Coatings M. H . Swann, M. I . Adorns, and G. G. Esposito, Coating and Chemical laboratory, Aberdeen Proving Ground, Md.
T
HIS BIENNIAL REVIEW covers the period from January 1965 through December 1966 and includes the authors’ choice of important contributions to the analysis of coating materials. It is hoped that the attempt to be selective has not caused omission of commendable contributions. There is a noticeable increase in foreign publications concerning coating analysis much of which appears to duplicate work that was reported in earlier years. Other reviews of a similar nature have appeared in this period (113, 111) in addition to reviews on special analytical or coating subjects. The annual reviews of the literature (93) on the composition and characteristics of fats and oils was prepared for 1965but omitted in 1966. A 20-page review of quantitative methods of analysis of certain plastics (8) contained procedures for such polymers as polyvinyl, polyamide, and cellulose-type materials, including the identification of plasticizers, antioxidants, stabilizers, and monomers. The largest number of reviews to appear in this period concerned the subject of gas chromatography and its application to analysis of coating materials. The most recent is comprehensive in subject matter ( 6 1 ) ; another treats the analysis of solvents and resins only (43), and a third (96) concerns all types of chromatography as related to the paint field. The review by Kelly (74) outlines the procedures used for solvents, monomers, additives, polyols, carboxylic acids, oils, and resins. The gas-liquid chromatographic analysis of polymers after pyrolysis, along with solvents and fatty acids was outlined (48). A review of the application of gas chromatography to the analysis of rubbers and synthetic resins (106) contained a table of pyrolysis products of a wide range of polymers. hrndt (4) discussed the history, basic principles, and recent advances in gas chromatography and summarized its application t o problems encountered in the paint industry. A larger number of books than usual concerning various phases of coating analysis have appeared in this period. h book by Haslam and Willis (63) on the identification and analysis of plastics contains many procedures applicable to coatings and includes such subjects as polymers, copolymers, plasticizers, stabilizers, and antioxidants, in addition to a chapter on gas-liquid chromatography and a library of nearly 100 infrared spectra. Ke (71) edited a book present-
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ANALYTICAL CHEMISTRY
ing newer methods of polymer characterization and another (72) on thermal analysis of high polymers. The latter included synthetic fibers, linear polyesters, polyurethane elastomers, polybutene, and polyethylene. Mitchell and Billmeyer (101) edited a book on the analysis and fractionation of polymers and the third volume of the 6th edition of “Standard Methods of Chemical Analysis” (142) appeared in this period. Part I1 of this volume on instrumental analysis, contains a chapter on paint, varnish, and lacquer. Hummel (62) included polymers, resins, waxes, plasticizers, monomers, and solvents in his publication of infrared spectra in the medium and long wavelength regions. A chapter on the analysis of vegetable oils appears in the 4th edition of Williams’ book (144) on the examination of oils, fats, and fatty foods. h chapter on the analysis and characterization of polyunsaturated acids appears in volume 9 of the “Chemistry of Fats and Other Lipids” edited by Holman (60). In “Plasticization and Plasticizer Processes” as edited by Gould (46), one of the chapters evaluates the various forms of chromatography as methods for the analysis of plasticizers and for the identification of the saponification products of ester-type plasticizers. The 7th volume of a series of abstracts on gas chromatographic methods, was edited by Knapman (77). This series, started in 1958, contains many subjects of interest to the industry, such as the analysis of solvents, polyols, plasticizers, terpenes, fatty acids, and pyrolyzed resins. GENERAL ANALYTICAL SCHEMES
The general principles of gas chromatography and the mechanism of pyrolysis were discussed by Guillet (49) who presented examples of chromatograms obtained with polymers. The complementary nature of infrared spectrometry and gas phase chromatography was stressed in a publication (60) that summarized and illustrated the application of both techniques to polymer analysis. Jain and associates (66) illustrated the identification of 41 paints by the combination of pyrolysis and gas chromatography, The behavior of certain chemical groups during pyrolysis as determined by gas chromatography was described in a paper (34) that also contained characteristic chromatograms obtained from many polymers. The applications of gas chromatography in the
paint field were described in an article (42) that stressed the examination of hydrocarbon solvents and polymers following pyrolysis. Cianetti and associates (23) described a method of thermal degradation and the chromatogram that resulted from its application to various members of the cellulose family of plastomers. Berton ( 1 4 ) studied the pyrolysis products of plastics and other materials by gas chromatography and demonstrated the use of selective detectors for such products as saturated, aromatic, and olefinic hydrocarbons, aldehydes, alcohols, ketones, and halogenated compounds. He applied his technique to a broad spectrum of materials including paint. Scholz and associates (121) investigated the characterization of polymeric compounds by gas chromatographic analysis after oxidative degradation. X new detector was described by Ford and Kennard (38) which can be used in conjunction with column chromatography. They described applications to the field of coatings including analysis for monomer, dimer, and trimer acids. The basic technique and research applications of thin layer chromatography mere discussed by Privett and Blank (115) including the application to the analysis and fractionation of fats and oils. A bibliography of literature on the thin layer chromatographic technique was compiled (75) that included 1041 references and 121 classifications including sections on pigments, resins, fatty acids, and plastics. This work is updated semi-annually. Paper chromatography has been applied to the identification of such waterproofing agents and paper coatings as urea- and melamine-formaldehyde, styrene and copolymers, and protein resins (89)‘
Page and Bresler (109) applied nuclear magnetic resonance spectroscopy to the determination of molecular weight and the acid end-group content of glycol polyesters. Foster et al. (40) examined various polymers as films in the 1.0 to 2.7-micron spectral region and reported on its usefulness for reaction kinetics , degradation studies, and the quantitative measure of polymer blends. Low and Inoue (88) obtained infrared emission spectra on the surfaces of paint, paper, rubber, and polyethylene and concluded that empirical methods could be developed for specialized applications, such as quality control of pigments and coatings. Al-
though not so versatile as various betterknown techniques of absorption spectrometry, it offers the advantages of simplicity of sample preparation and examination. A technique was outlined (90) for the preparation of wedgeshaped KBr disks whiah can be used in differential spectroscopy. Spectra were illustrated for plasticizer mixtures, a plasticized poly(viny1 acetate), and an alkyd where one or more components of each are placed in thc: wedge which in turn is positioned in the reference beam so as to compensate fcr the corresponding absorbance arising in the disk of the sample. Rozentals (119) ob .ained spectra of the gaseous products of pyrolysis of various elastomers in the ultraviolet spectral region, 185-260 mp. Characteristic spectra were obtained for most of the synthetic rubbers and polystyrene and the author recommended extending the procedure to the examination of other materials. References to the analysis of paint, dyes, pigments, and ink were included in a new book (143) on the subject of reflectanci: spectroscopy. Rahder (116) has recommended the application of dry distillation with lime as a preliminary test in analyzing synthetic resins and included his preference for qualitative tests to be applied to the solution of the volatile products in water. A paper was published (ti) that covered in detail the use of modern analytical techniques for identifying traces of paint. Differential thermal analysis has been applied (134) to the identification of synthetic coating resins in an investigation that included alkyds, amino-alkyds, epoxy esters, amino-epoxy esters, vinyl and related polymers, and ester gum. Atlas and Mark (5) surveyed modern methods of determining polymer properties in solution and in solid state. Characterization in the solid state included the use of x-ray, electron beam diffraction, infrared and ull.raviolet spectrophotometry, differential thermal analysis, etc. SPECIFIC CLASSES OF HIGH POLYMERS
&lost of the contributions that appeared in this period on the analysis of specific polymers, concerned rosin products and most of these utilized gas chromatography. Sone papers treated only the methods of pxparing the esters for separation. The retention time of the methyl esters of rosin acids were tabulated (19) using flame ionization type of detector. Chang and Pelletier (20) demonstrated the separation of seven of the most common resin acids as methyl esters using a column prepared with QF-1 (trifluoropropylmethyl silicone). Brooks et al. (17) used a polyamide liquid phase (Versamid 900). Another investigation (138) reported
relative retention data for methyl esters of ten resin acids on columns of polar polyesters and nonpolar Apiezon N grease (10%) on hexamethyldisilazanetreated Chromosorb W. Hetman and associates (54) formed methyl esters of rosin acids directly in the injection port of the chromatograph a t 400' C by decomposition of the tetramethylanimonium salts. In order to study the relationship of the dimer content of rosin to crystallization time, Leonard et al. (84) separated the methyl esters on a lowloaded, deactivated column. The column mas prepared by treating diatomaceous earth with dimethyldichlorosilane and trimethylchlorosilane which reacted with the reactive sites on the column and a t the same time deposited a small amount of silicone to serve as the liquid phase. In a similar investigation (120), the composition of various types of rosin was determined by gas chromatographic separation of the methyl esters and related to crystallizing tendencies. Hummel and Pohl (63) published a paper that discusses the infrared absorption of abietic acids and their derivatives in an attempt to shoiv how exact knowledge of the bands for different carbonyl functions in the derivatives, could simplify subsequent analytical work. Resin acid methyl esters have also been separated by thin layer chromatography (148) using alumina impregnated with silver nitrate. The developing solvent was 25% ethyl ether in light petroleum. The detection of melamine in lacquers or dried films was accomplished by paper chromatography (147). The sample was first hydrolyzed with hydrochloric acid, dried, and dissolved in ammonium hydroxide. The developing solvent was a 3 : 1 mixture of phenol and dilute aqueous formic acid, and the paper was sprayed with aqueous ammoniacal copper acetate. Phthalic acid was also detectable if the sample contained alkyd resin. Infrared spectrometry was used (18) to identify the diol components of polyester resins prepared from the condensation of mixed maleic and phthalic anhydrides with ethylene, diethylene, and propylene glycols. The spectral region from 7.1 to 7.5 microns was used. Another technique (86) for identifying the components of unmodified polyesters and polyester-type urethanes, made use of GLC after pretreatment and separation of diamines from the polyols. In order to determine the epoxy value of materials not suited to the hydrobromic acid titration, Fioriti and associates (37) used picric acid as colorimetric reagent and included two commercial epoxy resins in the variety of samples used to demonstrate the applicability of the method. Weatherhead (141) used thin layer chromatography for the analysis of bisphenol-epichloro-
hydrin resins. Using silica gel G on glass plates, chloroform as developing solvent, and chromic acid as spray reagent, he was able to distinguish between similar resins from different manufacturers, measure the monomer content quantitatively, and isolate the hydrolgzable chlorine. Spell and Eddy (130) separated the various molecular species of epoxy resins very sharply by thin layer chromatography and characterized each from the infrared spectra. Cellulose esters were determined without removal of plasticizers or stabilizers by quantitative methanolysis followed by separation of the methyl esters with a gas chromatograph having a flame ionization detector (140). Infrared spectrometry \\-as used (136) to determine the poly(viny1 acetate) content of the copolymer with vinyl chloride; the calculation was based on absorbance intensities of the bands a t 5.74 microns and 7.02 microns. A potentiometric method ivas also described (128) for measuring the vinyl acetate in a copolymer with vinyl chloride. I n this method, the sodium acetate formed b y saponification of the vinyl acetate was titrated with hydrochloric acid. In another, very similar procedure (83),the copolymer is first refluxed with acetone to induce swelling before treatment with alkali. Heylmun et al. (65) determined the vinyl content of silicone gums by treatment with phosphorus pentoxide and measured the ethylene formed with gas-liquid Chromatography. An infrared spectrometric study of propylenevinyl chloride copolymers was made (94) and spectra of the polymer films were presented. Senn (127) analyzed butadiene-styrene copolymers by nuclear magnetic resonance spectroscopy. Pyrolysis combined with gas chromatography was employed (69) to determine the styrene content of styrene-polyethylene graft copolymers. Debowski (27) applied infrared spectrometry to the determination of styrene in the ternary copolymer styrene-vinyl acetate-maleic anhydride. He used the band a t 14.1 microns and worked with samples dissolved in acetone. Post (114) outlined an absorbance ratio method for the, determination of styrene a t the SO-lOO% level in butadiene copolymers using the absorbance a t 3.25 and 10.3microns. She described her technique for isolating and purifying the copolymer. Secrest (124) made a comprehensive study of the infrared spectra of phenolic resins and discussed in detail the structures, assignment of absorption bands, and the use of assigned frequencies. He was able to distinguish heat reactive forms from nonreactive resins, establish relative degree of substitution, and identify resins after reaction with oils. iln investigation was conducted (44) to determine the yields of methacrylate VOL. 39, NO. 5, APRIL 1967
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and acrylate monomers from their copolymers by pyrolysis. The monomers were measured by gas chromatography, the correction factors were assigned, and quantitative results were reported. A method for measuring methyl methacrylate in the presence of methyl acrylate (112) was based on saponification of the former, followed by oxidation with permanganate to form formaldehyde which was determined colorimetrically with Schiff reagent. There was no interference from methyl acrylate. The composition of chloropyrene-methyl methacrylate was determined (99) from the infrared spectra using characteristic bands a t 5.80 and 6.02 microns. SPECIFIC CONSTITUENTS
Bright and associates (16) measured styrene monomer in polyesters by gasliquid chromatography and from ultraviolet absorption. I n the former, they used the supernatant liquid from methanol precipitation of the polymer; in the spectrophotometric method, they used the bands a t 290-293 mp with a monomer-free sample of polymer in the reference beam. The gas chromatographic separation was also used in another investigation (30) in which larger amounts of styrene monomer, ranging from 1347% were present as cross-linking agents. The combination of ultraviolet absorption and gas chromatography was also used by Crompton et al. (26) to calculate the styrene monomer and other aromatic volatiles in conventional and modified polystyrene. Monomeric styrene, methylstyrene, and dimethylstyrene were determined potentiometrically (7) by titration of the acetic acid formed when the monomers reacted with mercuric acetate in methanol. A temperature programmed gas-liquid chromatographic method was described (39) for measuring n-butyl acrylate, vinyl acetate, and 2-ethylhexylacrylate residual monomers in vinyl acetate polymer emulsions. An internal standard was used for quantitative work. Crompton and Buckley (25) published a polarographic procedure for both the residual acrylonitrile and styrene monomers in the copolymers. MacWilliams and associates (92) extracted acrylamide monomer from the polymer and copolymer using solvent, treated with an ion exchange resin, then provided both polarographic and spectrophotometric procedures. The former method was considered more specific. The working range was from 0.01 to 0.1% of the monomer. Jankowski and Garner (68) determined the carboxylic acids present as esters in plasticizers and polymers by transesterification and gas chromatographic separation. Sodium methoxide in methanol and methyl acetate as reagent gave quantitative yield of the 44 R
ANALYTICAL CHEMISTRY
esters which were extracted and chromatographed with diphenyl ether as internal standard. Ten dicarboxylic and four fatty acids were included but no mention was made of maleic or fumaric, and it is presumed that they could not be differentiated by the technique. Dicarboxylic acids have also been identified (102) as their methyl esters by GLC using glass beads. Novak (108) supplied procedures for the polarographic analysis of three combinations of acids in alkyds and polyesters. Included were phthalic, maleic, fumaric, citraconic, and mesaconic acids. Traxton (136) evaluated published polarographic methods for determining dicarboxylic acids in various coating resins and presented his preferred technique for determining maleic, fumaric, and phthalic acids in polyester resins and plasticizers. He also studied the degree of isomerization of maleic to fumaric acid during hydrolysis of resins prior to polarographic determination. Another polarographic method was published (78) for trimellitic, pyromellitic, tetrachlorophthalic, and chlorendic acids without interference from phthalic, maleic, and fumaric acids. Thin layer chromatography has been applied to the problem of separating mixed acids (80) and polyhydric alcohols (79). Five different developing systems were studied and the work included 30 dicarboxylic and monocarboxylic acids and 17 alcohols. By the comparison of two potentiometr ric titration curves of polyesters in acetone-ethanol solution and in acetonewater mixture, it was possible to calculate the proportion of acid anhydrides, free acids, and carboxyl end-groups (35). A gravimetric method for determining the amount of phthalic acid in various products was described (47) in which the acid is precipitated as the mercurous salt. The isolated depotassium salts in water are acidified with acetic acid, mercurous nitrate is added in excess, the sample is boiled, and the salt collected, dried a t 130' C, and weighed. An alternate technique was described in which the excess mercurous nitrate was titrated. Characteristic bands in the infrared spectra of acids separated by saponification, have been used to detect alkoxyethanedicarboxylic acids in polyesters (76). The diols and polyols used in making polyesters have been identified (36) by paper chromatography in the solution remaining after removal of the dicarboxylic acids by saponification. April (3) estimated the ratio of maleic to phthalic anhydrides in polyesters and alkyds by a combination of infrared spectroscopy and gas chromatography. Schrotter (199) demonstrated the technique of acetylation in ethyl acetate a t room temperature in the presence of perchloric acid as a catalyst for obtaining the hydroxyl value of alkyd resins. The reaction is complete in 6 minutes
and the unchanged acetic anhydride is measured in the usual manner. Sullivan and Hahn (133) tested various standard methods for determining hydroxyl content on copolymers of styrene with allyl alcohol, but obtained results lower than theoretical in all cases. They developed a suitable procedure based on esterification with n-decanoic acid. Hydroxymethyl groups were determined (146) in phenolic resins by the differencebetween a total hydroxy group determination and titration of the phenolic hydroxy groups. The former analysis was made by infrared in the 2.78 to 3.33-micron region. A procedure was outlined (118) for determining the amount of free phenol in phenolic resins and varnishes. After steam distillation of a weighed sample and diluting the distillate to definite volume, the absorption was measured a t 269 mp. Gas chromatography was used by Stevens (131) to extend a previous method (132) to include the analysis for the unreacted aldehydes in phenolacrolein and phenol-furfural resins. The first procedure to appear in the literature (1) for determining isophthalic acid in lacquers, utilized the infrared spectra of both the solvent-free film and of an acetone solution of air-dried film to give values for nitrocellulose, isophthalic, and for phthalic anhydride if present. Clarkson and Robertson (24) explained a refined calculation for nitrogen in nitrocellulose when determined from the infrared absorption. Doerffel (28) reported the determination of nitrile groups in polymers from infrared spectra through the use of KBr tablets. He also investigated the use of potassium ferrocyanide and thiocyanate as internal standards. Tjltraviolet spectrophotometry was used for the analysis of methylphenylsiloxane resins to measure their phenyl group content (139). Chloroform was used as solvent and the extinction was measured a t 260, 266, and 272 mp. A report is available (73) that describes a method for the hydrolysis of polyamide and amine-adduct curing agents for epoxies that permits subsequent quantitative separation and identification of the constituents. A procedure was developed (21) for determining both fluorine and chlorine in the same sample of polymer by the gamma-activation method. The amount of each halogen was calculated from the total induced activity following irradiation for 20 minutes. Small quantities of both free chlorine and resinbound chlorine were measured (137) in epoxy resins by potentiometric titration with silver nitrate in 85y0 acetic acid. The sample was dissolved in dioxane containing anhydrous acetic and the same technique was applied directly to the untreated sample and again after hydrolysis to obtain total chlorine. A
report was prepared (Si.) for the analysis of five reactive diluents used in solventless epoxy compounds. The analysis is applied directly to the product tested in most cases and programmed-temperature gas chromatography was used for the separation. The method is quantitative for the diluents with the exception of butanediol diglycidyl ether. OILS A N D FATTY ACIDS
Four methyl ester primary standards were used by Pons and Frampton (113) to study the precision and accuracy of gas chromatographic methods for the separation of fatty methyl esters. Hofstetter et al. (59)determined the equivalent chain length on 79 methyl esters and 7 ethyl esters of unsaturated fatty acids with gas chromatography. Nikelly (107) presented chromatograms and quantitative analytical data for the separation of free fatty acid,; on a micro glass bead column containing a liquid phase along with an acidic material. A comparison was made (103) of chromatograms obtained from untreated, unsaturated fatty esters with those produced by hydrogenated methyl esters, for identification purposes. A special hydrogenation accessory was located in the injection port. The fatt:; acids from soya bean and fish oils were used. Jamieson and Reid (t'7) studied methods of transesterification used for the analysis of oils and fats. A rapid method was published (100) for saponification followed by rapid esterification for use with triglycerides and lipids. McGinnis and Dugan (91) described a rapid method for preparing methyl esters of fatty acids. They first form a sulfuric-fatty acid complex a t the temperature of a dry ice-acetone bath which then forms methyl esters when methanol is added. Litchfield and associates (87) made a study to determine the optimum operating conditions for affec i n g quantitative recovery of model triglyceride mixtures by gas chromatography. Similarly, Kuksis (82) reviewed available techniques and discussed optimum separation and recovery conditions. In another paper (70), thin layer chromatography was demonstrated with sunflower oil as a means of separating triglycerides. Wood el al. (145) compared the retention times of derivatives of hydroxy fatty acids. They prepared trimethylsilyl ether derivatives of the methyl ester of riconoleic acid, 'ound the formation to be quantitative, and the derivatives to emerge from the gas chromatographic column in much less time than the acetates. Paper chromatography was used to separate arid identify fatty acids (22), with benzyl and phenacyl halides used as reagents. Evans and
associates (33) made use of column chromatography to investigate the nature of the polymeric products formed in oils by the action of heat and oxygen. Reversed-phase paper chromatography was used (105) to separate the acids of tall oil. In another publication, ultraviolet spectrophotometry was used (98) to determine the concentration of rosin acids when mixed with fatty acids. Zxamination of the ultraviolet spectrum from 220 to 360 mp, and measurement of the absorbance a t 315 mp, was employed (41) to determine the amount of fish oil in linseed oil. The method was applicable to quantities not exceeding 1Sy0fish oil. A review of known methods for the iodometric determination of peroxide in fats was made (126) and the causes and elimination of error in determining peroxide number of oils were discussed. A procedure was published (64) for determining the iodine number of fats and oils by the use of N-bromosuccinimide. ASSOCIATED MATERIALS
The use of thin layer chromatography was described (15) for separating and identifying plasticizers. Hancock and associates (52) used gas chromatography, column chromatography, and a gravimetric procedure for determining the diethyl phthalate in lacquers, varnishes, and paints. Gas chromatography was used (45) for the detection of plasticizers used for vinyl chloride polymers and copolymers. Included were such materials as adipates, azelates, citrates, sebacates, phthalates, and fatty acid esters. Ultraviolet spectra have been used (129) to identify and determine mixtures of phenolic antioxidants and ultraviolet absorbers in polypropylene. Commercial grades of chlorendic anhydride have been analyzed (29) for constituents through the use of potentiometric nonaqueous titration. The degree of resinification and the effects of various storage conditions on turpentine was studied (104) using thin layer chromatography. A highly selective liquid phase was used (32) t o separate aromatic hydrocarbons from paint thinners, by gasliquid chromatography. Benzene can be used as internal standard. Toluene and xylene are readily identified and other aromatics can be classified and measured. Hudy (61) described a technique for analyzing lacquer solvents by gas chromatography without prior removal of the vehicle or pigment, but presented no quantitative data. -4nother paper (86) concerned the analysis of the composition of individual technical grade lacquer solvents by GLC, using toluene as standard. High-resolution spectra of inorganic pigments and extenders in the mid-
infrared region were recorded and discussed ( 2 ) . The usefulness of the method for qualitative analysis and the technique for preparing disks are described in detail. There were 78 pigments included in this work and the authors describe an absorbance ratio method for quantitatively determining the per cent of rutile in mixtures with anatase titania. Jackson and Whitehead (65) determined 27 trace elements in titanium dioxide by spark-source mass spectrography. The interest in the trace elements is due to the effect they have on the relative brightness of the pigment. Seivers (125) measured the titanium dioxide content of bauxite by gas chromatography. The oxide was converted to the chloride by reaction with carbon tetrachloride a t elevated temperatures. Berger and Cadoff (11) compared their polarographic technique to chemical methods for measuring lead and zinc in white pigments containing white lead and zinc oxide. The acetic acid-ammonium acetate buffer they used served as both digestion medium and subsequent electrolyte. The same buffer was used for the polarographic determination of titanium dioxide in paint pigments. After formation of the EDTA complex with titanium. The analysis of mixed paint pigments for both chromium and zinc content has been combined into a single procedure (81) which utilizes the complexometric method for the zinc and iodimetric titration of the chromium. Another complexometric procedure for determination of lead in lead pigments has been published (95). Ion exchange chromatography was used (13) to separate alkaline-earth metals from zinc oxide as a preliminary step to the colorimetric determination of the magnesium and calcium in mixed paint pigments. Rathi (117) presented tests for distinguishing similar pigments of similar colors, mostly organic-type pigments. A technique was outlined (10) for measuring the apparent density of organic pigments with an accuracy of approximately 0.4%. Barker et al. ( 9 ) published routine methods for determining toxic metals in toys, school materials, and paint, including such metals as antimony, arsenic, barium, cadmium, chromium, and lead. Berger (12) supplied a method for the spectrophotometric analysis of mercury in latex paints in which the metal is complexed with diphenylthiocarbazone after treatment with sulfuric acid. A number of procedures for fungicidal preparations in paint were presented by Hoffmann and associates. An iodimetric method was used for phenylmercuric compounds (58), ultraviolet spectrophotometry for salicylanilide and toluene-p-sulfonamide (57), and chlorine analysis was combined with spectrophotometry for pentachlorophenol and VOL. 39, NO. 5, APRIL 1967
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N-(trichloromethylthio)
phthalimide
(66). Three different procedures were described by Sciarra (123) for determining the volatile content of aerosol products. A rapid total solids procedure (97) was based on the use of a hot-wire drying element in place of the usual oven. The tared drying element is dipped into the sample solution, quickly reweighed, then plugged into the apparatus described and the heating rate adjusted to maximum drying rate without decomposition. LITERATURE CITED
(1) Adams, 11. L., Keiser, J. R., J . Paznt Technol. 38, 163 (1966). (2) Afremow, L. C., Vandeberg, J. T., Ibid., p. 169. (3) ilpril, A., Chamie Peint. 27, 301 (1964); J . Appl. Chem. (London) 16, 463 (1966). (4) Arndt, R. R., Plastics, Paint and Rubber 8, 72 (1964). (5) Atlas, S. ll., Mark, H. F., ChemieIngr-Tech. 37, 1192 (1965); J . Appl. Chem. (London)16,461 (1966). (6) Aufroix, L., Double Lzason No. 119, 21; no. 120, 15 (1965). (7) Bslyatinskaya, L. N., Kreshkov, 8.P., Turyan, Y. I., Zhur. Anal. Khim. 19, 1025 (1964): Anal. Abstr. 12, 6573 (1965). 18) Baranowski. P.. Pracu Zakresu Tow\
,
aroznawst. Chern.’ W y z s ~ aSzkola Ekon. Pornan. Zeszyty S a u k . , Ser. I , 20, 83 (1965); C.A. 65, 15583 (1966). (9) Barker, J. H., Chapman, W. B., Harrison, A. J., J . Assoc. Publ. Analysts 2 (4) 89 (1964); -Anal. -4bstr. 13, 1664
(1966). (10) Beresford, J., Brack, R., J . Oil Colour Chemists’ Assoc. 49, 150 (1966). (11) Berger, H. W.,Cadoff, B. C., Ofic. Dig. Federation SOC.Paint Technol. 37, 28, 35 (1965). (12) Berger, H. W., J . Paint Technol. 38, 371 (1966). (13) Berger, K., Hering, I., Plaste Kautschuk 10, 767 (1963); Anal. Abstr. 12, 1191 (1965). (14) Berton, rl., Chim. Analyt. 47, 502 !1965); J . Appl. Chem. (London) 16, 36s i1966). (15) Braun, D., Chimia 19, 77 (1965); C.A. 62, 11968 (1965). (16) Bright, K., Farmer, B. J., hlalpass, B. W.. Snell. P.. Chenw Ind. No. 14, 610 (1965). (17) Brooks, T. W.,Fisher, G. S., Joye, s.AI., AXIL. CHEM. 37, 1063 (1965). (18) Brudkowska, B., Hippe, Z., Jablonski, H., Chem. -4nal. (R’arsaw) 11, 497 (1966); C.A. 65, 15583 (1966). (19) Brunn, H. H., Pensar, G., Acta Chem. Scand. 19, 531 (1965); C.A. 63, 1989 (1965). (20) Chang, C. W. J., Pelletier, S. W., ANAL.CHEX.38, 1247 (1966). (21) Chepel, L. T., Shemarov, F. V., Dokl. d k a d . .)-auk SSSR 158, 682 (1964); .Inal. Abstr. 13, 255 (1966). (22) Churacek, J., Mikrochzm. Acta (1-2) 196 (1966); C . A . 65, 4118 (1966). (23) Cianetti, E., Pecci, G., Scuderi, G., Rass. Chzm. 17, 149 (1965); C.A. 65, 10730 (1966). (24) Clarkson, A., Robertson, C. )I., ANIL. CHEM.38.522 i1966). (25) Crompton, T. R., Biickley, D., Analvst 90. 76 11965). (26) C;omptbn, T. R., Myers, L. W., Blair, D., Brit. Plastics 38, 740 (1965). \ - - - - ,
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ANALYTICAL CHEMISTRY
(27) Debowski, Z., Chemia analit. 10, 469 (1965); J . Appl. Chem. (London) 16, 279 (1966). (28) Doerffel, K., Wiss. 2. tech. Hochsch. Chem. Leuna-Merseb 7, 71 (1965); Anal. Abstr. 13, 4974 (1966). (29) Emelin, E. A., Smyslova, S . F., Tsarfin. Y. A.. Zavodsk. Lab. 29. 1169 (1963);’ Anal. Abstr. 11, 5604 (1964): (30) Esposito, G. G., J . Gas Chromatog. 3, 192 (1965). (31) Esposito, G. G., U . S. Dept. Commerce, Off. Tech. Serv., Rept. No. AD-615-955N f 1965). (32) Esposito, G. G‘., Swann, M. H., J . Paint Technol. 38, 377 (1966). (33) Evans, C. D., McConnell, D. G., Frankel, E. N., Cowan, J. C., J . Am. Oil Chemists’ SOC.42, 764 (1965). (34) Feuerberg, H., Weigel, H., 2. Anal. Chem. 199, (2) 121 (1963); Anal. Abstr. 12, 232 (1965). (35) Fijolka, P., Plaste Kautschuk 10, 582 (1963); Anal. Abstr. 12, 237 (1965). (36) Fijolka, P., Radowitz, W.,Ibid., 12, 207 (1965); J . Appl. Chem. (London) 16, 370 (1966). (37) Fioriti, J. A., Bentz, A. P., Sims, R. J., J . Am. Oil Chemists’ SOC.43, 37 (1966). (38) Ford, D. L., Kennard, W., J . Oil Colour Chemists’ Assoc. 49, 299 (1966). (39) ,Fossick, G. N., Tompsett, A. J., Ibzd.. D. 477. (40) Foster, G. N., Row, S. B., Griskey, R. G., J . Appl. Polymer Sci., 8, 1357 ,
I
(1964) \-----/.
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VOL. 39, NO. 5 , APRIL 1967
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