Chocolate
Chocolate
g
/
_ c) models. Values of r and _ c were obtained and tted
to the dierent models by using the Rheowin Data
Manager V. 2.5 software.
2.4. Measurement of colour
Colour of samples was measured in a Hunter colo-
rimeter, Labscan II model, using 6 cm diameter and 3.8
cm height cells and a 0.5 in. diaphragm. Translucency of
samples was previously checked by measuring diused
reection of a 3.5 cm layer thickness on both black and
white (X =78.5, Y =83.32, Z =87.94) backgrounds, ac-
cording to Judd and Wyszecki (1967). Reection spectra
were registered and CIELAB colour parameters for 10
vision angle and D65 illuminant (L
+
: brigthness, a
+
:
redness, b
+
: yellowness, C
+
: saturation, and h
+
: hue) were
calculated. Measurements were done in triplicate on
each of two subsamples.
2.5. Statistical analysis
Analysis of variance of two factors and interactions
were applied to the dierent sets of data. Least signi-
cant dierences were calculated by the Fisher's test
(a 60:05). These analyses were performed using the
Statgraphics Plus 3.1 software.
3. Results and discussion
3.1. Characterization of ow. Inuence of temperature
The variation of shear stress (r) values with shear rate
( _ c), determined at two temperatures (25C and 5C) on
samples of the rst lot, were tted to Newton, Ostwald-
de Waale, and Bingham models (Table 2). At 25C, the
ow of samples 1, 2, and 3 was practically Newtonian
with n values higher than 0.925 while that of samples 5,
6, 7, and 8 tted better to Ostwald-de Waale model with
ow indices ranging between 0.747 and 0.849. The latter
samples also showed a good tting to the Bingham
model with yield stress values higher than 100 mPa
(150:20 < r
0
< 503:80 mPa). Samples 4 and 9 showed
an intermediate behaviour. In general, ow behaviour of
Table 1
Soluble solids, pH values and price levels of chocolate milk beverage samples
Sample Milk type
a
Hydrocolloid
a
Soluble solids (Brix)
b
pH
b
Price level
c
1 Non-fat & whole Alginate 16.25 (0.22) 7.35 (0.05) L
2 Non-fat & whole Alginate 16.30 (0.21) 7.20 (0.31) M
3 Low-fat Carrageenan 18.17 (0.25) 6.71 (0.03) H
4 Non-fat & dairy solids Alginate 17.75 (0.13) 6.79 (0.07) M
5 Low-fat Carrageenan 18.02 (0.36) 6.86 (0.04) H
6 Low-fat Carrageenan & CMC 17.60 (0.21) 6.83 (0.04) H
7 Low-fat Carrageenan & MCC 17.77 (0.12) 6.98 (0.06) H
8 Whole & dairy solids Carrageenan 18.40 (0.38) 6.87 (0.03) H
9 Non-fat Carrageenan 17.50 (0.08) 7.05 (0.06) L
a
Declared in the label.
b
Mean values of four measurements at 20C, Standard deviations within parentheses.
c
H: High ; M: Medium; L: Low.
230 M. Yanes et al. / Journal of Food Engineering 51 (2002) 229234
these products was qualitatively similar to that of milk.
Although for most practical purposes milk is a nearly
Newtonian uid with viscosity values between 2.2 and
2.5 mPa s (Prentice, 1992), its ow behaviour is complex
and strongly dependent on temperature, on the applied
shear rate and on both concentration and physical state
of the dispersed phase, the latter being mainly due to the
hydrodynamic volume of the casein micelles and to fat
content (Van Vliet & Walstra, 1980). Depending on the
conditions of measurement (shear strain rates and tem-
perature) and on the type of viscosimeter used (capillary
tube, rotational steady shear or controlled stress), the
ow of milk has been characterised by dierent authors
as Newtonian, shear thinning or Bingham plastic
(Kristensen et al., 1997; Phillips et al., 1995; Wayne &
Shoemaker, 1988). Quantitative dierences in the rhe-
ological parameters between milk and the analysed milk
beverages are due to the addition of sucrose and hy-
drocolloids to the latter. Qualitative dierences could be
Table 3
Viscosity of chocolate milk beverages from dierent lots, at 250:1C
a
Sample
b
Lot 1 Lot 2 Lot 3
1 2.67 (0.05) 3.99 (0.18) 4.10 (0.06)
2 3.77 (0.02) 3.83 (0.01) 3.72 (0.24)
3 4.59 (0.09) 4.74 (0.68) 4.94 (0.16)
4 4.27 (0.21) 5.98 (0.33) 5.33 (0.46)
5 8.40 (0.87) 8.32 (0.27) 8.38 (0.39)
6 9.64 (0.12) 6.08 (0.05) 5.24 (0.03)
7 18.68 (1.7) 13.01 (1.19) 15.84 (1.14)
8 10.85 (0.09) 5.58 (0.21) 11.87 (0.13)
9 4.81 (0.28) 6.07 (0.02) 5.83 (0.01)
a
Mean values (n = 4) in mPa s and standard deviations within
parentheses.
b
Identication of samples in Table 1.
Fig. 1. Viscosity of samples from all lots at 25 0:1C.
Table 4
Viscosity of chocolate milk beverages from dierent lots at 5 0:1C
a
Sample
b
Lot 1 Lot 2 Lot 3
1 6.89 (0.66) 7.27 (0.12) 8.37 (0.48)
2 8.51 (0.53) 6.65 (0.10) 6.96 (0.11)
3 9.86 (0.65) 8.72 (0.59) 9.40 (0.30)
4 8.45 (0.33) 10.22 (0.47) 10.28 (0.32)
5 18.19 (0.91) 19.13 (2.33) 14.02 (1.71)
6 20.41 (1.12) 11.82 (1.21) 10.63 (0.65)
7 32.13 (2.21) 21.61 (1.65) 23.70 (2.76)
8 30.07 (0.65) 10.38 (0.97) 20.11 (0.53)
9 9.99 (0.30) 11.19 (0.01) 9.45 (0.04)
a
Mean values (n = 4) in mPa s and standard deviations within pa-
rentheses.
b
Identication of samples in Table 1.
Table 2
Flow behaviour of chocolate milk beverages
a
Sample
b
Temperature (C) Newton Ostwald Bingham
g (mPa s) r K (mPa s
n
) n r r
0
(mPa) g
/
(mPa s) r
1 25 2.70 0.965 3.24 0.966 0.966 9.69 2.65 0.966
2 25 3.76 0.982 3.45 0.990 0.982
c
3 25 4.52 0.984 6.76 0.925 0.986 40.48 4.33 0.985
4 25 4.44 0.943 13.59 0.792 0.957 100.30 3.94 0.953
5 25 8.63 0.986 19.45 0.849 0.993 150.20 7.88 0.992
6 25 9.55 0.985 24.48 0.825 0.995 182.40 8.65 0.993
7 25 16.90 0.972 65.61 0.747 0.997 503.80 14.40 0.992
8 25 10.92 0.975 39.14 0.762 0.996 314.50 9.37 0.993
9 25 5.02 0.978 11.63 0.843 0.985 87.13 4.59 0.984
1 5 6.44 0.991 3.69 0.999 0.993
2 5 8.89 0.996 7.59 0.999 0.996
3 5 9.40 0.996 5.98 0.999 0.997
4 5 8.21 0.996 7.84 0.999 0.996
5 5 17.59 0.995 31.73 0.890 0.998 211.80 16.54 0.998
6 5 19.62 0.992 43.36 0.853 0.998 322.00 18.03 0.997
7 5 24.76 0.984 73.64 0.797 0.998 558.60 21.99 0.995
8 5 29.61 0.970 126.90 0.729 0.999 952.20 24.91 0.993
9 5 10.21 0.996 7.52 0.999 0.997
a
Fitting of values of shear stress versus shear rate for samples of lot 1, measured at two temperatures (5C and 25C), to dierent models. Flow
parameters values and correlation coecients.
b
Identication of samples in Table 1.
c
Not tting to model.
M. Yanes et al. / Journal of Food Engineering 51 (2002) 229234 231
attributed mainly to the dierent types of milk used in
their formulation (Table 1), to the concentration and
type of hydrocolloid and to the possible interactions
between them and the casein micelles.
These beverages are frequently consumed cool. On
decreasing the temperature from 25C to 5C (Table
2), an increase in Newtonian viscosity was clearly
observed, as expected, in all samples. Also consistency
(K) values of pseudoplastic or shear thinning samples
and both yield stress and plastic viscosity of samples
tted to the Bingham model were higher. Fitting of
rheograms obtained at 5C to the three considered
models conrmed that samples 5, 6, 7, and 8 were less
Newtonian than the rest. Without knowing the exact
composition of the analysed samples it is dicult to
interpret the detected dierences in rheological beha-
viour. However, it can be assumed that the plasticity
detected in samples 5, 6, 7, and 8 could be due to the
formation a carrageenan/casein micelle network
(Langendor et al., 2000) and that addition of carra-
geenan or alginate to the rest of samples simply pro-
duced an increase in viscosity of the whole system
without contributing to the formation of network
structures.
3.2. Rheological properties of samples. Eects of sample
and lot
Rheological data obtained at 25C for samples of lots
2 and 3 showed slight variations compared to the results
for lot 1. In order to facilitate comparison and based on
Table 5
Opacity evaluation
a
Sample
b
L
+
on black
plate
c
L
+
on white
plate
c
t value
d
1 33.65 (0.12) 33.68 (0.09) 0.9534
2 37.20 (0.14) 37.48 (0.16) 1.686
3 31.63 (0.61) 31.76 (0.27) 0.638
4 25.67 (0.11) 25.50 (0.13) 1.417
5 41.28 (0.09) 41.29 (0.13) 0.329
6 46.60 (0.18) 46.46 (0.06) 0.799
7 53.54 (0.02) 53.55 (0.14) 0.144
8 45.78 (0.09) 45.45 (0.57) 0.876
9 36.17 (0.44) 35.71 (1.52) 0.210
a
L
+
values of samples, measured on black and on white background,
and experimental Student t values.
b
Identication of samples in Table 1.
c
Mean values of four measurements. Standard deviations in paren-
theses.
d
Student t value from tables (a = 0:05) =2.353.
Table 6
Colour of chocolate milk beverages
a
Lot Sample
b
L
+
a
+
b
+
C
+
h
+
1 1 33.68 (0.09) 11.99 (0.04) 14.58 (0.24) 18.87 (0.20) 50.56 (0.43)
1 2 37.48 (0.16) 13.07 (0.17) 15.09 (0.33) 19.96 (0.18) 49.10 (0.90)
1 3 31.76 (0.27) 11.03 (0.08) 15.26 (0.53) 18.83 (0.40) 54.11 (1.05)
1 4 25.50 (0.13) 11.43 (0.25) 15.95 (0.74) 19.68 (0.61) 54.35 (1.5)
1 5 43.72 (0.03) 10.84 (0.02) 16.35 (0.20) 19.62 (0.15) 54.59 (3.3)
1 6 46.46 (0.06) 12.19 (0.05) 19.00 (0.13) 22.57 (0.08) 57.32 (0.28)
1 7 53.00 (0.08) 9.71 (0.08) 15.12 (0.27) 17.96 (0.26) 57.29 (0.40)
1 8 45.45 (0.57) 12.01 (0.31) 17.86 (0.07) 21.53 (0.19) 56.12 (0.70)
1 9 35.71 (1.51) 13.95 (0.38) 17.19 (0.41) 22.14 (0.24) 50.91 (1.28)
2 1 38.46 (0.37) 11.59 (0.06) 16.0 (0.36) 19.81 (0.29) 54.22 (0.60)
2 2 37.97 (0.61) 13.3 (0.14) 14.76 (0.45) 19.76 (0.26) 47.47 (0.35)
2 3 31.45 (0.33) 11.01 (0.17) 17.23 (0.62) 20.45 (0.19) 57.30 (0.93)
2 4 25.68 (0.08) 11.71 (0.28) 15.62 (0.62) 19.52 (0.37) 53.13 (1.6)
2 5 41.88 (0.13) 10.93 (0.26) 14.73 (0.50) 18.34 (0.27) 53.40 (1.5)
2 6 42.13 (0.11) 11.72 (0.19) 17.81 (0.79) 21.32 (0.56) 56.62 (1.55)
2 7 53.55 (0.14) 9.89 (0.12) 14.72 (0.06) 17.73 (0.10) 56.10 (0.29)
2 8 41.26 (0.24) 12.71 (0.10) 17.39 (0.27) 21.37 (0.13) 53.83 (0.41)
2 9 18.31 (0.29) 11.97 (0.20) 18.10 (0.42) 21.70 (0.39) 56.52 (0.69)
3 1 38.20 (0.52) 11.08 (0.23) 14.08 (0.05) 17.91 (0.38) 51.80 (1.25)
3 2 36.59 (0.49) 11.51 (0.18) 14.13 (0.19) 18.22 (0.15) 50.82 (0.68)
3 3 33.83 (0.12) 10.85 (0.06) 18.28 (0.53) 21.26 (0.43) 59.76 (1.6)
3 4 44.99 (0.39) 12.31 (0.26) 15.62 (0.44) 19.89 (0.32) 52.12 (1.46)
3 5 41.28 (0.09) 10.85 (0.17) 14.70 (0.39) 18.27 (0.23) 53.56 (1.1)
3 6 45.66 (0.19) 12.59 (0.19) 18.00 (0.73) 21.97 (0.49) 54.99 (1.4)
3 7 50.62 (0.09) 11.28 (0.10) 16.24 (0.09) 19.77 (0.01) 55.21 (0.31)
3 8 40.14 (0.26) 13.93 (0.19) 20.70 (0.29) 24.95 (0.23) 56.04 (0.60)
3 9 41.71 (0.90) 14.28 (0.58) 18.79 (0.33) 23.60 (0.11) 52.70 (1.59)
a
L
+
; a
+
; b
+
; C
+
; and h
+
mean values (standard deviations within parentheses) of samples from three lots.
b
Identication of samples in Table 1.
232 M. Yanes et al. / Journal of Food Engineering 51 (2002) 229234
the slight dierences of behaviour found, as outlined
above, the viscosity of all samples were computed by
tting to the Newton model (Table 3). Mean values
showed quite a wide variation between samples, going
from a very uid beverage with similar viscosity to that
of plain milk (2.67 mPa s for sample 1 from lot 1) to
rather thick and creamy type of product (18.68 mPa s
for sample 7 from lot 1). Two samples, 5 and 6, showed
moderate viscosity (around 810 mPa s) and the rest
were thinner (lower than 5 mPa s).
An analysis of variance of viscosity data, considering
samples and lots as sources of variation, showed that
interaction between sample and lot eects was signi-
cant (a 60:05) (F value =27.09, F from tables =2.03).
Dierences in viscosity between lots for samples 6, 7,
and 8 were responsible for this, as can be observed in
Fig. 1. The other six samples showed consistent viscosity
values through lots, indicating an adequate rheological
control of the commercial beverage.
Viscosity data obtained at 5C (Table 4) conrmed
the expected increase in viscosity for all samples. An
analysis of variance considering sample and temperature
eects as sources of variation showed that their inter-
action was not signicant (a 60:05) (F=2.33, F from
tables =2.04), which means that the viscosity variation
due to temperature was similar for all samples.
3.3. Opacity and colour
Before measuring colour, the samples degree of
opacity or translucency was checked by comparing the
L
+
values obtained on black and on white backgrounds.
Results showed that no dierences were detected be-
tween two such measurements (Table 5), which means
that, for the sample thickness used (3.5 cm), they can be
considered totally opaque. Consequently, all colour
measurements were carried out on a white background
using the instrument plate (X =78.5, Y =83.32,
Z =87.94).
Brightness (L
+
), redness (a
+
), yellowness (b
+
), satu-
ration (C
+
), and hue (h
+
) values for the nine chocolate
milk beverage samples from each of the three lots are
given in Table 6. A wide range of brightness values was
found going from very light coloured samples (L
+
=53.5
for sample 7 from lot 2) to very dark ones (L
+
=18.3 for
Table 7
Inuence of samples and lots on chocolate milk beverages colour
a
Eect L
+
C
+
h
+
Lot 777.62
b
32.78
b
1.01
c
Sample 2167.27
b
253.53
b
36.49
b
Lot sample 469.45
b
36.96
b
6.85
b
a
F values of two-way ANOVA of L
+
; C
+
; and h
+
data.
b
Signicant at a = 0:05.
c
Not signicant.
Fig. 2. Reectance spectra of a light sample (a) and a dark one (b).
a
b
c
Fig. 3. L
+
versus a
+
plots of colour of samples from lots 1 (a), 2 (b), and
3 (c).
M. Yanes et al. / Journal of Food Engineering 51 (2002) 229234 233
sample 4 from lot 2). Reection spectra of two repre-
sentative colours that could be described as light brown
or cream and dark chocolate, respectively, are shown in
Fig. 2, where the typical distribution of reectance val-
ues for brown coloured materials can be observed.
On plotting L
+
versus a
+
values for samples from each
lot (Fig. 3), it can be observed that variations in
brightness of samples were dierent between lots and
that dierences in redness (a
+
values) were also impor-
tant not only between samples but also between lots,
showing lack of homogeneity probably due to a decient
control of colour.
An analysis of variance of two factors, lot and sam-
ple, and interactions, applied to the three main param-
eters representing colour attributes, L
+
(brightness), C
+
(saturation), and h
+
(hue) (Table 7), showed a signicant
interaction for parameter L
+
, mainly due to considerable
dierences among lots for samples 4 and 9 while for the
rest of the samples L
+
values were consistent throughout
the lots (Fig. 4(a)). The lotsample interaction was also
signicant for C
+
values but in this case all samples ex-
cept 4 and 6 showed variations between lots (Fig. 4(b)),
which shows the diculty in monitoring colour satura-
tion from batch to batch. The eect of lot on values of h
+
was not signicant, the hue being rather constant
throughout the lots. Signicance of the interaction is
due to some dierences found for samples 1, 2, 3, and 9
(Fig. 4(c)). In spite of the above-mentioned dierences, a
rather acceptable uniformity in colour attributes
through lots was observed in most samples.
Acknowledgements
To CICyT of Spain for nancial support (Project
AGL2000-1590) and to PROMEP-SEP and UJAT of
Mexico for the fellowship awarded to author Yanes.
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Fig. 4. L
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234 M. Yanes et al. / Journal of Food Engineering 51 (2002) 229234