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Dynamic oscillat ory shear t est ing of foods Ð select ed applicat ions
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Abstract
The objective of the present work was to study the rheological changes of yoghurt at dierent stages in the manufacturing process
and to try to gain some measure of understanding of the morphological changes that occur. Rheological measurements were made
on yoghurt samples for dierent post-sampling periods, allowing the study of the in¯uence of time in the structure and ¯ow
properties of the material to be performed. This was accomplished using both steady and oscillatory rheometry. Up and down shear
rate sweeps, constant and oscillatory shear measurements were carried out. The study of the eect of temperature allowed the
observation of two distinct regions of temperature dependency, in all samples, the transition point being approximately 25°C. The
structural and rheological changes that occurred during post-incubation were observed during the analysis of several yoghurt
samples, indicating that there is a partial structure recovery upon cessation of ¯ow. Ó 2000 Elsevier Science Ltd. All rights reserved.
Once thermally treated milk has been inoculated, the The stirred yoghurt contained 22.2% total solids, 3.12%
starter culture begins to produce lactic acid; the resulting protein and 1.9% fat (average values), these values being
decrease in pH lowers the net negative charge of the supplied by the producer.
casein particles and the colloidal calcium, which binds All the samples, except those collected after the ®lling
the casein micelles together, is leached out into the se- process, were collected by the same worker, using ster-
rum. Thus, the micelles begin to aggregate and eventu- ilised utensils, and were preserved in sterilised ¯asks.
ally coagulate into a network of small chains as the Samples were immediately cooled in an ice bath and
casein is precipitated. At a certain pH, coagulation is then kept in the refrigerator, at a temperature of 5±7°C.
initiated and as pH approaches the isoelectric point of Two yoghurt batches were sampled for this study.
casein (pH 4.6±4.7) maximum curd ®rmness is obtained, The actual rheological measurements were made on
entrapping the fat globules and residual serum. yoghurt samples for dierent post-sampling periods
The protein network has interstitial spaces containing (speci®ed in Section 3), thus allowing the study of the
the liquid phase and it also has void spaces in which in¯uence of time in the structure and ¯ow properties of
starter culture is present. After incubation, the co- the material. Up and down shear rate sweeps, constant
agulum of stirred yoghurt is broken up mechanically and oscillatory shear measurements were carried out.
before cooling and packaging, thus inducing consider- Most of the measurements were performed on a TA
able changes in the rheological properties. Instruments Weissenberg Rheogoniometer, using a
Benezech and Maingonnat (1992) studied the in¯u- parallel plate geometry 4 cm in diameter.
ence of cooling conditions on the ¯ow properties of Sample loading obeyed a strict procedure. First, the
stirred yoghurt, observing that even at low wall shearing sample was carefully removed, by means of a ¯at spoon,
conditions during cooling the viscosity reduction is sig- from mid-depth of an undisturbed yoghurt container/
ni®cant. ¯ask and placed on the bottom plate of the rheogonio-
Several studies have been reported on yoghurt gels meter. Then, small pieces of fruits were gently removed
and several methods have been introduced to evaluate with tweezers (this procedure was only carried out in
their rheological properties (Arshad, Paulsson & De- IBC and IBF yoghurt samples). The top plate was
jmek, 1993; Benezech & Maingonnat, 1994; Bouzar, slowly lowered until the gap was between 2400 and 2500
Cerning & Desmazeaud, 1997; R onneg ard & Dejmek, lm, as measured by the equipment, in order not to
1993). squash the sample. The gap value varied, as it was re-
The objective of the present work is to study the ferred before, since the slice of sample removed did not
rheological changes of yoghurt at dierent points in the have a constant height. Therefore, in order to avoid the
manufacturing process and to try to gain some measure damage of sample by squashing, small dierences in the
of understanding of the morphological changes that gap value had to exist. Finally, the excess yoghurt was
occur. This will be accomplished using both steady and removed from the edges of the plate.
oscillatory rheometry. Therefore, the objective of this Up and down shearing experiments were conducted
study is simply to demonstrate how Rheology, when in a continuous ramp mode, the shear rate sweeps
correctly used and fully explored, helps to complement ranging from 0.001 to 100 sÿ1 , the ascent and descent
information obtained by other means. times of 5 min, at 10°C. In experiments designed to
study structure break-up under shear, the samples were
sheared at a constant shear rate of 5 sÿ1 , during 15 min,
2. Materials and methods also at 10°C.
Development of structure during manufacture of
Samples at dierent stages during production of stirred yoghurt was studied by means of oscillatory
stirred yoghurt were obtained from a local dairy that rheological measurements. Initially, an amplitude
supported this research. The points of sampling were the sweep, at a constant frequency of 1 Hz, and displace-
following: ment ranging from 1 ´ 10ÿ4 to 0.1 rad, was carried out,
IBT ± yoghurt coagulum (sampling performed in the so that the viscoelastic region of the yoghurt samples
fermentation tank at the end of fermentation pro- could be determined. Once this was done, log frequency
cess). sweeps were conducted at a constant displacement of
IBA ± cooled stirred yoghurt (sampling performed in 0.01 rad, with oscillation frequencies ranging from 0.001
a forced exit after the plate heat exchanger used in the to 10 Hz. In view of the limitations of the rheogonio-
cooling stage). meter to accurately control temperature at temperatures
IBC ± fruited stirred yoghurt (sampling performing below 20°C, for long periods (more than 5 min) these
after packaging stage, fruit addition done before experiments were carried out at this temperature and
packaging). each experiment was repeated three times.
IBF ± ®nal stirred yoghurt (sampling after 3 h in the The study of the in¯uence of lagged time between
incubation room). sampling and the analysis was carried out using both
I.M. Afonso, J.M. Maia / Journal of Food Engineering 42 (1999) 183±190 185
steady and oscillatory shear measurements. Samples at the same shear stress. Assuming that the temperature
were analysed 2, 7 and 14 days after sampling. The data dependency of the apparent viscosity can be character-
presented below are average results, with an average ised by the Arrhenius-type equation (g KeE=RT ), the
error of 4.7%. displacement factor can also be de®ned as aT g(T)/
The temperature eect in the rheological properties of g(reference), where E is the activation energy. E is an
yoghurt was studied by means of apparent viscosity indication of material sensitivity to temperature varia-
measurements at dierent spindle speed rotation, at tions.
temperatures of 5°C, 15°C, 20°C, 25°C, 30°C, 35°C, Based on the displacement factors (aT ) determined for
40°C and 45°C, the experiments being performed using a a reference temperature of 20°C, it was possible to
Viscometers ELV-8 model with a TCU-3 module, using evaluate the temperature dependency of the displace-
coaxial cylinders with spindle TL7. In the experiments ment factor through the Arrhenius equation, for all
carried out at temperatures higher than 20°C, the TCU- yoghurt samples, shown in Fig. 1. In this ®gure it is
3 module was switched on to keep the temperature possible to observe the existence of two dierent regions,
constant. Initially, the sample temperature was previ- that express a ¯ow behaviour showing dierent tem-
ously stabilised in a thermostatic bath at the tempera- perature dependencies.
ture selected for the experiment. Simultaneously, the The existence of two regions with dierent tempera-
temperature of the TCU-3 module was stabilised during ture dependencies is evident from the changes in the
a period of approximately 30 min (this procedure was energy activation values of the samples. From the slope
only carried out at temperatures higher than 20°C). In values (E/R, R 8.31451 J Kÿ1 molÿ1 ) shown in Fig. 1
agreement with the equipment manual, 9.5 ml of sample the activation energy values were determined, as shown
was used in each experiment. After the sample loading in Table 1. For temperatures below 25°C, all samples
(with a syringe) spindle speed rotation sweeps were showed activation energy values rather lower than those
conducted ranging from 0.3 to 60 rpm, at constant for temperatures above 25°C. The reasons for this be-
temperature. Each experiment was repeated three times. haviour are probably related with the re-start of the
This study was only carried out in IBA, IBC and IBF bacteria activity. In addition, the IBA sample shows a
yoghurt samples, since to study IBT the yoghurt coa- greater activation energy value than IBC and IBF, for
gulum would have to be destroyed. the same temperature interval, in the lower temperature
Also, the study was done in order to verify if the range. This dierence may be due to the fact that the
temperature dierence between the steady (10°C) and IBA protein structure is less disrupted than IBC and
oscillatory (20°C) rheometry experiments was accept- IBF, since this sample was collected in a prior stage of
able in terms of material structure. The reason for this is production.
the (already mentioned) fact that the Weissenberg On the basis of this weak dependency of viscosity on
Rheogoniometer does not control accurately the tem- temperature, below 25°C, it is assumed that it is valid to
perature below 20°C, for long time experiments (such as perform steady and oscillatory rheometry experiments
the ones involved in oscillatory experiments). at 10°C and 20°C, respectively, since bacteria activity
has not re-started yet.
In the ¯ow curves of yoghurt samples shown in Fig. 2,
3. Results and discussion it is possible to observe the thixotropic character of
stirred yoghurt and the extent of structural breakdown
In the study of the temperature eect in the rheo-
logical properties of stirred yoghurt it was possible to
observe, as it was expected, that the apparent viscosity
of the yoghurt samples decreased as the temperature
increased, for all samples, this eect being more pro-
nounced for temperatures higher than 25°C. This study
allowed the application of the well-known shear rate±
temperature superposition method (see, for example,
Nielsen, 1977), whereby a correspondence between data
obtained under certain experimental conditions, i.e.,
certain shear rate and temperature ranges, can be used
to predict the ¯ow behaviour of the material at other
equivalent ones, i.e., at the same shear stress.
The displacement factor is mathematically de®ned as
_
aT c(reference)/ _ ), where c(reference)
c(T _ is the shear Fig. 1. Temperature dependency of displacement factor (aT ) for IBA,
rate at the reference temperature at a de®ned shear stress IBC and IBF yoghurt samples. Symbols are: (n) IBA; (M) IBC; (r)
_ ) is the shear rate at a determined temperature T,
and c(T IBF.
186 I.M. Afonso, J.M. Maia / Journal of Food Engineering 42 (1999) 183±190
Table 1
Energy activation values, at constant shear stress, for IBA, IBC and IBF yoghurt samples
Fig. 2. Representative upward and downward ¯ow curves of yoghurt Fig. 3. Representative plot of reduced apparent viscosity (gAPP /gAPP0 )
during dierent stages of stirred yoghurt manufacture. versus shear stress, (upward cycle) of yoghurt during dierent stages of
stirred yoghurt manufacture.
during shearing. The hysteresis loop of yoghurt co- fermentation process (IBT) exhibited two points of
agulum (IBT) indicates that this sample was subjected to sudden decay of (g/g0 ), one at a shear stress of ap-
a major structural degradation during the upward cycle. proximately 37.5 Pa and a second one at 83 Pa. These
This was expected since in this sample the protein net- points may correspond to critical values of shear stress
work was intact. At low shear rates the viscosity in- at which signi®cant structure breakdowns occurs, as will
creased with increasing shear because this region be explained below. All the experiments were performed
corresponds to a transient stress growth at start-up of 14 days after sampling (the importance of this time lag
steady shear. In the other samples the structure will also be further discussed below).
breakdown was not so signi®cant since they were col- The sudden decreases of apparent viscosity were
lected along the post-incubation stages (stirring, pum- similar to that observed in systems where wall-slip is
ping, cooling and packaging) where the yoghurt gel was present, i.e., wall depletion eects, due to the displace-
already broken. ment of the disperse phase away from solid boundaries,
The dierences in structural degradation among leaving a lower viscosity, liquid-depleted layer (Barnes,
stirred yoghurt samples can also be observed in Fig. 3 in 1995). In fact, this wall-slip eect is most likely due to
which average plots of reduced (g/g0 ) apparent viscosity the displacement of the whey away from the protein
versus shear stress during the upward cycle are shown. networks as the disruption of this structure occurs.
IBA, IBC and IBF samples have similar (g/g0 ) behav- These sudden decreases of apparent viscosity are
iours. In the ®rst two cases, the viscosity is approxi- consonant with a model proposed by van Marieke
mately constant (excluding transient eects at the start- (1998). In this, it is proposed that protein particles build
up of shear) up to a shear stress of approximately 8 Pa up aggregates which in turn build up `super-aggregates'.
after which there is a sudden, dramatic decrease in (g/ The super-aggregates can be disrupted at shear rates
g0 ). In the IBF yoghurt sample this sudden decrease of lower than 10 sÿ1 , and the primary gel particles are
(g/g0 ) occured at a shear stress of 10 Pa. This decrease is disrupted at a shear rate range from 10 to 447 sÿ1 , at the
similar to that observed in systems where wall-slip is used experimental conditions. Shear rates greater than
present, this point being further discussed later. The 447 sÿ1 result in the disruption of the primary aggregates
sample collected in the fermentation tank at the end of into protein particles. This is in accordance with a model
I.M. Afonso, J.M. Maia / Journal of Food Engineering 42 (1999) 183±190 187
Fig. 4. Reproducibility study of IBA, for two dierent production sets. Fig. 6. Storage and loss moduli for all samples.
188 I.M. Afonso, J.M. Maia / Journal of Food Engineering 42 (1999) 183±190
Fig. 8. Storage and loss moduli of IBA in function of storage time. Fig. 9. Cox±Merz diagram of IBA.
I.M. Afonso, J.M. Maia / Journal of Food Engineering 42 (1999) 183±190 189
The in¯uence of storage time on the yoghurt samples sugar concentration and the swelling of pectins present
was also studied for IBT, IBC and IBF and the results in these concentrates). This behaviour is not observed in
are shown in Figs. 10±12, respectively. In IBT, which the IBF sample though one can verify an increase of the
corresponds to undisturbed yoghurt coagulum, there are dynamic parameters with time, but the dierences are
no signi®cant structural changes as storage time in- not so signi®cant, since this yoghurt sample was sub-
creases, only small dierences having been observed due mitted to a thermal stabilisation after the addition of
to the increase in consistency. This strongly contrasts fruit concentrate and the packaging stage.
with the behaviour observed for IBA (see Fig. 8). Ramaswamy and Basak (1992) studied the eect of
In IBC, a signi®cant increase in storage and loss the addition of raspberry concentrate on the rheology of
moduli as storage time increases is observed. This hap- stirred yoghurt concluding that the addition of concen-
pens due to the addition of fruit concentrate which trate resulted in increased yoghurt viscosity and shear
results in increased consistency (due to the increase in degradability. These conclusions are consistent with the
higher structure recovery observed with long storage
times for IBC when compared with IBA, although the
shear viscosities are very similar.
4. Conclusions
Acknowledgements Cox, W. P., & Merz, E. H. (1958). Correlation of dynamic and steady
¯ow viscosities. Journal of Polymer Science, 28, 619±622.
Harwalkar, V. R., & Kal ab, M. (1986). Relationship between
The authors would like to thank LACTOGAL for microstructure and susceptibility to syneresis in yoghurt made
having kindly supplied the yoghurt samples that were from reconstituted nonfat dry milk. Food Microstructure, 5, 287±
used in this study and, in particular, to Ms. Regina Brito 294.
and Ms. Maria Jose Ramos, from the Vila do Conde unit Hess, S. J., Roberts, R. F., & Ziegler, G. R. (1997). Rheological
for their colaboration. One of us (IMA) would also like properties of nonfat yogurt stabilised using lactobacillus delbrueckii
ssp bulgaricus producing exopolysaccharide or using commercial
to thank Mr. Francisco Miranda, from FRULACT, for stabilizer systems. Journal of Dairy Science, 80, 252±263.
the helpful discussions in the early stages of the work. Macosko, C. W. (1994). Rheology principles, measurements & applica-
tion. New York: VCH Publishers.
Nielsen, L. E. (1977). Polymer rheology. New York: Marcel Dekker.
References Rajagopal, S. N., & Sandine, W. E. (1990). Associative growth and
proteolysis of streptococcus thermophilus and lactobacillus bul-
Arshad, M., Paulsson, M., & Dejmek, P. (1993). Rheology of buildup, garicus in skim milk. Journal of Dairy Science, 73, 894±899.
breakdown, and rebodying of acid casein gels. Journal of Dairy Ramaswamy, H. S., & Basak, S. (1992). Pectin and raspberry
Science, 76, 3310±3316. concentrate eects on the rheology of stirred commercial yogurt.
Barnes, H. A. (1995). A review of the slip (wall depletion) of polymer Journal of Food Science, 57, 357±360.
solutions, emulsions and particle suspensions in viscometers: its RaÏsik, J. L., & Kurman, J. A. (1978). Yoghurt ± Scienti®c Grounds,
cause, character and cure. Journal of Non-Newtonian Fluid Technology, Manufacture and Preparations. Technical Dairy
Mechanics, 56, 221±251. Publishing House, Copenhagen.
Benezech, T., & Maingonnat, J. F. (1992). Flow properties of stirred Ronneg ard, E., & Dejmek, P. (1993). Development and breakdown of
yogurt: Modelling and in¯uence of cooling conditions. In P. structure in yoghurt studied by oscillatory rheological measure-
Moldenaers, R. Keunings, Theoretical and applied rheology pro- ments. Lait, 73, 371±379.
ceedings. XIth international congress on rheology, Brussels, Belgium. Sta, M. C. 1998. Cultured milk and fresh cheeses. In R. Early, The
London: Elsevier. technology of dairy products (pp. 123±144). London: Blackie
Benezech, T., & Maingonnat, J. F. (1993). Flow properties of stirred Academic & Professional.
yoghurt: structural parameter approach in describing time-depen- Tamime, A. Y., & Deeth, H. C. (1980). Yogurt: technology and
dency. Journal of Texture Studies, 24, 455±473. biochemistry. Journal of Food Protection, 43, 939±977.
Benezech, T., & Maingonnat, J. F. (1994). Characterization of the Tamime, A. Y., & Robinson, R. K. (1988). Fermented milks and their
rheological properties of yoghurt ± a review. Journal of Food future trends. Part II. Technological aspects (review). Journal of
Engineering, 21, 447±472. Dairy Research, 55, 281±307.
Bouzar, F., Cerning, J., & Desmazeaud, M. (1997). Exopolysaccharide van Marieke, M. (1998). Structure and rheological properties of yoghurt
production and texture-promoting abilities of mixed-strain starter gels and stirred yoghurts. Ph.D. Thesis, University of Twente,
cultures in yogurt production. Journal of Dairy Science, 80, 2310± Enschede, The Netherlands.
2317.