The 1st Thammasat University International Conference on Chemical, Environmental and Energy Engineering

Adsorption of Mixed Cationic/Nonionic Surfactants on Polymer Surfaces and its Relation to Wetting Phenomena
Benchawan Thongpae1, Sumaeth Chavadej1, John H. OHaver2, and Boonyarach Kitiyanan1 1. The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand 10330 2. Department of Chemical Engineering, University of Mississippi, Mississippi, USA 38677-1848

Abstract
Adsorption and wetting on different hydrophobic surfaces with aqueous mixed solutions of cetylpyridinium bromide (CPB), a cationic surfactant, and polyoxyethylene octyl phenyl ether (TX-100), a nonionic surfactant, were investigated at different molar fractions of the nonionic surfactant of 0.25, 0.50, and 0.75. Mixed surfactant systems showed a positive effect as the molar fraction of nonionic surfactant increased. The adsorption of CPB was enhanced with increasing molar fraction of the nonionic surfactant because of the reduction of electrostatic repulsion between the head groups of adsorbed cationic surfactant molecules. However, the maximum CPB adsorption at the plateau region decreased with increasing molar fraction of TX-100 due to the obstruction of the adsorbed TX-100 molecules. Interestingly, TX-100 was found to more preferentially adsorb onto the studied plastic surfaces than CPB. In addition, wetting of the studied plastic surfaces was found to increase with increasing polarity of surfaces. Keywords: cetylpyridinium bromide, polyoxyethylene octyl phenyl ether, adsorption, wetting.

1. Introduction
The adsorption of surfactants at the solid/liquid interfaces, especially mixed surfactants systems are widely employed in several applications such as detergency, printing, and textile. This is because the mixtures of two or more different types of surfactants often show a synergistic interaction, resulting in having higher performance than a single surfactant [1, 2]. For surfactant adsorption on low-energy solid surfaces, an addition of the nonionic surfactant into ionic surfactant system reduce the electrostatic repulsion between the ionic head groups which leads to the improvement of surfactant adsorption [3-5]. As a result, the wettability of mixed surfactant solutions is better than any individual surfactant solution [6, 7]. Hence, the adsorption of mixed ionic/nonionic surfactants on hydrophobic surfaces and its relation to wetting phenomena are of interest and were investigated in this study.

The goal of this work was to study the correlation between the surfactant adsorption and the wettability of mixed surfactant solutions onto different hydrophobic surfaces. Cetylpyridinium bromide (CPB) and polyoxyethylene octyl phenyl ether (TX-100) were used as cationic and nonionic surfactants, respectively, at various molar fractions of TX-100 in mixtures. Six plastics used for this study were polyvinylchloride (PVC), high density polyethylene (HDPE), polycarbonate (PC), polymetylmetacrylate (PMMA), polyhexamethylene adipanide (Nylon66), and acryonitrile butadiene strylene (ABS). The ability of aqueous mixed surfactant solutions to wet the plastics was investigated by contact angle measurement. The effect of the polarity of hydrophobic plastics on the wettability of such solutions was also determined.

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2. Materials and Methods

2.1 Studied Surfactants Cetylpyridinium bromide (CPB) with 97% purity was purchased from Sigma-Aldrich.

UV-Vis spectrophotometer (Shimadzu, UV2550) at wavelengths of 254, and 282 nm, respectively, in which the pyridinium and the phenyl groups have strong adsorption bands. Surface tension measurement. The surface tension of surfactant solutions (LV) was measured at 30C by using a contact angle tester (Krss, DSA10). Contact angle measurement. The contact angles, , of all studied solution samples on the studied surfaces were measured using the sessile drop technique by the contact angle tester. A volume of 0.01 ml drop of surfactant solutions or pure water was placed onto studied plastic smooth sheets and the contact angle was measured after 2 min to allow equilibrium to occur. During the measurement, the chamber temperature was kept at 30C and saturated with water vapor to prevent the drop evaporation effect [9].

Polyoxyethylene octyl phenyl ether (TX-100) with 99% purity was supplied by Fluka. The studied surfactants were used as
received with further purification. 2.2 Plastics Six plastics used in this study were high density polyethylene (HDPE), polycarbonate (PC), polyvinylchloride (PVC), acrylonitrile butadiene styrene (ABS), polymethyl methacrylate (PMMA), and polyhexamethylene adipamide (Nylon66). Plastic pellets were ground into a powder by a grinder. The ground plastic samples were subjected to measure their specific surface areas by a BET surface area analyzer (Quantachrome, Autosorb-1) using nitrogen adsorption. 2.3 Methods Adsorption experiments. Adsorption experiments were carried out by mixing 20 ml of surfactant solutions having different concentrations with 0.25 g of a plastic powder sample and the mixtures were incubated for 5 d at 30C in a water bath. The molar fraction of nonionic surfactant in mixture solutions was varied to 0, 0.25, 0.50, 0.75, and 1. The supernatant solutions which were obtained by filtering with nylon syringe filters were taken for analysis of surfactant concentration. Surfactant adsorption on plastic surfaces () is calculated from the difference between the initial (Co, M) and equilibrium (C, M) solution concentrations by the following equation:

3. Results and Discussion

3.1 Hydrophobicity of studied plastic surfaces As shown in Table 1, all studied plastic samples have extremely low specific surface areas. The contact angle of pure water on HDPE is the highest and follows by PC, PVC, ABS, PMMA, and Nylon66, respectively. This result indicates that the degree of hydrophobicity of plastics increases in the order of HDPE > PC > PVC > ABS > PMMA > Nylon66. Table 1: Contact angles of water and the specific surface areas of HDPE, PVC, PC, ABS, PMMA, and Nylon66
Plastics HDPE PC PVC ABS PMMA Nylon66 Contact angle of water (degree) 92.78 89.63 84.24 83.86 77.56 69.80 BET surface area (m2/g) 1.443 1.640 1.812 3.103 1.013 6.353

( C C) V , = 0 Wplastic a s

(1)

where V is the volume of a surfactant solution, l; Wplastic is the weight of a powdered plastic sample, g; and as is the specific surface area of the powdered plastic sample, m2/g [8]. Analysis of surfactant concentration. Cationic surfactant and nonionic surfactant concentrations were determined by using a

3.2 Critical micelle concentrations (CMCs) The surface tension isotherms of CPB, TX-100, and their mixtures are shown in Fig. 1. For any given surfactant system, the surface tension (LV) decreased with increasing surfactant concentration and remained almost

The 1st Thammasat University International Conference on Chemical, Environmental and Energy Engineering

80 70

LV (mN/m)

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Initial surfactant concentration (M)

100

1000

10000

Figure 1: Surface tension isotherms of () CPB, () TX-100, and their mixtures with = () 0.25, () 0.50, and () 0.75. Table 2: CMC values for mixed CPBTX-100 solutions at different TX-100 molar fractions ()
0 0.25 0.50 0.75 1.0
10.0

CMC (M) 6.0 10-4 5.0 10-4 4.0 10-4 3.0 10-4 2.0 10-4

(mol/m2HPPE)

a)

1.0

Slightly polar

Non polar

unchanged after reaching the CMC. The CMC values determined from the inflections in the isotherms are listed in Table 2. The CMC of the cationic surfactant (CPB) solution decreases with increasing molar fraction of the nonionic surfactant.

Table 3: Maximum mixed surfactant adsorption, (mol/m2), having different TX-100 fractions on different plastic surfaces
HDPE PC PVC ABS PMMA Nylon66 0 2.04 2.29 2.85 4.02 5.89 6.36 0.25 3.06 3.25 3.63 4.70 6.39 7.06 0.50 3.16 3.37 4.03 5.03 6.79 8.00 0.75 4.29 4.89 5.14 5.96 6.97 8.75 1 4.64 5.12 6.08 6.69 7.93 10.30

3.3 Mixed Surfactant Adsorption The adsorption isotherms of CPB, TX-100, and their mixtures on all studied plastic surfaces have similar shapes, as shown in Fig. 2. For any studied plastic surface, the surfactant adsorption increased with increasing surfactant concentration and reached the plateau at about the CMC which the maximum surfactant adsorption could be determined. Table 3 summarizes the maximum adsorption on all studied plastics of various surfactant systems. From Table 3, for any given plastic, the maximum surfactant adsorption of the pure CPB solution was much lower than that of the pure TX-100 solution. For mixed surfactant solutions, their maximum adsorptions were in between the pure surfactant systems. For any non-polar plastic surface and any given nonionic surfactant fraction, the maximum surfactant adsorption was less than that of any slightly polar plastic surface. Moreover, the presence of nonionic surfactant in the mixtures showed a positive effect because of the reduction of electrostatic repulsion between the head groups of adsorbed cationic surfactant molecules [2, 4]. Table 4: Maximum CPB adsorption, (mol/m2 of plastic), of mixed surfactant solutions having different TX-100 fractions on different plastic surfaces HDPE PC PVC ABS PMMA Nylon66 0 2.04 2.26 2.85 4.02 5.89 6.36 0.25 2.25 2.43 2.77 3.54 4.78 5.30 0.50 1.57 1.69 2.08 2.54 3.43 4.03 0.75 0.97 1.22 1.31 1.52 1.76 2.20

0.1 1 10 100 1000 10000

Equilibrium surfactant concentration (M)

Figure 2: Adsorption isotherms of () CPB, () TX-100, and their mixtures with = () 0.25, () 0.50, and () 0.75 on HDPE.

The 1st Thammasat University International Conference on Chemical, Environmental and Energy Engineering

3.4 CPB Adsorption The maximum amounts of CPB adsorbed obtained at the plateau region from the mixtures on different plastic surfaces are shown in Table 4. For any given plastic surface, the CPB adsorption decreased when the molar fraction of TX-100 increased. The explanation is that TX-100 adsorbed more preferably onto the hydrophobic surfaces than CPB. Another possible reason is the masking of negative charge plastic surfaces by the TX-100 monomeric adsorption. These two reasons may be responsible for the decrease in CPB adsorption at higher molar fractions of nonionic surfactants [3]. 3.5 TX-100 Adsorption An increase of absorbed TX-100 obtained in the plateau region with increasing molar fraction of TX-100 is shown in Table 5. It can be explained that TX-100 more preferentially adsorbs onto the studied plastic surfaces [10]. Furthermore, the result can be explained in terms of the formation of mixed surfactant clusters [3]. Initially, the monomers of nonionic surfactant get adsorbed on the surfaces which were involved in hydrophobic chain-chain interactions with the adsorbed CPB monomers. It was conceivable that due to these interactions, mixed surfactant clusters were formed at the interface. However, because of higher surface activity of nonionic surfactants, additional monomers of nonionic surfactants could get abstracted into these mixed clusters with their hydrophobic group oriented toward the mixed clusters and hydrophilic group oriented toward the solution phase. These additional monomers were thereby involved in chain-chain interactions with the monomers of CPB and TX-100 adsorbed, giving rise to increase adsorption. 3.6 Wettability of Surfactant Mixtures From Fig. 3 and 4, for any studied plastic surface, the contact angle decreased significantly with increasing surfactant concentration, and at a very high surfactant concentration, the contact angle remains almost unchanged. Moreover, the wettability on any plastic surface with solutions of TX-100 and CPBTX-100 mixtures was much better than that of single CPB solution. TX-100 gave the highest wetting efficiency, and the wetting

Table 5: Maximum TX-100 adsorption, (mol/m2 of plastic), of mixed surfactant solutions on different plastic surfaces HDPE PC PVC ABS PMMA Nylon66
100

0.25 0.81 0.82 0.57 1.16 1.61 1.77

0.50 1.59 1.68 1.95 2.50 3.36 3.97

0.75 3.32 3.67 3.84 4.44 5.21 6.55

1 4.60 5.12 6.16 6.71 7.93 10.30

a)
80

(degree)

60

40

20 10

Initial surfactant concentration (M) b)

100

1000

10000

100

80

(degree)

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20 10

Initial surfactant concentration (M) c)

100

1000

10000

100

(degree)

80

60

40

20 10

Initial surfactant concentration (M)

100

1000

10000

Figure 3: Contact angle as a function of surfactant concentration on a) HDPE, b) PC, and c) PVC for the solutions of () CPB,

The 1st Thammasat University International Conference on Chemical, Environmental and Energy Engineering

() TX-100, and their mixtures with = () 0.25, () 0.50, and () 0.75.

100

a) (degree)
80

hydrophobicity of plastics, as shown in Table 1. It can be concluded that an increase in the polarity of the plastics can affect the wettability. 4. Conclusions

60

The effects of the composition of mixed CPB-TX-100 solutions on the surfactant adsorption on different hydrophobic plastic surfaces were studied. The
mixed surfactant systems showed a positive effect with increasing molar fraction of TX-100 a nonionic surfactant, leading to wetting improvement. The adsorption of CPB was enhanced by the presence of nonionic surfactant because of the reduction of electrostatic repulsion between the head groups of adsorbed cationic surfactant molecules. However, the CPB adsorption in the plateau region decreased with an increase in molar fraction of TX-100 due to the obstruction of the adsorbed TX-100 molecules. Interestingly, TX-100 was found to more preferentially adsorb onto the studied plastic surfaces than CPB. In addition, wetting of the studied plastic surfaces was found to increase with increasing polarity of surfaces. Acknowlegements This research was financially provided by The National Excellence Center for Petroleum, Petrochemical and Advanced Materials and The Research Unit of Applied Surfactants and Pollution Control. Thai Plastic and Chemicals Public Co., Ltd., Thai Polyethylene Co., Ltd., Diapolyacrylate Co., Ltd., IRPC Public Co., Ltd., and SY Smile Co., Ltd. are acknowledged for providing plastic samples for this research. References
[1] Ogino, K., and Abe, M., Physicochemical Properties of Mixed Surfactant Systems, Holland, P.M, and Rubingh, D.N., Ed., ACS Symp. Ser. 501, Am. Chem. Soc., Washington, 1992. [2] Rosen, M.J., Surfactant and Interfacial Phenomena, 3rd ed., John Wiley & Sons, New Jersey, 2004. [3] Desai, T.R., and Dixit, S.G., Coadsorption of cationic-nonionic surfactant mixtures on polytetra fluoroethylene (PTFE) surface, J. Colloid Interface Sci., Vol. 179, pp. 544-551, 1996. [4] Somasundaran, P., Huang, L., Maltesh, C., Adsorption behavior of cationic and nonionic surfactant mixtures at the alumina-water

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Figure 4: Contact angle as a function of surfactant concentration on a) ABS, b) PMMA, and c) Nylon66 for the solutions of () CPB, () TX-100, and their mixtures with = () 0.25, () 0.50, and () 0.75. efficiency was improved by increasing molar fraction of the nonionic surfactant. It means that CPB and TX-100 in a mixture performed a synergism in the wettability on all studied plastic surfaces [5]. For any surfactant system, the contact angle increased in the following order: HDPE > PC > PVC > ABS > PMMA > Nylon66 which correlates to the order of the degree of

The 1st Thammasat University International Conference on Chemical, Environmental and Energy Engineering

[5]

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interface, J. Colloid and Interface Sci., Vol. 177, No. 1, pp. 222-228, 1996. Esumi, K., Nagahama,T., and Meguro, K., Colloid Polym. Sci., Vol. 269, No. 12, pp. 12741280, 1991. Bogdanova, Yu.G., Dolzhikova, V.D., Badun, G.A., and Summ B.D., Wetting effect of aqueous binary mixed solutions of cationic and nonionic surfactants, Russian Chemical Bulletin, Vol. 52, No. 11, pp. 2352-2359, 2003. Soboleva, O.A., Yaroslavtsev, A.A., Badun, G.A., and Summ B.D., Mixed surfactant adsorption layers of nonionic and cationic surfactants on quartz, Kolloidny. Zh., Vol. 66, No. 4, pp. 470-476, 2004. Kharitonova, T.V., Ivanova, N.I., and Sumn, B.D., Adsorption of cationic and nonionic surfactants on a SiO2 surface from aqueous solutions: 1. adsorption of dodecylpyridinium bromide and triton x-100 from individual solutions, Kolloidny. Zh., Vol. 67, No. 2, pp. 274-280, 2005.

[9] Puttharak, A., Surfactant Adsorption on Hydrophobic Surfaces, M.S. Thesis, The Petroleum and Petrochemical College, Chula-longkorn University, 2006. [10] Pipithvittaya, N., Admicellar Polymerization in a Continuous Stirred Tank Reactor for Surface Modification of Silica: Process Optimization Using Commercial Grade Mixed Surfactants, M.S. Thesis, The Petroleum and Petrochemical College, Chulalongkorn University, 2006.