The Effect of pH and Temperature on the Rheological Behavior

of Dulce De Leche, A Typical Dairy Argentine Product

CLARA 0. ROVEDO, PASCUAL E. VIOLLAZ, and CONSTANTINO SUAREZ
Departamento de lndustrias
Facultad de Ciendas Exactas y Naturales
Ciudad Universitaria
1428, Buenos Aires, Argentina

ABSTRACT second is preferred for confectionery purposes

because of its greater viscosity. This increased
The rheological behavior of commer- viscosity results from the starch added during
cial samples of Dulce de Leche (sweet
its preparation.
milk) for household and confectionery An important characteristic of Dulce de
use was studied. Both products have thix- Leche is the texture, because textural defects
otropic and pseudoplastic characteristics. often render the product unacceptable to the
Apparent viscosity, determined at 25, 40, consumer. Rheological characterization of the
and W C , demonstrated that this magni- product is also important for operating evapora-
tu& decreased with increased tempera- tion equipment as well as for handling (12).
ture. Activation energies were 9.9 and Little information exists in the literature con-
10.4 kcaYmo1 for household and confec- cerning the rheological behavior of commercial
tionery types, respectively. Dulce de Leche. Most studies were conducted
Apparent viscosities of household with milk concentrates, with and without sugar
samples were detennined at pH = 3.0, addition, and total solid contents less than 30%
6.1, and 8.3. At acid pH, the apparent (5). However, Hough et al. (9) has observed
viscosity was lower than that of the origi- that the flow properties of Dulce de Leche are
nal sample (pH = 6.1); at alkaline pH markedly different from that determined by
viscosity was higher than that of the Higgs and Norrington (8) for sweetened con-
original. The effect of pH becomes more densed milk. As pointed out by Hough et al.
pronounced with time. (9), such differences are due to the total con-
From shear stress and shear rate flow centration of solids, which in the case of Dulce
diagrams, the Herschel-Bulkley model de Leche, may vary from 54 to 70% depending
was adequate for both types of Dulce de on the method of preparation.
Leche investigated. The objective of this study was to measure
(Key words: rheology, Dulce de Leche, flow properties of commercial samples of
Argentina) household and confectionery Dulce de Leche,
to evaluate the effect of temperature (25 to
INTRODUCTION 55'C) on rheological behavior, and to predict
flow properties near the processing tempera-
Dulce de Leche is similar in composition to tures and for the cooling process.
sweetened condensed milk and is typically pre- As pH has an important effect on protein
pared with milk concentrated at atmospheric stability, its effect on the flow curves was also
pressure in the presence of added sucrose. A investigated using commercial samples of
small amount of sodium bicarbonate is also household DuIce de Leche. A wide range of pH
added to prevent protein coagulation. There are was investigated, even though alkaline pH is of
two types of this product: Dulce de Leche for little practical interest.
household use and of confectionery type. The
first is generally used as a dessert, and the
MATERIALS AND METHODS

The Dulce de Leche used for the experi-

Received April 19, 1990. ments was manufactured by Gandara S. A.
Accepted December 3, 1990. (Provincia de Buenos Aims, Argentina) and
1991 J Dairy Sci 741497-1502 1497
1498
purchased in a supermarket. The composition
of household Dulce de Leche was 80% milk,
16% sucrose, and 4% glucose syrup; the con-
fectionery type has a similar composition plus
2% starch as thickener. Total solid contents for
both samples was 71%. Seventeen samples,
including six for replications, were tested.
The pH of homogenized samples of Dulce
de Leche was measured with a glass electrode
on a Metrohm pH meter E632 previously cali-
brated with appropriate buffer solutions. Sam-
ples of Dulce de Leche for household use were
used to study the effect of pH on the rheologi-
cal curves. Four samples of different pH (3.0;
4.7; 8.3; and 9.4) were prepared by adjustment
with 10% HC1 and 10% NaOH solutions. The
pH of the untreated or original sample was 6.1.
The effect of time on the rheological behav-
ior of Dulce de Leche at each pH condition was
also studied. For each pH, the rheological curve
was measured after 24,48,72,96, and 120 h of
storage at room temperature. No appreciable
change was observed.
Vlscorneter
The flow properties of Dulce de Leche were
measured with a concentric cylinder viscometer
(Haake RV 12 Rotovisco) with a M O O mea-
suring head. The h4V II type sensor system was
used for household type Dulce de Leche and
the MV III sensor system was used for the
confectionery type. It was not possible to use
1W-
0
.
Figure 1. Experimental r h g ~ a m
o w e d by increas-
ing and decreasing shear rate (3 min per cycle) of the
sample of Mce de Lcche for household usc at 25C and
pH 6.1.
Journal of Dairy Scimce Vol. 74, No. 5, 1991
ROVEDO ET AL.
the same sensor for both products because con-
fectionery Dulce de Leche was too viscous to
obtain results within the shear rates range in-
vestigated
The viscometer was operately automatically.
The shear rate was varied from 0 to 32 rpm.
Shear stress versus revolutions per minute dia-
grams were obtained in the following manner.
Speed was continuously increased from 0 to a
maximum speed in 1.5 min while simultane
ously recording torque, then immediately
decreased to the starting point (3 Wcycle).
For each tested sample, this procedure was
continuously performed until the ascending
speed curve coincided with the descending one
to verify that thixotropic breakdown had been
effective. Once such condition was reached, the
revolutions per minute (W) and torque (S)read-
ings of the viscometer were converted to shear
rate @) and shear stress (2) by means of the
following equations:
2 (Pa) = A x S
D (d)= M x W
where the values of A and M are provided by
the manufacturer for each sensor system. Ap-
parent viscosity ( P a s ) was obtained from q = T/
D.
RESULTS AND DISCUSSION
Characteristic flow curves, in terms of
torque versus rotation speed corresponding to
Dulce de Leche for household use, are shown
1 in Figure 1. It was observed that the major
;65
2
2
l i ~
55
6 0;
----___
Timelsl
1
6 --l 150
-~ -
-
-
203
Figure 2. Variation of shear slress with lime at constant
shear rate.
 RHEOLOGY OF DULCE DE LECHE
x3
OO 10 20
Shear rote, D I<]
30
Figure 3. Effect of time on rheological curves of Dulce
de Leche for household use at 25C and pH 3.0.
change in the rheological behavior occurred
during the first shearing cycle. To confirm the
thixotropy of the product, shear stress was plot-
ted in Figure 2 as a function of time at a shear
rate of 32 rpm.The shear stress decreased with
time of shearing. After 24 h of rest, the same
decreasing curve was obtained. This complete
recovery of the structure allows us to conclude
that thixotropy is present. Such thixotropic be-
havior differs from other thixotropic foods in
the number of loops before overlapping occurs.
For apple sauce, mayonnaise, and mustard,
practical overlapping takes place after the sec-
ond cycle (1). However, for household Dulce
de Leche this overlapping occurred in the tenth
cycle (approximately 30 min of shearing) as
can be seen in Figure 1. The time required for
the structural breakdown of Dulce de Leche
(household and confectionery) decreases as
temperature increases (results not shown).
Is.pical flow curves, in terms of shear rate
and shear stress values, at acid and alkaline pH
are shown in Figure 3 and 4, respectively.
When the apparent viscosity is defined as q =
z/D, apparent viscosity increases with storage
time (results were similar at pH 4.7 and 9.4).
These results indicate that after the pH has been
1499
OO IO 20
Sheor rate, D(s1
30
Figure 4. Effect of time on rheological curves of Dulce
de Leche for household use at 25C and pH 8.3.
changed, the product evolves very slowly be-
fore reaching a rheological behavior indepen-
dent of time. Such an increase in the apparent
viscosity with the storage time, also observed
for sweetened condensed milk (8), might be
because a certain period of time is required for
proteins of Dulce de Leche to reach an equili-
brium cdguration. Figure 3 illustrates that at
acid pH the apparent viscosity is lower than
that corresponding to the original sample @H =
6.1); at alkaline pH the opposite effect is ob-
served (Figure 4).
From research of Reiner (15), the lowest
viscosity of a protein corresponds to the isoe-
lectric point, increasing when pH increases or
decreases. However, this was not observed
here, probably due to the chemical changes in
the native proteins of milk as the result of the
Maillard reaction between protein and sugar
compounds during cooking. Because acidic
products are produced by this reaction, pH
tends to decrease as does the isoelectric point
(4).
The effect of temperature on flow behavior
of Dulce de Leche for household use was stud-
ied at 25, 40, and 55C. The hysteresis loop
decreased with increasing temperature with the
consequent reduction of the time required to
Jomnal of Dairy Science Vol. 74. No. 5, 1991
1500 ROVED0 ET AL.

- model, fittin_g parameters,

TABLE 1. Rheolonical _ and mean relative deviation modulus for Dolce de -he.'
Household ConfectiOntry
Tempera-
Rheological model tare Q Po n P%2 b Po n p46

('c)
25 45.46 28.38 .6 .84 457 18.3 .43 .78
'E=vJ+lb.Dn 40 182 15.69 .6 1 .65 4.85 36.7 .47 1.24
(Herschel Bulldey) 55 9.65 5.7 .65 1.39 0 15.76 .47 1.37
25 2657 .86 .3 1.38 ... ... ... ...
e = $ + k D p 40 10.52 .7 1 .3 .89 ... ... ... ...
(Heinz-Casson) 55 7.06 .5 .4 1.51 ... ... ... ...
25 56.81 2.45 5 2.89 47.84 6.09 5 4.94
T~ = E': + (Ib-D)"40 22.19 1.84 .5 2.18 22.91 3.5 5 4.56
(Casson) 55 9.77 .77 .5 1.84 8.12 1.6 5 522
25 %.84 5.1 1.o 7.83 79.46 13.58 1.0 8.61
~ = % + p , y D 40 39.1 3.8 1.o 6.31 39.41 7.42 1.0 8.31
(Bingham plastic) 55 17.08 1.62 1.o 5.75 14.73 3.2 1.0 9.35
25 0 57.58 .45 6.06 0 82.62 .42 .73
'E = p(yLP 40 0 29.14 .46 4.38 0 41.24 .44 1.47
(Dower law)
~ 55 0 12.7 .46 5.67 0 15.68 .48 1.31
lRheolo@cal parameters: 'EO = yield stress; p~ = consistency index; D = shear rate; and n = flow behavior index.
~ P S= predicted percentage.

reach the thixotropic breakdown. This result confectionery, pH = 6.0) at 25, 40, and 55'C
agrees with that reported by Hough et al. (9). were fitted by means of the following mathe-
who found that during Dulce de Leche prepara- matical models: Casson (3), Bingham (2),
tion (temperature near ZWC), the product loses power law or Ostwaldde Waele (ll), Heinz-
its thixotropic characteristic. Casson (He&, 6). and Herschel-Bulkley (7).
Flow c w e s of three original samples at The five equations are given in Table 1. The
different temperatures (household Dulce de
Leche) are shown in Figure 5 . The apparent
viscosity was calculated for a shear rate range
from 1.35 to 28.35 s-l and correlated according
to Arrhenius relationship:

r( = A exp WT) [31

where E, is the activation energy (kcaVmol), R
is the gas constant, T the temperature rK),and
A a constant. The value of E, was determined
at different shear rates from regression analysis
of In q versus lfl. The mean value of & was
9.9 f .4 kcal/mol. The effect of temperature on
the flow curves of confectionery Dulce de
Leche is shown in Figure 6; the mean
corresponding to this product was 10.4 f .3
kcal/mol.
10 20 30
Modeling of the Flow Curves Shear rate, O C d

The flow curves of the original samples of Figure 5. Effect of temperature on flow curves of Dulce
Dulce de Leche (household, pH = 6.1 and de Leche for household use (untreated sample, pH 6.1).

Journal of Dairy Science Vol. 74. No. 5. 1991

 RHEOLOGY OF DULCE DE LECHE 1501

-6b
U
U
e
0
L
c
I

10 20 30
Shear rote, D Is)

Pigum 7. Cumparkon between experimental data and

mathematical models for household Dulcc de Leche @H
6.1, UT);power law (-h Haschel-Bulkley (-. -); .
Casson (-.-); Singham (---); and experimental (A).

5 10 15
- Bulkley model gave the best fit, although accu-
rate fitting was also obtained with Heinz-Cas-
Shear rate, D(S1
son and Casson models. For confectionery
Figure 6. Effect of temperalure on flow a w e s of Dulce Dulce de Leche, good fits were obtained with
de Leche for confectionery use @H 6.0). Herschel-Bulkley and power law models.
Flow behavior index (n) resulting from the
various tested models was less than unity, indi-
cating that Dulce de Leche is a pseudoplastic
values of the parameters corresponding to each fluid Data at 25, 40,and 55C showed that n
equation were obtained by a nonlinear regres- was not appreciably affected by temperature.
sion method and are also given in Table 1. The This weak influence of temperature on flow
fit of the models to the experimental data was
behavior index was also observed by other
calculated by means of the mean relative devia-
tion modulus defined as follows (10): investigators for Dulce de Leche and other food
products (9, 13).

where ~i = measured shear stress, Zpi = pre

dicted shear stress, N = number of observa-
tions. The P values equal to or less than 5% TABLE 2. Yield stress values.
can be considered to represent a good fit to the
data (10). The comparison between experi-
mental data and predicted curves is shown in Tanperahm Household confecti~ilery
Figure 7 for household Dulce de Leche in order cc) Pa)
to give a clear picture of how well each model 25 54.5 27.2
fits. From probability values given in Table 1, 40 22.6 16.3
for household Dulce de Leche, the Herschel- 55 11.3 5.4

J o d of Dairy Science Vol. 74, No. 5, 1991

1502 ROVED0 ET AL.
The plastic behavior of Dulce de Leche was
demonstrated; to initiate flow a shear stress
higher than a critical value, the yield stress, TO,
had to be applied Yield stress values obtained
from the rheograms are shown in Table 2.
Values in Table 2 differ from those calcu-
lated from the models in Table 1. This lack of
agreement was also observed by other investi-
gators (12) and may be attributed to the thix-
otropic effect, which modifies the value of the
rheological parameters that define the flow be-
havior. Each of the five models predicted %
values for both products which indicates that
this parameter depends on both the material and
the model selected. As was reported in the
literature (ll),the values of TO calculated from
mathematical models are not totally reliable
when used for subsequent calculation of un-
known rheological parameters.
CONCLUSIONS
The apparent viscosity of Dulce de Leche
(household use) is affected by temperature and
pH of the sample. Acidification decreased the
apparent viscosity, and alkaline pH increased it.
For alkaline and acid samples the apparent
viscosity increased with storage time.
The Herschel-Bulkley model gave the best
fit for the flow data for household and confec-
tionery Dulce de Leche. The comparison of the
consistency index, h,and flow behavior index,
n, for household and confectionery Dulce de
Leche indicates that the latter has more consis-
tency (larger h) and is more pseudoplastic
(lower n) because of the small amount of starch
added during its preparation. For the range of
shear rates investigated, the product showed
plastic flow with measurable yield stress.
Joumal of Dairy Science Vol. 74, No. 5, 1991
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