, image analyses and by final concentrations of 3, 5 and 7 % of CBE calculated in
visual inspection [11]. the chocolates obtained.
Fat bloom can be prevented by good control of the pre- For measurement of curves of relative reflectance,
crystallization process, addition of foreign fat (through different commercial dark chocolates taken from the
proper formulation), or a combination of both [12]. Cocoa market were used for comparison with laboratory made
butter alternatives can be classified into three groups: (1) chocolate.
cocoa butter substitutes (CBS), fats based on palm kernel
oil or coconut oil, (2) cocoa butter replacers (CBR), non- Methods
polymorphic non-lauric fats based on partially hydroge-
nated oils, and (3) cocoa butter equivalents (CBE), poly- Preparation of Chocolate Mass Samples
morphic non-lauric fats that are defined as fat or fat blends for Pre-Crystallization Process
with a similar melting profile, composition and polymor-
phism as CB, which should be compatible with cocoa The pre-crystallization of the refined chocolate mass was
butter [13]. On the other hand, cocoa butter alternatives performed in a laboratory precrystallizer—a modified
cost considerably less than cocoa butter, and have a more Brabender farinograph. The process of pre-crystallization
uniform nature [14]. Legally, such vegetable fats are per- was controlled indirectly by the changes of the mass
mitted at levels up to 5 % in the EU for a product to be sold resistance during mixing, which is registered on a force/
as chocolate [15]. time diagram—the thermoreogram. The scheme of pre-
The aim of this study was to investigate the influence of crystallization process is shown in Fig. 1 [17].
cocoa butter equivalent (CBE) of moderate hardness on The torque value is a criterion for the viscous behavior
physical properties of chocolate and to compare those results of the chocolate mass and it depends on the crystallization
to the influence of soft CBE (published in a previous paper). extent of the chocolate mass [18].
The concentration of cocoa butter equivalent that was
added to the chocolate mass was 10, 15 and 20 % calcu-
Materials and Methods lated on the total fat content, or 3, 5 and 7 % calculated on
the chocolate mass. Total fat content in the chocolate mass
Materials increased from 34.55 % in reference chocolate to 39.13 %
in samples of chocolate with the addition of the highest
The chocolate mass for dark chocolate producing was amount of CBE. The same level of fat in the reference
produced in ‘‘Banat’’ (Vršac, Serbia) and obtained after sample and samples of chocolate mass with the addition of
24 h of the conching process at 72 C. Fat content was 10 and 15 % of investigated CBE were corrected by adding
34.55 %. cocoa butter. The content of fat in all tested samples was
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J Am Oil Chem Soc (2014) 91:39–48 41
123
42 J Am Oil Chem Soc (2014) 91:39–48
Therefore, the linear regression equation was obtained The Value of Maximum Torque (Mmax
o )
by using a full quadratic model, Eq. (2): of the Chocolate Mass
z ¼ B0 þ B1 c þ B2 t þ B3 c2 þ B4 ct þ B5 t2 ð2Þ
Regarding the influence of temperature and concentration it
where B0…..B5 are polynomial regression coefficients, appeared that again only the temperature exerts a signifi-
The explanatory variables c is the concentration of CBE, cant influence. The dependence of the maximum torque of
t is the temperature of pre-crystallization of chocolate mass the chocolate mass (Mmax
o ) on CBE concentration and pre-
The response variable z is the characteristic value of the crystallization temperature is described by the regression
thermoreogram and color parameters equation Eq. (4):
In CIE, CIELab and Hunter systems, results are given as Momax ¼ 1146 35:31t ð4Þ
the mean values for three measurements. Significance of
differences between the results obtained was analyzed by where is Mmax o Torque maximum (Nm), t pre-
the Analysis of Variance (ANOVA) and Tukey Test. crystallization temperature (C).
For all calculations, statistical software Statistica 8.0 The fit is described with R2 = 0.99, adjR2 = 0.99,
(Statsoft, Tulsa, USA) was used. p \ 0.001.
Statistical analysis of parameters of thermoreographic
measurements confirm that processing conditions in pre-
Results and Discussion crystallization phase do not depend on the amount of CBE
used, but only on the pre-crystallization temperature. It
Thermoreographic Measurement means that the CB and CBE used are highly compatible
and they give chocolate of optimal quality at a lower pre-
Statistical analyses were carried out only for those crystallization temperature which favors shorter nucleation
parameters of thermoreographic measurements whose time and a higher maximum torque of the chocolate mass.
values we supposed depended on the temperature of pre-
crystallization or/and concentration of CBE. Solid Fat Content
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J Am Oil Chem Soc (2014) 91:39–48 43
Fig. 2 SFC curves of chocolates with and without of moderate hardness CBE at pre-crystallization temperatures of 25, 27 and 29 C (error bars
were within symbol size)
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44 J Am Oil Chem Soc (2014) 91:39–48
Table 1 Results of color measurement in CIE, CIELab and Hunter systems before the thermo-cycle test are presented in dependence on CBE
concentration and pre-crystallization temperature
Before thermo-cycle test Pre-crystallization temperature
Parameters 25 C 27 C 29 C
Concentration of CBE
0% 3% 5% 7% 0% 3% 5% 7% 0% 3% 5% 7%
CIELab system
a* 17.42h 10.50b 9.87a 11.01e 12.07g 10.74d 10.56bc 11.14e 10.69cd 11.13e 11.48f 10.45b
b* 7.29a 10.20f 9.84e 10.08f 10.76g 10.05f 10.09f 11.61h 10.77g 9.63cd 9.58b 9.78de
* a b b c efg de c def cd fg cd
L 23.70 25.80 25.59 26.27 26.93 26.64 26.24 26.79 26.50 27.07 26.50 27.12g
DE*ab 71.38 g
68.16 f
68.21 f
67.78 e
67.44 bc
67.36 b
67.73 de
67.53 bc
67.59 cd
66.96 a
67.57 cd
66.80a
DC*ab 17.36 g
13.12 c
12.42 a
13.41 d
14.65 f
13.19 c
13.09 c
14.57 f
13.65 e
13.20 c
13.43 d
12.79b
DL*ab -68.55 a
-66.45 c
-66.66 b
-65.98 d
-65.32 h
-65.60 f
-66.01 d
-65.46 g
-65.75 e
-65.18 i
-65.75 e
-65.12j
DH*ab 9.70 g
7.65 bc
7.43 a
7.81 cde
8.16 f
7.72 bcd
7.66 bcd
7.92 e
7.74 bcd
7.83 de
7.94 e
7.62b
CIE-system
k (nm) 620.0f 593.7bc 593.7bc 595.0cde 594.5bcde 594.3bcde 594.2bcd 591.0a 593.0b 595.8de 596.0e 620.0bc
Hunter-system
LHu 20.02a 21.63f 21.47c 22.00e 22.51d 22.29f 21.97f 22.40h 22.18 g
22.62c 22.18bc 22.67b
Table 2 Results of color measurement in CIE, CIELab and Hunter systems after the thermo-cycle test are presented in dependence on CBE
concentration and pre-crystallization temperature
After thermo-cycle Pre-crystallization temperature
test
Parameters 25 C 27 C 29 C
Concentration of CBE
0% 3% 5% 7% 0% 3% 5% 7% 0% 3% 5% 7%
CIELab system
a* 9.70d 9.00a 9.83f 10.14g 10.39j 9.64c 9.42b 10.30i 10.23h 9.74de 9.77e 10.36j
* f i i j h b c k g e a
b 9.87 10.35 10.38 10.57 10.19 9.40 9.58 10.80 10.05 9.81 9.28 9.73d
* f h g b i e d j c e c
L 32.98 33.30 33.11 30.94 33.54 32.87 32.74 34.35 31.55 32.83 31.55 30.85a
DE*ab 60.98 c
60.62 b
60.96 c
63.15 g
60.62 b
61.01 c
61.12 d
59.92 a
62.50 f
61.13 d
62.30 e
63.15g
DC*ab 12.32 c
12.19 b
12.78 e
13.13 g
13.03 f
11.95 a
11.91 a
13.41 h
12.82 e
12.31 c
11.95 a
12.70d
DL*ab -59.27 b
-58.94 b
-59.14 b
-61.30 a
-58.71 b
-59.38 b
-59.51 b
-57.90 c
-60.70 a
-59.42 b
-60.70 a
-61.40a
DH*ab 7.38cd 7.17a 7.45e 7.56f 7.61fg 7.33c 7.27b 7.62g 7.56f 7.39d 7.37cd 7.59fg
CIE-system
k (nm) 593.0a 591.0a 592.0a 592.0a 594.0a 594.0a 593.0a 593.0a 594.0a 592.50a 594.0a 594.0a
Hunter-system
LHu 27.44f 27.71h 27.54g 25.74b 27.91i 27.34e 27.23d 28.60j 26.24c 27.31e 26.24c 25.67a
concentrations of CBE act as an inhibitor of blooming at In addition, compared to soft CBE Illexao 30-71, CBE
lower temperatures, but at 29 C, despite the absence of of moderate hardness Illexao 30-61 exhibit a higher degree
blooming, appear less effective. of resistance to the phenomenon of blooming, probably due
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J Am Oil Chem Soc (2014) 91:39–48 45
Surface Color
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46 J Am Oil Chem Soc (2014) 91:39–48
Table 3 Measured DE*ab values obtained for chocolate with CBE in relation to the reference starting chocolate sample before and after the
thermo-cycle test
Pre-crystallization temperature (C) Before the thermo-cycle test After the thermo-cycle test
DE*ab Eye perception DE*ab Eye perception
Table 4 WI values for the chocolate surface by CIELab system before and after the thermo-cycle test
WI Pre-crystallization temperatures
25 C 27 C 29 C
CBE Illexao 30-61 concentration
0% 3% 5% 7% 0% 3% 5% 7% 0% 3% 5% 7%
Before thermo-cycle test 21.40a 24.37a 24.30a 24.77a 25.16a 25.18a 24.81a 25.04a 24.95a 25.60a 24.99a 25.73a
ef g f a h e d i b d c
After thermo-cycle test 31.57 31.90 31.60 29.40 31.97 31.53 31.41 32.68 30.06 31.42 30.24 29.40a
Difference 10.17 7.53 7.30 4.63 6.80 6.35 6.60 7.63 5.11 5.82 5.24 3.68
Average difference 7.41 6.85 4.96
Average difference* 6.49 6.86 4.91
Values are means of three determinations
Values of the same row with the same superscript are not statistically different (P \ 0.05)
WI Whiteness index
* Control (reference) sample not included
degree of loss of surface gloss (sensory is not specified). Total Color Difference of Chocolate (DE*ab)
Also, it shows significantly lower values of characteristic
peaks at wavelengths in the chromatic and achromatic part In Table 3 the measured values DE*ab of laboratory-made
of spectrum compared to the values of the same parameters chocolate samples with addition of CBE are given in
of reflectance curves of completely gray samples of dark relation to the reference chocolate sample before and after
commercial chocolate produced by manufacturers 1 and 2 the thermo-cycle test. The range of DE*ab values refers to
(Fig. 4a, b). the portion of 3–7 % CBE.
Compared with samples of chocolate with the addition Values of DE*ab measured after thermo-cycle test were
of soft CBE Illexao 30-71, it has the same values of peaks not in accordance with visual estimation of gloss loss
at characteristic wavelengths as chocolate with the addition during the thermo-cycle test 32/20 C, namely the fastest
of 3 % tempered at 25 C, and lower values in relation to gloss loss was noticed in chocolate samples tempered at
chocolate with the addition of 7 % tempered at 29 C [17]. 29 C which had the lowest DE*ab values.
This confirms the possibility of using recorded reflectance In comparison to the reference chocolate without CBE,
curves as a measure of color quality and surface appear- the values of DE*ab measured in samples tempered at 25
ance of chocolate samples based on the values of r (%) in and 27 C were perceptibly different to the human eye
the chromatic spectrum. As curves were recorded in sam- before thermo-cycle testing than after the test. In the case
ples of chocolate before thermo-cycle testing, based on of samples tempered at 29 C, the human eye did not
their r (%) values in the achromatic part of the spectrum, it register the change of spatial differences in color after the
can be seen that the higher values indicate a recent phe- test in relation to spatial differences of color before the
nomenon of loss of gloss and blooming in relation to thermo-cycle test. Measured values of DE*ab after the test
chocolates with minor r values (%) at wavelengths 700 and are in accordance with the visual assessment of the
775 nm. dynamics of gloss loss in the thermo-cycle test 32/20 C,
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J Am Oil Chem Soc (2014) 91:39–48 47
i.e. chocolate samples tempered at 29 C had the fastest The amount of added CBE affected the visual properties
loss of surface gloss and, on the other hand, the lowest of the studied samples such as the prevention the gloss loss
values of DE*ab. Also, the average measured value of of the chocolate surface and inhibition of blooming.
DE*ab of chocolate samples tempered at 27 C is slightly Recorded curves of reflectance in fresh chocolate sam-
larger than the average value of the same parameter of ple that had higher values of relative reflectance in the
chocolate samples tempered at 25 C, which is not in achromatic part of the spectrum (700 and 775 nm) pre-
accordance with the dynamics of sensory evaluation of dicted the gloss loss sooner than in chocolate samples with
gloss loss of chocolate, because the samples tempered at lower values of relative reflectance in the same part of
27 C lost their gloss slightly slower in comparison with spectrum.
the samples tempered at 25 C. The appearance of a
complete blooming of chocolate was not registered in any Acknowledgments This work was supported by the Ministry of
Education, Science and Technological Development (Project number
of the samples regardless of the temperature of pre- TR 31014).
crystallization.
These relations indicate agreement with the interpreta-
tion of the same samples of chocolate with the addition of
soft CBE Illexao 30-71, i.e. it could be explained by the References
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