Thin polymers

Four possible mechanisms for solid-state extraction (a) adsorption onto a solid substrate (b) absorption into a thin polymer or chemical film coated on a solid substrate (c) metal-ligand complexation in which the ligand is covalently bound to the solid substrate and (d) antibody-antigen binding in which the receptor is covalently bound to the solid substrate. 

Fig. 15. Schematic of the interfacial polymerization process. The microporous film is first impregnated with an aqueous amine solution. The film is then treated with a multivalent cross-linking agent dissolved in a water-immiscible organic fluid, such as hexane or Freon-113. An extremely thin polymer film...

An excellent review of composite RO and nanofiltration (NE) membranes is available (8). These thin-fHm, composite membranes consist of a thin polymer barrier layer formed on one or more porous support layers, which is almost always a different polymer from the surface layer. The surface layer determines the flux and separation characteristics of the membrane. The porous backing serves only as a support for the barrier layer and so has almost no effect on membrane transport properties. The barrier layer is extremely thin, thus allowing high water fluxes. The most important thin-fHm composite membranes are made by interfacial polymerization, a process in which a highly porous membrane, usually polysulfone, is coated with an aqueous solution of a polymer or monomer and then reacts with a cross-linking agent in a water-kniniscible solvent. 

The changes in the optical absorption spectra of conducting polymers can be monitored using optoelectrochemical techniques. The optical spectmm of a thin polymer film, mounted on a transparent electrode, such as indium tin oxide (ITO) coated glass, is recorded. The cell is fitted with a counter and reference electrode so that the potential at the polymer-coated electrode can be controlled electrochemically. The absorption spectmm is recorded as a function of electrode potential, and the evolution of the polymer s band stmcture can be observed as it changes from insulating to conducting (11). 

It has been also shown that when a thin polymer film is directly coated onto a substrate with a low modulus ( < 10 MPa), if the contact radius to layer thickness ratio is large (afh> 20), the surface layer will make a negligible contribution to the stiffness of the system and the layered solid system acts as a homogeneous half-space of substrate material while the surface and interfacial properties are governed by those of the layer [32,33]. The extension of the JKR theory to such layered bodies has two important implications. Firstly, hard and opaque materials can be coated on soft and clear substrates which deform more readily by small surface forces. Secondly, viscoelastic materials can be coated on soft elastic substrates, thereby reducing their time-dependent effects. 

A. Milchev, K. Binder. Dewetting of thin polymer films adsorbed on solid substrates A Monte Carlo simulation of the early stages. J Chem Phys 705 1978-1989, 1997. 

G. Reiter. Dewetting of thin polymer films. Phys Rev Lett 62 75-78, 1992. 

G. Reiter. Unstable thin polymer films rupture and dewetting process. Langmuir 9 1344-1351, 1993. 

G. Henn, D. J. Bucknall, M. Stamm, P. Vanhoorne, R. Jerome. Chain end effects and dewetting of thin polymer films. Macromolecules 29 4305 313, 1996. 

Poly-1,2-1//-azepines, produced by gas-phase photopolymerization of aryl azides yield, after oxidation, electrically conducting films.103 By photolyzing 4-(pcntyloxy)phenyl azide in the gas phase, a flexible polyazepine is produced which can be deposited directly as a thin polymer film onto a suitable surface. 

Despite the above comments on the application of roughening to thin polymer crystals it is certainly possible that thermal effects could cause a significant number of surface steps, and that this is all that is required to lead to a breakdown of the nucleation argument. 

While thin polymer films may be very smooth and homogeneous, the chain conformation may be largely distorted due to the influence of the interfaces. Since the size of the polymer molecules is comparable to the film thickness those effects may play a significant role with ultra-thin polymer films. Several recent theoretical treatments are available [136-144,127,128] based on Monte Carlo [137-141,127, 128], molecular dynamics [142], variable density [143], cooperative motion [144], and bond fluctuation [136] model calculations. The distortion of the chain conformation near the interface, the segment orientation distribution, end distribution etc. are calculated as a function of film thickness and distance from the surface. In the limit of two-dimensional systems chains segregate and specific power laws are predicted [136, 137]. In 2D-blends of polymers a particular microdomain morphology may be expected [139]. Experiments on polymers in this area are presently, however, not available on a molecular level. Indications of order on an... 

Thin polymer films may also be investigated by TEM and high resolution images are obtained for e.g. thin films of liquid crystalline polymers [64]. Usually thin microtome cuts from bulk samples are investigated, but also epitaxial growth of polyoxymethylene on NaCl [152], chain folding of polyethylene crystals [153], epitaxial crystallization of polypropylene on polystyrene [154] or monomolecular polystyrene particles [155] are observed. The resolution is, however, in most cases not comparable to STM. 

Tong HM, Nguyen LT (eds) (1990) New characterisation techniques for thin polymer films, J Wiley, New York... 

Thus, the pipe friction chart for a Newtonian fluid (Figure 3.3) may be used for shearthinning power-law fluids if Remit is used in place of Re. In the turbulent region, the ordinate is equal to (R/pu2)n 0 fn5. For the streamline region the ordinate remains simply R/pu2, because Reme has been defined so that it shall be so (see equation 3.140). More recently, Irvine(25j has proposed an improved form of the modified Blasius equation which predicts the friction factor for inelastic shear-thinning polymer-solutions to within 7 per cent. 

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. 

The mechanical properties of tyrosine-derived poly(iminocarbon-ates) were investigated using the procedures described in ASTM standard D882-83 (Table 2). Solvent-cast, thin polymer films were prepared, cut into the required shape, and tested in an Instron stress strain tester. Since the films were unoriented, noncrystalUne samples, the results are representative of the bulk properties of the polymers. In order to put these results into perspective, several commercial polymers were tested under identical conditions. In addition, some literature values were included in Table 2. 

Grohens, Y, Hamon, L., Reiter, G., Soldera, A. and Holl, Y. (2002) Some relevant parameters affecting the glass transition of supported ultra-thin polymer films. Eur. Phys. J. E, 8, 217-224. 

Keddie, J. L., Jones, R. A. L. and Cory, R. A. (1994) Interface and Surface Effects on the Glass-Transition Temperature in Thin Polymer-Films. Faraday Discuss., 98, 219-230. 

CavaDo, A., Muller, M Wittmer, J. P Johner, A. and Binder, K. (2005) Single chain structure in thin polymer films corrections to Flory s and Silberberg s hypotheses./. Phys. Condens. Matter, 17, S1697-S1709. 

Muller, M. (2002) Chain conformations and correlations in thin polymer films a Monte Carlo study. /. Chem, Phys, 116, 9930-9938. 

Kraus, J., Muller-Buschbaum, P., Kuhlmann, T., Schubert, D. W. and Stamm, M. (2000) Confinement effects on the chain conformation in thin polymer films. Europhys. Lett., 49, 210-216. 

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