Anal. Chem. 1990, 62. 44R-50R (E114) Blum, L. J.; Oautler, S. M.; Coulet. P. R. Anal. Left. 1988, 27 (5), 717-26. (€115) Karsten, Angellka; Plaschnick, Dieter; Zschuppe, Ingolf; Knabe, Guenter; Ihme, Benrd; Raetzsch, Manfred; Dorschner, Helmut Oer. (fast) 1987, 5 pp. Photographic materials with irradiated geiatln-containing subbing layer. (€116) Abdel-Latif, Monzlr S.; Gullbault, George G. Anal. Chem. 1988, 60 (24), 2671-4. (€117) Wangsa, Julie; Arnold, Mark A. Anal. Chem. 1988. 60(10), 1080-2. (€118) Walters, Bonnie S.; Nielsen, Timothy J.; Arnold, Mark A. Tabnta 1988, 35 (2), 151-5. (E119) Trettnak, Wolfgang; Wolfbeis, Otto S. Fresenius' 2. Anal. Chem. 1989, 334 (5), 427-30. (€120) Junker, B. H.; Wang, D. I. C.; Hatton, T. A. Biotechnol. Bioeng. 1988, 32. 55-83. (€121) Trettnak, Wolfgang; Leiner, Marc J. P.; Wolfbeis, Otto S. Analyst (London) 1988, 773 (lo), 1519-23. (E122) Wolfbeis. Otto S.: Posch. Hermann E. Fresenius' 2. Anal. Chem. ' 1988, 332 (3), 255-7. (€123) (%novesi, Llna; Pedersen, Henrik; Slgei. George H., Jr. R o c . SPIfInt. Soc. Opt. fog. 1989, 990(Chem., Blochem., Environ. Appi. Fibers), 22-8
(€l%)-'Posch, Hermann, E.; Wolfbeis, Otto S. Ml&rochim. Acta 1989, 7 11-2). 41-50.
(€128) Kulp, Thomas J.; Camins, Irene; Angel, Stanley M. Roc. SPIE-lnt. Soc.Opt. fng. 1988, 906 (Opt. Fibers Med. 3). 134-6. (E127) Luo. Shufang; Walt, David R. Anal. chem. 1989, 67 (lo), 1069-72. (€128) Trettnak, Wolfgang; Leiner, Marc J. P.; Wolfbeis, Otto S. Blosensorr, Volume Date 7988 1989, 4 ( l ) , 15-26. (E129) Klalner, Stanley M.; Harrls. J. Milton Proc. SfIf-Int.Soc. opt. fng. 1988, 906 (Opt. Fibers Med. 3). 139-47. (E130) Lowe, Christopher R.; Goldfinch, Michael J. Methods fnzymol. 1988, 737 (Immobilized Enzymes Cells, Pt. D), 338-48. (E1311 Dominguez, 0.D.; Giuliani, J. F. J . Biol. Phys. 1987, 75(4), 75-80. (E1321 Voeiki, K. P.; Opitz, N.; Luebbers, D. W. A&. Exp. hfed. Biol. 1988, 222 (Oxygen Transp. Tissue lo), 199-204. (E133) Albin, G. W.: Horbett, T. A.; Miller, S. R.; Ricker, N. L. J . Controlled 1987, 6 , 267-91. (E134) AbdeCLatif. M. S.; Suleiman, A. A.; Guiibault, G. G. Anal. Left. 1988, 27 (6), 943-51. (E135) Downs, Mark E. A.; Warner, Philip J.; Turner, Antony P. F.; FothergNi, John C. Biomteriels 1988, 9 (I), 66-70. (E136) VanDyke, David A.: Cheng, Hung Yuan Anal. Chem. 1989, 67 (6). 633-6. (E137) Rogers, Kim R.; Valdes, James J.; Eldefrawi, Mohyee E. Anal. Bbchem. 782 (2), 353-9. (E138) Walt, David R.; Luo, Shufang; Munkholm, Christiane Roc. SPIf-Int. Soc. Opt. Eng. 1988, 906 (Opt. Fibers Med. 3), 60-4. (E139) Kruli, Uirich. J.; Brown, R.; Stephen; Safarzadeh-Amiri, A. Roc. S P I f - h t . Soc. Opt. fng. 1988, 906(0pt. Fibers Med. 3), 49-56.
Thermal Analysis D. Dollimore Department of Chemistry and College of Pharmacy, Universi'ty of Toledo, Toledo, Ohio 43623
INTRODUCTION This re ort covers the period in Chemistry Abstracts Thermal ffnalysis (CA Selects) from December 1, 1987, to November 1989. The author admits to a personal bias in the selection of works cited but believes that those mentioned are worth of comment, while in order to keep the review within boun& imposed by the editor some items of merit have been omitted. Those active in the field of thermal analysis (TA)will have been saddened by the deaths of two leading experts in the field, Madame Watelle and Jeno Paulik. The most important event must be the Ninth International Conference on Thermal Analysis, held in Jerusalem, Israel, August 21-25, 1988 (I), and the extra volume entitled TA Highlights (2). This latter volume contains useful workshop reports and plenary lectures on TA education (3), calorimetry in surface science and catalysis (41, kinetics (51, the use of T A in studying organic materials (6), superconducting materials (7), thermometry (81, temperature-dependent factors affecting mechanical and surface roperties of solids (9), treatment of TA data (IO),the , diagnostics use of $A in studyin ancient artifacts ( l l ) and of inorganic materiafs by diffusion structural analysis (12). A conference on compositional analysis by thermogravimetry was published by ASTM (13). Papers presented at the 11th Nordic Symposium on Thermal Analysis and Calorimetry appeared in J. Therm. Anal. (14). Other conference proceedings appearing in Thermochimica Acta include the Vacuum Microbalance Techniques Proceedings 1987 (151,the Eighth Ulm Conference on Calorimetry (16), the issue dedictated to Professor Oswald Kubaschewski (17), and the special issue of invited papers under the title Calorimetry and Thermal Analysis in Chemical Thermodynamics dedicated to Professor Ed ar F. Westurm, Jr. (18). The book by hidmann and Riesen on thermal analysis is arranged in alphabetical form containing terms, methods, and applications (19). The Introduction t o Thermal Analysis by Brown will probably form the text for emergin graduate courses in the subject (20). A more specialist pubfication by Sloan and McGhie deals with the techniques of melt crystallization (21). There is a succinct review on T A b Turi et al. in A Guide to Materials Characterization and Jhemical Analysis (22). The IUPAC has produced updated versions 44 R
B
of books dealing with uantities, Units and Symbols in Physical Chemistry (23, chemical terminology (24), and analytical nomenclature (25), which has a direct bearing on the reporting of TA studies. There have been numerous papers dealing with the application of TA to study ancient artifacts. One can cite as examples, Weidemann's studies with others on terra cotta warriors of the in Dynasty (26) and his Mettler plenary lecture on the su ject (11). A TA investigation of ancient Egyptian mortars showed that the decomposition of the CaC03 content occurred at temperatures dependent u n the the amount of gypsum present (27). According to Liptay number of papers on TA increased from 1827 to 2544 between 1975 and 1987. The largest proportion of these papers used TG as the main technique.
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REACTION KINETICS Reaction kinetics is considered before other topics because 1989 marks the 100th Anniversary of the Arrhenius equation (29). Its introduction met stern opposition from Harcourt and Essen (30). A similar equation to the Arrhenius equation had in fact been introduced by Hood (31)who, however, failed to generalize the use of this relationship. Expressed in present day nomenclature the equation takes the form
Ea In k = In A - -
RT
(where k is the specific reaction rate, .4 is the frequency factor, Ea is the energy of activation, R is the gas constant, and T is the temperature in kelvin). Harc0ul.t and Ewen persistently claimed that the relationship k = cohstant X T"' (where m is ositive) was of general applicability. However, a more usefufvariation was the introduction of the relationship
Ink = B 1 + C l n T -
Ea RT
as a more accurate re resentation of k with temperature which could be cited as inxicating that the Arrhenius equation is
0003-2700/90/0362-44R!$09.50fO 0 1990 American Chemical Society
THERMAL ANALYSIS D. Dollhore received his B.S. (1949). W.D. (1952). and D.Sc. (1976) degrees from London Univeristy. He held a postdoclorate position at Exeier University (1952-1954) and held a faculty appointment at St. Andrews University (1954-1956) before joining me Universily of Salford (1956-1962) where he held a Facuny position as Reader. He has been a Prolessor of ChemiStry at the University Of Toledo since 1962 and holds a similar position in the College 01 Pharmacy at that University and serves in an Adjunct camcity in the Geolmv Deoanment. He is on' the'editorial boa; o f ' Thermochimica % Acta. was the Menler Award Winner in 1979. and was Chairman 01 the Brilish Thermal Methods Croup (1969-1971). He is the author of severaI books and editor of various Conference Proceedings: In 1966 Or. Dolli&re anended the lCTA Conference to receive the DuPOntIlCTA Award in Thermal Analysis. He is President ot a consulting firm dealing with problems in surface science and heat treatment of solids.
/
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only approximate (32, 33). However, many reactions have measurable changes in specific reaction rate over a restricted range of temperature where the Arrhenius approximation is appropriate. This introduction is timely and pertinent here because the spate of studies on nonisothermal kinetics and on solid-state kinetics continues and has opened up questions concerning the applicability of the Arrhenius equation. Too, often, however, the only result of these studies is to quote single values of A and E. There is a need to learn from Arrhenius that the real test of the equation is the plot of In K versus 1/T when the many deviations from the simple Arrhenius relationship becomes recognizable. The Avrami-Erofeev equation -In ( 1 - a) = Kt"
An alternative approach is to use the isoconversional method which represents the results of several non-isothermal tests as
where 8,is the heating rate in the jth test, Tc,and a,(temperature and degree of decomposition) are the coordinates of the ith experimental point on the j t h kinetic curve, F ( a ) is the model of the process, and A and E are the effective Arrhenius parameters. This can be used to calculate E without identification of the reaction model and F(a). Vyazovkin and Lesnikovich (50) suggest that the value of A can be determined from the apparent compensation relationship. While the value of E in isothermal models is largely independent of F ( a ) ,this is not so in nonisothermal kinetics. This is a point that is addressed in some studies both for simple and complex reaction processes 6 - 5 3 ) , There are some problems in the analysis of nonisothermal kinetic data which arise from the particular technique em-. ployed. The use of DTA for this purpose is discussed hy Girgls and Petro (54). However, Kirsh (55) points out that some modification appropriate to the technique of DTA is necessary because the reaction rate may not be proportional to the DTA signal AT. In a review on the kinetics of heterogeneous solid-state decomposition, Reading (58)makes a strong case for the use of constant-rate thermal analysis to establish the Arrhenius parameters.
OTHER PHYSICAL CHEMISTRY STUDIES Edwards and Thompson (57)point out that a plot of vapor pressure versus temperature as log Pversus 1 / T constitutes a phase diagram with the condensed phase in the region above the line and the vapor phase below. They show that a single vaporization experiment with the proper experimental design where a is the fraction decomposed, t is the time, and n an can produce results equivalent to those accumulated from integer becomes more and utilized as one of the common many isothermal TG runs. The method utilized by which equations to be considered in thermal decomposition. This Edwards obtained such data is a Knudsen cell and a torequation is usually derived by consideration of a formal theory sion-effusion method (58). A Knudsen cell-mass spectrometer of nuclei rowth followed by ingestion and overlapping of unit has been used in similar studies by Portman et al. (59). nuclei. Ur%anoviciand Segal(34), however, contend that such The liquid-solid and solid-solid transformations in silver a model leads to equations that are incompatible with the iodide isolated by penetration of the AgI into a porous material Avrami-Erofeev equation. The use of the same model applied were dependent upon the pore structure (60). The lowering tu nonisothermal conditions leads to an integral equation that of the melting point can be used as a method of determining cannot be analytically resolved. This may be a particular the purity of a substance hut the units employed are moles result hut in general the integral of kinetic analysis fail because of impurity, which is not always convenient. The application of an inability to analytically integrate the integral Je.-EIRT of DSC for this purpose is described (61,62). The purity of dT. Comment on this point figures prominently in reviews AIF, has been determined by using the thermal effect of the on the topic of kinetic analysis by nonisothermal methods rhombohedral-cubic phase transformation (63). Earnest has (35-37) where complications in experimental design and used DSC tu investigate the a-6 transition of barium carbnate prehistory of samples are also noted. It does not necessarily (64). DTA/DSC techniques can also be used tu follow changes follow that comparisons between isothermal and nonisothin metal systems (65-69). The DTA/DSC technique's ability ermal studies should show agreement. This was found in to detect and measure transformatlons can he used to constudies based on the dehydration of CuS0,.H20 (38). Koch struct phase diagrams of binary systems (7&72). A thoughtful (39) points out that a computer can he applied to a search discussion on the use of DSC tu determine these binary phase for a model reaction by analysis of TA data using methods diagrams has been presented by Courchinoux et al. (73). The which he compares with chess computer strategies. Reich et method can be adapted by using the high-pressure DTA/DSC al. (40) continue to publish computer-determined kinetic cell to study pressure-induced phases (74). Changes in the parameters from TG curves. Reich has also reported on the base line of the DSC/DTA plots can be used tu determine the use of spreadsheets in thermal analysis (41). Some of the variation in the specific heat with temperature. Flynn and algorithms developed by Reich and Stivala were applied by Levin report on a modification of the method applicable to House et al. with some success to the decomposition of (NH,),CO ,NH,HCO ,and ~ ~ u ~ ~ - [ C O ( N H ~ ) ,(42). C ~ ~ ] Bsheet ~ O ~materials ~ H ~ O (75). Oya (76) deals with adaption of the method to ultrafine particles. Criado et al. find that if the activation energy is known, a The glass transition point in polymeric systems is an imsimple and precise method can be used to determine the portant phenomenon investigated by DTA/DSC. An article reaction mechanism from nonisothermal TA data (43). Other on the detection of conformational disorder by thermal studies set out to use the computer to discriminate among analysis by Wunderlich outlines basic thermodynamics asmechanisms relating to thermal decomposition in the solid sociated with this topic (77). The subject is also discussed state and include attempts tu utilize integral methods (4447). by Sestak (78). The quasi-static method of using the DSC One method employed in isothermal kinetic analysis is the apparatus in a step-heating mode on cooling and warming was use of reduced time. Vyazovkin et al. (48)pursue an earlier used by Claudy et al. (79) to study the glass transition of suggestion of using reduced-temperature plots. Their apglycerol. At temperatures higher than the glass transition plication of these ideas to CaC03 shows that discrimination temperature an exothermic crystallization may he observed. on this hasis is not possible when the decomposition kinetics The kinetic aspects of this process relative to silicate glasses shows more than one mechanism is operating. Another atwas examined by Branda et al. (80). They made a rough tempt (49) at analysis of nonisothermal kinetic data is to estimate from these studies of the ability of the glass to form represent the kinetic expression such that nuclei. There is a diversity of language with respect to this d a / d t = k ( l -@-In ( 1 - a))P phenomena. Research workers have blurred the distinction ANALYTICAL CHEMISTRY. VOL. 62. NO. 12, JUNE 15. 1990
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THERMAL ANALYSIS
between the glassy state and the amorphous state. The identification of a lassy state is considered here to be that of a supercooled fiquid whereas the disordered state in amorphous materials enerally need not result from supercooling from a liquif state. Glasses must therefore be “re arded as a special division of the amorphous state”. ‘here are ap lications of TA methods in surface and colloid chemistry. DfC is used in the determination of water dynamics and ag egate structure in reversed micelles at subzero temperature &).TG has been used to rovide an analysis of com ounds absorbed on solid surfaces &2). A ran e of TG units (ETA,TG, and EGA) were used to study the ackorption of heavy water by sepiolite and palygorskite (83). Gast et al. (84) ap lied gravimetric measurements to describe the oxidation finetics of a Poco graphite in COz at lo00 “C and the determination of specific surface area before and after oxidation.
SUPERCONDUCTING OXIDES AND RELATED STUDIES There are a wide range of articles on the su erconductor YBazCu30,, many of them confirming what is &eady known. A number of reviews are available (7,8588). The typical ceramic route for preparation is by heating a powder mixture, comprised of BaC03, Y203,and CuO (89-91). However, there is always a danger that insufficient mixing will leave the barium carbonate unaffected by the heat treatment. Intimate mixing results in the interaction of the oxides with the barium carbonate and liberation of CO at a much lower temperature than would be recorded for 60, alone. In an alternative synthesis route the barium is present as the superoxide (92, 93). Heatin coprecipitated carbonates has been reported too, again to ac ieve more intimate mixin (941, and similarly synthesis routes via coprecipitated oxafates have been published (95,%). A sol-gel process is possible for preparing the necessary precursors, using oxalic acid and nitrates as starting materials (97). Other sol-gel processes utilize hydrolysis of alkoxides (85) or processing from nitrates or acetates hydrolyzed with aqueous NH3 (98). A preparative route employing citrates has also appeared (99, la)).These methods prepare the product oxide as a powder, which is then compacted and sintered. There is a description of the preparation of YBa2Cu307*as fibers from acetate solution (101). The oxide has also been prepared as a film starting from mixed 2ethylhexanoates of yttrium, barium, and copper (102). On heatin precursor materials various decompositions may be seen o%servable on TG and DTA (85) which are followed finally by erovskite formation with loss of oxy en and loss of CO if I!aCO3 is present. Taking the enera7 formula as YBaz6u30,, the value of x varies accordiing to the partial pressure of oxygen above the sample, which makes TG a useful tool for such investigations (86,103,104). Plots can be made for YBazCusO, of log PO,against 1 / T that are linear, which straddles a phase transition from orthohombic to tetragonal (96). There have been many investi ations of this phase transition which can be studied by D T I and dilatometry and y the atmosphere shown to be reversible at 650 OC by c from nitrogen to oxygen (104, 105).Re uction in hydrogen at 980 “C produces an end roduct of composition YBa CU30 (106) but which is ciemically a mixture of 2Ba6, (1/2)tZo3,and 3Cu. From this reduction experiment the oxygen content in any sample can be calculated. The melting point of BazYCu30 is also a function of the oxygen content as can be shown by h A . There are various attempts utilizing TA methods to provide details of the phase transitions involved, which are complicated by the tendency already noted of the oxygen content to come into equilibrium with the ambient oxy en pressure (107-109). There are also complicatin factors we!n heating of the materials is carried out in humi8 atmospheres or water. Water liberates oxygen with a reduction and decomposition of the solid phase, while CO leads to formation of BaCO (86, 107, 110). The work on the YBazCu30,compound has promoted a host of studies on other related oxide systems (85). OTHER ASPECTS OF INORGANIC
f
potential as routes to more complex oxide systems. An example is the interaction of a-Fe O3 and NaN03 (112). The production of new types of hylrous titanium oxides was claimed by precipitation from TiCl, solution using urea (113). TA was used to characterize vanadium pentoxide/titania (114) and antimony-doped rutile systems (115). A new sol-gel synthesis of barium titanate is described by using barium acetate and titanium(IV) isopro xide (116). Other complex oxides studied by TA include rarium aluminate hydrates (117),lithium niobate (118,119), and ruthenium hydrate and its ability to mediate the oxidation of water (120). The thermal analysis study of AgzC03 has proved to be interesting (121,122). This material seems to be a candidate as an example of the Smith-Tople effect for some other system than dehydration. The Ag&O shows a phase transition followed by decomposition to Ag28, which subsequent1 dissociates to Ag. At low partial pressure of C02 the A formed is amorphous, while at hi h partial pressures of the AgzO formed is crystalline. #he thermal decomposition of oxalates attracts attention. Examples of studies on simple oxalates include sodium oxalate (123) and calcium oxalate (124). Wiedemann et al. (125)used TG to study the formation of whewellite and weddelite by displacement reactions. Thermal analysis has also been used to determine the isotopic ratio of hydrogen and deuterium in heavy water by in situ pyrolysis of calcium oxalate monohydrate (126). There is a report on nickel oxalates doped with traces of other metal ions coauthored by Brian Hall who was attending high school at the time (127). Another paper describes the decom osition kinetics of Zn[Zn(Cz04) ]HzO (128). There is a s t u g of the inhibition of calcium oxafate crystallization by sodium dodecyl sulfate (129). Gimblett et al. (130) record the thermal and related studies of basic Zr carbonate, nitrate, and sulfate. Allen et al. (131) describe, thermal studies on fumaric acid and crotonic acid compounds of Co(I1) and Ni(I1). A series of papers by a group of research workers makes the point that thermal decomposition work utilizing TA techniques needs to be substantiated by microsco y, chemical analysis, NMR measurements, etc. These s t u i e s by Brown, Galwey, and others include detailed kinetic analysis of copper(I1) maleate, copper(I1) fumarate, nickel acetate, nickel malonate, silver squarate, and related materials (132-135). In a study of pyrotechnic systems Griffiths et al. (136) used TA to study systems of Mg with various nitrates. Paulik et al. undertook TA studies of Ni(N03)z (137) and Mg(NO&
8
89,
(138).
A careful and extensive kinetic analysis of the dehydration of Li S04-Hz0is reported (139). It appears that if a-Zr(HPC! ) is refluxed with solutions of Cr(0Ac) TA methods could used to characterize the formation of chromium interlayers in the phosphate (140). Thiel and Seifert (141) have used DTA to study the double chlorides of alkali metals with samarium. Galwey et al. (142) have studied the role of additives in the thermal decomposition of ammonium perchlorate and identified nitryl perchlorate as the essential reaction intermediate. Galwey and Laverty (143) show that the heat treatment of MgCl2.2Hz0produces MgO, HCl, and HzO.
ORGANIC COMPOUNDS AND POLYMERIC MATERIALS In the synthesis and characterization of metal-free and metal derivatives of crown ethers it is found useful to use TA techniques (144). Other studies on complexes are aimed at assessin stability, examples being zirconium(1V) complexes with 8-diketones (145) and monohalogen benzoylhydrazine Ni(I1) complexes (146). DSC was used to determine thermodynamic properties in a study of chiral discrimination in the structures and energetics of association of stereoisomeric salts of mandelic acid with a-phenethylamine, ephedrine, and pseudoephedrine (147). Some studies concentrate on using TA methods to find details of the decomposition route, examples are azobenzene derivatives (148)and nitroguanidine (149). Other studies use established kinetic analysis methods to characterize the decomposition (150). There are studies
CHEMISTRY
The relationship between amorphous and crystalline structures in alloys has been reviewed by Taylor et al. (11I ) . The interaction of oxides with each other or with salts has 46R
ANALYTICAL CHEMISTRY, VOL. 62, NO. 12, JUNE 15, 1990
systems. It finds a use in characterizing products resulting
THERMAL ANALYSIS
from synthesis routes. Typical of this use are the synthesis and characterization of pol (methylene terephthalate) (1551, p l y ( 7 l e n e sulfides) (1561 and poly(urethane ureas) (157). lynn iscusses in detail how to make lifetime predictions for polymers from TA ex eriments (158). McNeil and Barbour (159) follow the pyrohic degradation of Na and Zn salts of ethylene-methacrylic acid co olymers using thermal volatilization analysis. Jabarin andEofgren (160) used TG to show that absorbed moisture effects the thermal degradation of hi h-nitrite barrier polymers. h e purpose of other work on polymers is to use TA to show the effectiveness of fiie retardants. The examples quoted here deal with the treatment of cellulose. There are papers dealing with the kinetics of cellulose decom osition (161). The influence of fine retardants on the celrulose can be measured by various techniques, which include DTA and infrared gas analysis (162). An innovative technique to establish flammability has been to establish characteristic flash ignition temperatures (163). Research continues in the area of elastomers, and as an example one can quote the efforts of Ivan and Danila (164)to prevent O3degradation of tire rubber by waxes. A review on the characterization of the mechanical ro rties of rubbers in the transition zone has been presented y ane et al. (165). A review of the role of thermal analysis in the study of thermoplastic polymers has been performed by Cheng and Wunderlich (166). In the field of epoxy resins the concentration of effort lies in the area of the effect of diluents (167) and the effect on the thermal degradation kinetics (168). There is an industrial application in most cases, thus Prime et al. (169) report that in the manufacture of an epoxy-phenolic magnetic ink, DMA and TG were effective in quality control measurements.
lee
BIOLOGICAL AND PHARMACEUTICAL STUDIES The application of chemical thermodynamics and kinetics to pharmaceutical compounds is discussed by Marti with respect especially to the stability of polymorphic forms of sulfathiazole (170). Heat capacity data on the unfolding of lysozyme in solution has been reported (171). The relationship of the melting behavior of model biomembranes to their thermal history has been achieved by using DSC (172). Battistel et al. (173)have used DSC to show that in a globular protein a single sharp transition occurs which can be attributed to a cooperative unfolding of the protein structure. DSC was also used to make a thermokinetic study of bacterial metabolism (174). It was found also by using DSC that water compartmentalized by networks of gelatin gels or starch gels remained unfrozen when rapidly cooled and crystallized on subsequent warming in small cavities (175). Other applications of TA to biological and pharmaceutical sub'ecta are to end products. There is a study of li sticks by DSb to provide characterization features (176). ?he physicochemical properties and composition of apple and citric pectins and their solutions and gels were determined b using a wide ran e of TA equipment (177). The aging of ge s from starches oPdifferent amylase/am lo ectin content was followed b a kinetic analysis of DJC {ata (178). It was also shown t i a t oat globulin under conditions inducin gelation was not extensively denatured and exhibited highb cooperative transition characteristics (179). Another paper deals with the characteristics of starch networks within nce flour noodles and mungbean starch vermicelli (180). The progressive changea can be followed by DSC (181). The thermogravimetry and pyrolysis of date stones is reported by Al-Badri et al. (182). The application of TA, mainly DSC, to characterize milk and milk products is reported in several publications (183,184). In a study on cocoa butter the crystallization was studied in the presence and absence of sorbitan monostearate (185). The characterization of margarines b thermal weight reduction was followed using TG and DSC!(186).
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MINERALS AND ENERGY RELATED TOPICS A general review of the application of T A to minerals has been resented by Yariv (187). Kinetic data on limestones have L e n determined from TG data and a compensation effect is reported (188). The experiments were repeated in a suspension reactor and the activation energy in air was found
to be less than that obtained from TG experiments. It is reported that V206and fly ash inhibit the calcination rate of CaC03 (189). Dubrawski and Warne used DSC to follow the decom osition of mineral carbonates occurring in coal (190). It has 8,en found convenient to assess free quartz resent in marble by DTA (191). DSC in flowing C02 and ZRD were used to study the dolomite-ferroandolomite-ankerite series of carbonate minerals and it was found that the enthalpy values varied linearly with Fe substitution (192,193). Most TA studies on clays center around the dehydroxylation reaction. TG has been used in a study of the kinetics of this process for kaolinite (194). Gomes and Worrall used DTA in a study concerning the occurrence of dickite in Yorkshire fireclays (195). Yariv et al. (196) studied the adsorption of rhodamine 6G by smectite minerals. Grillet et al. (197) found that sepiolite heated under vacuum underwent changes in surface area and porosity that could be associated with chemical and physical transformations in the material. Some applications of thermal analysis to cement h drates have been reviewed by Bushnell-Watson et al. (198). ?he major interest lies in the determination of the hydration process by estimation of the Ca(OH)2phase (199). TA was used to follow the hydration process for periods up to 3 years for blended cement pastes containing fly ash (200). It was found possible to divide the noneva orable water content into two regions, water held as Ca(Oh), and water held in other reaction products. Abdelrazig et al. (201) used DSC to estimate the degree of hydration in a study designed to investigate the mechanism of accelerators in cement paste. In another study TG was used to investigate the influence of cement chemistry on concrete attack (202). Investigation of pyrite is important when considering hi h sulfur content fuels. There are problems with using $A methods applied to pyrite which necessitate a careful study of ex rimental variables (203). An example of the direct use of Teeand DTA to various coals is to be found in the study by Janikowski and Stenberg (204). Earnest applies these techniques to a detailed examination of single coal seam low-temperature ash components (205). Another aspect of TA applications in this field is to determine combustion efficiency and calcium utilization when coal-limestone mixtures are burned (206). TA methods find extended applications in assessing oils. It is possible to use TG to determine volatile and nonvolatile fractions of kerogen (207).A paper by Agrawal (208) discusses the use of TG to determine compositional analysis of solid waste and refuse-derived fuels. Brown (209) has produced a review of the application of TA to a characterization of energetic materials.
INSTRUMENT DEVELOPMENT AND APPLICATION The use of techni ues for as analysis has become wide-
spread but the methA is u s d y em loyed in conjunction with other TA techniques. A combinerfTG unit with an atmospheric ionization mass spectrometer (APCI-MS) and its use have been described by Dyszel(210). A time of flight mass spectrometer continues to be used to study flame-retardant systems (211). Fragmentation of evolved ases can cause difficulties. The combination of TG and M8 becomes es ecially useful in studying desorption from surfaces (212). &as chromatography is an alternative analysis technqiue and an example that may be cited is the heat treatment of some substituted poly(N-vinylcarbazoles) (213). FT-IRsystems coupled with a TG unit can ulqed to d e F and identify small gaseous molecules and also gwe information regarding the functional roups present in evolved organic species. An integrated #G/FT-IR system is described by Compton et al. (214) which finds application to olymeric systems. Other systems integrating FT-IRwith TG Rave been described (215, 216). A new dilatometer operatin in the tem erature range 25-2000 "C has been described &!17). The cdbration of this kind of experimental equipment has also been published (218). Other reports on calibration and accuracy have been made on the basis of comparison of different units (219) and by careful standardization (220). An example of the application of dilatometry is its use to study lass transition and crystallization of Cu-Zr amorphous ri%bons (221). The use of dynamic mechanical thermal analysis is continually increasing. Wetton and Williams (222)illustrate t h s ANALYTICAL CHEMISTRY, VOL. 62, NO. 12, JUNE 15, 1990
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THERMAL ANALYSIS
point by a detailed study of acrylate copolymer compatibilities with polyepichlorohydrin. Wetton et al. (223) also use this equipment to show that orientation can affect the glass temperature. Grentzer et al. (224) also demonstrate the versatility of the techni ue by reporting on its use in the characterization of sheet mofiing compounds during thickening and curing. Dlubac et al. (225) makes a comparison of the complex dynamic moduli as measured by three different apparatus. Other thermal analysis equipment a pearing in the literature include high-temperature X-ray &fraction techniques (226)and photocalorimeter units for the study of photosensitive materials (227). New DSC equipment continues to be desi ed usually for specific purposes, e.g., high heating and coo& rates (228), high-temperature measurements (229),and measurement of thermal conductivity (230,231). In order to study polymer glasses, Hutchinson et al. (232)found it necessary to offer a method for corrections for thermal lag to be made. Sandu and Singh (233)offer mathematical and physical reasons for the justification of current practice for estimating enthalpy of physical transformations. A high-pressure DTA cell is described by Hiramatsu and Inove (234). There have been design develo ments in the construction of TG balances and an example t a t may be noted is the symmetrical microthermobalance described by Emmerich and Kaiserberger (235).
R
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THERMAL ANALYSIS
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115. (204) Janikowskl, S.; Sterberg, V. I.Fuei 1089, 68, 95. (205) Earnest, C. M. Thernwchim. Acta 1087, 727, 71. (206)Culmo, R. F.; Fyans, R. L. ASTM Spec. Tech. Pubi. 1088, 997(Corn pos. Anal. ThermGravim.) 245. (207)Kramer, R.; Levy, M. Fuel 1988, 68, 702. (208) Agrawai, R. K. ASTM Spec. Tech. Publ. 1088, 997 (Compos. Anal. Thermogravim.) 259. (209) Brown, M. E. Thermochim. Acta 1088 (Published 1989), 748, 521. (210)Dyszel, M. ASTM Spec. Tech. Pubi. 1088, 997(Compos. Anal. Thermogavim.), 135. 1211) Price. D.: Milnes. G. J.: Lukas. C.:PhiiiDS. A. M. J . Ami. ADD/. PMOlvActa 1088, 728, 115. (213) Trebacz, E. Thernwchim. Acta 1089, 743, 51. (214) Compton, D. A. C.; Johnson, D. J.; Mittleman, M. L. Res. D e v . 1080 37. 88. (215)’ Ichimura, K.; Ohta, H.; TaJima, T.; Okino, T. Mikrochim. Acta 1087 (Published 1988), 7 , 157. (216) Wieboit. R. C.: Lowrv. S. R.: Rosenthai, R. J. Mikrochim. Acta 1087 . (Published 1988), 7 . 179. (217) Kaisersberger, E.; Kelly, J. Int. J. Thernwphys. 1080, 70, 505. (218) Henderson, J. E.; Emmerich, W. D.; Wassmer, E. J . Thermal. Anal. 1887. 32. 1905. (219) Taylor, T. J.; Khanna, Y. p. Thennochlm. Acta 1080, 749, 215. (220) Dyer, A.; Saghal. M. A. Thermochim. Acta 1088. 132, 127. (221) Etchessahar, E.; Harmelin, M.; Debulgne, J. Thermochim. Acta 1080, 742, 29. (222) Wetton, R. E.; Williams, P. J. P o r n . Mater. Sci. Eng. 1988, 59, 848. (223) Wetton, R. E.; De Wok, R. Kuntstoffe 1080, 79. 80. (224) Grentzer, T. H.; Gill, P. S.; Sichina, W. J.; Sauerbrunn, S. R. Roc. Japan-US Conf. Compos. Meter, 4th 1988 (Pub l989),458.
ANALYTICAL CHEMISTRY, VOL. 62, NO. 12,JUNE 15, 1990
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Anal. Chem. 1990, 62, 5QR-7QR
Nuclear and Radiochemical Analysis William D. Ehmann,* J. David Robertson, and Steven W. Yates Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055
For our third review under the present title, we have added a coauthor whose expertise will provide added depth to several areas of our review. Welcome aboard Dave! In examining the recent literature, we note that there has been a significant growth in the number of a plications of Rutherford backscatterin spectroscopy (RB ), particle-induced y-ray emission (PIGb), particleinduced X-ray emission (PIXE), and nuclear microprobe techniques. Because PIXE is adequately covered in other reviews, our coverage of this technique will be limited to those applications where it is used simultaneously with nuclear reaction techniques. Similarly, we have chosen not to review research papers dealin solely with health physics, nuclear spectroscopy (unless firectly related to analysis), plasma desorption mass spectrometry, nuclear engineering, fusion, fallout, radioactive waste disposal technology, nuclear and particle physics, radioimmunoassay, Mossbauer spectroscopy,and isotope dilution anal sis with stable enriched isotopes. These topics are covered aiTuately in other reviews. Papers on nuclear dating methods an tracer techniques are often directed toward specific ap lications and are treated only briefly here. However, Table fdoes include references to selected new books and current reviews on many of the above topics in order to guide the reader to other sources of information. The reader should be aware that references to the books and reviews in section A and Table I of this review are not necessarily repeated in later sections which deal with research ublications on specific topics. Finally, in the section entitled kelated Topics we free ourselves of the above restrictions and briefly highlight some nonanalytical topics that we feel may be of general interest to radiochemists. This year’s review is based rimarily on a computerized search of Chemical Abstracts (EA),Index Volumes 108-111, covering the period January 1,1988, to November 1, 1989. Articles appearin late in 1989, or in less widely circulated journals, may not%e included here due to the time required for abstracting. The rimary search term “radiochemical analysis” yielded 631 afstracb, excludin patents. A search based on the term *isotopic dating” profuced an additional 78 references. When ion beam techniques were found to be underrepresented in the CA search, an independent computerized search of the INSPEC (Information Service for Physics and Engineering Communities) database for the same period found approximately 250 publications under the keywords “PIXE” and “ion beam analysis”. Surprisingly, most of the latter were not duplicated in the CA search. In addition to excluding patents, we have also generally excluded agency, laboratory, or industry reporb that do not receive wide circulation, less accessible conference proceedings, and publications in the less common languages. Exceptions are made where the material is unique and not well represented in other ublications. In the latter case, and for all non-English u&ications, Chemical Abstracts or Physics Abstracts (Pi) citations are appended to the references. It should be noted that many pa ers on nuclear methods of analysis are also listed on the &IS (International Nuclear Information System) computerized database, operated by the International Atomic Energy Agency, Box A-1400, Vienna, Austria. The latter database was not searched for this review
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and the degree of overlap with CA and PA is not known to us at this time. We again urge authors to use the keywords “radiochemical analysis” in any list provided to the publishers, since the abstracting services catagorize most nuclear methods of analysis under this phrase. In response to a general request by the Editor of the Fundamental Reviews issue, we have attempted to shorten the review this year. We do not claim that the citations we have included are a complete coverage of the field; however, it is our hope that our selections will provide the readers with pathways to other literature in their fields of interest.
A. BOOKS AND REVIEWS As in our previous reviews, we have separated comprehensive books and reviews from original research contributions. A classified list of these works is presented in Table I (AI-Al29). We are particularly pleased to note that many new books have been published in the fields of nuclear chemist radiochemistry, nuclear methods of analysis, and relaterkubjects. As has been our practice for such special contributions, we will provide a brief summary of the contents of some of these mono aphs. Nuclear fiuironmental Chemical Analysis by J. Tolgyessy and E. H. Klehr ( A I I I ) is a verv useful reference book for scientists who wish to apply radioanalytical methods to the field of environmental science. The first chapter includes a survey of techniques that have been applied to environmental samples. Included are concentration ranges, selectivity, analysis time, a proximate cost, and various specific advantages and disadktages of each method. In Chapter 2, an excellent review is provided of methods of samplin the atmosphere, natural waters, biological samples, and tke lithosphere, with illustrations of many of the most common types of sampling devices. The thiid chapter provides a brief review of reference standards suitable for environmental analyses and advice on preanalysis sampling handling. In the remaining cha ters, the basic rinciples of the various radioanalytical rnet\ods that have {een a plied to environmental samples are discussed. These metfods include direct measurement of natural and man-made radioactivities, isotope dilution analysis, radioreagent (includin radiorelease) methods, nuby scattering absorption clear activation analysis, and and X-ray fluorescence. The final chapter consista of a listing of sources of information that are available on different aspects of environmental chemistry and the analytical techniques employed in the field. The book will be useful to scientist8 in the field of environmental chemistry who wish to evaluate the potential a plications of nuclear methods to analysis and will also provile the radioanalytical chemist with much valuable information on environmental sampling, handling, and storage techniques. Activation Analysis with Charged Particles by C . Vandecasteele (A26)is part of the Ellis Horwood continuing series in analytical chemistry. This rather ex ensive volume is directed to the analytical chemist with lit& or no experience in nuclear methods of analysis. The first three chapters cover
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