Rheological and optical properties of commercial

chocolate milk beverages

Mario Yanes, Luis Duran, Elvira Costell
*
Instituto de Agroqumica y Tecnologa de Alimentos (CSIC), P.O. Box 73, 46100 Burjassot, Valencia, Spain
Received 29 September 2000; accepted 7 March 2001
Abstract
Flow behaviour and colour of nine commercial samples from three dierent lots of chocolate avoured milk beverages were
analysed. Experimental shear stressshear rate relationships, obtained at 25C, tted mostly to the Newton model, as for plain milk,
though some samples tted better to Ostwald-de Waale and Bingham models. Newtonian viscosity values ranged from 2.67 to 18.68
mPa s for samples of one lot. At 5C, as expected, Newtonian viscosity of samples was higher and pseudoplasticity increased (n
values were lower). Six of the nine samples showed consistent viscosity values through the lots. Main dierences in colour of samples
were detected for parameter L
+
(brightness), ranging from very light (L
+
= 53:5) to dark (L
+
= 18:3) samples. Except for two samples
brightness values were consistent through the lots. Hue (h
+
) values were consistent for all samples. However, chromaticity (C
+
)
values diered from one lot to the other, except for two other samples, showing the diculty in controlling this attribute in in-
dustry. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Rheology; Colour; Milk beverages
1. Introduction
Milk beverages of dierent avours for direct con-
sumption are common in Spain and other countries.
Their nutritional and sensory characteristics as well as
their convenience, mainly when presented in individual
packs, favour their consumption by several groups of
consumers like young and elder people. Chocolate a-
voured products are the most popular ones. Basically,
they are formulated with milk, sucrose, cocoa powder
and some hydrocolloids, added to improve consistency
and prevent sedimentation of cocoa particles. Dairy
solids are sometimes included. The particular charac-
teristics of the dierent ingredients fat content of milk,
alcalinity and colour of cocoa powder, type and con-
centration of hydrocolloid should produce noticeable
dierences in the nal composition and in the specic
physical and sensory properties of the formulated
products. Some literature references can be found re-
porting on the dependance of the sensory properties of
these products or of those obtained by dilution of in-
stant powdered chocolate milk in water on some com-
positional factors, such as milk fat content (Raats &
Shepherd, 1992), hydrocolloid, sucrose, and cocoa
powder contents (Folkenberg, Bredie, & Martens, 1999;
Hough & Sanchez, 1998). Inuence of composition on
consumer acceptance of these products has also been
reported (Hough, Sanchez, Barbieri, & Martinez, 1997;
Pangborn, 1988; Scriven & Petty, 1990). There is prac-
tically no information on physical properties of a-
voured milk beverages, particularly on colour and ow
behaviour, despite their evident dependence on initial
formulation and their considerable inuence on con-
sumer acceptance.
The eects of fat content on colour and on vis-
cosity (Kristensen, Jensen, Madsen, & Birdi, 1997;
Phillips, McGi, Barbano, & Lawless, 1995; Wayne &
Shoemaker, 1988), the relations existing between
physicochemical characteristics of casein micelles and
ow behaviour (Kristensen et al., 1997; Prentice, 1992)
and the eect of hydrocolloids on ow behaviour
(Langendor et al., 2000; Oakenfull, Miyoshi, Nishi-
nari, & Scott, 1999; Schmidt & Smith, 1992) have
been studied on milk, the major component of these
beverages. It is to be expected that ingredients like
sucrose, cocoa, and hydrocolloids may exert their in-
uence on both optical and rheological properties of
milk beverages.
Journal of Food Engineering 51 (2002) 229234
www.elsevier.com/locate/jfoodeng
*
Corresponding author. Tel.: +34-963-900022; fax: +34-963-636301.
E-mail address: ecostell@iata.csic.es (E. Costell).
0260-8774/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S0260- 8774( 01) 00061- 9
The aims of this work were to analyse ow behaviour
and colour of commercial chocolate milk beverages, to
study dierences between brands and lots and the eect
of consumption temperature (5C or 25C) on their ow
behaviour.
2. Materials and methods
2.1. Samples
Samples of nine dierent brands, covering the com-
mercial range in the Spanish market, were selected and
acquired on three dierent dates (lots): September 1999
(lot 1), December 1999 (lot 2), and March 2000 (lot 3).
Their main characteristics are given in Table 1.
2.2. Soluble solids and pH
Soluble solids were determined in a digital refrac-
tometer (ATAGO RX-100) at room temperature and
the results expressed as degrees Brix at 20C. A digital
potentiometer (CRISON 2001) was used to measure pH
at room temperature. Both measurements were done in
quadruplicate.
2.3. Rheological measurements
A coaxial cylinders viscosimeter (Haake VT 550) with
a NV double gap cell, monitored by a Rheowin Job
Manager V. 2.5, Haake Software OS 550, was used.
Shear stress values were measured at shear rates from
1.00 to 300 s
1
with a 120 s ramp, holding the samples in
a thermostated bath at 25 0:1C or at 5 0:1C.
Measurements were done in duplicate in each of two
subsamples. Experimental data were tted to Newton
(r = g_ c), Ostwald (r = K _ c
n
) and Bingham (r = r
0

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
+
(a), C
+
(b), and h
+
(c) values for samples from three lots.
234 M. Yanes et al. / Journal of Food Engineering 51 (2002) 229234