Coatings George G. Esposito U.S. Army Environmental Hygiene Agency, Aberdeen Proving Ground, MD 270 70
Martha L. Adams Petroleum and Materials Department, MERDC, Fort Belvoir, VA 22060
This review includes analytical methods of coating interest that have appeared in the literature since the last published survey (112), or were not included in the previous review, and it covers the literature through November 1974. Some selectivity has been exercised to include only those procedures especially pertinent or those, which in the authors’ judgment could be adapted easily to analytical coating problems. A number of books on various phases of coating analysis have been published in this two-year period. In previous years, ASTM Standards on paint were included in parts 20 and 21 of the “Annual Book”. However, in 1974, all of the ASTM standards on paint and related products were published in volumes 27-29. Part 27 ( 4 )contains 190 standards of which 37% are new, revised, or changed in status. Part 28 (5) contains 140 standards of which 24% are new, revised, or changed in status. Among the new standards in this volume are a recommended practice for qualitative identification of polymers in emulsions, chemical analysis of phthalocyanine blue and green pigments, and analysis of white zinc pigments. Volume 29 ( 6 )includes 240 standards, 12% which are new, revised, or changed in status, and contains a new test for aromatics in mineral spirits by gas chromatography (GC). Haken’s book, ( 4 1 ) , “Gas Chromatography of Coating Materials,” covers the GC analysis of a broad range of raw materials and finished coatings. Litchfield published a monograph (62) describing the chromatographic analysis of triglycerides. A book by Crippen (25) emphasized the combination of organic functional group analysis along with GC retention data and solubility studies for the identification of organic compounds, many being of coatings significance. “Experiments in Polymer Science” (21) contained experiments for determining molecular weight distribution, morphology, and thermal properties of polymers. Haslam et al. (48) published a second edition of “Identification and Analysis of Plastics.” This edition contains a new 80-page chapter entitled, “Instrumentation Methods”; the remaining chapters are similar to those in the first edition. “Gas Chromatography in the Chemistry of Polymers” (10) covered fundamentals of GC, monomer, and solvents analysis. Other chapters deal with kinetics and reactions of high polymer formation, and the determination of unreacted monomers, pyrolytic GC, and the analysis of additives. The GC analysis of terpenes was described in “Advances in Chromatography’’ by Giddings and Keller (37). During the period since the previous Coatings Review, very significant advances have been made in high-efficiency liquid chromatography (HELC) using controlled flow a t high pressure, continuous detection, and small particle size column packing material. The modes of separation are based on adsorption, partition, ion-exchange, and molecuAuthors have not been supplled with free reprints for free distribution. Extra coples of the revlew issue may be obtalned from Special issues Sales, ACS, 1155 16th St., N.W., Washlngton, DC 20036. Remlt $4 for domestlc U.S. orders: add $0.50 for additlonai postage for foreign destinatlons.
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lar size separations or gel-permeation chromatography (GPC). The intense interest in HELC is reflected by the large number of articles described in other sections for polymers (9, 20, 22, 29, 30, 107, 1091, oils and fatty acids (33, 47, 49, 761, aromatic acids (7, 82), plasticizers ( 3 6 ) ,and pigments (104).
GENERAL ANALYTICAL SCHEMES Cooper, and coworkers (22) discussed the current status of GPC instrumentation and demonstrated its application to polymer analysis. A summary of three papers (107) concerned with specific aspects of modern liquid chromatography was the subject of a paper by Simpson. Bellens ( 9 ) reported the GPC separation of alkyd resins and used infrared (IR) spectrophotometry to examine isolated fractions. The fundamentals of liquid chromatography were discussed in detail by Pusey (94);the subject matter included coating applications of thin-layer chromatography (TLC), classical column chromatography, and HELC. Smith (109) reviewed the fractionation of polymers using GPC, TLC, solubility, and ultracentrifugation. The principles and hardware for laser fragmentation pyrolysis of polymers was described by Vanderborgh and Ristau (115).They recommended laser pyrolysis as a complementary technique rather than a substitution for other types of pyrolytic GC analysis. A reproducible pyrolysisGC system ( 7 1 ) ,with a Curie-point pyrolyzer and porous polymer column, was proposed for the analysis of paints and plastics. Schmitz (99) compared transmission spectra by IR and attenuated total reflectance (ATR ) of paint and resin films. He also compared methods for obtaining ATR spectra and illustrated changes in the ATR spectra during the “baking” of an acrylic resin. Another ATR study (73) dealt with the analysis of paper coatings such as styrenebutadiene, poly(viny1 acetate), casein, starch gum, acrylic, and copolymers, as well as calcium carbonate and barium sulfate pigments. Minimum detectable amounts were also discussed. Charalambous (18)reported IR reflectance spectra of both hot-melt and water-based interior beer can coatings. In addition, the film weight variance of epoxy and vinyl beer can coatings was determined by differential scanning calorimetry. Applications of integrated nuclear magnetic resonance (NMR) intensities were used by Hammerich and Willeboordse (46)to obtain information on epoxy resins and polycaprolactone polymers. The average number of repeat units in these polymers were determined as well as a set of statistical parameters inherent to the choice of proportioning. Another application of NMR was described by Kulkarni and Pansare ( 6 1 ) ,in which they determined proportions of methyl alcohol, methyl acrylate, ethyl benzene, and water in mixtures occurring during the production of methyl acrylate from acrylamide sulfate and methanol. Drisko and Crilly (28) used IR to determine curing and weathering, and the combination of generic types within a single paint. The article discussed the drying mechanism
George 0. Esposlto, a research chemist at Aberdeen Proving Ground, has been working with paint and related materials for the past 24 years. His work experience includes paints, plastics, resins, pigments, plasticizers, and solvents. His main field of endeavor is the development of analytical methods and instrumentation capabilities for both research and quality control. He received his education at Loyola College and the University of Maryland. He has published 5 1 papers and is author of the chapter, "Chromatography," in the GardnerISward. "Paint Testing Manual" published by ASTM. He is a member of the American Chemical Society and the American Society for Testing and Materials.
Martha L. Adams, originally from Springfield, IL, did her undergraduate work at the College of William and Mary and then received her MS from the University of Maryland. She taught general chemistry at the St. Helena Extension of the College of William and Mary before moving to the Coating Chemical Laboratory at the Aberdeen Proving Ground where she worked for 23 years as a research analytical chemist. She has had wide experience on the applications of spectrophotometric analysis to coating materials, specializing in methodology development for resinous products. She is coauthor of 21 papers.
for paints, alkyds, catalyzed polyesters, coal tar and asphalt coatings, epoxies, coal tar epoxies, catalyzed urethanes and vinyls. In their paper on IR Fourier transform spectroscopy, Low and Mark (63) discussed the characterization of food container coatings and films. A paper (116) was published on the application of X-ray analysis of forensic samples using a scanning electron microscope, pointing out its usefulness for the examination of paint chips. Differences in the elemental composition of automobile paints, other than white paints, were shown by use of laser-beam emission spectroscopy (69). Wilks (120) described the theory of internal reflection spectroscopy in great detail and demonstrated applications to paints and finishes. Different thermal techniques (113) were applied to the analysis of paint binders. Seemingly, differential thermal analysis provided the most characteristic results; however, a combination of thermal methods was required to distinguish between the classes of resins studied. Seymour and Owen (105, 106) reviewed the concepts involved in the characterization of polymers utilizing thermal methods, absorption spectra, GC-pyrolysis, viscosity, and solubility parameters.
resins in combination with oil or alkyd modifiers and the quantitative determination of the latex and modifiers. Articles describing the NMR spectra pf polybutene ( I l l ) , vinyl chloride-isobutene copolymers (16), and polyvinyl alcohol (81) have appeared. Differences in thermogravimetric analysis decomposition of a urethane polymer derived from 2,4-toluene diisocyanate and a poly01 a t different heating rates were confirmed by the appearance of a second DTA peak a t the higher heating rates (74). Methacrylate polymers were separated by TLC (70) and polyethylene by TLC-gel permeation (87). A computer program was established which served to identify unknown materials using six major IR absorption bands for a series of vinyl polymers and copolymers (52). Fijolka and others (34) outlined procedures for hydrolyzing, separating, and determining the components of linear and cross-linked polyurethanes. Pritchard and Serra (91) reacted poly(viny1 acetate) with iodine forming a red complex having an absorption maximum a t 510 nm. Comparison of methods for the determination of saponification values of alkyd resins was presented in a recent publication (51). Chemical methods (17) were developed for determining the composition of a reaction mixture for urea-formaldehyde resins. Reviews of UV (1) and NMR (97) techniques for vinyl resin copolymer determinations were found in the literature.
SPECIFIC CLASSES OF COATING RESINS Ellis (30, 31) used GPC for quality control applications of coating formulations based on acrylics, alkyds, polyvinyl acetate, polyvinyl chloride, and nitrocellulose. Phenolformaldehyde resins were fractionated on a series of six POlystryene type GPC columns with tetrahydrofuran as the carrier solvent; fractions corresponding to individual peaks were then separated by TLC (29). Christensen and coworkers (20) used GPC for the examination of tall oil alkyds, and they concluded that no obvious correlation exists between molecular size distribution of tall oil alkyds and their drying times. Haken and McKay (44) studied the degradation behavior of alkyl polyacrylate and alkyl methacrylate homopolymers using a Curie-point pyrolysis system. In a separate investigation, the same authors described a procedure ( 4 5 ) for distinguishing between copolymers and homopolymers using a similar technique. Furthermore, Haken and others (43) identified the major pyrolysis products from the pyrolytic degradation of poly(methy1 acrylates). Progress of an interlaboratory study (30 collaborators) t o establish the precision of the pyrolytic GC of polymers was reported (24). Results using standard conditions of pyrolysis on samples of styrene-butadiene, styrene-acrylate emulsion paint, phenol-formaldehyde condensate, and a gloss paint film indicated that pyrolysis conditions, rather than column performance, is the major factor in obtaining reproducible analytical results. Krishen and Tucker (60) employed Curie-point pyrolysis to determine copolymer composition of elastomers. In a two-part investigation, Post (92, 93) described an IR spectrophotometric method for the identification of latex
SPECIFIC CONSTITUENTS Two chromatographic methods were used for the analysis of ester-type plasticizers. In one method (12), GC and TLC were applied to the analysis of low and high molecular weight phthalate esters. In the other procedure (110), a series of dimethyl, methyl ethyl, and dipropyl esters of the homologous normal diacids from malonic to sebacic were separated on a capillary GC column. The British Standards Institute (15) published multiple standard tests for the analysis of plasticizers. Keller and associates (57) used TLC to measure hexamethylene diisocyanate, toluene diisocyanate, and 4,4'diphenylmethane diisocyanate in working atmospheres. The procedure is based on the TLC determination of the ureas from the reaction of isocyanate with N-4-nitrobenzyl-N-a-propylamine. The selective determination of terephthalic acid in caprolactam copolymers (26) was based on polymer hydrolysis with HC1 and UV determination of the precipitated terephthalic acid. Differential scanning calorimetry and thermogravimetric analysis were used to select suitable combinations of intumescing agents and binders (96). The study included the examination of various blowing agents, catalysts, and carbonific materials, singularly and in formulated coatings. Using an ion-exchange column, the series from benzoic to benzene-hexacarboxylic acids were separated by HELC ( 7 ) . Another ANALYTICAL CHEMISTRY, VOL. 47, NO. 5 , APRIL 1975
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HELC method (36) for the determination of phthalate esters was reported. This study included the analysis of organic mercury compounds, making use of a multiple detection system consisting of refractive index (RI), UV, and flame ionization detectors. Styrene, isopropylbenzene, propylbenzene, and xylene isomers were separated on a GC column composed of Bentone-34/silicone polymer stationary phase (88). Karnishin and Bulygin (56) combined GC, polarography, and titrimetry for the determination of HCN in the pyrolysis products from the thermal decomposition of polyurethane resins. A procedure was published (58) for determining water in methanol, ethanol, butanol, acetone, and ethyl ether using an interferometric technique. Regulations restricting the use of benzene, toluene, ethyl benzene, and xylene in coating solvents and analytical methods providing a means for their determination were reviewed (90).
tion. In support of this effort, atomic absorption (AA) has been used to an increasing extent for elemental analysis. Brandt (13)presented an AA method for determining trace metals in paint using the Delves cup technique for lead. Henn ( 5 0 ) reported on a similar AA method for lead in paint. Details concerning instrument operating conditions, sampling, and calibration were presented. A simple, rapid, one-step AA technique (79)was developed for the determination of lead in pencil paint. The sample was scraped from a pencil, weighed into a nickel cup, and introduced into an air-acetylene flame. Hodson and Lord (53)used AA for the determination of toxic metals in paint scraped from toys. Activation analysis (65) with a 252Cfsource was shown to be a reliable nondestructive method for the determination of P b in paint a t levels of 1%.Trace amounts of As, Cd, Hg, Pb, Se, and soluble Ba have been measured in 149 types of organic pigments. Methods included AA, emission and X-ray fluorescence spectrometry, neutron activity, and OILS A N D FATTY ACIDS gravimetry ( 3 ) .The determination of Cu, Hg, and As in anA GPC method for determining the dimer content of tifouling paints by X-ray fluorescence was reported (77). corn oil was presented by Ferren and Seery (33).They used A comparative study (95) was made of four portable Xnarrow-line NMR to verify the identity of the chromatoray fluorescence analyzers for determining lead on painted graphic peaks. Harris and associates (47) used GPC for desurfaces. I t was concluded that, with nontechnical personnel, the analyzers were effective in qualitatively detecting termining the monomer, dimer, and trimer content of polyP b when its concentration exceeded 1 mg/cm2 (even when merized fatty acids. HELC and mass spectrometry were used to isolate and identify trans-3,5-dimethoxystilbene P b was contained in layers far below the outside surface from high quality tall oil fatty acids (76). paint) but, a t best, results were only semiquantitative. Seal and Maity (100) reported on a chemical method for deterThree significant papers concerned the formation of fatty acid methyl esters. Greeley (39) recommended reactmining lead. Lead was precipitated as lead chromate and ing fatty acids with tetramethylammonium hydroxide folchromate ion was determined by titration with thiosulfate. lowed .by the addition of iodobutane; esterification ocSeymour and Fritz (104) described a HPLC method for curred in about 10 minutes. Middleditch and Desiderio the determination of lead(II), in which lead was retained on an anion exchange column from 0.5M HC1 and eluted with (75) found that methyl esters formed quantitatively when trimethylanilinum hydroxide salts of fatty acids were intro8M HCl. The National Bureau of Standards (40)has develduced into a heated precolumn containing 1%SE-30 on sioped a “lead in dried paint” standard reference material lanized diatomaceous earth. Reaction-GC (27) was used to which has a certified lead content of 11.87%, as determined by AA, neutron activation analysis, polarography, and elecesterify fatty acids with diazomethane, thereby reducing the time and hazards usually associated with diazomethane trodeposition on platinum electrodes. A review (2) was made of existing and proposed standards for lead content esterifications. of paint, and includes an examination of methods that can A study of the effects of sample size, carrier gas flow rate, and column temperature on the GC determination of fatty be used to determine lead as well as other heavy metals that might be included under future controls. The volumetacid methyl esters was conducted (102). The molecular ric determinations of zinc oxide and iron blue in composite weight distribution and fatty acid composition of triglycerpigments were described by Seal and Roy (101). Outlines ides, ranging from 28 to 54 carbons, were determined by for the TLC separation and identification of four classes of GC-mass spectrometry (84). Linear sweep voltammetry organic pigments (98) has been presented. A turbidimetric (72) was proposed for determining the tocopherols content of vegetable oils. Triglycerides have been determined on method ( 1 1 ) was used to determine carbon black in blackpigmented poly(ethyleneterephtha1ate) materials. TLC plates coated with silica gel containing ammonium sulfate, and rendered fluorescent upon heating and exposASSOCIATED MATERIALS ing to UV radiation (114).Mitcham et al. used IR spectra Haken (42) utilized reaction GC to classify solvent peaks to illustrate individual uniqueness of long-chain odd-carby chemical reaction or adsorption of specific functional bon-number saturated fatty acids and monounsaturated classes of compounds. Zambrini (121) examined the evapoeven-number carbon fatty acids, their isomers, and polyration of solvents from alkyd and malamine based paint morphic modifications (78).Lunde (64)determined organically bound arsenic, phosphorus, and bromine in raw, refilms a t specific temperatures using GC. The solvent confined, bleached, and hydrogenated marine oils. TLC (35) tent of paints was determined by an azeotropic distillation procedure using water as entraining agent for solvent based was used to identify and determine oils and fatty acids paints and carbon tetrachloride for water paints ( 1 17-119). used in the paint industry. The homologous series of fatty acids, formic through stearic, were separated using an elecRetention data for a variety of solvents used in the manufacture of polyurethane polymers was obtained on porous trophoretic method, isotachaphoresis (8). Hellwig and polymer columns (66). The methyl ester-trimethyl ethers Schoellner (49) investigated GPC for characterizing oil of the alkaline hydrolysis products of shellac were analyzed modified polyesters. by GC ( 1 9 ) ,and the results were compared with TLC and PIGMENTS column chromatographic patterns of different methyl ester fractions. Electron-probe microanalysis (108) was used for The implementation of health and safety regulations by the examination of paint flakes, glass, and soil for forensic Federal, State, and Local agencies has resulted in a noticepurposes. The author described methodology and advanable increase in the number of contributions concerned tages of the technique. Seymour and Owen published a dewith metal analysis due to the emphasis on toxicity reduc40R
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tailed scheme (105) for characterizing resins of paint significance using crystallinity, tacticity, and IR spectrophotometry. A report on the spectrophotometric determination of abietic acid in rosin (83) was made in which available ethanol solutions of rosin were measured a t 242 nm, applying the curvature inversion technique. Morozowich (82) separated a number of aromatic organic acids on a new anionexchange stationary phase using high pressure liquid chromatography. Kreiner (59) described his method of separating 11 epoxy plasticizers using TLC. An analytical procedure ( 1 4 ) has been proposed for the identification of various epoxy resins and hardening agents. The study made use of chemical methods for nitrogen, epoxy groups, and diphenylolpropane structure, along with TLC and GC analysis of pyrolyzates. Another method (38) describing the identification of resin hardeners and catalyst using TLC was presented. Peace and coworkers developed a method (89) for determining the epoxide equivalent of high molecular weight epoxy resins in the presence of higher molecular weight aliphatic and aromatic amines. Jackson and Solomon ( 5 4 ) used IR and NMR spectra for "backbone" structure identification and determined functionality by determining isocyanate equivalent. Gas chromatography (23) was used to separate various bisphenols used in the preparation of epoxy resins. A method (80) for the identification of polymers was proposed, which consisted of the analysis of phenolic pyrolysis products using a combination of GC and TLC. TLC (32)was used to determine the solvency characLITERATURE CITED (1) Acosta, J. L., Sastre, R., Rev. Piasf. Mod., 26, 67 (1973). (2) Anon., Paint Varn. Prod., 64, 34 (1974). (3) Anon.. Am. Ink. Maker, 51, 31 (1973). (4) ASTM, "Annual Book of ASTM Standards, Part 27, Paint-Test for Formulated Products and Applied Coatings", Philadelphia, PA. (1974). (5) lbid., "Part 28. Paint-Pigments, Resins, and Polymers". (6) lbid., "Part 29, Paint-Fatty Oils and Acids, Solvents, Miscellaneous, Aromatic Hydrocarbons, Naval Stores". (7) Aurenge, J., J. Chromatogr., 64, 285 (1973). (8) Beckers, J.L., Eneraerts. F.M., Houtermans, W. J. M., J. Chromafogr., 76, 277 (1973). (9) Bellens, G., Helme, J. P., Leautey, J., DoubieLiaison, 20, 223 (1973); Chem. Abstr., 79, 116046e (1973). (10) Berezkin, V.. Alishaev. V. R., Nemirovskaya, I. B., "Gas Chromatography in the Chemistry of Polymers", Nauka, Moscow, USSR (1972); Chem. Abstr.. 77, 165251k (1972). (11) Berger, W., Ewert, K., Faserforsch Texfiitech., 24, 169 (1973); Chem. Absfr., 79, 32444v (1973). (12) Bloom, P. J., J. Chromafogr., 72, 35 (1972). (13) Brandt, J., Am. Paint J., 57, 28 (1973). (14) Braun, D.. Lee, D. W.. Kunstsfoffe, 62, 571 (19721. (15) Brit& Standards, Brit. Stds. institute, BS 4835 (1973). (16) Bruek, D., Hummei, D. 0.. Makromoi. Chem., 163, 281 (1973): Chem. Abstr., 78, 84941d (1973). (17) Bulygin, B. M., Aleksandrova, L. A,, Borodkina. N. I., Zh. Prlki. Khim., 46, 1868 (1973). (18) Charalambous, G., Bruckner, K. J., Hardwich, W. A,, Tech. 0.Master Brew. Assoc. Am., 11, 26 (1974). (19) Chauhan. V. S.. Sriram, N.. Subramanian. G. B. Y.. Singh, H., J. Chromafogr., 84, 51 (1973). (20) Christensen, G., Fink-Jensen, P. H., Farbe Lack, 79, 301 (1973); Chem. Absfr., 78, 138046m (1973). (21) Colline, E. A,, Bores, J., Billmeyer. F. W., "Experiments in Polymer Science", Wiley and Sons, Inc., New York. NY, 1973.
teristics of petroleum distillates. In this method, the normal operating procedure for TLC analysis was reversed, a standard dye was spotted on a TLC plate and the sample was used as the mobile phase. Rf values, thus obtained, were related to the solvent power of the solvent. Karasek and Laub (55) discussed modern instrumental techniques and their application to various materials including organic coatings. An improved IR method (86) for determining nitrogen in nitrocellulose was the subject of a paper by Norwitz and Chasan. Infinite dilution GC (85)was used for solvent volatility determinations of a large number of polymer-solvent systems. Several papers concerned with the determination of hydroxyl groups in resins have been published. Selig (103) reacted phosgene with hydroxyl groups forming chloroformates which were treated with 3-chloroaniline and titrated potentiometrically with 0.02N silver nitrate. Majewska published two papers dealing with the determination of hydroxyl groups in poly(ethy1ene terephthalate). In one method (67), he used an acetylation mixture consisting of tetrahydrofuran, pyridine and acetic anhydride and, in the other procedure ( 6 8 ) ,acetic anhydride, pyridine, and p - toluenesulfonic acid were used.
ACKNOWLEDGMENT The authors are indebted to Lt. Col. Charles R. Ritchey for his critical reading of the manuscript. They also thank Mrs. Mary Rich for assisting in the literature search and Mrs. Jean Brown for typing the manuscript and references.
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80, 75 (1973). (46) Hammerich, A. D., Willeboordse, F. G., Anal. Chem., 45, 1696 (1973). (47) Harris, H. C., Crowell. E. P., Burnett, 8. B., J. Am. Oli Chem. SOC.,50, 537 (1973). (48) Haslam, J., Willis, A,. Squirrell, D. C. M., "Identification and Analysis of Plastics", 2nd ed., Bunerworth. London, England, 1972. (49) Hellwig, J., Schoellner, R.. Plasfe Kaut., 20, 216 (1973): Chem. Absfr., 78, 991133 (1973). (50) Henn, E. L., Paint Varn. Prod., 63, 29 (1973). (51) Herry, F., Janmot, J. L., Double-Liaison. 20, 228 (1973); Chem. Absfr., 80, 604429 (1974). (52) Hippe, A,, Kerste, A,, Scr. Sci. Chlm., 21, 395 (1973); Chem. Absfr., 79, 32368y (1973). (53) Hodson. T., Lord, D. W., J. Assoc. Public Anal., 9, 80 (1971). (54) Jackson, M. B., Solomon, D. H., Anal. Chem., 44, 1074 (1972). (55) Karasek, F. W., Laub, R. J., Res./Dev., 25, 36 (1974). (56) Karnishin. A,, Bulygin, B. M., Zavod. Lab., 39, 1063 (1973): Chem. Abstr., 80, 8 4 0 0 6 ~ (1974). (57) Keller, J., Dunlap, K. L., Sandridge, R . L., Anal. Chem., 46, 1845 (1974). (58) Krachanov, Kh. G., Kuncheva, M. Y., Ignatov, G. I., Mlkrochim. Acta. 6, 969 (1973); Chem. Abstr., 79, 152642e (1973). (59) Kreiner, J. G., J. Chromafogr., 75, 271 (1973). (80) Krishen, A,, Tucker, R. G., Anal. Chem., 46, 29 (1974). (61) Kulkarni, S. Y., Pansare, V. S.. J. Appl. Chem. Biofechnoi., 23, 479 (1973). (62) Litchfield, C., 'Analysis of Triglycerides", Academic Press, New York, NY, 1972. (63) Low, M. J. D.. Mark, H., J. Paint Technoi., 44, 52 (1972). (64) Lunde. 0.. J. Am. Oil. Chem. SOC., 50, 26 (1973). Lutz. G. J., Anal. Chem., 46, 618 (1974). MacDonald. J. C., Am. Lab., 6, 11 (1974). Majewska, J., Glinka, Z.,Polimery, 17, 265 (1972): Chem. Absfr., 77, 128162m (1972). (68) Majewska, J., Poiimery, 18, 142 (1973); Chem. Absfr., 79, 79207k (1973). (69) Manura, J. J., Saferstein. R., J. Assoc. Offic. Anal. Chem., 56, 1227 (1973). (70) Matsuzaki, K.. Kanai, T., Kono, Y., Yoshida,
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T., J. f a c . Eng., Ser. A, #lo, 64 (1972). (71) May, R. W., Pearson, E. F., Porter, J., Scothern. M. D., Analyst(London), 98, 364 (1973). (72) McBride, H. D.. Evans, D. H., Anal. Chem., 45, 446 (1973). (73) Mitchell. A. J., Appita, 26, 25 (1972); Chem. Abstr., 77, 125107m (1972). (74) Mickeison. R. W., Thermochim. Acta, 5, 329 (1973); Chem. Abstr., 78,444224 (1973). (75) Middleditch. B. S., Desiderio. D. M., Anal. Left,5, 605 (1972). (76) Min. D. B. S.,Chang, S. S.,J. Am. Chem. SOC.,94, 675 (1972). (77) Miniussi, C. L., Perez, R. H., J. Oil Coiour Chem. Assoc., 57, 83 (1974). (78) Mitcham, D., Bairley, A. V., Tripp, V. W., J. Am. OiiChem. SOC.,50,446 (1973). (79) Mitchell, D. G..Aldous, K. M., Ward, A. F., At. Absorp. Newsi. 13, 121 (1974). (80) Mlejnek. O., Viadimir, V., J. Chromatogr., 79, 91 (1973). (81) Moritani, T., Kuruma, I., Shibatani, K., Fujuwara, Y., Macromolecules, 5, 577 (1972). (82) Morozowich. W., J. Chromatogr. Sci.. 12, 453 (19741 (83) Moskvrn, A. F., Doktorova, L. I., Shushkina. E. N., Zavod. Lab., 39, 1327 (1973): Chem. Abstr., 79, 653012 (1973). (84) Murata, T., Takashashi, S.,Anal. Chem., 45, 1816 (1973). (85) Newman, R. D., Prausnitz, J. M., J. Paint Technoi., 45, 33 (1973). (86) Norwitz, G., Chasan, D., Talanta, 20, 73 (1973).
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d.
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Fertilizers C. W. Gehrke and P. I?.Rexroad University of Missouri, Columbia, MO 6520 7
This review covers the literature reported from January 1, 1973 to December 31, 1974, and includes procedures recorded in readily available journals, in Chemical Abstracts, and in Fertilizer Abstracts (46). Some selectivity has been exercised to include only those procedures especially pertinent for direct application to fertilizers, easily adapted to fertilizers, or containing information related to research in fertilizer methodology.
GENERAL The Association of Official Analytical Chemists (AOAC) have published the 12th edition of “Official Methods of Analysis” (130). The fertilizer section covers 26 pages. These methods are the official methods of regulatory chemists of the North American continent and are widely respected throughout the world. The Fertilizer Institute has published the 3rd edition of the manual, “Fertilizer Sampling and Analytical Methods” ( 4 7 ) . This 230-page, loose-leaf manual was edited by the Institute’s Product Quality Committee. It provides detailed descriptions of analytical methods and includes a section on “rapid methods”. A 129-page bulletin was prepared by Johnson (76) and published by the Tennessee Valley Authority setting forth Authors have not been supplled wlth free reprlnts for free dlstribution. Extra copies of the revlew issue may be obtained from Speclal issues Sales, ACS, 1155 16th St., N.W., Washlngton, DC 20036. Remit $4 for domestlc US. orders: add $0.50 for addltlonal postage for forelgn destlnatlons.
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information for developing countries contemplating the adoption of fertilizer control legislation. Areas covered were methods of sampling, specifications for labeling, investigational allowances, definition of terms and products, and analytical methods for N, P, K, H20, and biuret. Yamazoe (204) discussed revisions made in “Official Methods of Analysis of Fertilizers”, September 1972. The official publication is available in Japanese and an English translation. Gehrke e t al. ( 5 4 ) have reviewed literature covering January 1,1971, to December 31, 1972. The methods for analyses of fertilizers for N, P, and K were presented with a section covering secondary and micronutrients. Ninety references were discussed. Rund’s General Referee reports (156, 157) on AOAC work covered a broad range of information regarding fertilizer analyses. Evaluations of current work and recommendations for the future were included. Rexroad (149) reported on the use of automated systems of analyses allowing 7000 samples per season to be analyzed for N, P, and K using approximately the same manpower formally required for 2700 samples. A review of automated analysis was compiled by Van Gemert (183) including instrumentation and applications. A table of accessories used with the Technicon AutoAnalyzer in modifications or special techniques was given. A list of 21 commercially available analyzers with some comparison of potential was included. References listed total 455.
