The organization of aliphatic chains in ultra-thin layers and its importance for layer properties

The Phase Behaviour of Amphiphilic Monolayers

Amphiphilic monolayers display a wealth of condensed phases. It is only recently that these have been widely recognised as being distinct, but they are in fact quite analogous to the well-known lamellar gel phases of bulk lyotropic and thermotropic mesogens. An understanding of these phases has proved to be important for controlling the defect structure of the monolayers used in the fabrication of Langmuir-Blodgett films. This understanding is being achieved by developments in a number of techniques, including X-ray diffraction and isotherm miscibility. The phase diagrams of the materials studied so far are all very closely related, lending new credibility to the principle of corresponding …

A new interpretation of the 22-tricosenoic acid Langmuir-Blodgett structures identified as triclinic by Rheeds

Abstract One of the original structural studies on Langmuir-Blodgett (LB) multilayers of 22-tricosenoic acid using the technique of reflection high-energy electron diffraction was performed by Peterson and Russell (1984, Phil. Mag. A, 49, 463). In their paper, four distinct structural arrangements of the long-chain fatty acid were identified, where the arrangement adopted by a particular sample was found to depend on the substrate and deposition conditions. The identification of the C2 H4 subcells in each of these arrangements was made on the basis of a number of assumptions, some of which have subsequently been shown to be erroneous. In particular, the identification of a triclinic subcell…

X-ray study of LB multilayers of cadmium soaps in the vicinity of the break up point

Temperature dependent SAXS measurements were carried out on multilayers of two different salts, cadmium palmitate (hexadecanoate) and behenate (docosanoate). The pattern characteristic of layer structure disappears at a transition temperature well below the bulk melting point in both cases. Examination by means of optical microscopy shows that the LB films break up at a temperature close to this transition. Measurements in its vicinity demonstrate that over a certain temperature range just below the transition a second set of peaks arises in the diffraction pattern. During this transition region of about 3 °C width two d-spacings for both salts were found, suggesting the simultaneous existe…

An electron diffraction study of deposited docosanoic acid monolayers

Docosanoic acid monolayers deposited on thin polymer films under different water surface conditions have been investigated using transmission electron diffraction at normal and tilted incidence. Diffraction patterns obtained from the L2 and L2' phase are quite similar, but distinctly different to samples coated from the CS phase. The former were consistent with molecules perpendicular to the substrate, arranged in a texture of grains with unusual orthorhombic packing. There is evidence for a phase transition from a liquid crystalline phase on the water surface.

Structural Relationships between Floating and Deposited Monolayers of Docosanoic Acid

Floating docosanoic acid (behenic acid) monolayers in the SmI and SmH phase were deposited with the Langmuir-Blodgett technique onto thin polymethylmethacrylate (PMMA) and Formvar substrates and investigated by electron diffraction. The molecular packing of the monolayers on the substrates vary from those on the water surface and are different for different substrates. On PMMA four phases (H, SmB, SmI, SmL) have been identified, depending on the deposition conditions. While SmB and SmI are known for docosanoic acid on the water surface, H and SmL have only been unequivocally observed in other substances or on other subphases. The monolayer structure on Formvar was identical under all deposi…

Phase diagrams of monolayers of the long chain fatty acids

Tilted phases of fatty acid monolayers

X‐ray diffraction data from water‐supported monolayers of fatty acids with chain lengths from 19 to 22 is presented. The structures of the tilted mesophases L2’, L2, and Ov are characterized in detail. The contributions to the unit cell distortion from the tilt and the ordering of the backbone planes of the molecules are separated. It is shown that at the swiveling transition L2’–L2, not only the tilt azimuth but also the packing of the backbone planes change discontinuously. We demonstrate that the tilting transition LS–L2 is accompanied by the ordering of the backbone planes and may be discontinuous. Evidence is presented for a herringbone ordering transition within the L2 region. The dis…

X-ray scattering studies of fatty acid films on water and on Cdcl2 solutions

X-ray diffraction methods for Langmuir films on the surface of water are briefly presented, together with recent results for docosanoic acid monolayers on pure water and for eicosanoic acid monolayers on an ionic subphase.

Grazing-Incidence X-ray Diffraction Study of Octadecanoic Acid Monolayers

We report the observation of X-ray scattering profiles from monolayers of octadecanoic acid in the vicinity of room temperature and evidence for the existence near room temperature of all four hexatic rotator phases L2d, Ov, L‘1, and LS, which differ in the details of their molecular tilt. While the incontrovertible triple-reflection signature of the chiral L‘1 phase was not observed, we propose that the previously reported rapid annealing behavior in this phase can lead to the disappearance of one, and in some cases two, of the three peaks.

Monolayer phases of the fatty acids and their ethyl esters

The miscibility correspondence between water-surface monolayer phases of the fatty acids and their ethyl esters was determined. Ester phases were found corresponding to all the known phases of the acids, and vice versa, in similar relative positions of the π-T diagram. Evidence is presented for the existence of a ninth distinct miscibility category, represented by a phase in each of the pure materials, and a tenth found only in mixtures. We propose a tentative correspondence to bulk smectic miscibility categories.

Organic Materials for Nonlinear Optics

A novel configuration for the optical characterization of waveguiding layers

When a transparent layer of sufficient thickness is suitably coated on both sides with metal, the structure supports one-dimensionally bound optical modes which propagate in two dimensions but which can be detected externally in a very simple manner. We show that this configuration can be used to determine the optical constants of the layer.

An Analysis of the Broadening Induced by Beam Damage in Transmission Electron Diffraction Spots from an Oriented Aliphatic Monolayer

We have analysed the progressive changes in diffraction spot shape during prolonged transmission electron diffraction observation of a soap monolayer supported on a thin polymer film. The material used to form the monolayer was cadmium eicosanoate (arachidate). The observed changes cannot be explained at all in terms of the chemical crosslinking which is known to occur as a result of beam damage, nor completely in terms of the strain fields caused by unbound dislocation defects of the crystalline lattice. The most plausible explanation involves the formation of linear dislocation aggregates which resemble grain boundaries but yet which are not linked into a continuous network. The evolution…