Substrate/surface characterization

Wedge test results suggest that the curing process (e.g., percent crosslinking) of the epoxy-polyamide primer system is not affected by the addition of organosilanes, but may be affected by NTMP. The results of substrate surface characterization, adsorption behavior of applied films, and evaluation of candidate inhibitors by chemical, mechanical, and electrochemical test methods are presented. Mechanisms to explain the observed behavior of the various phosphonate and silane polymer systems are discussed. 

I.P.P.D and its relatives have become standard procedures for the characterization of the structure of both clean surfaces and those having an adsorbed layer. Somoijai and co-workers have tabulated thousands of LEED structures [75], for example. If an adsorbate is present, the substrate surface structure may be altered, or reconstructed, as illustrated in Fig. VIII-9 for the case of H atoms on a Ni(llO) surface. Beginning with the (experimentally) hypothetical case of (100) Ar surfaces. Burton and Jura [76] estimated theoretically the free energy for a surface transition from a (1 x 1) to a C(2x 1) structure as given by... 

Surface Morphology. The initial Integrity of an adhesively bonded system depends on the surface oxide porosity and microscopic roughness features resulting from etching or anodization pretreatments. (17) The SAA surface characterized in this study consists of a thick (9 ym), porous columnar layer which provides excellent corrosion resistance in both humid and aggressive (i.e., Cl ) media. I The thinner FPL oxide provides a suitable substrate surface for evaluating the candidate inhibitors. 

Substrate types characterizing these habitats included surfaces of dead coral, fine and coarse sands, organically rich mud-sand mixtures, wood and steel surfaces on wrecked ships, algal mats, attached macroalgae, and seagrass beds. Water depths at the various sites ranged from 0.2 to 25 meters. 

Overlap between p orbitals leads to cohesive energies of typically less than 0.4 eV molec The much stronger ionic and covalent bonding have binding energies of 10 and 3 eV atom respectively. Finally, physisorption is the weakest form of absorption to a solid surface characterized by a lack of a true chemical bond (chemisorption) between substrate and adsorbate and will be discussed in Chapter 4 (see e.g., Zangwill, 1988). 

Figure 3.18. Thin TTF-TCNQ film (thickness 1 um) HV-grown on a KCl(lOO) substrate, (a) Topography and (b) amplitude TMAFM images. The scale is 5 p.m x 5 ]xm. (c) FTIR spectra of the CN stretching mode in neutral TCNQ (powder) and in a TTF-TCNQ thin film (thickness 1 um) HV-grown on KBr(lOO). Reprinted from Surface Science, Vol. 482 85, C. Rojas, J. Caro, M. Grioni and J. Fraxedas, Surface characterization of metallic molecular organic thin films tetrathiaful-valene tetracyanoquinodimethane, 546-551, Copyright (2001), with permission from Elsevier.

A Au-coated substrate is another model surface, to which many surface characterization methods can be applied. To achieve surface-initiated ATRP on Au-coated substrates, some haloester compounds with thiol or disulflde group were developed [80-84]. Self-assembled monolayers (SAM) of these compounds were successfully prepared on a Au-coated substrate and used for ATRP graft polymerization. Because of the limited thermal stability of the S - Au bond, the ATRP was carried out at a relatively low temperature, mostly at room temperature, by using a highly active catalyst system and water as a (co)solvent (water-accelerated ATRP). 

A similar strategy has been employed in construction of SA multilayers from methyl 23-(trichlorosilyl)tricosanoate, H3C02C-(CH2)22SiCl3 [194]. Chemisorption of this surfactant onto substrates resulted in a well-behaved SA monolayer whose exposed ester moieties could be reduced to alcohol groups which, in turn, could serve as the reactive sites for chemisorption of a subsequent layer of surfactant. Repetition of this process led to structures which contained up to 25 equally thick layers in a SA multilayer (Fig. 21) although surface characterizations indicated an increasing disorder in the surface hydroxyl groups [176, 194]. 

The substrate/silane interphase and the silane/matrix interphase are equally important in considering the mechanism of reinforcement by silane coupling agents in composites. The mineral oxide/silane interphase is more well defined than a metal/silane or a silane/matrix interphase. For example, in the case of a metal substrate, surface oxides may dissolve into the silane layer or form a complex. In the case of the silane/matrix interphase, a diffuse boundary layer may exist due to dispersion of physisorbed silanes in the matrix phase or penetration of the matrix resin into chemisorbed silane layers. Many features of the interaction of a silane coupling agent with a polymer matrix are specific to the system, and thus the chemistry of the silane/matrix interphase must be characterized and defined for each system. 

Adhesion of polyimides to inorganic substrates is of great importance to the microelectronics industry [1, 2]. The polyimide films are deposited most often by spin coating the polyamic acid (PAA) usually from a TV-methylpyrrolidone (NMP) solution onto the substrate surface followed by thermal imidization at temperatures up to 400<>C. The most studied polyimide is the pyromellitic dianhydride-oxydianiline (PMDA-ODA), which exhibits excellent mechanical and dielectric properties, but not so good adhesion characteristics. The latter has been generally overcome by application of an adhesion promoter, such as y-aminopropyltriethoxysilane [3-7]. The reactions of APS (coated from water solution) with the silicon dioxide surface as well as with polyamic acid have been well characterized by Linde and Gleason [4] however, we do not have such detailed information available on APS interaction with other ceramic surfaces. 

Fourier-transformed infrared spectroscopy (FT1R), either in the transmission mode(70), the grazing incidence reflection (GI) mode(7,5) or the attenuated total reflection (ATR) mode(7,2), has been the most widely used experimental tool for the characterization and structure determination of SA monolayers. GI-IR is especially useful in determining the molecular orientation in the film structures because it senses only the vibrational component perpendicular to the substrate surface(7,5). Polarized ATR-IR can also be used to study molecular orientation(7,77). McKeigue and Gula-ri(72) have used ATR-IR to quantitatively study the adsorption of the surfactant Aerosol-OT. 

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