Anal. Chem. 1988. 60. 90R-106R (23) Andrews, S. B.; Mazurklewicz, J. E.; Kirk, R. 0. "The distribution of Intracellular ions in the avian salt gland". J. Cell Biol. 1983, 9 6 , 1389-1 399. (24) Sexton. W. Computer Techniques for Image Processing in Nectron Microscopy; Academic: New York, 1978. (25) Fiori, C. E.; Gotien, K. E.; Gibson, C. C. "Comments on the computerization of an analytical electron microscope". Proc, 39th Annual EMSA Meetlng (Chitors Publishing, Baton Rouge, LA, 1981) pp 246-249. (26) Zubin, J.; Wiggens, J. Rev. Sci. Instrum. 1980, 51, 123. (27) Strahm, M.; Butler, J. 37th Ann. R o c . Elect. Microsc. SOC.Am. 1979. 598. (28) Strahm, M.; Butler, J. H. "Fast Digital Data Acquisition and on-line Processing System for an HB5 Scanning Transmission Electron Microscope". Rev. Sci. Instrum. 1081, 52(6); 840-848. (29) Leapman, R. D.; Fiori, C. E.; Gorien. K. E. "Elemental Imaging by EELS an EDXS in the Analytical Electron Microscope: It's Relevance to Trace Element Research". 6bi. Trace Element Res. 1986. (30) Leapman, R. D. Electron Microscopy in Medical Research and Diagnosis-Present and Future Directions: Electron Energy Loss Spectroscopy". J. Electron Micros. Tech. 1988, 4 , 95-101. (31) Leapman, I?.D. "Quantitative Electron Energy Loss Spectroscopy and Elemental Mapping in Biology". Microbeam Analysis ; San Francisco Press: San Francisco, CA, 1986; pp 187-192. (32) Leapman, R. D. "STEM Elemental Mapping by Electron Energy Loss Spectroscopy". Ann. N.Y . Acad. Scl. 1986, 483, 326-338. (33) Leapman, R. D.; Fiori, C. E.; Gorien, K. E.; Gibson, C. C.; Swyt, C. R. "Combined Elemental and Structural Imaging in a Computer Controlled Analytical Electron Microscope". Ultramicroscopy 1884, 12, 281-292. (34) Kowarski, D. "Intelligent interface for a microprocessor controlled scanning transmission electron microscope with X-ray imaging". J. Nec tron Microsc. Tech. 1084, I , 175-184. (35) Gorien, K. E., Barden, L. K., Dei Priore, J. S., Fiori, C. E., Gibson, C. C., and Leapman, R. D. "A Computerlzed Analyticai Electron Microscope for Elemental Imaging". Rev. Sci. Instrum. 1984, 55, 912-921. (36) Fiori, C. E.; Leapman, R. D.; Swyt, C. R.; Andrews, S. B. "Quantitative X-Ray Mapping of Biological Cryosections". Ultramicroscopy 1988, 24, 237-250.
(37) Goidstein, J. I.; Newbury, D. E.; Echiin, P.; Joy, D. C.; Fiori, C. E.: Lifshin, E. Scanning Electron Microscopy and X-Ray Mlcroanalysls: A Text for Siologists, Materials Sclentlsts, and oeologists; Plenum: New York, 1981; 873 pp. (38) Legge G. J. F.; Hammond, I."Total quantltative recording of elemental maps and spectra with a scanning microprobe". J. Microsc. 1979, 117, 20 1-2 10. (39) Statham, P. J. "A Comparative Study of Techniques for Quantitative Analysis of the x-ray Spectra Obtained with a Si(Li) Detector". X-Ray Spectrosc. 1976, 5 , 16-28. (40) Somiyo, A. P. "Compositional mapping in biology: x-rays and electrons". J. Ultrastruct. Res. 1084, 88, 135-142. (41) Newbury, D. E.; Joy, D. C.; Echiin, P.; Fiori, C. E.; Goldstein, J. I.Advanced Scanning Electron Mlcroscopy and Microanalysis, Plenum: New York, 1986; 454 pp. (42) Leapman, R. D.; Fiori, C. E.; Swyt, C. R. "Mass thickness determination by electron energy loss for quantitathre x-ray microanalysis in biology", J. Microsc. 1984, 133, 239-253. (43) Leapman, R. D.; Fiori, C. E.; Swyt, C. R. "Mass Thickness by Inelastic Scattering in Microanalysis of Organic Samples". Analytical Nectron Microscopy, Williams, D. B., Joy, D. C., Eds.; San Francisco Press: San Francisco, CA, 1984; pp 83-88. (44) Kitazawa, T.; Shuman, H.; Somlyo, A. P. "Quantitative electron probe analysis: problems and solutions". Ultramicroscopy 1083, 11, 251-262. (45) Shuman, H.; Somlyo, A. V.; Somiyo, A. P. "Quantitatlve electron probe microanalysis of biological thin sections: methods and validity". Ulhamlcroscopy 1976, 1 , 317-339. (46) Goldstein, J. I.; Williams, D. B.; Cliff, G. "Quantitative x-ray analysis". I n Principles of Analyfical Nectron Microscopy; Joy, D. C. Romig, A. D., Goidstein. J. I., Eds.; Plenum: New York, 1986; Chapter 5. (47) Hail, T. A.; Gupta, 8. L. "EDS quantitation and application to biology". I n Principles of Analytlcal Electron Microscopy; Joy, D.C., Romig, A. D.. Eds., Plenum: New York. 1986; Chapter 6. Goidstein, J. I., (48) Pratt, W. K. Digltal Image Processing; Why-Interscience; New York, 1978. (49) Gonzaiez. R. C.; Wintz, P. Digltal Image Processing; Addison-Wesley: Reading, MA, 1977.
Mossbauer Spectroscopy John G. Stevens* Department of Chemistry, University of North Carolina at Asheville, Asheville, North Carolina 28804-3299
Lawrence H. Bowen Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204
Katherine M. Whatley Department of Physics, University of North Carolina at Asheville, Asheville, North Carolina 28804-3299
The first review of Mossbauer spectroscopy that appeared as part of the Analytical Chemistry fundamental review was published in 1966 making the current review the 12th in the series. The last nine of these have used the facilities of the Mossbauer Effect Data Center. Papers that are included in the current review are those papers that have been received and surveyed by the data center since the last review (1). Papers that are included in the review are mostly from 1985-1987. During the last two years approximately 2500 papers on Mossbauer spectroscopy have been processed by the data center. It is from this compilation of 2500 papers that approximately 300 papers were selected to be in this review. The process for identifying the papers to be used in the review is most difficult. Certainly, the selection process leans toward the individual interests of the three of us. But despite this difficulty, the review represents a good summary of what has been happening in the field of Mossbauer spectroscopy during the past two years. The extensive proceedings of three conferences have been published. The proceedings of the International Conference 90 R
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on the Applications of the Mossbauer Effect that was held in Alma-Ata, USSR,in September of 1983 have been published as a four-volume wries. Included in it are over 400 short papers and 17 longer invited papers. Topic3 that were covered in the conference and proceedings include the application of the Mossbauer effect in magnetism, chemistry, and material science (2). The proceedings of the International Conference on the Applications of the Mossbauer Effect that was held in Leuven, Belgium, September of 1985, were published as three volumes in the journal Hyperfine Interactions. The proceedings include over 20 invited talks in addition to several hundred shorter papers. Topics of the conference included noncrystalline materials, magnetism electronic structures, metals and alloys, mineralogy, radiation damage, dilute systems, lattice dynamics, biological systems, applications in industry, and developments in theory and experiment (3). The third major proceedings publication was that of the Symposium on the Industrial Applications of the Mossbauer Effect that was held in Honolulu, HI, in December 1984. This volume contains 42 chapters on a variety of topics related to 0 1988 American Chemical Society
MOSSBAUER SPECTROSCOPY
JOm Q. Slovens b R d e ~ 01 ~ Chsmisby n at me University 01 Nwlh Carollna at Ashe vlile and was name4 Feldman RotIn 1984. m recshw his B.S. ( 1 9 ~w ) e e in cheml61v and W.D. (1969) in physical chemiswy hom me Nwth Carolina State University. He spent three Summers at Arwnne National Laboral-. a leave of a b
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..I, and ns appiicawn to me stw of antimony compaunjs and wed clay mat&k. HIS a+ i dnional interests are with problems 01 evaluation and disseminatbn or sc~entltlc data and information. He Is the director 01 the M6ssLmuer Eflect Data Center and medk Msbeuer EHBct Reference and Data &-I. He k on me executive board 01 me internationai Commission tar ~ppiicatlonsa i the M6ssPbawr EHect (KAME) and an the edltorlal boards 01 Hyperfine Inferacllons. Megnetlc Re~onance Review, and CRC Handbook of Spechorcopy. He is a member 01 me American Chemical Society. AmerC can Physical Society. and Sigma xi. H. BOWHI is Fmlaswr d C h e m at Nlxm Carolina State University. He received hb 0.5. horn Virginla Miiltary Insfflute in 1956 and me Ph.D. in physical W s B e c h M s institute chemism horn of Tecmolos, h 1961. He has been on Me lacuity at North Carolina State University slnce September 1961. His research interests currently are the application 01 Mossbawn spemoscopy as a" analvticai technique In soil minerabgl and me study 01 magnetic properties 01 SUbStltVted Iron oxides and related compounds. He was on SBbLmtlCBi leave dwlng the tail of 1987 at me Labaatwy 01 Magnetism 01 me State University 01 Gent. Belgium. He 1s a memiber of the American Chemical Society. American Physical Society. and Sigma Xi.
La-
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KaIhdne Y. WhaUmy 1s Assistant Roles sor 01 mysb at me university d NO& Cermna at AshsvRe. She received ha B.S. Wee in PhVslcD h m Wake Fw& university in 1977 and me W.D. in nuclear physics hcm Duke University In 1982. She has been On the laculty st the University 01 Nwth Carollna a1 AshevM since A q w t of 1982. Her research interests Include t.%sbauer studies 01 tdiwium compounds and pOnety. she 18 a member 01 me American Wyslcal Soclety and Sigma XI.
the industrial applications of the Mdsbauer effect. Some of the general topics included in this volume are steel, amorphous alloys, coal, minerals, and catalysts ( 4 ) . In addition to these proceedings, three books on M h b a u e r spectroscopy have been published. These include the second volume of M6ssbauer Spectroscopy A p p l i ~ dto Inorganic Chemiatrv, edited by G. J. Laog (5). It contains 12 chapters on a variety of topics of interest in inorganic chemistry. These include ion implantation Mossbauer effect studies (H.de Waard and L. Kiesen), Mosshauer effect studies of microcrystalline materials 6.Morup), Mosshauer spectroscopy of mixed-valent compounds (H.Eckert). Mmshauer effect studies on low dimensional magnetic solids (M. F. Thomas), chemical influence on supertransferred hvperfine fields (F. Grandjean), Mmshauer spertrnscopy of reduced ferritin (R.B. Frankel), Mussbauer effect studies of metallic glasses ( G . I.onporth), "YTe Mossbauer spectroscopy in the characterization of tellurium compounds IF.J. Berry). Mosshatier spectroscopv with iodine isompes iR. V. P&h), Mosshauer spectrosropic studies of compounds of 5d transition metals (A. F. Williams), Mhshauer effect studies of actinides tR. D. Dunlap), and iron oxides and oxyhydmxiden (E. Murad and J. H. Johnston,. ' h e other IWO books are a genrral treatment of Mossbauer spectroscopy. The smaller of the two puhlications 1119 pages, is titled Miisshauer Speclroscop? and Its App/lrations and is witten hy T. E. Cranshaw. R. W. Dale. C . 0. Longworth, and
C. E. Johnson (6). The book contains 13 chapters. Most of them are short and generally written on various application areas of Mksbauer spectroscopy. Examples are applications to chemistry, applications to magnetism, and applications to surface science. The other volume is much more extensive and is titled MOssbauer Spectroscopy, edited by D. P. E. Dickson and F. J. Berry (7). The book contains six chapters. They are titled as follows: 'Principles of Mossbauer Spectroscopy" (D. P. E. Dickson and F. J. Berry), "Mksbauer Spectroscopy and the Chemical Bond" (R. V. Parish), "M&sbauer Spectroscopy as a Structural Probe" (G.J. Long), "Mkshauer Spectroscopy of Magnetic Solids" (M. F. Thomas and C. E. Johnson), "Time-Dependent Effects and Relavation in Mossbauer Spectroscopy" (S. Dattagupta), and the 'Dynamics of Nuclei Studied by Mossbauer Spectroscopy" (E. R. Bauminger and I. Nowik). We noted in our review of two years ago that the most active area of application of Mossbauer spectroscopy was the study of amorphous materials. Since then the use of Mossbauer spectroscopy to study amorphous substances has increased almost twofold, making it by far the most active area of Mossbauer research with close to 400 papers being published during the last two years. Other topics in which there have heen over a hundred papers published during the same time are the studies of minerals (including soils and meteorites) although it should be noted that the activity in this area is noticeably less than what is has been in previous years. Another area that continues to receive a lot of attention is the application of the Mossbauer effect to the study of catalysts in which there also have been over a hundred papers published during the last two years. Areas that show increased interest are the investigation of semiconductors, steels, and defects in materials. The study of high-temperature superconductors by the Mossbauer effect has been of recent great interest and is reported elsewhere in this review. The instrumental technique that has shown the widest increase is conversion electron Mosshauer spectroscopy (CEMS) in which there have been over 200 studies using the CEMS geometry. There also has been an increased interest in various kinds of scattering experiments, the use of synchrotron radiation, and irradiation experiments. A general increased interest in Mosshauer instrumentation is noted and is primarily due to advances that are being made in the computer technology of interfacing and the use of computers throughout the different parts of the instrumentation. There also has been an increased interest in the kinds of detectors used in Miisshauer spectroscopy. The only major area in which there has been a decreased interest, in addition to that of minerals, has been relaxation studies. The favorite isotope in Mossbauer spectroscopy continues to be S7Fe. I t has become by far the most common isotope not only because of the relative ease in doing the experiment but also because of the abundance of problems in this area that can be studied hy using Mossbauer spectroscopy. In more recent times, it has become increasingly difficult to obtain commercial sources for the other isotopes. For example, even in the case of the second most popular Mosshauer isotope, %n, there is currently only one commercial supplier for this particular radioactive isotope in the West. Almost none of the other Mosshauer isotopes are available commercially and must he obtained through special laboratory procedures. In spite of the difficulty in the experiments and the additional difficulty of obtaining sources, there have been over 200 publications in which the Mosshauer isotope was neither 57Fe nor i19Sn. The most popular isotope after i19Sn is I5'Eu with the next three most popular isotopes being Iz1Sb,Iz9I,and "Te. In each of these three cases there have been 30 or more publications. Other isotopes in which there have been more than 10 uhlications are, in descending order of popularity, 237Np,I 8Au, I6'Dy, 67Zn,and lS5Cd, We noted 4 years ago in our review the developing interest in Mossbauer spectrnscopy in China. During the last two years we have seen the results of that interest grow substantially. Approximately 200 papers have been published recently in China on Mossbauer spectroscopy. Many of these papers, however, are written in Chinese, although more and more of them are being written in English. A general book on Mossbauer spectroscopy has been written by Hsia, Ye, and Zhang, titled Mossbauer Effect and Its Application (8).The more than 400-page hook contains over 10 chapters. In a recent Chinese review Cheng (9)summarizes the applications ANALYTICAL CHEMISTRY. VOL. 60. NO. 12. JUNE 15, 1988
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of the Miissbauer effect in frozen solutions. In another review Y. Hsia (10) looks a t the recent develo ments and achievementa in Miissbauer spectroscopy by hinese scientists. Over the years we have been expecting a decrease in the number of reviews on Mbssbauer spectroscopy, but we have received over 150 reviews during the last two years. They cover a wide diversity of subjects and provide excellent resources for interest in various specific areas. We have selected approximately a third of the reviews to be noted here. General reviews of Mossbauer spectroscopy have appeared in the journals of many different countries. The most recent addition to this list is a publication by B. Kolk, which appeared in the South African Journal of Science, and discussea the applicationsof Miwsbauer spectroscopy at low temperatures (11). Another general paper (12)is in the Encyclopedia of Material Science and Engineering. A general review on the applications of Mossbauer spectroscopy in biology has been written by Dickson and Johnson (13) and a general chemistry review of recent applications of the Mossbauer spectroscopy is by Clark, Donaldson, and Grimes (14). Specific biological application areas include iron proteins (15),magnetically ordered biological materials (16),and slow motions in macromolecular systems (17). By far the area that drew the attention of most reviews is the application of the Mossbauer effect in the areas of materials research. The reviews include those on semiconductors (18),semiconducting glasses (19), catalysts (20, 21), metals and alloys (22-261, minerals (27,281,and a Japanese review on steel (29). There also have been general reviews on industrial applications (30) and on materials research (31). Reviews on special topics in chemistry include actinide chemistry (32,33),gold chemistry (34),and electrochemistry (35). Other reviews are on the topic of relaxation (36, 37), Rayleigh scattering (38-40), ion implantation (41, 42), and surface studies (43, 4 4 ) . Several different Mossbauer techniques also have been extensively reviewed. They include emission Massbauer spectroscopy (45, 46), conversion electron Mossbauer spectroscopy (47), and capillary Mossbauer spectroscopy, a new method of studying liquids (48). Another paper has reviewed the coherent transients in Mbssbauer spectroscopy (49).There were no new Mossbauer transitions reported during the last two years. As in previous years, the facilities of the Mossbauer Effect Data Center have been used to pre are this review. The Center continues to publish the Mossfauer Effect Reference and Data Journal with the completion of the tenth volume of this series in 1987. A complete liiting of all the papers that were considered for this review can be found in the 1986 and 1987 volumes of the journal.
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INSTRUMENTATION There continue to be many papers on the improvement of the instrumentation for Mossbauer spectroscopy. Many papers are directing their attention to detectors, especially those for conversion electron Miissbauer spectroscopy. Others suggest improvements in the spectometer. These include papers describing programmable function generators. In one of the papers Belozerskii et al. (50) describe a generator that provides sawtooth, triangular, sine wave, trapoizoidal, and square wave signals. The frequencies are from 0.5 to 32 Hz. The differential nonlinearity for this system is fO.l%. Theopold et al. (51) describe a programmable function generator to be used in polarized beam Mossbauer experiments in which two drives are used. Their particular system provides for high precision for double-motion Mossbauer drives. Also described in the literature are controllers for the electrodynamic drive. In the one case, a controller provides for speed nonlinearity in the range of f15 mm/s of 0.10% and speed mm/s (52). Another controller provides noise of 15%)above the magnetic transition temperature in zero field. Changes in the magnetic properties of amorphous Fe-Zr alloys induced by hydrogenation have been studied by Fries et al. (157). Hydrogenation of sputtered amorphous Fe-Zr alloys was shown to lead to an increase in the Curie temperature and the average hyperfine field at 4.2 K. Stadnik et al. (158)used 61Ni Mossbauer spectroscopy to perform measurements on the metal glasses FemNiloZrloand FeI0Niz Zrlo at 4.2 K. The presence of large hyperfine fields in bo& materials demonstrates that Ni atoms participate in the magnetization of the glasses. Sumiyama et al. (159)combined Mossbauer measurements with X-ray diffraction and magnetization measurements to study Fel-,Mo, alloys produced by vapor quenching. For 0.3 < x < 0.6, an amorphous phase is obtained. In this region the intermetallic compounds with topologically close-packed structure are stable in the equilibrium phase diagram. The local atomic configuration of the amorphous alloy resembled that of the intermetallic compound with a SiMilar composition. Adachi et al. (160) looked at the spin glass state of liquid-quenched Cu-Fe alloys up to 9% Fe. Change of the spin-glass nature by annealing and the clustering effect of Fe atoms was observed. Several papers were concerned with the Fe-B system. The magnetic moment per iron atom in amorphous FelwxB, was studied by Matz and Hermann (161)for boron concentration within the region of high glass-forming ability (15 < x < 25). Results confirmed the nonlinear dependence of p on boron concentration. Hoving and Van der Woude (162)used the semiempirical model of Miedema and Van der Woude to extract information from isomer shift data about the packing in amorphous Fe,Bl-, alloys (10 atom % < x < 90 atom %). The samples on the ironrich side have an open structure which transforms to a strained one on the boronrich side. Ackerman et al. (163)examined the crystallization behavior of amorphous FelocrxBxby using a combination of CEMS and transmission Mossbauer spectroscopy. Crystallization usually starts at the surfaces, triggered by sublimation and/or selective oxidation of the boron. The atmosphere used in the heat treatment had a strong influence on the crystallization process. Varret et al. (164)performed angular investigations of Mossbauer line intensities on a sputtered sample of amorphous F e d & The material was found to have in-plane magnetic texture. Spin orientation fluctuations of the amorphous FeslBle alloy at temperatures below the onset of crystallization were shown by Lomonosov et al. (165)in a time-scanning experiment at 250 "C. The data provide strong support for the domain-wall fluctuations model. Li et al. (166)investigated the structural relaxation and crystallization of a similar system, F a z 0 . It was found that the crystallization process in FmPZ0was slow and that it proceeds from the outside in. Two papers, Chien et al. (167)and Xiao (168)considered amorphous Fe-Sb alloys. The former concentrated on the hyperfine interactions and magnetic properties of a wide composition range of Fe,Sblwx. The latter paper investigated the concentration dependence of the quadrupole splitting and its distribution. The quadrupole splitting of crystalline FeSbz was found to be larger than that of amorphous FeSbz by a factor of 3. Mirebeau et al. (169)made use of both inelastic neutron scattering and Mossbauer measurements on the to deduce the canting reentrant alloy (Feo.7ssMno.235)75P16B6Al~ temperature. Iron and cobalt impurities diluted in Pd were the subject of study of Andrianov et al. (170).Both impurities polarize neighboring host atoms, forming giant magnetic moments. Fe spins are shown to be misoriented with respect to external fields as weak as 1 kOe but the spins of Co atoms are not oriented along the external field even if it is stronger than 10 kOe. Zemcik et al. (171)tested the long-term stability of the coercivity and the magnitude and average orientation of the hyperfiie induction at 150 "C in three TM-M type amorphous ANALYTICAL CHEMISTRY, VOL. 60, NO. 12, JUNE 15, 1988
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alloys for up to 5000 h. The alloys under study were FemB17, FeaNi4J3zo, and CoMFe5Cr7Si8B1,.A correlation was found between the coercivity and the average hyperfine induction orientation, probably due to the anisotropy energy. Walter and Berkowitz (172) performed a series of experiments on the ( x = 2,4, and 6 atom %) system. The elements Fe82-xMxB18 Ni, Co, Pt, Au, Si, Mo, Cr, Nb, and V were added to replace the Fe. Variations in the magnetic properties were observed to relate to changes in the chemical short range order (CSRO) of the alloys. Addition of elements to the left of Fe in the periodic table decrease the CSRO and the Curie temperature while additions of elements to the right of Fe increase the CSRO and the Curie temperature. The temperature dependencies of the width and average of the hyperfine field disare tribution, isomer shift, and the. intensity ratio 12,5/13,4 x= reported for amorphous F e ~ l z N i ~ l z C r x M o z( S i l 0-5) ~~ by Prasad et al. (173). The spin-wave constant determined from the temperature dependence of the average hyperfine field is larger than that determined from net magnetization data for x = 5. Anavekar et al. (174) report on Mossbauer effect studies of zinc borate glasses containing iron. Several papers considered the properties of rare-earth amorphous alloys. Maurer and Friedt (175) compared experimental determinations of the distributed hyperfine parameters at 16*Dyin amorphous DyX (X = Au, Al, Ga) alloys with theoretical predictions from a quadratic crystalline electric field (CEF) model. Good agreement was found, demonstrating that the higher order CEF terms are neglgible in amorphous Dy alloys. Felner and Nowik (176) performed magnetization and 57FeMossbauer studies of YFexA1lz-x(x = 4.0,4.5, 5.0,5.5,6.0) at temperatures from 4.1 to 350 K. In YFe4A18 the iron orders antiferromagnetically and in We& ferrimagnetically. The samples with x = 4.5,5.0, and 5.5 order magnetically at a temperature T,and at a lower temperature TGtransform to spin glasses. The nature of the magnetic order was determined by the relative iron occupation of three crystallographic inequivalent iron sites. Spin glass behavior was also observed by Buhannic et al. (177) below 15 K in the Fep,z5ZrSzintercalation compound. These compounds are most likely anisotropic spin-glasses. The anisotropy results from spin-orbit coupling effects due to the nonzero orbital moment of the octahedral Fe(I1) ground state. Eibschutz et al. (178)reported and analyzed room temperature paramagnetic and 4.2 K Zeeman 57FeMossbauer spectra for crystalline and amorphous NaFeF,. A picture of amorphous NaFeF, as a continuous random network of predominantly four-coordinated trans-terminal FeF6 octahedra with sodium ions filling the hole is presented. Silicate glasses were discussed in a collection of papers. De Guire et al. (179) studied the coordination and valence states of the transition-metal cations in high-ferrite-content silicate glasses and in the spinel ferrites crystallized from them during quenching. The two compositions (in mol %) 40 MnFez04, 60 SiOz, and 42.8 CoFezOC 57.1 SiOz were melted and splat-quenched,and the resulting materials were analyzed with a variety of techniques including Mossbauer spectroscopy. The quenched Co-containing composition contained small olivine and spinel precipitates in a glassy matrix. Boge et al. (180) performed Mijssbauer and magnetization measurements on borosilicate glasses containing neptunium. The 59.5-keV Mossbauer resonance in 237Npwas used to characterize the valence states in glasses and to study hyperfine interactions. In another study of borosilicate glasses, Dormann et al. (181) considered data from Mossbauer and susceptibility measurements from 1.4 to 300 K on sodium borosilicate glasses with varying amounts of Fe,O, content. Small isolated particles of paramagnetic Fez+were detected. In addition, two Fe3+particle distributions coexist with a few Fe3+isolated ions. The Fe3+environments in alkali silicate glasses were the subject of a study by Hsia et al. (182). Results indicate that Fe occurs in octahedral and tetrahedral surroundings. Local distortions in the glasses produce a distribution of hyperfine parameters which broadens the line width of the Mossbauer subspectra. A distribution fitting program was used to obtain information about the distortions of octahedral and tetrahedral Fe ion surroundings from the distribution of the electric field gradient. Zhou et al. (183) also found ferrous and ferric cations in both octahedral and tetrahedral coordination in the matrix Si0z-Naz0-A1z03-Zn0 glass systems. The ratio of the number of Fez+ions in tetrahedral coordination to the total 96R
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number of Fez+ions is approximately constant to 0.6 and is not composition dependent. The line width is aLS0 not affected by varying iron content and reducing condition of the glass. Zemcik and Cimbalsikova (184) proposed a correlation between color and thermal history for submillimeter glassy particles from the Soviet LUNA-24 landing. Thin iron oxides deposited by a spray pyrolysis technique on glass coated with a semiconducting film were analyzed by Nomura and Ujihira (185) using CEMS. The iron oxide films obtained by spray pyrolysis were dependent on the kinds and the temperature of the semiconductive materials coated on the glass. Girnus et al. (186) investigated amorphous rareearth iron garnets prepared by coprecipitation of hydroxides in ultrasonic fields in order to determine their short and medium range order and to find their magnetic properties as a function of their annealing temperatures. Engelmann et al. (187) also considered short range order, but in amorphous LiNb03 doped with 0.22 atom % Fe203. The sample was prepared using the twin roller quenching technique. The short range order structure was found to be similar to that of the crystalline phase. Fe2+and Fe3+valence states, both octahedrally coordinated, were observed. Calcium-lead-borate glasses were studied by Mostafa et al. (188) in order to determine both their Debye temperature and their transformation temperature during heating. The recoil-free fraction decreased and the mean square amplitude of the Mossbauer atom increased as the temperature was increased. The experimentally determined transformation temperature was found to be 665 K, which may be slightly less than the real value. Nishida and Takashima (189) examined the Mossbauer spectra of a series of potassium vanadate glasses containing 10 mol % Fe203. Results indicate that the introduction of the alkali oxide KzO into the Vz05 results in a structural change of the V5+and V4+ ions from V 0 5 tetragonal pyramid or trigonal bipyramid to VO, tetrahedral units. Tanaka et d. (190) followed the crystallization process of iron phosphate glass (0.7Fez03-0.3Pz05)by means of ESR and Mossbauer spectroscopy in order to understand the state and the behavior of iron ions in the glass. The Mossbauer parameters showed that Fe3+ions in this glass were laid on distorted octahedral ligand fields. The glass was found to be paramagnetic at room temperature. Nishida et al. (191) conducted a structural study of silver borate glasses containing 20 or 30 mol % AgCl and 1 mol % Fez03. The distinct decreases in the Mossbauer parameters observed in the borate glasses with AgzO contents higher that 10 mol % indicated that chloride ions are ionically bonded with tetrahedral iron or boron atoms as nonbridging chlorine. Chloride ions appear to be ionically bonded with Ag+ ions at the interstitial sites of the three-dimensional network composed of BO3, BO,, and Fe04 units when the Ag,O content is lower than 10 mol %. Sumiyama et al. (192) combined Mossbauer spectroscopy with a variety of other analysis techniques in order to characterize amorphous Fel,Te, alloys. Amorphous Te prepared by Te ion implantation and vapor quenching WBS investigated by Pattyn and Bukshpan (193). Previous measurements on the structure of amorphous Te were confirmed. For the sample prepared by ion implantation, the onset of amorphisation is abrupt and occurs at an implantation dose of around 1015 atoms/cm2. Mossbauer site and Raman spectroscopy are recommended by Boolchand (194) as complementary probes of medium range order in network glasses. Specific examples of the application of these spectroscopiesto the chalcoginide glasses g-GeSez, g-GeS,, and g-Gel-,Sn,Sez are given. Many other papers involve studies of these same materials. Ruffolo and Boolchand (195) found close parallels in Mossbauer-site signatures of Gez-~Sn,S3glasses and crystalline alloys. A drastic loss of glass-forming tendency was observed for x > 0.62 which correlates with a change in the molecular structure of the corresponding crystals. A microcrystalline origin of glass formation is indicated. Niederriter et al. (196) measured the electrical conductivity of g-Gel,Sn,Sez bulk alloy glasses and correlated the results with results of Mossbauer and Raman spectroscopy. Enzweiler and Boolchand (197) examined the molecular structure of Gez-zxSn2xSe3, which has an unusual glass-forming tendency. This unusual tendency is thought t o be due to the existence of a floppy molecular fragment of zigzag chains of GeSe, tetrahedral units, based on the structure of c-GeSnS,. In two papers, Bresser et al. (198,199) examined
MOSSBAUER SPECTROSCOPY
the '29 Mcissbauer spectra of g-GexSel-, and GeSe,Te, alloys. The g-Ge,Sel, spectra displayed a local maximum in the site-intensity ratio at the critical composition x, = 0.23 f 0.02. The critical composition was identified with the onset of percolation of a s ecific molecular fragment based on the layered form of c-8eSe2. The GeSe2,Te, spectra indicated the presence of two distinct clustered Te sites. The characteristic size of the cluster was found to be 60-75 A. Alloys of composition g-A~&3e~-~Te~, studied by Boolchand et al. (200),exhibited similar behavior. Evidence of a heterogeneous network consisting of at least three distinct molecular structures was observed by Grothaus and Boolchand (201)in bulk glasses formed by (GeSz)l,(SnS2), alloy melts over the composition range 0 < x < 0.65. A h e a r decrease of the glass transition temperature with alloy composition was also observed. This decrease provides macroscopic confirmation of the idea of molecular phase separation. Other studies by Wells and Boolchand (202)indicate lz5Te absorption and la9I emission Mossbauer spectroscopy yield consistent results when used to study chalcogenide glass systems and are chemically equivalent.
MATERIALS STUDIES This topic allows a broad range of papers to be mentioned. The main criterion is that they are ones where Mossbauer spectroscopy plays a central role in elucidating the properties of materials. Major research areas included in this section are phase transitions, defect structures, surface pro erties, lattice dynamics, and specialized applications inclu ing external fields, high pressure, and ultralow temperature. Probably the most discussed new class of materials during the past review period is that of the high-temperature superconductors. Among the many papers dealing these materials are two independent Mossbauer studies, both concerning lslEu Mbssbauer effect in Ba2EuCu30,+ , one of the compounds which exhibits superconductivity a6ove liquid nitrogen temperature. Both Eibschutz et al. (203)and Coey and Donnelly (204)fiid the Eu as entirely Eu3+. Both papers report isomer shift vs T values showing a relatively high Debye temperature. Coey and Donnelly show agreement of isomer shift and peak area data with a Debye temperature of 285 K, while Eibschutz et al. find no appreciable variation of isomer shift with temperature. Neither authors observed any anomaly in Mhsbauer parameters at the superconducting transition. Coey and Donnelly also studied a sam le doped with 5"Fe at the Cu sites and found no magnetic or&ring down to 4 K. Although no direct relation between M6ssbauer parameters and the electrical properties was observed in these studies, they are important in showing that the Mossbauer technique can contribute to this rapidly expanding field of materials studies. Application of Mossbauer techniques to another important class of electronic materials, semiconductors, has not been as active as in prior years. Two pa ers deserve mention, both dealing with isotopes other than RFe. Nasredinov et al. (205) used the l19Sn resonance to study donor centers in PbS and PbSe. Both Sn2+and Sn4+states were observed. Sodium and thalium acceptor impurities induced a two-electron exchange with tin in PbSe. Weyer et al. (206)measured isomer shifts for 12%b in 111-V and 11-VI semiconductors. They used emission experiments with ion implantation of the 121Xe precursor and compare results from isoelectronic, impurity donor, and acceptor sites. Order-disorder phenomena, especially magnetic ones, and defect structures in materials continue to be of interest. Helms et al. (207)studied the ferrimagnetic ordering in Cr(NH3)6FeCb by Mbssbauer and ma etic susceptibility techniques. A phase transition occurs at a g u t 2.8 K. Rancourt et al. (208) review evidence on clustering in iron-nickel Invar and report new studies of the supermoment dynamics by Mossbauer spectroscopy. Cranshaw (209)has studied ordering in nearly single crystals of NiaFe by the Mossbauer technique. The various ordered and disordered sites for Fe can be differentiated and their magnetic properties are discussed. Pasternak (210)used lz9Iand ll9Sn Mbssbauer spectroscopy to study short-range disorder in the solid electrolytes RbAg,15 and Ag,Se. Measurements in both the superionic and normal phase are described and related to microscopic properties. Gibb (211)reports detailed magnetic properties of the defect structure in SrFe03, from Mossbauer studies over a temperature range 4-900 K. An electron transfer occurs above
B
550 K which produces electron delocalization at the Fe sites. This first-order phase transition has been further investigated by Fourngs et al. (212)with high-temperature Mossbauer spectroscopy. Becker and Wurmb report high-temperature Mossbauer spectra up to 1300 OC for magnetite (213)and hematite (214). The dependence of the spectra on oxygen activity was studied and interpreted in terms of cation diffusion mechanisms. Surface properties of materials containing Mbssbauer isotopes can be robed with CEMS and other techniques sensitive to Mijesgauer resonance in the surface atoms. Magnetic properties of iron compounds are especially suited to investigation and the recent literature has a number of examples of such studies. Belozerskii and Semenov (215)used the angular dependence of Mossbauer absorption to study the amorphous ferromagnet FeeoBzo. Spin texture of both the contact and noncontact surfaces was studied and compared with crystalline a-Fe. Finkler et al. (216)used CEMS to investigate the effect of H2 on TiFe and Ti,Fe20. The latter oxygen-stabilized phase has two iron environments for the hydrides. Both transmission and CEMS were used by Yamauchi et al. (217)to study the photolysis of 151Euoxalate. Changes in surface oxidation state could be seen in the CEMS spectra. Walker (218)reports experimental studies of the temperature dependence of ma netization at the surface of epitaxial (110) iron f i i s , using igFe-enriched surfaces on 5sFe films. The results were variable with the interfacial covering layer. Surface Mossbauer studies on (110) iron films are also reported by Korecki and Gradmann (219)both for a free surface and one silver-coated. These authors report evidence for a spatial oscillation in magnetization between first and second monolayers, as predicted from theory. Artificial superstructure films of iron and magnesium were prepared and studied by Kawaguchi et al. (220).Films with Fe monolayers were included in this investigation as well as bulk Fe-Mg films with composition similar to the superstructured films. The monolayer Fe films had long-range magnetic ordering at 4 K. D6zsi et al. (221)used emission Mossbauer spectroscopy to study cobalt silicide phases. Three compounds were differentiated, CoSi,, CoSi, and CozSi, all of which are diamagnetic. These authors propose that Mossbauer spectroscopy can be useful in studying interfacial reactions between Co and Si. Van Wonterghem et al. (222) report Mossbauer measurements on a ferrofluid com osed of iron microcrystals suspended in mercury. Enriched RFe was used to prepare the sample because of the large scattering of the 14 keV y-ray by Hg. At 15 K two distinct magnetic components are observed, the one with higher field being ascribed to interfacial surface atoms. Surface studies have also been carried out with isotopes other than 57Fe. Leidheiser et al. (223)used 119Snto study corrosion protection layers on steel by emission Mossbauer spectroscopy. The tin is Sn4+ and tightly bound in the polymer coating. Stadnik et al. (224)report 61NiMossbauer experiments on small metallic nickel particles coated with SiO. Two samples were studied with average diameters of 500 and 50 A. Decreased magnetic fields from surface atoms were observed in the smaller particles. Several papers report Mijesbauer measurements at very low temperatures by using He dilution cryostats. Shinjo and Kusuda (225)studied Fe foil, Fe-Mg film and the Fe3+cluster compound [Fe30(CH3COO)6(H20)3] C1-6Hz0at temperatures below 0.1 K. The polarization of the Fe foil spectrum indicates a temperature of 5 mK. Magnetic ordering occurs for the cluster compound at very low temperatures. Langouche et al. (226)studied the nuclear orientation for lz5Iimplanted in Si and a-Sn in the mK tem erature range by using a moving Mg3Te06absorber. The agantages of this low-temperature orientation for studying defect-induced field gradients are pointed out. This same group, in a paper by Berkes et al. (223,report determination of the sign of the magnetic moments for lS1Ptand lg30sand the quadrupole moments for lPSrnTeand lz9Teby mK nuclear orientation. Examples of the use of externally applied fields in Mksbauer spectroscopy are discussed in several other sections. Three additional examples are mentioned here. Emission spectra from single crystals of LiNb03(57Co)in applied fields up to 5 T at 4 K are reported by Doerfler et al. (228).The electronic substrate populations for Fe3+varies with the angle between crystal and magnetic field. The angular dependence ANALYTICAL CHEMISTRY, VOL. 60. NO. 12, JUNE 15, 1988
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low Fe3+concentration are required to prevent formation of is interpreted as due to intersystem crossin caused by oroxyhydroxide species. Prietsch et al. (243) studied a different bit-lattice interaction. McCammon et al. (2297 have prepared type of intercalated Fe, stage 2 FeCl,-graphite. Both valence Fe2+-richhypermagnetite and studied this unstable material states of Fe were observed in the Mossbauer spectra, and the by Miissbauer spectrcacopy with and without an applied field. anisotropic nature of the absorbers was investigated by vaTying They propose a model for the site distribution. Yang et al. the angle between absorber and y-ray. Both the relaxation (230) studied the nature of the magnetic fluid composed of behavior due to electron transfer between Fez+and Fe3+and Fe30 particles coated with an organic surfactant by the low-temperature ma netic ordering were studied. The Mosabauer spectroscopy at 5 K in a longitudinal applied field. layered compound FeP& can be intercalated with alkali The presence of Am = 0 lines in the spectrum indicates metals and the Li intercalate has been studied by Fatseas et noncollinearity of the internal magnetic field. al. (244). Intercalation gives rise to a second doublet comHigh-pressure Mossbauer experiments have been utilized ponent in the Miissbauer spectra. In contrast to the expected in several studies of materials. Kapitanov et al. (231) inincrease in isomer shift due to electron transfer to the Fe vestigated a polydisperse system of small tin particles up to d-band, this second doublet has a decreased isomer shift. This 200 kbar. The O-Sn to Sn I1 phase transition occurs at higher unusual effect is interpreted as due to formation of an FeO pressures for small particles. Long and Hutchinson (232)used species with greater overlap distortion of core orbitals and/or both high-pressure and ap lied field techniques to study spin increased 4s electron population. The high-resolution equilibria in iron(I1) poly(?-pyrazoly1)borate complexes. InMossbauer resonance of 81Tahas been used by Eibschutz et terconversion between low- and high-spin states can be inal. (245)to study Li intercalation in single crystal 2H-TaSe2. duced reversibly by high pressure, but the stable low-pressure Charge transfer from the Li induces a change in valence state form depends on the complex. Meissner et al. (233) report for Ta from Ta4+to Ta3+and an increase in ionicity. an anomalous pressure dependence of the recoilless fraction f for the spin crossover compound [ F ~ ( ~ - ~ ~ C - N D ~ ) ~ ] C ~ ~ . E ~ O D . MINERALS, SOILS, AND METEORITES Around the spin transition temperature of 147 K the f value has a marked increase in its pressure dependence. This effect Environmental samples and related synthetic compounds is explained with a model treating the solid as an elastic continue to be of interest to Miiasbauer spectroscopistsbecause isotropic medium. Pasternak et al. (234)used lZeIMbssbauer of their iron content and varied structure. Layered silicates spectroscopy to study the behavior of elemental iodine at high are among the most studied minerals. Magnetic ordering in pressure. The metalization observed is attributed to formation ironrich samples has been shown to be a common occurrence of first chain and then two-dimensional networks of I molif the temperature is low. As part of a series of ordering in ecules. Potzel et d. (235) review high-pressure Mosskauer layered silicates, Ballet et al. report Mossbauer and magnetic experiments on magnetic Np intermetallic compounds and results on chlorite minerals (246). These have 2:l:l layered present new results for NpAs. They discuss the connection structure with 2:l silicate sheets separated by octahedral between the observed hyperfine parameters and X-ray difM3(OH)6brucite layers. The magnetic ordering in the ironrich fraction results. thuringite is shown to be a short-range ferromagnetic one. The Mossbauer recoilless fraction f gives information on Long-range coupling between Fez+is destroyed by the Fe3+ solid-state lattice dynamics. Kemerink et al. (236)report the present in the silicate layer. Cardile and Johnston (247)have first systematic study off values for lB1. Compounds studied studied a series of montmorillonites by Mossbauer spectrosinclude the alkali iodides, CUI, SnTe, and ZnTe (the latter copy. These dioctahedral smectites contained no Fe2+and two compounds being used as sources of lZsmTe).The results the Fe3+peaks were best fit by three doublets: two major ones are compared with models for the lattice dynamics. Kosova corresponding to octahedral coordination and a small doublet et al. (237) studied molecular mobility in a series of liquid with low isomer shift and quadrupole splitting -0.1 mm s-l crystal polymers using ferrocene and ferrocenealdehyde as attributed to tetrahedral iron. These authors assign both label molecules for Mossbauer measurements. The temperoctahedral doublets to trans-OH sites as opposed to nontronite ature dependence of f values for the label molecules relates where only cis-OH sites are occupied. However, they do point to the intramolecular mobility of the liquid crystal polymers. out that the broad lines indicate a variety of sites for which Both magnetic and dynamic properties of small particles of the assumption of only two for fitting is an oversimplification. F e N i and Fe-Co alloys were studied by Morrish and Pollard Dyar and Burns (248) present Mossbauer results on 15 (238). Application of an external field of 5 T induces collintrioctahedral micas where both trans- and cis-OH sites are earity of the magnetic moments of these 50-60-nm particles. occupied. These two sites clear1 produced distinguishable doublets for both Fe2+ and Fe3Y in biotites, with the Fez+ Oxides present in the samples appear to have independent dynamic properties and are thus not simply surface coatings. preferentially occupying cis sites. Tetrahedral Fe3+with its The polycrystalline form of iron known as nanocrystalline iron lower isomer shift was prominent in ferriphlogopite and was studied by Herr et al. (239). In this form the crystallites ferriannite as predicted by their stoichiometry. Using synare on the order of 1-10 nm and are separated by interfacial thetic trioctahedral micas, Ferrow (249)varied systematically regions. The Mossbauer spectra consist of two sextets, one the size of both tetrahedral and octahedral layers and measharp and characteristic of the crystalline regions and one sured the effect of the distortions on the Mossbauer parambroad with a hyperfine field which, although larger at low eters at different sites. For tetrahedral Fe3+the quadrupole temperature, decreases more rapidly than that of the cryssplitting increases with increasing layer rotation. For both talline region with increasing temperature. Both source and octahedral Fe2+the QS increases as Ge is substituted for Si absorber experiments with impurity 57Fehave been used by in the tetrahedral layer. However no trend was seen for Wordel and Wagner (240) to study diffusion and lattice disoctahedral Fe3+. tortions in hydrides and deuterides of Nb. Although diffusion A nonlayered silicate, almandine (Fe3A12(Si04)&,was rates were the same for the two isotopes, the hydrides prostudied by Murad and Wagner (250). Both a synthetic and duced a larger mean square displacement for the probe nucleus a natural nonstoichiometric sample were investigated by and thus lower f values a t high temperatures. The authors Mossbauer spectroscopy down to 4 K. The high-temperature discuss these effects in terms of displacement of iron by spectra required two doublets for proper fitting even though neighboring interstitials. the ideal structure has only one site. These samples were both As a concluding topic in this section, mention should be ordered magnetically at 4 K and required two magnetic patterns for fitting. This is attributed to a noncollinear spin made of the considerable interest in intercalated materials, orientation with two distinct angles between the spins and layered structures with metal ions between the layers. A wide the field gradient axis. Vanleerberghe and Vandenberghe variety of these materials has been studied. One type of (251)report an interesting application of an external field to interest is the pillared clay structure, a layered silicate with separate the overlapping quadrupole splittings of the A and intercalated oxides expanding the distance between layers. B sites in the spinel Fe2TiOl. The success of this technique Gangas et al. (241) report studies of an iron oxide intercalated depended on the fact that these two sites produce quadrupole nontronite. The intercalated iron increases the magnetic coupling of opposite sign. Both sites have a distribution of ordering temperature of the iron in the silicate layers, presplittings. That of the A site varies markedly with tempersumably through magnetic bridging. Berry et al. (242) studied ature as predicted from its geometry. iron-exchanged montmorillonite clays. Both Fe3+and Fez+ Iron oxides and oxyhydroxides continue to be important were used and the reaction conditions for best intercalation subjects for Mossbauer investigation. DeGrave et al. (252) could be monitored by the Mossbauer spectra. Low pH and 98R
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have studied a series of lepidocrocites, y-FeOOH, of differing crystallinity. The magnetically ordered state has a broad distribution of hyperfine fields and a transition region of about 20 K. Neither of these is changed appreciably by changing crystallinity. The latter does however affect the quadrupole distribution in the paramagnetic state, giving rise to distinct surface species with higher quadrupole splitting and different orientation of the field gradient axis from the core. Amarasiriwardena et al. (253) report Mksbauer analysis of synthetic Al-substituted goethite (a-FeOOH) and hematite (a-Fe2O3) mixtures. They show that quantitative ratios can be obtained from spectra in the temperature range 12-130 K only by using a fitting technique assuming a distribution of hyperfine fields for both components. Koch et al. (254)have studied the effect of heating microcrystalline goethite at 60-105 “C on the spectral properties. Although no change in cell dimensions was observed, desorption of water increased the magnetic transition temperature. Murad and Bowen (255) compare Mossbauer spectra of two Al-rich goethites with different crystallinities and find marked difference in the temperature range over which both magnetically ordered and paramagnetic species coexist. For both samples a distribution of hyperfine fields is observed which differs for the two at 80 K but becomes similar a t 13 K. Murad and Schwertmann (256) report room-tem erature Mijssbauer spectra of a series of hematites with Al suktitution up to 10% and varying particle size. They give correlations of hyperfine field and line width with A1 content and mean crystal diameter in the [OOl] direction. Both parameters make significant contribution to the reduction of hyperfine field and to broadening of the lines. Four examples are mentioned here illustrating the application of Mossbauer spectroscopy to soils and sediments. Hilton et al. (257) studied an anaerobic sediment from a eutrophic lake in England both as is, after oxidation, and after chemical extraction to remove iron oxides and organic matter from the clay minerals. The combination of Mossbauer spectroscopy with sequential extraction helped clarify the interpretation of the deceptively simple spectra and showed that not only ferric oxides but easily oxidizable amorphous Fez+ also contributed appreciably to the original spectra. Postglacial marine clays from eastern Canada have been studied by Torrance et al. (258). These were examples of so-called “quick clays” which have the property of becoming fluid when subjected to remolded shear. Mossbauer spectra showed the presence of small amounts of iron oxide (hematite or magnetite), which seemed to affect the yield stress behavior when removed by chemical extraction. Vandenberghe et al. (259)report a Mossbauer study of goethite and hematite in a red soil from Tunisia. Hyperfine field distributions were fitted to the 80 K spectra. No Morin transition was detected for the hematite component even though the X-ray patterns indicated rather large particles. This lack of Morin transition is attributed to Mn substitution in the hematite component. The complexes of iron with soil fulvic acids have been studied by using Mossbauer and EPR spectroscopy by Goodman and Cheshire (260). The products formed vary with pH and with fulvic acid content. At low pH Fe3+ is reduced to Fez+. A magnetic component with high field (-58 T) was present in the 77 K spectra with increasing intensity as the fulvic acid content increased and was attributed to a magnetically dilute, mononuclear Fe3+ complex. Environmental samples studied by Miissbauer spectroscopy in the past several years include a number of meteorites. Scorzelli and Danon (261) report a study of order-disorder processes in iron-nickel alloys from the Santa Catherina meteorite. Three components are present in the room temperature Massbauer spectrum: a noncubic ordered magnetic phase, a disordered magnetic phase, and a parmagnetic cubic phase. Order-disorder transformations due to thermal and mechanical treatment were observed. Madsen et al. (262)used Mossbauer spectroscopy in external fields to reinvestigate the superparamagnetic component of the Orgueil meteorite which had previously been attributed to small magnetite particles which order only below 65 K. The spectra show that the superparamagnetic component is not magnetite but a poorly crystalline Fe3+compound with low net magnetization and probably antiferromagnetic ordering. Three samples of the type SNC achondrite meteorites have been studied by Vieira et al. (263) in particular to determine iron oxidation. They relate their results to other studies of meteorites and give
general conclusions regarding the relationship of iron oxidation to planetary evolution.
INDUSTRIAL APPLICATIONS This section includes papers on coal analysis, transformations in steel, nuclear waste glass, and cement. By far the most active area for Mossbauer spectroscopy related to industrial application is the study of catalysts and the papers reviewed below reflect that activity. There were fewer papers dealing with coal than in the previous review period. One which should be mentioned is that of Audley et al. (264), which presents a method to quantify the Mossbauer determination of pyrite in coal by using iron foil as an internal standard and micronizing the sample to avoid effects of granularity. Corrosion of steel by acid and the effects of inhibitors were studied by Choudhury et al. (265). In addition to transmission experiments, they used electron reemission Mossbauer spectroscopy to estimate a rate constant for the diffusion-controlled reaction. Stewart and Tricker (266)used CEMS to study air oxidation of 310 stainless steel foil and in particular the effect of chromium depletion on the spectra and on the kinetics, which were more rapid than those predicted from thick samples. Ladriere and He (267) report Mossbauer studies of austenite concentration in a dual-phase Fe-Mn-C steel following mechanical deformation and thermal treatment. The retained austenite is transformed to martensite during deformation. Cook (268) used both CEMS and X-ray Mossbauer techniques to study martensite formation at the surface of 316 stainless steel when subjected to strain. Using hyperfine field distributions for fitting, he shows a relation between the fields observed and the impurity concentration on neighboring sites. Moncoffre et al. (269)report CEMS studies of nitrogen implantation on both a low alloyed steel (0.05% C) and a chromium alloyed one (1.1% C, 1.4% Cr). The nitride phases formed were determined as function of implantation temperature. The preparation of ceramic glasses for nuclear waste disposal requires strict control over the redox environment. Goldman and Bewley (270)have analyzed simulated nuclear waste glass for Fe2+-Fe3+ratios by Mossbauer spectroscopy and compared results with chemical analysis. They conclude that Mossbauer analysis overestimatesthe Fez+somewhat and peak line shapes deviate from Lorentzian especially with hi her Fez+ glasses. They propose a rapid technique for Feg?+-Fe3+analysis using three velocities. Related to high alumina cement, the Ca-Al-Fe mixed oxide system has been studied with Mossbauer spectroscopy by Dalton et al. (271). Submicrometer particles were prepared and their superparamagnetic properties related to the particle size. A wide variety of papers have appeared over the last several years dealing with Mossbauer spectroscopy of catalysts. Those papers included below had to be chosen somewhat arbitrarily but are hopefully representative of the work in this field. Christensen et al. (272)studied the superparamagnetism of a-Fe in carbon catalysts by applying an external field. Their analysis gives the average particle size as 2.5 nm. Lin and Phillips (273) analyze the Mossbauer spectra of carbon-supported iron carbide catalysts using a relaxation model. The nature of the carbon support influences the iron carbide interaction. Particle size (10-17 nm) could be estimated from the model. Gatte and Phillips (274)present a more detailed modeling routine and use it to generate spectra for comparison with experimental data on the iron carbides formed during Fischer-Tropsch synthesis. In situ Mossbauer experiments on Fe/A1203and Fe/ThOz Fischer-Tropsch catalysts were performed by Vaishnava et al. (275). Transformations occurring during calcination, reduction, carburization, and synthesis reactions were monitored by the Mijssbauer spectra. Iron oxides supported on a variety of oxide substrates were characterized by Mijssbauer spectroscopy after treatment with CO-C02 gas mixtures a t elevated temperature in work reported by Rethwisch and Dumesic (276). Evidence is presented for surface reaction between the iron oxide and its support. The interaction between Fe and Ru and with the AZO3or Si02support was studied in situ by Berry et al. (277) for Fe-Ru Catalysts with hydrogen reduction. The performance of these catalysts in CO hydrogenation was also evaluated and related to the Mossbauer results. Lazar et al. (278)report a high-field, low-temperature Mossbauer study of Fe-Ru catalysts on Cab-0-Sil, these catalysts being prepared from ANALYTICAL CHEMISTRY, VOL. 60, NO. 12, JUNE 15, 1988
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carbonyl cluster compounds of the metals. Their results show the presence of paramagnetic Fe-Ru bimetallic particles of small particle size. Niemantsverdriet and van der Kraan (279) studied Fe-Ir catalysts on SiOz by Mossbauer spectroscopy and other techniques. Iron is present both as Ir-rich alloy and ferric oxide. The oxide phase is highly disperse. Iron-exchanged silicon-substituted zeolites, active in catalysis of N20 decomposition, were studied by using Mossbauer techniques by Aparicio et al. (280). Effects of oxidation and adsorption of H20or CO were observed. In addition to 57Festudies, there are catalysts with other Mossbauer isotopes. Kuznetsov et al. (281) report Il9Sn Mossbauer studies of Pt-Sn/A1203 reforming catalysts. The effect of C1- on the properties of the support is important. A wide variety of Sn species is seen after H2 reduction at 823 K.
MISCELLANEOUS APPLICATIONS In addition to the applications of Mossbauer spectroscopy reviewed above, there are numerous additional categories of studies that are currently under way. Kopcewicz and Kopcewicz (282) analyzed the magnetic properties of industrial and urban aerosols collected from various locations in Poland and the concentration and size of iron-containin particles found in the samples. Inoue et al. (283) studiefi emission sources of urban particulate matter using 57FeMossbauer spectroscopy. A high-spin F2+component indicates that the particulate emission is from soils and silicate minerals. A magnetic hyperfine-splitting component gives evidence that the particulate emission is generated by human activity. Mossbauer spectroscopy continues to be a useful tool in the study of ancient pottery. Stevens and Zhu (284) published a brief review of the information that can be obtained from the Mossbauer spectra of ancient pottery. Deriu et al. (285) performed detailed studies of Phoenician, Etruscan, and Gabi type amphoras dating from the seventh to sixth centuries B.C. They were able to differentiate between Phoenician and Etruscan amphoras and were able to classify the Gabi amphoras as Etruscan in origin. The Gabi type amphoras show morphological characteristics similar to both the Phoenician and Etruscan types and had been previously classified as Phoenician. Ortalli et al. (286) analyzed two different clays from the Umbria region of Italy. Two samples of pottery from near the town of Todi had been fired at temperatures substantially different from those of the other samples and thus came from different potteries. A sample of a bond clay cake, found among the burial objects in a collection of tombs near Colfiorito, was shown to have the characteristics of a light clay known as "Terra Angelica", lon used for medicinal and religious purposes. This result incficates that the properties of the Angelica clay were known by the sixth century B.C. Ten pieces of Egyptian pottery ware and 11slit samples collected at Hierakonopolis on the Nile River were studied by Stevens and Zhu (287). Three pottery sherds were refired through a series of temperatures in order to determine the original firing temperature. The temperature at which the magnetic sextet area increases dramatically is the temperature to which the sherds were most likely fired. Three silt samples were examined to determine if they were possible sources of the clay used for pottery manufacture. The silt samples were also heated through a series of temperatures to examine how the Mbssbauer parameters changed. Wagner et al. (288,289) performed experiments on sherds of Incan ceramics and samples of unfired clay from various locations in Peru in order to obtain information on the firing conditions of the ceramics. The sherds were refired in air at temperatures increasing in steps of 50 "C from 100 to 1200 OC. The clay samples were fired in air or in a reducing atmosphere, also at temperatures increasing in steps of 50 "C from 100 to 1200 "C. A new clay sample was used for each temperature. A Mossbauer spectrum was measured after each firing step. The temperature dependence of the Mossbauer parameters of the sherds and the clay is presented rather dramatically on three-dimensional plots. Data from the clay samples were used as reference data and indicated that most of the sherds were originally fired in a reducing atmosphere. The refiring behavior of each type of sherd was found to be different, so that assessing the firing conditions of large numbers of sherds is difficult without a complete refiring series for each. No general method for the determination of original firing conditions was proposed. 100R
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Medical applications of Mossbauer spectroscopy include a study of oxyhemoglobinsby Oshtrakh and Semionkin (2%). Quadrupole splitting and isomer shift data allowed them to distinguish between normal adult, fetal, and leukemic oxyhemoglobins. The differences in the Fez+electronic structure and the active site molecular structure of the oxyhemoglobins were also analyzed. Stroink et al. (291) presented data from a study of autopsied lung tissue from Canadian asbestos mine workers and lung tissue from an individual not occupationally exposed to respirable asbestos. Lung tissue from asbestos mine workers was found to contain significantly more iron than normal lung tissue, as predicted. A universal and relatively simple method designed for a numerical reconstruction of the time correlation function of an arbitrary system of interacting particles by a Fourier analysis of its Mossbauer absorption spectrum is proposed by Tsankov (292). The applicability of this method is demonstrated for the case of the Brownian motion of particles suspended in a fluid, by numerical simulation of the spectra. In two papers, Bauminger et al. (293, 294) studied the dynamics of iron and europium in Nafion polymer membranes. These materials are interesting because they display spectra typical of bounded diffusion phenomena observed in biopolymers. The dynamical properties are observed through the recoilless fraction and results are interpreted in terms of bonded diffusive motion of the metal ion using a model based on overdamped harmonically bound Brownian motion. The temperature dependence of the f factor was found to change with the amount of water contained in the polymer. Several papers were concerned with the dynamics of proteins. Parak (295) discussed a model in which fragments of the protein molecule make strongly damped Brownian oscillations around an average position. This model was verified by Mossbauer spectroscopy and X-ray structure investigations of protein dynamics. A generalized moment expression which provides an effective algorithm for approximation of the time-dependence of observables that monitor stochastic processes was proposed by Nadler and Schulten (296). The algorithm is applied to the Mossbauer absorption spectrum of a Brownian particle in certain two- and three-dimensional potentials, which serves as a model for the motion of the heme group in myoglobin. There were numerous papers reporting on the use of Miissbauer spectroscopy in the field of ion implantation. Dezsi et al. (297) presented further evidence for the formation of natural chemical bonds of '29 resulting from '%Te implanted in Ge and a-GeTe. Miura et al. (298) paired Mossbauer spectroscopy with internal conversion measurements for a study of radioactive lz5Iimplanted into seven different metal matrices. A value of ARIR for the 35.46-keV M1 transition of lz5Tewas derived that is slightly larger than previous experimental values but which agrees well with theory. Many ion implantation experiments used copper as the crystalline matrix. Andreasen et al. (299) investigated the properties of isolated molecules of SbF,, SbO,, and SbCl, embedded in a copper matrix. Hofsass et al. (300) combined Mossbauer effect measurements with channeling and perturbed y-y angular correlation measurements in order to study the system composed of radioactive In isotopes implanted into Cu single crystals. This combination of measurements makes possible complementary studies of impurity-defect interactions in ion-implanted solids on an atomic scale and lattice location studies at low implantation doses and low-impurity concentrations. Ogale et al. (301) used CEMS, small-angle X-ray diffraction, and resistivity measurements to study the effects of ionbeam-induced atomic mixing and subsequent thermal treatments on the single interface Fe/A1203 structure. The interfaces in as-deposited and ion-beam-mixed samples exhibited different features under thermal treatment. An in-beam Mossbauer experiment, performed by Menningen et al. (302), demonstrated the direct implantation of Fe atoms into interstitial sites in A1 at temperatures below 200 K. The interstitial implantation appears to be closely related to the small solubility of Fe in Al. Sawicka et al. (303) measured the Mossbauer spectra of a-Fe film sandwiched between thin copper layers during and after implantation with deuterium at 100 K. Results indicated that the deuterium is mainly trapped at defects in the a-Fe lattice or reemitted. A complete recovery of the normal a-Fe spectrum was observed after
MOSSBAUER SPECTROSCOPY
annealing the Sam les at room temperature. Langouche et ~ liquid He temal. (304) implantei Si targets with 6 7 Cat perature. The Massbauer spectra indicated that a fraction of the Co atoms occupied regular interstitial sites. Other methods of analysis have shown that the Co atoms occupy substitutional sites when implanted at room temperature. CEMS has established itself as a valuable technique in a variety of study arem, including the study of steels. kaldokhin et al. (305)were able to investigate the structure of the surface fracture of a 44N14-grade steel undergoing an FCC-BCC martensitic transformation during fatigue failure by examining very thin layers adjacent to the fracture surface. A redistribution of carbon atoms was observed in the surface layer of an impact-fati e fracture. Mukhopadhyay et al. (306) irradiated thin S&02 stainless steel samples with 100-keV proton beams at various doses and used CEMS to analyze the damage. Many investigators applied CEMS to the study of corrosion products. Fujinami and Ujihira (307) examined the chemical-state transformation of corrosion products deposited on steel exposed to low concentrations of hydrogen sulfide. Gancedo and Gracia (308) presented preliminary data on the differences in the corrosion products of pure iron and CORTEN type steel in highly contaminated SOz atmospheres. Cook (309) studied the corrosion Products formed on the surface of Type 316 stainless steel exposed to chlorinated seawater and on weathering steel, ASTM A242 Type 1, exposed to either a marine or inland rural environment. Oxides were found on the stainless steel after short exposures to seawater. The initial corrosion products were y-FeOOH and ferrihydrite which form semicohesive f h on the surface. The weathering steels exhibited a crusty protective layer of amorphous hydroxyoxide over a-FeOOH. The chemical and physical state of iron oxide f i i prepared by reactive rf sputtering was the subject of a CEMS study by Fujinami and Ujihira (310). They confirmed that the initially deposited iron oxide is a nonstoichiometric magnetite and that the easy axes of magnetic spin in the Fesx04 f i i are inclined perpendicular to the surface. Gries et al. (311)used 67Fe-implanted copper to demonstrate that CEMS combined with other methods of surface analysis can reveal phase and chemical transformations of Mossbauer-active impurities in very small volumes. This type of information is fundamental for understanding the development of surface topography in sputtering. In an effort to characterizethe surface properties of Fe$ezo during the amorphous-to-crystalline transformation, Cusido and Tejada (312)combined CEMS with electron microscopy. They were able to observe the crystallization process in considerable detail. Babikova et al. (313) studied mass transport in sample surfaces irradiated with nanosecond single laser pulses. Pulsed laser radiation produced layers with different phase composition on the surface. CEMS is well-suited to the study of such layers. Depth profiling of solid surfaces using CEMS continues to be an important technique for the nondestructive analysis of the composition and structure of surfaces. Chumakov and Smirnov (314) describe a method of depth profiling based on measuring the angular dependence of the photoelectron emission near the critical angle for total internal reflection. This method is applied to directly measure the range of depths that can be probed by selective detection of conversion electrons for the case of 14.4-keV y-rays interacting with an iron target. The superposition technique proposed can be applied to specimens of arbitrary structure and requires only one specimen. Bara and Bogacz (315)investigated the depth selectivity of the X-e- coincidence technique. It was found that this technique improves the depth sensitivity of CEMS spectra recorded with a He/CH4 flow proportional counter. Itoh et al. (316) applied depth selective CEMS to the study of rare-earth iron garnet films. The spin orientations were determined as a function of depth, The spin-tilt angle from the surface normal was found to increase toward the surface up to 30". This effect can be explained by the widening of the domain wall width toward the surface. Many papers dealt with studies of the effect of irradiation on various materials. The effect of the implantation of 150keV Ar+ ions at different doses on the surface of amorphous Fe&Ji&, and the changes in the bulk properties following proton irradiation were the subjects of Bhagawat et al. (317).
The surface measurements established that a correlation exists between the total Mossbauer absorption and the total energy deposited by incident Ar+ ions. The bulk data indicated that proton irradiation had a considerable effect on the local short range order around the Fe atoms in the amorphous material. amorphous alloys Zentko et al. (318) considered FesoNisoBzo irradiated by neutrons. Information was obtained on the magnetic properties and nearest-neighbor arrangement of the irradiated alloys. The long-range exchange interaction responsible for the magnetic ordering in this alloy was shown to be depressed by the rearrangement of the amorphous structure after irradiation. Two ferrimagnetic oxides, Y3Fe5012 and BaFelzOl ,irradiated with very energetic Ar, Kr, and Xe ions were stuiied by Toulemonde et al. (319). Evidence was found for a damage mechanism based on the electronic stopping power. Drastic changes in the bulk orientation of the hyperfine magnetic field were observed in Y3Fe5012. Zhetbaev and Donbaev (320) found that the temperature range of the Morin transition in hematite changes depending on the neutron irradiation dose and that the radiation defects causing changes in the Morin transition disappear on annealing of the hematite in air at temperatures of 400-500 K. The results of various types of laser annealing of materials have been the subject of Mossbauer spectroscopic studies. Safonov et al. (321) applied CEMS to the study of the phase composition of subsurface layers of steel after treatment of the surface with a continuous C02 laser. In several papers, Carbucicchio and Palombarini (322) and Carbucicchio et al. (323,324)also discuss the effects of laser treatments on steels. The melting behavior and phase transformation were investigated. Atmosphere composition and carbon content of the steel were found to have considerable impact on the effect of laser treatments. Matteazzi et al. (325) compared the effects of continuous laser annealing and conventional heat treatment on amorphous FeaNiSl4B6 (Metglas 2826) ribbons. Continuous laser annealing was found to produce improvement of soft magnetic properties. Lanotte et al. (326) also considered the effects of laser heat treatment of amorphous alloy ribbons. The changes in the metallic glass structure depended to some extent on which surface of the alloy, smooth or rough, was irradiated. The investigated effects can be related to the occurrence of surface and/or bulk crystallization. The use of synchrotron radiation as a source for Mossbauer experiments is complicated by the presence of a large background signal. Gerdau and Riiffer (327,328)have obtained monochromatization of synchrotron radiation by nuclear Bragg diffraction in yttrium iron garnet. This method of resonant filtering preserves the unique properties of synchrotron radiation and should allow its use in Mossbauer experiments. Helisto et al. (329) used pulses of resonant y radiation to study prominent nonlinear transient effects due to thickness saturation in the 57Fe Mossbauer resonance. Transient methods are well-adapted to studies where knowledge of the actual line shape of the absorber is important. Several papers dealt with the development of y-ray lasers (GRASERS). The minimum requirements for superradient y-ray emission were derived by Baldwin and Feld (330) by applying the semiclassical theory of coherent spontaneous emission to the case of nuclear transitions in a crystal host. They found that if a pure sample of a storage isomer can be rapidly transferred into an inverted population for a recoilless transition, less than 1013nuclei should suffice for an experimental demonstration of nuclear superradiance. Hoy (331) proposed three experimental techniques for the unambigious observation of the Mhsbauer effect in the long-lived (lifetime = 40 s) lWAgfirst excited nuclear state: CEMS, coincidence Mossbauer spectroscopy, and gravitational line sweeping. The use of polarized y-rays in 57FeMossbauer spectroscopy was the subject of several studies. Gonser and Fischer (332) discuss dichroism effects in the spectra of samples with large effective thickness. Kovalenko et al. (333)propose an original method for determining the degree of polarization of y-rays produced by passing unpolarized radiation from a 57C0 Mossbauer source through a 57Fepolarizer. Ullrich et al. (334) used polarized y radiation produced by a 57C0source in a polarized foil of natural iron to demonstrate the existence of parallel, antiparallel, and frustrated magnetic moments in FeNi Invar alloys. A new kind of hyperfine field distribution ANALYTICAL CHEMISTRY, VOL. 60, NO. 12, JUNE 15, 1988
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also containing the probability for magnetic field values was obtained. New Mossbauer methodology that does not utilize Doppler modulation is reported by Sakai and Sekizawa (335). The energy modulation of y-rays is achieved by the Zeeman effect on Fe nuclei in a paramagnetic PdFe source held at liquid helium temperature. This method is effective in separating the absorption lines into individual sublattice contributions in antiferro- and ferrimagnetic materials. The usefulness of a magnetized paramagnetic Mossbauer source in measuring a polarimetric Doppler-mode Mossbauer spectrum is also discussed. A variety of papers discussed the application of Mossbauer spectroscopy to kinetic studies. Gupta et al. (336)studied the effect of an ultrasonic field on the stability of the amorphous alloy FeBSigBl1CZ.The response of the alloy to the ultrasonic field depends on the temperature at which it is exposed to ultrasonics. At elevated temperatures ultrasonics markedly enhance the crystallization process. The observed results suggest that an ultrasonic field causes a lowering of the activation energy of crystallization. Genin et al. (337) thoroughly discuss the kinetics of oxidation and the role of the chlorine concentration during the oxidation of iron in chlorinated aqueous medium. The hyperfine structure of two ferrous hydroxides, Fe(OH)*and [2Fe(OH),,FeOCl], and Green Rust I were analyzed. Zemcik et al. (338) compared Mossbauer, resistometric, and coercivity data on isothennic crystallization of a series of amorphous Fe84-xV,B16alloys to find two crystallization phases. The activation energies of these processes are near the metal diffusion energies and increase with vanadium content. Vanadium addition was found to stabilize the amorphous Fe-B-base structure. The broadening of the 57FeMossbauer line due to diffusion jumps of iron atoms in a copper single crystal was measured by Steinmetz et al. (339)as a function of crystal orientation and temperature between 1060 and 1313 K. Resulb indicate that Mossbauer studies of this type may contribute to the understanding of unexplained diffusion mechanisms where the jump vector is unknown. Raj and Sathyamoorthy (340) report the first Mossbauer results on the hydrogen diffusion parameters in the @-hydrideregion with x > 1.0. The method discussed is based on the assumption that hydrogen diffusion causes a decrease in the f factor and that the temperature dependence of the diffusion-induced mean-square displacement of probe atoms is proportional to the mean-square displacement of hydrogen atoms. Many other papers covered a variety of topics. Pott et al. (341) examined correlations between measurements of the orientation of the easy magnetization axis of magnetic particles in magnetic recording media using magnetic methods and using Mossbauer spectroscopy. A combination of both methods yielded excellent magnetic characterization of the recording media. Morup et al. (342) show that Mossbauer spectroscopy can be used to determine the size of particles in a frozen ferrofluid in applied magnetic fields. The temperature dependence of the M-bauer spectra gives an upper limit for the magnetic anisotropy of the particles which is considerably smaller than that for crystalline a-iron particles. Thermal and microstructural processes which lead to the formation of iron-doped rare-earth oxides were studied by Vajpei et al. (343)with both Mijssbauer spectroscopy and ESR spectroscopy. The local composition mode of aggregation and effective dispersion of microcrystals of orthoferrites critically depend on the characteristic microstructure and magnetic properties of the host rare-earth oxide. Dubiel and Le Caer (344) found evidence of the third harmonic of spin-density waves in the ll9Sn Mossbauer spectra of Sn-doped metallic chromium. Perlow et al. (345) report that 700-MHz radio frequency current pulses passing through a 57Co-in-copper-foil Mossbauer source immersed in liquid helium at 4.2 K cause large increases in transmission of the y-rays. Experiments were performed at temperatures from 2 to 78 K. The increases are associated with heat transfer instabilities at the He-metal interface. The observed effect was much larger than expected. Electron back scattering Mossbauer spectroscopy complemented by X-ray photoelectron spectroscopy was applied by Brett et al. (346)to study the nature of passive films or iron. The films were found to resemble T-FeZO3.No hydroxyl ion was present within the passive films. Stevens et al. (347) examined six clay samples each fired to six different temperatures in the range 1000-1250 O C . The 102R
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physical properties of the resulting fired bricks were examined to determine the quality of each brick. Two clays not suitable for the production of good brick could be distinguished from the others by their Mijesbauer parameters. Taneja et al. (348) studied iron phases in thermal plant ash. Thermal plant ash is of interest because of its potential to cause corrosion and other damage to power stations and because of the environmental dangers presented by its disposal.
ACKNOWLEDGMENT We wish to acknowledge Vivian Coman and Joyce Weatherspoon who assisted in the preparation of this review. We also wish to note our appreciation to Mary Alice Goforth and Chris Boss who aided in the retrieval and organization of the literature. The authors acknowledge Chemical Abstracts Service for providing'access to STN International to aid in the literature search used in the preparation of this work. Finally, we wish to acknowledge the support of the National Science Foundation to L. H. Bowen (Grant No. EAR-85-0656). LITERATURE CITED ( 1 ) Stevens, J. G.; Bowen, L. H.; Whatley, K. M. Anal. Chem. 1986, 5 8 , 250R-64R. (2) Applicatlons of the Mssbauer Effect (Proceedings of the International Conference, Alma-Ata, 1983);Kagan, Yu M., Lyubutin, I. S., Eds.; Gordon and Breach Sclence Publishers: New York, 1985; 5 Volumes, 1984 pages. (3) Applications of the Mossbauer Effect (froceedlngs of the Internatlonal Conference on the Applicetions of the Mssbauer Effect ; Leuven 1985) Hyperfine Interac .; Coussement, R., Langouche, G., Eds.; 1986, 27/29, 1656 pages. (4) Industrial Applications of the Mossbauer Effect; Long, G. J., Stevens, J. G., Eds.; Plenum: New York, 1987; 806 pages. (5) Mijssbauer Spectroscopy Appllsd to Inorganic Chemistry; Long, G. J., Ed.; Plenum: New York, 1987; Vol. 2, 642 pages. (6) Cranshaw, T. E.; Dale, D. W.; Longworth. G. 0.; Johnson, C. E. Mossbauer Spectroscopy and Its Applications ; Cambrldge University Press: Carnbrldge, 1985; 119 pages. (7) Mijssbauer Spectroscopy; Dlckson, D. P. E., Berry, F. J., Eds.; Cambridge University Press: Cambridge, 1986; 269 pages. (8) Hsla, Y.-F.; Ye, C.-H.; Zhang, J.-A. Mossbauer Effect and Its Applications; Atomic Energy Publishers: Beijing, 1984; 423 pages (in Chinese). (9) Cheng, H. S. K ' o Hsueh Fa Chan Yueh K'an 1988, 14, 245-60 (in Chinese). (10) Hsla, Y.-F.; Zheng. Y.-F. Hyperfine Interac. 1986, 27, 69-79. (11) Koik, B. South Afr. J . Sci. 1985, 81, 662-5. (12) Stevens, J. G.; Ruiz, M. J. Encyclopedia of Materials Science and Engineering; Bever, M. B., Ed.; Pergamon: Oxford, 1986; pp 3117-3121. (13) Dickson, D. P. E.; Johnson, C. E. StructuralandResonance Techniques in Biological Research; Rousseau, D. L. Ed.; Academic: London, 1984; pp 245-293. (14) Clark, S. J.; Donaklson, J. D.; Grimes, S. M. Spechoscopic Properties of Inorganic and Organometallic Compounds Volume 18; The Royal Society of Chemistry, Burlington House: London, 1985; pp 343-448. (15) Huynh, B. H.; Kent, T. A. Advances in Biochemistry; Eichhorn, G. L., Marzilli, L. G., Eds.; Elsevier Science: New York, 1984; pp 163-223. (16) Dlckson, D. P. E. Hyperflne Interac. 1987, 33, 263-273. (17) Mijssbauer. R. L. Hyperflne Interac. 1987, 33, 199-222. (18) Regel, A. R.; Seregin, P. P. Sov. Phys. Semicond. (Engi. Trans/.)1964, 18, 723-734. (19) Boolchand, P. fhysical Properties of Amorphous Materials; Alser, D., Schwartz, B. E., Steele, M. C., Eds.; Plenum: New York, 1985; pp 221-260. (20) Burriesci, N.; Petrera. M.; Gennaro, A. Chim. Ind. (Milan) 1985, 67, 494-499. (21) Topsoe, H.; Clausen. B. S.; Topsoe, N-Y; Pedersen, E. Ind. Eng. Chem. Fundam. 1986, 25, 25-36. (22) Gonser, U.; Wagner, H-G. Hyperfine Interac. 1985, 2 4 / 2 6 , 769-792. (23) Zemcik. T. Alma -Ata Mossbauer Conference; Gordon and Breach: New York, 1985; Vol. 1, pp 369-394. (24) Gonser, U. Topics ln Current Physics: Microscopic Methods in Metals; Gonser, U., Ed.; Springer-Verlag: Berlin, 1986; pp 409-448. (25) Gonser, U. Alma-Ata Miissbauer Conference: Gordon and Breach: New York, 1985; Vol. 1, pp 141-168. (26) Meurer, M.; Friedt, J. M. Hyperfine Interac. 1986, 27, 135-146. (27) Maddock, A. G. Chemical Bondlng and Spechoscopy in Mlneral Chemistry; Berry, F. J., Vaughan, D. J. Eds.; Chapman and Hall: London, 1985; pp 141-208. (28) Dyar, M. D. Am. Mineral. 1987, 72, 102-112. (29) Ujihka, Y. Bunseki 1985, 231-241. (30) Montano, P. A. Hyperfhe Interac. 1986, 27, 147-159. (31) Stevens, J. G. MRS Bull. 1988, 11(6), 14-7. (32) Kalvius, G. M. Hyperflne Interac. 1985, 2 4 / 2 6 , 793-816. (33) Kalvlus. G. M. J . Less-Common Met. 1986, 121, 353-378. (34) Mehik, M.; Parish, R. V. Coord. Chem. Rev. 1986, 127, 353-378. (35) Vertes, A.; Czako-Nagy, I. I z v . Khlm. 1986, 19, 360-398. (36) Afanas'ev, A. M. Alma-Ata Mossbauer Conference; Gordon and Breach New York, 1965; Vol. 1, pp 23-61. (37) Cianchi, L.; Moretti, P.; Mancinl, M.; Spina, G. Rep. frog. Phys. 1986, 4 9 , 1243-1291.
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Ion-Selective Electrodes Robert L. Solsky
E. I . du Pont de Nemours, Inc., Imaging Systems Department, New James Street, Towanda, Pennsylvania 18848
INTRODUCTION This review focuses on the more significant contributions to the understanding and use of ion-selective electrodes (ISEs).There is a strong interest in this field as over 1400 articles and abstracts were found during the writing of this review which covers the period from January 1986 through December 1987. The major analytical and electrochemical journals were read and a hand search of Chemical Abstracts uncovered the remaining articles. Unlike previous fundamental reviews, this paper will not attempt to list all the pertinent papers on ISEs. Rather, the more interesting works and applications are covered to illustrate examples of the general trends and directions of ISE interests.
BOOKS AND REVIEWS There have been a host of review papers and publications during the time period covered by this fundamental review. It is very useful to include bibliographies such as that provided by Moody and Thomas in 1986 (1)in that they can provide a much more comprehensive listing of the literature than is possible in this short space. A discussion of the history and analytical uses of ISEs has been prepared by Koryta (2)while Cammann reminds us of the pros and cons of potentiometric analysis (3). The more important developments of potentiometric methods, including theory and applications, have been reviewed (4) and comparisons are drawn between the potentiometric and amperometric methods (5,6). Four of the more recently developed sensors were reviewed by considering the fundamental processes that govern electrode response (7) while others focused on the methods that can be used to increase the accuracy and precision of potentiometric measurementa (8). The following paragraphs summarize the reviews that discuss topics found in the remaining five main sections of this fundamental review and are organized accordingly. The response mechanism of the chalcogenide glass electrodes and electrodes based on other oxide glasses has been reviewed in the areas of electron conduction (9) and analytical behavior of membrane materials (IO). The Ruzicka-type solid-state matrix electrodes were reviewed by considering which silver salts, salt mixtures, and substrates could be used for potentiometric analysis ( 1 1 ) . The development of rareearth ISE’s was outlined from construction and materials selection to analytical applications (12). An interesting aper documented the cases of response of solid-state electroles to quarternary ammonium ions (13). Liquid membrane and solvent polymeric ISE publications once again have represented the majority of papers published in this field. Increasingly, authors from the Peoples Republic of China are becoming involved in this area. Both a general review on electrodes based on ion associates and a review of liquid membrane anion-selective electrodes illustrate this (14, 15). Poly(viny1 chloride) remains the most significant support polymer of choice as described by Thomas (16, 17). Four different classes of polymer-based electrodes have been described for conventional ISE construction and use (18). The most frequently used mediators of the solvent polymeric electrode have been the neutral ion-sequestering agents. Crown ethers and other neutral complexin agents have been reviewed from their structurefunctional refationships to their 106 R
analytical applications in solvent polymeric electrodes (19-22). The desi of ligands suitable for ion-complexing agents was discusseEhile illustrat ’ the improved kinetic performance of modified crown etherxrivatives (23). Long carbon-chain ammonium compounds have also been studied and used as selective ion-sequestering agents where the relation of structure and selectivity were discussed (24). Coated-wire electrodes have been shown to be successful extensions of the conventional polymeric electrodes. Freiser and Cunningham have reviewed the principles of operation and construction techniques (25) while Freiser has summerized the practice and applications of coated wire electrodes (26-28). Specific reviews have been written that cover selected liquid membrane and polymeric electrodes for nitrate (29),lithium (30),and sulfate and phosphate (31). Buck and Cosofret discussed the principles and practice of drug sensors based on liquid membrane electrode structures (32). The combination of ion-selective and gas-selective electrodes with nature’s enzymes has proven to be one of the more fruitful areas of academic research as well for analytical applications. Rechnitz has summarized some of the recent developments and outlined the future prospects for their biocatalytic sensors (33, 34). Another extensive review in this ever-developing biosensor area describes potentiometric biosensors as well as these biosensors based on other modes of detection (35)as do two additional works which extend the realm of biosensors to immunochemistry (36, 37). Enzyme electrodes have been reviewed extensively and include discussions of general principles through analytical applications (38-48). The obvious evolution of enzyme electrodes to include designs that are based on the microbes and tissues that yielded the enzymes has been developed (49, 50). Koryta further describes these strategies and reviews the biological principles that govern these electrode’s behavior (51). As more attention is focussed on the development of immunologically sensitive sensors, the establishment of potential differences at both blocked and unblocked interfaces must be understood as Buck describes (52). The use of potentiometric electrodes as detectors for immunoassays was surveyed by Monroe (53, 54) while Rechnitz looks to the future with several strategies for the creation of more novel biosensors (55). Clinical applications of ISEs have always been the crown jewel for analytical chemists. The potential difficulties have led to several setbacks in the commercial acceptance of these devices in routine use (56). However, ISE-based ap lications do continue to gain acceptance through the intro uction of better and more appropriate analyzers (57,58). Progress in the acceptance of these devices will continue and future applications are being discussed (59, 60). Biosensors are especially suited for use in clinical chemistry (61-65)while many of the basic electrodes find use as well (66-69).Ion-selective microelectrodes have found great utility in physiology and biomedical research. There remains certain fundamental obstacles as a discussion of 30 years of microelectrode use attests (70). The specific design of ionophores for liquid membrane rnicroelectrodea was extensivelyreviewed by Simon et al. and describes the requirements for the desired functional properties (71). Many other reviews discuss principles and design while others focus on specific applications (72-77). Finally, I a m recognizing the dissertations that were published during the time period covered by this fundamental
0003-2700/88/0360-106R$O1.50/00 1988 American Chemical Society
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