Journal of the University M. Chemical Technology and Metallurgy, 40, 4, 2005, 323-328 of Karsheva, S. Georgieva, G.

Birov

FLOW BEHAVIOUR OF TWO INDUSTRIALLY MADE SHAMPOOS

M. Karsheva, S. Georgieva, G. Birov

University of Chemical Technology and Metallurgy 8 Kl. Ohridski, 1756 Sofia, Bulgaria E-mail: mik@uctm.edu

Received 11 November 2005 Accepted 28 November 2005

ABSTRACT
The rheological behaviour of two industrially made shampoos: Green apple and Eggs was studied. They were found to be non-Newtonian and exhibited shear thinning rheological behaviour. The rheological parameters of the powerlaw model were found. Using the components and the percentage for preparing of both products the influence of the different compounds was investigated. The influence of electrolyte addition was found to be especially important. The electrolyte plays the role of thickener for the shampoos. For both products the salt curves were derived and the optimal quantity of the salt was found. The influence of the temperature on the flow parameters was studied in the interval 20 to 50oC. The data obtained could be used in calculation of power requirements for transport and mixing of such compositions. Keywords: shampoos rheology, salt curves, temperature dependence.

INTRODUCTION
Shampoos are based on complex systems of surfactants and their basic function is to cleanse the hair. Because of everyday use of these products, it is not surprising that the shampoo market for example, comprises approximately 12 % of the personal-care industry [1]. These products are complex systems, consisting of about 80 % water, 10 % surfactants, less than 5 % viscosity modifiers, about 2 % preservatives, fragrance and colorants and about 3 % of performance additives [2]. Primary surfactant is the key foaming/cleansing agent of the shampoo. One of the most popular primary surfactant is sodium lauryl sulphate (SLS). In more

recent years it is partly replaced by ammonium lauryl sulfate (ALS) [3]. Secondary surfactant is very often used to reduce the drying effect of the primary surfactant and modify the aesthetic properties of the shampoo. The most popular secondary surfactant is the ether sulfate analogue of the primary surfactant. The second most popular secondary surfactant is the betaine. Betaines (usually cocamidopropyl) have a permanently quaternized nitrogen. Because of that they could be a good hair conditioning agent and also complexing with the sulfate to build viscosity thus improving the clarity [3]. Viscosity builder. Few things are more important to consumers than using a thick (rich) shampoo,

323

Journal of the University of Chemical Technology and Metallurgy, 40, 4, 2005

directly correlating this property with value and concentration. The shampoos are expected not only to be easy to use, but also to meet sensory criteria that will appeal to the customer. The thickness and the flow characteristics of shampoos are described by the term viscosity. Viscosity affects both the cleansing efficiency and the consumer perception of a product. The rheology affects also the foaming properties, production filling, packaging, storage and stability of the product [4]. There are many possible to use in cosmetic chemistry rheological additives. Their choice depends both on the desired rheological properties of the final product and the compatibility of the thickener with the other components in the composition. Historically alcanoamides first have been used to increase the viscosity. But it was found that they do not actually build-up viscosity but only change the position of the salt curve, or in other words less salt is required to increase the viscosity. Other more effective viscosity builders include betaines. They make complex with anionics to form an enlarged surfactant micelle that build the viscosity. Additionally they contribute electrolyte (sodium chloride) that also builds the viscosity. Elec-

trolytes are almost always used to build the viscosity of shampoos. They are inexpensive and effective [3]. It is well established that a great deal of cosmetic products exhibit non-Newtonian behaviour, which is strongly dependent not only on the products composition but also on the operational conditions during formulation. The aim of this study was to investigate the dependence of flow behaviour of shampoos during their formulation and the influence of different conditions on the rheological parameters.

EXPERIMENTAL
Materials and methods The rheological behaviour of two industrially made shampoos in dependence on the constituents and operational conditions has been studied. The compositions investigated are listed in Table 1a, b. It includes Texapon Na lauryl sulphate as a primary surfactant of anionic type, Empigen BB-lauril betaine and Empilan 250 as secondary surfactants of amphoteric

Table 1a. Products compositions (Green apple).

No 1 2 3 4 5 6 7 8

Component, mass % Texapon Empigen BB Empilan250 Fragrance Euksil Alantoin NaCl Water

1 7.5

a) Shampoos composition 2 3 4 5 6 7.5 7.5 7.5 7.5 7.5 1 1 1 1 1 1.4 1.4 1.4 1.4 0.3 0.3 0.3 0.06 0.06 0.1 91.5 0.06 89.8 89.74 89.64

92.5

7 7.5 1 1.4 0.3 0.06 0.1 3.5 86.14

Table 1b. Products compositions (Eggs).

No 1 2 3 4 5 6 7 8 9 Component, mass % Texapon Empigen BB Empilan250 Fragrance Euksil Empipurl Eggs flour NaCl Water 1 9 b) Shampoos composition 2 3 4 5 6 9 9 9 9 9 1.5 1.5 1.5 1.5 1.5 1.0 1.0 1.0 1.0 0.2 0.2 0.2 0.06 0.06 1.5 89.5 88.5 88.3 88.24 86.74 7 9 1.5 1.0 0.2 0.06 1.5 0.1 86.64 8 9 1.5 1.0 0.2 0.06 1.5 0.1 3.3 83.34

91.0

324

M. Karsheva, S. Georgieva, G. Birov

type, Euksil K100 2-bromo-2-nitropropane-1,3-diol as a preservative, Alantoin and eggs flour as an active agent for Green apple and Eggs shampoo, correspondingly; Empipurl for pearl effect, NaCl as a viscosity builder, fragrance and water. These two products were chosen because of the similarity in their use and composition. For rheological measurements a rotational viscometer Rheotest RV2.1 (Germany) with S1 cylinder was used. The flow behaviour of all compositions listed in Table 1a, b was studied in dependence on consisting components. The influence of the temperature on the flow behaviour of the products was studied in the range 20 to 50 oC. In order to determine the possible thixotropic character of the systems was obtained up-curve (corresponding to agitation time t = 0) for increasing shear rates, along  with different down-curves (decreasing values) after different agitation times. Agitation was carried out with the same cylinder at = 1320 s 1 . The viscosity  was found to remain practically constant, so the products exhibited no noticeable thixotropic behaviour.

Fig. 1. Flow curves for both products: n Green apple.

eggs shampoo; u -

RESULTS AND DISCUSSION

In Fig. 1 typical flow curves for both products investigated are presented. They are non-linear without intercept. So their flow behaviour could be described by the power-law rheological model of Ostvald-de Waele:

= K . n

(1)

 here t is the shear stress, Pa, is the shear rate, s-1, K n is the consistency index, Pa.s , characterising the product consistency, n is dimensionless flow index. When n < 1 the fluids are shear-thinning (their apparent viscosity is decreasing with shear rate increase) and on the contrary, when n > 1 the products are shear thickening (their apparent viscosity increases with shear rate increase). More n differs from unity, more non-Newtonian is the fluid. The values of power-law model parameters K and n were found statistically by least squares method. They are summarized in Table 2. It is evident that the Eggs shampoo is quite more viscous than Green apple. Following the industrial composition the influence of different additives on

Fig. 2. Flow curves for different compositions for Green apple and Eggs shampoos respectively.

the flow behaviour of products was studied. The results are presented in Figs. 2a and 2b. From the composition Table 1 and coefficients of the power-law model it is evident, that most constituents for both compositions are similar, but the quantities vary. (All the concentrations are presented in % of mass.) So, for instance the surfactants are the same, but for the case of Eggs shampoo the primary surfactant is taken in 9 % of the composition, for the Green

325

Journal of the University of Chemical Technology and Metallurgy, 40, 4, 2005

Table 2. Rheological parameters of the power-law model in respect to products composition.

green apple, Pa.sn 1 2 3 4 5 6 7 8
Fig. 3a. Influence of the electrolyte addition on the flow properties of Green apple.

n green apple 0.6219 0.6005 0.5746 0.5607 0.4989 0.6272 0.7568

EggsPa.sn 0.0522 0.07241 0.0705 0.0597 0.0605 0.0642 0.0556 21.569

nEggs 0.5288 0.4779 0.4879 0.5119 0.5075 0.5181 0.5392 0.3617

0.0852 0.0289 0.0371 0.0411 0.0473 0.0235 3.3357

Fig. 3b. Salt curve for the Green apple shampoo for

Fig. 4a. Temperature dependence of consistency index for Green apple.

 = 9s 1 .

Fig. 3c. Salt curve for the Eggs shampoo for

 = 9s 1

Fig. 4b. Temperature dependence of consistency index for Eggs.

326

M. Karsheva, S. Georgieva, G. Birov

Fig. 5a. Temperature dependence of flow index for Green apple.

Fig. 5b. Temperature dependence of flow index for Eggs.

apple its percentage is 7.5; the secondary surfactant Empigen BB is taken in 1.5 and 1.0 %, correspondingly. That could be the explanation for the differences in rheological parameters (see Table 2). For example the consistency index for composition 2 (C2) of Eggs is 2.5 times greater than that for C2 of Green apple; the flow index n for Eggs is 0.48, and for Green apple 0.6. So the role of surfactants for the non-Newtonian behaviour of the products is important. Nevertheless their basic importance is to provide long-term stability to emulsions by preventing droplet coalescence. They adsorb at the water-oil interface and increase the repulsive interac-

tion among droplets. The addition of different components does not influence strongly the flow behavior of the compositions C1 to C7 for the Eggs and C1 to C6 for Green apple. The last additive for both products studied as a thickening agent was NaCl. It was proved its ability to regulate the viscosity properties of cosmetic gels. When comparing C7 and C8 compositions of Eggs and C6 and C7 of Green apple it could be seen that the addition of 3.5 % of NaCl to the composition results in 388 times increase of the consistency index K for the first product and in 141 times increase of K for the second one. The importance of the electrolyte addition to the flow properties of the composition could be demonstrated by Fig. 3a. The influence of the electrolytes (salts) as viscosity regulators is well known [5] but for every case it is necessary to obtain the salt curve to reach the desired viscosity. That was the reason for us to find the salt curves for both products. They are presented in Fig. 3b and 3c. From Fig. 3 it is evident that for the case of Green apple shampoo it is possible to reduce the NaCl concentration to 2.5 % without any change in the apparent viscosity values. For Eggs shampoo an optimal salt concentration is applied. For the final compositions studied were found apparent vis cosities in the range 4 < app < 6 Pa.s at values of 9 s-1. The usual apparent viscosity for the cosmetic gels is 5 < app < 25 Pa. s [6]. So, the final products satisfied the market demands for viscosity. The influence of the temperature on the rheological behaviour of the final compositions was also studied. In Figs. 4 and 5 the dependence of the rheological parameters on the temperature is presented. It could be seen that increasing of the temperature from 20 to 50oC leads to an exponential decrease in the consistency index K and almost does not affect the flow index n values for the Green apple shampoo. For the case of the Eggs shampoo the dependence of K on the temperature is the same, but the flow index n is also strongly dependent on the temperature (see Fig. 5). The dependence is parabolic and could be described by polynomial relationship of second degree. The temperature dependence of consistency index could be described by Arrhenius-like relationship:

K = K 0 exp (E RT )

(2)

327

Journal of the University of Chemical Technology and Metallurgy, 40, 4, 2005

Here K0 is the collision factor and E is the flow activation energy. The values of the exponential dependence for both products were calculated.

REFERENCES
1. Drug Chain Review, 22, 2, 2000, 15-18, 21, 22, 24, 26. 2. Hl. Leidreiter, U. Maczkiewitz, Utilizing Synergystic Effects in Surfactant mixtures, Th. Goldschmidt AG, Essen, Germany, 1996. 3. K. Klein, Shampoo formulation: the basics, Cosmetics &Toiletries magazine, 119, 5, 2004, 6468. 4. H. Leidreiter, K.Jenny, U. Maczkiewitz, Rheology of toiletry products- Physical properties and sensory assessment, Th. Goldschmidt AG, D-45116 Essen, Germany, 1995. 5. A.M Howe., A.E. Flowers, Allureds Cosmetics& Toiletries Magazine, 115, 12, 2000, 63-69. 6. S.Pascal, Demande de brevet dinvention, No 2755370, Composition nettoyante sous la forme dun gel transparent rincable, 04.11. 1996.

CONCLUSIONS
A study on the dependence of rheological properties of shampoos on their composition and temperature was done. The quantities of electrolyte (NaCl) necessary to build proper viscosity were found. It was found that the temperature influences strongly the all studied compositions rheology. Its increase leads to exponential decrease in consistency index and almost does not affect the flow index n for the case of the Green apple and for the case of Eggs the K dependence on the temperature is the same, but the flow index depends also on the temperature. This dependence could be described by 2nd degree polynomial relationship. The data obtained could be used in design of reactors, pipelines and pumps for such products.

328