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

second is preferred for confectionery purposes because of its greater viscosity. This increased The rheological behavior o f commerr o m the starch added during viscosity results f cial samples of Dulce de Leche (sweet its preparation. m i l k ) for household and confectionery An important characteristic of Dulce de use was studied. Both products have thixLeche 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 magniproduct is also important for operating evaporatu& decreased with increased temperation equipment as well as for handling (12). ture. Activation energies were 9.9 and Little information exists in the literature con10.4 kcaYmo1 for household and confeccerning 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 origithat the flow properties of Dulce de Leche are nal sample (pH = 6.1); at alkaline pH markedly different from that determined by f the viscosity was higher than that o Higgs and Norrington (8) for sweetened conoriginal. 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 conFrom shear stress and shear rate flow f solids, which in the case of Dulce centration o diagrams, the Herschel-Bulkley model de Leche, may vary from 54 to 70% depending was adequate for b o t h 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 55'C) on rheological behavior, and to predict INTRODUCTION flow properties near the processing temperaDulce de Leche is similar in composition to tures and for the cooling process. sweetened condensed milk and is typically preAs pH has an important effect on protein pared with milk concentrated at atmospheric stability, its effect on the flow curves was also f added sucrose. A investigated using commercial samples of pressure in the presence o s m a l l 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. f confectionery type. The household use and o first is generally used as a dessert, and the
ABSTRACT MATERIALS AND METHODS

Received April 19, 1990. Accepted December 3, 1990. 1991 J Dairy Sci 741497-1502

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

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ROVEDO ET AL.

purchased in a supermarket. The composition of household Dulce de Leche was 80% milk, 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% HC1 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.
Vlscorneter

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 w a s 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 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)readings 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

The flow properties of Dulce de Leche were measured with a concentric cylinder viscometer (Haake RV 12 Rotovisco) with a M O O measuring head. The h4V I I 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

where the values of A and M are provided by the manufacturer for each sensor system. Apa s obtained from q = T/ parent viscosity ( P a s ) w D.
RESULTS AND DISCUSSION

1W-

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

0
2

Figure 1. Experimental r h g ~ a m o w e d by increasing and decreasing shear rate (3 min per cycle) of the sample of M c e de Lcche f o r household usc at 2 5 C and pH 6.1.

l i ~
----___
1 Timelsl 6
--l

; 65 2
55

-~

0;

150

203

Figure 2. Variation of shear slress with lime at constant shear rate.

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RHEOLOGY OF DULCE DE LECHE

1499

OO

x3
10

20

30

OO

I O

20

30

Sheor rate, D(s1

Shear rote, D I<]

Figure 3. Effect of time on rheological curves of Dulce de Leche for household use at 25C and pH 3 . 0 .

Figure 4. Effect of time on rheological curves of Dulce de Leche for household use at 25C and pH 8.3.

change in the rheological behavior occurred during the first shearing cycle. To confirm 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). 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

changed, the product evolves very slowly before reaching a rheological behavior independent of time. Such an increase in the apparent viscosity w i t h 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 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 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 The effect of temperature on flow behavior o f 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
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(4).

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TABLE 1. Rheolonical g parameters, and mean relative deviation modulus for Dolce de h e . ' - model, fittin_ _
TemperaRheological model tare Q Household
ConfectiOntry
P%2

Po
28.38 15.69 5.7 .86 .7 1
.5

n .6 .6 1 .65 .3 .3 .4
5

b
457 4.85

Po
18.3 36.7 15.76

n
.43 .47 .47

p46

( ' c )

'E=vJ+lb.Dn

25 40

(Herschel Bulldey) 55 25 40 55 25 T~ = E ': + (Ib-D)"40 (Casson) 55 25 ~ = % + p , y D 40 (Bingham plastic) 55 25 'E = p(yLP 40 (Dower l a w ) 55
~

45.46 182 9.65 2657 10.52 7.06 56.81 22.19 9.77

%.84

.84 .65 1.39 1.38

...
...
47.84 22.91 8.12 79.46 39.41 14.73
0

e = $ + k D p (Heinz-Casson)

2.45
1.84

.89 1.51 2.89 2.18 1.84 7.83 6.31 5.75 6.06 4.38 5.67

...

... ... ...

6.09 3.5 1.6 13.58 7.42 3.2 82.62 41.24 15.68

...
...

.78 1.24 1.37

...
5

...
4.94 4.56 522 8.61 8.31 9.35 .73 1.47 1.31

... ...

.5
.5

39.1 17.08
0

0 0

.77 5.1 3.8 1.62 57.58 29.14 12.7

5 5

1.o 1.o 1.o .45

1.0 1.0 1.0 .42

.46 . 4 6

0 0

.44 . 4 8

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 agrees with that reported by Hough et al. (9). who found that during Dulce de Leche preparation (temperature near ZWC), the product loses its thixotropic characteristic. Flow c w e s of three original samples a t 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(

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 Ostwaldde Waele (ll), HeinzCasson (He&, 6). and Herschel-Bulkley (7). The five equations are given in Table 1. The

= A exp W T )

[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

2 0

30

Modeling of the Flow Curves

Shear rate, O C d

The flow curves o f the original samples of Dulce de Leche (household, pH = 6.1 and
Journal of Dairy Science Vol. 74. No. 5. 1991

Figure 5. Effect of temperature on flow curves of Dulce de Leche for household use (untreated sample, pH 6.1).

RHEOLOGY OF DULCE DE LECHE

1501

6 b
U U

e
c

0
L

I
10

20

3 0

Shear rote, D Is)

Pigum 7. Cumparkon between experimental data and mathematical models for household Dulcc de Leche @H 6.1, UT);power l a w (-h Haschel-Bulkley (-. -); Casson (-.-); Singham (---); and experimental (A).

Bulkley model gave the best fit, although accurate fitting w a s also obtained with Heinz-CasShear 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. F l o w behavior index (n) resulting from the various tested models was less than unity, indicating that Dulce de Leche is a pseudoplastic values of the parameters corresponding to each f l u i d 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 f l o w fit of the models to the experimental data was behavior index w a s also observed by other calculated by means of the mean relative deviainvestigators for Dulce de Leche and other food tion modulus defined as follows (10): products (9, 13).
5

10

15

where ~i = measured shear stress, Zpi = pre dicted 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 1, for household Dulce de Leche, the Herschel-

TABLE 2. Yield stress values.

Tanperahm
Household
confecti~ilery

cc)
25 40 55

P a )
54.5 2 2 . 6
11.3 27.2 1 6 . 3 5.4

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REFERENCES

The plastic behavior of Dulce de Leche w a s demonstrated; to initiate flow a shear stress higher than a critical value, the yield stress, TO, had to be applied Yield stress values obtained n Table 2 . from the rheograms are shown i 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 rheological parameters that define the flow behavior. Each of the five models predicted % values for both products which indicates that this parameter depends on both the material and n the the model selected. As was reported i literature (ll),the values of TO calculated from mathematical models are not totally reliable when used for subsequent calculation of unknown 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 confectionery Dulce de Leche. The comparison of the and flow behavior index, consistency index, h, n, for household and confectionery Dulce de Leche indicates that the latter has more consistency (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.

lBarbosa Canovas, G. V., and M. Peleg. 1983. Flow parameters of selected commercial semi-liquid food products. J. T e x t u r e Stud. 14213. 2 B i ~ g b m E. , C. 1922. Fhidity and plasticity. McGrawW, New York, NY. 3Casson, N. 1959. A flow equation for pigmented-oil suspension o ft h e printing ink t y p e . . Page 82 in Rheclogy of dispersc systems. c. c. Mill, 4. Pergamon Press. New York. NY. 4 Evans. E. W.1985. Interactions of milk components in food systans. Page 241 in Interactions of food c o m p eents. G. G. Birch and M. G. Liodley, ed. Elsevier Appl. Sci. hbl., London, Engl., New York, NY. 5 P d e z - M a r t i n , F. 1972. Influence of temperature and composition on some physical properties of milk and milk comxntrates. I I .V i s c o s i t y . J. D a i r y Res. 39: 75. 6Fincke, A. 1961. Beiirage ZUI Losung rheologischer Problane in der Schokoladentechnologie. F'h.D. Diss., TH Karlsruhe. Germany. (Quoting Heinz, 1959.) 7Hasche1, W. H., and R. Bulkley. 1926. Konziztemmcssungen von gommibensollosugen. Kolloid-Zeitschr. 39291; Proc. ASTM 26:621. 8Higgs. S. J., and R J. Norrington. 1971. Rheological properties of selected foods&. Rocess Biochem. 6: 52. 9Hough. G., 0. Mom,J. Segura, and N. Calvo. 1988. Plow properties of Dulce de b h e , a typical Argentine dairy product. J. Dairy Sci. 71:1783. 10Loma1~0, C. I., A. S. Bakshi, and T.P. Labum. 1985. Evaluation of food moisture sorption isotherm equations. Part II: milk, coffee, t e a , nuts, oilseeds, spices and starchy foods. Lebensm. Wiss. Techuol. 18:118. 11 Ofoli, R Y . , R. G.Morgan, and J. P. Steffe. 1987. A -g ' rheological model for inelastic fluid foods. J. Texture Stud. 18:213. 12Pauletti, M.S . ,A. Vernier, D.Stecbina, N. Sabbag, E. Castelao. 1988. Caracterizaci6n reol6gica del Dulce de &he. Rev. Agroqah. Techool. Aliment. 28(2):303. 13Ra0, M . A., M. C. Bourne, and H . J. Cwlcy. 1981. Flow properties of tomato concentrates. J. Texture Stud. 12521. 14Rciner, M. 1949. Deformation and f l o w .Lewis, London, 1 . 15Sherman, P. 1970. Industrial rheology. Academic Press, New York, Ny; London, EngL

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