Carbohydrate Polymers 64 (2006) 4149 www.elsevier.

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Inuence of hydroxypropylmethyl cellulosesodium dodecylsulfate interaction on the solution conductivity and viscosity and emulsion stability
Verica J. Sovilj *, Lidija B. Petrovic
Department of Applied and Engineering Chemistry, Faculty of Technology, Bul. Cara Lazara 1, 21000 Novi Sad, Serbia and Montenegro Received 12 December 2004; received in revised form 8 September 2005; accepted 27 October 2005 Available online 5 December 2005

Abstract The conductivity, viscosity and rheological measurements were used to study the interaction of HPMC with an anionic surfactant-sodium dodecylsulfate (SDS) in aqueous solutions of different concentrations. The properties of HPMC solutions (0.11.0%) with increasing SDS concentrations (02.0%) were investigated. On the basis of following the changes of the system during the HPMCSDS interaction, the characteristic concentrations of SDS at which interaction starts (the critical aggregation concentration (CAC)) and at which it ends (polymer saturation point (PSP)), were determined, and an interaction mechanism was proposed. The linear relationship between the PSP and HPMC concentrations was found, while CAC remained constant. To show that the interaction of the components in the continuous phase of dispersed systems can change their properties, the changes of stability of HPMC-stabilized oil-in-water emulsions with SDS addition were also examined. It was found that stability of the emulsions was inuenced by the HPMCSDS interaction. After the preparation, stability of emulsions increased with increase in continuous phase viscosity and stability changed with time according to the mechanism of HPMCSDS interaction in the continuous phase. q 2005 Elsevier Ltd. All rights reserved.
Keywords: Polymersurfactant interaction; Conductivity; Viscosity; Rheology; Emulsion stability

1. Introduction Interactions between polymers and surfactants have been widely investigated in the recent decades, because the complexes thus formed may have a signicant inuence on the system properties. Polymer-surfactant mixtures are often used in food products, pharmaceutical formulations, personal care products, paints, pesticides, etc. The effects of polymersurfactant interactions are useful in practice to achieve emulsication, colloidal stability, viscosity enhancement, gel formation, solubilization, and phase separation (Goddard, 1993a; Goddard, 2002). The properties and structure of surfactant-polymer complexes depend on the molecular characteristics of the polymer and surfactant (Lindman & Thalberg, 1993; Winnik & Regismond, 1996; Li & Dubin, 1994). Interaction is most pronounced in the system consisting of the oppositely charged polymer and surfactant, often accompanied by phase separation. Then come the

* Corresponding author. Tel.: C381 21 350122x416; fax: C381 21 450413. E-mail address: miso@uns.ns.ac.yu (V.J. Sovilj).

0144-8617/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbpol.2005.10.030

systems uncharged polymer-charged surfactant, and weakest interactions exist between uncharged polymer and surfactant (Goddard, 1993b,c; Wang, Kimura, Huang, Dubin & Jaeger, 1999; Kastner, Hoffmann, Donges & Ehrler, 1994; Thalberg & Lindman, 1991; Hormnirum, Sirivat & Jamieson, 2000; Ridell, Evertsson & Nilsson, 2002). There are two polymersurfactant interaction mechanisms of different intensity, viz. electrostatic and hydrophobic. Depending on the polymersurfactant system and surfactant concentration, the surfactant may adsorb onto the polymer in the form of individual molecules or small aggregates. Mixed micelles may be formed with surfactant molecules and hydrophobic polymer segments. At sufciently high surfactant concentrations, only free surfactant micelles are formed in the solution. As the polymer-surfactant interaction takes place, the properties of the systems change, and they can be detected by various techniques like tensiometry (Persson, Nilsson & Sundelof, 1996; Avranas & Iliou, 2003), viscometry (Jiang & Han, 2000), rheometry (Kulicke, Arendt & Berger, 1998a; Sovilj, Dokic & Petrovic, 2003) electrochemical methods (Minatti & Zanette, 1996; Sovilj, 1998), equilibrium dialysis (Arora, Singh & Singhal, 1984), NMR (Hammarstrom & Sundelof, 1993), uorescence (Winnik & Regismond, 1996; Garca Mateos, Perez & Velazquez, 1997), and some others.

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V.J. Sovilj, L.B. Petrovic / Carbohydrate Polymers 64 (2006) 4149

Water-soluble nonionic derivatives of cellulose, like hydroxypropylmethyl cellulose (HPMC), are physiologically harmless and are preferred for the use in foodstuffs and pharmaceutical industry (Zhang, 2001). The introduction of methyl and hydroxypropyl groups renders the cellulose molecule hydrophobic and thus it acquires surface-active properties, so that HPMC can be regarded as a representative of polymeric surfactants (Kulicke, Arendt, & Berger, 1998b). In the presence of low molar mass surfactant, such as sodium dodecylsulfate (SDS), the hydrophobic centers on the HPMC molecules represent potential adsorption sites for surfactant molecules (Kulicke et al., 1998a). When the polymer hydrophobicity increases, the interactions become stronger, and the properties of the system change in different ways, depending on the interaction mechanism involved (Kientz, & Holl, 1994; Clasen & Kulicke, 2001). Because of that the HPMCSDS interaction has to be studied separately for each degree of substitution. Since the majority of commercial products are dispersed systems, of special interest is also to study the effect of interaction of the continuous phase components on their stability. Therefore the studies of polymer-surfactant interactions are important from both theoretical and practical point of view. The aim of the present work was to study the HPMC SDS interactions by conductometric, viscometric, and rheometric methods, in a wide range of SDS concentrations, up to well above the critical micelle concentration (CMC) and at HPMC concentrations up to above the critical overlap concentration (C*). The objective was to use the obtained results to determine the characteristic SDS concentrations of the beginning and ending of the interactions. Also, it was of interest to investigate the inuence of HPMCSDS interactions in the continuous phase on stability of oil-in-water emulsions. 2. Experimental 2.1. Materials Hydroxypropylmethyl cellulose (HPMC), (trade name Methocel K4M CR, methoxyl content 22.7%, hydroxypropyl content 8.9%), obtained from Colorcon Ltd., England, was used without any further purication. Viscosity average molecular mass was MvZ91,500 g/mol, determined at 20 8C. Sodium dodecylsulfate (SDS), purity O99%, was obtained from Merck, Germany. Bidistilled water was used as solvent. Stock solution of HPMC was prepared by dispersing proper amount of HPMC in water at 80 8C (above the gel point which is approximate 70 8C for a 2% aqueous solution), by gentle stirring. The stock solution was left for 24 h at room temperature before its further use. Stock solution of SDS, 3.0 g/100cm3, was used after preparation. 2.2. Conductivity Conductivity measurements were carried out at 30 8C in a jacketed beaker by adding the proper volume of 3.0 g/100cm3

SDS solution to the 50 cm3 of HPMC solution of the following concentrations: 0.05, 0.1, 0.2, 0.35 and 0.5 g/100cm3. After adding each portion of the surfactant, the solution was stirred with magnetic stirrer until a steady conductance value was attained (Sovilj, 1998). The pH value of HPMC solutions was around 5, and changed only a little with the SDS addition (DpH was 0.18 for HPMC solutions without and with maximal concentration of SDS added), because there are no ionic interaction between SDS and HPMC molecules (Clasen &. Kulicke, 2001). Specic conductance of the solution was measured on a microprocessor conductivity meter Model MA 5964 (Iskra, Slovenia), using a cell with the cell constant of 1.000. All solutions were prepared with bidistilled water of a specic conductance between 2 and 3 mS/cm at 30 8C. 2.3. Viscosity Viscosity measurements of diluted HPMC solutions were performed on an Ubbelhode capillary viscometer (ow time for bidistilled water was 195.6 s at 30 8C), immersed in a water thermostat at 30 8C. To the volume of 15 cm3 of HPMC solution the proper volumes of 3.0 g/100cm3 SDS solution were added to obtain a desired SDS concentration. For each solution, 35 viscosity measurements were taken and average values were calculated. The results were expressed as specic, reduced and intrinsic viscosities. Specic viscosity hsp Z hKh0 tKt0 z h0 t0 (1)

h and h0 are the solution and pure solvent viscosities, respectively; t and t0 are the ow times in the viscometer of the solution and pure solvent, respectively. Reduced viscosity hred Z hsp C (2)

C is the HPMC concentration. Intrinsic viscosity is a limit of the reduced viscosity when the concentration tends towards zero: h  sp h Z (3) C CZ0 The standard Huggins extrapolation procedure was employed to determine intrinsic viscosities. The viscosity-average molecular mass was calculated from the MarkHouwink equation:
a h Z KMv

(4)

where Mv is the viscosity-average molecular mass and K and a are the constants whose values depend on the solvent and temperature. For HPMC in water at 20 8C, the reported values are aZ0.88 and KZ3.39!10K4 100cm3/g (Alvarez-Lorenzo, Gomez-Amoza, Martinez-Pacheco, Souto & Concheiro, 2001). The critical overlap concentration (C*) was estimated as 1/[h] (Hormnirum et al., 2000).

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43

2.4. Rheological measurements Rheological measurements were performed using rotational viscometer RV20 (Haake, Germany) at 30 8C. An SVI measuring sensor was used. The solutions of 1.0 g/100cm3 concentration of HPMC in the presence of various SDS concentrations were investigated. Continuous loop hysteresis method was applied (Sovilj & Dokic, 1996). Shear stress t (Pa) was determined with continually changing shear rates D (sK1) from zero (DZ0) to a maximal value and reverse (after 10 min shearing at Dmax), by an acceleration/deceleration of the viscometer rotor revolution of 400 minK2. To avoid the Weissenberg effect at high shear rates, maximal value of shear rate was Dmax Z360 sK1. The apparent viscosity ha (Pas) was calculated as: ha Z t Pas D (5)

oil droplets. The extent of creaming was characterized by the creaming index, H. The higher the creaming index the worse the emulsion stability (Kelley & McClements, 2003): HZ 100Hs %: HE (8)

As the interaction in the emulsion may cause the changes in aggregation, coalescence, oil droplet size and droplet size distribution, viscosity, properties of adsorption layer, etc., which are reected on the value of creaming index (Becher, 1996; Friberg, Larsson, & Sjoblom, 2004), these phenomena will not be the subject of this study. Although the creaming index provides indirect information about emulsion stability, it is a good indicator of the changes in the emulsion due to the HPMCSDS interaction in the continuous phase.

The obtained ow curves (in the range of shear rates used) show a non-Newtonian pseudoplastic behavior and can be presented by the known OstwaldReiner power law: t Z KDn Pa and ha Z KDnK1 Pas (7) (6)

3. Results and discussion 3.1. Effect of SDS on the conductivity of HPMC solutions Conductometric titration is one of the most often used techniques to determine critical micelle concentration (CMC) of ionic surfactant, as well as to examine the nonionic polymerionic surfactant interaction in dilute solution (Minatti & Zanette, 1996; Sovilj, 1998; Garca-Mateos et al., 1997). The addition of surfactant to the water caused a linear increase of specic conductance up to the surfactant concentration at which micelle formation began, i.e. up to the CMC. After the CMC, the conductance increased further linearly, but with a smaller slope than before the CMC. The break on the conductance-concentration titration curve gives the CMC of the surfactant. For the SDS, the CMC determined by conductometric titration was 0.252 g/100cm3 at 30 8C (Fig. 1). In the presence of HPMC, the relationship between conductance and SDS concentration (Fig. 1), like with most of ionic surfactant-nonionic polymer systems (Minatti & Zanette, 1996; Goddard, 1993b), shows two break points. In the classical proles of conductivity investigation of ionic surfactantnonionic polymer interaction, the breaks are related to the beginning of surfactant binding to the polymer, the so-called critical aggregation concentration (CAC), and saturation point of the polymer by the surfactant (PSP) (Zanette, Soldi, Romani & Gehlen, 2002). In the ionic surfactant-nonionic polymer solutions there are no interactions until the surfactant concentration reaches the CAC value. The CAC is always lower than the CMC of the surfactant (Li & Dubin, 1994), implying that the surfactant-polymer complex formation is energetically more favorable than the formation of micelles (Avranas & Iliou, 2003). Addition of SDS to HPMC solution causes a linear increase in conductivity, with the same slope as for SDS without HPMC. After reaching CAC, there is an evident decrease in the slope, which can be explained by the depletion of free ions of the surfactant from solution, either by adsorption on, or by cluster formation with the polymer. This binding continues until the saturation of HPMC molecules with SDS, which is determined by the second breaking point, i.e. polymer saturation

where the coefcient K is a measure of consistency of the system, and n (0!n!1) is the degree of non-Newtonian behavior. The lower n, the more pronounced non-Newtonian ow (Zhang, 1999). 2.5. Emulsion stability A stock of oil-in-water (O/W) emulsion was prepared by dispersing 20% (w/w) of sunower oil (Sunce, Sombor) in the HPMC solution at 30 8C by means of an Ultraturrax T-25 (Janke&Kunkel, Germany) homogenizer at 6000 rpm for 10 min. Droplet sizes of stock emulsion were measured from microphotography and expressed as volume-surface mean diameter, dv/p (Djakovic, Dokic, Radivojevic, Sefer & Sovilj, 1987). The obtained value was dv/pZ7.35 mm, the standard deviation (distribution width) being sZ2.61 mm. To this emulsion with preadsorbed HPMC, which is a surface active polymeric emulsier (Kiekens, Vermeire, Samyn, Demeester & Remon, 1997; Kulicke et al., 1998a,b), various amounts of 3.0 g/100cm3 SDS solution were added to achieve desired concentrations in 1.0 g/100cm3 HPMC. After the SDS addition the emulsions were shaked only manually. The emulsions prepared this way had the uniform droplet size and droplet size distribution (same as the stock emulsion). For stability tests, the emulsions were transferred into graduated cylinders and stored at room temperatures for two months. During the storage, the emulsions separated into the cream layer at the top and transparent serum layer at the bottom of the cylinder. Total height of the emulsion HE and the height of serum layer HS were measured with time. Oil concentration of 20% was chosen to enable faster creaming of

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V.J. Sovilj, L.B. Petrovic / Carbohydrate Polymers 64 (2006) 4149

HPMC, g/100cm3 0.50 30C PSP 0.35 0.20 0.10 Conductivity CAC 0.05 SDS

CMC= 0.252 g/100cm3

0.0

0.2

0.4

0.6

0.8

1.0

cc SDS, g/100cm3
Fig. 1. Plots of conductivity (relative scale units) versus SDS concentration for water, and for various HPMC concentrations.

consequence, mobility of laurylsulfate ions is reduced, so that the break on the conductivity curve at the CAC is more pronounced. With a further increase in SDS concentration, micellar structures are formed around each individual substituent, the network structure is destroyed, ion mobilities are not restricted, and the conductivity is almost proportional to the addition of SDS. Because of that the second break point (i.e. PSP) is less pronounced. The dependence of CAC and PSP on the HPMC concentration is presented in Fig. 2. It can be seen that CAC is 0.141 g/100cm3 (4.8 mmol/dm3), independent on HPMC concentration, and is lower than the CMC of SDS, while PSP increases linearly with the HPMC concentration. Parameters of linear relationship for PSP are shown in Fig. 2. The intercept represents the value of the PSP without the presence of polymer, and it amounts to 0.255 g/100cm3, which is very close to the CMC of SDS itself. The slope of the linear dependence of PSP on polymer concentration amounts to 0.792 and it represents grams of SDS bound per gram of HPMC (Sovilj, 1998), or 2.7 mmol SDS bound per gram of HPMC. 3.2. Effect of SDS on viscosity of HPMC solution When an ionic surfactant adsorbs onto a nonionic polymer via its hydrophobic tail it changes the nonionic polymer into a polyelectrolyte-like polymer, and the electrostatic repulsions between ionic heads of the surfactant molecules cause an expansion of the macromolecule, which is easily detectable by viscosity measurement. Thus, information about the conformational changes that the polymer molecules undergo in the interaction with a surfactant is obtained mainly by viscometry (Nilsson, 1995; Jiang & Han, 2000; Hormnirum et al., 2000). Because of that, viscometric measurements were performed to study SDS interaction with diluted HPMC solution, to get a detailed insight into the changes taking place in the system
0.7 0.6 0.5 0.4 0.3 ~CMC 0.2 0.1 0.0 0.0 CAC=0.141(g/100cm3) Y=0.255+0.792X r=0.9996 PSP

point. With the further addition of SDS conductivity dependence is again linear, with the same slope as for SDS without the polymer, after reaching the CMC value. Between CAC and PSP there is the region of interaction, i.e. of binding SDS molecules to HPMC, observed as a nonlinear dependence. It has been suggested (Minatti & Zanette, 1996) that this nonlinearity could be related to a step in the binding process that corresponds to saturation of the available sites of the polymer with monomeric surfactants or micelles of low aggregation number; after that micelles with larger aggregation number begin to form. The nonlinearity changes its form in dependence of HPMC concentration. At the HPMC concentrations below the critical overlap concentration, C*, a break at PSP is more pronounced, whereas at the concentrations exceeding C* there is a break at CAC. For HPMC solution, the critical overlap concentration is C* Z0.146 g/100cm3 at 30 8C. At HPMC concentrations !C*, interactions takes place at a molecular level, i.e. there is no intermolecular binding of the adjacent polymeric chains. When the CAC is reached, SDS molecules begin to bind to HPMC molecules, forming thus smaller or bigger micellar structures around the substituent of each individual polymer molecule, which are in equilibrium with SDS molecules in the solution. Mobility of the surfactant ions in the solution is not decreased signicantly, and thus neither is the measured conductivity. Further addition of SDS yields formation of bigger micellar structures and intramolecular binding by SDS micelles, whereby the ion mobilities are signicantly lowered, and the second break point (i.e. PSP) is more pronounced. At HPMC concentrations OC*, after reaching CAC, intermolecular binding takes place via micellar aggregates that are formed around the substituents of the adjacent polymer chains, yielding the formation of network structures. As a

cc SDS,g/100cm3

0.1

0.2

0.3

0.4

0.5

0.6

cc HPMC, g/100cm3
Fig. 2. Characteristic concentration breaks (CAC and PSP) on the conductometric titration curves as a function of HPMC concentration.

 V.J. Sovilj, L.B. Petrovic / Carbohydrate Polymers 64 (2006) 4149

45

40 30C 35 30 25 !red 20 15 10 5 0.0

CAC

HPMC, g/100cm3
0.10 0.125 0.15 0.20 0.275 0.35

0.1

0.2

0.3 cc

0.4

0.5

0.6

0.7

0.8

SDS,g/100cm3

Fig. 3. Reduced viscosity, hred, for the HPMCSDS solutions as a function of SDS concentration for different HPMC concentrations.

during the interaction, and postulate the possible interaction mechanism. Results of viscometric investigations of HPMCSDS interaction at 30 8C are presented in Fig. 3. For each set of measurements, the polymer concentration was kept constant while the SDS concentration varied. At SDS concentrations up to w1.41 g/100cm3 the reduced viscosity, hred, is insensitive to the amount of SDS present, which suggests that there is no interaction between SDS and HPMC molecules. This concentration of SDS is the same as the value of CAC obtained by conductometric titration. After the CAC has been reached, the changes of reduced viscosity are very sensitive to the SDS addition and behave differently for the HPMC concentrations that are lower or higher than the critical overlap concentration C* (Nilsson, 1995; Shimabayashi, Uno, Oouchi & Komatsu, 1997). At HPMC concentrations !C*, after the CAC has been reached, there is an evident decrease in hred, which passes through a minimum around the CMC of SDS. At HPMC concentrations OC*, the reduced viscosity has a maximum at the SDS concentrations around CMC, which becomes more pronounced with increase in the HPMC concentration. At the SDS concentrations that are higher than 0.6 g/100cm3, for all polymer concentrations, the value of reduced viscosity is constant and lower than the corresponding values before CAC. These changes in reduced viscosity are inuenced by various mechanisms of the HPMCSDS interaction and conformational changes of the HPMC molecules. At concentrations of HPMC !C*, when the CAC has been reached, the SDS molecule start to bind to HPMC molecules and form small micelles around the binding sites, i.e. around the hydroxypropyl and methyl substituents. As the HPMC concentration is too low, the intermolecular binding is restricted, while intramolecular is favored. Hence, one micellar aggregate can solubilize two binding sites on the same molecule, leading to the shrinkage of the polymer coil, and

reduction in viscosity. With further addition of SDS, the redistribution and binding of SDS to HPMC continues, the micelles grow in size, the intramolecular connections are gradually lost, the polymer coil expands and viscosity increases. At the saturation point, all binding sites on the HPMC molecule (i.e. hydrophobic substituents) are separately solubilized in normal micelles, viscosity is insensitive to further increase in SDS concentration, and only free micelles of SDS are formed. At the polymer concentrations OC*, after the CAC has been reached, the SDSHPMC interaction tends to become more intermolecular in nature, i.e. one bonded micelle is shared by two or more polymer molecules, creating a threedimensional network, which leads to a signicant increase in reduced viscosity. As the SDS concentration increases further, the binding continues and the hydrophobic sites of neighboring polymer chains are solubilized separately and polymernetworking tendency is gradually lost. The reduced viscosity decreases until it reaches a constant value after the complete saturation of HPMC with SDS molecules. The value of reduced viscosity after the saturation of polymer tends to be the same and independent on SDS and polymer concentration. From Fig. 3, it can be seen that with increasing HPMC concentration the region of increased viscosity tends to be wider, because there is more intermolecular bonds, and higher SDS concentrations are needed for their solubilization, i.e. their breaking. It is obvious that the HPMCSDS interaction inuences conformational changes of the polymer molecule. Therefore, the determination of intrinsic viscosity of HPMC molecules at the characteristic SDS concentrations may give a better insight into the mechanism of HPMCSDS interaction. In Fig. 4 are presented the values of hred for various HPMC concentrations without SDS and in the presence of characteristic concentrations of SDS. At an SDS concentration of 0.06 g/100cm3 the value of reduced viscosity decreases linearly with HPMC
24 22 20 18 16 !red 14 12 10 8 6 4 0.00 0.05 0.10 0.15 0.20 0.25 0.30

SDS, g/100cm3 0 0.06 0.25 0.70 1.25

cc HPMC, g/100cm3
Fig. 4. Reduced viscosity, hred, for the HPMCSDS solutions as a function of HPMC concentration for different SDS concentrations.

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V.J. Sovilj, L.B. Petrovic / Carbohydrate Polymers 64 (2006) 4149

concentration, while intrinsic viscosity is the same as for HPMC without SDS ([h]Z6.52 100cm3/g). This conrms the assumption that no HPMCSDS interaction takes place at this SDS concentration. At the SDS concentration of 0.25 g/100cm3, which is in the range of interaction maximum, it is evident that there is a nonlinear relationship between the reduced viscosity and decreasing HPMC concentrations, i.e. the complex behaves like a polyelectrolyte (Jiang & Han, 2000; Goddard, 1993b; 2002). At the beginning, there is a signicant reduction in viscosity with decreasing HPMC concentration, caused by breaking intermolecular bonds. A further decrease in the HPMC concentration leads to increased hred values, due to the expansion of HPMC molecules caused by the electrostatic repulsion between similarly charged groups of bound SDS molecules. At the SDS concentration of 0.7 g/100cm3, when the interaction is completed, the reduced viscosity changes linearly with decreasing HPMC concentration. The value of intrinsic viscosity obtained from the linear relationship for this SDS concentration is [h]Z5.90 100cm3/g, while before the interaction it was [h]Z6.52 100cm3/g, indicating that the interaction yields the HPMCSDS complex that is more folded than HPMC molecules before interaction. After interaction, the HPMCSDS complexes are solubilized with SDS micelles and because of the presence of free SDS micelles in the solution, electrostatic repulsion between them causes folding of the complexes. Also, increased concentration of free sodium ions tends to screen the net negative charge of the HPMCSDS complex, so that the polyelectrolyte effect is lost. The linear dependence on HPMC concentration indicates that intermolecular forces are still present. With a further increase in SDS concentration the folding of complex is more pronounced and at a sufciently high SDS concentration reduced viscosity is constant, i.e. insensitive to HPMC concentration. Therefore at an SDS concentration of 1.25 g/100cm3, the reduced and intrinsic viscosities are the same, with the value of [h]Z 5.08 100cm3/g. In order to quantify the changes in coil conformation of HPMC molecule after interaction, the coil expansion factor was calculated as aZ[h]SDS/[h], where [h]SDS is the intrinsic viscosity of HPMC in the presence of SDS, and [h] is the intrinsic viscosity of the HPMC solution in the absence of SDS (Muller, Garces, Torres, Scharifker & Saez, 2003). For the SDS concentrations of 0.7 and 1.25 g/ 100cm3, coil expansion factor a is 0.90 and 0.779 respectively, showing shrinkage of the HPMCSDS complexes. Viscometric investigation gave valuable information about the mechanism of the HPMCSDS interaction and conformational changes on HPMC molecules, but the concentrations at which the interaction is ended could not be undoubtedly determined. 3.3. Rheological characteristics Since the HPMCSDS interaction yields structural changes in the solution, it can be supposed that these changes will be sensitive to the inuence of shear rate in the rheological

measurements. Inuence of interaction on the rheological characteristics of the system was investigated on the 1.0 g/100cm3 HPMC solutions in the presence of various SDS concentrations. Changes of apparent viscosity ha with SDS concentrations, obtained at constant shear rates, are presented in Fig. 5. Signicant increase in the apparent viscosity is obtained for the range of SDS concentration from 0.15 g/100cm3 (which is very close to the CAC obtained by conductometric and viscometric measurements) to 0.45 g/100cm3. After that the viscosity decreases and at SDS concentrations exceeding 1.25 g/100cm3 tends toward a constant value independent on shear rate. In the region of interaction, between CAC and 1.25 g/100cm3 SDS, the viscosity depends very strongly on shear rates, indicating the changes in solution structure caused by shearing. Flow curves of HPMC solutions in the presence of various SDS concentrations exhibit a pseudoplastic behavior. The parameters of power-law equation, K and n, as well as the coefcient of correlation r are listed in Table 1. Changes of apparent viscosity with shear rate are presented in Fig. 6(A) and (B). With increase in SDS concentration up to 0.45 g/100cm3 (Fig. 6(A)), the pseudoplastic behavior is more pronounced, i.e. shear tinning is observed due to orientation and deformation of the formed complexes (Clasen & Kulike, 2001). After that concentration (Fig. 6(B)), pseudoplastic behavior decreases, and at the SDS concentration of 1.25 g/100cm3 and higher, the solutions show a Newtonian behavior with a constant value of viscosity independent on shear rates. In the same manner changed also the rheological parameters K and n of ow curves, showing a good correlation with experimental data (in Fig. 6(A) and (B), the points are experimental and the lines represent the experimental data tted by ow curves). The value of K, which is a measure of consistency, increases with increasing SDS concentration up to
1.0 0.9 0.8 0.7 !", Pas 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 cc SDS, g/100cm3
Fig. 5. Changes of the apparent viscosities, ha, of 1.0 g/100cm3 HPMC solutions with SDS concentrations at various shear rates.

D, s1 30C 14.24 106.8 320.0

 V.J. Sovilj, L.B. Petrovic / Carbohydrate Polymers 64 (2006) 4149 Table 1 Parameters of ow curves for 1.0 g/100cm3 HPMC solutions in the presence of various concentrations of SDS at 30 8C SDS g/100cm3 0 0.06 0.15 0.20 0.25 0.35 0.45 0.65 0.75 0.85 1.00 1.25 1.50 2.00 K 0.900 0.794 1.043 1.717 2.704 3.527 2.818 1.659 0.899 0.653 0.294 0.116 0.096 0.050 N 0.6715 0.6856 0.6709 0.6342 0.6032 0.6000 0.6540 0.7230 0.8004 0.8390 0.8987 0.9651 0.9030 0.9920 r 0.9985 0.9974 0.9980 0.9985 0.9973 0.9933 0.9971 0.9974 0.9996 0.9988 0.9994 0.9968 0.9966 0.9957

47

the maximum, while the coefcient n decreases, showing a more pronounced non-Newtonian behavior (Table 1). After that, the viscosity and non-Newtonian behavior show a decrease. At the SDS concentrations of 1.25 g/100cm3 and higher, the ow curves show a Newtonian behavior, with a constant value of viscosity, hawK (Fig. 5, Table 1) and n very close to 1. After the system becomes Newtonian, the viscosity decreases further, although there is no more interaction. This is in agreement with conformational changes in the HPMCSDS complexes after solubilization. Namely, the complexes become more folded, behave like individual particles, and the viscosity of the solution falls to below that of the surfactant-free polymer solution (Kulicke et al., 1998a). The above investigations showed that a complete picture of the interaction and changes in the system on the molecular level as a consequence of interactions could be obtained by combining results of different methods. However, this does not exclude the possibility of using only one method, depending on the interaction effect to be investigated. 3.4. Inuence of HPMCSDS interaction in the continuous phase on emulsion stability

A 1.1 1.0 0.9 0.8 0.7 !a, Pas 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 B 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0 50 100 150 50 100 150 200 250 D, s1 300 350 400 SDS (g/100cm3) 0.00 0.06 0.15 0.20 0.25 0.45

To investigate the inuence of HPMCSDS interactions in the continuous phase on the emulsion stability, SDS concentrations were selected so to cover the regions before, during, and after the interaction. As all the emulsions were prepared from the same stock emulsion, having thus an identical droplet size and droplet distribution, the emulsion stability depends only on the HPMCSDS interaction in continuous phase and on the oil droplet surface. The changes of emulsion stability (expressed as the creaming index H) and apparent viscosity ha of the continuous phase, in dependence of SDS concentration (at DZ14.24 sK1), are presented in Fig. 7. The introduction of SDS to the HPMC-stabilized emulsion inuences emulsion stability (Dickinson, 2003; Kelley & McClements, 2003). Comparing with the stock emulsion

80 SDS (g/100cm3) 0.45 0.65 0.75 1.00 1.25 1.50 2.00 70 60 48 h 2 months 15 days

1.4 1.2 1.0 0.8 0.6 0.4 0.2 !a, Pas

!a, Pas

50 H, % 40 30 20 10

200 250 D, s1

300

350

400

0 0.0

0.5

1.0 SDS, g/100cm3

1.5

0.0 2.0

Fig. 6. Dependence of the apparent viscosity, ha, on the shear rate for 1.0 g/100cm3 HPMC solutions at SDS concentrations from 0 to 0.45 g/100cm3 (A) and from 0.45 to 2.0 g/100cm3 (B).

Fig. 7. Values of apparent viscosity, ha, of continuous phase (1.0 g/100cm3 HPMC, DZ14.24 sK1) and creaming index of emulsions, H, obtained at various times, as a function of SDS concentrations.

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(without SDS) all emulsions in the presence of SDS show an increase in the creaming index, i.e. a decrease in sedimentation stability. After 48 h, stability of the emulsions follows the changes in viscosity of continuous phase, i.e. the creaming index decreases with increasing viscosity. Namely, before addition of SDS, the emulsion is stabilized only with HPMC molecules (Wollenweber, Makievski, Miller & Daniels, 2000; Kulicke et al., 1998b). After the SDS addition, based on the previous investigations of the polymer-surfactant interaction (Friberg, 1997; Friberg et al., 2004; Goddard, 1993b; Sovilj, Djakovic, Dokic, 1993), it can be assumed that in the interaction region there is a competition between the HPMC molecules and the HPMCSDS complexes formed at the oil droplet surface. This process is very slow due to the increase in viscosity of the continuous phase (McClements, 2000), and creaming index is low. At SDS concentrations in the region of completed interaction, SDS solubilizes HPMC molecules; the complexes formed are not surface active, so that it can be assumed that the emulsion is stabilized only with SDS molecules. The viscosity of continuous phase is very low, which enhances the creaming index. It is evident from Fig. 7 that the changes in emulsion stability with time are more pronounced in the HPMCSDS interaction region, indicating that the stabilization of adsorption layer around the oil droplet surface takes time. After two months of storage, the changes of emulsion stability were opposite to those observed after 48 h, so that the emulsion stability in the interacting region was worse compared to the one without interaction and at the end of interaction. Also, a thin oil lm appeared at the top layer of the emulsions, indicating that the HPMCSDS interaction yielded a reorganization of the molecules in the adsorption layer around oil droplet surface and disturbance of the adsorption layer, resulting in the aggregation, coalescence and eventually in phase separation. Changes in the creaming index of HPMC-stabilized emulsions with addition of SDS show that the presence of interaction in continuous phase of emulsions can change their stability. Specic changes of emulsion properties caused by the HPMCSDS interaction require further studies. 4. Conclusion Studies of the HPMCSDS interaction by conductometric, viscometric and rheological measurements showed that a complete picture of the HPMCSDS interaction can be obtained by combining results of different experimental methods. The measurements allowed the determination of the SDS concentration at which the HPMCSDS interaction begins (CAC) and ends (PSP). It appeared that CAC does not depend on HPMC concentration, whereas PSP is linearly dependent on this concentration. On the basis of the equation of linear dependence for each HPMC concentration it was possible to determine the SDS concentrations needed for attaining a certain degree of interaction. Also, the investigations showed that the HPMCSDS interaction in the continuous phase of HPMC-stabilized oil-in water emulsion

inuenced emulsion stability. After preparation, the highest emulsion stability was observed in the region of interaction due to the increase in continuous phase viscosity. With time, stability in this region becomes the lowest because of the competition between HPMC molecules and HPMCSDS complexes in the adsorption layer around oil droplets. The data obtained in this study are important for understanding the inuence of polymer-surfactant interaction on the properties of solution and stability of dispersed system. On the basis of these investigations, stability and compatibility tests for various agents added can be assessed, which is relevant to emulsion technology. Acknowledgements This work was supported by the Ministry of Science and Environmental Protection of the Republic of Serbia. The authors are thankful to Colorcon Ltd. (England) for the generous gift of the HPMC sample. References
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