Ordered Molecular Films

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. 

The second way of preparing L-B monolayer structures, the horizontal lifting method, was introduced by Langmuir and Schaefer. In this method, a compressed monolayer first is formed at the water-air interface, and a flat substrate is then placed horizontally on the monolayer film. When the substrate is lifted and separated from the water surface, the monolayer is transferred onto the substrate, as depicted in Fig. 15(d). 

Multiayer L-B films can be prepared in both methods, by repeated deposition of monolayer on the substrate, with the molecular direction changing alternatively after each deposition (Y-type), or keeping the same molecule direction in all monolayers (X-type or Z-type). 

Self-assembled monolayers are formed spontaneously by the immersion of an appropriate substrate into a solution of active surfactant in an organic solvent. After the substrate is immersed for a time from minutes to hours, it is rinsed with ligroin, methanol, distilled water, and dried in a steam of nitrogen. An apparent effect of the monolayer coating is the drastic change in wettability of the surface so that the measurement of the contact angle can be considered as an effective way to detect the formation of the SAMs. 

Molecules that constitute the self-assembled monolay- 

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Finally, there is another category of lubricants, including the laminated materials, highly ordered organic mono-layers, and various thin solid hlms, which provides effective lubrication via their properties of low shear strength or high wear resistance. Lubrication via ordered molecular films and other solid lubricants, which have been considered by some investigators as a sub-discipline of boundary lubrication, will be discussed more specifically in Section 4. 

Fig. 15—Sketch of preparation of L-B films (a) spread amphiphilic molecules on water surface, (b) compress the molecules using the barrier to get close packed and ordered molecular film, (c) transfer the film onto a substrate through the vertical immerse/retreat process, (d) transfer the film by horizontal lifting.

Readers who want more systematic information on ordered molecular films are referred to the book by Ulman [31]. 

Tribology performances and applications of ordered molecular films have been a long-standing research subject in SKLT, the workplace for the authors of this book. Hu and Luo [42] prepared SAMs of fluoroalkylsilane (FAS) and poly-fluorealkylmethacrylate (PFAM) on the magnetic head of computer hard disk drivers. Experiment results show that the molecular films greatly improve the performance of the... 

Study on mechanisms of ordered molecular films as a model lubricant is of particular importance in the field of micro and nano-tribology, for it would help to understand how molecules contribute to the creation of friction and wear. The understanding has been much improved in recent years through MD simulations, performed by investigators around the world, to detect interactions between the molecular films in relative motion, and to reveal the process and specific mode of energy dissipation. 

Fig. 10.14 Diagram of the attachment of functional molecules to the surfaces of solids [B.95]. Left a) adsorption, molecules are mobile, b) contact between neighboring molecules, c) several molecules create stable islands, d) an ordered molecular film develops. Right Above a critical concentration amphiphilic molecules aggregate spontaneously and form microscopic micelles in the liquid phase...

Surface SHG [4.307] produces frequency-doubled radiation from a single pulsed laser beam. Intensity, polarization dependence, and rotational anisotropy of the SHG provide information about the surface concentration and orientation of adsorbed molecules and on the symmetry of surface structures. SHG has been successfully used for analysis of adsorption kinetics and ordering effects at surfaces and interfaces, reconstruction of solid surfaces and other surface phase transitions, and potential-induced phenomena at electrode surfaces. For example, orientation measurements were used to probe the intermolecular structure at air-methanol, air-water, and alkane-water interfaces and within mono- and multilayer molecular films. Time-resolved investigations have revealed the orientational dynamics at liquid-liquid, liquid-solid, liquid-air, and air-solid interfaces [4.307]. 

Reactions on the surface are interesting. The adsorptions of unsaturated organic molecules on the surface provide a means for fabricating well-ordered monolayer films. Thin film organic layers can be used for diverse applications such as chemical and biological sensors, computer displays, and molecular electronics. 

Unlike traditional textbooks of tribology, in this book we regard boundary lubrication as a limit state of hydrodynamic lubrication when film thickness is down to molecular dimension and independent of the velocity of relative motion. The discussions are based on the existing results, some from literatures but mostly from the authors own work. The topics are mainly focused on the mechanical properties of boundary films, including rheology transitions, molecular ordering, and shear responses. Ordered molecule films, such as L-B films and SAM, are discussed, with emphasis on the frictional performance, energy dissipation and the effects from structural features. Boundary films can be modeled either as a confined substance, or an adsorbed/reacted layer on the... 

In order to improve the tribological properties of molecular films, molecular surface modification is the first choice to make an approach. A Diblock polymer polystyrene-poly(ethylene)oxide (PS-PEO) thin-films were studied in our previous research because of its interesting structure (one... 

As an example of the use of array methodology to study chemical sensor properties let us consider the thirteen molecular structures reported in Figure 5. To investigate the sensing properties of these molecules we studied the behaviour of the response of thickness shear mode resonators (TSMR) sensors, each coated with a molecular film, to different concentration of various volatile compounds (VOC). Analyte compounds were chosen in order to have different expected interaction mechanisms. 

Fet us start this section with real-time measurements of the crystallization process of highly ordered thin films of the molecular organic radical / -NPNN grown from the vapour phase on glass substrates (Caro et al, 2000). These films exhibit 2D... 

In order to evaluate quantitatively the orientation of vibrational modes from the dichroic ratio in molecular films, we assume a uniaxial distribution of transition dipole moments in respect to the surface normal, (z-axis in Figure 1). This assumption is reasonable for a crystalline-like, regularly ordered monolayer assembly. An alternative, although more complex model is to assume uniaxial symmetry of transition dipole moments about the molecular axis, which itself is tilted (and uniaxially symmetric) with respect to the z-axis. As monolayers become more liquid-like, this may become a progressively more valid model (8,9). We define < > as the angle between the transition dipole moment M and the surface normal (note that 0° electric field of the evenescent wave (2,10), in the ATR experiment are given by equations 3-5 (8). 

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