J. Phys. Chem.

1992,96, 6839-6843
(6) Spanhel, L.; Henglein, A.; Weller, H. Ber. Bunsen-Ges. Phys. Chem. 1987,109,6632. (7)Henglein, A.; Gutilrrez, M.; Weller, H.; Fojtik, A.; Jirkovsky, J. Ber. Bunsen-Ges. Phys. Chem. 1989,93,593. (8)Rabani, J. J . Phys. Chem. 1989, 93,7707. (9)Gerischer, H.; Labkc, M. J . Electroanal. Chem. 1986,204, 225. (10) Vogel, R.;Pohl, K.; Weller, H. Chem. Phys. Lett. 1990,174,241. (11) Hotchandani, S.;Kamat, P. V. Chem. Phys. Lett. 1992, 191,320. (12)Levy, B. In Photochemical Conversion and Storage oJSolar Energy; Pelizzetti, E., Schiavello, M., Eds.; Kluwer Academic Publishers: Boston, 1991;p 337. (13)Kamat, P. V.; DimitrijeviE; Fessenden, R. W. J . Phys. Chem. 1989, 92,2324. (14)Spanhel, L.; Anderson, M.A. J . Am. Chem. SOC.1991,113,2826. (15)Hotchandani, S . ;Kamat, P. V. J. Electrochem. Soc. 1992,139,1630. (16) Kamat, P. V.; Patrick, B. J . Phys. Chem., preceding paper in this issue. (17)Kamat, P. V.; Das, S.;George Thomas, K.; George, M. V. Chem. Phys. Lett. 1991,178, 75.

6839

(18) Baral, S.;Fojtik, A.; Weller, H.; Henglein, A. J . Am. Chem. Soc. 1986,108, 375. (19) Kamat, P. V.; Ebbesen, T. W.; DimitrijeviE, N. M.; Nozik, A. J. Chem. Phys. Lett. 1989,157,384. (20) Kaschke, M.; Ernsting, N. P.; Muller, U.; Weller, H.Chem. Phys. Lett. 1990,168,543. (21) Hodes, G.; Albu-Yaraon, A.; Decker, F.; Motisuke, P. Phys. Rev. B 1987,36, 4215. (22)Vlachopoulos. N.; Liska, P.; Auustynski, J.; Gritzel, M. J . Phys. Chem. 1988, 110, 1216. (23)ORegan, B.; Moser, J.; Anderson, M.; Griitzel, M. J . Phys. Chem. 1990, 94,8720. (24)ORegan, B.; Griitzel, M.; Fitzmaurine, C. Chem. Phys. Lett. 1991, 183,89. (25)Mening, R. Top. Curr. Chem. 1988,143,81. (26) (a) Fan, F.-R.; Faulkner, L. J. Chem. Phys. 1978,69,3341. (b) Slgui, S.; Hotchandani, S.; Baddou, D.; Leblanc, R. M. J. Phys. Chem. 1991, 95,8807.

Concentration Dependence of Micellar Size and Composltion in Mixed Anionlc/Cationic Surfactant Solutions Studied by Light Scattering and Pulsed-Gradient FT-NMR Spectroscopy
Tadashi Kato,* Hidetomo Takeuchi, and Tsutomu Seimiya
Department of Chemistry, Faculty of Science, Tokyo Metropolitan University, Minamiohsawa, Hachioji, Tokyo 192-03, Japan (Received: March 13, 1992)

Light scattering and pulsed-gradient lT-NMR spectroscopy (PGNMR) have been measured for aqueous solutions of sodium decanesulfonate (Cl,,S03)/octyltrimethylammonium bromide (OTAB) and sodium octanesulfonatefOTAB as a function of total surfactant concentration, c, at different mixing ratios (the mole fraction of OTAB in the total mixed solute, x2, is 0.145). From the analysis of self-diffusion coefficients of surfactants obtained by PGNMR, the mole fraction of OTAB in the mixed micelle, xZm, is determined. At concentrations much higher than the critical micelle concentration (cmc), xlm is close to x2. As c is decreased toward the cmc, x2"' is increased toward equimolar composition. These results suggest that micelles grow with decreasing concentration. Light-scattering results are consistent with this prediction. It is also shown that in the CI,,S03/OTABsystem, the mixed micelles grow rapidly when x~~ exceeds about 0.4.

Introduction It is well-known that dectratatic repulsion between like charges of headgroup of ionic surfactants is a major factor which inmases the free energy of micelle formation.' If other surfactants with oppositely charged headgroups are incorporated into the micelles, the micelle aggregation number is therefore expected to increase. So the composition of mixed micelles is important for discussing micellar properties in mixed anionic/cationic surfactant solutions. In our previous s t ~ d i e s ,we ~ *have ~ measured the light-scattering intensities and self-diffusion coefficients of surfactants in dilute solutions (below 0.035 m ~ l d m - ~ of) a sodium dodecyl sulfate (SDS)/octyltrimethylammoniumbromide (OTAB) system. In this system, precipitation occurs in the range c = (1-3) X or x2 = 0.35-0.95 where c is the total surfactant concentration and x2 is the mixing ratio expressed by the mole fraction of OTAB in the total mixed solute. So the measurements have been made in one phase region, Le., a mixed micelle region. From the analyses of the self-diffusion coefficients and light-scattering intensities, it has been shown that in the SDS-rich side, as the phase boundary between the m i x e d micelle region and the precipitation region is approached, i.e., as x2 is increased or c is decreased, the fraction of OTAB in mixed micelles, xZm, increases and m i c e l l a r growth occurs. It has been also shown that the mixed micelles grow rapidly when x~~exceeds about 0.25. Although intereating phase behaviom of anionic/cationic system have been reportedIc8 there are only a few papers dealing with micellar properties,e12and none of them discusses the dependence of micellar composition on the total surfactant concentration. In the present study, therefore, we extend the above line of approach

to sodium decanesulfonate (Cl$303)/0TAB and sodium octanesulfonate (C8S03)/0TABsystems in order to examine the generality of our previous results. These systems were chosen because precipitation does not occur, so the critical micelle concentration (cmc) can be observed at room temperature. At the same time, the procedure for determining micellar composition is partly modified.

Experimental Section Materials. The sample of OTAB was purchased from Tokyo Kasei Co. Ltd. (>98%) and purified by recrystallization from acetone/diethyl ether mixed solvent. The samples of Cl&03 and C8S03were purchased from Tokyo Kasei Co. Ltd. for ion pair chromatography and were used without further purification. Water triply distilled from alkaline permanganate was used for the light-scatteringmeasurements. For PGNMR measurements, deuterium oxide purchased from Showa Denko Co. Ltd. (99.75%) was used. Light Scattering. Light-scattering intensities were measured by using a H t N e laser (NEC GLC 5601) and a photon-counting system composed of photomultiplier (Hamamatsu R649), homemade discriminator, and universal counter.13 Absolute intensities were calculated using the Rayleigh ratio of benzene at 632.8 nm, 1.184 X cm-l.14 PulSed-Grpdkat ET-NMR. PGNMR measurements were made on protons at 99.6 MHz using an internal D 2 0 lock on a JEOL FX-100 Fourier transform NMR spectrometer. The details of the measurements are similar to those already r e ~ 0 r t e d . lThe ~ absolute magnitude of the field gradient was calibrated against

0022-3654/92/2096-6839$03.00/0 0 1992 American Chemical Society

6840 The Journal of Physical Chemistry, Vol. 96, No. 16, 1992
the value of the self-diffusion coefficient of water at 25 "C, 2.30 X m2 s-l, as reported by Mills.I6 The selfdiffusion coefficient of OTAB, D2, was obtained from the echo signals for methyl groups bonded to nitrogen by using the equation
'42(6)/A2(0) = exP[-B(6)D21
(1)

Kat0 et al.

ti'
I

B(6)

( Y C ~ ) ~(A 6/3)

2 \
e:
8

where A2(S)/A2(0) are the ratio of peak heights in the presence and absence of the gradient, 7 is the gyromagnetic ratio, G is the magnitude of the gradient, 6 is the duration of each gradient pulse, and A is the time between the two gradient pulses. In our experiments, G and A were kept constant at about 0.087 T m-l and 40-60 ms, respectively, and 6 is changed. The selfdiffusion coefficient of Cl,$03 (or C8S03),D,, cannot be determined directly because there are no peaks which can be assigned to C$O3 (C8S03)alone in the observed spin-echo spectra. So we measured the peak heights of the methylene (or sometimes methyl) signals of the alkyl groups which can be expressed as
A12(6)/A12(0) = (1 - Y z ) exP[-B(6)DI1

C/lO-'mol.

dm-3

Figure 1. Light-scattering intensity (Rayleigh ratio for a 90 scattering 0.3 (A),and 0.5 angle) vs total surfactant concentration at x2 = 0.2 (0), (0) for the Cl,,S03/0TAB system where x2 is the mole fraction of OTAB in the total mixed solute.

+ Yz exp[-B(W21

(2) where y2 represents the contribution from OTAB. In the present systems, however, the observed AI2(6)/AI2(O)values could be fitted to a single-exponential function within experimental errors. This indicates that the difference between D1 and D2 is small and/or either y, or y2 is much smaller than unity. Equation 2 can be rearranged as A12(6)/Al2(0)

v) I

\4

- Y2 exP[-B(6)D21

e:
= exp[-Bt6)D11

1 -Y2

(3)

If y2 is known, D, can be calculated by plotting the left-hand side of eq 4 against B(6) (D2can be determined from eq 1). Taking into account that the echo amplitude in the absence of the gradient is proportional to exp(-2A/ T2) (T,:the spinspin relaxation time) and that the line width is inversely proportional to T,, y2 can be expressed as

10 20 30 C/ 10-2 mol. dm-3

Figure 2. Light-scattering intensity (Rayleigh ratio for a 90 scattering 0.3 (A), and 0.5 angle) vs total surfactant concentration at x2 = 0.1 (0), (0) for the C8S03/OTABsystem where x2 is the mole fraction of OTAB
in the total mixed solute.

where xZH is the fraction of methylene protons of OTAB and T2(1) and T2(2) are the Tis for CI,$03 (C8S03) and OTAB, respectively. Unfortunately, it is not possible to determine T2(1) and T2(2) in mixed systems. Therefore, we calculated D, by using eq 3 for two cases; i.e., y 2 = 0 and y 2 = yZH.In both cases, the left-hand side of eq 3 could be fitted to a single-exponential function within experimental error. However, the former gives better fittings than the latter does, suggesting that y 2 is much smaller than x ~ This ~ . may be explained as follows. In the SDS/OTAB system, the self-diffusion coefficient of SDS can be determined directly from the signals of methylene group bonded to oxygen. In this system, y 2 was found to be much smaller than x ~ This ~ comes . from the fact that most of the OTAB molecules form micelles while there exist many SDS monomers; that is, T2(1) > > T J 2 ) where 1 and 2 represent SDS and OTAB, respectively. This does not always hold true in the present systems. However, the analysis of diffusion coefficients obtained for y 2 = 0 shows that the fraction of OTAB in micellar states is larger than that of C 1 8 0 3 or C8S03(Plm/P2m < 1, see later) for x2 < 0.5. The same results were obtained even for y2 = xZH. In the present paper, therefore, D, values obtained for y 2 = 0 are employed. The maximum differences between D, values for y 2 = 0 were 23% for both systems.
ReSUltS Llgbt-Scattertog Iateasities. Figures 1 and 2 show the concentration dependences of the light-scattering intensities (expressed by the Rayleigh ratio for a 90 scattering angle, Rw) for the CI,$03/OTAB and C8S03/OTABsystems, respectively. It can

be seen from these figures that the light-scattering intensity begins to increase at a certain concentration, Le., around 0.01 and 0.05 m~ldmfor ~ the CI&O3/0TAB and C8S03/OTAB systems, respectively. These concentrations can be regarded as the critical micelle concentration (cmc) of a mixed surfactant solution and are much lower than the cmc's of pure surfactant solutions, Le., 0.041, 0.15, and 0.14 m~l.dm-~ for C1,$03,17 CgS03,17and 0TAB,I8 respectively. S i results have been reported for other anionic/cationicsystems and extensively discussed by Rosen and ZhuIg and Rubingh and Figures 1 and 2 also demonstrate that as x2 is increased, the slope of the RW* curve is increased rapidly, indicating micellar growth with x2. It should be noted that the Rm-c curves for x2 = 0.2 and 0.3 in Figure 2 have points of inflection at about 0.1 and 0.06 moldm", respectively. These results will be discussed later. S e l l - ~ C o e f f i c i e P t s i a d ~ ~ o f M i x d ~ Figures 3 and 4 show the concentration dependences of D, and D2 at different mixing ratios for the Cl$03/OTAB and C8S03/OTABsystems, respectively. These fgum illustrate that both D1 and D2 decrease rapidly with increasing concentration. In our previous paper,U the method for determining the micellar composition from the data on the selfdiffusioncoeffients of both surfactants has been developed for the SDS-rich region in the SDS/OTAB system. In this method, it is assumed that (a) only one type of micelle exists, (b) all the OTAB molecules form mixed micelles with SDS, and (c) the self-diffusion coefficient of the SDS monomer is equal to that of SDS below the cmc in pure SDS solutions. Assumption b cannot be used in the present systems because the selfdiffusion coefficients of both surfactants decrease

Mixed Anionic/Cationic Surfactant Solutions

The Journal of Physical Chemistry, Vol. 96, No. 16, 1992 6841

5t

0'
0

10

15

20

25

-0

C/ lO-'m~l.dm-~

10 20 30 C / 10-' mol dm-3

Figure 3, Self-diffusion coefficients of CI&303(closed symbols) and OTAB (open symbols) vs total surfactant concentration at x2 = 0.2 (0, 0 ) ,0.3 (A,A), and 0.5 (m,0 ) .

Figure 6. Mole fraction of OTAB in a mixed micelle vs total surfactant concentration at different mixing raitos for the C8S03/OTAB system. The symbols are the same as in Figure 2.
30

I
In I

25

>
* z

2 20
15 10 5

0'
0

10 20 30 C/ 10 ' mol dm-3

0

'

'

'

'

10 20 30 40 50 c-c,,/10-~ g.cmq3

Figure 4. Self-diffusion coefficients of C&O, (closed symbols) and OTAB (open symbols) vs total surfactant concentration at x2 = 0.1 (0, 0 ) ,0.3 (A,A), and 0.5 (m, 0 ) .
0.6

Figure 7. Debye plot for the Cl&301system. The symbols are the same as in Figure 1.

the extrapolation of xtmas c for x2 = 0.5.*'

cmc seems lower than 0.5 except

0.5
RN

X 0.4

0.3

0.2

5 10 15 20 25 C/ 1O-' mol. dm-3

Discussion The observed concentration dependences of x2"' in Figures 3 and 4 suggest that micelles grow with decreasing concentration except for x2 = 0.5. Similar results have been obtained in our previous study on the SDS/OTAB system. In this system, in fact, the light-scattering intensity increases with decreasing concentration and diverges below a certain concentration. In the present systems, on the other hand, such an anomalous behavior is not observed in the light-scattering intensity itself. However, the existence of points of inflection in the h - c curves in the Cl$03 system may be correlated with the change in micelle aggregation number. So we tried to calculate the reciprocal of the apparent micellar weight, W ,obtained from the Debye equation: 1/W = H(c - CO)/(& - RwO) (5)

Figure 5. Mole fraction of OTAB in a mixed micelle vs total surfactant concentration at different mixing raitos for the Cl&303/0TAB system. The symbols are the same as in Figure 1.

H = (47r2$ / h4NA) (dv / dc)

where c and co are the total surfactant concentration and the cmc tn g ~ m - respectively, ~, Rwo is the Rayleigh ratio at the cmc, v 1s the refractive index, X,is the wavelength under vacuum, and N A is Avogadro's number. Figure 7 shows the plots of 1 / W against c - co for the Cl$03 system. If the micellar weight and composition are independent of concentration, 1/W can be expressed as 1/M* = (l/M)[l + k(c-co) + ...I (6) where k is proportional to the second virial coefficient of the osmotic pressure. In the Cl$03/OTAB system, the plots for x2 =0 . 2and 0 . 3 have break points at c * 0 . 0 2 3 and 0.015 g - ~ m - ~ (0.1 and 0.06 moldm-'), respectively. From the initial slopes for

rapidly with concentration, suggesting that the existence of OTAB molecules in the monomeric state cannot be neglected. However, we have found that x2"' can be determined without assumption b for most systems. The modified procedure is described in the Appendix. F ' i i 5 shows the concentration depend" of x p at different mixing ratios for the Cl&03/OTAB systems.21 It can be seen from the figure that at higher concentrations, x2"' is close to x2. As the total concentration is decreased toward the cmc, however, x2"' is increased toward the equimolar composition.22 Similar results have been obtained in the C8S03/OTABsystem although

6842 The Journal of Physical Chemistry, Vol. 96, No. 16, 1992
600 r

Kat0 et al.
is decreased toward the cmc, x2" is increased toward the equimolar composition. When the micellar composition exceeds a certain value, the micelle aggregation number increases rapidly. In some systems where hydrophobic interactions between surfactant molecules are strong, like the SDS/OTAB system, further changes in the micellar composition induce the precipitation.

500

.
I

91
I I

2001 100

i
0.3

0 0.2

x;

0.4

0.5

Figure 8. Apparent aggregation number vs mole fraction of OTAB in a mixed micelle for the C,,+303system. The symbols are the same as in Figure 1.

x2 =. 0.2 and 0.3 in the Cl$03/OTAB system, k values were obtained to be about 80 and 110 cm3g1,respectively, using eq 6. For pure C1$03 solutions, on the other hand, k is obtained to be about 120 cm3.g-l from the data of Tartar and Lelong." For spherical micelles of radius a, k may be expressed as23 k = u(8

Conclusions We have measured the light-scattering intensities and selfdiffusion coefficients of surfactant molecules in Cl$03/OTAB and C8S03/OTABsystems (x2 = 0.14.5)where precipitation does not occur. The results may be summarized as follows. 1. The micellar composition (xZm) is nearly equal to the bulk composition (x2)at concentrations much higher than the cmc. As the concentration decreases toward the cmc, however, the fraction of cationic surfactant in mixed micelles increases toward the equimolar composition. 2. Such a change in micellar composition suggests micellar growth with decreasing concentration. Light-scattering results are consistent with this prediction. 3. Taking into account the results in the previous study on the SDS/OTAB system, the above results seem general in mixed anionic/cationic surfactant solutions whether precipitation occurs or not.
Acknowledgment. This work was partially supported by a Grant-in-Aid for ScienMic Research (No. 02740235) to T.K. from the Ministry of Education (Japan). The present PGNMR measurements were camed out at the Instrumental Center of IMS.

+ 2 4 i p dx (1 + ~

) ~ -e-u(x)/(kn]) [ 1

(7)

x = (r - 2a)/(2a)

where u is the specific volume in a micelle, r is the distance between the centers of two micelles, and V(x) is the intermicellar interaction potential. Equation 7 demonstrates that k takes positive values when repulsive interactions between micelles are dominant. If repulsive interactions become weak, k is therefore decreased. In the SDS solutions, for example, addition of only 0.01 mol~dm-~ NaCl reduces the k value to half its initial value.24 The addition of surfactants with oppositely charged headgroups decreases the electrostatic repulsion between micelles far more effectively than an inorganic salt does. If the initial slope is determined by intermicellar interactions alone, it is therefore expected that k is decreased rapidly with increasing x2.25 However, the k values obtained from the initial slope for x2 = 0.3 is larger than that for x2 = 0.2 and nearly q u a l to that for pure Cl$03 solutions. The same holds true in the C8S03system. The k values for x2 = 0.1 and 0.3 were obtained to be about 30 and 50 c " & , respectively, which are nearly equal to or larger than that in the pure C8S03 system" (about 30 cm3*g-l). These results can be explained if the micellar weight itself decreases with increasing concentration. The slope above the break points in Figure 7 may correspond to intermicellar repulsion because micellar composition depends on concentration only slightly (see Figure 5 ) and hence the micellar weight is considered to be almost constant in this concentration range. In Figure 8, the apparent aggregation number obtained from eq 5 and26 m* = M*/[(l - x J M I + x2M21 (8) is plotted against the micellar composition for the Cl$03/OTAB s y s t e m where MI and M 2are the molecular weight of C,&03 and OTAB, respectively. In spite of the fact that the data on various mixing ratios and total surfactant concentrations are included, most of them fall on almost the same line; when xZm exceeds a certain value, about 0.4, the apparent aggregation number increases rapidly. We have already reported such a plot for the SDS/OTAB system. In this system, the apparent aggregation number begins to increase at x2, = 0.25, which is lower than in the Cl$03/0TAB system. Thus, the dependences of composition and aggregation number of micelles on the concentrationobserved for these systems seem general in mixed anionic/cationic surfactant solutions. At concentrations much higher than the cmc, x2, is close to x2. As c

Appendix In a mixed micelle composed of surfactants 1 and 2, the micellar composition ( x 2 9 can be written as
X2"

= PpX2/[Plm(l - x2) PpX2] = X2/[(PI"/P2")(1 - x2) + xzl

('41)

where Pim( i = 1, 2) is the fraction of surfactant molecule i in a micellized state. When only one type of mixed micelle exists, the self-diffusion coefficient of each surfactant can be written as
D I = (1 - Plm)Dlf+ PI"Dm
0 2

(A2a) (A2b)

= (1 - P2")D,'

+ P2"Dm

where D,' ( i = 1,2) and D, are the self-diffusion coefficients of the monomeric and micellized surfactant molecules, respectively. For pure surfactant solutions, below the cmc, the self-diffusion coefficient of the surfactant ion, Dp, is almost independent of concentration. So D,' in eqs A2a and A2b may be replaced by Dp. Combining eqs A2a and A2b, we obtain
1

The 0: values are observed to be 5.73 X 1O-Io, 5.41 X and 5.86 X lo-" m 2 d for C8S03,cI$03, and OTAB, respectively. In the present systems, the value of DIo- DI is much larger than that of D20 - Dlo at higher concentrations. Even at the lowest amcentrationnear the cmc, these two values are in the same order. Taking into account that PIm is much smaller than unity near the cmc, we can replace eq A3 by the following equation with a good approximation:
PIm =P2" DIo- DI
D 2 O

- D2

644)

Inserting eq A4 into eq A l , we can determine x2, from the observed values of D1,D2, DIo,and D20. R e g i s t r y No. OTAB, 2083-68-3; sodium decanesulfonate, 13419-61-9;
sodium octanesulfonate, 5324-84-5.

References and Notes

( 1 ) For example: Tanford, C . The Hydrophobic Effecf. Formarion of Micelles & Biological Membranes; Why-Interscience: New York, 1980.

J. Phys. Chem. 1992, 96,6843-6848

(2) Kato, T.; Iwai, M.; Seimiya, T. J. Colloid Interjace Sci. 1989,130,439 and references therein. (3) Kato, T.; Takeuchi, H.; Seimiya, T. J. Colloid Interface Sci. 1990,140, 253. (4) Chen. D. H.; Hall, D. G. Kolloid Z . Z . Polym. 1973, 251, 41. (5) Barker, C. A,; Saul, D.; Tiddy, J. T.; Wheeler, B. A.; Willis. E. J . Chem. SOC.,Faraday Tram. I 1974, 70, 154. (6) Jolela, P.; Jonsson, B.; Wennerstrom, H. Prog. Colloid Polym. Sci. 1985, 70, 17. ( 7 ) Stellner, K. L.; Amante, J. C.; Scamehorn, J. F.; Harwell, J. H. J . Colloid Interface Sci. 1986, 123, 186. (8) Jokela, P.; Jonsson, B.; Khan, A. J . Phys. Chem. 1987, 91, 3291. (9) Anacker, E. A.; Underwood, A. L. J . Phys. Chem. 1987, 85, 2463. (10) Malliaris, A.; Binana-Limbele, W.; Zana, R. J. Colloid Interface Sci. 1986, 110, 114. (1 1) Hoffmann, H.; Klaus, J.; Schwander, B. Ber. Bunsen-Ges. Phys. Chem. 1987, 91, 99. (12) Yu, Z.; Zhao, G. J. Colloid Interface Sci. 1989, 130, 414. (13) Kato, T.; Anzai, S.;Seimiya, T. J . Phys. Chem. 1990. 94, 7255. (14) Pike, E. R.; Pomeroy, W. R.; Vaughan, J. M. J . Chem. Phys. 1975, 62, 3188. (15) Kato, T. J . Phys. Chem. 1985.89, 5750. (16) Mills, R. J . Phys. Chem. 1973, 77, 685. (17) Tarter, H. V.; Lelong, A. L. M. J . Phys. Chem. 1956, 59, 1185. (18) Klevens, H. B. J . Phys. Colloid Chem. 1948,52, 130. (19) Zhu, B. Y.; Rosen, M. J. J. Colloid Interface Sci. 1984, 99, 435.

6843

(20) Holland, P. M.; Rubingh, D. N. In Cationic Surjactants. Physical Dekker: New York, 1991; Chemistry: Holland, P. M., Rubingh, D. N., Eds.; p 141. (21) It should be noted that these xZm values are calculated using D, values obtained for y 2 = 0 (see the Experimental Section). We have also calculated xZm values using D , values obtained for y 2 = x2". The differences between these two x2"' values were 2-27% and 6-12% for the Cl$Ol/OTAB and C8SOl/OTAB systems, respectively. However, the concentration dependences of xZm are almost the same, and the discussion in the following section is not affected by these differences. (22) Motomura et al. have developed a method to determine the micellar composition at the cmc from the dependence of the cmc on x2 using the phase separation model (Motomura, K.; Yamanaka, M.; Aratono, M. Colloid Polym. Sci. 1984, 262, 948). It may be interesting to compare xZmvalues obtained by their method with the extrapolated value of xZmas c cmc. However, the data points in the present study are not enough to calculate (&tnc/a~~ which )~,~ is necessary for determining xZm. (23) Corti, M.; Degiorgio, V. J . Phys. Chem. 1981, 85, 711. (24) Calculated from the data of Huisman: Huisman, H. F. Proc. K.Ned. Akad. Wet. Ser. B Phys. Sci. 1964, 67, 388. (25) In the C,$OI/OTAB system, the concentration of OTAB is increased from 0.003 to 0.018 mol-dm-' as c is increased from the cmc to 0.06 moldm" at xz = 0.3. (26) In eq 8, xz should be replaced by xZm.However, this replacement does not affect tn* values very much because M ,and M 2 are not so different.

Relaxation Spectra and Dipolar Correlations for Flexible Polymers with Bulky Side Groups
Ricardo Dhz-Calleja,f Evaristo Riande,*.* and Julio San R o m h *
Departamento de Quimica- F@a. ETSI!, Universidad PolitScnica de Valencia, 46071 Valencia, Spain, and Instituto de Ciencia y Tecnologia de Polimeros (CSIC). 28006 Madrid, Spain (Received: January 24, 1992)

The experimental intramolecular correlation coefficient gintra = 1 + Cizj( cos y,,) for poly(2-biphenyl acrylate) (PBPA) chains, where yv is the angle between the dipoles d a t e d with the i andj repeating units, is 0.694 at 30 O C and its temperature coefficient, d In gi,,/dT, has a value of 1.9 X lo-' K in the interval 30-60 OC. A two rotational states scheme developed earlier for poly(pheny1acrylate) (PPA) gives a good account of the experimental values of gin, and d In gh,/dT for PBPA chains. The correlation coefficientg that includes inter- and intramolecular interactions is only somewhat lower than gin,, suggesting that intermolecular correlations are not very important in this polymer. The dielectric spectrum for the polymer in the bulk presents a glass-rubber relaxation, named a absorption, followed by two processes in the subglass region called y and @ secondary absorptions. Results obtained by using thermally stimulated discharge (TSDC) techniques indicate that the mechanisms involved in the lower temperature process (y peak) have an activation energy that is significantly smaller than that corresponding to the mechanisms that produce the @ relaxation. The dielectric strength of the combined subglass relaxations are discussed in terms of conformational changes associated with the side groups. The coupling scheme is used to interpret the dielectric and mechanical glass-rubber relaxations. On one hand, important conclusions are obtained related with the relative complexity of the dielectric and mechanical a relaxations; on the other hand, the anomalous temperature dependence of the glass-rubber relaxation is discussed in terms of the bulkiness of the side group.

Introduction A relaxation process is characterized by its strength and location in the timetemperature domain. In general, relaxation losses in the frequency domain are described by the Kohlrauch-Williams-Watts (KWW)

4(t) = exP(-t/.o)g

(1)

in which the exponent 9 seems to be dependent on the nature of the physical proces involved in the relaxation. Most of the results at hand seem to suggest that the value of this quantity is larger for a dielectric glass-rubber process than for a mechanical one as a consequence of the comparatively wider distribution of relaxation times exhibited by the a mechanical relaxation! On the other hand, whereas secondary relaxations exhibit Arrhenius behavior, the temperature dependence of the relaxation times of glass-rubber relaxations is governed by the free volume and
*Institute de Ciencia y Tecnologia de Polimeros (CSIC).
Universidad Polit&nica de Valqcia.

therefore is described by the Vogel-Fulcher-Tammann-Hesse (VFTH) equation5 T = 70 exp[B/(T - T,)] (2) where T, is a reference temperature and B is proportional to both the reciprocal of the volume of the segment intervening in the relaxation and the minimum required volume for a relaxation process to take place.6 Therefore, B must be dependent on both the material and the nature of the physical process that intervenes in the relaxation. In recent years, a model has been developed that predicts that the product TB for a given material must be invariant (independent of the probe),'-*so that an important relaxationship is established between two variables that define the location of the a! process in the timetemperature domain. Testing the validity of this theory requires, using different physical methods, the study of the glass-rubber transition of polymers with different structures. This is one of the aims of the present work where the dielectric and mechanical glass-rubber relaxations of polymers with bulky side groups such as poly(Zbipheny1 acrylate) (PBPA) are studied and

0022-365419212096-6843$03.00/00 1992 American Chemical Society