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Rheological Properties and Phase Separation of Xanthan-Sodium Caseinate Mixtures Analyzed by a Response Surface Method
Abdelkader HadjSadok a; Nadji Moulai-Mostefa b; Mounia Rebiha a a Institut de Chimie Industrielle, Universit de Blida, Route de Soumaa, Blida, Algeria b LPTRR, Universit Yahia Fares de Medea, Ain D'Heb, Medea, Algeria Online publication date: 03 March 2010

To cite this Article HadjSadok, Abdelkader, Moulai-Mostefa, Nadji and Rebiha, Mounia(2010) 'Rheological Properties and

Phase Separation of Xanthan-Sodium Caseinate Mixtures Analyzed by a Response Surface Method', International Journal of Food Properties, 13: 2, 369 380 To link to this Article: DOI: 10.1080/10942910802532531 URL: http://dx.doi.org/10.1080/10942910802532531

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International Journal of Food Properties, 13: 369380, 2010 Copyright Taylor & Francis Group, LLC ISSN: 1094-2912 print / 1532-2386 online DOI: 10.1080/10942910802532531

RHEOLOGICAL PROPERTIES AND PHASE SEPARATION OF XANTHAN-SODIUM CASEINATE MIXTURES ANALYZED BY A RESPONSE SURFACE METHOD Abdelkader HadjSadok1, Nadji Moulai-Mostefa2, and Mounia Rebiha1
1 2

Institut de Chimie Industrielle, Universit de Blida, Route de Soumaa, Blida, Algeria LPTRR, Universit Yahia Fares de Medea, Ain DHeb, Medea, Algeria

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Effects of xanthan and sodium caseinate concentrations on the rheological properties of their mixture in an aqueous medium were investigated at neutral pH. It was deduced from the use of an experimental design methodology, the existence of a critical concentration of sodium caseinate, which depends on the xanthan quantity, and beyond which repulsive segregation interactions occur, generating a weakening of the elastic modulus and an embitterment of the colloidal system structure. In addition, it was observed that when the Casson viscosity value of the aqueous solution was above 0.1 Pa.s, phase separation of the system was observed. The phase diagram of the solution was established using a polynomial fit. Keywords: Xanthan, Sodium caseinate, Rheology, Interactions, Response Surface Method.

INTRODUCTION Proteins and polysaccharides are commonly used in many food industries because of their potentiality to improve texture, stability and dietetic aspect of the products with complex structure, in particular the food emulsions where both biopolymers are present.[1,2] The proteins are used for their surface properties, to stabilize the oily droplets, while polysaccharides are usually added to increase the viscosity of the continuous phase. In an aqueous medium, phase separation due to the thermodynamic incompatibility results in mutual repulsive interactions of segregation of the two biopolymer macromolecules. In this case, the polysaccharide-polysaccharide or protein-protein interactions are sufficiently high in comparison to the biopolymer-solvent interactions.[3] Conditions of incompatibility depend on several factors, in particularly, temperature, pH, ionic force, concentration and conformation of biopolymers.[4,5] On the other hand, in the case of flocculation by depletion, the non-adsorbed polymer is excluded from the internal space of the two colloidal particles, as their surface of separation becomes smaller than the polymer chain size.[6] An osmotic pressure difference is then created and consequently flocculation

Received 30 March 2008; accepted 7 October 2008. Address correspondence to Nadji Moulai-Mostefa, LPTRR, Universit Yahia Fares de Medea, Ain DHeb 26001 Medea, Algeria. E-mail: moulai_nadji@yahoo.fr 369

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of the two particles is observed. In the case where the inter-colloids attraction interaction is significant, the system can record a phase separation.[7] The proteins of sodium caseinate are a mixture of four caseins. They are amphiphilic and anionic macromolecules (above isoelectric point) and can form aggregates in an aqueous medium by hydrophobic interactions, in the form of sub-micelles.[8] It was shown, by means of the multiangle laser light scattering that sodium caseinate solutions not purified (with its lipidic matter) had a radius gyration (Rg) values ranged from 50 to 120 nm.[9] Recently, by dynamic light scattering, we have found that sub-micelles of sodium caseinate (purified and in presence of 100mM of NaCl), have a dynamic radius of about 11 nm.[10] The xanthan gum is an anionic natural biopolysaccharide, produced by the Bacterium of Xanthomonas Campestris and made up of various monosaccharides, mannose, glucose, and glucurinic acids. The macromolecules of xanthan can have the conformation of a simple, double or triple helicoidally flexible chains,[11] which are able to interact beyond a critical concentration of 0.005 % approximately and to form aggregates starting from 0.07 %.[12] Thus, this biopolymer has the capacity to increase the viscosity of the solution.[13] Knowledge of rheological behavior of food preparations based on soluble biopolymer content is quite important in quality control, storage and processing. The rheological and structural properties of proteinpolysaccharide mixtures depend on biopolymer interactions that can be influenced by the concentration and molecular structure of biopolymers.[14,15] Knowledge of the types of interactions that occur in polysaccharideprotein systems is important for providing optimum food quality and for the design of new products with attractive structures and textures. Recent studies on the aqueous mixture containing sodium caseinate (NaCN) and xanthan, at neutral pH, were carried out by using apparent viscosity, confocal microscopy[16] and dynamic light scattering,[17] in order to investigate the phase behavior and the mixture microstructure. It was found that both biopolymers produce a phase separation, when the xanthan concentration is about 0.5% (in wt.%) with 5% of NaCN. However, the authors did not determine the phase diagram of the system. In conventional multifactor design, experiments are usually carried out by varying a single factor while keeping all other factors fixed at a specific set of conditions. It is not only time-consuming, but also usually incapable of reaching the true optimum due to ignoring the interactions among variables. Thus, it is desirable to develop an acceptable process in shortest possible time using minimum number of men, hours, and raw materials. The technique of the experimental design is an efficient method of indicating the relative significance of a number of variables and their interactions.[18] For this purpose, response surface method (RSM) was proposed to determine the influences of individual factors and their interactive influences. RSM is a statistical technique for designing experiments, building models, evaluating the effects of several factors and their interactions.[19] In this work, the interactions between the ingredients in sodium caseinate-xanthan mixtures by determining the rheological properties were investigated. RSM was used to determine the effects of the two biopolymer concentrations on the rheological behavior of their aqueous mixture at neutral pH. In particular, investigations were focused on the negative inter-biopolymer interactions, which can take place, and are generally responsible for phase separation. The phase diagram of the colloidal system was determined using a polynomial fit.

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MATERIALS AND METHODS Materials Sodium caseinate (NaCN) was obtained from Armor Proteins (France), containing 0.09 wt% calcium, 1.45 wt% sodium, 2.67 wt% phosphate, and 5.8 wt% moisture. Xanthan gum was purchased from Rhodia (Algeria). All the other used chemicals were of analytical grade and were obtained from Sigma Chemical Co (Switzerland). Preparation of Xanthan/Protein Mixtures The mixtures concentrations of sodium caseinate and xanthan, in the solution, were varied from 16% and from 00.5% (in wt.) respectively. The quantities of powder of the two ingredients were dissolved simultaneously under stirring in distilled water, during 20 hours at room temperature. A quantity of 0.01% (in wt.) of sodium azide was added in order to protect the mixture from microbial contamination. The pH of all samples was adjusted to 7 by slow addition of 0.01M NaOH under continuous stirring. Rheological Analysis Rheological measurements were performed using a controlled stress rheometer (Paar Physica MCR 300, equipped with the US software 200), in a steady and oscillatory shear with coneplate geometry. The flow properties were measured by applying a sequence of constant stress values to the samples and measuring the corresponding shear rate. Oscillatory stress sweep tests were always performed at a fixed frequency in order to know the linear viscoelasticity range. For this test, the colloidal solutions were subjected to a ramp of a small oscillatory deformation at a frequency of 10Hz and at a temperature of 20C. All the frequency sweep measurements were performed well within the linear range. Phase Separation The phase separation of the aqueous mixture was obtained under normal conditions. The samples were put in transparent test tubes at room temperature and the phase separation (an upper phase rich in xanthan and a lower phase rich in NaCN) was detected for a period of six months. However, in spite of the presence of sodium azide in the solutions, a beginning of mixture degradation was observed after three months. Under these work conditions, it was not possible to measure the heights of the two phases, because they vary slowly in the time, and thus it was not possible to know the time of their stabilization. From this analysis, a characteristic response of the system state stability (St) was obtained, St = 1, the mixture is stable and St = 0, there is a macroscopic phase separation. Experimental Design The influence of varying concentrations of xanthan and NaCN was studied using in particular a D-optimal design. The D-optimal method is relatively a new technique, related to response surface methodology, used for carrying out the design of experiments, the analysis of variance, and the empirical modeling.[20] Table 1 presents the levels of predictor variables tested following D-optimal design of experiments. The design consisted

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HADJSADOK, MOULAI-MOSTEFA AND REBIHA Table 1 Experimental Matrix (Factor levels and responses). hc (Pa.s) 0.005 0.151 0.015 0.112 0.041 0.026 0.104 0.133 0.099 0.079 0.011 0.079 0.081 0.080 0.077 t0 (Pa) 0.00 0.41 0.00 2.29 1.59 0.66 0.36 0.29 2,04 2.25 0.00 1,15 1.24 1.16 1.28

Test 01 02 03 04 05 06 07 08 09 10 11 12 13 14 15

NaCN (%) 1 6 6 1 1 1 6 6 4.33 2.66 4.33 3.50 3.50 3.50 3.50

Xanthan (%) 0 0.50 0 0.50 0.33 0.16 0.16 0.33 0.50 0.50 0 0.25 0.25 0.25 0.25

Go (Pa) 0.70 1.57 0.70 12.60 6.57 2.27 1.50 1.66 15.00 14.30 0.70 4.80 5.00 5.12 4.50

St 1 0 1 1 1 1 0 0 1 1 1 1 1 1 1

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of 15 experiments including four repetitions for the calculation of the pure error. The mathematical model suggested, binds the NaCN and xanthan concentrations with the rheological parameters, noted Y, and is of polynomial quadratic type. It takes into account the effects of both biopolymers and their interactions:

Y = a 0 + a1NaCN + a 2 Xant + a11NaCN 2 + a 22 Xant 2 + a12 NaCN.X ant

(1)

The quality of this model and its power of prediction, are related to the variance coefficient, R2 and to prediction coefficient, Q2 respectively. The responses fixed as objectives in this formulation are the rheological parameters of the Casson model (hc (Pa.s) and s0 (Pa)); the elastic modulus G0 (Pa), and the parameter of the state of stability St. The model of surface response corresponding to the D-optimal experimental design takes into account all the principal retained factors and their interactions. RESULTS AND DISCUSSION Rheological Behaviour of Xanthan/NaCN Solutions The initial part of the experimental plan was devoted to the analysis of the flow behavior of xanthan solutions and its dependence on the protein concentration. The mechanical behavior of the solutions studied is presented in Fig. 1. The shear stress was varied from 1 to 1000 Pa at 20C. A clearly non-Newtonian behavior of a shear-thinning (pseudoplastic) fluid was observed. Similar curves were obtained for all preparations. The shear rateshear stress data at all biopolymer concentrations were well described by the power law model with yield stress values. Some rheological models were tested, but did not adequately fit the flow curves, n such as Oswald ( s = s 0 + K g , ), Herschel Bulkley ( s = K g n + h g , ), Sisko n ( s = K g + h g , ) and generalized Casson ( s = s 0 + h g + K g ). g is the shear rate and

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12 Experimental Casson 10

(Pa)

0
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100

200

300

400

500

600

700

(s1)

Figure 1 Typical rheogram and its adjustment by the Casson model, at T = 20C[10].

s is the shear stress. From Fig. 1, it was noticed that the experimental data can be fitted to the Casson model, with a satisfactory correlation (R close to 1) for all the concentrations considered. The Casson model is given by the equation:

s 1 / 2 = s 1 / 2 + (h c g )1 / 2 0

(2)

The characteristic parameters of this model are the Casson viscosity, hc obtained when the shear rate is infinite ( h c = (s / g )( g ) ) and the yield stress s0 obtained at g = 0 . Xanthan solutions were also examined under oscillatory shear conditions (Fig. 2), in order to define the upper limit of the linear viscoelastic range and determine the mechanical spectrum for each concentration level. The experimental data obtained from stress sweep tests performed at 10 Hz are shown in Fig. 2. A typical curve of the variation of the elastic modulus, G, according to g, is presented. G0 represents the plateau of the curve in the range of linear viscoelasticity.

Statistical Analysis Table 1 summarizes the characteristic parameters values of the selected tests obtained from the realization and characterization of the different mixtures. The examination of these experimental values shows that the values of yield stress, so and elastic modulus G0 are strongly correlated: s0 = 0.190G0 0,154; R = 0.94. Consequently, these two characteristics are dependent and are controlled by the same phenomena. So it is judicious to keep only one of them (it was proposed to keep only the response G0). The parameters of the polynomial model associated to the two characteristics (Log(G0), hc are calculated

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10

G'0

G' (Pa) 1
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0.1

10

Figure 2 Typical curve of variation of the elastic modulus, G, according to g.[10]

by the multilinear regression method, by using the experimental values of G0 and hc corresponding to the concentrations of NaCN and xanthan:

Log (G0 ) = 0.40 + 0.26 NaCN + 4.23Xant 0.04NaCN 2 0.33 NaCN Xant 2.45Xant 2 nc = 0.07 + 0.03NaCN + 0.05Xant + 0.01NaCN 2 + 0.001NaCNXant 0.02Xant 2 X

(3)

(4)

Statistical testing of the model was performed with the Fishers statistical test for analysis of variance (ANOVA). The ANOVA of these responses demonstrated that the model is highly significant as is evident from the value of Fstatistic (the ratio of mean square due to regression to mean square to real error), (Fmodel (a) = 29,9228 and Fmodel (b) = 13,3230) and a very low probability value (P = 0,001). Obviously, the quality of these three equations is satisfactory. This leads us to determine, by simulation, the concentration effects of each component, on the characteristics of the aqueous mixture, in the domain of study. Influence of Xanthan and NaCN Concentrations on the Elastic Modulus In Figs. 3 and 4, are shown the simulated curves of the effects of xanthan and NaCN respectively on the elastic modulus (G0). The two figures are equivalent, but allow us to appreciate the intrinsic effects of each of both substances. Figure 3 shows the effect of xanthan at various levels of NaCN (from 1% to 6%) and experimental reference curve of xanthan solution (CNaCN = 0%). Obviously, the effect is positive, but tends to decrease with the high NaCN concentrations. In this case, polysaccharide loses its aptitudes of stabilization, and if it is used with a relatively high concentration, the aqueous mixture which results (tests 2, 7, and 8) develops a phase separation (St = 0). The upper phase is rich in NaCN and the lower phase is rich in xanthan. This phase separation could be caused by

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18 16 14 12
G'0 (Pa)

Xanthan = 0% 0.125% 0.25% 0.375 % 0.5%

10 8 6 4 2

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3 NaCN (%)

Figure 3 Na-CNs curves influence on the storage modulus (Go) at various xanthan concentrations.[10]

depletion interaction, as that proposed in the case of casein-guar,[21] casein-carrageenan,[22] casein-pectin,[23] or casein-xanthan systems.[16] However, attraction by depletion of the protein particles generally generates a rise in the viscosity of the system.[24] In our case, phase separation was accompanied by a drastic loss of the storage modulus parameter value (G0). Thus, rare are the authors who worked with the NaCN-xanthan systems in an aqueous medium. Among them, Nash et al.[17] showed, by using confocal microscopy, that

14 12 10 G'0 (Pa) 8 6 4 2 0 0.0

NaCN = 0% 1% 2% 3% 4% 5% 6%

0.1

0.2

0.3 Xanthan (%)

0.4

0.5

0.6

Figure 4 Xanthans curves influence on the storage modulus (Go) at various Na-CN concentrations.[10]

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the NaCN-xanthan system is not controlled by the same mechanism of interaction as that of the casein-xanthan system (depletion flocculation). According this author, in the case of NaCN-xanthan system, the mixture appears not homogeneous and the aggregate proteins of NaCN are not visible on the microscope. Indeed, we have showed, in a recent study[10], by using dynamic and static light scattering that the increase of the concentration of caseinate, does not produce an increase of the apparent hydrodynamic radius of submicelles and their apparent molar mass. Therefore, there is no aggregation of NaCN molecule due to the increase of the concentration of caseinate. It was possible to deduce that the thermodynamic incompatibility mechanism supported by the electrostatic repulsive interactions, is responsible for the phase separation because the two biopolymers have the same charges.[3] Figure 4 shows the effect of NaCN on G0, with various xanthan concentrations. Except for the curve associated with 0% of xanthan, all the curves are no monotonous, with an increasing section of G0 and another decreasing section of G0. Obviously, there is a critical concentration of NaCN, from which the structure rigidity, with its storage modulus G0 decreases. In this last case, the segregation interactions of xanthan-NaCN can be occurred. The critical NaCN concentration, denoted NaCN*, corresponds to the beginning of reduction in G0, and depends on the xanthan concentration. However, it should be noticed that this concentration is not synonymous of a macroscopic phase separation of the mixture. The critical concentration, NaCN*, is associated with the optimal value of the polynomial expression given by the Eq. 3. Therefore:

G o =0 ( NaCN )

for NaCN = NaCN *

(5)

A simple calculation shows that it is expressed as follows:

NaCN* = 4.24 Xant + 3.39

(6)

The maximum critical value of NaCN* (3.39%), associated to 0% of xanthan, corresponds to the value, to which, the least quantity of the added xanthan would give rise to negative interactions. Moreover, the minimal critical concentration of NaCN* (1.27%) corresponds to the quantity which can potentially develop segregative interactions with the maximum of quantity of xanthane (0.5%). Thus, For CNaCN 1.27% and 0% Cxanthan 0.5%, there is no segregative interactions between the two biopolymers, and thus would be co-soluble. Influence of Xanthan and NaCN Concentrations on the Casson Viscosity Figure 5 shows the response surfaces for Casson viscosity as a function of the xanthan and caseinate concentrations. As can be observed the Casson viscosity increased as biopolymers concentrations increased. ANOVA applied to the results indicated that biopolymer concentration significantly influenced the viscosity. Tavares et al.[25] reported the same behavior for frozen concentrated orange juice. They found that the index consistency is influenced by fruit concentrate related to pectin content, fibers, and pulp content. The limiting Casson viscosity (hc) is a parameter which explain the structural state of the matter, when this one is in extreme flow associated to an infinite shear deformation.

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0.16 0.14 0.12 0.10

c (Pa.s)

Xanthan 0.1% 0.3% 0.5%

0.08 0.06 0.04 0.02 0.00

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NaCN (%)
Figure 5 Na-CNs curves influence on the Casson viscosity at various xanthan concentrations.[10]

The macromolecules in suspension, under the effect of this maximum shearing, record a total disintegration accompanied by an alignment of the chains according to the direction of shearing. The attractive or repulsive interactions under these conditions are negligible compared to repulsion forces of shearing. Consequently, the effect of the addition of xanthan or NaCN can be only positive on hc because the increase in the number of chains or sub-micelles and thus of obstacles in the solution, generates more resistance to the flow. However, Hemar et al.[16] noticed that the apparent viscosity at high shearing rate ( g >1000 S-1) of the mixture containing xanthan and NaCN is qualitatively constant, according to the addition of NaCN. Phase Separation of the Polymeric Mixtures In Fig. 6 is shown the dependence of the state of stability of the polymeric mixture in solution to hc. It was observed clearly that the macroscopic phase separation, one rich in xanthan and the other in NaCN, cannot take place unless the limiting Casson viscosity is beyond a critical value, hc = 0.1 Pa.s. This critical Casson viscosity corresponds in fact to the state where the system contains an important number of sub-micelles of NaCN and chain of xanthan. So segregative interactions become intense, and they will lead the aqueous system to a phase separation. Thus, while replacing, in Eq. (4), the Casson viscosity hcby the critical value, noted hc* = 0.1 Pa.s, the implicit equation of the binodal line is obtained (Eq. (7)), which separates the domain on two areas: a macroscopic phase corresponding to a homogeneous phase and a biphasic system.

0.07 + 0.03 NaCN + 0.05 Xant + 0.01NaCN 2 0.1 = 0 + 0.001NaCN Xant 0.02Xant 2

(7)

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Stability
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0 0.00

0.05

0.10 c (Pa.s)

0.15

0.20

Figure 6 State of macroscopic stability of the aqueous mixture according to the variation of the viscosity of Cassons model.[10]

6 biphasic systems

bin
NaCN % 4 homogen systems

oda

l lin

e
0.1 Pa.s

2 0.01 Pa.s 1 0.0 0.1 0.04 Pa.s 0.2 0.3 Xanthan % 0.07 Pa.s 0.4 0.5

Figure 7 Phase diagram of the solution mixture as a function of the simultaneous variation of Na-CN and xanthan concentrations.[10]

In Fig. 7 is shown the phase diagram, obtained by simulation, in which the two domains are separated by the binodal line. It appears that the critical Casson viscosity variation depends strongly on the xanthan concentration. When the xanthan quantity is relatively high, the viscosity decreases and becomes sensitive to NaCN concentration. Unfortunately, there is no literature that gives the phase diagram of xanthan-NaCN systems to compare these results.

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CONCLUSION In this work, effects of sodium caseinate and xanthan concentrations and their interactions on the rheological properties of their aqueous mixture were studied. For this purpose, series of tests were prepared and characterized, and the results were modeled by polynomial functions, with the assumption to consider that these effects are nonlinear and that the interactions of order one can exist. It arises from this effect study on the rheological properties, that beyond a certain NaCN concentration which depends on the xanthan quantity used (pH 7 and 3mM of sodium azide), repulsive interactions occur and consequently a decrease in the storage modulus Go is obtained. This phenomenon does not generate systematically a macroscopic phase separation. However, in the case where the Casson viscosity exceeds a critical value (0.1 Pa.s), segregative interactions between xanthan and NaCN inevitably will lead the system to a phase separation, one rich in NaCN and the other in xanthan. Thus, only the repulsive interactions, which are responsible for the brittleness of the polymeric network are of thermodynamic nature, and are probably caused by the differences on the chemical structure of the hydrocolloidal and polymeric surfactant. REFERENCES
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