Anal. Chem. 1985, 57, 15R-29R (5Q) Burse, V. W.; Needham, L. L.; Korver, M. P.; Lapeza, C. R., Jr.; Llddle, J. A.; Bayse, D. D. J. Assoc. Off. Anal. Chem. 1983, 6 6 , 40-45. (6Q) Buser, H. R.; Rappe, C. Anal. Chem. 1984. 56, 442-448. (7Q) Cochrane, W. P.; Miles, W.; Wakeford, B.; Slngh, J. Pestlc. Chem.: Hum. Welfare Envlron., Proc. Int. Pestlc. Chem. 5th 7982 1983, 4 , 341-348. Edited by Mlyamoto, J.; Kearney, P. C.; Pergamon, Oxford, UK. (80) De Kok, A.; Qeerdlnk, R. 6.; De Vrles, G.; Brlnkman, U. A. T. Int. J. Envlron. Anal. Chem. 1982, 12, 99-122. (9Q) Duinker, J. C.; Hiliebrand, M. T. J. Bull. Environ. Contam. Toxlcol. . isat, 31, 25-32. (lm)Fawkes, J.; Albro, P. W.; Waiters, D. 6.; McKlnney, J. D. Anal. Chem. 1082, 54, 1866-1871. (IIQ) Gutlerrez, A. G.; McIntyre, A, E.; Lester, J. N.; Perry, R. Envlron. Technol. Lett. 1983, 4 , 521-528. (I2Q) Harless, R. L.; Lewis, R. G.; Dupuy, A. E.; McDanlel, D. D. Envlron. Scl. Res. lg83, 26, 161-171. (13Q) Kennedy, P. A.; Roberts, D. J.; Cooke. M. J. Chromatogr. 1982,249, 257-265. (14Q) Levlne, S. P.; Homsher, M. T.; Sullivan, J. H. J. Chromatogr. 1983, 257, 255-268. (15Q) Lewis, E.; Jamleson, W. D. Int. J. Mass Spectrom. Ion fhys. 1983, 48, 303-306. (I6Q) Llbertl, A.; Clccloll, P.; Brancaieonl, E.; Ceclnato, A. J. Chromatogr. 1982, 242, 111-118. (17Q) Marquez. A. I.€€€ Trans. Power Appar. Syst. 1984, PAS-703 ( 3 ) . 589-592. Chem. Abstr. 1984, 100, 141801g. (l8Q) Mathar, W.; Beck, H. Lebensmlttelchem. Gerlchtl. Chem. 1983, 37, 147-148. Chem. Abstr. 1984, 700,173236t. (l9Q) McKlnney, J. D.; Moore, L.; Prokopetz, A.; Welters, D. B. J. Assoc. Off. Anal. Chem. 1984, 6 7 , 122-129. (20Q) McMurtrey, K. D.: Wlldman, N. J.; Tal, H. Bull. Envlron. Contam. Toxled. 1983, 31, 734-737. (21Q) Mes. J.; Davles, D.; Bryce, F. Int. J. Envlron. Anal. Chem, 1983, 15, 25-37. (22Q) Mlllar, J. D.; Thomas, R. E.; Johnson, D. E. U . S . Envlron. Rot. Agency, Off. Res. Dev., [Rep.] €PA, EPA-80014-82-023, 1982, p 220. (23Q) Mullins, M. D.; Pochlnl, C. M.; McCrlndle, S.;Romkes, M.; Safe, S.H.; Safe, L. M. Environ. Scl. Technol. 1984, 18, 468-476. (24Q) Newton, D. A,; Laskl, R. R. J. Chromatogr. Scl. 1983, 21, 161-185. (25Q) Oehme, M.; Stray, H. Fresenlus' Z . Anal. Chem. 1982, 317, 665-673. (26Q) O'Keefe, P.; Meyer, C.; Dlllon, K. Anal. Chem. 1982, 54, 2623-2625. (27q) Onuska, F. I.; Komlnar, R. J.; Terry, K. A. J. Chromatogr. 1983, 279, 111-1 18. (28Q) Parlar, H.; Mansour, M. Pergamon Ser. Envlron. Scl. 1982, 7 , 241-247.
(29Q) Parris, R. M.; Guenther, F. R.; May, W. E.; Cheder, S. N. NBS Spec. Pub/. ( U . S . ) 1984, NO. 674, 27-32. (30Q) Peakall, D. 6.; Lew, T. S.; Springer, A. M.; Walker, W., 11; Rlsebrough, R. W.; Monk, J. G.; Jarman, W. M.; Walton, B. J.; Reynolds, L. M.; et ai. Arch Envlron. Contam. Toxlcol. 1983, 72, 523-528. (31Q) Pelllzzarl, E. D.; Moseiey, M. A.; Cooper, S. D.; Harry, J. V.; Demlan, 8.; Mullin, M. D. Adv. Exposure, Health Environ. Eff. Stud. PCB's, Symp. PfOC. 1982 1983, (LSI-TR-507-137B, P884-135771), 4-80. Edlted by Davenport, R. J.; Bernard, B. K.; NITS: Sprlngfleld, VA. (32Q) Peters, T. L.; Nestrick, T. J.; Lamparski, L. L. Walter Res. 1984, 18, 1021-1 024. (33Q) Peterson, J. C.; Freeman, D. H. Int. J. Environ. Anal. Chem. 1982, 12, 277-291. (34Q) Rappe. C.; Nygren, M.; Buser, H.; Masuda, Y.; Kuroki, H.; Chen, P. H. Envlron. Scl. Res. 1983, 2 6 , 241-253. (35Q) Russell, D. J.; McDuffle, B. Int. J. Envlron. Anal. Chem. 1983, 15, 185- 183. (36Q) Ryan, J. J.; Pllon, J. C. J . Chromatogr. 1982, 248, 409-415. (37Q) Safe, S.; Parkinson, A.; Robertson, L.; Sayer, T.; Bandlera, S. Report 1983, EPA-600/D-83-098; Order No. PB83-247486, 25 pp. Avail. NTIS, from Gov. Rep. Announce. Index ( U . S . ) 1983, 8 3 , 6058. (38Q) Schulte, E.; Mallsch, R. Fresenlus' 2. Anal. Chem. 1984, 319, 54-59. (39Q) Schwartz, T. R.; Campbell, R. D.; Stalling, D. L.; Little, R. L.; Petty, J. D.; Hogan, J. W.; Kaiser, E. M. Anal. Chem. 1984, 56, 1303-1308. (40Q) Smith, G. C.; Gauger, G. A.; Frey, R. M. I€€€ Trans. Power Appar. Syst., 1982, PAS-101, 2260-2267. Anal. Abstr. 1983, 4 4 , 3C85. (41Q) Smith, R. M.; O'Keefe, P. W.; Hllker, D. R.; Jelus-Tyror, B. L.; Aldous, K. M. Chemosphere 1982, 1 1 , 715-720. (42Q) Splttler, T. M.; Natl. Conf. Manage. Uncontrolled Hazard. Waste Sites 1983, 105-107. Chem. Abstr. 1984, 100, 220890~. (43Q) Stelnwandter, H. Fresenlus' 2.Anal. Chem. 1982, 373, 538-538. (44Q) Stelnwandter, H. Fresenlus' Z . Anal. Chem. 1983, 314, 129-130. (45Q) Stelnwandter, H. Fresenlus' 2. Anal. Chem. 1983, 376, 493-494. (46Q) Takamlya, K. Bull. Environ. Contam. Toxlcol. 1983, 30, 600-605. (47Q) Tulnstra, L. 0. M. T.; Traag, W. A. J. Assoc. Off. Anal. Chem. 1983, 66, 708-717. (48Q) Voyksner, R. D.; Hass, J. R.; Sovocool, G. W.; Bursey, M. M. Anal. Chem. 1983, 55, 744-749. (49Q) Weeraslnghe, N. C. A.; Meehan, J. L.; Gross, M. L.; Galnes, J. J. Agrlc. Food Chem. 1983, 31, 1377-1378. (50Q) Westerberg, R. B.; Allbrando, S. L.; Van Lenten, F. J. J. Chromatogr. 1984, 284, 447-456. (51Q) Wong, A. S. U S . Envlron. Prot. Agency, Off. Res. Dev., [Rep.] EPA-600/4-82-028, 1982 p 51. Anal. Abstr. 1983. 45, 2H107.
Coatings D. G. Anderson* a n d J. T.Vandeberg DeSoto, Inc., 1700 South Mt. Prospect Road, DesPlaines, Illinois 60018
INTRODUCTION This review covers analytical techniques applicable to the examination of coatings and coatings raw materials, substrates upon which coatings are placed, etc., since the last review in 1983 (14). The compiled references were extracted after searching Chemical Abstracts, Analytical Abstracts, World Surface Coatings Abstracts, and the Journal of Coatings Technology. The contents are divided into 18 categories for ready access to the reader. Readers are advised to survey the entire review for the analysis of specific paints, coatings, or related materials may be found in each section. The five most highly referenced categories are Chemical and Electrochemical, Gas Chromatography, Nuclear Magnetic Resonance Spectroscopy, Surface, and Thermal Analysis. New or unique applications to estab!ished analytical techniques also appear throughout this remew. Several general review articles have appeared dealing with the use of analytical techniques for the examination of coatings (1,21,22,23). General analytical papers were also published on more narrow aspects of coatings technology, including emulsion paints (28,311, realistic paint testing (23),and fire retardant coatings (17). The role of ASTM in coatings research and development was the subject of a recent publication (36). Analysis of inks also received special attention (29)as 0003-2700/85/0357-15R$06.50/0
did general polymer analysis as detailed in a comprehensive book on this subject (16). The increasing role of the coatings analyst in dealing with customer complaints was the subject of a presentation (15)which cited four examples of how unique analytical approaches are frequently required to reach a resolution to a problem. The examination of coatings for forensic applications has found continued interest during this period (24,30,32)as has the analysis of fine art for conservation purposes (35). Special studies also appeared, including methods of latex cleaning prior to analysis (241, paint solubility testing (36), and a mathematical treatment of methods for calculating the flash point of liquids (34). The American Society for Testing and Materials (ASTM) has continued to provide methods for the examination of coatings. Methods relative to the determination of flash point received special attention, including the use of the Setaflash Tester (9,131, the use of a flash-no flash equilibrium method (ll),and the more traditional Tag cup apparatus (3, 7). ASTM procedures have also dealt with the examination of diatomaceous silica (6) and liquid paint driers (5). Standard practices have also appeared for the testing of specific coatings types, for example, wood furniture lacquers (81, lac resins (2), and clear and pigmented lacquers ( 4 ) were completed during this period. Ultraviolet cured coatings are a new area of @ 1985 American
Chemical Society
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concern for ASTM, as illustrated by standard practices for the evaluation of package stability (12) and cure time (10). During this period, the British Standards Institution developed new methods for testing the pH of an aqueous suspension (19), the determination of oil absorption for pigments (18),and the determination of soluble lead in liquid paints (20). The International Standards Organization published general methods for the testing of binders for aqueous paints and varnishes (26). In a recent paper, a French proposal for the revision of International Standards Organization Method 6713 (determination of soluble lead in paint) was proposed (27).
CHEMICAL AND ELECTROCHEMICAL Gravimetric techniques continue as a vital tool in coatings characterization. Several standards producing organizations have revised their general procedures for measuring the nonvolatile content of coatings (9,25, 37, 38,54). Systems which were the object of special methodology include polyester paints and varnishes (30),as well as cellulosics, emulsions,resin solutions, shellac, and varnishes (13). A standard guide for the determination of volatile and nonvolatile content of pigments was approved by ASTM (12). The concern over appropriate methodology for assessing volatile organic content (10) and volume solids (39) continues to be expressed through updated procedures. Specific components of vehicles and coatings also received attention, specifically ash content (14, 31) and pigments and extenders (18). The use of titrimetric procedures for the characterization of pigments have appeared. Among the recently reported studies were calcium carbonate content in precipitated pigmenb (%), chemical analysis of zinc chromate yellow ( I ) , and the determination of water soluble sulfates, chlorides, and nitrates in prime and extender pigments (29). Two specialized procedures were noted for measuring the resistance of coatin s to chemicals (24) and the determination of phthalic anhydricfe in an alkyd polymer using an ion exchange resin (51). Numerous methods have been reported or updated for the measurement of acid content in paints and varnishes (41), chemical intermediates (7),rosin (3),and the aqueous extract from pigments (19). An exhaustive study of methodology for the determination of hydroxyl content in polymers was published (23). The workers used factorial experimental design to minimize the number of experiments required to achieve optimum reaction time and functional group stoichiometry. In a similar study concerning the measurement of hydroxyl groups in polyester olymers, the investigators evaluated chloroform and pyri ine as potential solvents for an acetylation reaction (57). To extend the measurement of hydroxyl content to low levels, dimethylformamide was found to be required as the solvent (45). Epoxy resins continue as important vehicles for high-performance coatings. Studies were reported dealin with the determination of epoxide content (33,42) and hygoxyl content following reaction with lithium aluminum hydride (52). The unsaturation present in fatty acids and oils (17), as well as paint and varnish binders (48), was again measured via iodine uptake. Certain functional groups require chemical degradation or hydrolysis prior to titrimetric analysis. Ester functionality continues to be studied through the use of saponification and titration of the excess base (2,8,40,44). The degradation of polyurethanes in magnetic tape coatings was traced to hydrolysis catalyzed by hydrochloric acid (35). The hydrolysis of ether linkages by hydriodic acid (Zeisel reaction) was reported as a mechanism for the characterization of ureaformaldehyde oligomers (53). Titrimetric measurement of species present in coatings and coatings raw materials has led to a renewed evaluation of the Karl Fisher procedure for water determination (11) and measurement of residual formaldehyde in amino resins (46). Titration was also used to determine the isoelectric point in amphoteric latices (43) and to evaluate the dissociation constants of carboxymethylated cellulose (55, 56). Elemental analysis of olymers and plastics continues to be studied. A revised metgod for nitrogen content in polymers was published (5) as was the determination of carbon, hydrogen, nitrogen, sulful, bromine, and copper in phthalocyanines (49). Studies on pigments continue to appear, including the determination of iron(I1) in iron oxide (27), potassium ferrocyanide in Prussian Blue (50),and the surface
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properties of alumina coated rutile pigments (20,21). Special reports were published concerning the automation of titrations in coatings laboratories (22), evaluation of oxygen uptake of unsaturated fatty acid esters (59), and the fractionation of epoxy oligomers by precipitation (47). Few electrochemical studies have been performed during this period. Among those published were several review papers on evaluating the protective properties of paints and coatings (16,36,58). The leaching of organotin antifouling compounds was measured using pulse polarography (15) as was residual styrene in butadiene/styrene oligomers (32). In conclusion, coated naval steel sheets were examined using alternating current techniques (26) and surfactant sensitive electrodes were used to study surfactant adsorption in colloidal suspensions (34).
GAS CHROMATOGRAPHY Gas chromatography remains an important analytical tool for the examination of coatings systems. Studies related to the determination of solvents continue to appear (32,60). In addition, the use of gas chromatography to measure propellants and solvents in aerosol coatings was reported (29) as was the viability of gas chromatographic techniques in solving solvent problems within coatings systems (43). The automation of coatings analysis was demonstrated in a recent paper (13) with particular emphasis on chromatographictechniques. Trace or residual solvent determinations continue as excellent examples of the sensitivity available using modern gas chromatographic systems (27,42,54),as was the determination of specific coatings components, such as pentachlorophenol in wood preservatives (33), water in solvents (15), and monomer composition in a feedstock prior to polymerization (44). ASTM has again provided standardized methods; includin the determination of monocyclic aromatic hydrocarbons (47 and o-xylene (5). Several new approaches to the determination of residual monomers in latex polymers have been reported. Among the specific techniques developed were inert gas purging with vapors absorbed on activated charcoal (18),headspace analysis (9, 311, extractive distillation (41), and removal of volatile species using a pyrolyzer at 220 "C (55,56). The determination of unreacted neopentyl glycol in an epoxy ester polymer was also presented (57). In addition, a standardized method was developed to measure the monomeric diisocyanate content in isocyanate resins (11). The high molecular weight and low volatility of binders used in coatings limits the direct analysis of these materials via gas chromatography. Pyrolysis techniques provide a mechanism for generating volatile species amenable to analysis. During this period, a general paper on the examination of paints for forensic characterization (6) and an examination of "fingerprint" type chromatograms related to hygiene problems (14) have been published. Specific studies concerning the pyrolysis of addition type polymer systems included the examination of hydrocarbon polymers (25),polystyrene (36,40), and polybutadiene (26,46). Pyrolysis also has found application in the characterization of condensation type polymers, such as, unsaturated polyesters (49) and polyurethanes (58). Of more general interest for the analysis of condensation polymers is chemical degradation which is followed with gas chromatography of the hydrolysis products. Among the studies reported were the examination of polyamides (23) and polyimides (22) and the determination of phthalic anhydride and polyhydric alcohols in alkyd resins (34). Zeisel degradation of ester and ether linkages, via hydriodic acid, remains popular, as evidenced by papers dealing with acrylic polymers (37), polysaccharides (17), cellulose ethers (19), and melamine-formaldehyde condensates (28). Gas chromatography continues to be used to evaluate raw material quality and composition. Several new studies were published detailing the free fatty acid content of natural oils (12,59), mono-, di-, and triglyceride analysis (10,45, 53), as well as the measurement of fatty acid composition of oils followin saponification and derivative preparation ( I , 48). Two ratter unique applications of gas chromatography involved the separation of oligomers in epoxy resins (24) and the measurement of chain length distribution in shellac wax (50). Monitoring the progress of polyester synthesis was followed by gas chromatographic techniques (16,47) as was the progress
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cure kinetica (12). and the development of a method for calibrating gel permeation chromatographic columns for the analysis of epoxy oligomers (8). Poly(ethy1eneoxide)polyol studies were reported (9.20) as was the characterization of poly(or anosiloxanes) (5). Relative to the analysis of low molecufar weight or monomeric species, gel permeation chromatography was used to measm the residual d i i i a n a t e monomer content in segmented polyurethanes (1). Among the basic studies of interest to coatings analysts were the effects of flow rate on efficiency (4). the use of a densitometric detector (3, and the analysis of degradation products formed from polystymne during an examination of the kinetics and mechanism of this process ( 6 ) .
HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY The nonvolatile nature of many species pesent in coatings dramatically increases the utility of high-performanceliquid chromatography for solving coatings problems. Ion paired HPLC was recently used to fingerprint polymers in cathodic electrodeposition paints with excellent results (6). In another study, the sol fraction in partially cured acrylate networks was evaluated via liquid chromatographic techniques (11). Among the specific polymeric and oligomeric systems examined during this period were epoxy polymers (3,4,9),oligosaccharides (2), phenol-formaldehyde condensates (15),melamine oligomers and triglycerides io natural oils (13, 14). Specific components in coatings formulations have also received specific attention. The separation of surfactant mixtures and their homolo es was obtained using reverse phase techniques (16). Low E e l s of wax in uncured polyester resins were measured following extraction into tetrahydroftuan and 2.2,4-trimethylpentane (19). Essentially monomeric species, such as initiators for radiation curable coatings (12), antioxidants and ultraviolet stabilizers in polymers (7),and polyols consumed during polyurethane synthesis (8) were measured using high-performance liquid chromatographic techniques. The determination of residual monomers in coatings r e ceived special attention. Formaldehyde has been measured using fluorescence detection following derivitization via the Hartzoch reaction (20), (diphenylaceto)indane-1,3-dione1hydrazone (21).and diacetyldihydrotolutidine (18). Clycidyl amine and residual Bisphenol A were recently determined in epoxy resins via HPLC techniques (I), as were phthalates in cured epoxy resins following extraction from the resin matrix
(In,
of addition polymerization of e n y l (52) and acrylate (To) containing polymers. The volatile producta formed during the curing of alkyd/melamine systems ( 2 , 3 )led to valuable information on the kinetics and mechanisms of the process. Special studiea continue to a p r a r in the !iterafure. Among the most interenting reporte during this period were the characterization of ultrafiltration membranes ( 8 ) ,the rate of oxidation of paint materiala (301,the determination of solubility parameters (35, a), evaluation of activity coefficients (7).and polyntyrene oligomer separation using supercritical fluid chromatography ( 1 4 ) .
GEL PERMEATION CHROMATOGRAPHY Gel permeation or size exclusion chromatographycontinues vehicles, me of to gmw relative to the major contribution during this period is the increaseeasing trend toward t h e w of high-performance chromatographicsystems for measuring the molecular size distribution of polymers. Cathodic electrodeposition paints received special attention during this period (21). The use of gel permeation chromatography for the quality assurance of coatings systems has of a general paper (z4)and a report specific been the to ultraviolet curable coatings (10). A general paper on the characterization of copolymers was published ( 1 1 ) as was a discussion of the limits of this technique for the examination of alkyd and acrylic polymers (3). specific polymer system studied were unsaturated polyesters (13,16),organometaUic copolymers (22),the determination of gel content in acrylic latices (19).and radiation wed poly(vinyl chloride) containing coatings (14). Low to medium molecular weight polymers and oligomers continue to be studied via gel permeation chromatograph Condensation products from the reaction of formaldehydk with urea (23, E), phenol and melamine (2). and furfuryl alcohol (18)were reported. Epoxy resins, due to theu extreme flexibility in formulating high-performance eoatings, have led to several general studies (15. In, the evaluation of epoxy min
.
(5).
Two special high-performance liquid chromatographic studies were performed during this review period. These included measuring latex particle size using porous silica packing8 (IO)and evaluating the influence of the position of unsaturation in fatty acid esterified glvcerine on the oxidation rate of triglycerides (22).
THIN-LAYER CHROMATOGRAPHY With the increased utility of liquid chromatography in the examination of coatings, papers related to thin-layer chromatography have decreased dramatically. Papers have appeared using TLC for the separation of household paints (I) and artists Paints (3). Thin-layer chromatography was comPared to other chromatographic techniques for the characterization of copolymers (2). Nitrogen-contsining polymers and Oligomerswere also examined, Particularly relative to the kinetics and mechanism of the urea-formaldehyde reaction in Particle board (5) and the (6). The most unique application using thin-layer chromatography involved the use of a flame ionization detector for studying the morphology and grafting of poly(buty1 acrylate)/Poly(styrene) core/shell emulsion polymers (4).
ATOMIC SPECTROSCOPY Commisaione Prodotti Vernicianti Unichim (4) uaed atomic absorption spectroscopy for determining soluble metals in paint. This particular publication concerned the determination of the total chromium content in the liquid fraction of a paint. The determination of lead in paint continues to receive emphasis. HausknFht et al., (7)used a modified ashing procedure and atomic absorption spectrophotometry. TakANALYTICAL CKMISTRY. VOL. 57. NO. 5. APRIL 1085 a 17R
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ahashi et al. (12) applied the same instrumentation to determine the lead content in anticorrosive coatings. Soluble lead in paint was also determined with atomic absorption spectrophotometry after extraction with acid (5). A furnace atomic absorption procedure for determining titanium dioxide in soap was reported (11). The soap is dispersed in water, and the titanium content is directly determined without preliminary treatment using acids/bases for titanium dioxide solubilization. Flameless atomic absorption was cited for the determination of total mercury (1). Japanese workers, Kenjo and Mabuchi (9),quantitatively determined the copper, iron, and manganese content in lacquers by atomic absorption. Soluble barium was determined using atomic absorption (emission) (61, and barium in organic pigments was determined using similar methodology by Kondrachoff and Declerck (10). Henden (8) attempted to eliminate interferences in the determination of arsenic, antimony, tin, and germanium with the hydride generation technique coupled with molecular emission cavity analysis. Interferences are reported. Many ions suppress the emissions, but interferences were eliminated and the peaks broadened, by masking with EDTA. Browner and co-workers (3) investigated the aerosol transport model for atomic absorption. The transport of aerosol in an atomic absorption system is explained in terms of the interaction of a primary generation process, with various secondary and tertiary aerosol modifyin steps. These authors cite 27 references. Boorn and Browner reported the effects of organic solvents in inductively coupled plasma/atomic absorption spectroscopy. The tolerance of a low power argon inductively coupled plasma to 30 common solvents was discussed. Good correlation existed between limiting aspiration rates and evaporation factors for a number of solvents. Apparently, solvent vapor loading is the major influence for plasma stability with organic solvent introduction. Forty-six references are cited.
b)
INFRARED SPECTROSCOPY Infrared spectroscopy analysis of organic coatings, including sample preparation and analytical techniques for the identification of polymers, plasticisers, and antioxidants, are briefly described (34). Josse (24) reviewed the application of FT-IR to study synthetic polymers. The theory, advantages, and instrumentation are provided. IR bands of polymers with distortions in structural periodicity have been examined (28). The authors list 142 references in their publication. Fowkes et al. (15) used IR to investigate acid/ base complexes of polymers with solvents. They explained the weakness of the solubility parameter concept in predicting solubility of polymers with polar groups by consideration of acid/base complexes. The complexes are destabilized by heating. Yoshimura (40) followed the reaction of 3-methylphenol with tung oil using IR, NMR, and HPLC. Free phenol in aqueous solutions of phenol-formaldehyde condensates was determined by IR techniques (31). Time-lapse IR investigation of alk d and linseed oil cure was accomplished by Hartshorn (19). *he interaction of esters and polyesters with chlorinated solvents was examined using IR and NMR (16). Biernacka et al. (4) used IR to determine free fatty acids in castor oil. Estimation of the properties of a reactive three-component system related to the reaction kinetics of the components was done using IR, thermal, viscosity, and tensile measurements (12).
Polymerization studies were accomplished using IR techniques for the copolymerization of monomethyl itaconate (51, followin curing of thermosetting acrylate varnish films (27), and stu&ng the degradation, interactions, and kinetic studies of epoxy resins (10, 35, 36). Allen et al. (1) used IR, fluorescence/phosphorescence,and UV/visible methods to elucidate the nature of the species responsible for the sensitivity of the resins on exposure to sunlight. Reflection absorption IR was reported to study diffused residues on a humidity/temperature-aged urethane pressure-sensitive adhesive (11). Impurities in diphenylmethane diisocyanate were measured by IR (20). IR was used to follow the synthesis and characterize polyester-based polyurethanes (32) and establish cure kinetics of polyurethane coatings as 18R
ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
influenced by polysulfide sealants (38). FT-IR and TMA methods were used to study the cure kinetics of blocked isocyanate-containingcoatings (7) and to determine uretidione and isocyanurate groups in polyurethanes (26). The cure kinetics in polyester gel coat systems were investigated by IR, DSC, and DMA (30). IR was used to determine hydroxyl concentrations in prepolymers (25) and hydrogen bonding in polymer systems (6). Several articles appeared where IR was used to study the degradation of polymers, such as cross-linked acrylic/melamine coatings (2,3,13), polymeric coatings on mirrors (39), and plasticised poly(viny1 chloride) (21). Hummel et al. (23) describe computer-aided IR for plastics analysis. Hummel and Votteler (22) identified the multicomponents in plastics and copolymers by IR. The identification of the paint binder in cured silicate and carbonate containing ~aintswas accomdished bv Rebhan and Luigart (33) using YR. Fowkes et al. (14)predicted enthalpies of interfacial bonding of polymers to reinforcing pigments using IR, adsorption isotherms, and adsorption calorimetry. Pigment photodecomposition in paint was followed by applying diffuse reflectance FT-IR (9). The photodecomposition mechanism is postulated. Coatings to coat glass fibers were characterized by FT-IR
(17). The reaction of polyester with zinc oxide was investigated by IR (37). The cross-linking mechanism is described after comparing the reactions of several metal oxides. IR spectroscopy has been used to analyze several pigments, including basic lead silicochromate (B), surface modifications of anatase titanium dioxide caused by potassium oxide addition (29))and a new phase in a barium carbonate/barium sulfate system (18).
NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY NMR techniques have been employed extensively to characterize paint, a variety of polymers, films, pigments, solids, etc. This review includes proton NMR, 13CNMR, 15N NMR, ?F NMR, and %i N M R with 13CNMR being the most emphasized technique in the last 2 years. Marshall (31) characterized paint media using proton NMR and 13CNMR methods. Alkyd and epoxy resins are discussed. Ishida (21)reviewed recent progress in the studies of molecular and microstructure of interfaces in composites, coatings, and adhesive joints. 13CNMR with magic angle spinning and cross polarization capability were most helpful in studying the glass silane interface. C culations of Alfrey-Price Q-e values from 13CNMR data were accomplished (7). Separate equations for the calculation of Q and e values of stvrene. chlorinated olefins. acrvlates. mechacrylates, vinyl echers and esters, nitrogen-'coniaining monomers, allyl compounds, and miscellaneous olefins were developed. Several illustrative examples for the characterization of copolymers by lSC NMR were provided (22). This text included 54 references. Solid polymers were reportedly analyzed by Havens and Koenig (19) using 13C NMR. The authors discussed several exam les and included 208 references in their paper. Stejskal et al. 66)used 13Cand lSNNMR techniques to study polymers, as did Cais, Kometani, and Solzman (10). Other polymers which have been investigated by 13C NMR include reaction between ethylene glycol or 1,2-propylene glycol with diphenylmethane 4,4'-diisocyanate (43),polyesters from propanediol and phthalic anhydride (23),hydroxy-terminated polyesters (18), polyols in aliphatic and aromatic polyesters (ZO),epoxy resin networks (12),urea-formaldehyde condensation products (42, 50)) vinyl chloride/vinylidiene chloride copolymers (26), vinyl chloride/vinyl acetate copolymers (54),vinyl alcohol/vinyl acetate copolymers (51,551, polystyrene (41, 40), alternating copolymers of a-methylstyrene with methyl methacrylate and methyl acrylate (36), linear and branched polyethylene (14),phenolic novolacs (a), cresol novolac resins (11),benzenoid and heterocyclic aromatic polymers (8), asphaltmes (33),xanthan gum (3) and ,partially hydrolyzed acrylic polymer colloid (48). Methyl acrylate and a-fluorostyrene copolymers were first synthesized and then their structure was confirmed by I3C and 19FNMR (29). Solid-state 13CNMR was used to characterize wood (49).
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Aganon and Antonovsky (1)reported using 13C NMR to obtain the spectra of organic peroxides. NMR and vibrational spectroscopy methods were used to investigate the structure in solvents and solutions (47). A review of academic work is presented. The solvents studied were methanol and water, while selected bases, aprotic solvents, and probe molecules were the solutes. Fifty-two references are cited. Estimation of reactivity ratios of acrylic copolymers by NMR was reported by Nithianandam et al. (37). A new esterification method for resin acids was also published (3). A number of new esters were subsequently identified by NMR, IR, and MS. Proton NMR studies were performed on several types of polymers: eutectic bodied oil (25),curing epoxy resins with anhydrides (32),polyisocyanurates (52),urethane ionomers (16),aliphatic/aromatic polyamideimides from diisocyanates (13,35),styrene methyl methacrylate copolymers (17,45,53), styrene/methy methacrylateln-butyl acrylate texpolymers (% isotactic I)methyl , methacrylate (2),poly(ethy1ene-co-vinyl acetate)-g-vinyl chloride solutions ( 4 4 , and phenol-formaldehyde resins (34). The investigation of structure of polymeric micro emulsions by proton NMR was reported by Ballet and Candau (4). Water content affects the mobility of the ethylene oxide units in the toluene/water/polystyrene poly(ethy1eneoxide) graft copolymer/2-propanol environment. Sankaram et al. (39) used PMR to characterize vinyl monomers based on undecanoic acid. Several vinyl monomers are discussed: vinyl ether, vinyl ester, allyl ether and ester, methacr lic ester, and acrylic ester. The olefinic protons are analyzedl in detail. Krecheldorf (27) did lSN NMR characterization of copolgamides and polypeptides. 15NNMR spectra are inferior to C NMR spectra when quantitative evaluation of copolyamide sequences is required. Analysis of the primary hydroxyl content of polyethers by differential reaction rate studies and by 19FNMR were accomplished (56). In general, the results from both methods were in good agreement; the NMR technique appears more reliable and efficient. Polymers prepared by reacting their end groups with 4-fluorobenzoyl peroxide were then analyzed using 19FNMR (6). The studies were done with polymethyl methacrylate and polystyrene. Silicon-29 NMR chemical shifts were reported for cyclic dimethylsiloxane oligomers (9). This technique was also utilized for the characterization of polymers and paints (30). Rigid lattice proton NMR was used to investigate the constitutive water of rutile, anatase, and amorphous oxide titanium oxides (15). The hydration of the anatase surface is more stable than that of other phases. Broad-line NMR studies of molecular motion in cured epoxy resins were made by Banks and Bryan (5). The conformation of network chain segments in a ri id glassy 4,4’-diaminodiphenylmethane cured bisphenol if epoxy resin has been determined using a rotational isomeric-slate model and confirmed by conformity of experimental NMR second moments with a theoretical estimate based on the model.
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SURFACE ANALYSIS This section begins with emphasis on review articles which concentrate on surface analysis. Next, X-ray photoelectron/electron spectroscopy for chemical analysis will be covered. This area of surface analysis technology definitely received the most emphasis within the past 2 years. Infrared spectroscopy, secondary ion mass spectrometry, Auger spectroscopy, Raman, etc., coverage will follow to complete this section. Surface analytical techniques: a review was published by Allen (3). This author summarizes the essential features of eight surface analytical techniques. Baun (8)compared ion scattering spectroscopy and SIMS techniques. Emphasis is on the analysis of metal surfaces by ion spectroscopy. The basic principles of photoelectron and article spectroscopy techniques are reviewed by Carrick (157. Five primary techniques are included; computer-aided surface analyses are emphasized. Sparrow and Drummond (44) describe how to select a technique and an instrument for surface analysis. Valenty (50) discussed the utility of surface analytical instrumentation for coatings problem solving and product de-
velopment. A short review appeared including modern methods of surface testing for the electroplating and painting industries (34). More specifically, steel surface chemistry affecting the performance of organic coatings was reported (38). Paintability and phosphating behavior are confirmed. Baun (9)used modern surface analytical methods to establish the site failure. Adhesive bonds are studied. Surface analysis by Auger and XPS are applied to corrosion (37). Takaoka (47) published a Japanese article concerning methods for surface analysis in the paint industry. Karen (32) used XPS and SIMS to investigate defects in paint on phosphated steel, insufficient adhesion on aluminum, yellowing in chlorinated rubber, and weathering of an e oxy paint. Interfacial interactions between paint systems anfvarious metals using XPS and AES techniques were investigated (51). Paint to metal adhesion is demonstrated. It is shown that during ageing of paint/metal bonds in agressive environments, changes of the interfacial chemical composition may occur. In all cases studied, paint delamination is cohesive not adhesive, i.e., the result of formation of a very thin weak boundary layer. Baer and Thomas (5) used five surface analytical techniques to examine metal corrosion. Others (30) did surface characterization of anticorrosive phosphate coatings by XPS and AES. Chromate conversion coatings were analyzed for structure and composition by XPS and SEM (48). Understanding the mechanism of adhesion of paint and lacquers to pretreated surfaces is postulated. XPS studies of a ferricyanide accelerated chromate aint pretreatment film on aluminum surface were reporte (49). The results are used to consider the mechanism of the ferricyanide accelerator. Briggs (12) used the XPS analytical technique to study polymer surface modifications and adhesion mechanisms. XPS is used to elucidate the mechanism of surface modification of low-density polyethylene by corona discharge and by chromic acid treatment. Precision of functional group analysis is described. The role of residual chromium on the adhesion of metal deposited on olymer surfaces is discussed. Separately, Clark (18,19)descriied advances in XPS applied to polymer characterization. Thirty-one references are cited. Briggs (13) also published on chemical analysis of polymer surfaces, emphasizing XPS, IR, IS, and Raman. Many reports exist on the surface analysis for specific polymer films. XPS was used to study the surface derivatization of hydroxyl functional copolymers (24),nitrocellulose (21),the degradation of bisphenol A polycarbonate in O2and N2atmospheres (22),sulfate groups on polystyrene latices (&), ozonation of polystyrene film (40),plasma polymerization of perfluoro-2-butyltetrahydrofuran (20), and the electrical discharge treatment of low density polyethylene (14). Chan ( I 7) used XPS to study the failure of an adhesive joint between two polymers. Two commercial polyamic acids, Le., uncured polyimide, fiis, and a vapor-deposited aluminum alloy were treated with y-aminopropyltriethoxysilaneand examined by XPS (35). The results, including penetration of the silane into the polymer, are discussed. Owen (26,39)studied silicone release coatings and their relationship between surface properties and release behavior. Contact angle measurements were found to generally not correlate with release measurements. However, research indicates that XPS may provide an additional tool to understand anomalies. IR and Raman spectroscopy were used to study corrosion inhibitors on metal surfaces (36). Sensitivity of the spectra to pH of the solutions and chemically bonded polymer-like materials to the iron surface were confirmed. Rouxhet et al. (41)employed X P S to investigate the surface chemistry of pi ments and related substances. Titanium dioxide, silicon cfioxide, iron oxides, and chromium pigments and polymers are included in the publication. Others (27) reported using XPS to analyze uncoated and silica-coated titanium dioxide. Distinction of the surface treatments is readily apparent. The surface of steel cleaned in various ways was characterized by XPS, before and after heat treatment in air (16). The spectra show a layer structure of, sequentially, metal/ oxide/hydroxide/polar organic/hydrocarbon/water. On heating, the growth of oxide and reductions in water and hydrocarbon developed. Cathodic disbondment of the well characterized steel/coating interfaces assisted further char-
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acterizations. Yamamoto et al. (53)showed eth lene/acrylic acid copolymers bonded to lead tin alloys gave a&esive failure due to anodic dissolution o f t e alloy. Coating degradation was investigated by AES (43). SIMS and AES were used to study water adsorption on titanium dioxide (23).The amount of adsorbed water can be related to surface stoichiometry, i.e., 0:Ti ratio. Using IR, Fowkes (29)demonstrated that only acid/base interactions, and not dipole/dipole interactions control adsorption and adhesion at interfaces. Experimental data are presented for adsorption and adhesion of acid and base olymers on surface controlled acidity, and the competition E3tween polymer and solvent for active sites on pi ents and extenders in which film properties depend on t e relevant acid/base balance. Sultaka (46)used IR to investigate polymer coating/metal substrate interaction. The orientation of poly(2-cyanoacrylate) in films on anodically oxidized and chemically polished aluminum is deduced (10). The distribution of polyacrylic acid between unbound and bound states adsorbed on tricalcium phosphates was shown by FT-IR. This is a function of the pH of the depositing solution. Allara (1) described using IR, Raman, and optical spectroscopy to analyze surfaces and thin films. Fifty-four references are included. Adsorbates on metal surfaces have been analyzed using a double modulation FT-IR approach (25). Computerized dispersive IR with DSC and DMA were used to study the curing behavior of a commercial epoxy used to bond fluorocarbons to metal (6). Specular reflectance IR was used by Allen and Stevens (4)to investigate films of y-glycidoxypropyltrimethoxysilane primer to aluminum substrates. Chemical bonds, via hydroxyl bonding, proved most dominant in the thinnest films. Hare and Vickerman (31)investigated precipitated alumina structures by SIMS. They emphasized the structure of an alumina coating precipitated on rutile titanium dioxide. SIMS and ISS methods were reported for the surface characterization of olymers (7) and polystyrene latices (28).Scheifers et al. (42fcharacterized organic dyes by SIMS. Berner (11)developed an ESR technique which distinguishes between surfactant deposition and penetration when de osited on surfaces. h e i n and Pincus (33)described interaction between surfaces with adsorbed polymers and poor solvents. Voas (52)used newly developed, extremely sensitive surface scanners to characterize coated surfaces. Raman spectroscopy was employed by Allara, Murray, and Bodoff (2)as a useful tool in examining the surface regions of polymer films on roughened silver surfaces.
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ULTRAVIOLET-VISIBLE SPECTROPHOTOMETRY Harold (13) reported a new microprocessor-controlled spectrocolorimeter for use in measurements of paints and coatings. The International Standards Organization reported spectrophotometric methods for “soluble”metal content in paints and coatings (16) and total arsenic in water (17). A lead acetate spot test for the detection of colorless chromate films on zinc coatings was published (4). This methodology could be adapted to spectrophotometry. Visible spectrophotometry was also used for determining copper resinate in antifouling points (12). Color complexes were analyzed using spectrophotometry to determine the level of cobalt in paints and coatings (10). Toxic metals in paint products were determined by conventional visible spectrometry (8). Stannine polydye additives for latex paints were analyzed usin general spectrophotometry methods (6). Billmeyer et af (5)identified organic pigments by solution spectrophotometry. Visible spectrophotometry has been reported for determining formaldehyde in air (19),ita release from particle board (14, in wood based panels (23),and from fabrics (7). Sukhanova and Shuvalova (25)authored a rapid method for the determination of methylol groups in phenol-formaldehyde and amino-formaldehyde resins. Photometric determination of small amounts of isocyanates in polyurethane solutions was reported by Korzyuk and Smigullin (20). A calibration curve is constructed using toluene-2,4-diisocyanatein ethyl acetate after dilution with acetone and addition of sodium sulfite. Primary aromatic 20R
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amines do not interfere. The method is suitable for determining isocyanate concentrations in the range 0.005 to 0.02%. A spectrophotometric method for the quantitative amounts of thiols in resins for can coatings was published (24).The ori inal article is in Bulgarian. 8reenish blue colors in bisphenol A epoxy resin cured with (4,4’-diaminodiphenyl)methaneare analyzed by UV, visible, IR, and ESR spectrometry (3). The color is to an initial interaction between molecular oxygen and secondary amine groyw. Tieke et al. (26)used visible spectrophotometry, transmission electron microscopy, and electron microscopy to follow redox reactions of poly(l,4-phenylene) in thin transparent films. A combination of UV, NMR, IR, and chromatography methods were used to identify the cornposition of fatty acids obtained by decomposition of castor oil fatty acid estolides (21).
Hoffmann (15)developed a rapid method for the detection of poly(ethy1eneglycols) in wood. The method is qualitative but ado tion to visible spectrophotometry should be possible. Stanlard test methods for aldehydes (I) and p-tert-butylcatechol(2) in styrene monomer are reported. After the thermal polymerization of styrene, the formation of oligomers and intermediates was followed using UV spectroscopy (18). Kinetic formulas and reaction rate constants are obtained. It is possible to describe the formation of oligomers and intermediates a t temperatures of 137 and 180 OC with 97% monomer conversion. Nencioni and Russo (22)obtained UV absorption spectra of styrene copolymer model compounds. Their work supported the hypochroism correlation attributed to strong interactions between the carbonyl groups of methyl methacrylate ester and the styrene phenyl rings. Garcia-Rubio (9) used UV absorption analysis to correlate the effect of composition, sequence length, and tacticity of styrene copolymers. The microstructure of styrene copolymers is reviewed. Visible and UV spectro hotometric studies on hard and soft shellac resins were done t y Goswami and Prasad (11). Their intent is to correlate spacial polar groups in the resins with hard and soft character.
X-RAY ANALYSIS X-ray analysis was applied to film thickness measurements, extender, and/or pigment concentrations in films, and to determine microdomains in polymeric elastomers. Duncan (3) used electron spectroscopy to study chromated galvanized steel Eiheet after heating, water immersion, or outdoor weathering. Changes in surface chemistry are assessed. Marked chromium loss developed after water soaking or outdoor exposure. 0-Backscatter vs. X-ray fluorescence for coating thickness measurements are composed by Latter (7). X-ray fluorescence is preferred for measuring thin coatings and coated areas of small, complex shapes. The determination of lead in paint by energy dispersive X-ray fluorescence spectrometry was reported by Kuntz and Towns (6). The minimum detection limits provide good sensitivity; the matrix correction feature renders the model ideal for quality control. A kinetic study on leaching of ilmenite ore in concentrated hydrochloric acid solution during the manufacture of high urity titanium(1V) oxide by the chloride process employed %-ray techniques (9). The rates are well expressed by an equation based on the rate determining step of the surface chemical reaction. An X-ray diffractometry technique, using an internal standard, was developed for the quantitative measurement of chrysotile asbestos content in a wide variety of building materials (4). The method has been used to determine chrysotile asbestos in a concentation range between 0.5 and 50%.
Michell and Ng (8) used X-ray powder diffraction for measuring the stabilizing influence of basic lead carbonate in plasticised poly(vin 1 chloride). Pigment analysis in t e forensic examination of paints using X-ray diffraction was reported by Curry, Rendle, and Rogers ( I ) . Drabaek and Christensen (2)determined major and minor components in paint products with nondistractive X-ray fluorescence. Studies included evaluations on an anticorrosive primer and an emulsion paint.
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Small-angle X-ray scattering studies on the microdomain structure in segmented polyurethane elastomers was reported by Koberstein and Stein (5). Two model polyurethane elastomers were studied and characterized. Information is used to construct a new model for polyurethane hard segment microdomain structure. The model takes into account the effects of hard segment sequence length distribution and allows for folding of the longer hard segment sequences back into the hard segments domain. Forty-five references are mentioned.
SPECTROSCOPY-MISCELLANEOUS TECHNIQUES This section covers mass spectrometry, electron spin resonance spectroscopy, photoacoustic spectroscopy, and other lesser developed spectroscopy methods. Ramjit (28,29) pursued trends in kinetic behavior durin ester/ester exchange reactions in polyesters by MS. Foti ant! Montaudo (16) reviewed the advances using MS techniques to analyze several polymer systems. Eighty-nine references are mentioned. Others (21) used FD-MS, LC, and ATR-IR to characterize several types of tackifyihg resins. Resins prepared under different manufacturing conditions show additional series of oligomers which are identified. MS and NMR were reported for industrial polymer analysis (27). Complete breakdown of polymer structure and analysis of components along with additive determination are discussed. Pyrolysis techniques coupled with MS were emphasized by several workers. B use of these combinations, polyurethane and epoxy resins 6 5 , 24), lacquers (3, and methacrylates, poly(viny1 chloride), polystyrene, and styrene/isoprene copolymers (18) were successfully analyzed. The conversion of toluene 2,4-diisocyanate into biuret and urea derivatives by mearis of hydrated sodiuni sulfate was monitored using MS and GPC analyses (23). A scheme for the mechanism of formation of prepolymers is proposed. Mass analyzed ion kinetic energy spectrometry/collision induced dissociation (MIKES/CID) was used to locate the double bond position on fatty acid methyl esters (10). The spectra of the pseudomolecular ions formed by chemical ionization, using ammonia as the reaaeht gas, show two intense signals, allowing the location of the amino group, and, consequently, the position of the double bond in the molecule to be investigated. The method has been applied to fatty acids derived from bacteria. ESR was used to investigate the macroradical reactivity, network density, viscosity, and monomer dimensions of poly(ethy1ene glycol) dimethacrylates (81, polystyrene (5),and er films, such as thermosetting acrylic/melamine films
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Panenko and Vlasov (26) employed ESR to determine chromium ions in samples of commercial and laboratory anatase powders. The technique is described in detail. Fluorescence techniques have been used to analyze old Japanese paintings (21, paint and varnish layers (14), forensic science (13), and certain organotin compounds (4). Luminescence spectroscopy was reviewed by Allen (1). Applications mentioned are study of structure and molecular weight, analysis for polymer type, analysis of additives, and pigments in polymers. Fifty-one references are included. Inelastic electron tunneling spectroscopy (IETS) was used to examine some thermosetting polymers, i.e., epoxy resin with two aliphatic amine hardeners (12),and to study epoxy and cyanoacrylate adhesives (25). Photoacoustic spectroscopy (PAS) was utilized by Kirkbright and Menon (19) to determine the combined vinyl acetate in vinyl chloride/vinyl acetate copolymer and by Krishnan et al. (20) to decipher orientation measurements from polymer surfaces. In the latter, FT-IR-PAS was used to demonstrate the potential of this technique dichroism as a complementary technique to ATR dichroism, especially on Sam les with rough or brittle surfaces. IdPentification of pigments of artistic, forensic, and industrial importance usin the Raman microprobe and SEM with energy-dispersive $-ray analysis was discussed by Andersen (3). Light scattering and F& were used in studies of the thermal polymerization of styrene (11). Quasi-elasticlight scattering spectroscopy (QLSS) was used to probe polymer adsorption by small particles (31). A rapid survey technique for the detection of asbestos fibers
was based on differences in the profiles of chrysotile and amphibole scattered light distributions (30). Caroline (9) did data fitting in photon correlation spectroscopy (PCS) studies of dilute polymer solutions. Mossbauer spectroscopy was used to investigate the atmospheric corrosion of iron (22) and to study the photochemical degradation of organotin stabilized poly(viny1 chloride) (6).
MICROSCOPY Optical or light microscopic studies have been reported dealing with the examination of automotive coatings for forensic purposes (7), the discrimination of Trade Sales gloss paints through the use of an integrated microspectrophotometer ( I 7) and the application of ultraviolet illumination to monitor the progress of curing in thermosetting polymer systems (3). S m i n g electron microscopy '(SEM) continues to be widely used for the characterization of coatings systems and the substrates on which the coatings are placed. A general paper on the use of scanning electron microscopy in the forensic sciences used coatings as several of the examples cited (14). The orientation of an aluminum flake pigment in automotive coatings was studied using SEM with considerable success (19). The physical properties of emulsion paint systems were correlated with pigment volume concentration measured using scanning electron microscopic techniques (6). A similar study was also reported for filled unsaturated polyester resin films (28). Chalking phenomena continue to be of major concern to the coatings analyst. Two recent studies (11,121 present new approaches to the examination of this phenomenon. Organic species were also extensivelystudied using s c ~ i n electron microscopy. Several new procedures were publishe to examine emulsion polymer systems, including techniques for the contrasting of acrylic copolymer latices (22), the morphological properties of vinyl acetate/butyl acrylate latex films (21), and the ordered structure of highly charged, monodisperse, latex particles (10). Organic pigments also received special attention in a study which contrasted data from scanning and transmission electron microscopy with information obtained using ultrasedimentation techniques (8). Antifouling materials were examined in several coatings matrices. The microstructure of marine paints containing tributyltin oxide was related to several theoretical leaehing models (25) and the polymerization of organotin containing monomers was studied relative to the use of these vehicles in wood preservatives (27). Polymer blends continue to be studied, with papers appearing on the use of chemical contrast techniques to establish polymer distribution in a film (9), the morphology of interpenetrating networks (30), and the evaluation of sphere size in diblock copolymers (2). The utilization of scanning electron microscopy for evaluating inorganic substrates and pigments has led to a diversity of publications. Metallurgical techniques have been used to study fine art and sculpture (I), as well as pigments and dyestuffs (16). The dispersion characteristics of acicular particle powders was also evaluated via scanning electron microsopy (29). Among the specific pigment types evaluated during this period were chrome yellow (24) and molybdenum orange and red (23). Surface pretreatments for metal was the subject of a review paper (20), in addition specific studies related to adhesion on aluminum ( 4 ) and iron corrosion (13, 15). Finally, the problems encountered in the measurement of asbestos via SEM received attention in publications dealing with sample preparatioh and quantitation (5),the definition of asbestos particles (18),and the effect of common instrumental and operator errors on the accurate measurement of asbestos content (26).
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THERMAL ANALYSIS Thermoanalytical techniques for determining cross-linking and aging of paint were reviewed (36). Powder coatings, solvent-based systems, and polycondensation cross-linking reactions are investigated. A method was approved for measuring the thermal resistance of coatings (9). Widmann (53) described usin thermal analysis for surface coatings. DSC, TMA, and T 8 A are described and their applications listed. A carbon dioxide laser method was reported for the thermal conductivity meaurement of enamel paint (27). Electrically insulating and conducting substrates with thin ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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conductive paint coatings were used to demonstrate the use of this technique. Roller (37) explained Tg information and correlated it with polymerization data, cure reactions, and the interactions of various components of the formulated polymer product. Hay (24)published a treatise on the thermal methods of analysis of polymers. Various techniques, including TGA, EGA, EGD, DTA, DSC, TMA, and DTM, are included. In a separate publication, Czekaj and Kapko (14) made theoretical calculations of Tg temperatures of plasticized polymers. Polymer ignition studies were accomplished by couplin TGA with photometry (26). Information such as char yiel$ decomposition kinetics, ignition detection, and smoke generation are obtained. DTA was used in the characterization of electron-beam adhesives (6). The studies are reported on acrylated bisphenol A epoxy resin. UV cured acrylic resins have been studied using DTA methods (34). Induction periods and rates of reactions are obtained. The method is less accurate for heats of polymerization. Varnell, Harrison, and Roberts (52)utilized DSC to study oligomers. The thermal degradation of acrylic copolymers was studied using TGA, DTA, and IR (49). Kobayashi (28) studied the sequence distribution and Tg of acrylic resins for industrial paints. Others (33)followed the thermal decomposition and Tg of poly(ethy1 methacrylate) and poly(n-butyl methacrylate). The bulk of polymerization of acrylic and methacrylate monomers was studied by DSC (32). The courses of reaction, copolymerization enthalpies and parameters, and the specific constants of the rate of polymerization were determined. Singh et al. (44)followed the thermal behavior of homo- and copolymers of styrene, methyl acrylate, and acrylonitrile by TGA. The thermal stabilities of the copolymers are discussed in relation to the homopolymers. Thermal analysis techniques were used to investigate a variety of epoxy chemistry. Clayton and Clewes (8) used DSC to follow the curing behavior of liquid epoxy paints. DTA was used to analyze epoxy formulations with different hardener combinations or under varying reaction conditions (21).The data are used to predict reactivity, hardness, and film flexibility. Epoxy tank linings performance was correlated to TGA measurements (35). Inaccurate metering of the resin and hardener is detectable. Similar reports were published by Sickfield and Heinze (41) and Levy et al. (31). Epoxy adhesives were analyzed using DTA (43). Epoxy resin cure with ultrasonic and thermally stimulated current measurements were correlated from DSC data (5). Flammersheim et al. (18) used DSC to study the kinetics of addition of bisphenol A diglycidyl ether and benzylamines. Isothermal measurements agreed well with calculations using the specified rate equation. Van Der Linde and Belder (50, 51) used DSC thermal analysis to study the curing of polyester powder coatings with epoxies. They found that the carboxylic acid/epoxy reaction is probably pseudo first order and linearly dependent on catalyst concentration. A method is presented for the rapid determination of optimum curing conditions for any specific composition. Styryl-pyridine based epoxy resins were synthesized and characterized by TGA and IR (54). A review by Sickfield and Mielke (42)presents the use of the most common thermoanalytical methods, and they use epoxy resins as examples for the applicability of the different TA methods. These authors cite 124 references. Banks and Ellis (2) review the Tg temperatures of highly cross-linked epoxy networks. The specific heat capacities of several polyepoxides were reported (23). The data were generated using DSC techniques. DSC was employed by Crandall and Mih (12) to trace the cure of an epoxy prepolymer. Curing kinetics of unsaturated polyesters with styrene (13), degradation of polystyrene (48),and temperature measurements on several styrene copolymers (30)have been accomplished using thermoanalytical methods. The kinetics of thermal dissociation of blocked isocyanate cross-linersemployed TGA (29). The activation energies and frequency factors were measured, and a method of calculating dissociation temperatures is proposed. Degradation mechanisms of styrene polyester copolymer were studied by TGA, DTA, IR, pyrolysis GC, and GC/MS 22 R
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(15).It is concluded that there are two first order degradation reactions during thermal degradation in air. The first involves scission of weak cross-links with liberation of free linear chains. The second step involves random scission of the free linear chains into smaller segments. Others (38) used DTA and NMR in the synthesis, characterization, and kinetics of thermal degradation of copolyesters. Kinetic order, heat and entropy of fusion, and activation energy for their thermal decomposition were obtained. Heat capacity measurements were obtained on polymers and copolymers of itaconic acid esters exhibiting two glass transitions (11). Cowie et al. (10) gave a theoretical description of the heat capacity change at low Tg of poly(alky1itaconates) exhibiting dual Tg behavior. The specific heats of three polymorphic forms of trilaurin, trimyristin, tripalmitin, and tristearin were determined by DSC (22). The results were compared with literature values determined by classical methods. Farkas (16) prepared and studied isocyanate polymers, especially their thermal stability. Others (17) used DSC, specifically, in the study of polyurethane formation from poly(ethy1ene adipate) and toluene diisocyanate. The kinetic order and temperature dependence was established. Using DSC and 13CNMR, Sebenik et al. (40)studied the reaction between urea and formaldehyde. At high pH the peak in the DSC curve splits into two peaks, one which belongs to the addition of formaldehyde to urea and the second to the subsequent condensation of the latter. For both reactions, the activation energy, heat of polymerization, reaction order, and temperature maximum were determined. DSC was used to study the curing of polysulfide sealants (4). The influence of plasticizers, accelerators, sulfur, and water on the curing reaction is investigated. The curing of novolacs with paraformaldehyde was reported (1). Under the conditions studied, the curing kinetics follow an overall second-order law. Takaoka (45-47) has done extensive studies on the interaction of synthetic resin and pigment using thermoanalytical techniques. His studies include lead chromate/linseed oil modified alkyd resin mixtures, inorganic pigments/linseed oil-modified alkyd resin mixtures, and silica, lead chromate, and lead oxide/linseed oil modified alkyd resin (separate) mixtures. The catalytic activity of pigments for castor oil oxidation has been explained by Fukui et al. (19). Their work utilized DTA methods. They classified pigments into three groups: (I) promoters of oxidation of castor oil, (11)no influence on oxidation of castor oil, and (111)inhibitor of the oxidation of castor oil. DTA and DTGA were used to investigate the ilmenite concentrate sulfating (39). Test results, yields, etc. are discussed. Carraher (7) reviewed (331 references) the characterization of inorganic and organometallic polymers by thermal analysis. Ganguli and Bhattacharga (20) characterized the different hydrated forms of Prussian blue using TGA, electrical conductivity, and NMR. Three different stages of hydration to ether with the anhydrous form have been identified by T8A. The bound water molecules and electrical conductivity studies confirm the existence of the four forms by four different values of the activation ener y. Hoffmann (25)used thermal mettods to identify the behavior of plastic materials in a fire. Bhatnagar and Vergnaud (3)reviewed the literature between 1967 and 1982 regarding DTA and DSC studies on polymers containing fire retardants. Synthetic and natural polymers are covered.
ENVIRONMENTAL AND INDUSTRIAL HYGIENE Studies continue on the detection and measurement of potentially hazardous species in atmospheres surrounding the manufacture and use of coatings and coatings raw materials. An updated manual of analytical methods useful in industrial hygiene studies was published by the National Institute for Occupational Safety and Health (NIOSH) (16).The underlying aspects of toxicity and toxicity testing related to the coatings industry was the subject of a publication during this period (10). General guidelines documenting sampling techniques in measuring water quality were discussed (6) as was a review of applicable analytical methods for the determination
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of hexavalent chromium (3). Two special studies of interest in this area dealt with an evaluation of sampling and analytical procedures for assaying skin contamination (7)and the devel0 ment of a test for measuring the toxicity of combustion profucts (4). The determination of residual isocyanate monomer in polyisocyanate polymers was the subject of a study which compared the applicability of thin layer, gel permeation, highperformance liquid and gas chromatography for this measurement (15). The search for techniques to monitor toluene diisocyanate in the air has led to two reports dealing with the use of a coated piezoelectric crystal (I, 2) and the use of a sampling tube containing glass wool impregnated with an amine type derivitizing agent (18). A similar study related to the measurement of diphenylmethane diisocyanate (MDI) in industrial atmospheres produced a paper dealing with the use of derivitizing agents followed by examination of trapped species via high-performance liquid chromatography (14). Gas chromatography was the method of choice for 1,6-hexamethylene diisocyanate, once this material was converted to the corres onding diamine (5). Formald3ehyde vapor continues as a material of concern for environmental and industrial hygiene analysts. Reports were published dealing with the use of an electrochemical fuel cell sensor for detecting atmospheric formaldehyde (20) and the modification of a commercially available instrument to measure formaldehyde vapor in domestic environments (8). The emission of formaldehyde vapor during the curing of paint films was evaluated using a variety of analytical methods (17). Of more general interest was a recommendation from the Intersociety Committee of the American Public Health Association that 3-methyl-2-benzothiazolone hydrazone be used for measuring the airborne concentration of all aldehydes except formaldehyde (11). This same study recommended the use of Chromatropic Acid for the determination of formaldehyde vapor. Another paper (9) indicates that 13X molecular sieve is the adsorbent of choice for formaldehyde monitoring. Industrial hygiene studies for three other materials of concern to coatings analysts were published. Air sampling techniques and analytical methodology for evaluating exposure to acrylic acid were reported (19) as was a study dealing with acrylate and methacrylate esters (12). Finally, a sampling method, based on a charcoal adsorbent, was utilized to study the presence of airborne dimethylformamide during the production of urethane polymers (13).
MISCELLANEOUS TECHNIQUES Rates of permeation of water and chloride ions through clear and pigmented films of phenolic and alkyd resins were reported to monitor control of metallic corrosion (28). Permeability to chloride ions was about 200 times smaller than that for water molecules. Pommersheim et al. (17)developed conceptual, mathematical models to describe the principal phenomena occurring in the corrosion performance of polymeric coatings. Results predicted by the models are discussed in terms of the improvement of the protective function of the membrane. Single polarization curves were used to evaluate corrosion current (1). Silverman (22) applied EMF/pH diagrams to corrosion production. The organic film developed on iron, aluminum, and copper surfaces when exposed to seawater was studied chemically by Kristofferson et al. (9). Fifteen amino acids are identified as well as two monosaccharides and four main fatty acid constituents. Anticorrosive paints were evaluated (21). Koopmans and Reijnders (8) used electrochemical methods to predict the anticorrosive properties of paints. Comparative kinetic studies were done on various corrosion protection testing methods (14). Numerous impedance methods were reported for measuring corrosion rates. They included a rapid automatic analysis (7), methods for selecting corrosion protective paints (6, 16), methods to monitor and research corrosion (reviews) (13,18), monitoring coated metal behavior (12), measurements on thick organic coatings on mild steel substrates (15,19), studying organic coatings (20, 23, 24), and recording and analyzing impedance data for corrosion studies (11). This section includes other miscellaneous techniques used to analyze coatings. For example, a capillary flow technique
was used to measure the critical surface tension of wetting as a criterion of disperson for a number of commercially available pigments (4). Interrelationships between pigment surface energies and pigment dispersions in polymer solutions are discussed. A pycnometer method for determining the density of pigments and extenders was sanctioned (2). The thermal hazard evaluation of styrene polymerization by accelerating rate calorimetry was done by Whiting and Tou (27). Lee (10) used a contact angle analytical method to determine the surface energy of solid polymers. A thermodynamic theory for adhesion is established experimentally. Several authors (26) describe an EEC method for the determination of the global migration of plastic constituents into fatty food simulants. There may be applicability to lacquers, plastics, and laminants. Devay et al. (5) performed a dielectric study of paint and lacquer coatings. Results of measurements based on free corrosion potential, polarization resistance, and impedance measurements on electrocoated phosphated steel were reported (3). Turner (28) used the photoelectron microscope to reveal surface structure and chemical composition (25). The instrument and its potential are discussed.
MISCELLANEOUS MEASUREMENTS (INCLUDING PHYSICAL TESTS) The physical testing technology discussed in this section includes methods for determining the viscosity and viscoelastic properties of coatings and polymers, hardness measurements, the examination of coating film thickness, impact resistance tests, solubility parameters, and a method for evaluating paint settling. The American Society for Testing and Materials has again reviewed the use of Brookfield viscometers for measuring the rheological properties of non-Newtonian fluids (1). Pigment structure and composition were recently examined relative to their effects on the rheology of acrylic emulsion paints (19) and polymer solutions (18). Rheological measurements were also found to be useful for evaluating the cure kinetics of unsaturated polyester resin solutions (12) and an acrylic/ melamine resin blend (16). In complementary studies on the characterization of cured coatings, one standardized method (4) and an exhaustive review paper (25) appeared on the advantages of pendulum hardness measurements. Dynamic mechanical measurements are finding increasing importance as tools for the total characterization of coatings systems. Several eneral(21,22,27) and two review papers (14,29) appeared uring this period. Dynamic spectroscopic studies related to the curing kinetics of industrially important coating polymers were also published, including the examination of thermosetting acrylic resin systems (15) and thermally cured epoxy oligomers (26). A two volume book appeared dealing with the physicochemical aspects of polymer surfaces (20). Several general papers were also published relating to a systematic evaluation of test procedures for coatings systems (6,30). Surface adhesivity of acrylic emulsion adhesives received special attention (8) as did the measurement of coatin film thickness (3,13, 24). Among the routine mechanicaf tests which received special attention were indentation hardness (23), Taber abrasion measurement (2), and impact testing using a falling weight (5). In conclusion, chemically related physical measurements led to renewed interest in the determination of polymer solubility parameters via gas chromatography (9), evaluation of adhesion tension between solvents and pigments (II), contact angle measurements (7,31), the effect of condensation and fungal growth on the roperties of coatings (32), evaluation of settling in paints (28r a laboratory evaluation of polymer flammability (I 7),and a chemiluminescent procedure for the measurement of hydrogen peroxide in polymers and resins (10).
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ACKNOWLEDGMENT The authors wish to express their gratitude to DeSoto, Inc., for allowing publication of this manuscript and to the staff of DeSoto’s Information Center for their assistance during the preparation of this review. Special appreciation is given to ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
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Ellen Postal for her help in typing the manuscript. LITERATURE CITED INTRODUCTION (1) Aiessi, P. Pinure Vernlci 1983, 59, 33-41. (2) American Society for Testing & Materlals, ASTM D 29-81; 1982 Annual Book of ASTM Standards, Part 28, 8-23. (3) American Society for Testing & Materials, ASTM D 56-82; 1983 Annual Book of ASTM Standards, 06.03, 12-18. (4) American Society for Testing & Materials, ASTM D 333-81; 1982 Annual Book of ASTM Standards, Part 27, 73-80. (5) American Society for Testing & Materials, ASTM D 564-81; 1982 Annual Book of ASTM Standards, Part 29, 103-5. (6)American Society for Testing & Materials, ASTM D 719-81; 1982 Annual Book of ASTM Standards, Part 28, 188-9. (7) American Society for Testing & Materials, ASTM D 1310-82; 1983 Annuai Book of ASTM Standards, 06.03, 165-73. (8) American Society for Testing & Materials, ASTM D 2571-81; 1982 Annuai Book of ASTM Standards, Part 27, 509-1 l. (9) American Society for Testing & Materials, ASTM D 3278-82; 1983 Annuai Book of ASTM Standards, 06.03, 452-61. (10) American Society for Testing & Materials, ASTM D 3732-82; 1983 Annual Book of ASTM Standards, 06.01, 780-1. (11) American Society for Testing & Materials, ASTM D 3934-82; 1983 Annual Book of ASTM Standards, 06.03, 532-5. (12) American Society for Testing & Materials, ASTM D 4144-82; 1983 Annual Book of ASTM Standards, 06.01, 907-8. (13) American Society for Testing & Materials, ASTM D 4206-82; 1983 Annual Book of ASTM Standards, 06.03, 554-8. (14) Anderson, D. G.; Vandeberg, J. T. Anal. Chem. 1983, 55, 1R-18R. (15) Anderson, D. G. ACS. Div. of OWL, Papers 1983, 49, 491-5. (16) Bark, L. S., Alien, N. S., Eds. ”Analysis of Polymer Systems”; Applied Science Publishers: London 1982; xii 311 pp. (17) Bhatnagar, V. M.; Vergnaud, J. M. faintindia 1982. 32, 7-10. (18) British Standards Institution, BS 3483: Part 87: 1982, 3 pp. (19) British Standards Institution, BS 3483: Part C4: 1982, 3 pp. (20) British Standards Institution, BS 3900: Part 83: 1983, 8 pp. (21) Brushweii, W. Am. faint J. 1982, 66, 53-6. (22) Brushweii, W. Am. faint J. 1982, 66, 63-6. (23) Buiiett, T. R. Farg Lack 1983, 29, 122-8. (24) Castle, D. A. J. Forensic Sci. SOC. 1982, 2 2 , 179-86. (25) El-AAsser, M. S. ”Science & Technology of Polymer Colloids Voi 11”; NATO AS1 Series E No 68, Martinus Nijhoff Publishers 1983; pp 442-48. (26) International Standards Organization, I S 0 7143, 1982, 3 pp. (27) Joiy, A. M. Bull. du CERIfEC 1982, No 56, 37 pp. (28) King, A faint Resin 1983, 53, 27. (29) Novak, M. T. Am. Inkmaker 1982, 60, 14 (4 pp.). (30) Raaschou Nieisen, H. K. ACS, Div. OWL, Papers 1983, 49, 480-5. (31) Ray, 0. faintlndia 1961, Annual, 85-8. (32) Ross, P. Austral. OCCA R o c . News 1983, 20, 4-5. (33) Seiiars, I. C.; McLoskey, M. folym. feint Coi. J. 1982, 172, 733 (3 PP.). (34) Shebeko, Yu N.; et ai. Lakokras. Mat. 1981, 65-6. (35) Stoiow, N. R o c . Internat. Symp. on Conservation & Restoration of Cultural fropetty, Tokyo 1978, 1-16. Kraus, S.; Lerner, B.; Hendrickson, B. NBS Spec. fubl. (36) Thornton. J. I.; 1982, NO. 480-40, 16 pp. (37) Weaver, J. C. Mod. Paint Coatings 1983, 73. 51-4.
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CHEMICAL AND ELECTROCHEMICAL (1) American Society for Testing & Materials, ASTM D 444-81; 1982 Annual Book of ASTM Standards, Part 28, 130-8. (2) American Society for Testing & Materials, ASTM D 464-82; 1983 Annual Book of ASTM Standards, 06.03, 933-5. (3) American Society for Testing & Materials, ASTM D 465-82; 1983 Annual Book of ASTM Standards, 06.03. 936-8. (4) American Society for Testing & Materials, ASTM D 521-81; 1982 Annual Book of ASTM Standards, Part 28, 151-5. (5) American Society for Testing & Materials, ASTM D 1013-81; 1982 Annuai Book of ASTM Standards, Part 28. 234-6. (6) American Society for Testing & Materials, ASTM D 1135-81; 1982 Annuai Book of ASTM Standards, Part 28. 237-44. (7) American Society for Testing & Materials, ASTM D 1813-81; 1982 Annuai Book of ASTM Standards, Part 29, 209-11. (8) American Society for Testing & Materials, ASTM D 1617-81; 1982 Annuai Book of ASTM Standards, Part 29, 217-9. (9) American Society for Testing & Materials, ASTM D 2369-81; 1982 Annuai Book of ASTM Standards, Part 27, 474-6. (10) American Society for Testing & Materials, ASTM D 3960-81; 1982 Annual Book of ASTM Standards, Part 27, 872-4. (11) American Society for Testing & Materials, ASTM D 4017-81; 1982 Annual Book of ASTM Standards, Part 27, 901-3. (12) American Society for Testing & Materials, ASTM D 4139-82; 1983 Annual Book of ASTM Standards. 06.02, 502-3. (13) American Society for Testing & Materials, ASTM D 4209-82; 1983 Annual Book of ASTM Standards, 06.02, 509-1 1. (14) Association Francaise de Normalisation, NF T 30-012; 1981: BSI Worldwide List Stand. 1982, June, 50. (15) Battals, A.; et ai. Analusis 1982, IO, 426-32. (16) Bombara, G.; Bernabai, U. Surf. Technoi. 1980, 71, 393-401. (17) British Standards Institution, BS 684, Section 2.13; 1981, 4 pp. (18) British Standards Institution, BS 3483, Part BE; 1982, 3 pp. (19) British Standards Institution, BS 3483, Part C3; 1982, 3 pp. (20) Corneii, R. M.; Posner, A. M.; Quirk, J. P. Colloid folym. Sci. 1983, 267. 137-42.
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QAS CHROMATOGRAPHY (1) Aibertyn, D. E.; et ai. J . Chromatogr. 1982, 247, 47-61. (2) Aiessi, P.; Gladrini, D.; Torriano, 0.; Voipe, S. Ind. Vernice 1982, 36, 12-7. (3) Aiessi, P.; Giadrini, D.; Torriano, G.; Volpe, S. Ind. Vernice 1982, 36, 12-9. (4) American Society for Testing & Materials, ASTM D 2360-82, 1983 Annuai Book of ASTM Standards, 06.03, 705-9. (5) American Society for Testing & Materials, ASTM D 3797-82, 1983 Annual Book of ASTM Standards, 06.03, 81 1-5. (6) Cardosi, P. J. J. Forensic Scl. 1982, 27, 695-703. (7) Castelis, R. C.; Arancibia, E. L.; Nardiiio, A. M. CIDEPINT Anales 1982, 215-26. (8) Cherkasov, A. N.; et ai. Colloid J. USSR 1982, 43, 661-4. (9) Crosby, N. T. Anal. f r o c . 1982, 19, 428-30. (10) D’Aionzo, R. P.; Kozarek, W. J.; Wade, R. L. J. Am. OilChem. SOC. ’ 1982, 59, 292-5.. (11) Deutsches Institut Fuer Normung, DIN 55 956, 1982: BSI Worldwide List Stand. 1983, Apr. 38. (12) Deutsches Institut Fuer Normung, DIN 55 957, 1983: BSI Worldwide List Stand. 1984, Jan, 49. (13) De Wit, J. Proc. 16th FATIfEC Congress, Liege 1982, I , 85-101. (14) Dimitriev, M. T.; Mishchikhin, V. A. Gig. Sanit. 1982, No 7 , 46-8. (15) Fiiippov, A. M.; et ai. Khim. from. 1982, No 2 , 89-90, (16) Fomin, A. S.; Kondakova, N. N.; Korzhov, V. D.; Ignatov, V. A. Lakokras. Mat. 1982, No 1 37-8. (17) Friese, P. Fresenius’ 2.Anal. Chem. 1980, 303, 279-88. (18) Goring, H-W. Plaste Kautschuk 1983, 30, 650-2. I
COATINGS (19) Griese, P. fapier 1982, 36,601-8. (20) Guiilot, J.; Guerrero, L. R. Makromol. Chem., Macromol. Chem. fhys. 1982, 783, 1979-2008. (21) Grozdov, A. G.; Rakhmanov, A. A. Zh. Anal. Khim. 1982, 37, 698-700. (22) Haken, J. K.; Obita, J. A. J. Chromatogr. 1982, 244. 259-64. (23) Haken, J. K.; Obita, J. A. J. Macromoi. Sci. 1982, A77, 203-15. (24) Henriks-Eckerman, M.-L. J. Chromatogr. 1982, 244, 378-80. (25) Hirayanagi, S.; Kimura, K.; Sato, M.; Harada, K. Nlppon Gomu Kyokalshl 1982, 55, 241. English transi. in Int. folym. Scl. Technol. 1982, 9 , T/89-96. (26) Hu, J. C.-A. J. Chromatogr. Scl. 1981, 79, 634-8. (27) IwaMa, M.; Ito, Y.; Ogawa, S. Bunseki Kagaku 1982, 37,T89-T90. (28) Jentzsch, R.; Fiack, J. Daehre, K-H.; Ziese, U. flaste Kautochuk. 1983, 30, 530-1. (29) Koenig, H.; Hermes, M. Chromatographia 1981, 74, 351-4. (30) Konovaiov, 0. K.; Zhakarov, F. I. Lakokras. Mat. 1983, No 7 , 42-3. Contlnent, faint Resin News 1983, 27, Abs 427. (31) Krockenberger, D.; Gmerek, H. Fresenius' 2.Anal. Chem. 1982, 377, 485-9 1. (32) Kuwata, K.; et ai. J. Chromatogr. 1983, 256, 303-12. (33) Lamour, M. Material Organlsmen 1982, 77, 67-79. (34) Laurinat, B.; Hellwig, J. flaste Kautschuk 1982, 2 9 , 710-1. (35) Leca, M.; Enache, M. Rev. Roumaine Chim. 1983, 28, 287-91. (36) Lehrie, R. S.; Peakman, R. E.; Robb, J. C. Eur. folym. J. 1982, 78, 517-29. (37) Li, P. Fenxl Huaxue 1982, 70, 143-7. (38) Lipson, J. E. G.; Guillet, J. E. J. Coatings Technol. 1982, 54, 89-93. (39) Mayr, M.; Lorbeer, E.; Kratzi, K. J. Am. Oil Chem. SOC. 1982, 59, 52-7. (40) Mertens, J. J. R.; Jacobs, E.; Callaerts, A.; Buekens, A. Makromol. Chem., Rapid Common. 1982, 3, 349-56. (41) Miller, W. K.; Harper, E. L. J. Appl. folym. Sci. 1983, 28, 3585-8. (42) Myers, J. R. Am. Lab. 1982, December, 34 (5 pp). (43) Peplinkski, R. Flexo. Tech. J. 1982, 7 , 15-8. (44) Petrak, K. L.; Pltts, E. Polymer 1983, 2 4 , 729-32. (45) Podiaha, 0.; Toregard, B.; Petersson, B. Fette Selfen Anstrich. 1982, 84, 17-20. (46) Radhakrishnan, T. S.; Rao, M. R. J. folym. Sci., folym. Chem. 1981, 79, 3197-208. (47) Radovici, A.; Stan, V.; Uglea. C. Mat. flast. 1981, 78, 186-8. (48) Raie, M. Y.; Iqbal, M. L. Fette Selfen Anstrich. 1983, 85, 194-5. (49) Ravey, M. J. folym. Sci., folym. Chem. 1983, 27. 1-15. (50) Schmidt, H. Feffe Selfen Anstrich. 1982, 84, 478-86. (51) Schmitz, F. P.; Kiesper, E. folym. Commun. 1983, 2 4 , 142-4. (52) Schrijver, J.; Ammerdorffer, J. L.; German, A. L. J. folym. Sci., folym. Chem. 1982, 20, 2693-703. (53) Soe, J. B. Feffe Selfen Anstrich. 1983, 85, 72-6. (54) Stepanova, M. I.; Karpova, N. M.; Shaposhnikov, Yu K. Lakokras. Mat. 1983, No. 3, 62-4. Continent. Paint Resin News 1983, 2 1 , Abs 831. (55) Takeda, N.; et ai. Takeda Kenkyushoho 1980, 39, 140-5. (56) Takeda, N.; Matsuura, Y.; Watanabe, H. Takeda Kenkyushoho 1980, 39, 146-50. (57) Van Dijk, J. H.; Janssen, P. C. G. M.; Van Der Ven, L. G. J. froc. 76th FATIfEC Congress, Llege 1982, I 253-65. (58) Voorhees, K. J.; Lattimer, R. P. J. folym. Sci., folym. Chem. 1982, 20, 1457-67. (59) Williams, M. G.; MacGee, J. J. Am. OilChem. SOC.1983, 60, 1507-9. (60) Yamazaki, Y.; et al. Kogai to Taisaku 1981, 77, 1121-9. GEL PERMEATION CHROMATOQRAPHY
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(13) Helias, P.; Durand, D.; Busnei, J. P.; Bruneau. C. M. Eur. folym. J. 1982, 78, 647-50. (14) Heliman, M. Y.; Bowmer, T.; Taylor, G. N. Macromolecules 1983, 76, 34-8. (15) Hiton. I . G. Brit. folym. J. 1983, 15. 47-9, (16) Kastanek, A.; Zeienka. J.; Hajek, K. J. Appl. Poiym. Scl. 1981, 26, 4117-24. (17) Kuzaev, A. folym. Sci. USSR 1980. 22, 2284-90. (18) Laszlo-Hedvig, 2.; Szesztay, M.; Faix, F.; Tudos, F. Angew. Makromol. Chem. 1982, 707, 61-73. (19) Malihi. F. B.; Kuo, C.-Y.; Provder, T. J. Liq. Chromatogr. 1983, 6, 667-83. (20) Murphy, R.; et ai. J. Chromatogr. 1981, 2 7 7 , 160-5. (21) Nomayr. H.; Rothbacher, H.; Korn, A. Farbe Lack 1983, 89, 351-3. (22) Parks, E. J.; Johannesen, R. B.; Brinckman, F. E. J. Chromatogr. 1983, 255, 439-54. (23) Richard, B.; Gourdenne, A. Spectra 2000 1982, 70, 44-7.
(24) Runyon, J. R. J. Appl. folym. Sci. 1983, 28, 559-66. (25) Schurz, J.; Eigner, W. D.; Krassig, H. Angew. Makromol. Chem. 1982, 702, 199-213. HIGH-PERFORMANCE LIOUID CHROMATOGRAPHY
(1) Crozier, D.; Morse, 0.; Tajima, Y. S A M E J 1982, 78, 17-22. (2) Curtis, M. A.; Rogers, L. B. J. Liq. Chromatogr. 1982, 5 (Suppi 2), 319-29. (3) Eppert, G.; Liebscher, G.; Stief, C. J. Chromatogr. 1982, 238, 385-98. (4) Eppert, G.; Liebscher, G. J. Chromatogr. 1982, 238, 399-407. (5) Favini, G.; Cortesl, N.; Brillo, A. Riv. Ita/. Sostanze Grasse 1983, 60, 22-4. (6) Foionari, C. V.; Garlasco, R. J. Chromatogr. Scl. 1981, 79, 639-42. (7) Francis, V. C.; Sharma, Y. N.; Bhardwaj. I.S. Angew. Makromol. Chem. 1983, 773, 219-25. (8) Guise, G. B.; SmAh, G. C. J. Chromatogr. 1982, 247, 369-73. (9) Guiino, D.; et ai. Makromol. Chem., Macromoi. Chem. fhys. 1983, 784, 411-29. (10) Kato, T.; Takami, H.; Takahashi, A. Kobunshi Ronbun. 1982, 39, 487-92. (11) Kloosterboer, J. 0.; et al. ACS, Div. ORPL. Papers 1983, 48, 445-9. (12) Kuo, C.; Provder, T.; Kah, A. F. froc. 8th Internat. Conf. in Organic Coatlngs Science & Technology, Athens 1982, 455-94. (13) Merritt, C., Jr.; et ai. J. Am. 011 Chem. SOC. 1982, 59, 422-32. (14) Brown, H. G.; Snyder, H. E. J. Am. 0llChem. SOC. 1982, 59, 280-3. (15) Much, H.; Pasch, H. Acta folym. 1982, 33, 366-9. (16) Nakamura, K.; Morikawa, Y. J. Am. Oil Chem. SOC. 1982, 59, 64-8. (17) Oguri, H. J. Jpn. SOC.Col. Mat. 1982, 55, 812-7. (18) Reidy, S. K.; Tiedge, W. F. T A f f I Non-wovens Symp. 1982, Notes 83-90. Abs. Buil. Inst. faper Chem. 1982, 53, Abs 5664. (19) Schroer, J. W.; Wolever, R. D. Res. Disc/. 1982, 234-5. (20) Suzuki, Y.; Tani, K. Bunseki Kagaku 1980, 29, 849-53. (21) Swarin, S. J.; Lipari, F. J. Llq. Chromatogr. 1983, 6, 425-44. (22) Wada, S.; Koizumi, C. J. Am. Oil Chem. SOC. 1983, 60, 1105-9. THIN-LAYER CHROMATOGRAPHY
(1) Home, J. M.; Laing, D. K.; Dudley, R. J. J. Forensic Sci. SOC.1982, 2 2 , 147-54. (2) Inagaki, H.; Tanaka, T. Pure Appl. Chem. 1982, 54, 309-22. (3) Miiovanovic, G. A.; Ristic-SoiaJic,M.; Janjic, T. J. J. Chromatogr. 1982, 249, 149-54. (4) Min, T. I.;Klein. A.; El-Aasser, M. S.; Vanderhoff, J. W. J. Polym. Sci., folym. Chem. 1983, 27. 2845-61. (5) Nair, B. R.; Francis, D. J. Polymer 1983, 24, 626-30. (6) Nowak-Ossorio, M.; Braun, D. Holz Roh-Werkstoff 1982, 40, 255-9. ATOMIC SPECTROSCOPY
(1)
Association Francaise de Normalisation, NF T 30-217, 1983: BSI Woridwlde List Stand. 1984, Jan. 49. (2) Boorn, A. W.; Browner, R. F. Anal. Chem. 1982, 54, 1402-10. (3) Browner, R. F.; Boorn, A. W.; Smith, D. D. Anal. Chem. 1982, 54, 1411-9. (4) Commissione Prodotti Vernicianti Unichim, UNICHIM M.U. 536, Pitture Vernici 1982, 58, 63-4. (5) Commissione Prodotti Verniciantl Unichim, UNICHIM M.U. 535: Pitture Vernici 1981, 57, 61-2. (6) Commissione Prodotti Vernicianti Unichim, UNICHIM MU. 533, Pitture Vernici 1982, 58, 56-7. (7) Hausknecht, K. A.; Ryan, E. A.; Leonard, L. P. Atom. Spectrosc. 1982, 3, 53-5. (8) Henden, E. Analyst 1982, 707, 872-8. (9) Kenjo, T.; Mabuchi, H. R o c . Internat. Symp. on Conservation & Restoration of Cultural Properly, Tokyo 1978, 63-9. (IO) Kondrachoff, W.; Decierck, R. folym. faint Col. J. 1982, 772, 257 (7 PPJ. (11) Lercari, C.; Sartorei, B.; Sedea, L.; Toninelii, G. J. Am. OilChem. SOC. 1983, 60, 856-7. (12) Takahashi, K.; Minami. S.; Shigematsu, M.; Ohyagi, Y. J. Jpn. SOC. Col. Mat. 1982, 55, 553-7. INFRARED SPECTROSCOPY
Alien, N. S.; et ai. folym. fhotochem. 1982, 2 , 97-107. Bauer, D. R. J. Appl. folym. Scl. 1982, 2 7 , 3651-62. Bauer, D. R. ACS, Div. O R R , Papers 1983, 48, 737-41. Biernacka, T.; Witwicka, J.; Jamroz, M.; Stroinska, M. Chem. Anal. (Warsaw) 1982, 27, 11-23. (5) Boudevska, H.; Piatchkova, S.; Todorova, 0. Makromol. Chem., Macromol. Chem. fhys. 1982, 783,2583-91. (6) Cangelosl, F.; Shaw, M. T. folym. Engng. scl. 1983, 23, 669-75. (7) Carlson, G. M.; Neag, C. M.; KUO, C.; Provder, T. ACS, Div. O W L , Papers 1983, 49, 284-8. (8) Carter, J. R.; Cody, C. A.; DiCarlo, L.; Hatcher, J. T. M o d . Paht Coatings 1983, 73, 18-21. (9) Chase, D. B.; Amey, R. L.; Holtje. W. G. Appi. Spectrosc. 1982, 36, 155-61. (10) Chen, C. S.; Bulkin, B. J.; Pearce, E. M. J. Appl. Polym. Sci. 1983, 28, 1077-91. (11) Debe, M. K.; Tushaus, L. A. J. Adhes. 1983, 75, 287-306. (12) Dekker, T. T.; Van HuIst, J. A. R o c . 76th FATIf€C Congress, Liege 1982, I I I , 331-46. (13) English, A. D.; Chase, D. B.; Spineiii, H. J. Macromolecules 1983, 76, (1) (2) (3) (4)
.--- . .
$639-7
(14) Fowkes, F. M.; McCarthy, D. C.; Woife, J. A. ACS, folym. freprlnts 1983, 24, 228-9. ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
25R
COATINGS (15) Fowkes, F. M.; Tischler, D. 0.; Wolfe, J. A.; Halllwell, M. J. ACS, Div. O W L , Papers 1982, 46, 1-6. (16) Garton, A,; Cousin, P.; Prud‘homme, R. E. J. folym. Scl., folym. phvs. 1983, 27 2275-85. (17) Garton, A.; Stolow, A.; Wlles, D. M. J . Mat. Scl. 1981, 16, 3211-4. (18) Hajek, B.; Ondracek, J.; Muck, A. Collect Czech. Chem. Commun. 1982, 47, 1-6. (19) Hartshorn, J. H. J . Coatlngs Technol. 1982. 54, 53-61. (20) Hesse, D.; et al. Acta folymerlca 1982, 33, 344-5. (21) Hlll, C. A. S. J . Appl. folym. Scl. 1982, 2 7 , 3313-27. (22) Hummel, D. 0.; Votteler, C. Angew. Makromol. Chem. 1983, 777, 171-94. (23) Hummel, D. 0.; Votteler, C.; Winter, M. Kunststoffe 1983, 73, 193-8. (24) Jasse, B. “Developments In Polymer Characterisation 4”; Dawklns, J. V., Ed.; Applled Science Publlshers. 1983; pp 91-129. (25) Kim, C. S. Y.; Dodge, A. L.; Lau, S.-F.; Kawasaki, A. Anal. Chem. 1982, 54, 232-8. (26) Kopusov, L. I.; Zhokhova, F. A.; Zharkov, V. V. flast. Massy 1980, 49. English transl. in Int. folym. Scl. Technol. 1983, 70, T/57-8. (27) Krejcar, E.; Dlaskova, M. Chem. R u m . 1983, 33, 491-3. (28) Kumpanenko, I.V.; Chukanov, N. V. Russ. Chem. Rev. 1981, 50, 850-64. (29) Morterra, C.; Chiorino, A.; Ghiotti, G.; Fisicaro, E. J . Chem. SOC., Fare day Trans. 1 1982, 78, 2649-59. (30) Neag, C. M.; Carlson, G. M.; Provder, T.; Kuo, C. ACS, Dlv. O W L , Papers 1983, 49, 404-8. (31) Panettl, M.; Cangelosi, A.; Ferrero, F. Ann. Chlm. (Rome) 1981, 7 1 , 743-8. (32) Rajendran, G. P.; Mahadevan, V.; Srinivasan, M. Eur. folym. J . 1982, 78, 953-6. (33) Rebhan, H.; Luigart, F. Farbe Lack 1983, 8 9 , 425-6. (34) Sanyal, S. K.; Mukherjee, R. N. falntlndla 1981, Annual, 89-91. (35) Stevens, G. C. J . Appl. folym. Scl. 1981, 26, 4259-78. (36) Stevens, G. C. J . Appl. folym. Scl. 1981, 26, 4279-97. (37) Szllagyl, A.; Izvekov, V.; Vancso-Szmercsanyi, 1. Magyar Kemial Folyolrat 1981, 8 7 , 209-13. (38) Usmani, A. M. ACS, Dlv. O W L , Papers 1983, 49, 259-63. (39) Webb, J. D.; et al. folym. freprlnts 1982, 2 3 , 213-4. (40) Yoshlmura, Y. J. Appl. folym. Scl. 1983, 28, 1147-58. I
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NUCLEAR MAQNETIC RESONANCE SPECTROSCOPY
(1) Aganov, A. V.; Antonovsky, V. L. I z v . Akad. Nauk Ser. Khim. 1982. 271-5. (2) Allen, P. E. M.; Mair, C.; Fisher, M. C.; Williams, E. H. J. Macromol. Scl. 1982, A 77, 61-76. (3) Arlmoto, K.; Zinkel. D. F. J . Am. Oil Chem. Soc. 1982, 59, 166-8. (4) Ballet, F.; Candau, F. J . folym. Scl., folym. Chem. 1983, 2 7 , 155-63. (5) Banks, L.; Bryan, E. J. folym. Sci., folym. fhys. 1982, 20, 1055-67. (6) Bevington, J. C.; Huckerby, T. N.; Vlckerstaff, N. Makromol. Chem., Rapid Commun. 1983, 4 , 349-52. (7) Borchardt, J. K.; Dalrymple, E. D. J . folym. Sci., folym. Chem. 1982, 20, 1745-64. ( 8 ) Brown, C. E.; Khoury, I.;Bezoarl, M. D.; Kovacic, P. J . folym. Scl., folym. Chem. 1982, 20, 1697-707. (9) Burton, D. J.; et al. folym. Commun. 1983, 24, 278-81. (IO) Cals. R. E.; Kometanl, J. M.; Salzman, N. H. Anal. Roc. 1983, 20, 579-82. (11) Carothers, J. A.; Gipstein, E.; Glemlng, W. W.; Tompkins, T. J . Appl. folym. Scl. 1982, 2 7 , 3449-54. (12) Cholli, A.; Ritchey, W.; Koenlg, J. ACS, Dlv. O W L , Papers 1983, 48, 450-4. (13) De Abajo, J.; De La Campa; J. G.; Nieto. J. L. Makromol. Chem., Rapld Commun. 1982, 3 , 505-8. (14) Dechter, J. J.; et al. J . folym. Scl., folym. fhys. 1982, 2 0 , 641-50. (15) Doremieux-Morin, C.; Enriquez M.-A.; Sanz, J.; Fraissard, J. J. Collold Interface Sci. 1983, 95, 502-12. (16) Egboh, H. S.; et al. Polymer 1982, 23, 1167-71. (17) Dlnan, F. J.; Uebel, J. J. ACS folym. freprlnts 1983, 24, 241-2. (18) Gregory, D. MSc Thesis, Unlv. of Lancaster, 1980, T/917, 106 pp. (19) Havens, J. R.; Koenig, J. L. Appl. Spectrosc. 1983, 37, 226-49. (20) Hvilsted, S.; Jorgensen, N. U. folym. Bull. 1983, 10, 236-43. (21) Ishida, H. “Adhesion Aspects of Polymeric Coatings”; Mlttal, K. L., Ed.; Plenum Press: New York, 1983; pp 45-106. (22) Ivln, K. J. Pure Appl. Chem. 1983, 55, 1529-40. (23) Judas, D.; Fradet, A.; Marechal, E. Makromol. Chem., Macromol. Chem. fhys. 1983, 184, 1129-42. (24) Kobayashi, M. J . Jpn. Soc. Col. Mat. 1983, 56, 509-17. (25) Koley, S. N. falntlndla 1983, 33, 7-10. (26) Komoroski, R. A.; Shockcor, J. P. Macromolecules 1983, 16, 1539-43. (27) Kricheldorf, H. R. Pure Appl. Chem. 1982, 54, 487-81. (28) Mackey. J. H.; Tiede, M. L.; Sojka, S. A,; Wolfe, R. A. folym. frepr. . 1983, 24; 179-80. (29) Majumdar, R. N.; Nlknam, M. K.; Harwood, H. J. ACS folym. frepr. 1982. 23. 07-8. . (30) MarshakG. L. Brit. folym. J . 1982, 74, 19-22. (31) Marshall, M. JOCCA 1983, 68, 285-93. (32) Matejka, L.; et al. J. folym. Scl., folym. Chem. 1983, 21, 2873-85. (33) Murphy, P. D.; Gerstein, 8. C.; Weinberg, V. L.; Yen, T. F. Anal. Chem. 1982, 54, 522-5. (34) Navratii, M.; Pospisil, L.; Fiala, 2. flaste Kautschuk 1982, 29, 6-11. (35) Nieto, J. L.; De La Campa, J. G.; De Abajo, J. Makromol. Chem. Macromol. Chem. fhys. 1982, 183, 557-89. (36) Nlknam, M. K.; et al. Makromol. Chem. Rapid Commun. 1982, 3 , 825-33. (37) Nithianandam, V. S.; Kaleem, K.; Srinivasan, K. S. V.; Joseph, K. T. J . folym. Scl., folym. Chem. 1983, 21, 761-5.
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ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
(38) Rlnaudo, M.; Milas, M.; Lambert, F.; Vlncendon, M. Macromolecules 1983. 76. 816-9. (39) Sankaram, A. V. 8.; Kulkarnl, N. G.; Krishnamurtl, N.; Chatterjee, P. C. JOCCA 1982, 65, 390-2. (40) Sato. H.; Tanaka, Y.: Hatada. K. Makromol. Chem., RaDM Commun. 1982, 3, 181-5. (41) Sato, H.; Tanaka, Y.; Hatada, K. J . folym. Scl., folym. fhys. 1983, 21, 1867-74. (42) Schindlbauer, H.; Schuster, J. KunststoffelGerman flssflcs 1983, 73, 21-3. (43) Sebenlk, A.; Kastelic, C.; Osredkar, U. J . Macromol. Scl. 1983, AZO, 341-53. (44) Spevacek, J. Makromol. Chem., Rapld Commun. 1982, 3 , 629-33. (45) Srivastava, A. K.; Mathur, G. N. Polymer 1982. 23, 20-1. (46) Stejskal, E. 0.; et al. Pure Appl. Chem. 1982, 54, 461-6. (47) Symons, M. C. R. Chem. Soc. Rev. 1983, 72. 1-34. (48) Tarcha, P. J.; Fltch, R. M. “Sclence & Technology of Polymer Collolds Vol 11”, NATO AS1 Series E No 68, Martinus NlJhoff Publishers, 1983; pp 589-99. (49) Taylor, M. G.; et al. Tappl 1983, 66, 92-4. (50) Taylor, R.; Pragnell, R. J.; McLaren, J. V.; Snape, C. E. Talanta 1982, 2 9 , 489-94. (51) Toppet, S.; Lemstra, P. J.; Van Der Velden, G. Polymer 1983, 24, 507-12. (52) Trub, E. P.; Boitsov, E. N. Lakokras. Mat. 1982, 38-9. (53) Uebell, J. J.; Dlnan. F. J. J . folym. Scl., folym. Chem. 1983, 27, 2427-38. (54) Van Der Velden, G. Macromolecules 1983, 76, 1336-40. (55) Van Der Velden. 0.; Beulen, J. Macromolecules 1982, 15, 1071-5. (56) Williams, D. A. R.; Dyke, R.; Malcomson, S.; Massy, S. J . Cell. flsst. 1983, 19, 121-4. SURFACE ANALYSIS
(1) Allara, D. L. ACS Symp. Ser. 1982, 33-47. (2) Allara, D. L.; Murray, C. A.; Bodoff, S. “Physlcochemlcal Aspects of Polymer Surfaces Vol I”; Mlttal, K. L., Ed.; Plenum Press: New York, 1983; pp 33-43. (3) Allen, K. W. “Adheslon 6”; Applied Science Publishers, 1982 pp 83-94. (4) Allen, K. W.; Stevens, M. G. J . Adhes. 1982, 74, 137-44. (5) Baer, D. R.; Thomas, M. T. ACS Symp. Ser. 1982, 257-82. (6) Bailey-Hiergesell, S. R.; Eddy, C. 0.; McGriff, R. B. ACS, Dlv. ORPL, Papers 1983, 49, 569-73. (7) Baun, W. L. Pure Appl. Chem. 1982, 54, 323-36. (8) Baun, W. L. “Surface Analysls & Pretreatment of Plastics & Metals”; Applied Science Publishers, 1982; pp 45-72. (9) Baun, W. L. “Adheslon Aspects of Polyrnerlc Coatlngs”; Mlttal, K. L. Ed.; Plenum Press: New York, 1983; pp 131-46. (IO) Beiton, D. J.; Stuff, S. I. “Adheslon Aspects of Polyrnerlc Coatlngs”; Mlttal, K. L., Ed.; Plenum Press: New York, 1983; pp 235-42. (11) Berner, B. J . ColbU Interface Scl. 1982, 86, 422-31. (12) Brlggs, D. J . Adhes. 1982. 72, 287-301. (13) Briggs, D. “Surface Analysis & Pretreatment of Plastics & Metals”; Applied Science Publlshers, 1982; pp 73-94. (14) Brlggs, D. “Adheslon 6”, Applied Science Publlshers, 1982; pp 111-21. (15) Carrlck, A. JOCCA 1983, 66, 259-63. (16) Castle, J. E.; Watts, J. F. Corrosion Control by Organlc Coatlngs Symposium, Lehlgh Unlv. 7980, Edltedfroc., NACE 1981, 78-86. (17) Chan, C. M. J . Adhes. 1983, 75, 217-24. (18) Clark, D. T. Pure Appl. Chem. 1982, 54, 415-38. (19) Clark, D. T. ”Physicochemical Aspects of Polymer Surfaces Vol I ” Mlttl, K. L., Ed.; Plenum Press: New York, 1983; pp 3-32. (20) Clark, D. T.; Abrahman, M. 2. J . folym. Scl., folym. Chem. 1982, 20, 691-706. (21) Clark, D. T.; Fowler, A. H. K. folym. Commun. 1983, 24, 140-1. (22) Clark, D. T.; Munron, H. S. folym. Deg. Stab//. 1982, 4 , 441-57. (23) De Pauw, E.; Marlen, J. J. fhys. Chem. 1981, 85, 3550-2. (24) Dickie, R. A,; Hammond, J. S.; De Vries, J. E.; Holubka, J. W. Anal. Chem. 1982, 54, 2045-9. (25) Dowrey, A. E.; Marcott, C. Appl. Spectrosc. 1982, 36, 414-6. (26) Duel, L. A.; Owen, M. J. J . Adhes. 1983, 76, 49-59. (27) Egerton, T. A.; Parfltt, 0. D.; Kang, Y.; Wlghtman, J. P. Collolds Surfaces 1983, 7 , 311-23. (28) Fifiekl. C. C.; Fltch, R. M. J . Dispersion Scl. Technol. 1981, 2 , 267-80. (29) Fowkes, F. M. “Physlcochemlcal Aspects of Polymer Surfaces Vol 2”; Mittal, K. L., Ed.; Plenum Press: New York, 1983; pp 583-603. (30) Garbassi, F.; Tescari, M.; Falcone, F. Rlv. Col. 1983, 76, 158-64. (31) Hare, A. S.; Vickerman, J. C. J . Chem. Soc., Faraday Trans. 1 1983, 79, 185-93. (32) Karen, A. Farg Lack 1982, 28, 37 (7 pp), 56-8. (33) Klein, J.; Pincus, P. Macromol. 1982, 75, 1129-35. (34) Kwlatkowski, L.; Sztandor, J. fowbkl Ochronne 1981, 9 , 21-8. (35) Leary, H. J., Jr.; Campbell, D. S. ACS, Div. ORPL, Papers 1982. 46, 433-5. (36) Lynch, P. F.; Brown, C. W.; Heldersbach, R. COffOSiOn 1983, 39, 357-63. (37) Lyons, L. E. Corros. Australas 1982, 7 , 4-8. (38) Maeda, S. frog. Org. Coat. 1983, 7 7 . 1-18. 139) Owen. M. J. T A f f I Hot-Men Adhesives & Coatlnas Short Course, San ‘ biego 1081, 13-9. (40) Peeling, J.; Jazzar, M. S.; Clark, D. T. J. folym. Sci.. folym. Chem. 1982, 20, 1797-805. (41) Rouxhet, P. G.; Cappelle, P. G.; Palm-Gennen, M. H.; Torres, Sanchez, R. M. IXth Internat. Conf. on Organlc Coatlngs Sclence & Technology, Athens 1983, 205-24. (42) Schelfers. S. M.; Verma. S.; Cooks, R. G. Anal. Chem. 1983, 55, 2260-6.
COATINGS
(43) Skledar, S.;Zalar, A.; Zavasnlk, R. R o c . 16th FATIfEC Congress, Liege 1982, 11, 335-50. (44) Sparrow, 0. R.; Drummond, I.W. Ind. Res. Dev. 1981, 23, 112-5. (45) Stone, W. E. E.; Stone-Masul, J. H. “Science & Technology of Polymer Collolds Vol. 11”; NATO AS1 Series E No. 68;Martlnus Nijhoff Publlshers, 1983;pp 480-502. (46) Suetaka, W. ”Adhesion Aspects of Polymeric Coatlngs”; Mktal, K. L., Ed.; Plenum Press: New York, 1983;pp 225-33. (47) Takaoka. K. J. Jpn. SOC.Col. Mat. 1982, 55. 319-27. (48) Treverton, J. A.; Amor, M. P. Trans. Inst. MetalFln. 1982, 60, 92-6. (49)Treverton, J. A,; Davles, N. C. Surf. Interface Anal. 1981, 3 , 194-200.
(50) Valenty, S.J. Roc. 8th Internat. Conf. in Organic Coatlngs Sclence & Technology, Athens 1982, 705-43. (51) Van Oolj, W. J.; Leijenaar, S. R.; Van Den Bergh, B. Roc. 16th FATIPEC Congress, Liege 1982, 271-88. (52) Voss, H. Paper, BfBIF Conf. on Coating for the O OS, Slough 1980, 12 PP. (53) Yamamoto, F.; Yamakawa, S.; Wagatsuma, M. ”Physlcochemlcal Aspects of Polymer Surfaces” Mlttal, K. L., Ed.; Plenum Press: New York 1983;VOi. 2,pp 1181-97.
(18) Israel, S. C.; Bechard, M. J.; Abbot, M. ACS, folym. Preprlnts 1983. 24, 159-80. (19) Kirkbright, G. F.; Menon, K. R. Anal. Chim. Acta 1982, 373-7. (20) Krlshnan, K.; HIII, S.; Hobbs, J. P.; Sung, C. S. P. Appl. Spectrosc. 1982, 36. 257-9. (21) Lattimer, R. P.; Hooser, E. R.; Diem, H. E.; Rhee, C. K. Rubber Chem. Technol. 1982, 55, 442-55. (22) Leldheiser, H., Jr.; Music, S. Corros. Sci. 1982, 22, 1089-96. (23) Lesiak, T.; Clemniak, G.; Czerwinskl, W. Angew. Makromol. Chem. 1983, 713, 203-17. (24) Marshall, G. L. Europ. folym. J. 1983, 19, 439-44. (25) Oxley, D. P. “Adhesion 8”; Applied Science Publishers, 1982; pp 123-34 _.
(26) Panenko, V. V.; Vlasov, L. A. Ind. Lab. 1981, March, 897-900. (27) Pierre, J.; Van Bree, J. KunstsoffelGermanPlastics 1983, 73, 18-20. (28) Ramjlt, H. 0. J . Macromol. Scl. 1983, AZO, 859-73. (29) Ramjlt, H. G. J. Macromol. Scl. 1983, A19, 41-55. (30) Rlis, P.; Chatfield, E. J. Proc. NBS/EPA Asbestos Standards Workshop 1980,NBS Specialfubl. No. 619, 108-20. (31) Ullmann, G.; Phlliles, G. D. J. Macromolecules 1983, 16, 1947-9.
ULTRAVIOLET-VISIBLE SPECTROSCOPY
MICROSCOPY
(1) Amerlcan Soclety for Testlng & Materials, ASTM D 21 19-82,1983 Annual Book of ASTM Standards, 06.03,674-8. (2) American Soclety for Testlng 8 Materlals, ASTM D 2120-82,1983 Annual Book of ASTM Standards, 08.03 677-9. (3) Atherton, N. M.; Banks, L. G.; Ellls, B. J. Appl. folym. Sci. 1982, 27, 2015-23. (4) Blestek, T.; Kallnowska. G. fowlokl Ochronne 1982, 3, 23-41. (5) Bllimeyer, F. W., Jr.; Saltaman, M.; Kumar, R. Col. Res. & Appl. 1982, 7 , 327-37. (6) Carraher, C. E., Jr.; Venkatachalam, R. S.; Tlernan, T. 0.; Taylor, M. L. ACS, Dlv. of ORfL, Papers 1982. 47, 119-23. (7) Ferrero, F.; Gozzellno, G. Tinctorla 1981, 78, 197-202. (8) Fillpska, M.; Kamlnska, E. follmery 1983, 26, 20-3. (9) Garcla-Rublo, L. H. J . Appl. Polym. Scl. 1982, 27, 2043-52. (10) Garcia Sanchez, F.; Navas, A.; Laserna, J. J.; Arbalzar, A. Analyst 1982, 107. 35-40. (11) Goswami, D. N.; Prasad, N. JOCCA 1982, 65, 223-6. (12) (kebennlkova, 0.D.; Vinogradova, N. I.Lakokras. Mat. 1983, 2 , 52-3. (13) Harold, R. W. Mod. faint Coat/ngs 1982, 72, 31-4. (14) Hoetjer, J. 4.; Koerts, F. Holz Rah Werkstoff 1981. 39, 391-3. (15) Hoffmann, P. Studles Consewat. 1983, 26, 189-93. (16) Internatlonal Standards Organlsatlon, I S 0 3856/1.1980,8 pp. (17) Internatlonal Standards Organisatlon, I S 0 6596,1982: BSI Worldwide List Stand. 1982,Dec 4. (18) Klrchner, K.; Rlederle, K. Angew. Makromol. Chem. 1983, 117, 1-16. (19) Klochkovskii, S. P.; Tslnman, I.D.; Kagramanyan, N. P. Gig. Sanlt. 1981, 7 , 47-48. (20) Korzyuk, E. L.; Samlgullin, F. K. Zavod. Lab. 1982, 48, 19-20. (21) Lakshmlnarayana, 0.; et al. J. Am. OllChem. Soc. 1982, 59, 238-40. (22) Nencionl, M.; Russo, S. J . Macromol. Scl. 1982, A17, 1255-61. (23) Schrlever, E. Holz Roh-Werkstoff 1981. 39, 227-9. (24) Shkenderov, S.; Sugarcheva, M. Izv.-Durzh. Inst. Kontrol Lek. Sredstva - i g a i . 14. 34-8. (25) Sukhanova,-’N. A.;-Sh&alova, L. M. Lakokras. Mat. 1981, 47-8. (26) Tleke, B.; Bubeck, C.; Lieser, G. Makromol. Chem., Rapld Commun. 1982, 3 , 261-8.
(1) Banik, 0.; Schreiner, M.; Malrlnger, F.; Stachelberger, H. fraktlsche Metallographle 1982, 79, 24 (6 pp). (2) Berney, C. V.; Cohen, R. E.; Bates, F. S. Polymer 1982, 23, 1222-6. (3) Billingham, N. C.; Calvert, P. D.; Ghaemy, M. G. Brit. folym. J. 1983, 15, 62-5. (4) Brockmann, W.; Hennemann, 0.-D.; Kollek, H. Int. J . Adhes. Adhesives 1982, 12, 33-40.
X-RAY ANALYSIS
(1) Curry, C. J.; Rendle, D. F.; Rogers, A. J. Forenslc Scl. SOC.1982, 22, 173-7. (2) Drabaek, I.; Christensen, L. H. Farg Lack 1983, 29, 172 (5 pp). (3) Duncan, J. R. Surf. Technol. 1982, 17, 265-76. (4) Dunn, H. W.; Stewart, J. H., Jr. Anal. Chem. 1982, 54, 1122-5. (5) Kobersteln, J. T.; Stein, R. S. J. folym. Scl., folym. fhys. 1983, 21,
1439-72.
(8) Kuntz, G. S.; Towns, R. L. R. J . Coatlngs Technol. 1982, 54, 63-9. (7) Latter, T. D. T. Product Fin. 1982, 35,9 (3 pp). (8)Mlchell, E. W. J.; Ng, K. Y. J . Chem. Tech. Blotech. 1982, 32, 382-92. (9) Tsuchlda, H.; et ai. Bull. Chem. SOC.Jpn. 1982, 55, 1934-8. SPECTROSCOPY-MISCELLANEOUS
(1) Ailen, N. S. “Analysis of Polymer Systems”; Bark, L. S., Ailen, N. S., Eds.; Applled Science Publlshers, 1982;pp 79-102. (2) Akiyama, T. Roc. Int. Symp. on Consewatlon & Restoration of Cultural Property, Tokyo 1978, 17-24. (3) Andersen, M. E. ”Microbeam Analysls”; Heinrich, K. F. J., Ed.; San FranCISCO Press: San Franclsco, CA, 1982;pp 197-201. (4) Arakaway, Y.; Wada, 0.; Manabe, M. Anal. Chem. 1983, 55, 1901-4. (5) Bartos, J.; Tino, J. Chem. Zvestl 1982, 36, 213-21. (6) Brooks, J. S.;et al. folym. Deg. Stabil. 1982, 4 , 359-83. (7) Burmester, A. Archaeomefry 1083, 25, 45-58. (8) Caragheorgheopoi, A.; et al. Rev. Roumalne Chlm. 1982, 27, 969-72. (9) Caroline, D. Polymer 1982, 23. 492-5. (10) Cervllla, M.; Puzo, 0. Anal. Chem. 1983, 55, 2100-3. (11) Chu, B. T. P.-N.; Fytas, 0.Macromolecules 1982, 75, 561-9. (12) Comyn, J.; et al. Brit. folym. J . 1983, 75, 50-5. (13) Creer, K. E. Forensic Scl. Int. 1982, 20. 179-90. (14) De La Rle, E. R. Studies Consewat. 1982, 27, 1-7. (15) Evans, N. Anal. Roc. 1981, 18. 535-8. (16) Fotl, S.;Montaudo. G. “Analysis of Polymer Systems”; Bark, L. S.. Allen, N. S., Eds.; Applied Sclence Publlshers, 1982;pp 103-54. (17) Gerlock, J. L. Anal. Chem. 1983, 55, 1520-2.
(5) Cook, P. M.; Marklund, D. R. Proc. NBS/EPA Asbestos Standards Workshop 1980,NBS Specialfubl. 1980, No. 619, 53-87. (6) Culhane, W. J.; Smith, D. T.; Chiang, C. P. J . Coatings Technol. 1983, 55, 53-8. (7) Hammer, P. S.J . Foreqslc Scl. SOC.1982, 22, 187-92. (8) Herbst, W. Aust. OCCA R o c . News 1982, 19, 8-13. (9) Hobbs, S. Y.; Watklns, V. H. J . folym. Sci., fo/ym. fhys. 1982, 20,
651-8. (10) Ise, N.; et al. J . Chem. fhys. 1983, 78, 536-40. (11) Kampf, 0.; Papenroth, W.; Volz, H. G.; Weber, G. Roc. 16th FATIEC Congress, Liege 1982, 111 167-74. (12) Kampf, G.; Papenroth, W.; Volz. H. G.; Weber, G. AFTfVXVth Congress, Cannes 1983, 232-4. (13) Kasslm, J.; Balrd, T.; Fryer, J. R. Corros. Sci. 1982, 22, 147-58. (14) Keeley, R. Optical & €lectron Microscopy 1983, 8-9. (15) Kiss, K.; Coll-Palagos, M. ACS, Div. of Anal. Chem, Abs of Papers 184th Meetlng, Kansas City, 1982;Abs. 121. (16)Kuhn, H. R o c . Internat. Symp. on Conservatlon & Restoration of Cultural Property, Tokyo 1978, 27-38. (17) Laing, D. K.; Dudley, R. J.; Home, J. M.; Isaacs, M. D. J. Forensic Sci. Int. 1982, 20, 191-200. (18) Lee, R. J.; Kelly, 3; F.; Walker, J. S. Proc. NBSlEPA Asbestos Standards Workshop 1980,A!BS Speclalfubl. 1980;No. 619, 132-7. (19) Mahar, R. W.; Flint, R. B. froc. 16th FATIPEC Congress, Liege 1982, I I , 301-33. (20) Mansfield. F.; Lumsden, J. B.; JeanJaquet.S. L.; Tsai, S. Corrosion Control by Organic Coatlngs Symposium, Lehigh Univ . 1980, Edited froc NACE 1981, 227-37. (21) Misra, S. C.; Pichot, C.; El-Aasser, M. S.; Vanderhoff, J. W. J. folym. Scl., folym. Chem. 1983, 21, 2383-96. (22) Paszuda, K.; Cynarska, 2. follmery 1982, 27, 312-3. (23) Rouxhet, P. 0.; Somme-Dubru, M. L.; Cappeile, P. G. Roc. 16th FATIfEC Congress, Liege 1982, 11, 291-300. (24) Somme-Dubru, M. L.; et al. J . Coatlngs Technol. 1981, 53, 51-6. (25) Soroczak, M. M.; Eaton, H. C. ACS. Dlv. of OWL, Papers 1982, 46, 56-60. (26) Steel, E. B.; Small, J. A.; Sherldan, P. Proc. NBSlEPA Asbestos Standards Workshop 1980,NBS Speclal fubl. 1980, No. 679, 162-8. (27) Subramanlan, R. V.; Mendoza. J. A.; Garg, B. K. Holzforschung 1981, 35,253-9. (28) Tsubota, M.; Ueki, K. J. Jpn. Col. Mat. 1982, 55, 69-75. (29) Varlamov, A. V.; Loznevoi, G. I.Lakokras, Mat. 1982, 33-5. (30) Widmaler, J. M.; Yeo, J. K.; Sperllng, L. H. Colloid folym. Sci. 1982, 260, 878-84. I
.I
THERMAL ANALYSIS
(1) Adabbo, H. E.; Williams, R. J. J. J. Appl. folym. Sci. 1982, 27, 893-901. (2) Banks, L.; Ellis, B. Polymer 1982, 23, 1466-72. (3)Bhatnagar, V. M.; Vergnaud, J. M. J . ThermlAnal. 1983, 27, 159-200. (4) Brun, C. H.; Buhrer, H. Farbe Lack 1982, 88, 636-41.
(5) Bunton, L. G.; Daly, J. H.; Maxwell, I.D.; Pethrlck, R. A. J. Appl. Polym. SCl. 1982, 27, 4283-94. (6) Campbell, F. J. ACS, Div. OWL, Papers 1983, 48, 235-6. (7) Carraher. C. E., Jr. J. Macromol. Sci. 1982, A17, 1293-356. (8) Clayton, 0.; Ciewes, W. D. froc. UK Corrosion ‘83 Conf. Blrmingham was, 11-5. (9)Comlte Superieur Normaiisatlon Republique Bulgarie, BDS 15474,1982; BSI Worklwlde List Stand. 1983,June, 37. Ferguson, R.; McEwen, I.J.; Pedram, M. Y. Macro(10) Cowie, J. M. 0.; molecules 1983, 16, 1155-8. (11) Cowie, J. M. G.; McEwen, I.J.; Pedram, M. Y. Macromolecules 1983, 16, 1151-5. (12) Crandall, E. W.; Mih, W. C. ACS, Div. ORPL, fapers 1982, 47, 592-4. (13) Cuadrado, T. R.; Borrajo, J.; Willlams, R. J. J.; Clara, F. M. J. Appl. folym. Scl. 1983, 28, 485-99. ANALYTICAL CHEMISTRY, VOL. 57, NO. 5, APRIL 1985
27R
COATINGS
(14) Czekaj, T.; Kapko, J. Europ. fo/ym. J . 1881, 77, 1227-9. (15) Das, A. N.; Baljal, S. K. J . Appl. Polyn. Sci. 1982,2 7 , 211-23. (16) Farkas, F. Magyar Kemkmok Lapja 1982,37, 398-405. (17) Ferrlllo, R. G.; Arendt, V. D.; Granzow, A. H. J . Appl. Polym. Scl. 1983, 28,2281-9. (18) Flammershelm, H.J.; Hothold, HrH.; Bellstedt, K.; Klee, J. Makromol. Chem., Macromol. Chem. fhys. 1983, 784,113-21. (19) Fukul, H.; Saito, T.; Tanaka, M. J . Jpn. SOC. Col. Mat. 1083, 56, 349-55. (20) Qangull, S.;Bhattacharya, M. J . Chem. Soc., Faraday frans. 7 1983, 7 9 , 1513-22. (21) Qaschke, M. M.; SchneMer, bV. Mod. faint Coathgs 1982, 72, 42-7. (22) Hampson, J. W.; Rothbart, H. L. J . Am. Oil Chem. SOC. 1983, 6 0 , 1102-4. (23) hartmann, B.; Lee, G.; Long, M. J . Appl. folym. Scl. 1882, 27, 289-300. (24) Hay, J. N. “Analyslg of Polymer Systems”; Bark, L. S., Allen, N. S., Eds.; Applied Science PublIshBrs, 1982;pp 155-208. (25) Hoffmann, R. Swiss Plastics 1982,4,31-4. (26) Johnson, 8. B.; Chlu, J. Thermochlm. Acta 1981,50, 57-67. (27) Kachwalla, 2.; Barratt, K. V.; Goldsmld, H. J. J . Coatlngs Technol. 1984, 708. 64-9. (28) Kobayashl, M. J . Jpn. SOC. Col. k t . 1983,56, 518-24. (29) Kordomenos, P. I.; Dervan, A. H.; Kresta, J. J . Coatings Technol. 1982,54,43-51. (30) Krause, S.; Lu, 2.-H.; Iskandar, M. Macromolecules 1982, 16, 1076-82. (31) Levy, J. H.; Stuart, W. I.; Whittern, R. N. J . Thermal Anal. 1982,25, 359-66. (32) Malavasic, T.; Osredkar, U.; Anzur, I.; Vltovlsek, I.J . Macromol. Sci. 1983,A 79, 967-97. (33) Malhotra, S. L.; Mlnh, L.; Blanchard, L. P. J . Macromol. Scl. 1983, A 79, 559-78. (34) Manley, T. R.; Scurr, G. JOCCA 1983,66, 43-8. (35) Mlelke, W.; Slckfeld, J. Farbe Lack 1983,8 9 , 147-52. (36) Mohler, H.i Wellert, R. Farbe Lack 1982,88, 722-30. (37) Rolter, M. B. J . Coatings Technol. 1982,54,33-40. (38) Ronnusamy, E.; Balakrlshnan, T.; Kothandaraman, H. Makromol. Chem., Mairomol. Chem. fhys. 1983, 784,1279-84. (39) Samollova, G. G.; Sadykov, R. M.; Kalinlna, R. B. Lakokras. Mat. 1982, IS-& (40) Sebenlk, A.; Osredkar, U.; Zlgon, M.; Vlzovlsek, I.Aiigew. Makromol. Chem. 1982, 7U2, 81-5. (41) Slckfeld, J.; Heinze, B. R o c . 8th Internat. Conf. in Organlc Coatings Science & Technology, Athens lB82,541-61. (42) Slckfeld, J.; Mlelke, W. frog. Org. Coat. 1984, 72, 27-116. (43) Schlraldl, A.; Wagner, V.; Samannl, G.; Rossl, P. J . Thermal Anal. 1981,27, 299-307. (44) Singh, P. K.; Mathur, A. B.; Mathur, G. N. J . Thermal Anal. 1982,25, 387-90. (45) Takaoka, K. J . Jpn. SOC.Col. Mat. lS82,55, 857-63. (46) Takaoka, K. J . Jpn. SOC.Col. Mat. 1983,56,293-300. (47) Takaoka, K. J . Jpn. SOC.Col. Mat. 1883,56, 395-402. (48) Toh, H. K.; Funt, E. L. J . Appl. fo/ym. Scl. 1982,2 7 , 4171-8. (49) Tomescu, M,; Demetrescu, I.; Segal, E. J . Appl. folym. Sci. 1981,26, 41(13-18. (50) Van Der Llnde, R.; Belder, E. 0. R o c . 7th Internat. Conf. in Organlc Coatings Sclence & Technology, Athens 1981,359-78. (51) Van Der Llnde, R.; Belder, E. G. froc. 76th FATIfEC Congress, Liege 1982,I I , 205-25. (52) Varnell. W. D.; Harrison, I. R.; Roberts, D. R. J . Appl. folym. Scl. 1982, 2 7 , 3591-5. (53) Wldmann, G. Coatlng 1981, 14,262 (4 pp). (54)Yan, H.J.; Pearce, E. M.; Bulkln. B. J. ACS, Div. O W L , Papers 1982, 46,482-8. ENVIRONMENTALAND INDUSTRIAL HYGIENE
(1) Alder, J. F.; Isaac, C. A. Anal. Chim. Acta 1981, f29, 163-74. (2) Alder, J. F.; Isaac, C. A. Anal. Chlm. Acta 1981, 729, 175-88. (3) Bhargava, 0.P.; et ai. Am. Ind. Hyg. Assoc. J . 1983, 44,433-6. (4) British Standards Institution, PD 6503: 1982,8 pp. (5) Esposlto, G. 0.; Dolzlne, T. W. Anal. Chem. 1982,54, 1572-5. (6) International Standards Organlsatlon, I S 0 5667/2,1982: BSI Worldwide List Stand. 1982,Oct 5. (7) Keenan, R. R.;Cole, S. B. Am. Ind. Hyg. Assoc. J . 1982,43,473-6. (8) Matthews, T. G. Am. Ind. Hyg. Assoc. J . 1982,43. 547-52. (9) Matthews, T. G.; Howell, T. C. Anal. Chem. 1982,54, 1495-8. (10) McNulty, D. P. Austral. OCCA froc. News 1982, 79, 16 (6 pp). (11) Mlksch, R. R.; Anthon, D. W. Am. Ind. Hyg. Assoc. J . 1982, 43, 362-5. (12) Komrakova, E. A,; Kuznetsova, L. V. Gig. Sanit. 1981,43-5. 28R
ANALYTICAL CHEMISTRY, VOL. 57,
NO. 5,
APRIL 1985
(13) Rlmatorl, V.; Carelll, 0. Scand. J . W o k €nvlron. Heahh 1982,8 . 20-3. (14) Rosenberg, C.; Pfaffll, P. Am. Ind. Hyg. Assoc. J . 1982,43,160-3. (15) Slewerdt, R.; Clarenz, W. R o c . 76th FATIPEC Congress, Liege 1982, I , 267-75. (16)Taylor, D. G. (Coordinator) DHHS (NIOSH) Publlcatlon No 82-100,1981, 224 pp. (17) Tlnkelenberg, A.; Verslwt, b. R o c . 76th FATIfEC Congress, Liege 1982,I I , 131-53. (18) Tucker, S. P.; Arnold, J. E. Anal. Chem. 1982,54,1137-41. (19) Vincent, W. J.; Gulent, V., Jr. Am. Ind. Hyg. Assoc. J . 1982, 43, 499-504. (20) Williams, P. M.; WhitesMe, I.R.; Jones, T. P. Int. Environ. Saf. 1981, 15-20. MISCELLANEOUS TECHNIQUES
(1) Barnartt, S.; Donaldson, M. Corrosion 1983,39, 33-5.
(2) British Standards Institution, BS 3483: Part BE: 1982,4 pp. (3) Cerlsola, G.; Bragglo, E.; Bonora, P. L.; De Anna, P. L. fltfure Vernicl 1983,59,48-51. (4) Cheever, 6. D.; Ullcny, J. C. J . Coatlngs Technol. 1983, 55, 53-63. (5) Devay, J.; Meszaras, L.; Janaszlk, F. C m l o n Control by Organic Coatings Symposium, Lehigh Univ. 7980, Edlted R o c , NACE 1981, 56-6 1. (6)Googan, C. G, froc. U.K. NabnalCorroslon Conf., London 1982,13-8. (7) Kendlg, M.; Mansfield, F. Corroslon 1983,3 9 , 466-7. (8) Koopmans, A.; Reljnders, J. M. G. R o c . 76th FATIPEC Congress, Liege 1982,I I I , 71-86. (9) Krletoffersen, A.; Rolla, 0.; Sonju, T.; Janteen. E. J . Collohl Interface Scl. 1982,9 0 , 191-6. (IO) Lee, M. C. H. ACS, Dlv. of ORfL, Papers 1983,48,12-7. (11) Mansfeld, F. B. froc. Corroslon 81, 755: Corros. Abs. 1982, 27, 307. (12) Mansfeld, F.; Kendlg, M. W.; Tsal, S. Corroslon 1982, 38, 478-85. (13) Mansfeld, F.; Kendlg, M. W.; tsal, S. Corrosion 1882, 38, 570-80. (14) Muller, K. fleste Kautscfiuk 1982,29, 606-8. (15) Naraln, S.;Bonanos, N.; Hocking, M. Q. JOCCA 1983,66,48-52. (16) Plens, M.; Verblst, R.; Vereecken, J. IXfh Int. Conf. in Organic Coatings Science & Technology, Athens 1983, 137-53. (17) Pommershelm, J. M.; Campbell, P. G.; McKnlght, M. E. NBS Rept. TN 1150,1982,94 pp. (18) Power, G. Corros. Australas. 1981,6 , 7-10. (19) Scantlebury, J. D.; Ho, K. N.; Eden, D. A. ASTM STP 727, 1981, 187-97 (20)- Scantlebury, J. D.; Sussex, 0. A. M. Corrosion Control by Organic Coathgs Symposium, Lehlgh Unlv. 1980, €dited R o c , NACE 1981, 51-5. (21) Schromek. N.; Torriano, G. Mefallurgia ItaliSna 1980, 7 2 , 487-93. (22) Sllverman, D. C. Corrosion 1982,38, 541-9. (23) Szauer, T. frog. Org. Coat. 1982, 10, 171-83. (24) SZaUW, T. frog. Org. Coat. 1982, 70, 157-70. (25) Turner, D. W. Chem. Internat 1982,4-8. (26) Van Battum, D.; Rljk, M. A. H.; Verspoor, R.; Rossl, L. Food Chem. ToX. 1982. 20,955-9. (27) Whiting, L. F.; Tou, J. C. J . Thermal Anal. 1982,24, 111-32. (28) Yaseen, M. Corrosion Control by Organlc Coatlngs Symposium, Lehigh Univ. 1980, Editedfroc, NACE 1981,24-7. I
MISCELLANEOUS MEASUREMENTS (INCLUDING PHYSICAL TESTS)
(1) American Society for Testing & Materials, ASTM D 2196-81: 1982 Annual Book of ASTM Standards, Part 27. 392-7. (2) American Society for Testing & Materials, ASTM D 4060-81: 1982 Annual Book of ASTM Standards, Part 27,918-20. (3) Anon. f i g . Resln Tech. 1982, 1 1 , 4-11. (4) A6soclatlon Francalse de Normallsation, NF T 30-010, 1981: BSI Worldwide List Stand. 1982,June, 50. (5) Association Francalse de Normallsation, NF T 30-039. 1981: BSI Worldwide List Stand. 1982,June, 50. (6) Beranek, E. Farbe Lack 1983,89, 337-9. (7) Bodrova, N. V.; Indelkln, E. A.; Sobaklna, 0. V. Lakokras. Mat. 1981, 37-8. Continent. faint Resin News 1982,2 0 , Abs 230. (8) Cretenot, C.; Vlgouroux, A. Double Liaison 1982,2 9 , 9-16. (9) DlPaola-Baranyl, G.Macromolecules 1982, 75, 622-4. (10) Ehrllch, S. H.; Capone, S. M. Res. Disc/. 1982,64. (11) Fujltanl, T.; Satoh, T. J . Jpn. SOC.Col. Mat. 1982,55, 459-68. (12) Han, C. D.; Lem, K.-W. J . Appl. folym. Scl. 1983,28, 3155-83. (13) Hantschke, B.;Hebben, H. Farbe Lack 1982,88, 361-4. (14) Izumo, T. J . Jpn. SOC.Col. Mat. 1982,55, 499-508. (15) Izumo, T.; Yamamoto. S. J . Coatlngs Technol. 1984,5 6 , 45-50. (16) Izumo, T.; Yamamoto, S. J . Jpn. SOC.Col. Mat. 1982,55, 804-11. (17) Klshore, K.; Mohandas, K. J . Macromol. Sci. 1982, A18, 379-93. (18) Korolevlch, A. N.; Khalrulllna, A. Lakokras. Mat. 1982,39-41. (19) Kruba, L. E.; Amfiteatrova, T. A.; Kozlov, L. V. Lakokras. Mat. 1981, 20-2. (20) Mlttal, K. L., (Ed.) “Physlochemlcal Aspects of Coatings Surfaces, Vols. 1 and 2”;Plenum Press: New York, 1983;1250 pp. (21)Oesterb, K. M. Roc. 76th FAtIfEC Congress, Liege 1982,I V , 41-90. (22) Potln, C.; Pleurdeau, A.; Bruneau, C. M. Double Liaison 1982. 29,No. 322i3,15-28;NO. 324,35-43. (23) Rehacek, K. Farbe Lack 1982,88, 253-64. (24) Sachs, W. G. Stah/-Rept. 1980,35, 239-41. (25) Sata, K. J . Coatings Technol. 1984,56, 47-57. (26) Shcherbachenko, A. A.; et ai. Vysokomol. Sosd.8. 1983,44. English Transl. in Int. folym. Sci. Technol. 1983. 10, T/80-1. (27) Starkweather, H. W.. Jr.; Girl, M. R. J . Appl. Polym. Sci. 1982,2 7 , 1243-8.
Anal. Chem. lQ85, 57,29R-46R (28) Taiwan Central Bureau of Standards, CNS K6717, 1982 BSI Worldwide List Stand. 1983, Jan, 39. (29) Varadarajan, K. J . Coathgs Techno/. 1983, 55, 95-104. (30) Verkholantsev, V. V.: Gul’, T. I.; Karyaklna, M. I.: Malorova, N. V.
Lakokras. Mat. 1981, 45-7. (31) Vltovtova, 0. G.; Zimon, A. D.; Serebryakov, G. A. Lakokras. Mat. 1981, 29-36. (32) Wahl, G. P. Mappe 1982, 192, 494-7.
Pharmaceuticals and Related Drugs R. K. Gilpin* Department of Chemistry, Kent State University, Kent, Ohio 44242
L. A. Pachla Warner-LambertlPurke-Davis, Pharmaceutical Research, PharmacokineticslDrug Metabolism, Ann Arbor, Michigan 48105
The current review surveys pharmaceutical analysis and related methodology that has appeared in Analytical Abstracts or Chemical Abstracts between July 1982 and Jufie 1984. The article is directed exclusively toward the analysis of pharmaceuticals in unformulated m d dosage form and does not deal with biochemical or clinical aspects of the subject. Because of the extremely large number of references published during each review period, it is possible to cite only a representative sampling of the works published. In doing this an emphasis has been laced on references that have appeared to be significant an{ have been published in easily accessible journals. As in the past, the review is divided into 10 major sections: General, Alkaloids, Antibiotics, Inorganics, Nitrogen and Oxygen Containing Compounds, Steroids, Sulfur Containing Compounds, Vitamins, Techniques, and Miscellaneous. Most of the major sections are divided further into subsections. Because of space limitations and the desire to cite as many individual works as possible, a reference generally appears only as a single entry in the text.
GENERAL During the current review period a new Journal dealing with pharmaceutical analysis was introduced (1)and several books published including: “A Textbook of Pharmaceutical Analysis” (4),“Progress in the Quality Control of Medicines* (6),“Modern Methods of Pharmaceutical Analysis”, volumes 1and 2 (17,18),“Instrumental Data for Drug Analysis” ( I I ) , and Volume 11of a collective series concerned with individual compounds and their analytical profiles (8). A comprehensive review of the analysis of pharmaceutical compounds appeared. More than 800 references were cited (9). General aspects of chromatography as applied to the development of new drugs (2, 19,21) as well1 as specific aspects of compound analysis by capillary as chromatography (12),microbore (20) and conventional ?7,22) high-performance liquid chromatography, and high-performance (14) and reversed-phase (15)thin-layer chromatography were discussed. Likewise, a manuscript concerned with the chromatographic identification of major drugs of abuse was published (10). Other topical review dealt with electroanalytical (13)and membrane electrode (5) systems applied to drug analysis, computerization ( 3 )and data management (24)in the pharmaceutical laboratory, and various methods of stability testing (23). Finally, the determination of aromatic amines spectrophotometricallywas discussed (16). ALKALOIDS General. As has been the trend in the past, the chromatographic techniques continue to be employed most often for the analysis of alkaloids as well as pharmaceuticals in general. A book has appeared which discusses various aspects of thin-layer chromatography applied to the determination bf alkaloids ( I A ) . A number of compounds from the different classes have been separated by thin-layer (3A, 8A) and 0003-2700/85/0357-29R$06.50/0
high-performance liquid (6A)chromatography in combination with ion-pairing techniques. Use of organic modifiers has been found to improve the selectivityin the ion-exchange separation of morphine, dihydromorphine, cocaifie, ephedrine, and dihydrocodeine when chromatographed on alumina (5A). A number of opium, tropdne, and xanthine alkaloids have been measured simultaneously in street samples by a GC temperature-programmingmethod on a capillary column of SE-54 (2A). Additionally, several different alkaloids have been determined spectrophotometrically as their cobaltothiocyanates (7A). Ergotamine and codeine have been chromatographed and then quantitated as their 4-(dimethylamin0)benzaldehyde and molybdenum blue complexes, respectively (4A). Cinchona. Mostly, high-performance liquid chromatoaphic methods have been used to analyze cinchona alkaloids. or example, separations have been obtained on silica (11A, 12A, 14A), cyano (IOA),and octadecyl(13A) columns. The analysis of quinine which is a bacteriostatic agent in hair preparations is possible under reversed phase conditions using an ODS column and an ion-pairing mobile phase system (9A). Ergot. Collisionally activated dissociation mass spectrometric experiments have been carried out on 12 ergot peptide alkaloids. The procedure reportedly required less sample cleanup than with other methods (19A). Similarly LC-MS and MS-MS have been utilized in the analysis of several ergot alkaloids (15A, 16A). Liquid chromatographicconditions have been described for the analysis of ergocornine and a-and @-ergocryptineon an octadecyl column. Er ocornine and 6-ergocryptine were found to coelute except u n k r extremely high pH conditions (17A). An HPLC method for determining ergometrine in combination with oxytocin has been found to give assay results similar to those obtained by an approved colorimetric procedure (18A). Opium. In the current review period analytical methodologies and data have appeared for codeine (21A, 30A) and codeine in combination with other major opium alkaloids such as morphine, papaverine, and thebaine (24A,25A, 29A, 33A, 37A). Separations are possible either by HPLC on octadecyl (29A,33A) and amino (24A)columns or by GC after formation of the perfluoroacylated (25A) and TMS (37A) derivatives. The rate of degradation of codeine phosphate has been studied. The presence of citric acid or thiourea increases stability whereas the effect of pH ie greater under UV radiation (30A). Numerous procedures have been described for the analysis of diamorphine in illicit preparations and include the utilization of capillary gas chromatography (22A, 39A), highperformance liquid chromatography (28A, 36A), and a combination of GC and LC (35A). When a statistical evaluation of data obtained by several chromatographic methods was made, all were found to give satisfactory results (23A). TLC and HPLC have been used to detect and quantitative 03-monoacetylmorphine in diamorphine (31A). Minimum
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0 1985 American Chemical Society
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