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Article history: Chocolate milk with different carrageenans (jappa and lambda) and sugar concentrations was heat trea-
Received 4 March 2009 ted indirectly at 145 °C for 6 s using a bench-top UHT plant. The temperature of the milk in the preheating
Received in revised form 10 June 2009 and sterilizer sections, and the milk flow rate were determined to evaluate the overall heat transfer coef-
Accepted 10 July 2009
ficient (OHTC) for monitoring fouling during UHT processing. Kappa-carrageenan was more effective than
Available online 15 July 2009
lambda-carrageenan in providing stability against fouling during UHT processing. By optimizing concen-
trations of j-carrageenan and sugar, fouling could be minimized during UHT processing. The apparent
Keywords:
viscosity and sedimentation of UHT-processed chocolate milk increased with increasing concentration
Milk
UHT
of carrageenan and sugar.
Chocolate Ó 2009 Elsevier Ltd. All rights reserved.
Fouling
Carrageenan
0260-8774/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2009.07.008
180 S. Prakash et al. / Journal of Food Engineering 96 (2010) 179–184
5000
1000
0.03%
0.01% 4000 κ-carrageenan
800
α-carrageenan
600 3000
400 2000
0%
0.10% 0.05% 0% 0.01%
0.03%
200 0.05% 1000
0.10%
0 0
0 1000 2000 3000 4000 5000 0.00 0.02 0.04 0.06 0.08 0.10
Time of operation (s) Carrageenan concentration (%)
Fig. 1. Variation in OHTC with time of operation during UHT processing of Fig. 3. Interaction plot for run-times at various concentrations of j- and k-
chocolate milk with different concentrations of added j-car. carrageenan (SE = 37.26 s).
OHTC (kW/m C)
20
600
600
0.03% 400
400
0.05%
0.01% 0% 7%
9% 9%
200 0.10% 200
11%
11%
0 0
0 500 1000 1500 2000 2500 3000 3500 0 500 1000 3500 4000 4500 5000
Fig. 2. Variation of time of operation of the UHT system with different concentra- Fig. 4. Variation of time of operation of the UHT system with different concentra-
tions of added k-car. tions of added sugar.
182 S. Prakash et al. / Journal of Food Engineering 96 (2010) 179–184
Standard chocolate milk has a sugar concentration of 7% (van of carrageenan (P < 0.001). However there was no significant differ-
den Boomgaard et al., 1987). The role of sugar during UHT process- ence in amount of sediment obtained at similar concentrations in
ing of chocolate milk was investigated by increasing the concentra- the range 0.01–0.03% of the different types of carrageenan.
tion to 9 and 11% and keeping the concentrations of carrageenan The addition of sugar at 9% and 11% increased the apparent vis-
(0.03%) and cocoa powder (1.5%) constant. j-Car at 0.03% was used cosity of the milk and markedly reduced the run-time of the sys-
as it gave the longest run-time. The variation of OHTC with time of tem (Fig. 4). There was no significant difference in run-time of
operation is shown in Fig. 4 (some data points between 1000 and the plant during UHT processing of chocolate milk with 9% and
3500 s have been omitted in the graph to facilitate display of the 11% added sugar but these run-times were significantly different
short and long runs). Higher sugar concentration (9% and 11%) fo- from those with 7% added sugar (P < 0.001) (Fig. 4). The observed
uled the plant very quickly. viscosities and processing parameters, as shown in Table 2, suggest
that the higher apparent viscosity resulting from the higher sugar
3.2. Effect of j-car, k-car and sugar on apparent viscosity and contents caused shorter run-times and more sedimentation. There
sedimentation was no observable induction period and the decline phase was
steep for the two higher sugar levels (Fig. 4).
The initial OHTC and product outlet temperature (OHTC and Analysis was performed on the log-transformed data for the
outlet temperature at commencement of the experiment), appar- amount of sediment and apparent viscosity obtained with different
ent viscosity and sediment data of UHT-processed samples of choc- concentrations of sugar. There was a significant difference in the
olate milk with different concentrations of j-car and k-car are apparent viscosity and amount of sediment obtained between 7%
shown in Table 1. and 9% added sugar (P < 0.001 and 0.05), between 7% and 11%
The addition of j- and k-car significantly influenced the appar- added sugar (P < 0.001 and 0.01), and between 9% and 11% added
ent viscosity of the processed chocolate milk (P < 0.001). There was sugar (P < 0.01 and 0.01). The results (Tables 1 and 2) suggest that
a steady increase in apparent viscosity with increase in j- and k- sediment and apparent viscosity both increase with increasing car-
car concentration with 0.1% markedly increasing the apparent vis- rageenan concentration.
cosity of the UHT-processed chocolate milk. The increase in appar-
ent viscosity at 0.05% and 0.1% was accompanied by a reduction in
run-time of the plant, with 0.1% fouling the plant in less than 9 min 4. Discussion
(Figs. 1 and 2). The decreased initial product outlet temperature
and OHTC at higher j- and k-car concentration could be due to In this study UHT processing of chocolate milk without added
increasing apparent viscosity (thus decreasing turbulence in the hydrocolloid was practically impossible with the bench-top UHT
tubular heat exchangers) during heating (Table 1). A similar in- system. The dispersed cocoa particles in the milk interfered with
crease in viscosity was observed by Kastanas (1996) during fouling the processing causing constant fluctuation in temperature and
of concentrated milk. back-pressure. Addition of j-car stabilized the chocolate milk for-
A Tukey simultaneous test was performed for all pair-wise com- mulation to UHT processing with 0.03% j-car giving the best re-
parisons of apparent viscosity. The apparent viscosity of UHT-trea- sults, that is, the maximum run-time. This concentration is the
ted chocolate milk at 0.1% carrageenan was significantly different critical gelling concentration for j-car. The sulfated linear polysac-
from the apparent viscosity obtained at lower concentration charide j-car behaves as an adsorbing polymer and forms com-
(0.01–0.05%) with a significant difference (P < 0.05) in apparent plexes with the proteins in milk. The complex is primarily based
viscosity obtained with similar concentrations of different on electrostatic interactions between j-casein and j-car (Snoeren
carrageenans. et al., 1975). At elevated temperatures, caseins micelles in the pres-
Analysis was performed on log-transformed data for the ence of j-car form into clusters or ‘‘microdomains” which exclude
amount of sediment obtained from UHT-processed samples of the j-car; on cooling, the carrageenan strands associate with the
chocolate milk with different concentration of carrageenan. There casein on the periphery of the clusters and with other carrageenan
was a significant difference in the amount of sediment obtained molecules in solution via a double helix structure to form a strong
with j- and k-car (P < 0.001) and with the different concentrations gel network (Spagnuolo et al., 2005). The dispersed cocoa particles
Table 1
Effect of j- and k-carrageenan concentration on processing parameters, apparent viscosity and sedimentation of UHT-processed chocolate milk (average values, n = 2).
Amount of j-car (%) Sediment (g/100 g of milk) Apparent viscosity (mPa s) Initial product outlet temperature (°C) Initial OHTC (kW/m2°C)
j-car k-car j-car k-car j-car k-car j-car k-car
0 1.73 (0.03) 1.60 (0.04) 3.29 (0.10) 3.26 (0.37) 145.19 (0.12) 145.17 (0.04) 908 (1.41) 903 (2.12)
0.01 1.63 (0.01) 1.58 (0.03) 3.76 (0.08) 3.87 (0.27) 145.12 (0.08) 145.19 (0.09) 904 (2.12) 904 (2.83)
0.03 1.50 (0.01) 1.60 (0.03) 4.08 (0.11) 4.90 (0.14) 145.15 (0.13) 145.19 (0.02) 905 (2.85) 907 (1.41)
0.05 2.63 (007) 5.15 (0.16) 5.27 (0.10) 5.82 (0.06) 143.02 (0.06) 143.83 (0.14) 807 (2.83) 816 (2.83)
0.1 6.70 (0.27) 8.20 (0.21) >20 >20 141.04 (0.13) 142.62 (0.21) 731 (2.12) 729 (3.54)
Table 2
Effect of sugar concentration on sedimentation, apparent viscosity and run-time during UHT processing of chocolate milk containing 0.03% of j-car (average values, n = 2).
Amount of sugar (%) Sediment (g/100 g of milk) Apparent viscosity(mPa s) Initial product outlet temperature (°C) Initial OHTC (kW/m2°C) Run-time (s)
7 1.50 (0.01) 4.08 (0.11) 145.2 (0.11) 905 (2.1) 5000 (28.3)
9 8.73 (0.18) >20 142.7 (0.18) 805 (2.8) 480 (42.4)
11 11.48 (0.38) >20 140.2 (0.16) 701 (6.4) 420 (28.3)
in chocolate milk become incorporated into the casein–carra- concentrations. There was no significant difference in sediment
geenan gel network and as a result the cocoa particles are immobi- values at low carrageenan concentrations.
lized. The immobility is advantageous as it reduces the fluctuation The chocolate milk was stable to UHT processing up to a critical
in temperature and back-pressure and also sedimentation of cocoa j-car concentration, 0.03%, above which the excess carrageenan
particles in the balance tank as observed in this study. However remains in solution and flocculates the carrageenan-coated mi-
there needs to be enough carrageenan in the system to cover the celles by depletion causing sedimentation (Spagnuolo et al.,
particle surfaces and provide sufficient free polymer for the devel- 2005). The small increase in apparent viscosity at low concentra-
opment of a network that withstands the gravitational forces act- tions of carrageenan (0.01–0.03%) did not affect the run-time as
ing on the dispersed particles (Langendorff et al., 1997). This was the flow of the chocolate milk was similar to that of aqueous solu-
evident in the present study as below a minimum concentration tions of carrageenan without any intermolecular bonds which form
of added j-car (0.03%), the chocolate milk was unstable to UHT at higher j-car concentrations in milk due to formation of carra-
processing with fluctuation in temperature and back-pressure. geenan–casein micelle aggregates (Yanes et al., 2002a).
Apart from keeping the cocoa particles in suspension, the j-carra-
geenan–protein interaction provides stabilization of the milk
against precipitation by Ca2+ by shielding the calcium-sensitive 5. Conclusions
caseins, as- and b-caseins, from contact with Ca2+ (Lin and Hansen,
1970; Lin et al., 1972). Studies have revealed that j-car does not This study found that fouling of heat exchangers during UHT
influence the denaturation (unfolding) of b-Lg (Tziboula and processing of chocolate milk can be minimized by adding optimal
Horne, 1999) but accelerates the aggregation of denatured b-Lg concentrations of j-carrageenan and sugar. The effect of carra-
molecules (Capron et al., 1999). Grijspeerdt et al. (2004) have sug- geenan at the optimal concentration can be attributed to the for-
gested that the shorter the unfolded form is present in the UHT mation of a complex between it and casein which only
plant the longer the run-time. Therefore, the longer run-times with marginally increases the apparent viscosity and effectively holds
0.01% and 0.03% of j-car in chocolate milk could be associated with the cocoa particles in suspension, preventing them from interfering
the quicker aggregation of denatured b-Lg molecules. with the operation of the UHT plant. The results also indicate that
k-Car forms complexes with caseins similar to those with j-car j-car is more effective in providing stability against fouling during
(Spagnuolo et al., 2005) but in this study was unable to impart sta- UHT processing than k-car. This can be attributed to the abilities of
bility when added to chocolate milk at 0.01–0.1% during UHT pro- j-car to accelerate the aggregation of denatured b-Lg molecules
cessing. Although it cannot be confirmed from this study, the and stabilize casein against calcium-induced precipitation more
fluctuations in temperature and back-pressure suggest the inabil- effectively than k-car.
ity of the k-car–casein network to hold the cocoa particles in sus- The results suggest that while whey proteins and calcium are
pension. This is supported by the fact that k-car is less effective in important, caseins play a significant role in fouling during choco-
stabilizing as-casein against calcium-induced precipitation (Lin late milk processing. This is particularly evident when excessive
and Hansen, 1970). Studies have also shown that k-car lowers concentrations of sugar or carrageenan are added. Furthermore,
the degree of heat-induced aggregation of b-Lg. All these factors the higher concentrations of sugar and carrageenan contribute to
would contribute towards the shorter run-times obtained during increased sediment formation due to coagulation of caseins in
UHT processing of chocolate milk with added k-car compared with the UHT-processed milks. Both the fouling and sediment formation
those with added j-car. observed with higher sugar and carrageenan levels are associated
The viscosity of milk is between 2.2 and 2.5 mPa s and milk is a with very high viscosities after heat treatment. It is apparent that
Newtonian fluid (Yanes et al., 2002a,b). The difference in apparent excessive fouling and sediment formation only occur after the
viscosity between milk and chocolate milk is evident in this study apparent viscosity reaches some critical value. This value should
and can be attributed to the concentration of hydrocolloid, the pos- be determined to ensure optimum efficiency in UHT processing
sible interactions between hydrocolloid and casein micelles and of chocolate milk.
the sugar added. The increase in apparent viscosity with addition
of carrageenan is due to the linear macromolecular structure and Acknowledgement
polyelectrolytic nature of carrageenan. The mutual repulsion of
the many negatively charged half-ester sulfate groups along the The authors wish to thank Dairy Australia for their financial
polymer chain causes the molecule to be highly extended, while support of this work.
its hydrophilic nature causes it to be surrounded by a sheath of
immobilized water molecules. Both of these factors contribute to
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