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443. Colligan, J.S., W.A. Grant, and J.L. Whitton, eds., Technological Aspects of Surface Treatment and Analysis, Pergamon Press, 1984.

213. Lee, C.Y., J.A. McCammonn and P.J. Rossky, “The structure of liquid water at an extended hydrophobic surface,” J. Chemical Physics, 80, 4448-4455, (1984).

Molecular dynamics simulations have been carried out for liquid water between flat hydrophobic surfaces. The surfaces produce density oscillations that extend at least 10 Å into the liquid, and significant molecular orientational preferences that extend at least 7 Å into the liquid. The liquid structure nearest the surface is characterized by “dangling” hydrogen bonds; i.e., a typical water molecule at the surface has one potentially hydrogen‐bonding group oriented toward the hydrophobic surface. This surface arrangement represents a balance between the tendencies of the liquid to maximize the number of hydrogen bonds on the one hand, and to maximize the packing density of the molecules on the other. A detailed analysis shows that the structural properties of the liquid farther from the surface can be understood as effects imposed by this surface structure. These results show that the hydration structure of large hydrophobic surfaces can be very different from that of small hydrophobic molecules.

200. Kronberg, B., and P. Stenius, “The effect of surface polarity on the adsorption of nonionic surfactants, I. Thermodynamic considerations,” J. Colloid and Interface Science, 102, 410-417, (1984).

A thermodynamic model is used to predict the adsorption of nonionic surfactants on latexes with different polarity. The model, which is based upon the Flory-Huggins theory of polymer solutions, predicts that the adsorption decreases as the polarity of the latex increases. It is predicted that adsorption should occur even when it is unfavorable to replace a surface-water contact with a surfacesurfactant contact. This is due to a lower number of unfavorable hydrocarbon-water contacts when the surfactant is adsorbed, compared to when it is free in solution. It is also predicted that it is in principle possible to determine the latex polarity or solubility parameter, from adsorption measurements, provided that a similar experiment is carried out on a latex with known polarity, or solubility parameter.

42. Briggs, D., “New developments in polymer surface analysis,” Polymer, 25, 1379-1391, (1984).

Surface and interface characterization of polymeric materials has not enjoyed the multi-technique approach which typifies other types of materials. X-ray photoelectron spectroscopy (XPS) has dominated, despite several major disadvantages. New approaches are discussed which either improve XPS (particularly derivatization techniques) or utilize ‘static’ secondary ion mass spectrometry (SIMS) to overcome these limitations, with examples of their application in materials problem solving.

31. Bodo, P., and J.-E. Sundgren, “Adhesion of evaporated titanium to polyethylene: effects of ion bombardment pretreatment,” J. Vacuum Science and Technology, A2, 1498-1502, (1984).

Titanium films, 1 μm thick were electron‐beam evaporated onto polyethylene (PE) that had been pretreated in situ by 2 keV Ar+ bombardment. A measure of the film adhesion was obtained by measuring the pull strength required to remove the Ti films. A strong dependence of the adhesion on the ion dose was found. The pull strength had a maximum of approximately 20 MPa after a dose of 6×1014 ions/cm2 but decreased for higher ion doses. Without any ion bombardment prior to deposition, the adhesion was very poor with a pull strength of approximately 2 MPa. XPS analysis was used to examine the effect of the ion bombardment on the chemistry of the PE substrate and the Ti/PE interface. Untreated PE samples were contaminated with surface impurities and probably also with low molecular weight hydrocarbons. As the adhesion is maximized, most of the impurities are removed by the ion bombardment. The strong adhesion is suggested to be due to formation of a carbidelike Ti–C interfacial layer, detected by XPS.

1965. Allen, K.W., L. Greenwood, and T.C. Siwela, “Surface treatment of metal surfaces by corona discharge,” J. Adhesion, 16, 127-131, (Nov 1983).

Aluminium and titanium surfaces have been treated by corona discharge in air and gave bonds of strength similar to those obtained by conventional chemical treatment.

916. Sprecher, T.W., “Testing corona treatments,” Paper Film & Foil Converter, 57, (Nov 1983).

2373. Runck, W.A., “Corona discharge treatment roll,” U.S. Patent 4402888, Sep 1983.

1987. Bagnall, R.D., and P.A. Arundel, “Problems with the determination of surface free energy components by solving simultaneous equations,” J. Colloid and Interface Science, 95, 271-272, (Sep 1983).

1785. Busscher, H.J., A.W.J. Van Pelt, H.P. De Jong, and J. Arends, “Effect of spreading pressure on surface free energy determinations by means of contact angle measurements,” J. Colloid and Interface Science, 95, 23-27, (Sep 1983).

Contact angle measurements have been carried out on various solid substrates using water-propanol mixtures and α-bromonaphthalene as wetting liquids. These substrates were: polytetrafluorethylene, Parafilm, polyethylene, polyurethane, polystyrene, polymethylmethacrylate, fluorapatite, and hydroxyapatite. The dispersion and the polar components of the surface free energy, γsd and γsp have been calculated from the geometric mean equation. Two approaches have been considered: (1) neglecting the spreading pressure πe and (2) taking πe into account (Dann's method). The results show that both approaches actually yield the same results for the surface free energy, γs, if a proper interpretation of the approaches is considered. All data indicate, that approach (1) gives γs values determined on the adsorbed liquid layer, whereas in approach (2) the free energies of the bare solid surfaces are found.

1988. Dabros, T., and T.G.M. Van de Ven, “On the effects of blocking and particle detachment on coating kinetics,” J. Colloid and Interface Science, 93, 576-579, (Jun 1983).

926. Pennance, J.R., “Printing on plastic films: problems with surface tension,” Screen Printing, 73, 108-109, (Jun 1983).

1989. Sachler, E., “The possibility of 'standard' surface tension values for polymers,” J. Colloid and Interface Science, 92, 275-276, (Mar 1983).

2039. Saito, M., and A. Yabe, “Dispersion and polar force components of surface tension of some polymer films,” Textile Research Journal, 53, 54-59, (1983).

The surface tension and the dispersion and polar components of the surface tension for solids and liquids were estimated by contact angle measurement in order to apply these concepts to a detergency study. Two approximation methods, the extended Fowkes' equation and Wu's equation, were adopted for the calculations. Among the twelve experimental liquid pairs, methylene iodide/water and tricresyl phosphate/water gave values for paraffin, polyethylene, and polystyrene close to the average for the twelve pairs. Values for cellulost acetate and cellophane were there fore obtained using these two pairs. The results showed that the dispersion force component becomes larger with increasing degree of acetylation, while the polar force component becomes smaller.

1399. Markgraf, D.A., “Evolution of corona treating electrodes,” in 1983 Paper Synthetics Conference Proceedings, 255, TAPPI Press, 1983.

1343. Fowkes, F.M., “Acid-base interactions in polymer adhesion,” in Physico-Chemical Aspects of Polymer Surfaces, Vol. 2, Mittal, K.L., ed., Plenum Press, 1983.

479. Hobbs, J.P., C.S.P. Sung, K. Krishnann, and S. Hill, “Characterization of surface structure and orientation in polypropylene and poly(ethylene terephthalate) films by modified attenuated total reflection IR dichromism studies,” Macromolecules, 16, 193-199, (1983).

475. Hansen, C.M., and E. Wallstrom, “On the use of cohesion parameters to characterise surfaces,” J. Adhesion, 15, 275-286, (1983).

Examples of surface characterization using cohesive energy parameters and surface energy parameters are given. In general the two approaches yield essentially equivalent results. The predictive ability of the cohesive energy approach suggests its use where directed modification of surface properties is desired.

444. Collins, W.M., “Classical review of corona treatment,” in 1983 Coextrusion Conference Proceedings, 47+, TAPPI Press, 1983.

429. Briggs, D., and M.P. Seah, Practical Surface Analysis: By Auger and X-Ray Photoelectron Spectroscopy, John Wiley & Sons, 1983.

376. Wang, L.-H., and R.S. Porter, “The surface orientation of polystyrene measured by liquid contact angle,” J. Applied Polymer Science, 28, 1439-1445, (1983).

The surface contact angle of glycerol and of water on polystyrene (PS) films has been found to depend on the extent of uniaxial draw for atactic PS. The contact angle depends on direction for the smooth films of PS drawn by solid state coextrusion. Results as a function of draw ratio to values over 4 on these noncrystalline PS samples, Mw = 6 × 105, have also been interrelated with other measures of orientation such as the anisotropy of surface and bulk properties measured, respectively, by dichroic reflectance infrared spectroscopy and by birefringence.

367. Triolo, P.M., and J.D. Andrade, “Surface modification and characterization of commonly used catheter materials,” J. Biomedical Materials Research, 17, 129-147, (1983).

The effects of the modification of polystyrene (PS), polyethylene (PE), poly(vinyl chloride) (PVC), silicone rubber (SR), and fluorinated ethylene propylene (FEP) copolymer by radio frequency glow discharge in a helium environment were presented in part I. The hydrated polymer surfaces were characterized by XPS, SEM, visual microscopy, and by contact angle measurements. In general, exposure of the polymers to RFGD produced an oxidized hydrophilic surface, yet the roughness of the surface was unaltered by the relatively mild plasma conditions used. In this article, the frictional behavior of oxidized and unoxidized SR, PE, and FEP in distilled water, isotonic saline, and blood plasma environments is examined experimentally. The results are discussed in relation to the properties generally believed to affect frictional phenomena and to the surface properties as determined in part I. Results indicate that RFGD-treated SR generates less friction than untreated SR when dragged across all untreated and treated polymer surfaces, whether the medium is distilled water or an isotonic saline solution. Friction is consistently lower in a blood plasma medium between all surfaces investigated, most probably because of the presence of adsorbed proteins at the polymer interfaces.

41. Briggs, D., D.R. Kendall, A.R. Blythe, and A.B. Wootton, “Electrical discharge treatment of polypropylene film,” Polymer, 24, 47-52, (1983).

The previously observed, but unexplained, deleterious effect of high relative humidity on the efficiency of electrical (‘corona’) discharge treatment for rendering polypropylene film printable has been re-examined. The effect of film temperature during treatment has also been studied. A consistent explanation of both effects based on the degree of surface coverage by physically adsorbed water is put forward, supported by X-ray photoelectron spectroscopy analysis of treated film surfaces.

1990. Birdi, K.S., “Contact angle hysteresis on some polymeric solids,” J. Colloid and Interface Science, 88, 290-293, (Jul 1982).

2372. Ferrarini, E., “Corona effect surface treatment apparatus for sheet,” U.S. Patent 4334144, Jun 1982.

646. Lunkenheimer, K., “Problems involved in the practical performance of surface tension measurement of surfactant solutions by using the ring tensiometer,” Tenside Surfactants Detergents, 19, 272+, (May 1982).

1966. Sharma, A.K., and H. Yasuda, “Effect of surface energetics of substrates on adhesion characteristics of poly(p-xylylenes),” J. Adhesion, 13, 201-214, (Apr 1982).

In investigating the effect of the surface energetics of substrate materials on the adhesion characteristics of poly(p-xylylene) and poly(chloro-p-xylylene) by the “Scotch Tape” method, it was found that if the substrates had not been preconditioned (treated with argon or a methane plasma), the adhesion was poor. The characteristics of water resistant adhesion that were observed when coated substrates were boiled in 0.9% sodium chloride solution were found to vary from excellent (when the polymer did not peel from the substrate after three cycles of 8 hours of boiling and 16 hours at room temperature) to poor (when the polymer peeled off almost immediately). It was noticed that water resistant adhesion depends on the hydrophobicity of the substrate material (the greater the hydrophobicity, the greater the adhesion) and is not related to the dry adhesive strength of poly(p-xylylene). The oxygen glow discharge treatment of the substrates decreased both the dry and wet adhesive strength of the polymer. The effect of the argon glow discharge treatment depended on the surface energetics of the substrate, and the methane glow discharge treatment increased both the dry and wet adhesive strength of the polymer. These preconditioning processes are discussed in terms of the sputtering of the material from the wall of the reactor in contact with the plasma and the deposition of the plasma polymer of the sputtered material on the substrate surface.

2371. Imada, K., S. Ueno, and H. Nomura, “Method for modifying surface properties of shaped articles of vinyl chloride based resin with low temperature plasma,” U.S. Patent 4315808, Feb 1982.

1511. Dahm, R.H., “Surface treatments for polytetrafluoroethylene,” in Surface Analysis and Pretreatment of Plastics and Metals, Brewis, D.M., ed., 227-254, Applied Science, Feb 1982.

1510. Rance, D.G., “Thermodynamics of wetting: From its molecular basis to technological application,” in Surface Analysis and Pretreatment of Plastics and Metals, Brewis, D.M., ed., 121-152, Applied Science, Feb 1982.

1509. Briggs, D., “Chemical analysis of polymer surfaces,” in Surface Analysis and Pretreatment of Plastics and Metals, Brewis, D.M., ed., 73-94, Applied Science, Feb 1982.

1476. Brewis, D.M., ed., Surface Analysis and Pretreatment of Plastics and Metals, Applied Science, Feb 1982.

2864. Agbezuge, L., and F. Wieloch, “Estimation of interfacial tension components for liquid-solid system from contact angle measurements,” J. Applied Polymer Science, 27, 271-275, (Jan 1982).

A technique has been developed for estimating the hydrogen bonding and London dispersion force components of liquid surface tension and solid surface free energy levels. The technique relies on (a) measuring contact angles generated by sessile drops of liquids on solids and (b) performing calculations based on theories of thermodynamic wetting of solids by liquids. The technique is used to estimate interfacial force components of certain liquids and papers typical of those used in xerographic processing.

994. Briggs, D., and C.R. Kendall, “Derivatisation of discharge-treated LDPE: An extension of XPS analysis and a probe of specific interactions in adhesion,” Intl. J. Adhesion and Adhesives, 2, 13-17, (Jan 1982).

Specific reactions for the derivatization of oxygen-containing functional groups in polymer surfaces have been developed in order to improve the precision of analysis by X-ray photoelectron spectroscopy (xps). These have been used to probe the chemical composition of low density polyethylene (ldpe) surface-modified by electrical discharge treatment. Simultaneously the effect of derivatizing particular groups on the auto-adhesive behaviour of these surfaces has been examined. Two independent specific interaction mechanisms have been identified.

2784. Kato, Y., F.M. Fowkes, and J.W. Vanderhoff, “Surface energetics of the lithographic printing process,” Industrial & Engineering Chemistry Product Research & Development, 21, 441-450, (1982).

2335. Boenig, H.V., Plasma Science and Technology, Cornell University Press, 1982.

1820. Reichert, W.M., F.E. Filisko, and S.A. Barenberg, “Polyphosphazenes: Effect of molecular motions on thrombogenesis,” J. Biomedical Materials Research, 16, 301-312, (1982).

The effect and interrelationship between primary (segmental backbone) and secondary (side chain) molecular motions on thrombogenesis, independent of morphological order/disorder, crystallinity, and/or associated water is elucidated using an amorphous hydrophobic polymer of poly-[(trifluoroethoxy) (fluoroalkoxy)phosphazene], PNF. The results indicate that thrombogenesis for an amorphous hydrophobic polymer is sensitive and dependent on the degrees and types of primary and secondary molecular motions at the polymer interface.

1345. Briggs, D., “Surface treatments for polyolefins,” in Surface Analysis and Pretreatment of Plastics and Metals, Brewis, D.M., ed., 199-226, Applied Science, 1982.

944. Jensen, W.B., “Lewis acid-base interactions and adhesion theory,” Rubber Chemistry and Technology, 55, 881-901, (1982).

The above results are intended to be suggestive rather than definitive. Nevertheless, they strongly support the premise that a cross-fertilization of both concepts and experimental data from the apparently unrelated fields of Lewis acid-base chemistry and adhesion theory can lead to potentially valuable results for both fields, emphasizing again the value of using a generalized acid-base vocabulary in describing the phenomena of chemistry, whatever one's area of specialization.

658. Wu, S., Polymer Interface and Adhesion, Marcel Dekker, 1982.


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