ANALYTICAL CHEMISTRY, VOL. 50, NO.
5, APRIL 1978
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Thermal Analysis C. B. Murphy Xerox Corporation, Xerox Square, Rochester, New York 14644
This review covers the major trends in thermal analysis from the previous review (254) to October 1977. During this period, several major meetings have been devoted to thermal analysis, including the Fifth ICTA held in Kyoto, Japan, in 1977. the First European Symposium on Thermal Analysis held in the U.K. in 1976, and Termanal ’76 held in Czechoslovakia. At the Fifth ICTA, the fourth report of the nomenclature committee was made (225). As noted in the report, elements of the nomenclature reports have been accepted by ASTM (16),IUPAC (165),and I S 0 (163). More recently, IUPAC (166) has accepted additional terminology put forth by the committee. The major elements of nomenclature also have been presented in “For Better Thermal Analysis” (215), a brochure available from ICTA. Among the books that have appeared are “Thermal Analysis” ( 3 6 3 ,Vol. 5 of “Atlas of Thermoanalytical Curves” (214),“Thermal Analysis of Minerals” (349),and “Benchmark Papers in Analytical Chemistry, Vol. 2, Thermal Analysis” (366). The proceedings of the cited meetings also are available: “Thermal Analysis, Proceedings of the Fifth International Conference” (69),and “Proceedings of the First European Symposium on Thermal Analysis” (88). Among the reviews that have appeared, there has been one on the thermochemistry of explosives (76),and another on aging and oxidation of polymers (115).
DIFFERENTIAL THERMAL ANALYSIS-DIFFERENTIAL SCANNING CALORIMETRY Two papers have appeared presenting lower cost DTA equipment. The first (195) offered simple triac control to eliminate expensive temperature programming equipment. The second (230) was designed for teaching purposes from commercially available modular units and employed a calorimeter bath filled with 25% ethylene glycol in HzO. Modifications to improve DTA detection limits for trace components have been presented (244). Equipment for DTA under gas pressure has used an autoclave (110) for operation to 7 kbars and 850 “C. A one-cell, flow-type, high pressure apparatus has been devised (229) and was applied to the hydrogenation of coal. A DTA cell was fabricated from Teflon and was used to study the effects of pressure (8 X lo* Pa) on liquid crystals to -260 “C (303). A high pressure DTA cell was designed to use silicone oil as the pressure transmitting fluid (186) and was used to study the effects of pressure on melting, solid-solid transition, and crystallization of poly(tram-1,4-butadiene). A resistance-welded, stainless steel DSC cell was described (319) for use with volatile systems. A DSC cell was built into a high pressure housing and provided with an additional lead attached to a separate recorder (86). The latter could be used to monitor a time-base plot of A T , or to measure peak areas with an integrator. DTA and differential pressure analysis principles and use were discussed (346) and the combined techniques were applied to NaHC03 decomposition. Equipment for evolved gas analysis (EGA) and DTA and TG has been described (26). Equipment with a thermal conductivity sensor has been described for the same purpose (96). Equipment for TGDTA-EGA and pyrolysis/gas chromatography/mass spectrometry has been applied to dihalotin(1V) bis(diethy1dithiocarbamates) (46),tetrakis(diethyldithiocarbamato)tin(IV) ( 4 7 ) , and tin(1V)-dithiocarbamate complexes ( 4 5 ) . I t was assumed that a systematic error would occur in the determination of transition temperatures of ICTA standards by using the extrapolated peak onset temperature (371). However, it was shown that this was considered a fixed point, but not the transition temperature (119),which is at the peak apex. Expressions have been developed for the determination of the onset temperature (286) which show that it does not 0003-2700/78/0350-143R$Oi.O0/0
depend on the thermophysical properties of the material, heat transfer, or heat of reaction, but depends upon reaction kinetics and heating rate. Grinding has been shown to affect the curves obtained for methisazone (210) and kaolinite (199). The use of atmosphere control for peak differentiation and peak suppression has been demonstrated with siderite, FeC03 (363),to give greater accuracy in identification. An alternate method of computation of purity by DSC had been presented (78)and a computer program was developed for its application which the authors will make available. Analytical techniques have been developed for quartz in talc based on the a-P quartz transition ( 3 1 9 , for dolomite in calcite (83),and for austenite in low carbon tool steel (309). DSC has been employed to measure the heat capacities of AszS, ( x = 3 to 198) at 3W550 K (102),of CuFz and Au (104), of tetraphenylporphyrin (208),and of polystyrene (127). DTA has been used to measure heats of transition of KC104, RbC104, and CsC104 (123);and the heat and entropy of fusion of ZnSe (205). Determination of the heat of dissociation of poly(y-benzyl L- and D-glutamate) (17) by DSC gave 5.0 & 1.3 kJ/mol, in good agreement with 4 to 6 kJ/mol obtained by measurements of heat of solution. A new application of calorimetry, thermoporimetry, has been disclosed (293) in which the freezing and melting peaks of a known condensate in an unknown material make it possible to determine pore size and volume of the unknown. The method was applied to r-Al,O, during sintering. The advantages of plotting kinetic data using reduced time have been demonstrated (320) and reduced time expressions were given for a number of model processes. A mathematical analysis of thermokinetic curves was made a t the maximum rate of transformation (130),and a discussion of a variety of numerical methods applied to the determination of the rate constant and order of contracting interface reactions in the solid state was given (265) and the superiority of the Gauss-Newton method of nonlinear least squares was demonstrated. Kinetics of polymerization of the diglycidylether of bisphenol A with hexahydrophthalic anhydride and benzyldimethylamine were determined by DSC (283) using mathematical expressions derived from TG. Dynamic experiments indicated the reaction to be first order with an activation energy of 25 kcal/mol, while in the isothermal mode, the reaction was first order with some variation with temperature and the activation energy was 22 kcal/mol. The crystallization temperatures of Fe-Ni metallic glasses were determined by magnetic and calorimetric methods (218). The calorimetric method was useful near Tgand the magnetic method was more useful a t lower temperatures. When the time for the exothermic peak generation was plotted vs. l / T for isothermal experiments, linear plots were obtained which permitted calculation of activation energies. Application of these techniques to liquid samples appears to be increasing and worthy of some attention. Emulsions containing 75 wt 70 liquid paraffin and 25 wt % lanolin were homogenized with H 2 0 , ranging from 0.1 to 0.4 wt 70 (50). These were then cooled a t 2.5 “C/min to give exotherms between -37.5 and -40.5 “C, resulting from freezing of H 2 0 droplets. The emulsion obtained by melting the frozen emulsion was different from the original and gave freezing temperatures from -34.0 to -39.0 “C. Emulsions prepared from Sn-10% Bi alloy (mp 219 “C) in polyphenylether were subjected to DSC to measure nucleation (298). Melting points oxide)toluene, obtained of poly(2,6-dimethyl-l,4-phenylene when solution clarification occurred, were confirmed by DSC (196). On cooling, an exotherm occurred a t phase separation which decreased with increased scanning speed. Additional work (197) showed that two peaks (78 and 106 “C) could be generated a t high cooling rates which were attributed to two different forms of PPO. The lower melting modification is 0 1978 American Chemical Society
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ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
less perfect, but has a higher growth rate and, therefore, can be found a t the higher cooling rates. Temperatures of phase transitions have been determined in Ag,Te, 138 "C (231);Me4NC104,232 K (185);KCdF,, 243, 471,485 K (152);Pb(TcOJ2,370-386 "C (383);Rb3M003F3 (282); CoBr2, 648 K (275);and NH4GeF6,129 "C; NH4PF,, 125 "C; NH4BeF4, 234 "C; and NH4AsF6, 133 "C (71). Temperatures and heats of transformation have been determined for AgCrS,, 170 "C, 106.3 cal mol and AgCrSe2, 138 "C, 209 cal/mol (255);and the I1 I( 401 K, 1291 cal/mol; I 111, 389 K, 720 cal/mol; and I11 I1 transformation in KNOB,338-369 K, 571 cal/mol (361). Phase transitions have been determined in pressure DTA equipment for (NH4)3HS04 to 8.5 kbar (124);Ag,C03 and Rb2C03to 36 kbar (194);and NH4SCN, RbSCN, TlSCN, and CsSCN to -30 kbar (193). One of the more common uses of DTA and DSC continues to be the generation of phase diagrams. Among the elemental systems studies have been U-Ru ( 4 ) ,V-Rh (364), Li-Si (323), Y-Zn (235), Ca-Sb (264), and Au-C1 (169). Chalcogenide systems have been studied extensively and some of these have been SnSe-GeSe, (180), GaSe-GeSe (326),HgSe-CdSe (261), SnSe2-TlzSe (158),Ag,Te-Ag,Se (14),and GeTe-Biz-Te3Sb2Te3(5). Chalcogenide glass systems also have been studied, Le., Sb-Ge-Se system (27), AssSe3(99),and As2Se3containing In or Bi dopants (325) and it has been shown that T g(95,207) and heat of crystallization (95) deDend uDon heating rate. Among oxide systems, the following have been investrgated: Zr02-Sc203 (3111, Hf02-A1203(2161, Pr203-W03(315),and Na20-P,05-B O3 (246). Some of the other numerous studies have included Li2S-Bi2S3 (209), K2Cr04-CaCr04 (182), CaF2-AlF3 (80), CF3COOK-CF3COONa (82),CaCr04-CaCL-LiC1 (74),CaCr04-CaC12-KC1 (75),and the CIFs-IF, - low temperature system (334). An equipment for phase studies in alloy systems has been described (61). In the 50 w t % Au-Cu alloy, DTA has shown the Au-CUI Au-Cu I1 transformation at -419 "C and the disorder transformation at -425 "C (345). The La-Cu system has exhibited the compounds LaCu, LaCu2,LaCu5, and L a c k (73). Crystallization in an amorphous Fe-Ni alloy was investigated by DSC (67). I t has been reported that DSC analysis of Pb-Sn solders has a sensitivity of better than 0.5 "C corresponding to better than %0.4% alloy composition (108). The application of DTA and effluent gas analysis to the identification of second phases in steel has been reviewed (22) and extended application to carbide and nitride phases in steel (23) has demonstrated carbide precipitate concentration changes with heat treatment and disclosed phases not previously identified by other techniques. A similar approach was taken for identification of carbides, nitrides, and sulfides in a marging steel (307). Gypsum continues to be the subject of many publications. Dehydration was shown to be dependent on the partial pressure of H 2 0 (242). Setting of a-CaSO4.0.5 H 2 0 and pCaS04.0.5 H 2 0 in suspension and paste (146)and vapor phase hydration of the hemihydrate (353) have been investigated by DTA. I t has been shown (352) that gypsum dehydration conditions modify reactivity of the product and that only gypsum dehydrated in vacuum or very low H 2 0 pressure is likely to rehydrate. The rate of hydration and amount and type of hydration product formed in hydration of 4Ca0. Al2O3.Fe2O3depends on the initial H,O/solid ratio, temperature, and duration of hydration (296). In this work, DTA was found to be more sensitive than x-rays in identifying phases formed. High-alumina cement undergoes compositional change with aging: 3Ca0.~203.10 HzO 3Ca0.Al2O3.6 H 2 0 + A1203.3H 2 0 + 18 H20. In examination of cement with 70% conversion, DTA, quantitative DTA, DSC, and DTG gave analyses with standard deviations of 0.9,0.4, 1.4, and 0.3, respectively (245). The transformation was said to involve the dissolution of Ca0-A1203.10H,O and Ca0.Al,03.8 H 2 0 and crystallization of Ca0.A1203.6 H 2 0 (43) and to be strongly influenced by the original HzO/cement ratio. Simultaneous TG-DTA was applied to the system (304) and a method for predicting cement strength developed from DTG. a-CaO. Si02.H20was synthesized and was found to dehydrate endothermally a t 460-470 "C to Ca0.Si02 through an intermediate phase (172). The formation of ettringite, 3Ca0. Al2O3.CaSO4.32H20, in early stages of cement hydration was roughly proportional to the -130 "C peak associated with this material (36).
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DTA and DSC continue to be applied to determination of polymer decomposition temperatures. Polystyrene (192), poly(mhepta1dehyde) (2591, polyhydrazides based on N,N'biisomaleimide (11I ) , and phosphorylated poly(vinylcarbazo1e) (285) are materials that have been examined in this manner. Polymer melting points continue to be measured by these two techniques with a number of investigators examining polyethylene (39,287,373). Polyesters related to poly(ethy1ene terephthalate) (3791, polydioxolan (291), and poly(Nmethylimino)tetrafluoro-1,4-phenylene(198) are other examples. Heats of fusion have been determined for poly(ethylene oxide) (54) and isotactic poly(methy1 methacrylate) (203). However, melting phenomena have been shown to be quite complex. It has been pointed out that the conflict of endothermal heat of transition and exothermal heats of decomposition can seriously affect DTA results (3). Increasing the heating rate from 3 to 40 "C min lowered the melting point of cross-linked poly(viny1 a cohol) hydrogels as much as 27 "C (281). In bisphenol A polycarbonate, increased heating rates gave higher melting points and the melting points were depressed significantly by plasticizers (211). Poly(ethy1ene terephthalate), upon addition of poly(ethy1ene isophthalate), poly(2,2-dimethylpropyleneterephthalate), or poly(tetramethy1ene terephthalate) to the melt, was shown to undergo randomization which was reflected in T , melting point and crystallization temperature (56). The melfing point decreased and the melting interval broadened as the sebacate concentration increased in poly(tetramethy1ene sebacate terephthalate) random copolymer (232). Heating to increasing temperatures in this polyester increased the density and crystallinity and up to four melting peaks were observed. These results reflected a reduction of the number of terephthalate sequences which participate in the crystallization process. Drawn Nylon 6 yarns have shown a double melting peak (347)which was attributed to melting of perfect crystals simultaneously with crystallization and melting of the new crystals. When the drawn Nylon 6 yarn was prevented from shrinking during heating, only a single melting peak was observed (348). The double melting effect has been noted on DTA of poly(ethy1ene terephthalate) fibers (37), with the second melting endotherm attributed to heat set. Multiple melting endotherms also have been observed in poly(epichlorohydrin) (243) and evidence was presented that the higher melting endotherms did not result from crystallization of the lower melting endotherm material. p-Hydroxybenzoic acid polymer has exhibited a reversible crystalline transition a t 325-360 "C by DTA, DSC, dilatometry, and x-ray scans (101). Three crystalline forms were observed in poly(butene-1) (129)with the forms having melting temperatures of 110, 130, and 142 "C. Form I11 of isotactic poly(pentene-1) has been characterized (252) and found to have a mp of 70 "C by DTA. The random coil to @-form transition in silk fibroin was investigated by DSC, IR, x-ray diffraction, and dynamic mechanical measurements (228) and was found to be accompanied by reformation of hydrogen bonding above 180 "C, with thermally induced crystallization starting a t -190 "C. The phases of poly(viny1idene fluoride) have been studied by DSC, optical methods, and IR spectrometry (290) showing domains where the phases exist and indicating a time- and temperature-dependent crystal-crystal transition from a to y form occurs a t high temperature. The equilibrium mp (178 "C) and heat of fusion (1425 cal/mol) for the a-form were determined by DSC (365). Poly(pheny1ene sulfide), when subjected to DTA, gave an 85 "C T a premelt crystallization exotherm at -130 "C, and a crysta7line mp a t 285 "C (44). When annealed for 2 h at 204 "C, the premelt crystallization peak was not observed and T gwas barely discernible. Crystallinity of branched Nylon 3 increased through two successive exotherms a t 115 and 260 "C (60). The first was interpreted as "cold crystallization" and the second as crystallization occurring when the most imperfect crystalline regions begin to melt. The determination of crystallinity in poly(2,6-dimethylphenyleneoxide) was determined by DSC (33%), wide angle x-ray scattering (31%), and small angle x-ray scattering (25%) (368). I t was found (273)that in the case of isotactic polystyrene, both crystallinity and thermal stability increase with crystallization temperature. In this study, crystallinity by DSC and x-ray methods was found to differ, DSC values being lower. I t was suggested that the existence of islands of amorphous material, or separated
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ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
C. B. Murphy received his B.S. and M.S. degrees from the College of the Holy Cross in 1941 and 1942, respectively. After three years of Navy duty, he returned to Holy Cross as a member of the Chemistry Department faculty. In 1952 he received his Ph.D. from Clark University. In the same year he joined American Cyanamid's Stamford Research Laboratory. After 10 years with General Electric's Advanced Technology Laboratories, he joined the Xerox Corp. as manager of the Materials Analyses Area. He is now a Principal Scientist.
amorphous particles, may not be detected by x-ray methods, but would be incorporated in the calorimetric results. In a study of the effects of annealing, melting, and recrystallization of solution grown isotactic polystyrene crystals (274),the x-ray data were correlated with DSC results. Crystallization rates of poly(buty1ene terephthalate) and poly(ethy1ene terephthalate) were studied by DSC and depolarization microscopy (289) where it was found that slower crystallization half times were obtained by DSC. However, similar values were found for isotactic polypropylene. In the case of polyethylene fractions, DSC could be used to provide crystallization kinetics data in agreement with dilatometric results (148). However, a t low rates of crystallization, dilatometry was superior to DSC, and DSC was considered severely limited in studying secondary crystallization. The wide range of values obtained for the T onset temperature of polystyrene Standard Reference fiaterial 754 resulted in its rejection as a certified value (121). Variations substantially larger than 0.5 f 0.3 "C in the T were attributed to experimental conditions, to the DTA or d S C instruments themselves. The effects of interpretation method, extrapolation to 0 "C scan rate, polymer sample form, thermal treatment, and thermal cycling on polystyrene T, were investigated by DSC (135). Data at 8 "C/min were considered superior to those from extrapolation to 0 "C rate and thermal cycling improved reproducibility for sheet, but not granulated material. An enthalpy-relaxation study (233)has shown that the enthalpy relaxation rate for atactic polystyrene a t comparable temperature intervals below T, decrease somewhat with increasing molecular weight to the critical molecular weight range observed in the molecular weight dependence of T,. Poly(ethy1ene terephthalate) T, has been the subject of several investigations. Calculated T 's, using apparent activation energies for the process, agreed with experimental values (272). I t was shown that as the methylene chain increased, Tgdecreased (380). Contact angles of glycerol on poly(ethy1ene terephthalate) were determined over the range 20°-900 and peaks were found a t the DSC T -transition temperatures (262). Poly(viny1 carbazole), with k n ranging from 3.7 x lo3 to 2.7 X lo6,showed T, to be essentially linear with 1/Mn (134). Melt blends of poly(viny1idene fluoride) and poly(methy1 methacrylate), with different weight ratios, gave a single T, that shifted with composition as would be expected in a compatible system (277). Polyblends of butadiene-acrylonitrile elastomers and copolymers of vinyl stearate and vinyl chloride gave two T,'s, indicating immiscibility (175). Triblock copolymers of isoprene and methyl methacrylate of different molecular weights and isoprene contents gave two T i s (137),while in isoprene-styrene block copolymers, DSC results indicate that the isoprene blocks plasticize the styrene blocks (351). The influence of plasticizers on bisphenol A polycarbonate have been investigated by DSC (118,271). The effect of H20 on the T,.of polyamide homopolymers and copolymers has been examined (53) and the T , lowering was found to depend only on the average spacing of amide groups in the monomeric unit. The conflicting literature values for the T , of poly(viny1 pyrrolidone) were attributed to the hygroscopic nature of the polymer (375). Plotting T vs. weight % H20, a linear curve was obtained over the range6-16.1% H 2 0 , which might be used to determine the H 2 0 content of poly(viny1 pyrrolidone). In the poly(viny1 acetate)-toluene system, NMR indicated the four dielectric processes were: cy, segmented motion of PVA; p', motion of the side group; P, rotation of toluene; and y, local motions of
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PVA and toluene ( 7 ) . DTA showed only the (Y and /3 processes. Dilatometry and DSC showed that LiC1, LiBr, and KC1 (0-7 w/o) had no effect on the T of Nylon 6 (3513, but salts forming complexes, ZnC12 an% CoC12 with poly(propy1ene oxide) and poly(tetramethy1ene glycol), increased T, with oxygen cross-links (369). Polymer salt formation increased T in the ethyl acrylate-acrylic acid copolymer (338),Nafions (378), and polysulfones (267). Application of DTA to quenched cyclohexane (139) has shown the first example of plural T i s in a single compound. Examination of the T > Tgrelaxation, the Tl,itransition, has continued with styrene block copolymers with polybutadiene, hydrogenated polybutadiene, and polymethylsiloxane (125) where it correlated with polystyrene T, and molecular weight. DSC results from a series of polymers and different molecular weight polymers (109)have indicated that T,,,/T = 1.2. However, the existence of T,,,has been questionecf (276) and the phenomenon attributed to macroscopic flow. Cure and decomposition of cross-linked, modified phenolformaldehyde polymers were examined by simultaneous DTA-TG (10). DSC was applied to curing of injection molding compounds (327), with the rate of curing being calculated from the peak area. The peak temperature of the exotherm increased with increasing heating rate (1 to 50 "C/min), but the heat of reaction was maximum at 5 "C/min. Fast cure of poly(ecaprolactonetrio1) and chain-extended l,g-hexane diiscyanate with dibutyltin dilaurate catalyst was monitored kinetically by the temperature rise in an adiabatic reactor and DSC gave a heat of polymerization of 4 0 kJ equiv NCO (213). The state of cure of the diglycidyl et er of bisphenol A, cured with 4,4'-diaminodiphenylmethane,was determined by planimetry of the exothermic peak area associated with residual heat of reaction (49). Annealing of polytetraoxane, obtained by y-irradiation of tetroxane, was studied by DSC (257). Samples annealed in O2 give a broad melting endotherm indicating scission during annealing, while in N2 rearrangement occurs and gives rise t o double melting endotherms. ?-Irradiation of poly(ethy1ene oxide) in vacuum was shown by DTA to result in a melting point depression of 0.15 K/Mrad (204). DTA of radiationgrafted styrene and acrylonitrile to high density polyethylene was conducted (177). With styrene, an endothermal peak at 135 "C corresponds to melting of polyethylene, at 440 "C to polyethylene decomposition, and a t 482-488 "C to decomposition of grafted polystyrene. DSC of ?-irradiation-grafted isobutene to polyethylene gave a new peak a t -200 "C which increased with the per cent graft (324). DTA was applied to deoxycholic acid inclusion compounds with vinyl and diene monomers before and after y-irradiation (247). New peaks were observed in the irradiated samples which were attributed to polymer melting. The diene monomers were grouped into three classes based on the stability of the resulting polymers. I t was shown that induction times by DTA at 180-190 "C can be used to detect the presence of antioxidant and copper deactivator in polyolefins by runs made in oxidized Al, oxidized Cu, and Cu pans (370). The degree of chlorination, in mol % , of radiochemically-chlorinated poly(viny1 chloride) was related to T by the expression [ ( Tg- 78/103) X 1001 (157) when DSC heating rates of 8 "C/min. were used. A large number of the organic investigations have been concerned with liquid crystals. Among the materials that have been examined have been N,N'-bis(pphenylbenzy1idene)@,a'-bi-p-toluidine and N,N'-bis(phexyloxybenzy1idene)a,n'-bi-p-toluidine (168);eleven homologous series of alkanoates, w-phenyl-alkaneates, alkyl carbonates, and S-alkyl thiocarbonates of cholesterol, cholest-5-en-3/3-thiol and 5cycholestan-3P-01 (106);pentyl, hexyl, heptyl, and octyl cyanobi phenyls (181); cholesteryl acrylate (377); and 2-(4-rz-C1alkoxybenzylideneamino) anthracenes (314). The liquid crystal transformation temperatures and heats and entropies of transformation of a series of 2-[4'-n-alkoxy-bipheny1(4)]quinoxalines and 2-[4'-n-alkyl-biphenyl(4)]quinoxalines were determined by DSC (151) and phase diagrams for ,these materials with several other liquid crystal materials were given. Phase diagrams for 17 binary systems involving azoxy compounds and esters were determined by DTA (321). The melting point of rn-nitrophenol was found to be 35-40 "C by DSC (357) and polarized light microscopy indicated the existence of two forms, needles and prismatic needles. DSC
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showed the existence of two forms of sorbitol with melting points of 86 and 97 "C and heats of fusion of 165 and 157 J/g, respectively (339). X-ray diffraction and DSC were used to show a reversible 90° thermal transition in 2,3-dimethyl1,4-naphthoquinone (48). Two metastable crystalline phases, @ and 6, were found by DTA of cyclohexane (98)and transition temperatures and heats of transition were given. The melting temperatures and melting enthalpies of o-nitrochlorobenzene (304.3 K, 30.06 cal/g), m-nitrochlorobenzene (317.32 K, 27.0 cal/g), p-nitrochlorobenzene (356.02 K, 21.4 cal/g) were determined (13) and phase diagrams for their binary mixtures were determined. Low temperature DTA and heat capacity measurements were employed to study the polymorphic phases of tetramethylsilane (140) and the transition temperatures and heats and entropies of transition of the 0,@, and y phases were given. DSC has been used to determine phase diagrams for pyrene-picryl chloride (24),pentaerythrityl tetrabromidepolyethylene (333),and trioxane-poly(t-caprolactone) (372) systems. Purity measurements by DSC were made on naphthalene, benzil, methyl stearate, cholesterol, cholesteryl caproate and stearate, dicholesteryl adipate, pentaerythrityl tetracaproate, squalene, and polystyrene (251). DSC and TG were applied to a series of nine alkylperoxycyclohexadienones (52) to measure their melting points and heats of decomposition, and temperature range of stability. Decomposition of two hydroperoxides to 2,2'-methylenebis(4-methyl-6tert-butylphenol) was shown by DSC (340). Eleven different alkylphenols were incorporated into polyethylene and the samples were subjected to simultaneous DTA-TGDTG (154). The more effective the phenol was as a stabilizer, the longer was the plateau beyond the melting point, the greater was the initial reduction of the exothermic region, and the larger was the decrease in weight loss. DSC was used for selection of inhibitors for vinyl monomers (306) by measurement of the thermal autopolymerization enthalpies and reaction rate constants. Heats of polymerization and activation energies for styrene, methyl methacrylate, acrylamide, and N-tertbutylacrylamide determined in this work were in good agreement with literature values. Polymorphism was examined in 1-(5-oxo-hexyl)threobromine ( l o o ) ,in chenodeoxycholic acid (356), and in androsterone (42). The thermal decomposition of a number of bismuth medicinals was followed by DTA (294). The caffeine-sulfathiazole system was shown t o be simple eutectic type ( I I ) , while antipyrine-sulfathiazole (11) and antipyrine-sulfaguanidine (12) systems showed compound formation. DSC was applied to polyethylene pharmaceutical packaging, but was found to give less significant results than thermomechanical testing (131), which appeared to offer promise for evaluation of heat seals. DSC has been reported (91) capable of determining the protein denaturation temperature and enthalpy in 20-pL samples containing as little as 2 mg/mL of protein with heats of denaturation of 100 pcal. Lysozyme was shown (343) to exist as tetragonal and orthorhombic crystals, with reversible denaturation occurring in a single DSC endotherm in salt-free solution, but irreversibly with two endotherms in NaCl solutions, for the tetragonal form. The kinetics of the conversion of ovalbumin to S-ovalbumin in egg whites was investigated by DSC (94), and examination of freeze-dried ovalbumin preparations stored in the cold for 20 years showed partial conversion to an intermediate, but not to S-ovalbumin. Spectrophotometric and DSC studies have been made on metal binding to ovotransferrins (92, 93) and human serum transferrin (92, 350). A family of block copolymers derived from polyaddition of N,N'-dimethylethylenediamine to 1,4-bis(acryloyl)piperazine and lateral block of polystyrene were heparinized and found to be long-acting nonthrombogenic in animal experiments (114). The T i s of these polymers were determined by DSC and were found to increase with increased styrene content.
THERMOGRAVIMETRY Commercially available equipments for operation to 1000 "C (132)and to 1500 "C (179) have been described. The Cahn electrobalance was adapted for isothermal oxidation-reduction studies of CeOz-* (0 < x < 0.3) (299) and for determining sputtering yields in a magnetically confined low-pressure arc discharge (143). TG apparatus for gassolid interaction studies
to 1600 "C has been described (8). A stirred flow microbalance reactor, based on the Cahn recording balance, was developed for catalyst studies (236) and was applied to hydrogenation of butene-1 over a molybdena-alumina catalyst. A DuPont 950 TG equipment was modified to permit operation up to 30 atm, 1100 "C, with steam pressure to 20 atm (87). A dual quartz crystal oscillator microbalance, with a resolution of 7 x lo-" g., has been described (34)and was applied to a study of A1 oxidation. TG has been coupled with mass spectrometry in a number of systems (29, 30, 85, 382). Simultaneous DTA-TG equipment for operation to 1550 "C has been coupled to a quadrupole mass spectrometer (107). High pressure DTA-TG equipment was developed (183) and applied to a study of Na2S.9H20 in an O2 atmosphere. Decomposition of CdC204was studied by TG in the isothermal mode (90) and found to produce Cd and C02. However, even a t low pressures, some CdO and CO were produced, which was attributed to a highly active Cd surface a t the reaction temperature. ZnCOB decomposition was examined in various gaseous environments (31)and was found to be strongly influenced by water vapor. The decomposition temperature was lowered 100 "C in 17 mm H 2 0 pressure from that of decomposition in 8 mm C02. The influence of residual pressures from to 5 Torr on the thermal decomposition of gibbsite, Al(OH),, was examined (310). It was shown that control of residual pressure is of little value unless the decomposition rate also is controlled and that the residual pressure can affect the shape of TG curves and the nature of the products. (NH4),WSe4and (NH4),VS4were studied by simultaneous TG-DTG-DTA (288). The tetraseleno compound behaved differently under normal and reduced N2 pressure, which was attributed to deposition of Se from H2Se decomposition (180-260 "C) which subsequently volatilized a t higher temperatures. Several papers have appeared on the quasi-isothermal and quasi-isobaric dehydration of inorganic hydrates (278-280). BaPt(OH),-O.5H2O underwent dehydration at 100 "C and dehydroxylation at -300 "C to form BaPt0, ( I 17). On further heating to >650 "C, BaPtO, was formed. The oxygen content of these materials could be determined by TG in H2 which produced Ba(OH), and Pt. Anhydrous Sn(OH)2,subjected to TG in N2, lost H 2 0 in two stages, a t 126 and 195 "C (156). MnS03.3H20 decomposed to MnO and Mn,04 in N2 and 02, respectively (59). TG, DTG, and DTA were used to examine the decomposition stages which were found to be quite complex. Sulfide, for example, was found in the O2 atmosphere product, as well as sulfate. Decomposition of 5(NH4)20.12W03.5H20,5(NH4)20.12W03-llH20, and spray dried ammonium paratungstate was followed by TG and evolved gas techniques and x-ray diffraction (28)and the three materials gave blue tungsten oxide with similar decomposition kinetics. Absence of a diffraction pattern suggested amorphous ammonium metatungstate was the initial product. (M = Na, K, Rb) was prepared and M[NbO(C204)2F2].3H20 subjected to TG (322),and the K compound was found to behave differently from the other two. Na3[Fe(CN)5DMSO].2H20 (DMSO = dimethyl sulfoxide) was found to dehydrate endothermically a t 148 "C, while DMSO was liberated exothermically at 225 "C (25). TG in the isothermal mode, 160-225 "C, was applied to NH4EuF4,which was found to follow the contracting sphere equation with an activation energy of 23 f 1 kcal/mol (295). Kinetics of the B + Nz reaction were studied by TG a t 1479 to 1823 K using amorphous and @-rhombohedral B (77). Reaction rates indicated a mixed mechanism involving formation of BN and B,N. Oxidation of petroleum coke by 15% O2 in N2 was inhibited by 1% and 3% SO2 (376). In the SO2 experiments, S was found on the cooler walls downstream from the reactor, and mass spectrometry indicated the presence of COS and COz. Oxidation of pure Co and Ni and four Co-Ni alloys (20, 40, 60, 80% Co) in O2 and NO (10 Torr) a t 700 "C in a microbalance showed the kinetic curves were parabolic (341). Surface oxide layers were found to vary with Co concentration and oxidizing gas. Zircaloy-4, evaporationcoated with Sn of various thicknesses, was oxidized a t 500 "C in a microbalance (147). Oxidation decreased with Sn thickness and increased with O2 pressure. A transition observed in the parabolic oxidation curve was attributed to a p / n transition in ZrOz. Oxidation of Co-Cr alloys in air a t
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ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
900-1000 "C and in O2 a t 800-1000 "C was followed by T G (200). Alloys containing 3-5 wt % Cr had high oxidation resistance, but the activation energy increased suddenly a t 23 wt % Cr. Dilatometric measurements indicated the t-a lattice transformation boundary in the 23 wt % Cr region. Kinetics of Si and Sic oxidation were measured as a function of temperature and Oz partial pressure (153). Volatilization of CrCl, and CrC14was employed to study corrosion of Cr by C1, a t 650-800 "C (302), and it was found that the rate constant for CrZO, was 100 times smaller than that for Cr. Cr corrosion was inhibited in a Cl2-OZ mixture due to formation of a Cr203layer and to CrOZClzbeing the only volatile product. A piezoelectric quartz crystal microbalance was used to study Hzsorption by thin P d layers (55). TG also was used to study oxidation of PbS (170). TG and x-ray phase analysis were employed to synthesize and to confirm the structure of PbzNbMnOs and PbzWMnOs (301). The former is stable to 1040 "C, while the latter oxidizes in air a t 580 "C. In the case of PbzWMn06,the weight increase was greater than that for oxidation to Mn3+, indicating Mn4+ compounds also are formed. Oxygen stoichiometry also was investigated by T G in LaMnl-,Cu,03+ materials (358). TiOz, prepared by vapor phase reaction, and BaC03 reacted to form BaTiO, (335). TG curves showed that differences in reactivity resulted from atmosphere variations (Oz, C02),TiOz crystal type, and TiOz particle size. Dynamic and isothermal kinetics were studied for formation of LiFeOz from Li2C03and Fez03(116). TG was employed to measure the extent of KzOz and KOz formation when KOH was exposed to a sustained Oz glow discharge (313). Nitrogenation of PuH, and PuH, with NH, was investigated (253). Both reactions followed the same rate expression with activation energies of 22.6 and 18.8 kcal/mol, respectively. T G was used to determine the stability limits of C S [ B ~ ( S C N )and ~] C S ~ N ~ [ B ~ ( S C N 140 ) ~and ] , 200 "C, respectively (81). Therefore, these analytical precipitates may be safely dried a t 100 "C. Several transition metal pyridine-thiocyanate complexes were examined by TG, DTG, and DTA (2561, where it was shown that Mn and Ni complexes exhibit two-step depyridination, while Cu and Zn show only one. Transition metal complexes with methyl and dimethyl urea were subject to T G in air and vacuum (18)and TG and DTA were applied to Naz[Fe(CN)SN2H5].2Hz0 (184)and the decomposition products of these materials were identified. Simultaneous T G D T G D T A , as well as TG in the isothermal mode, were applied to cis-[CrC12tn]C1-0.5H20 (tn = trimethylenediamine) (381). The activation energy for dehydration, 42 kJ/mol, is almost equal to the heat of vaporization of H 2 0 , showing H 2 0 to be weakly bound. T G and DTA of metal complexes derived from 2-mercaptobenzothiazole and from 2-mercaptobenzimidazole established decomposition temperatures and reaction kinetics and enthalpies ( 174). [UOz(C3H~C00)&M.6Hz0(M = Mg, Mn) were subjected to TG showing decomposition products to be a mixture of MU04 and MU3OI0(308). Potassium hydrogen phthalate, used in the DTG mode, gives peak temperatures which are considered superior to the difficultly defined procedural decomposition temperatures (330),which resulted in its recommendation as a standard. Intercalation of UF6 into the graphite lattice was accomplished and T G was conducted on the product (38). T G showed weight loss was initiated slowly a t 60 "C, but was significantly less than expected for UF6 a t high temperatures. Mass spectrometry showed the major effluent to be CF,, with minor amounts of CZF6. The KC37insertion compound was prepared and soaked in organic solvents for a month to form ternary compounds (297). TG of the benzene compound showed K loss before all the CsH6 had been removed. Clathrate compounds of the type M(diam)M'(CN)4.2C6H, (diam = (NH3)Z. ethylenediamine, or trimethylenediamine; M = Cd, Ni, Cu; M' = Ni, P d , Cd, Hg) were prepared and subjected to simultaneous Tg-DTG-DTA and T G in the isothermal mode (268). Cd(en)Ni(CN),.2csH6 showed one C6H6released below 130 "C in a zero-order reaction and above 130 "C, the second CsH6 is released more slowly, involving two different mechanisms. X-ray, DTA, and TG indicate that y-zirconium phosphate immersed in aqueous solutions of ethylene oxide results in intercalation compounds of the latter (374). On heating, the 2-hydroxyethoxy derivative of yzirconium phosphate was formed.
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Poly(oxycarbonylimino-1,4-phenylene) did not give a DSC mp (187),but apparently sublimed on TG, condensing on cooler surfaces. The determination of thermal stability of polymers by TG was applied to a series of aliphatic polyaldehydes, where rapid decomposition was found above 150 "C (260);to vinyl acetate-ethylene copolymers, where it was found that thermal stability decreased as the vinyl acetate concentration increased from 12 to 33% (224);to differentiate between the thermal stability of cellulose phosphonate and two of its derivatives (161);and to show polypropylene to be more susceptible to pyrolysis and oxidation than polyethylene (240). When polystyrenes containing para substituents were subjected to TG, it was shown that polymers containing electron repelling groups (OMe, Me) were more stable than those with electron withdrawing groups (Cl, Br) (162). However, when a series of polyimides derived from 3 3 , 4,4'-benzophenone tetracarboxylic dianhydride and p,p'-, m,p'-, and m,m'-diaminobenzophenone andp,p'-, m,p'-, m,m'-, and o,p'-diaminophenylmethanes were subjected to TG (33), the data indicated little difference in stability resulting from isomeric structural configurations. The diaminophenylmethanes were less stable. Introduction of small mole fractions of vinyltriethoxysilane, vinyltriacetoxysilane, and vinylmethyldiethoxysilane into polystyrene lowered the thermal stability with respect to polystyrene (19). Polyhexamethylenetetraphenyldithiopyromellitimidinewas shown to lose 2% weight a t 200 "C, 10% a t 300 "C, and rapidly decompose above 300 "C (63),which indicated lower thermal stability than its oxo analogue (64). TG and DTA were applied to segmented polyurethane fibers derived from trimethylenediamine, 4,4'-diphenylmethane diisocyanate, and two polyether-based macrodiisocyanates (112). By comparing changes in weight loss and DTA peaks with chemical structure, it was found possible to separate soft from hard segment decomposition. High impact polystyrene, containing polybutadiene, was blended with antimony trioxide and/or decabromodiphenyloxide ( I 73). By comparing the experimental and calculated weight losses, definite evidence for condensed phase reaction was obtained when all three additives were present, the experimental weight loss above 300 "C exceeding the calculated. A series of nine prepolymers were prepared from 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid and aromatic diacetamido compounds and were subjected to TG in the isothermal mode (66). The weight loss indicated cyclization to polyquinazolones. Activation energies calculated from data a t 400-500 "C varied indicating complex degradation behavior of the polyquinazolones. In the vinyl acetate-methyl methacrylate copolymer, evidence was found for lactonization (224). The kinetics of anhydride formation in poly(acry1ir: acid) in porous A1203composites was investigated by TG (133). When relative weight loss was plotted vs. temperature, peaks were observed a t 200, 250. and 390 "C. The first was associated with tightly bound H 2 0 , and the second to anhydride formation. TG was employed to study the degradation kinetics of polyepichlorohydrin and epichlorohydrin-ethylene oxide copolymer (249). Activation energies for both materials were the same in NP, but in air the value for the copolymer was significantly lower. Samples compounded with Pb304as an acid acceptor were superior to uncompounded material a t lower temperature. Heats of depolymerization have been shown to be essentially equivalent to polymer degradation activation energies (192). This led to the conclusion that the initiation step is ratedetermining and requires most of the energy during conversion of polymer to monomer. In the case of poly(viny1 chloride) and polyacrylonitrile, the equivalence resulted in the speculation that monomer formation occurs and decomposes into HC1 and HCN, respectively, and residue. A relationship between effective activation energy of pyrolysis, calculated from DTG curves, and interlayer spacing of resulting carbons treated to 2700 "C has been proposed (206). For a number of polymers, materials yielding nongraphitizable carbons have activation energies less than 30 kcal/mol, while those giving graphitizable carbons have values in excess of 60 kcal/mol.
OTHER METHODS An apparatus for ac thermoelectrometry has been described (258) and was applied to ZrOz. Data plotted vs. 1 / T showed an activation energy change a t -850 "C which was not de-
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ANALYTICAL CHEMISTRY, VOL. 50, NO. 5, APRIL 1978
tected by DTA or thermodilatometry. Similarly, temperature-dependent conductivity measurements in the RbC1-CuC1 system showed a slope change a t 100-110 "C that was not associated with a DTA peak. When the technique was applied to a mixture of SrO and CuCl (58),DTA showed exothermic peaks at 270 and 390 "C and an endotherm a t 660 "C, but the 270 "C transition was not shown by thermoelectrometry. Therefore, thermoelectrometry can be highly sensitive in some cases. An anvil apparatus incorporating electrical resistance measurements to 80 kbar has been described (355). Conductivity changes occurred abruptly in AgCrS, a t 170 "C which also was detected by DSC (AH = 106.3 cal/mol), while AgCrSez showed changes a t 138 and 205 "C, also detected by DSC (AH = 209 and 60 cal/mol, respectively) (255). The Derivatograph, incorporating simultaneous measurement of electrical conductivity, was applied to a series of borates (336). Simultaneous DTA and conductance measurements were applied to the system CsC1-SrC12 (57),where the compound CsSrC13was shown to be formed. Thermoelectrometry has been used in the study of Sb2Te2,9-SnIz(167),Ti203-V203 (344), Er-Hz (329), and Ge-Te and As-Te (318) systems. Resistivity measurements on highly cross-linked, amorphous, resole-type phenolic polymer showed transitions at -200,349, and 473 K (362). Crystalline polyphenylacetylene disks gave log resistivity plots vs. 1 / T that were a series of straight lines for samples annealed a t different temperatures (155)and pressure (0.41-1.5 kbar) increased the log resistivity of the disks. Dielectric constant measurements were made on CuSO4.5Hz0and NaN03 as a function of temperature (41). The dielectric curve for NaN03 gave a peak a t -165 "C corresponding to the DTA peak a t the same temperature. CuS04.5Hz0,however, gave a stepped curve like that obtained with TG, with the steps occurring essentially a t the transition temperatures observed by TG and DTA. Dielectric measurements were applied to the poly(viny1 alcohol)-toluene system ( 7 ) as was previously mentioned. From dielectric measurements on polybenzoxazole (84)and other reports on dielectric measurements, it was concluded that the temperature of the /3 dielectric relaxation peak, measured a t the same frequency, is strongly dependent on the chemical constitution of the repeat unit; that the apparent activation energy is different from polymer to polymer; that H,O can act as a plasticizer or antiplasticizer for the 8 relaxation and affects the process existing in dry polymer; and that the effect of H20 on the loss maximum intensity differs and the weaker the relaxation phenomenon, the stronger is the effect of H20. In quinoxaline-phenylquinoxaline copolymers, torsional braid analysis was shown (149) to provide more meaningful information to substantiate cross-linking than DSC. The damping peak decreased in intensity and shifted to higher temperatures with cross-linking. A series of bibenzoxazole polymers were characterized by torsional braid analysis (126) where it showed secondary relaxations and flexibilities of fluorocarbon linkages were functions of the structure and position of these linkages. Application of torsional braid analysis and DSC to a series of partially hydrogenated cis1,4-polybutadienes gave evidence that the T of completely amorphous polyethylene would occur in the 1Sb200 K region (79). More publications have appeared on the T > T g transition in polymers: on polystyrene (128) and on styrene block copolymers (125). The relationship of torsion braid measurements to torsional pendulum measurements in epoxy resins has been discussed and it was shown (144) that a multiplicative constant was necessary to bring torsional braid shear modulus into agreement with absolute modulus determined by torsional pendulum. The damping factor was in good agreement by both methods. NH4N03 starts to decompose at 200 "C with the main product being N20,but some N2is produced (338). The yield of N 2 0 goes through a maximum with increase of either time or temperature. In the presence of transition metals, ",NO decomposition rate usually increases, but reaction is shifted toward formation of Nz, especially with Cr and Mn oxides. Quadrupole mass spectrometry was one of several techniques employed t o determine the decomposition steps on heating metal formates (89). A thermal conductivity detection system was employed for evolved gas detection from CY-, 8-, and y-FeOOH (164) and each was found to give marked peaks at 70, 180, and 260 "C. The variation in these peaks was studied
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as a function of aging and Cu(I1) content. Thermal decomposition of copper dimethyl- and diethyl-dithiocarbamates was followed by DTA and TG and the gaseous decomposition products were analyzed by a gas chromatography-mass spectrometry technique (316). For the dimethyl complex, CS2 and tetramethylthiourea were the main decomposition products, but, for the diethyl complex, the main products were CS2 and (C2H4)2N, with tetraethylthiourea as a minor product. A DTA equipment, coupled to commercially available HzO, COS,and SOz detectors, was used for effluent gas analysis of natural mineral mixtures (248). The coupled techniques clarified the often complex sequence of reactions, particularly when applied to a Cambrian shale. The thermal decomposition of Co(II1) ammine complexes at a heating rate of 10-OC intervals (270). These curves, with DTA and TG data, allowed complete interpretation of the decomposition of the complexes. An on-line system for pyrolysis-molecular weight chromatography was developed (188) and was applied to the thermal decomposition of polyethylene, polypropylene, and polyisobutylene (189) and polysulfones and polystyrene (190). Laser pyrolysis of polyethylene, polypropylene, and polystyrene in the presence of NaBH, increased the yield of monomer, with CH4 and CsHs formed by side chain cleavage (354). A laser microprobe-mass analysis technique has been described (219, 220) which indicated HC1, benzene, and toluene are evolved from irradiated poly(viny1 chloride). Decomposition of deuterium-labeled poly(viny1 chloride) indicated that the mechanism of benzene formation involved intramolecular cyclization rather than intermolecular Diels-Alder condensation (269). Dehydrochlorination of poly(viny1 chloride) in Nz a t 190 "C, using a conductometric method, indicated reaction was predominently initiated at sites of internal unsaturation (allylic chlorines), but initiation at tertiary chlorines and unstable end groups could not be discounted (I). A pyrolysissas chromatic method was applied to polystyrenes, reduced poly(viny1 chloride), and precursor poly(viny1chloride) with the pyrolysis products indicating the extent of branching in these systems (9). Pyrrone and POlyimide prepolymers were heated from 25 to 400 "C a t 2 "C/min. and the effluent was sampled by a gas chromatography-mass spectrometry technique at regular intervals (377). Pyrrone polymers were less than 80% converted, while POlyimides were 100%. Significant amounts of C 0 2were evolved, as well as expected HzO, in pyrrone polymer formation. A thermal volatilization analysis of polystyrene, as a function of molecular weight (241), showed a molecular weight dependence of the apparent Arrhenius preexponential factor. Polymer degradation products have been analyzed by thermal volatilization analysis when materials trapped a t -196 "C are allowed to warm up and the volatilization is monitored by a Pirani gauge (223). Pyrolysis-spectrometry for automatic identification of microbes was reviewed (239) and some of the problems associated with the effort were discussed. DSC was applied to Bacillus cereus I F 0 3131 spores (227) and were found to have endothermic peaks at 56, 95, and 103 "C. Perhaps the combination of these techniques would prove more beneficial than the individual methods. Determination of polymer flammability by thermal analysis methods has been reviewed (145) where DSC, TG, and effluent gas analysis were considered, as well as dynamic mechanical analysis for evaluating the effect of a fire retardant on the physical properties of a polymer. The addition of tris(2,3dibromopropy1)phosphate t o cellulose was shown to reduce the number of compounds normally observed in cellulose pyrolysis (120). The plasticizing and fire-proofing of 19 phosphate esters on poly(methy1 methacrylate) and poly(viny1 chloride) have been reported (300),with bromoalkyl chloroalkyl phosphates having the greatest fireproofing effect. TG has shown that effective fire retardants increased the amount of H 2 0 produced and the amount of char in poplar wood (328). Thermolysis in a Wood's metal bath was conducted with four polymer systems, including additives (360). The effects of polymer and additives on Br release from decabromodiphenyl oxide, measured by wet litmus above the system, were correlated with performance in a standard flammability test. A pyrolytic combustion apparatus, operating at 700 or 800 "C, with provision for infrared or gas chromatographic analysis of gases was described (250). It was applied to measurement of the combustion products of polyethylene, polystyrene,
ANALYTICAL CHEMISTRY, VOL. 50, NO.
Nylon 66, polyacrylamide, three polyester type polyurethanes, epoxy, poly(pheny1ene sulfide), urea-formaldehyde resin, melamine-formaldehyde resin, and cedar wood. The thermal oxidative degradation of two aromatic and one segmented polyurethane was studied (171) and a tentative mechanism for HCN formation was presented. I t was shown that evolution of HCN could be inhibited by Cu or its oxide. A review of the open literature for 25 years on the gaseous pyrolysis and thermal degradation of polymers and the toxicity of their emissions has been presented (176). Another government report (212) contains 105 abstracts covering combustion products from plastics and elastomers as related to their chemistry, fire safety, toxic gases, and burning rate. Decomposition of Mg(OH),, coprecipitated with 228Th,was followed by DTA and emanation thermal analysis (292). While both techniques registered peaks a t -390 "C, the flat base line of DTA gave no further information, but the decreasing emanation curve roughly followed that of the specific area and gave insight into product sintering. Density, porosity, surface area, and volatiles content of uranyl gels were related to the data from emanation thermal anal sis (21). The reaction of a-Fe203with 228Th-labeledZ n 8 was studied by emanation thermal analysis (20) where it was shown that reaction started a t 250-400 "C, not recorded by DTA or thermodilatometry. With increased heat treatment of Fe203, reactivity toward ZnO decreased. The technique also has been applied to polymers with success (141). A series of papers emanating from Westinghouse Research Laboratories are renewing interest in thermoparticulate analysis. Calling the technique organic particulate analysis, instrumentation has been described (284). The method has been applied to diazonium compounds (331), metal acetylacetonate chelates (332), and arenesulfonates (178). A reflex-type thermomicroscopy system has been described (202) which incorporates a thermopile for simultaneous DTA. Photomicrographs were taken of single stearic acid that showed the B to C phase change while it was being recorded on DTA. The scope of thermomicroscopy was recently illustrated (222) through presentation of a number of applications. The melting point of m-nitrophenol was investigated by DSC, dilatometry, and hot-stage microscopy (357). With DSC, the technique has been used to detect phase changes in cholesteric monomers (106, 160), liquid crystalline order in polymers with cholesteric side groups (159), and to determine phase diagrams for cholesteric ester systems (266). Mesophases in a series of 4-cyano-4'-alkenyl carboxylate biphenyls were characterized by a polarizing microscope equipped with a programmable heating-cooling stage (97). In the 4-vinylpyridinium salts of vinyl sulfonate, 2-acrylamido-2-methylpropane sulfonate, and p-styrenesulfonate, only the melting points of the first could be determined by thermomicroscopy. The melting points of the other two could only be determined by DSC a t 80 "C/min (315). Phase changes in lithium palmitate were determined by microscopy, DSC, and x-ray diffraction (359) where DSC heats of fusion of 5.0 to 6.3 kcal/mol reflected incomplete crystallization in different samples. The melting behavior of isotactic polypropylene (217 ) and poly(bipheny1 acrylate) (263),have been studied by microscopy. DSC and optical and electron microscopy were employed to determine the phase diagram for the poly(t-capro1actone)-trioxanesystem (372),which had a 314 K eutectic with a polymer volume fraction of 0.70. Hot-stage microscopy, DSC, and wide angle x-ray measurements were used to show that toroidal aggregate formed on high-pressure extrusion of poly(ethy1ene terephthalate) resulted from formation of fibrous crystals (136). A thermomechanical analyzer has been described (234) that will measure expansion over the range -150 to 1500 "C, penetration at -150 to 1000 "C, and elongation under tensile load from -150 to 300 "C. An absolute laser interferometric dilatometer also has been described (35). A dilution dilatometer for measurement of excess volumes was developed (201) using Hg as the working fluid. Bellows displacement measured by a linear variable differential transformer has been used to measure pressure-volume-tem erature relationships of polymers to 350 "C and 2200 kg/cm$ (384). Examination of CsCuCla by DTA, DSC, and dilatometry showed transitions a t 511 K and 538 K (113). With DTA and dielectric measurements, dilatometry showed a 365 f 5 "C transition in Na8Ti501, single crystal (342). The tetragonal-cubic transition
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in leucite at 625 "C was determined by dilatometry, DTA, and x-ray diffraction (150). With x-ray diffraction and DTA, dilatometry was used to study the H f 0 2 ~ T i 0(0-60 2 mol %) system (312),where low expansion coefficients for the 3&40% Ti02were attributed to microcracking. Differential dilatometry was applied to kaolin and the peaks shown were in excellent agreement with those observed by DTA (103). Dilatometry, DTA, TG, and x-ray diffraction were employed to show a series of strontium uranate compounds were formed in the temperature range 1273-1673 K in air (237). The T , of Ca(P0J2 glass was determined from the thermal expansion curve ( 2 ) . It was shown that crystallization of the bulk glass occurred below T and that T , increased with increased heating rate, 0 to 50 "C/min. Liquid crystal phase transitions in p-heptyloxyazoxybenzene was determined by dilatometry (15). The T 's of poly(butene-1-sulfone),poly(cyc1opentene sulfone), poly$bicycloheptene sulfone), and two sulfone terpolymers (72) and poly(ethy1ene terephthalate) (68) have been measured by the technique. The linear coefficient of expansion and Tg'swere measured on a series of styrene-methacrylic acid copolymers, with 0.61 to 9.0 mol % methacrylic acid (105). Experimental data agreed well with WLF theory except for methacrylic acid levels above 6%, where ions are clustered. High pressure dilatometry and DSC were used to establish a phase diagram for polyethylene up to -5000 kg/cm2 (226). Cross-linked polyethylene insulation materials were examined (138) and did not behave normally to permit determination of T . They were found to contract on initial heating, but expancfed on second heating, and melting was detected by a break between linear portions of the curve. The negative thermal expansion coefficients found along the length of ultra oriented polyethylene confirmed the existence of extended chains (62) and a transition in the c-axis expansion coefficient was found a t -45 "C. Isothermal dilatometry measurements were made on poly(vinyl chloride), plasticized with 20 or 40 parts di(2-ethylhexy1)phthalate per 100 parts PVC, to show the effects of annealing a t different temperatures (122). The T of Nylon 6, mixed with 0-7% LiC1, LiBr, and KC1, was unaffected by the type or content of the salt (6). DSC and a thermomechanical analyzer were used to determine the Tg's of a series of polyaramides containing sulfone ether units (70). Differences between T , values amounting to 10 "C were not explained. Because of several inflection points appearing in the thermomechanical curve of poly( 1,3-phenylene isophthalamide) (51), T , was difficult to interpret.
THERMAL ANALYSIS NOMENCLATURE The Nomenclature Committee has been attempting to standardize English nomenclature in the field of thermal analysis for the past 12 years. The following summation has been extracted from Mackenzie's most recent committee report (225). Thermal Analysis is defined as a group of techniques in which a physical property of a substance is measured as a function of temperature while the substance is subjected to a controlled temperature program. Specific techniques, then, are defined by specifying the specific property in this definition. Thermograuimetry specific property measured is mass. Rejected names are thermogravimetric analysis and dynamic thermogravimetric analysis. DeriGatiue Thermograuimetry: specific property is the derivative of mass with respect to temperature. Rejected names are differential thermogravimetry, differential thermogravimetric analysis, and derivative thermogravimetric analysis. Isobaric Mass-Change Determination: specific property is mass at a constant partial pressure of the volatile product(s). Rejected name is dehydration curve. Euolued Gas Detection: specific property is evolution of a gas. Rejected name is effluent gas detection. Evolued Gas Analysis: specific property is the nature and/or amount of volatile products. Rejected names are effluent gas analysis, gas effluent analysis, and thermovaporimetric analysis. Emanation Thermal Analysis: specific property is release of radioactive emanation. Thermoparticulate Analysis: specific property is release of particulate matter. Heating Curve Determination: specific property is the
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temperature. Rejected name is thermal analysis. Differential Thermal Analysis: specific property is temperature difference between sample and reference material. Rejected name is dynamic differential calorimetry. Differential Scanning Calorimetry: specific property is difference in energy inputs into a substance and reference material. Rejected names are differential enthalpic analysis and enthalprography. Thermodilatometry: specific property is dimensions. Linear thermodilatometry and volume thermodilatometry are distinguished on the basis of the dimensions measured. Therrnornechanical Analysis: specific property is deformation under nonoscillatory load. The mode, determined by type of stress applied (compression, tension, torsion, etc.) should always be stated. Dynamic Thermomechanometry: specific property is dynamic modulus and/or damping under oscillatory load. Torsional Braid Analysis is a particular case in which the material is supported on a braid. Thermosonimetry: specific property is sound emitted. Thermoacoustimetry: specific property is characteristics of imposed acoustic waves after passing through a substance. Thermophotometry: specific property is an optical characteristic. Specific characteristics give rise to more specific names: total light-thermophotometry, specific wavelength(s)-thermospectroscopy,refractive index-thermorefractometry, and luminescence-thermoluminscence. Observations under a microscope lead t o thermomicroscopy. Thermoelectrometry: specific property is an electrical characteristic. Resistance, conductance, and capacitance are most commonly used. Thermomagnetrometry: specific property is magnetic susceptibility. The conventions for reporting DTA and TG data were set forth by McAdie (221). The output from DTA and TG are curves, not thermograms. In the DTA curves, the following terms apply: Base Line: that portion of the DTA curve for which AT is approximately zero. Peak: that portion of the DTA curve which departs from, and subsequently returns to, the base line. Endotherm or Endothermal Peak: a peak where the sample temperature falls below that of the reference, Le., S T is negative. Exotherm or Exothermal Peak: a peak where the sample temperature rises above that of the reference, Le., AT is positive. Peak Width: the temperature interval between the points of departure from and return to the base line. Peak Height: the distance, vertical to the temperature or time axis, between the interpolated base line and peak apex. Peak Area: the area enclosed by the peak and the interpolated base line. Extrapolated Onset: the point of intersection of the tangent drawn a t the point of greatest slope on the leading edge of the peak and the extrapolated base line. In TG, the following terms apply: Plateau: that part of the TG curve where the mass is essentially constant. Initial Temperature: that temperature a t which the cumulative weight change reaches a magnitude that the thermobalance can detect. Final Temperature: that temperature a t which the cumulative weight change reaches a maximum. Reaction Znterual: the temperature difference between initial and final temperatures. LITERATURE CITED
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Titrations in Nonaqueous Solvents Byron Kratochvil Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada T6G 2G2
This review covers approximately the literature reported in Chemical Abstracts over the period January 1976 to 0003-2700/78/0350-153R$01.00/0
December 1977. As in the previous review, emphasis is on fundamental developments and methodology, with only a
D 1978 American Chemical Society
