.
(127) Olds, E. G., Ind. Quality Control 16, 18 (December 1959). (128) Orietas, J. N., J . Am. Leather Chemists’ Assoc. 56, 4-30 (1961). (129) Ornes, C. L., Ibid., 55. 372-86 (1960). (130) Page, E. S., Technometrics 3, 1-9 (February 1961). (131) Phifer, L. H., Maginnis, J. B., Tappi 43, 38-44 (1960). (132) Pierson, R. H., Fay, E. A., ANAL. CHEM.31. 258-338 (December 1959). (133) Pursgiove, S. D., ‘Chem. Processing 24, 23-4, 95-7 (August 1961). (134) Ralston, A., Wilf, H. S., ed., “Mathematical Methods for Digital Computers,” Part V, “Statistics,” Wiley, New York, 1960. (135) Rees, N. W., Brit. Chem. Eng. 5, 106-8 (1960). (136) Remmers, E. G., Ind. Eng. Chem. 53, 743-5 (1961). (137) Rohloff, A. C., Houle, R. J., J . Am. Oil Chemists’ Soe. 37, 219-22 (1960). (138) Sachs, R., J . Assoc. Ofic. Agr. Chemists 43, 741-8 (1960). (139) Sasien, M., Yaspan, A,, Friedman, L., “Operations Research. Methods and Problems,” Wiley, New York, 1959. (140) Scheffb, H., “Analysis of Variance,” Wiley, New York, 1959. (141) Schubert, E. J., Control Eng. 7, -146-50 - _ _ _f ~
1960).
(142) Schultz, J. S.,Reihard, D., Lind, E., Ind. Eng. Chem. 52, 827~30(1960). (143) Shatkin. L., Paint Varnzsh Producti& 50,59-6i (isso). (144) Sheldon, F. R., Ind. Eng. Chem. 52.507-9- f1960). (145) ShevaleevskiI, I. D., Nolimov, V. V., Vahnsteh, E. E., Zhur. Anal. Khim. 14, 396-403 (1959). I
\ - - - - ,
(146) Shewell, C. T., ANAL. CHEM.32, 1535 (1960). (147) Sigmann, J. A., Rubber World 141, 515-19 (1960). (148) Squires, F. H., ASTM Bull. No. 243, 27-8 (January 1960). (149) Sternberg, J. C., Stillo, H. S., Schwendeman, R. H., ANAL. CHEM. 32, 84-90 (1960). (150) Strickland, R. D., Mack, P. A., Childs, W. A., Ibid., 32. 430-6 (1960). (151) Sweeney, R. F., Davis, R. S., Lapidus, L., Roberts, S. M., Sax, E., Ind. Ena. Chem. 53. 329-36 11961). (152) Tanier, L., Mateiials Research and Standurds 1, 172-5 (March 1961). (153) Taylor, G. -4.R., J . SOC.Leather Trades’ Chemists 44, 467-77 (1960). (154) Terry, M. E., Materials Research and Standards 1. 273-5 (1961). (155) Thieme, O., Chem. Tech. (bed&) 11,151-3 (1959) (in German). (156) Tidrell, P. W., Ind. Eng. Chem. 52, 510-12 (1960). (157) Titchen, R. S., others, eds., “Quality Control and Applied Statistics Year Book.” Interscience. New York. 1959. (158) Traux, H. M., ‘MacDonald, I. A., J . Am. Oil Chemists’ SOC.37, 651-7 (1960). (159) Ulmo, J.. Compt. Rend. Congr. Intern. Chim. Ind., LiBge, 31st Congr., 1958; Ind. chim. Belge, Supp. 2,796-806 1959 (in French). (160) Vance, F. P., Ind. Eng. Chem. 51, 52A-6A (December 1959). (161) Vely, V. G., Gallagher, N. D., Naher, M. B., J . Am. Leather Chemists’ ASSOC.’ 55, 209-19 (1960). (162) Wade, P. F., Ind. Quality Control 18, 5-9 (August 1961). (163) Waser, J., March, R. E., Bergman, G., Acta Cryst. 12, 6OC-4 (1959). (164) Waters, T. F., Smith, H., Jr., Still-
man, R. C., J . Am. Oil Chemists’ SOC. 34, 527-31 (1959). (165) Watson, H. E., Chem. & Ind. (London) 1960, 523. (166) Weiss, W., J . Assoc. Ofi. Agr. Chemists 43, 118-19 (1960). (167) White, J. W., Jr., Subers, M. H., Ibid., 43, 774-7 (1960). (168) Williams, E. J., “Regression Analysis,” Wiley, Sew York, 1959. (169) Wilson, A. L., Analyst 86, 72-4 (1961). (170) Wilson, C. L., Ind. Eng. Chem. 52, 504-6 (1960). (171) Kilson, C. L., Wilson, D. W., eds., “Compreheniiive Analytical Chemistry,” Vol. IA, “Classical Analysis,” Elsevier, New York, 1959. (172) Wilson, W. K., hlandel, J., Tappa 43, 998-1006 (1960). (173) Wood, E. C., Chem. & Ind. (London) 1960, 522. 174) Woodward, T., J . Assoc. O$c. Agr. Chemists 43, 374-81 (1960). 175) Wortham, A. W., Smith, T. E., “Practical Statistics in Experimental Desien.” Dallas Publishinn House. Dallis, Tex., 1959. 176) Youden. W. J.. ANAL. CHEM.32, 23.4-6A1 28A-30A, ‘32.4, 34A-5A, 37A (December 1960). 177) Youden, W. J., Ind. Eng. Chem. 51, 79A-80A (October 1959). 178) Ibid., pp. 85X-6A (December 1959). 179) Youden, W. J., Materials Research and Standards 1, 26&72 (April 1961). (180) Youden. W. J.. Technomtrics 1. ’ 409-17 (1960). (181) Zawata. C. A.. Chem. Ena. 67. ’ 160 (‘ipri1’4, 1960),’ (182) Zemany, P. D., Pfeiffer, H. G., Liebhafskv. H. -4.. ANAL. CHEM.31. 1776-8 (1959).
-
Review of Fundamental DeveloDments in Analvsis
Differential Thermal Analysis C. 6. Murphy General Engineering Laboratory, General Electric
Tm,
Teviem, like its predecessors 69)1is not intended to cover comprehensively all publications in this field, but has for its purpose the indication of significant trends and application of the technique. This review covers the period from the last review (69) to the end of October 1961. “Differential Thermal Analysis as Applied to Building Sciences,” a pocketbook edition, was published by Ramachandran and Garg (78). Garn (34) has contributed a chapter on this subject to the “Encyclopedia of Spectroscopy.” Reviews have appeared on the applications of DTA t o polymers (46, 70), oil chemistry (is), and mineralogy (101). HIS
INSTRUMENTATION
A number of publications have described DTA apparatus. Wendlandt 298 R
ANALYTICAL CHEMISTRY
Co., Schenectady, N. Y.
(107) has described inexpensive but accurate equipment. Satava and Tronsil (90) have designed a n automatic program controller and a direct-recording thermograph employing semiconductive elements in their construction. Lodding and Hammell (61, 62) have described high-temperature pressure-vacuum apparatus. Vacuum equipment has been developed by Lehmann and Muller (59) and applied to a number of natural carbonates. Two equipments have been developed for the DTA of explosives (15, 85). Other pieces of equipment have been described by Lippmann (60), Campbell, Ortner, and Anderson (ZO), Markowitz and Boryta (GO), and Mazieres (67). Dunne and Kerr (26) have described a sample holder for DTA of corrosive materials. Sensitive equipment for simultaneous DTA and thermogravimetric analyses (TGA) has been described by Reisman (82). Other
equipments for simultaneous DTA and TGA have been described by Papailhau (75) and Kastner and Hartwig ($8). Hogan and Gordon (40) have developed apparatus to permit simultaneous visual observation of phenomena and recording of thermograms. Equipment for simultaneous electrical conductivity measurement and DTA also has been described (12, 19). Kleber and Koack (53) have reported on comparative dielectric and DTA measurements, and applied the techniques to a number of minerals, including quartz, calcite, boracite, and aragonite. The method failed to detect the /3 e a transformation in quartz, but detected other transformations. L O W TEMPERATURE APPLICATIONS
Although Vol’nova (103) described equipment capable of producing thermo-
grams over the range -150" to 300" back in 1953, little effort has been expended on this aspect of DTA until very recently. Kamiyoshi and Pamakami (47) reported a phase transition in ammonium nitrate (-8.5" heating, -30.5 cooling), but gave no description of apparatus. Proks and Siske (77) have modified previously described apparatus (96) so that a n aluminum sample holder moves through a tube having a -50" to 500" gradient. Nazieres (67) has described equipment employing liquid air or liquid nitrogen for cooling. Heating coils in the refrigerating chamber accelerate the removal of these liquids and provide for subsequent heating of the sample holder. This equipment was applied to the melting of niercury and detection of low temperature transitions in barium titanate. Reisman (82) has described a somewhat similar DTA cryostat for operation over the temperature range -190" to 400", capable of operation in controlled atmospheres, in vacuum, or under equilibrium pressures. Dannis (25) has employed a differential thermocouple with one junction inserted in a solid specimen and the other junction attached to the copper container. Liquid air cooled the sample to constant temperature ; then the system, placed in a precooled Den-ar flask, was allowed to rise t o 0 " t o produce thermograms. This equipment was employed to detect t h e r i i d changes occurring in natural and synthetic rubber. Several other subzero applications have been made (6, 4354 9 ) . SIMULTANEOUS G A S ANALYSIS
Interest has increased in the analysis of gases generated during the course of D T 1 in order to interpret the resulting thermograms better. A system has been devised (71) for collection of gases liberated during the generation of thermogram peaks. Subsequent mass spectrometry was used to associate liberation of hydrogen chloride during the lorn temperature endotherm of poly(vinyl chloride) and gases liberated during stages of the decomposition of cupric acetate monohydrate (39). Ayres and Bens (8) have swept a carrier gas through the DTA system and detected gas evolution from the sample by means of a thermal conductivity cell. Gas evolution profiles obtained from a nuniber of propellant constituents showed excellent correspondence with therniogram peaks. Gsrn and Kessler (55) have employed both thermal conductivity and gas density detectors in a study of the thermal decomposition of lanthanum oxalate. Again, excellent correspondence with DTA results was found. Doyle (24) has correlated the results of DTA, TGA, a n d GE's condensation nuclei detector in polymer studies. The last instrument measures the par-
ticulate during thermal decomposition. S o t z ( 7 4 , in a study of the thermal decomposition of uranyl sulfate hydrate, has employed differential thermocouples to determine the temperatures a t which water was released and sorbed by sulfuric acid and a t which oxygen was released and sorbed by alkaline pyrogallol solution. QUANTITATIVE ANALYSIS
Quantitative analysis by DTA is based on the relation of the graphic presentation for a heat effect to the quantity of material undergoing reaction. Whether the area of the peak or the peak width a t half amplitude is measured, many investigators have had little success in obtaining quantitative data, This is related, in part, to the materials that have been investigatedi.e., most quantitative work reported has been in the field of minerals and clays. Recently a number of investigations have been reported that help explain this difficulty. Mare1 (65) has found that enthalpy change of kaolinite a t 600" varies from 180 cal. per gram for coarse crystalline material to 100 cal. per gram for powder having a surface area of 80 sq. meters per gram. Legrand and Bertrand (58)found by x-ray analysis that grinding increased the aniorphous phase in mixed of cristobalite and/or tridymite with quartz. Takahashi (100) conducted a series of dry grinding experiments on talc. X-ray diffraction and differential thermal patterns were obtained for tales with from 0 to 528 hours of grinding. In the course of grinding the x-ray pattern lost all indications of crystallinity. The thermograms shoned the gradual disappearance of a 900" endotherm, the generation of a low temperature endotherm peaking at about 140",and the generation and ultimate disappearance of an exotherm a t about 800". It is obvious from these investigations that the grinding alters the nature of minerals and clays, a factor that could seriously affect quantitative results. Ganichenko et al. (35)have used the depression of the a s p inversion effect in quartz to differentiate the amount of amorphous material over the range 10 to 50%. This same transformation has been employed to determine residual quartz in silicate mixtures (57). Stone (98) has presented a method for determining the moisture content of cssentially dry powders based on vacuum DTA without application of the furnace. Veniale (102) reported the accuracy of the DTA determination of kaolin in clays to be about &5%, which confirms a prior report (42) with much simpler materials. Variables in packing, dilution (&), mixing (65),etc., also contribute to limiting the accuracy of analyses by this technique.
HEATS OF REACTION
Rao and his coworkers (80) have studied the exothermic peaks immediately follon-ing decomposition endotherms for a number of carbonates. Estimations of AH to =t257, for these reactions, attributed to the disorder -c order reaction, were obtained by coniparing the exotherni peak areas with the peak area of the cy e p inversion of quartz. Wendlandt and George (108) have determined the heats of dehydration of rare earth(II1) sulfates by DTA. Standardization was obtained from thermograms of n ell defined hydrates. Values ranged from 68 kcal. per mole for cerium sulfate pentahydrate to 152 kcal. per mole for ytterbium sulfate undecahydrate. Although dissatisfaction was expressed for several values obtained, analyses of three different samples of two of the hydrates, prepared by three different methods, gave the same AH values within 1 5 % . Heats of polymerization of phenylglycidyl ether and an epoxy resin with various catalysts have been reported by Klute and Viehmann (64). The heat of polymerization of the epoxy resin or ether was approximately 22 kcal. per mole. When copolymers of either of these monomers were made by reaction with amines containing several active hydrogen atoms, AH increased to approximately 26 kcal. per mole of epoxide. With their apparatus, the mean value of three determinations made in this range could be measured with a standard error of 0.37 kcal. per mole. Ke (50) has measured the degree of crystallinity of various polyethylenes. In this work it was assumed that if the heat of fusion of a perfectly crystalline polyethylene was known, the per cent crystallinity could be obtained from a given expression. The heat of fusion of a long-chain hydrocarbon was used for the crystalline polyethylene. Good agreement was obtained with crystallinity measurements determined by D T 4 and those reported in the literature. Wunderlich and Kashdan (109) also employed the DTA technique to measure the degree of crystallinity of polyethylene and found the data to agree well with calorimetric data. Ke (51) mas able to determine the heats of fusion of several polyethylcal. ene polymers (870 &70 to 970 =t.% per mole) from thermograms of polyethylene alone, and mixed with dotriacontane and phenanthrene. Subsequent applications (62) resulted in determination of heats of fusion and degree of crystallinity of polyamides. PHASE EQUILIBRIA
DTA was employed to obtain the solid-liquid phase diagram for a dipamide-sebacamide copolymer (62) and the phenanthrene-anthracene system (44). I n the last investigation, Joncich VOL. 34, NO. 5, APRIL 1962
299R
and Bailey (44) pointed out the sensitivity of the technique to determination of effectiveness of zone refining of some organic compounds. Some of the other systems that have been investigated, employing DTA as a principal method, are: alkali metal chloridescobalt(I1) chloride (94); plutonium trichloride with sodium and lithium chlorides ( I C ) , and potassium chloride (11);rubidium oxide-niobium pentoxide (83); lithium oxide-vanadium pentoxide (56); alkali metal chlorides-titanium dichloride (27); gallium-tellurium (73); and cadmium oxide-niobium pentoxide (81). hIazieres (67) has studied polymorphism in potassium nitrate sodium sulfate, and detected the transformation in thallium a t ea. 232". A rapid a e B transition was found by DTA in the quartz form of germania a t 1020" 1 2 0 " (87). A new transition has been reported (28) for calcium sulfate. Polymorphism in rare earth oxide-water systems has been investigated by Shafer and Roy (95) and several new phases were reported.
Altenpohl (3) has employed DTA to contribute to the understanding of the mechanism of the reactionbetween water and aluminum.
as applied to pyrolysis of polymers and has suggested the use of the latter for quantitative information and DTA as a qualitative adjunct.
KINETICS
OTHER APPLICATIONS
Wada (104) has applied DTA to the rapid evaluation of the activation energy of chemical reactions in solutions. Among the reactions studied were chromate oxidation of oxalic acid, decomposition of benzene diazonium chloride, and hydrolysis of 2-chloroethanol. Agarwala and Naik (1) have studied the kinetics of decomposition of yttrium and zirconyl oxalates by both DTB and TGA and obtained reasonable agreement by both methods. A simplification for a first-order reaction equation was given. Baumgartner and Duhaut (9) have employed DTA to follow the kinetics of reactions, but have maintained the reference junction of the differential thermocouple a t constant temperature. The method was applied to the alkaline hydrolysis of ethyl acetate. Results obtained compared favorably with those of Smith and Levenson (97).
SOLID STATE REACTIONS
The Derivatograph (76) was applied to the decomposition of potassium hydrogen phthalate (10) to show a three-step decomposition beginning a t 190" to 200". Stonhill (99) has employed DTA and TGA to study the thermal decomposition of uranyl and sodium uranyl carbonates. Satava (88) has used the same two techniques, with air, nitrogen, ammonia, and carbon dioxide atmospheres, to study the decomposition of ammonium metavanadate. Hegedus and Gad0 (38) used x-ray, DTA, and TGA to study the reaction of tungsten trioxide with carbon. Reisman and hlineo (84), with the help of DTA, identified five compounds in the cesium oxide-niobium pentoxide system. Gallant (32) has studied the lowering of decomposition temperatures of ammonium perchlorate by cupric ion. The thermal disproportionation reactions of niobium tetrachloride have been followed by DT$ and TGA (SO). Hogan and Gordon (41) have studied the metathetical reaction between potassium nitrate and barium chloride and have found potassium chloride and barium nitrate were the stable pair. I n this work it was suggested that the reaction mechanism involved micromelting of the salts a t crystalline interfaces, supporting Borchardt and Thompson's (16) reevaluation of the Hedrall effect (37). Wendlandt (106) has applied DTA and TGA to the study of the thermal decomposition reactions of ethylenediaminetetraacetic acid, its sodium salts, and metal chelates. DTA was also used (36) to study the thermal decomposition of potassium chlorate and perchlorate.
300R
ANALYTICAL CHEMISTRY
POLYMER APPLICATIONS
Systematic examination of some classes of materials has been made: polysaccharides (21), sulfated polysaccharides (21j , saturated polyesters (4), and polyamides (5.2). Thermal properties of various polymers were defined with the aid of DTA: copper bis (pdiketone) polymers (26) and amorphous poly(mphenoxy1enes) (17). Cobler and Miller (28) applied DT.4 to a number of synthetic polymers, including poly (a-methylstyrene), poly(vinyltoluene), poly(viny1 chloride), and poly(viny1idene chloride). It was observed in this work that cross linking in styrene-butadiene rubber decreased the tendency tou-ard thermal oxidation. Low temperature transitions in natural and synthetic rubbers were investigated by Dannis (23). Glass transition temperatures and crystallinity of ethylenepropylene rubber Ivere studied by Knox (56). The interaction of rubber and sulfur Tvas clearly shown by DTA (13). Schwenker and Beck (92) hal-e applied DTA t o a number of polymers employed as textile fibers, including Orlon, polyacrylonitrile, Dacron, and nylon. Differences n-ere observed between drawn and undrawn Dacron The detection of the glass transition in poly(ethy1ene terephthalate) has been reported (93). The measurement of polyethylene oxidation by DTA was reported t o be fast and reproducible (86). Polyethylene (60, 51, 100) and phenolformaldehyde resins (72) have been the subject of thorough investigations. Anderson (6) compared the results of DTA and differential thermogravimetry
The Curie temperatures of yttrium iron garnet (YIG) and garnets obtained by substituting samarium, praseodymium, neodymium, and lanthanum for yttrium were determined by DTA ( 2 ) . The substitutions caused an increase in the Curie temperature of YIG. Schreiber and Waldman (91) have applied the principles of DTA uniquely to the measurement of specific surface area and specific adsorption capacity of a number of carbon blacks with water, n-butane, and ethyl chloride. The heat of sorption by the carbon black z's. a sintered glass reference formed the bas's for the method. I t was proposed that equipment could be designed for 30 to 40 such determinations per day. The effects of x-ray and y-ray irradiation on ammonium perchlorate (20) and the effect of thermal neutrons on lithium fluoride and lithium hydride (63) n-ere studied by means of DTA. The technique has been shown to be useful for determining the thermal efficiency of kilns (79). Arseneau (7) has shown that the thermogram of balsam fir wood is simply a composite of the individual thermograms of n-ood components. Little evidence for interaction of the wood components was found. DTA and TGA were employed by Browne and Tang (18) to study the effect of flame retardants on wood. Satava (89) employed DTA and TGA to study the catalytic oxidation of sulfur dioxide by vanadium pentoxide. The Derivatograph (76) has been applied to the thermal decomposition of coal (105). DTA has been used to show that low rank coalinteracts endothermally with sodium hydroxide, ferric oxide, and ammonium sulfate (31). Stone (98) has employed DTA, under vacuum and oxygen, t o show the effect of oxygen pressure on the oxid:ition of instant coffee. LITERATURE CITED
(1) Agarwala, R. P., Saik, 11. C., Anal. Chzna. Acta 24, 128 (1961). ( 2 ) Aharoni, A,, Frei, E. H., Scheidlinger, Z.,Schieber, M., J . A p p l . Phys. 32, 1851 (1961). (3) Altenpohl, D. G., J . Electrochem. SOC.108, 603 (1961). (4) Anderson, D. A., Freeman, E. S., A N A L . CHEM. 31, 1697 (1959). ( 5 ) Anderson, H. C., Kature 191, 1088 (1961). (6) Anikin, A. G., Dugacheva, G. M., Doklady Akad. Nauk S.S.S.R. 135, 634 (1960). (7) Areeneau, D. F., Can. J. Chem. 39, 1915 (1961). (8) Ayres, W. M., Bens, E. hl., ANAL. CHEM.33, 568 (1961). (9) Baumgartner, P., Duhaut, P., BuU. sor. chim. France 1960, 1187. \ - - - - I
(10) Belcher, R., Erdey, L., Paulik, F., Liptay, G., Talanta 5 , 53 (1960). (11) Benz, R., Kahn, M., Leary, F., J . Phys. Chem. 63, 1983 (1959). (12) Berg, L. G., Burmistrova, N. P., Zhur. h’eorg. Khzm. 5, 676 (1960). (13) Bhaurnik, hl. L., Sircar, A. K., Banerjee, D., J . Appl. Polymer Sci. 4, 366 (1960). (14) Bjorklund, C. W., Reavis, J. G. Leary, J. A., Walsh, K. A., J . Phys, Chem. 63, 1774 (1959). (15) Bohon, R. L., ANAL.CHEM.33, 1451 119611. (16) Bdrchart, H. J., Thompson, B. A., J . Am. Chem. SOC.82, 5630 (1960). (l?) Brown, G. P., aftergut, S., Blackington, R. J., J . Chem. Eng. Data 6, 125 (1961). (18) Browne, F. L., Tang, W. K., Abstracts, 140th Meeting, ACS, p. 6K, Chicago, Ill., September 1961. (19) Bndnikov, P. P., Gorshkov, V. S., Titoskaya, V. T., Strottel. Malerialy 6 (12), 30 [ 1960); C A 55, 20379 (1961), (20) Camubrll. P. F.. Ortner. M. H.. ‘ Andrrsdn, 6. J., ASAL. CHEM. 33, 58 (1961 ). (21) Chester?, G., Thompson, S. O., Science 133, 275 (1961). (22) Cobler, J. G., Miller, D. L.. Abstracts, 136th Meeting, ACS, p. 16T, Atlantic City, September 1959. (23) Dannis, AI. L., personal communication; Abstracts, 140th Meeting, ACS, p. 3V, Chicago, Ill., September 1961. (24) Doyle, C. D., “Evaluation of Experimental Polymers,” WADD Tech. Rept. 60-283 (May 1960). (25) Drinkard, W.C., Ross, D., Tiesner, J., J . Org. Chem. 26, 619 (1961). (26) purine, J. A., Kerr, P. F., Am. AIzneralogist 45, 881 (1960). (27) Erlich, P., Schmitt, R., Z. anorg. u. allgem. Chem. 308, 91 (1961). (28) Fleck. TV. E. P.. Jones. M. H.. ‘ Kunte, R. A., McAdie, H. G., Can. J : Chem. 38, 936 (1960). (29) Freeman, E. S.,Anderson, D.- A. Campisi, J. J., J. Phys. Chem. 64, 1727 (1960). (30) Frere, P., Michel, A., Compt. rend. 252. 740 119611. (31) Gaineg, A. ’F., Partington, R. G., Fuel 39, 193 (1960). (32) Gallant, W.K. A., Abstracts, 137th Meeting, ACS, p. 17B, Cleveland, Ohio, April 1960. (33) Ganichenko, L. G., Egorov, M. M., Kiselev, V. F., Krasil’nikov, K. G., Iihodakov, G. S., Doklady Akad. Nauk S.S.S.R. 131, 597 (1960). (34) Garn, P. D., “Encyclopedia of Spectroscopy,” G. L. Clark, ed., Reinhold, Kew York, 1960. 135) Garn. P. D.. Kessler. J. E.. ANAL. CHEY.33., 952 (1961). ’ (36) Harvey, A. E., Wassink, C. J., Rodgers, T. A., Stern, K. H., Ann. N. Y . Acad. Sci. 79, 971 (1960). (37) Hedvall, J. A., ‘‘Einfuhrung in die FestkoDerchimie,” DD. 180 ff.. Fr. Viewee & Son,’Braunschdg, 1952. ’ \
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