International Conference on Thermal Engineering: Theory and Applications

Beirut, Lebanon, May 31-June 4, 2004.

Double Diffusion Session II: ICTEA-DD2-07 (June 2, 2004 at 12:20)

SLES Concentration Effect on the Rheology of Dish Washing Liquid

Ali Al-Shawabkeh
Chemical Engineering Department
University of Jordan, Amman 11942, Jordan
Tel.: +962-5355-000 (ext. 2797)
Fax: +962-5355-588
E-mail: shawabke@ju.edu.jo

Abstract:

The effect of the SLES (sodium lauryl ether sulphate) concentration on the apparent

viscosity of a dish washing liquid detergent (Hypex), manufactured in a Jordanian

industry, was investigated using a Brookfield viscometer. Keeping the active matter

of the detergent (the total concentration of surfactants) fixed at 21%, five

formulations (Hypex 1, Hypex 2, Hypex 3, Hypex 4, and Hypex 5) were prepared

with different SLES-LABSA ratio of 0.50, 0.68, 0.92, 1.25 and 1.57, respectively.

The apparent viscosities of these five formulations were examined at different shear

rates ranging from 5 to 325 s−1 under both forward and backward shearing at constant

25°C.

The Hypex detergents were found to be shear thinning liquids (pseudoplastic) and

time independent. The Hypex of higher SLES concentration could exhibit higher

apparent viscosity values. These measured values were satisfactorily modeled using

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the Ostwald-de Waele power-law model. The flow-behavior index was found to

increase with increasing the SLES-LABSA ratio in the range from 0.5 to 1.57.

Keywords:

detergent/ apparent viscosity/ rheology/ linear alkyl benzene sulphonic acid/ sodium

lauryl ether sulfate.

Nomenclature:

n : the flow-behavior (power-law) index

γ : the shear rate (s−1)

κ : the consistency index (cP⋅sn−1), and

µa : the apparent viscosity (cP)

Introduction:

Rheology is a very useful tool in numerous industries [1, 2]. Rheological

characterization of different systems is required to study and control several

processes at laboratory and in industry as well. In detergent industries, for instance, it

is typical to use rheometers or adapted viscometers as most of the process fluids and

products possess non-Newtonian behavior, i.e., they are shear rate dependent on the

measurement conditions [3]. Numerous works concerned with investigating the

rheological properties of non-Newtonian fluids had been published. Lindeberg et al.

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[4], Zakaria and Rahman [5], and Eremeeva and Bykova [6] studied the influences of

polymer concentration, temperature, pH on the rheological behavior of different

polymers. Other researchers investigated the rheological behavior of aqueous

polymers solutions in gas-liquid absorption [7, 8], and in fermentation processes [9].

The value of the apparent viscosity and the relation between flow behavior and the

shear rate is related directly with the quality of the final liquid detergent product.

Liquid detergents are gaining momentum in the market and are, by and by replacing

the powder detergents. Hand dishwashing liquid detergents are used for manual

washing up and are frequently used on almost daily basis. The average quantity of

surfactant used per washing up water is not easy to estimate. It may be within a range

of a factor 1 to 5, depending on several parameters like the product concentration and

other physical parameters such as: the shape and orifice diameter of the flacon, the

strength of pressure by the user on the flacon, and the viscosity and rheology of the

product [10]. The presence of different surfactants, such as SLES and LABSA, in

certain ratios can modify “build” the viscosity of the detergent, which helps to control

the dosage for both hand and automated dishwashing detergents. Furthermore,

according to some detergent manufacturers, a thicker product means better quality to

the consumer.

The main aim of the current paper was to investigate the influence of the

concentration of sodium lauryl ether sulphate (SLES), on the apparent viscosity of the

Hypex hand dishwashing liquid detergent.

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Experimental section:

Prepared Hypex formulations:

The dishwashing liquid utilized was mainly made up of the SLES surfactant (or as

called texapon), the anionic detergent dodecyl benzene sulphonate (or linear alkyl

benzene sulphonic acid, LABSA), comperlan, and formaldehyde. Five formulations

of the dishwashing liquid (Hypex 1, Hypex 2, Hypex 3, Hypex 4, and Hypex 5) were

prepared with different SLES-LABSA ratio of 0.50, 0.68, 0.92, 1.25 and 1.57,

respectively. These Hypex formulations were prepared with weight compositions as

shown in table I. The active matter contents (in wt%) of the SLES and LABSA were

reported as 70.50 and 96.12, respectively, so that the total active matter of the

dishwashing liquid was fixed at 21%. Surfactants give thickness to the end-products,

and usually the anionic surfactants do not exceed a concentration of 30% of the

product. The five dishwashing formulations differ in their SLES-LABSA ratios as

clearly shown in table II. This table also lists the corresponding pH values measured

for these formulations.

Measuring instrument:

The apparent viscosity of the detergent was studied using a Brookfield viscometer

(RV model viscometer) at different shear rates ranging from 5 to 325 s−1. In order to

ensure accurate viscosity test results, the temperature was controlled at 25±0.3°C

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using a circulating water bath. In a typical run, a constant sample volume of the test

detergent liquid was loaded into the viscometer.

The rheological properties of the detergents were investigated by measuring the

apparent viscosity of fresh Hypex formulations at different shear rates under both

forward shearing (increasing the shear rate) and backward shearing (decreasing the

shear rate). All measurements were conducted at 25°C.

Results and discussion:

The apparent viscosities of the five Hypex formulations were measured at shear rates

ranged from 5 to 325 s−1. Both forward and backward measurements were carried out

to investigate the time dependency of these formulations as can be seen in figures 1 to

5. As can be seen in these figures, all the five detergent formulations (Hypex 1, 2, 3,

4, and 5) were found to be shear thinning liquids (pseudoplastic) as the apparent

viscosity was decreasing with increasing the shear rate. Moreover, the forward

viscosity measurements were found identical to the backward ones for all the tested

detergents, which clearly indicates the time independency of these Hypex detergents

[11].

Figure 6, presenting the forward viscosity measurements for all the five Hypex

formulations, illustrates how shear may be expected to affect the apparent viscosity of

the Hypex formulation. A reduction of about 38%, 33%, 32%, 29%,and 26% in the

viscosities of Hypex 1, 2, 3, 4, and 5, respectively, was caused by a 30-fold increase

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in the shear rate (from 10 to 300 s−1). The Hypex of higher SLES concentration

exhibits higher apparent viscosity as can be noted in figure 7, which represents the

combined effect of SLES and LABSA concentration for samples sheared at 300 s−1.

This figure also shows that the measured values could be fitted properly by linear

regression. However, it is not easy to express the mere influence of SLES

concentration on the detergent viscosity because the active matter was kept unaltered

for all the samples prepared. It is believed that the SLES can confer some nonionic

character to the surfactant due to the presence of the two ethylene glycol groups [3].

The combination of anionic and nonionic surfactants (in certain proportions) gives a

molecular arrangement for a “gel” aspect and thus modifying the apparent viscosity

[10].

The non-Newtonian behavior of the Hypex detergent was modeled using the two-

parameter, power-law model (Ostwald-de Waele model) represented by the following

relation:

µ a = κ γ n −1 .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......(1)

The model results (the solid line curves) were plotted in figure 6 together with the

experiment-derived results.

The measured forward shearing data points were non-linearly regressed, and the

Ostwald parameters ( κ , and n) are listed in table III. The good agreement between

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the calculated and experimental apparent viscosities for all the Hypex formulations is

clearly shown in figure 8.

The deviation of the Hypex detergent from the Newtonian behavior (corresponding to

n equals unity) is elucidated in figure 9. In this figure, the flow-behavior index is

found to increase with increasing the SLES-LABSA ratio in the range from 0.5 to

1.57. One may conclude accordingly that the deviation is more notable with

detergents with larger SLES-LABSA ratio.

Concluding remarks:

The research work reported here explores the influence of the SLES surfactant on the

apparent viscosity of the hand dishwashing detergent, Hypex. The apparent

viscosities of the five Hypex formulations were tested at shear rates varied from 5 to

325 s−1 and at constant temperature of 25°C and the following findings could be

reached:

• The Hypex detergents were found to be shear-thinning liquids (pseudoplastic).

• The Hypex detergents were also found to be time independent.

• The Hypex of higher SLES concentration could exhibit higher apparent viscosity

values

• The measured apparent viscosities were satisfactorily modeled using the

Ostwald-de Waele power-law model.

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• The flow-behavior index was found to increase with increasing the SLES-

LABSA ratio in the range from 0.5 to 1.57.

Acknowledgment:

This research was financially supported by the Higher Council of Science and

Technology (the Industrial Research Fund, IRF) on the Faculty-For-Factory Program.

The author thanks the Jordanian Chemical Industries for providing the hand

dishwashing samples.

References:
[1] Gómez-Díaz D. and J. M. Navaza, “Effect of food stabilizers blends

composition upon the rheological behavior”, EJEAFChe, 1 (3), 1-12, 2002.

[2] Vázques G., J. González-Álvarez, F. López-Suevos, and G. Antorrena, “Holz

als Roh-und Werlstoff”, 60 (2), 88-91 (2002).

[3] Salager J., “Surfactants Types and Uses”, Firp Booklet # E300-A, Mérida,

Venezuela, 2002.

[4] Lindeberg J. J., H. Sirviö, and J. Martinmaa, Cellulose Chem. Technol., 21,

379-385 (1987).

[5] Zakaria M., and Z. Rahman, “Rheological properties of cashew gum”,

Carbohydrate Polymers, 29 (1), 25-27 (1996).

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[6] Eremeeva T. E., and T. O. Bykova, “SEC of mono-carboxymethyl cellulose

(CMC) in a wide range of pH; Mark-Houwink constants”, Carbohydrate

Polymers, 36 (4), 319-326 (1998).

[7] Álvarez E., J. M. Correa, C. Riverol, and J. M. Navaza, “Model based in neural

networks for the prediction of the mass transfer coefficients in bubble columns.

study in Newtonian and non-Newtonian fluids”, Int. Commun. Heat Mass

Transfer, 27(1), 93-98 (2000)..

[8] Kawase Y., T. Araki, K. Shimizu, and H. Miura, “Gas-liquid mass transfer in

three-phase stirred tank reactors: Newtonian and non-Newtonian fluids”,

Canad. J. Chem. Eng., 75, 1159-1164 (1997).

[9] Bueno S. M., and C.H. García-Cruz., J. Food Eng., 50, 41-46 (2001).

[10] European Eco-Label, “Hand Dishwashing Detergents”, Technical Study,

September 2000.

[11] Wilkes J. O., Fluid Mechanics for Chemical Engineers, Prentice-Hall PTR,

1999.

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Table I. Compositions (wt%) of the prepared dishwashing liquid
formulations
Formulation Hypex 1 Hypex 2 Hypex 3 Hypex 4 Hypex 5
LABSA 16 14.6 13.1 11.2 10.2
SLES 8.0 10.0 12.0 14.0 16.0
Sodium Hydroxide 5.9 5.4 4.8 4.2 3.8
Comperlan 2.0 2.0 2.0 2.0 2.0
Formalin 0.65 0.65 0.65 0.65 0.65
Other additives 0.15 0.15 0.15 0.15 0.15
Water 67.3 67.2 67.3 67.8 67.2

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Table II. SLES-LABSA weight ratios and the
corresponding measured pH values for the
prepared dishwashing formulations
Formulation SLES-LABSA (kg/kg) pH
Hypex 1 0.50 5.90
Hypex 2 0.68 7.00
Hypex 3 0.92 8.06
Hypex 4 1.25 6.03
Hypex 5 1.57 8.50

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Table III. Ostwald parameters for the prepared Hypex
formulations
n
Formulation κ (Pa⋅s ) n
Hypex 1 6.710 0.72
Hypex 2 6.840 0.76
Hypex 3 6.930 0.77
Hypex 4 7.200 0.80
Hypex 5 7.425 0.82

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Figure captions:
Figure 1. Measured apparent viscosity of Hypex 1 at different shear rates.

Figure 2. Measured apparent viscosity of Hypex 2 at different shear rates.

Figure 3. Measured apparent viscosities of Hypex 3 at different shear rates.

Figure 4. Measured apparent viscosities of Hypex 4 at different shear rates.

Figure 5. Measured apparent viscosities of Hypex 5 at different shear rates.

Figure 6. Measured and calculated apparent viscosities of the prepared Hypex

formulations at different shear rates.

Figure 7. The SLES-LABSA wt ratio influence on the apparent viscosities (shear

rate = 300 s-1).

Figure 8. Comparison between experimental and calculated apparent viscosities of

the prepared Hypex formulations at different shear rates.

Figure 9. Variation of the flow-behavior index with the SLES-LABSA wt ratio.

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 5000
Forward shearing
Bacward shearing

4000
µa (cP)

3000

2000

1000
0 60 120 180 240 300 360
γ (s-1)
Figure 1.
Measured apparent viscosity of Hypex 1 at different shear rates.

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 5000

Forward shearing
Backward shearing

4000
µa (cP)

3000

2000

1000
0 60 120 180 240 300 360
γ (s-1)
Figure 2.
Measured apparent viscosity of Hypex 2 at different shear rates.

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 5000

Forward shearing
Backward shearing

4000
µa (cP)

3000

2000

1000
0 60 120 180 240 300 360
-1
γ (s )
Figure 3.
Measured apparent viscosities of Hypex 3 at different shear rates.

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 5000

Forward shearing
Backward shearing

4000
µa (cP)

3000

2000

1000
0 60 120 180 240 300 360
γ (s-1)
Figure 4.
Measured apparent viscosities of Hypex 4 at different shear rates.

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 5000

Forward shearing
Backward shearing

4000
µa (cP)

3000

2000

1000
0 60 120 180 240 300 360
γ (s-1)
Figure 5.
Measured apparent viscosities of Hypex 5 at different shear rates.

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 5000
Hypex 1 (8 wt% SLES)
Forward shearing Hypex 2 (10 wt% SLES)
measurements Hypex 3 (12 wt% SLES)
Hypex 4 (14 wt% SLES)
4000
Hypex 5 (16 wt% SLES)
Ostwald model
µa (cP)

3000

2000

1000
0 60 120 180 240 300 360
-1
γ (s )
Figure 6.
Measured and calculated apparent viscosities of the prepared
Hypex formulations at different shear rates.

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 3000
µa (cP), samples sheared at 300 s-1

Measured
linear regression

2000

1000
0.0 0.5 1.0 1.5 2.0
SLES-LABSA ratio(kg/kg)
Figure 7.
The SLES-LABSA wt ratio influence on the apparent viscosities
(shear rate = 300 s-1).

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 5000

Hypex 1
Hypex 2
Hypex 3
4000 Hypex 4
Hypex 5
Linear regression
µa,exp (cP)

3000

2000

1000
1000 2000 3000 4000 5000
µa,cal (cP)
Figure 8.
Comparison between experimental and calculated apparent
viscosities of the prepared Hypex formulations at different
shear rates.

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 0.85

Hypex 5
Flow-behavior index, n

Hypex 4
0.80

Hypex 3
Hypex 2
0.75

Hypex 1

0.70
0.0 0.5 1.0 1.5 2.0
SLES-LABSA wt ratio (kg/kg)
Figure 9.
Variation of the flow-behavior index with the SLES-LABSA wt ratio.

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