Flow Properties of Dulce de Leche, a Typical
Argentine Dairy Product
Centro de Investigaei6n y Desarrollo en Criotecnologfa de Alirnentos
ABSTRACT
Dulce de Leche (caramel jam) is a
typical Argentine dairy product similar in
composition to sweetened condensed
milk. Its flow properties were measured
for solids content between 55 and 70%
and temperatures between 25 and 70°C.
Thixotropicity of the product was
quantified using Weltmann's model and
decreased with solids content. The
coefficient of thixotropic breakdown was
correlated with temperature for each
sample to allow prediction of thixo-
tropicity. F r o m shear stress-shear rate
flow diagrams the Herschel-Bulkley mo-
del was adequate for Dulce de Leche.
Except for the most concentrated sam-
ples at low temperatures, the flow index
was nearly constant with an average value
of .748, thus demonstrating Dulce de
Leche to be a pseudoplastic substance.
Yield stress and consistency index de-
creased with temperature increase and
increased with solids content. A single
expression to predict these parameters as
a function of temperature and solids
could not be found due to chemical
Received May 15, 1987.
Accepted December 4, 1987.
1988 J Dairy Sci 71:1783-1788
G U l L L E R M O H O U G H and O S V A L D O M O R O
Instituto Superior Experimental de Tecnologia Alimentaria
H. Irigoyen 931
6500 Nueve de Julio
Buenos Aires
Argentina
JUAN SEGURA
Calle 47 y 117
1900 La Plata
Argentina
NESTOR C A L V O
Instituto de Desarrollo Tecnol6gia para la Industria Qu(mica
Guemes 3450
3000 Santa Fe
Argentina
changes that occur during the cooking
process. An empirical exponential ex-
pression was used to correlate consistency
index and yield stress versus temperature
for each sample and a similar expression
to correlate these parameters versus solids
content at each temperature.
INTRODUCTION
Dulce de Leche (caramel jam) is a typical
Argentine dairy product. In order to design
and operate evaporation and other processing
equipment, rheological behavior and flow
properties must be known. There is no known
literature on flow properties of Dulce de Leche.
The influence of temperature and composition
on viscosity of milk concentrates [with no sugar
addition and less than 30% total solids (TS)] was
studied (4). Higgs and Norrington (5) studied
flow properties of sweetened condensed milk,
which is similar in composition to Dulce de
Leche; but the noticeable textural differences
do not suggest that their flow properties will be
similar.
Dulce de Leche is made by boiling a milk
and sugar mixture at atmospheric pressure at
approximately 100°C. Measurement of flow
properties at this temperature is difficult due
to product changes during measurement.
The objective of this work was to measure
rheological properties at different TS during
cooking and at temperatures between 25 and
70°C. With these measurements, tendencies
1783
 1784 HOUGH ET AL.

and correlations are sought in order to predict saturating the viscometer sensor system varied
flow properties at processing temperatures. For according to sample and temperature. These
the final product (TS = 70%), correlations are speeds are shown in Table 1.
also important for the cooling process.
Model Parameter Calculations
MATERIALS AND METHODS Shear stress versus speed (rpm) was cor-
Dulce de Leche was made in a 50-L pilot related according to the Herschel-Bulkley
plant cooker (Grimm and Dutrich, Santa Fe, model, which was adequate for Dulce de Leche.
Argentina). Initial formulation was milk (3.5% Calculation procedure is similar to that fol-
fat and 11.7% TS) 50 kg, sucrose 10kg, glucose lowed by other authors (3, 8).
syrup 2.5 kg, and sodium bicarbonate 40 g; this 1. Shear stress was calculated from the cali-
corresponds to a classical recipe for a home use brated sensor system constant.
product. During cooking, four samples ($1, $2, 2. A first approximation value of flow behavior
$3, and $4) were extracted including the final index ( n l ) is obtained by linear correlation
product. Total solids were measured by drying of log T versus log rotational speed (N).
in a vacuum oven according to Moro and Hough 3. Shear rate (D) is calculated from the fol-
(6) with the following results: $1, 54.6%, $2 lowing expression (1):
60.0%, $3 64.7%, and $4 70.0%.
In previous experiments with a Brook- D= 4 . "a'- N R~/n [11
field LV viscometer, a slipping effect was 60- n Re2/n - R~/n
noticed on the spindle's surface, specially at
temperatures above 40 °C. The flow pro- where R e = diameter of exterior cylinder
perties were measured with a concentric cyl- and R i = diameter of interior cylinder.
inder viscometer (Haake RV2) using a profiled 4. Yield stress (To) was calculated from the
MV-IP system to eliminate slipping. Experi- Casson model (7) by linear regression of
ments on the four samples were conducted at square roots of T and D.
25, 40, 50, 60, and 70°C using a Haake cir- 5. Consistency index (K) and n are calculated
culating bath to control temperature. $4 was by linear regression of log (T - TO) versus
too viscous at 25°C to obtain results within log (D) according to Herschel-Bulkley model
reasonable shear rates with the sensor system. (7):
A first set of experiments was performed
to study the thixotropic nature of Dulce de T -- T O = K • D n [2]
Leche. For all four samples and at temperatures
indicated, shear stress (T) versus time (0)was 6. Next, n is compared with n l . If they differ
measured at a constant speed of 32 rpm. The up to third decimal place, calculations are
flow index was constant for most samples and repeated as from step 3.
temperatures; therefore, 32 rpm corresponds to
an effective shear rate corrected for non-
Newtonian fluids (1) of 77 s- 1 .
Shear stress versus revolutions per minute
diagrams were obtained in the following man-
ner. Samples were first sheared at maximum TABLE 1. Maximum rotational speeds (rpm) used in
speed in sufficient time to produce thixotropic viscometer for obtaining shear stress-shear rate flow
breakdown. As a guide this time was taken where diagrams.
T reached an asympototic value in the T verus 0
curves. Then speed was continuously reduced Temperature, °C
to zero in 1 rain while simultaneously recording Samp~ 25 40 50 60 70
shear stress. An ascending speed curve was also
traced to verify whether it coincided with $1 512 512 512 512 512
the descending curve. This would verify that $2 512 512 512 512 512
$3 128 256 512 512 512
thixotropic breakdown had been effective. $4 .., 32 64 128 128
Maximum speeds that could be used without

Journal of Dairy Science Vol. 71, No. 7, 1988

 FLOW PROPERTIES OF DULCE DE LECHE 1785

TABLE 2. Parameters from Wehmann's model (see Equation [3] ) for Dulce de Leche samples with different
solids content at different temperatures. 1

Temperature Sample 1 Sample 2 Sample 3 Sample 4

(°C) A B A B A B A B

25 189 4.8 901 35 1455 95

40 . . . . . . 368 8.4 825 27 ---3056 i02
50 . . . . . . 244 7.2 435 16 1610 54
60 . . . . . . 136 5.1 248 7.1 873 20
70 . . . . . . 97 3.0 162 4.1 497 15

l A and B in din/cm 2 .

(n) for $3 at 2 5 ° C a n d $ 4 at 4 0 ° C was .69.

RESULTS AND DISCUSSION
F o r t h e s e samples at o t h e r t e m p e r a t u r e s a n d S1
a n d $2 at all t e m p e r a t u r e s , n was nearly con-
Thixot ropicity
stant. T h e m e a n was .748 w i t h a s t a n d a r d
T h e T versus 0 curves were correlated d e v i a t i o n o f .020. l n v a r i a n c e o f n w i t h t e m -
a c c o r d i n g to W e l t m a n n ' s m o d e l (2): p e r a t u r e or c o n c e n t r a t i o n has b e e n r e p o r t e d
for o t h e r food products like s w e e t e n e d
T = A -- B • In 0 [3] c o n d e n s e d milk a b o v e 4 0 ° C (5), fruit p u r e e s
(10), a n d t o m a t o c o n c e n t r a t e s (9).
w h e r e A = initial stress a n d B = c o e f f i c i e n t o f Values o f K a n d T O as a f u n c t i o n of
thixotropicity breakdown. t e m p e r a t u r e a n d for d i f f e r e n t TS are s h o w n
Values o f A a n d B o b t a i n e d f o r e a c h s a m p l e in Figures 2 (K) a n d 3 (To). To c o r r e l a t e t h e s e
a n d t e m p e r a t u r e are in T a b l e 2. All c o r r e l a t i o n data, first general e x p r e s s i o n s such as t h e fol-
c o e f f i c i e n t s a b o v e .98 i n d i c a t e W e l t m a n n ' s lowing were tried :
m o d e l is a d e q u a t e to m o d e l t h i x o t r o p i c i t y o f
d u l c e de leche. F o r $1 a b o v e 2 5 ° C n o ap- K -- a. e x p ( E a / R . t ) - T s b [41
p r e c i a b l e t h i x o t r o p i c i t y could b e o b s e r v e d ; f o r
o t h e r s a m p l e s it decreased w i t h t e m p e r a t u r e
increase a n d increased w i t h TS increase. T h e
value o f B, w h i c h iis indicative o f h o w fast
t h i x o t r o p i c i t y dissapears u n d e r c o n s t a n t s h e a r • Sl
+ $2
stress, is also p r e s e n t e d in Figure 1 w i t h linear
&S3
c o r r e l a t i o n s o f log B versus t e m p e r a t u r e . W h e n • S4
B < 2 . 5 d i n / c m 2, t h e c o r r e s p o n d i n g T versus 0
curve s h o w s negligible t h i x o t r o p i c i t y . Figure 1
i n d i c a t e s t h a t all s a m p l e s at c o o k i n g t e m p -
1.6 +
e r a t u r e ( 1 0 0 ° C) will n o t b e t h i x o t r o p i c . W h e t h e r
t h i s e f f e c t n e e d b e c o n s i d e r e d at l o w e r t e m -
p e r a t u r e s will d e p e n d o n t h e e n g i n e e r i n g
a p p l i c a t i o n . T h i x o t r o p i c i t y decrease w i t h in- ,g
crease in t e m p e r a t u r e was also o b s e r v e d in
s w e e t e n e d c o n d e n s e d m i l k (5). J*

HerscheI-Bulkley Parameters
0 ~ 3~ ~ ~ ~ ~ T e m ~ r a t ure ~)
S h e a r stress versus r o t a t i o n a l speed f l o w dia-
Figure 1. Coefficient of thixotropic breakdown
g r a m s were c o r r e l a t e d a c c o r d i n g to a Herschel-
(B) as a function of temperature for different samples
Bulkley model with correlation coefficients of Dulce de Leche. $1 54.6% total solids, $2 60%,
b e t w e e n .992 and .999. F l o w b e h a v i o r i n d e x $3 64.7%, and $4 70%.

Journal of Dairy Science Vol. 71, No. 7, 1988

1786 HOUGH ET AL.

For each sample (TS constant) K and TO can

be adequately correlated with temperature. The
classical Arrhenius-type equation (7):
110

K or TO = a- exp(Ea/R.t) [51
100 ~S~
+$2
AS3 and the equation proposed by Fernandez-
90 eS4
Martin (4) for concentrated milks:
8O
lnKorlnT 0=aa +a2"t+a3"t 2 [6]
7¢
where used. Sum of square differences between
GO, calculated and experimental values were smaller
for Equation [6] and therefore this last one
50, was chosen. Values of parameters and cor-
relation coefficients for the four samples are in
Tables 3 and 4 for K and TO, respectively.
Corresponding curves are presented in Figures 2
3O
and 3.
If the temperature is maintained constant,
correlations can be found for K and T O versus
10

30 t,O r,~ 60 70 Teml>erat urD t ~ )

Figure 2. Experimental values of consistency

index (K) as a function of temperature for different
samples of Dulce de Leche. Curves are correlations
of Equation [6]. S1 54.6% total solids, $2 60%,
330
l
$3 64.7%, and S4 70%. 300

270 • S1
+$2
AS3
where Ea = activation energy, R = gas law con- 240 • $4

stant, t = temperature, and a and b constants.

210
Equations [41 has been used successfully
for other food products (8) but was not ap-
180
plicable to Dulce de Leche. Applied to K and
TO, multiple linear correlation coefficients ~50
were .983 and .997, but calculated values
differed from experimental by as much as 67% 120
in the K correlation and 17% in the TO corre-
lation. The general quadratic expression used 9O

by Fernandez-Martin (4) could not be used

either. Apparently the reason a general ex-
pression cannot be used for Dulce de Leche
is because once the cooking process reaches
a certain point, chemical changes occur. There-
, i J
fore, the four samples measured differ in TS 3O 40 50 60 0 Temperature{'C)
and also in chemical components. Thus,
parameters such as those in Equation [4] Figure 3. Experimental values of yield stress (To)
as a function of temperature for different samples
cannot he expected to remain constant for of Dulce de Leche. Curves are correlations of
all four samples, as each one is really a different Equation [6]. S1 54.6% total solids, $2 60%, $3
product. 64.7%, and $4 70%.

Journal of Dairy Science Vol. 71, No. 7, 1988

 FLOW PROPERTIES OF DULCE DE LECHE 1787

TABLE 3. Correlation parameters o f equation In K = a~ + a~ . t + a 3 .t 2 , where K is consistency index (din/cm 2 ),

and t is temperature (°C) for different samples o f Dulce de Leche.

Correlation
S amp le a~ a2 a~ coefficient

S1 2.67 -.0372 -3.59.10 -s .997

$2 4.09 -.0453 -6.62.10 -s .992
$3 6.04 -.0929 3.59.10-* ,999
$4 7.52 -.0744 1.08.10 - 4 .991

TS. T h e e q u a t i o n s u s e d w e r e : experimental and calculated values was found.

K o r T O = a. T s b
K o r T O = a. e x p ( b . T S )
In or In T O = b l + b 2 " T S + b s ' T S 2
These three equations were correlated with
the experimental data, and then for each one
the sum of the squared differences between
E q u a t i o n [9] g a v e t h e b e s t fit. P a r a m e t e r s a n d
[7] correlation coefficients of equation [9] f o r
e a c h t e m p e r a t u r e a r e in T a b l e s 5 a n d 6 f o r K
[8] a n d TO, r e s p e c t i v e l y .
Although a general expression to predict K
and T O at any temperature and TS could not be
[9] d e r i v e d , E q u a t i o n s [6] a n d [9] a r e a d e q u a t e
for most design or processing calculations. The
correlation coefficients imply that good ap-
proximations are to be expected for extrapola-
tions to cooking temperatures (Ca 100°C).

T A B L E 4. Correlation parameters o f equation In T O = aa + a 2 - t + a 3 - t ~ , w h e r e T O is yield stress (din/cm 2)

and t is temperature C C ) for different samples o f Dulee de Leche.

Correlation
Sample at a2 a3 coefficient

S1 5.13 -.0616 1.02.10 - 4 .999

$2 7,07 -.0919 3.23.10 - 4 ,999
$3 6,88 -.0445 -1.62.10 -4 .999
$4 8.57 --.0810 2.37.10 - 4 .982

TABLE 5. Correlation parameters o f equation In K = b 1 + b2-TS + b3,TS 2, where K is consistency index

(din/cm 2) and TS is total solids (%) at different temperatures.

Temperature Correlation
CC) b2 b~ b3 coefficient

25 --20.0 .524 --2.38.10 - a .999

40 24.0 --.899 8.89.10 - a .992
50 17.5 --.710 7.37.10 - a .997
60 30.9 --1.15 1.08.10 - 2 .997
70 16.2 --.676 6.92.10 - a .997

Journal o f Dairy Science Vol. 71, No. 7, 1988

1788 HOUGH ET AL.

T A B L E 6. Correlation parameters o f equation In T O = b~ + b 2 .TS + b~ .TS a , where T O is yield stress (din/cm 2 )

and TS is total solids (%) at different temperatures.

Temperature Correlation
(°C ) b1 b2 b3 coefficient

25 -44.6 1.46 - 1.06.10 - 2 .999

40 -11.1 .304 -8.99.10 -4 .999
50 -19.3 .567 -3.14.10 -z ,998
60 1.05 -.121 2.48.10 - 3 .999
70 -3.03 5.70.10 - 3 1.35.10 - 3 .999

4 Fernandez-Martin, F. 1972. Influence of tem-

ACKNOWLEDGMENTS
The authors acknowledge the financial
support of the Argentine Scientific and Tech-
nological Secretariat (SECYT) and Mastellone
Hnos., Buenos Aires, Argentina.
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Journal of Dairy Science Vol. 71, No. 7, 1988