Structure of adsorbed layers of nitrophenoxy-tailed quaternary ammonium surfactants at the air/water interface...

The adsorbed layers of N,N,N-trimethyl-10-(4-nitrophenoxy)decylammonium bromide (PhiC(10)TAB) and N,N,N('),N(')-tetramethyl-N,N(')-bis[10-(4-nitrophenoxy)decyl]-1,6-hexanediammonium dibromide [(PhiC(10))(2)C(6)] at the air/water interface have been studied by neutron reflection. The coverage of the surfactants was obtained over the concentration range from critical micelle concentration (CMC) to CMC/100. The area per PhiC(10)TAB molecule changes from 50+/-3 to 390+/-60 A(2) over this concentration range and the area per (PhiC(10))(2)C(6) molecule changes from 139+/-3 to 288+/-10 A(2). The overall thicknesses (single uniform layer) of the surfactant layers at CMC are about 19 and 16 A for PhiC(10)TAB and (PhiC(10))(2)C(6) respectively. The distributions of the C(10) chains show that the chains of both surfactants are tilted away from surface normal, with the tilt increasing in the outer part of the layer. The distribution of C(10) chains in (PhiC(10))(2)C(6) is narrower than that in PhiC(10)TAB, indicating that the alkyl chains of (PhiC(10))(2)C(6) are more tilted. For both surfactants, the broad nitrophenoxy distribution may indicate significant positional disorder of the nitrophenoxy groups along the surface normal direction and their intermixing with alkyl chains in the adsorbed layer.