X-ray and neutron reflectometry investigation of Langmuir-Blodgett films of cellulose ethers

Langmuir-Blodgett films of a series of cellulose ethers are investigated by X-ray and neutron reflectometry. Two types of samples are considered: simple alkyl ethers of cellulose and derivatives obtained by the alkylation of (2-hydroxypropyl)cellulose (HPC). All of the cellulose ethers form stable monolayers at the air-water interface. Significant differences are, however, found in the surface pressure-area compression isotherms. Ethers prepared from HPC typically exhibit larger limiting molecular areas and higher surface pressures than the corresponding simple cellulose ethers. The ease of monolayer transfer to hydrophobic silicon substrates differs greatly from one type of molecule to another. Successful transfer conditions are found only for ethers that form stable monolayers at sufficiently high surface pressures. Surprisingly, deuterated HPC ethers, prepared for neutron reflectivity measurements, exhibit monolayer properties significantly different from those of their hydrogenated analogues. Although essentially identical limiting molecular areas are found, the surface pressure corresponding to a characteristic plateau transition in the compression isotherm is found to decrease by about 8-10 mN m(-1) upon side chain deuteration. X-ray reflectivity results show a linear increase of film thickness with the number of deposited layers, indicating a regular and reproducible transfer. Observed average layer spacings are, however, significantly smaller than the calculated length of fully extended side chains. Neutron reflectivity curves recorded for composite LB films composed of both deuterated and hydrogenated polymers exhibit regular Keissig fringes, but no Bragg peak. This result indicates that these LB films do not possess an internal periodic structure and the initial layer-by-layer organization is lost by large interlayer diffusion.