The Effect of pH and Temperature on the Rheological Behavior

of Dulce De Leche, A Typical Dairy Argentine Product

CLARA

o.

ROVEDO PASCUAL E. VIOLLAZ, and CONSTANTINO SUAR~Z

,
Departamento de Industrias
Facultad de Clenclas Exaetas Y Naturales
Ciudad Universitaria
1428. Buenos Aires, Argentina

ABSTRACT

The rheological behavior of commercial samples of Dulce de Leche (sweet

milk) for household and confectionery
use was studied. Both products have thixotropic and pseudoplastic characteristics.
Apparent viscosity, determined at 25, 40,
and 55C, demonstrated that this magnitude decreased with increased temperature. Activation energies were 9.9 and
10.4 kcaVmol for household and confectionery types, respectively.
Apparent viscosities of household
samples were determined at pH = 3.0,
6.1, and 8.3. At acid pH, the apparent
viscosity was lower than that of the original sample (pH = 6.1); at alkaline pH
viscosity was higher than that of the
original. The effect of pH becomes more
pronounced with time.
From shear stress and shear rate flow
diagrams, the Herschel-Bulkley model
was adequate for both types of Dulce de
Leche investigated.
(Key words: rheology, Dulce de Leche,
Argentina)
INTRODUCTION

Dulce de Leche is similar in composition to

sweetened condensed milk and is typically prepared with milk concentrated at atmospheric
pressure in the presence of added sucrose. A
small amount of sodium bicarbonate is also
added to prevent protein coagulation. There are
two types of this product: Dulce de Leche for
household use and of confectionery type. The
first is generally used as a dessert, and the

Received April 19, 1990.

Accepted December 3, 1990.
1991 ] Dairy Sci 74:1497-1502

second is preferred for confectionery purposes

because of its greater viscosity. This increased
viscosity results from the starch added during
its preparation.
An important characteristic of Dulce de
Leche is the texture, because textural defects
often render the product unacceptable to the
consumer. Rheological characterization of the
product is also important for operating .evaporation equipment as well as for handling (12).
Little information exists in the literature concerning the rheological behavior of commercial
Dulce de Leche. Most studies were conducted
with milk concentrates, with and without sugar
addition, and total solid contents less than 30%
(5). However, Hough et al. (9) has observed
that the flow properties of Dulce de Leche are
markedly different from that determined by
Higgs and Norrington (8) for sweetened condensed milk. As pointed out by Hough et al.
(9), such differences are due to the total concentration of solids. which in the case of Dulce
de Leche, may vary from 54 to 70% depending
on the method of preparation.
The objective of this study was to measure
flow properties of commercial samples of
household and confectionery Dulce de Leche,
to evaluate the effect of temperature (25 to
55C) on rheological behavior, and to predict
flow properties near the processing temperatures and for the cooling process.
As pH has an important effect on protein
stability, its effect on the flow curves was also
investigated using commercial samples of
household Dulce de Leche. A wide range of pH
was investigated, even though alkaline pH is of
little practical interest.
MATERIALS AND METHODS

The Dulce de Leche used for the experiments was manufactured by Gandara S. A.
(Provincia de Buenos Aires, Argentina) and
1497

1498

ROVBDO ET AL.

purchased in a supermarket. The composition

of household Dulce de Leche was 80% m.ilk.
16% sucrose, and 4% glucose syrup; the confectionery 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 calibrated with appropriate buffer solutions. Samples of Dulce de Leche for household use were
used to study the effect of pH on the rheological curves. Four samples of different pH (3.0;
4.7; 8.3; and 9.4) were prepared by adjustment
with 10% HCI and 10% NaOH solutions. The
pH of the untreated or original sample was 6.1.
The effect of time on the rheological behavior 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.
Viscometer

The flow properties of Dulce de Leche were

measured with a concentric cylinder viscometer
(Haake RV 12 Rotovisco) with a M500 measuring head The MV n type sensor system was
used for household type Dulce de Leche and
the MV ill sensor system was used for the
confectionery type. It was not possible to use

100-

Figure 1. Experimental rheogram obtained by increasing and decreasing shear ralc (3 min per cycle) of the
sample of Dulce de Lcche for household use at 25'C and
pH 6.1.
Journal of Dairy Science Vol. 74, No.5, 1991

the same sensor for both products because confectionery Dulce de Leche was too viscous to
obtain results within the shear rates range investigated.
The viscometer was operately automatically.
The shear rate was varied from 0 to 32 rpm.
Shear stress versus revolutions per minute diagrams were obtained in the following manner.
Speed was continuously increased from 0 to a
maximum speed in 1.5 min while simultaneously recording torque, then immediately
decreased to the starting point (3 min/cycle).
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) readings of the viscometer were converted to shear
rate (D) and shear stress (1:) by means of the
following equations:
1: (Fa) = A X S
D (S-I) = M x W

[IJ
[2J

where the values of A and M are provided by

the manufacturer for each sensor system. Apparent viscosity (Fas) was obtained from 1'\ = 1:1
D.
RESULTS AND DISCUSSION

Characteristic flow curves, in terms of

torque versus rotation speed corresponding to
Dulce de Leche for household use, are shown
in Figure 1. It was observed that the major

100-

150

Tlmels)

Figure 2. Variation of shear stress with time at constant

shear raIe.

1499

RHEOLOGY OF DULCE DB LECHE

F

'1

'1

c
8
A

6!.

B
A

300
F

<3
a.N

vi
<II

~ 2

U;

0<lJ

'-

~ ~ElpH;8'3

OJ

..c

U1

' 'I

46 h
72 h

iJl

B
C
D
E

120 h

untr~at~d sampl~.

pH;3.0

D
E

96 h

pH;6.1

0
0
DO

10

20
Shear rate, 0 [51)

Figure 3, Effect of time on rheological curves of Dulce

de Leche for household use at 2S'C and pH 3.0.

change in the rheological behavior occurred

during the first shearing cycle. To confinn the
thixotropy of the product, shear stress was plotted 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 behavior 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 second 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).
Typical 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 11 =
'tID, 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

10

Shear rote,

30

96 h
120h

un\rea\~d

20

o(s-l)

sample. pH;6.1

30

Figure 4. Effect of time on rheological curves of Dulce

de Leche for household use at 2S'C and pH 8.3.

changed, the product evolves very slowly before reaching a rheological behavior independent 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 equilibrium configuration. Figure 3 illustrates that at
acid pH the apparent viscosity is lower than
that corresponding to the original sample (pH
6.1); at alkaline pH the opposite effect is observed (Figure 4).
From research of Reiner (15), the lowest
viscosity of a protein corresponds to the isoelectric 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 studied at 25, 40, and 55C, The hysteresis loop
decreased with increasing temperature with the
consequent reduction of the time required to
Journal of Daily Science Vol. 74. No. S. 1991

1500

ROVEDO BT AL.

TABLE 1. Rheological model, fitting parameters. and mean relative deviation modulus for Dulce de Lecbe. 1
TemperaRheological model lure
'to

Household

J.Io

Confectionery
p%2

J.Io

To

p%

CC)
40
(Herscbel BuDdcy) 55

45.46
18.28
9.65

28.38
15.69
5.7

25

2657

.86

.3

.84
.65
1.39
1.38

+ (J.IoD)" 40

1052
7.06
56.81

.71
.5
2.45

.3
.4

.89
1.51

.5

22.19
9.77

1.84
.77

.5
.5

96.84
39.1
17.08

5.1
3.8
1.62

1.0
1.0
1.0

7.83
6.31
5.75

79.46
39.41
14.73

't

-fl

= to

= t:;

25

+ IloIjl

(Heinz-Casson)

55
25

..5 = 't~ + %.D)5 40

(Casson)
55
25
40
't = to + J.IoD
(Bingham plastic) 5.5
't

25

= J.Io.Ijl

40
55

(power law)

0
0
0

57.58
29.14
12.7

.6
.61
.65

.45
.46
.46

78.3
36.7
15.76

2.89

47.84

6.09

4.94

2.18
1.84

22.91
8.12

3.5
1.6
1358
7.42
3.2

5
.5
1.0
1.0
1.0

4.56
522

6.06
4.38
5.67

lRbeological parameters: to = yield stress; J.Io = consistency index; D

2p% = Predicted percentage.

reach the thixotropic breakdown. This result

agrees with that reported by Hough et al. (9),
who found that during Dulce de Leche preparation (temperature near lOOC), the product loses
its thixotropic characteristic.
Flow curves of three original samples at
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-1 and correlated according
to Arrhenius relationship:

.43
.47
.47

457
4.85
0

0
0
0

.42
.44

82.62
4124
15.68

= shear rate;

and n

.48

= flow

.78
1.24
1.37

8.61
8.31
9.3.5
.73
1.47
1.31
behavior index.

confectionery, pH = 6.0) at 25, 40, and 55"C

were fitted by means of the following mathematical models: Casson (3), Bingham (2),
power law or Ostwald~e Waele (11), HeinzCasson (Heinz, 6), and Herschel-BuIldey (7).
The five equations are given in Table 1. The

25'c

1'1

=A

exp {EJRn

[3J

where Ea is the activation energy (kcallmol), R

is the gas constant, T the temperature ("K), and
A a constant. The value of Ea was determined
at different shear rates from regression analysis
of In 11 versus Iff. The mean value of Ea was
9.9 .4 kcal/rnol. The effect of temperature on
the flow curves of confectionery Dulce de
Leche is shown in Figure 6; the mean Ea
corresponding to this product was lOA .3
kcallmol.

I/J'c

55't

10

Modeling 01 the Flow Curves

The flow curves of the original samples of

Dulce de Leche (household, pH = 6.1 and
Joumal of Dairy Scimce Vol. 74, No.5. 1991

20

Shear rate. DIs')

30

F"lgUre 5. Effect of temperature on flow curves of Dulce

de Leche for household use (untreated sample. pH 6.1).

1501

RHEOLOGY OF DULCE DE LECHE

25"(

250

200

4(J'C

'Cl
<1i

Vll

------w------

10

Shear rate. Dis')

55"c

10

15

Shear rate. DIs')

Figure 6. Effect of temperature on flow ClUVes of Dulce
de Leche for confectionery use (pH 6.0).

values of the parameters corresponding to each

equation were obtained by a nonlinear regression method and are also given in Table 1. The
fit of the models to the experimental data was
calculated by means of the mean relative deviation modulus defmed as follows (10):

where 'ti = measured shear stress, 'tpi = predicted shear stress, N = number of observations. The P values equal to or less than 5%
can be considered to represent a good fit to the
data (10). The comparison between experimental data and predicted curves is shown in
Figure 7 for household Dulce de Leche in order
to give a clear picture of how well each model
fits. From probability values given in Table I,
for household Dulce de Leche, the Hersehel-

Figure 7. Comparison between experimental data and

mathematical models for household Dulce de Leche (pH
6.1, 25'C); power law (-); Herschel-Bulkley (- .. -);
Casson (-. -); Bingham (- - -); and experimental (<1).

Bulkley model gave the best fit, although accurate fitting was also obtained with Heinz-Casson and Casson models. For confectionery
Dulce de Leche, good fits were obtained with
Herschel-Bulkley and power law models.
Flow behavior index (n) resulting from the
various tested models was less than unity, indicating that Dulce de Leche is a pseudoplastic
fluid Data at 2S, 40, and SsoC showed that n
was not appreciably affected by temperature.
This weak influence of temperature on flow
behavior index was also observed by other
investigators for Dulce de Leche and other food
products (9, 13).

TABLE 2. Yield stress values.

Dulce de Leche
Temperature

Household

CC)
25

- - - - (Fa> - - - -

40

55

54.5
22.6
11.3

Confectiouery

27.2
16.3
5.4

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

1502

ROVEDO 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 meograms are shown in Table 2.
Values in Table 2 differ from those calculated from the models in Table 1. This lack of
agreement was also observed by other investigators (12) and may be attributed to the thixotropic effect, which modifies the value of the
meological parameters that defme the flow behavior. Each of the five models predicted To
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 unknown meological 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 confectionery Dulce de Leche. The comparison of the
consistency index, J.lo, and flow behavior index,
n, for household and confectionery Dulce de
Leche indicates that the latter has more consistency (larger Ilo) 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.

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

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