Anal. Chem. 1986, 58, 1 R-6 R
Thermal Analysis W. W. Wendlandt Department of Chemistry, University of Houston, Houston, Texas 77004
As in the previous article (150),this review covers the time period in Chemical Abstracts, Thermal Analysis (CA Selects), from about December 1, 1983, to November 1, 1985. An attempt was made to keep the number of citations as small as possible and yet include the impact of thermal analysis studies to chemistry and allied fields. This was difficult because of the large number of publications in this area during the past 2 years. However, by a subjective evaluation process, a list of citations was chosen so that, in the author's opinion, they represented the essence of the work that was published during the above time period. The abbreviations used here conform to the recommendations of the International Confederation for Thermal Analysis (ICTA), except in'the cases where it was a new technique and the name has not yet been approved by this organization. Familiar abbreviations include T G for thermogravimetry, DTA for differential thermal analysis, DSC for differential scanning calorimetry, and EGA for evolved gas analysis. Newer terms are TCA for thermocentrifugometric analysis, TMA for thermomagnetic analysis (not thermomechanical analysis), TCS for thermally stimulated charge, and TVD for thermal voltaic detection. For abbreviations that are questionable, they are defined the first time that they are cited.
THERMOGRAVIMETRY, DIFFERENTIAL THERMAL ANALYSIS, AND DIFFERENTIAL SCANNING CALORIMETRY Biological Materials. Cholesterol and prostatic calculi were studied by TG, DSC, and DTA (26). A relationship was found between the peak area and cholesterol in mixtures of cholesterol and simulated calculi. Cholesterol contents in prostatic calculi determined by DSC were in good agreement with that found by enzymic assay. Diptheria toxin and its enzymically active A fragment were examined by DSC (83). The thermal stability was measured for various forms of these molecules. Twenty-two crystalline neutral amino acids were investigated by DSC (53). There were nine solid-state phase transitions found between 233 and 423 K. Certain of these phase transitions were described for the first time. At high water-to-starch (2:l) ratios, a single DSC endothermic peak was obtained for starch gelatinization (59). As the ratio was decreased, the peak area decreased and the starch developed a .trailing shoulder. The thermally induced unfolding of 60' with a a2-macroglobulin a t pH 7.5 occurred a t T,,, transition enthalpy of 17 J / g (20). A DSC curve for the linear DNA of plasmid pJL3-TB5 gave five separate peaks, including two main peaks in the 82-98' range, suggesting that the DNA melts independently as several cooperative blocks along the chain (96). The effects of p H and milk constituents on denaturation of @-lactoglobulin were investigated by DSC (112). For @lactoglobulin, the apparent reaction order of denaturation was 2.0 over the pH range of 4-9. The thermal denaturation of RNase A in aqueous solution of 2-methyl-2,4-pentanediol (MPD) was investigated by DSC at pH 5.8 (39). A two-state reversible denaturation occurred in aqueous (650%) MPD. Glass transition temperatures of hemicellulose and other materials were measured over a range of moisture contents by DTA (60). Comparison of Tgvs. moisture content curves indicated that the transition was derived essentially from lignin components. DTA of cotton of particle size 0.0094.063 and crystallinity degree 88.10 showed an exothermic reaction beginning at -300' and ending at 400' (54). This exothermic peak was interrupted by an endothermic peak centered at 310'. Fuels. A detailed investigation of the thermal characteristics of six Kentucky bituminous coals was made a t three
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0003-2700/86/03581R$O 1.50/0
different heating rates in an inert atmosphere (34). By use of DSC, the specific heats and enthalpy changes were determined, while T G was used to measure the resultant mass changes. Exothermic reactions from 300 to 550°, where the major mass loss occurs, were associated with the primary carbonization process. A new method, combining T G and thermomagnetometry (TMG), was used for the determination of pyrite content and proximate analysis in coal (4). Comparison of the TMG technique with the ASTM method indicates good agreement and comparable accuracy. A linear relationship was developed between the TG E and AH for coal decomposition (130). Two thermal parameters, initial volatilization temperature, Ti,and average volatilization rate, K,, have been determined by TG in Ar for 38 coal samples ranging from lignite to low-volatile bituminous (81). Ti increases gradually from -250 to 445' with increasing rank; however, a change in slope is observed in the region of high-volatile bituminous coals when Ti is plotted against percent volatile matter or percent fixed C. The gasification of two Turkish lignites was studied by high-pressure DSC under N or H a t 75-600' (19). A T G method was used to obtain a proximate coal or coke analysis in 615 min (149). Results were close to those obtained by the BS 1016 method. Some Australian oil shales were studied in 0 by T G and DTG to obtain kerogens oxidation profiles (90). EGA curves were also obtained by following the increase in optical absorption of IR bands of gaseous species evolved during heating. DTA was used to correlate the shale grade, gas composition, and particle size of an oil shale (87). Increasing the shale particle size affects the exothermic peaks. Volatile matter evolution and the kinetics of thermal decomposition of British Kimmeridge Clay oil shale were investigated by TG (159). The relationship oil yield (g/kg) = (TG volatiles, %
X
5.82) - 28.1 f 14.5 g/kg
was found to apply. Several simple carbonate minerals found in coal and oil shale decomposed at 6400' in air (148). These are siderite, rhodochrosite, and magnesite, the decomposition temperatures of which are lowered or raised (compared with air) in N or C02, respectively. In relation to petroleum recovery by in situ combustion of crude oil, the effects of sand, SO2,and kaolinite were studied by T G and DSC (147). Three regions, one distillation and two combustion cracking, were observed on all curves. A residue from a solvent coal liquifaction process and a residue from coal hydrogenation were studied by TG, DSC, and TMA (32). The volatile, fixed C, and ash contents were determined. DSC was used to obtain liquid heat capacities of coal liquids at high temperature (104). Measurements were made up to 530 'F on some of the compounds. A measurement technique, based on high-pressure DSC, was used to characterize the oxidation stability of liquid fuels under various conditions (24). The technique was sensitive to the chemical composition of shale-derived jet fuel and a marine diesel fuel. By use of DTG, the pyrolysis and oxidation of some heavy fuel oils and their separate paraffinic, aromatic, polar, and asphaltene fractions were studied (21). The thermal behavior of fuel oil can be interpreted in terms of a low-temperature (240°. F-containing ordered copolyamides were repared and studied by T G (97). Thermal decomposition egan a t 633-663 K with the compounds containing parasubstituted benzene rings the most stable. DSC was used to determine the time, temperature, and degree of curve for optimization of production conditions and setting quality control criteria for vinyl ester resins (25). The oxidation induction times of natural rubber stabilized by various antioxidants were measured by DSC (49). Various Arrhenius plots could he superimposed to form a single plot using a shift factor dependent on the oxidation peak tem-
E
MeOzC IV
lymorphism of semisynthetic Witepsol glyceride suppository were examined by DTA (139). On molten mass rooling, hard fat crystallizes in the a-or 8'-modification, depending on the solidification temperature. The effect of water vapor on the stability of ground mixture of nine crystalline drugs and manni-th microcrystalline cellulose was studied under
L
Me V
R
I1
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ANALYTICAL CHEMISTRY, VOL. 58. NO. 5. APRIL 1986
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THERMAL ANALYSIS
perature. The T15of rubber, as determined by TG, depends on the kind of carbon black and not on the kind of rubber or on the length (>1h) of HNO, treatment (162). Vulcanization of powdered rubber, obtained from scrap tires, by 2% S was a first-order reaction with an E of 106 kJ/mol, as determined by DSC ( 2 ) . Reaction Kinetics. 'I'he relationship 1 1 .- LY, = 1.062-nl-n well-known in nonisothermal kinetics and applied for the determination of the kinetic exponent n, is not universal (50). A more accurate modification of the equation is 1 - cr, = p(n,X,) where X, = E/KT,, the dimensionless Arrhenius criterion. An iteration method was presented where values of E and n are obtained concurrently by means of a computer, employing a previously reported criterion and a single DTA curve (122). A new method was proposed in which DTA is carried out under pseudoisothermal conditions, in which sample and reference materials are not heated and the temperature remains as isothermal as possible (100). The hydrolysis of acetic anhydride was used as the model of simple reaction for this method. The two-variable linear correlation method leads to values of the kinetic constants for which the difference between the calculated and measured values is comparable to or greater than the measurement precision (135). A detailed analysis of the merits and shortcomings of integral methods for the treatment of constant heating rate, nonisothermal kinetic data was presented (70). A computer program was developed for the numerical integration of the n-order isothermal unimolecular decomposition rate expressions, d a l d t = K ( l .-a)" to obtain values of LY (the degree of conversion) (123). An attempt was made to clarify some kinetic aspects of the use of a in rate equations, the fundamental relations describing nonisothermal reaction kinetics, and other problems (11). A generalization was given for the conversion function for first-order kinetics to make the method of Marotta et al. (1982) for extracting kinetic information from derivative DTA curves applicable for any kinetic decomposition law (117). A critical assessment of the so-called peak temperature methods, as proposed by Kissinger, was presented (94). It is argued that Kissinger's assumption, although not valid for DTA, holds for DSC. The only way to use kinetic parameters obtained from nonisothermal experimental data to describe both iso- and anisothermal kinetics is to take the same reaction rate equation for the two kinetics, as previously done by Henderson (1979). A novel procedure was presented for the discrimination of kinetic models and evaluation of kinetic parameters from TG data (125). The advantages of the method are that it is relatively simple to use and it permits the user to determine whether the data deviate from the kinetic model.
ELECTRICAL METHODS (NH,),(Mo~O~~).~H,O was studied by thermally stimulated charge (TSC), UTA, permittivity, and dielectric loss measurements at 113--300K (143). TSC resulted in a homocharge release with discontinuity in the vicinity of 200 K. DTA indicated an endothermic peak at 260 f 4 K. Powdered kirgiz coal samples were studied by dielectric constant (E)with temperature, d t l d t - t , and D'I'G (31). These methods gave results similar to those obtained by DTA and TG. Phase transitions in ferroelectric Rb,ZnCl, crystals were examined by dielectric measurements and DTA from -120 to 100' (35). DTA, electrical resistivity, and magnetization of Co,Cul,s (x = 0.5) showed anomalies at 950' indicating a transition from a less conductive state to a more conductive one (93). Galvanic cells of the type, (C + Cl,)(NaCl(s))(MCl,s))(MCl~(s))(C+ C121, give emfs > 280', which are due to the formation of ternary chlorides, Na,MCl,+, (128). The thermoelectrometry techniques of electrical conductivity, dielectric constant, thermovoltaic detection (TVD), and others were reviewed (151, 152).
EVOLVED GAS ANALYSIS SBK. rubber was identified by use of TG-atmospheric pressure chemical ionization MS (30). The molecular ions of 4R
ANALYTICAL CHEMISTRY, VOL. 58, NO. 5, APRIL 1986
54 for butadiene and 104 for styrene increased in intensity as pyrolysis took place. TG-EGA was used as a new, rapid, and precise analytical method for the determination of the Ago, AgzO, Ag, and AgzC03contents of Ag oxide cathodes (113). TG-MS was used to study the decomposition of M(CO), (M = Cr, Mo, W), M2(CO)lo(M = Mr, Re), Fe(COI9, C O ~ ( C O M3(C0)12 )~, (M = Fe, Ru, Os), M4(C0II2(M = Co, Rh, Ir), and Rh6(CO)16(36). Mass spectrometry, coupled with the T A techniques of DTA or TG, was used to study the thermal properties of cellulose (52),gas flame coal ( l o g ) , multicomponent systems (64),and the metal complexes with acetoacetanilides (72). An orifice system was described for coupling a simultaneous TG-DTA system with a quadrupole MS, for measuring quantitatively the vapor pressures of Se, Te, Pd, Ag, etc., up to 1200' (68). A system that was previously used for TA-MS was extended to include GC MS (163). The separation ability of the GC offers tremen ous advantage for analyzing complex gaseous mixtures. An apparatus was described for thermo-gas-titrimetric (TGT) as a unit of the equipment for simultaneous TG-DTA-EGA (derivatograph) (115). A simple TPD-MS device, which operates in a flow of He at normal pressure, was described (10). Quantitative calibration was obtained by a number of organic and inorganic substances. The application of emanation thermal analvsis (ETA) to the studv of ceramic sintering was described (6). Examples included T h o z at 660-850' and a-Fez03at 110-1200'. Fourier-transform IR (FT-IR-EGA) applications to EGA were described in detail (89). Atmlications to Dolvmers (101) and the decomposition of tobacco (5) were described.
d
MISCELLANEOUS METHODS The use of 'H NMR thermal scanning to study the behavior of coals pyrolyzed at atmospheric pressure while the sample is continuously flushed with N was reported (95). The results of the pyrolysis experiments on certain coals were used to illustrate the 'H NMR thermal scanning method. A new TG technique, called thermocentrifugometric analysis (TCA), was reported (88). The reacting solid is rotated at high speed; the rotation provides a strong centrifugal field in which the changing mass of the solid can be continuously monitored. Simultaneous DSCsmall angle X-ray scattering was described using a high flux afforded by a storage ring of a synchrotron, a linear positron-sensitive detector with rapid response time, and a DSC developed for optical microscopy (126). Coupled TG-colorimetric titration technique was described for compositional analysis of polymers (19). The apparatus uses a microprocessor-controlled titrator equipped with a dipping probe colorimeter. The detection of charge storage and charge decay processes in polyethylene electrets by means of thermally stimulated discharge (TSD) techniques alone is apparently limited by deficiencies in resolving power and reproducibility (119). Thermosonimetry was used to study a high SiO, content (-96%) Elkem Micro-Silica (56). A thermomagnetic analysis (TMA) apparatus was used to follow reactions under controlled conditions of temperature and pressure using the Faraday method (138). Relations giving the conversion degree yx a t a given time t as a function of sample susceptibility x were presented. An apparatus based on monitoring the time necessary for a finite change of a property (e.g., mass, volume, etc.) of the converted sample, the property being a linear function of the sample mass, was described (40). The identification of minerals by observing the changes in photoacoustic spectra on heating was examined for Fe oxides and oxyhydroxides, carbonates, and silicates (23). The near-IR region of the photoacoustic spectra of minerals is dominated by OH.
OPTICAL METHODS The thermal performance of a polymer can be characterized by a combination of the TA techniques of thermomicroscopy and thermophotometry, or thermomicrophotometry (TMP) (121). T M P can record slow and fast phase changes and monitor isothermal and nonisothermal processes and subtle thermal changes. Purity determinations can be carried out by DSC and simultaneous DSC-thermomicroscopy (156). A fast Fourier transformation technique (FFT)has been applied to the reconstruction of thermoluminescence (TL) curves (111). Eprozional.BHC1 (Brovel) (VII) was characterized by DSC, thermomicroscopy, and other techniques (108). VI1
THERMAL ANALYSIS
exists in three polymorph forms: I, mp 383'; 11, transition point 220'; and 111, mp 225'.
nNCH2CHzCHPhOH. HCi
MeOCHPhCH2N
I_/
vrr Reversible thermochroism in Bi203-containingborate glasses was studied by investigating the optical absorption at different wavelengths as a function of temperature, the microstructure, and the possibility of mass loss (129). The two polymorphs of khellin (VIII) were studied by hot stage microscopy, DTA, and other techniques ( I ) . Form I1 is a metastable form and 0 Me
OMe VI11
is transformed to form I either by heating or by suspending in water. Thermophotometry was used to show that selected guanidine salts exhibit light emission during their thermal decomposition reactions (153). This light emission is not due to oxyluminescence but is more like the light emission behavior of certain coordination compounds.
THERMOMECHANICAL METHODS TMA was used to study the effect of modification of urea-HCHO copolymers with caprolactam wastes on the adhesive and physicomechanical properties of particle boards (144). A TA method was developed for dynamic mechanical testing of thermosets that involve modification of the clamps of the instrument (51). An original system of DMA in the three points flexure made with a low-frequency oscillatory load was described (16). This technique is claimed to be more informative than DSC and more sensitive than TMA methods. The thermomechanical properties of a new series of precision casting molding sands based on a high-strength gypsum binder and various SiOz fillers (cristobalite, quartz, and mashalite), with and without portland cement, were studied by dilatometry (116). DMA always gives rapid qualitative characterization of multiphase polymer composites (42). The technique detects the occurrence of phase separation via observations of relaxation processes characteristic of each phase and hence is very sensitive. TMA-DTA curves were detected for polyethylene, mol wt 1.5 X lo6,after heat treatment (91). Reaction products were analyzed by pulsed TMA at different stages of the radiochemical curing of an unsaturated polyester (65). The change in T,during curing was studied also. The values of T and melt temperatures of nylon 12 films derived from the $MA curves showed nonlinear dependence on the applied stress (127). DMA and other TA techniques were used to study the structure-property relationships of polyurethane zwitterionomers and anionomers (136). Increased ionic content improved the tensile properties of the zwitterionomers and the thermal behavior of the anionomers. Recent developments in the Du Pont DMA used in conjunction with the Du Pont 1090 system were presented (45).
ACKNOWLEDGMENT The partial financial support of this work by the Robert A. Welch Foundation of Houston, TX, is gratefully acknowledged. LITERATURE CITED
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Raman Spectroscopy Donald L. Gerrard* and Heather J. Bowley BP Research Centre, Chertsey Road, Sunbury-on- Thames, Middlesex, England
The period of this review is from late 1983 to late 1985. During this time over 5000 papers have appeared in the scientific literature dealing with many applications of Raman spectroscopy and extending its use to several new areas of study. This large number of publications includes the proceedings of the 9th International Conference on Raman Spectroscopy held in Tokyo, Japan, in 1984 (1). As is usual with this type of review it is necessary to be highly selective in collecting material that has direct relevance to analytical chemistry. Where a topic has produced a considerable number of papers with a relatively low proportion of analytical interest, the appropriate reviews have been included to which the 6R
reader is referred for a more complete background. Many reviews on the general applicability of Raman spectroscopy have appeared (2-4)and it is particularly interesting to note that the technique is at last becoming more widely used as an industrial analytical method ( 5 ) . Reviews inclusion compounds have also appeared on zeolite studies (6), (7), Raman intensities (a), heterocyclic compounds (9), structural and conformational problems (IO), and combustion diagnostics (11). As in the previous review in this series (12) most of the applications relevant to solids are covered in one or other of the ten categories, which are the same as those used previously.
0003-2700/86/0358-6R$O 1.5010 0 1986 American Chemical Society
