Monolayer films liquid monolayers

One could ask whether the presence of an adsorbed surfactant is really necessary. The answer is yes. The soap layer, although only a monolayer thick, has a profound influence on the flow properties of the film liquid be-... 

The first theory for film fluctuations resembles Cahn s theory of spinodal decomposition of unstable bulk systems. A very simple mechanism was adopted for the liquid flow. It was assumed that because of the presence of the soap monolayers, the film surfaces were stagnant (see Section 11) and that the film liquid was pumped back and forth through a slab with thickness h according to Reynolds s law ... 

The automated pendant drop technique has been used as a film balance to study the surface tension of insoluble monolayers [75] (see Chapter IV). A motor-driven syringe allows changes in drop volume to study surface tension as a function of surface areas as in conventional film balance measurements. This approach is useful for materials available in limited quantities and it can be extended to study monolayers at liquid-liquid interfaces [76],... 

The succeeding material is broadly organized according to the types of experimental quantities measured because much of the literature is so grouped. In the next chapter spread monolayers are discussed, and in later chapters the topics of adsorption from solution and of gas adsorption are considered. Irrespective of the experimental compartmentation, the conclusions as to the nature of mobile adsorbed films, that is, their structure and equations of state, will tend to be of a general validity. Thus, only a limited discussion of Gibbs monolayers has been given here, and none of such related aspects as the contact potentials of solutions or of adsorption at liquid-liquid interfaces, as it is more efficient to treat these topics later. 

Photopolymerization reactions of monolayers have become of interest (note Chapter XV). Lando and co-workers have studied the UV polymerization of 16-heptadecenoic acid [311] and vinyl stearate [312] monolayers. Particularly interesting is the UV polymerization of long-chain diacetylenes. As illustrated in Fig. IV-30, a zipperlike process can occur if the molecular orientation in the film is just right (e.g., polymerization does not occur readily in the neat liquid) (see Refs. 313-315). 

Films spread at liquid-liquid interfaces or on liquids other than water are discussed followed by the important effects of charged monolayers on water. Finally, the most technologically important application of Langmuir films, the Langmuir-Blodgett film deposited on a solid substrate, is reviewed. 

Because of the charged nature of many Langmuir films, fairly marked effects of changing the pH of the substrate phase are often observed. An obvious case is that of the fatty-acid monolayers these will be ionized on alkaline substrates, and as a result of the repulsion between the charged polar groups, the film reverts to a gaseous or liquid expanded state at a much lower temperature than does the acid form [121]. Also, the surface potential drops since, as illustrated in Fig. XV-13, the presence of nearby counterions introduces a dipole opposite in orientation to that previously present. A similar situation is found with long-chain amines on acid substrates [122]. 

Bigelow WC, Piokett D L and Zisman W A 1946 Oleophobio monolayers. 1. Films adsorbed from solution in non-polar liquids J. Colloid Interface Scl. 1 513-38... 

In a separate study using the JKR technique, Chaudhury and Owen [48,49] attempted to understand the correlation between the contact adhesion hysteresis and the phase state of the monolayers films. In these studies, Chaudhury and Owen prepared self-assembled layers of hydrolyzed hexadecyltrichlorosilane (HTS) on oxidized PDMS surfaces at varying degrees of coverage by vapor phase adsorption. The phase state of the monolayers changes from crystalline (solidlike) to amoiphous (liquid-like) as the surface coverage (0s) decreases. It was found that contact adhesion hysteresis was the highest for the most closely packed... 

The terminology of L-B films originates from the names of two scientists who invented the technique of film preparation, which transfers the monolayer or multilayers from the water-air interface onto a solid substrate. The key of the L-B technique is to use the amphiphih molecule insoluble in water, with one end hydrophilic and the other hydrophobic. When a drop of a dilute solution containing the amphiphilic molecules is spread on the water-air interface, the hydrophilic end of the amphiphile is preferentially immersed in the water and the hydrophobic end remains in the air. After the evaporation of solvent, the solution leaves a monolayer of amphiphilic molecules in the form of two-dimensional gas due to relatively large spacing between the molecules (see Fig. 15 (a)). At this stage, a barrier moves and compresses the molecules on the water-air interface, and as a result the intermolecular distance decreases and the surface pressure increases. As the compression from the barrier proceeds, two successive phase transitions of the monolayer can be observed. First a transition from the gas" to the liquid state. 

It has been proposed recently [28] that static friction may result from the molecules of a third medium, such as adsorbed monolayers or liquid lubricant confined between the surfaces. The confined molecules can easily adjust or rearrange themselves to form localized structures that are conformal to both adjacent surfaces, so that they stay at the energy minimum. A finite lateral force is required to initiate motion because the energy barrier created by the substrate-medium system has to be overcome, which gives rise to a static friction depending on the interfacial substances. The model is consistent with the results of computer simulations [29], meanwhile it successfully explains the sensitivity of friction to surface film or contamination. 

Novotny et al. [41] used p-polarized reflection and modulated polarization infrared spectroscopy to examine the conformation of 1 -1,000 nm thick liquid polyperfluoropropy-lene oxide (PPFPO) on various solid surfaces, such as gold, silver, and silica surfaces. They found that the peak frequencies and relative intensities in the vibration spectra from thin polymer films were different from those from the bulk, suggesting that the molecular arrangement in the polymer hlms deviated from the bulk conformation. A two-layer model has been proposed where the hlms are composed of interfacial and bulk layers. The interfacial layer, with a thickness of 1-2 monolayers, has the molecular chains preferentially extended along the surface while the second layer above exhibits a normal bulk polymer conformation. 

Figure 8 shows H2SO4 droplets on mica at very low humidity (<5%). The contact line aronnd the drops is smooth and circnlar, revealing that no pinning has occurred [49]. Although the area between drops is flat, it does not correspond to clean mica but to a liquid film covering it of a few monolayers thickness. This is deduced from the hysteresis in the force versns distance experiments, where the tip is brought into contact with the surface and then pulled off. 

In this chapter we describe the basic principles involved in the controlled production and modification of two-dimensional protein crystals. These are synthesized in nature as the outermost cell surface layer (S-layer) of prokaryotic organisms and have been successfully applied as basic building blocks in a biomolecular construction kit. Most importantly, the constituent subunits of the S-layer lattices have the capability to recrystallize into iso-porous closed monolayers in suspension, at liquid-surface interfaces, on lipid films, on liposomes, and on solid supports (e.g., silicon wafers, metals, and polymers). The self-assembled monomolecular lattices have been utilized for the immobilization of functional biomolecules in an ordered fashion and for their controlled confinement in defined areas of nanometer dimension. Thus, S-layers fulfill key requirements for the development of new supramolecular materials and enable the design of a broad spectrum of nanoscale devices, as required in molecular nanotechnology, nanobiotechnology, and biomimetics [1-3]. 

Thin liquid films on a fluid surface were also employed for the construction of protein arrays [40]. The construction of a tightly chemically bound protein monolayer onto a solid support required detailed systematic study involving careful optimization of reaction conditions and comparison of the efficacy of several alternatives [46]. 

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