(310) Terent’ev, A. P., Luskina, B. M., Tr. Komis. p o Analit. Khim. Akad. Nauk S S S R 13, 20 (1963). (311) Terent’eva,,.E. A., Malolina, T. M., Zh. Analit. Khzm. 19, 353 (1964). (312) Terent’ev, A. P., Larikova, G. G., Bondarevskaya, E. A,, Zbid., 18, 514 (1963). (313) Terent’ev, A. P., Turkel’taub, A. M., Bondarevskaya, E. A,, Domochkina, L. A,, Dokl. Akad. hiauk S S R 148, 1316 (1963). (314) Thurauf, W., Thiemann, W., Brennst Chemie 44,275 (1963). (315) Tikhonova, V. I., Zzv. Vyssh. Ucheb. Zavedenii, Khim. i Khim. Tekhnol. 6 , 744 (1963). (316) Tikhonova, V. I., Zh. Analit. Khim. 19, 629 (1964). (317) Tiwari, R. D., Sharma, J. P., ANAL. CHEM.35. 1307 11963). (318) Tiwaii, R. D.,Sharma, J. P., Indian J . Chem. 2,173 (1964). (319) Tiwari, R. D., Sharma, J. P., 2.Anal. Chem. 195, 267 (1963). (320) Tolg, G., Zbid., 194, 20 (1963). (321) Trutnovsky, H., Mikrochim. Ichnoanal. Acta 1963,685. (322) Trutnovsky, H., Z . Anal. Chem. 198, 331 (1963). (323) Tsellinskaya, T. F., Ivanova, N. I., Zavodsk. Lab. 30, 536 (1964). (324) Tsuji, H., Kusaka, Y., Namikawa, Y., Bull. Chem. SOC.Japan 35, 2045 ( 1962).
(325) Uno, T.,
Miyajima, K., Chem. Pharm. Bull. Japan 11, 75 (1963). (326) Vajgand, V., Pastor, T., Glasnik Hem. Drustva, Beograd 28, 73 (1963). (327) Zbid., P. 1. (328) Van Hall, C. E., Safranko, J., Stenger, V. A,, ANAL. CHEM.35, 315 (1963). (329) Van Leuven, H. C. E., Gouverneur, P., Anal. Chim. Acta 30, 328 (1964). (330) Van Zanten, B., Decat, D., Leliaert,
G., Intern. J . Appl. Radiation Isotopes
14, 105 (1963). (331) Vecera, M., Mikrochim. Zchnoanal. Acta 1964,’196.’ (332) Vecera, M., Lakomy, J., Lehar, L., Talanfu 10, 801 (1963). (333) Vetter, G., Chem. Tech. Leipzig 15, 43 (1963). (334) Vitalina, M. D., Klimova, V. A., Zh. Analit. Khim. 17, 1105 (1962). (335) Vojtech, F., Chem. Prumysl 13, 473 (1963). (336) Von Schuching, S., Karickhoff, C. W., Anal. Biochem. 5, 93 (1963). (337) Vulterin, J., Collection. Czech. Chem. Commun. 28, 1391 (1963). (338) Wadelin, C. W., Talanta 10, 97 (1963). (339) Waechter, K. H.. Chimia 17, 113 ‘ (1963). (340) Waechter, K. H., Atomivirtschajt 8, 538 (1963). (341) Walisch, W., Trans. N . Y . Acad. Sci. 25, 693 (1963). (342) Wang, S.-L., Acta Chim. Sinica 30, 211 (1964). ’
(343) Wang, M.-H., Jen, M. L., Zbid., 29,301 (1963). (344) Weaver, E. A,, Chemist Analyst 53, 18 (1964). (345) Weitkamp, H., Korte, F., Chem.Zng.-Tech. 35, 429 (1963). (346) Westoo, G., Analyst 88, 287 (1963). (347) Wheeler, P. P., Richardson, A. C., Mikrochim. Acta 1964, 609. (348) White, D. C., Talanfu 10, 727 (1963). (349) Williams, T. R., Lautenschleger, M., Talanta 10, 804 (1963). (350) Willemart, R., Robin, J., Ann. Pharm. Franc. 21, 423 (1963). (351) Wilson, A. D., Lewis, D. T., Anahst 88, 510 (1963). (352) Wronski, M., Chem. Anal. (Warsaw) 8,299 (1963). (353) Wu, J.-X., Acta Chim. Sinica 29, 54 (1963). (354) Yeh. C.-S.. Microchem. J . 7, 303 (1963). ‘ (355) Yoshikawa, K., Mitsui, T., Zbid., 9. 52 (1965). (356) Yoshizaki, T., ANAL. CHEM. 35, 2177 (1963). (357) Zarinskii. V. A.. Gur’ev, I. A., ‘ Zh. Analit. Chem. 19,‘37 (1964). (358) Ziegler, K., Till, H., Schindlbauer, H., Mikrochim. Zchnoanal. Acta 1963, 1144. (359) Zugravescu, P. G., Rev. Chim. Bucharest 15, 297 (1964).
Chemical Microscopy G e o r g e G. Cocks, Cornell University, Ithaca,
T
previous review in this series by Cocks (58) covered the two-year period ending in October 1963. This review covers the two-year period ending in October 1965. However, there are some references to earlier publications that were missed in the previous review and there are a considerable number of references to publications in November and December of 1965. In gathering information for this review an attempt has been made to find books and articles of interest to chemists and chemical microscopists who may need to apply the techniques of microscopy to the solution of problems in chemistry. Therefore, no attempt has been made to cover publications on the biological, metallurgical, and geological applications of microscopy except for those which describe techniques or apparatus applicable to chemical microscopy. Electron microscopy is the subject of a separate review. References to publications in the fields of optics and crystallography which are potentially useful to the microscopist are included. The great diversity and number of publications, concerned with the microscope and its use in chemical studies, makes it impossible to find and review all of them. The author would appreHE
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ciate any comments and suggestions, particularly with regard to the omission of important articles. MEETINGS AND SYMPOSIA
The New York Microscopical Society holds regular semimonthly meetings a t which papers are presented on various subjects of interest to microscopists (111). In addition the Society sponsored a symposium on “New Paths in Industrial and Biological Microscopy.” This symposium was held in New York City, March 19-20, 1965, and included the following papers: “Fusion Methods Applied to the Interaction of Carcinogenic Compounds” by D. Laskowski, “Chemical Electron Microscopy” by G. G. Cocks, “Ultramicroanalysis” by W. C. McCrone, “Fusion Techniques in Chemical Microscopy’’ by F. Jones, “Longitudinal Sectioning of Fibers for Light and Electron Microscopy” by F. F. Rlorehead, and “Interference Microscopy Applied to the Study of Polymers” by R. Scott. These and other papers presented a t the symposium will be published by the NYMS. The series of symposia sponsored by McCrone Research Institute was con-
tinued, “Micro-64” being held in Chicago, June 17-19, 1964, and ‘ M c r o 65” being held at the University of Sheffield, in England, July 6-9, 1965. Many of the papers given a t “Micro-64” have been published and will be referred to under the appropriate headings. The papers given a t “Micro-65” were divided into four general groups; metallurgical microscopy with special reference to quantitative methods, particle sizing and counting, dusts, etc., fibers, crystals, and other materials, and general methods, instruments, etc. (198). During the Chicago meeting an organizational meeting was held to discuss a proposed new society, The International Microscopical Society (131s). Further discussions were held during the meeting a t the University of Sheffield. Information about the IMS can be obtained from W. C. McCrone Research Institute, 451 East 31st St., Chicago 16, Ill. The Royal Microscopical Society sponsored a “Symposium on the Microscopy of Fibrous Materials,” which was held a t the Manchester College of Science and Technology, April 6-8, 1964. Many of the papers presented were concerned with the microscopy of textile and paper fibers. Abstracts of these papers have been printed (g49). VOL. 38, NO. 5, APRIL 1966
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The papers presented a t the “Symposium on Resinographic Methods,” sponsored by the American Society for Testing and Materials (ASTM) in June 1963, have been published as a book (6). The ASTM has been active in the field of microscopy and in 1964 a new committee, E-23, on resinography was established, and Subcommittee 28 of Committee E-1 on methods of testing has been reorganized as a separate committee, E-25, on microscopy. This committee is concerned with “the promotion of knowledge and formulation of definitions, specifications, methods, recommended practices, and instrumentalstandards in the general field of microscopies including those which involve light, electrons, ions, or x-rays. The scope includes the development of standards for instruments and their pertinent accessories, and recommended practices for the evaluation of perfomance, the interpretation of images and patterns, and the preparation of specimens in the microscopical examination of materials. BOOKS AND ARTICLES OF GENERAL INTEREST
The historical aspects of microscopes and microscopy have been discussed by several authors. Cowan presented a short, general history of the microscope (66). At the “Tercentenary of the Microscope in Living Biology,” the first American meeting of the Royal RIicroscopical Society, held at Washington, D. C., in April 1963, Hughes presented a paper entitled “Progress in llicroscopy 1663-1673” (133). This paper was primarily concerned with Hooke’s pioneering work. Booth has presented a brief but very interesting history of the development of achromatic and high aperture objectives (26). The Medical Museum of the Armed Forces Institute of Pathology and its collection of microscopes was the subject of a paper by Sheridan (270). Richards talked on American microscope makers and introduced the collection of microscopes at the hledical Museum of the Armed Forces Institute of Pathology (233). American microscopists and microscopy was also the topic of Schaeffer (257) who confined his discussion to the nineteenth century. A more specialized type of history was presented by Frey-Wyssling (90) who dealt with the determination of submicroscopical structures by indirect methods. He compared the ideas of structure derived from such methods as polarized light microscopy and x-ray diffraction with the ideas which have been derived from electron microscopy. A “History of Microscopy,” concerned with the lives and works of great researchers in medicine, has been compiled by Freund and Berg (89). This work is in German. Three books designed to instruct those interested in learning to use a microscope
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have appeared recently. Barron (16) has produced a completely revised version of “The Intelligent Use of the Microscope,” by C. W. Oliver. This is a carefully written book which includes sections on the selection of microscopes, and the use of instruments including phase contrast and interference microscopes. It also has an extensive description of the methods of photomicrography. A new edition of Duddington’s book“ The Microscope” has been published (65). An American edition of Hartley’s book “HOWto Use a Microscope” (113) has been published as one of the “American Museum of Science Books” series. Lee and Friedman have authored this edition. Malies (187) has published an article in two parts intended for those who have had no formal training in microscopy. Part I is on condensers, and Part I1 on objectives. The teaching of biological microscopy in the colleges is the subject of an article by Ronkin (244). He discusses the poor quality of the instruction in microscopy given to biologists, and suggests the actions which educational institutions, microscope manufacturers, and learned societies might take to remedy this situation. He also presents some ideas on the teaching of microscopy and gives a list of courses offered to biologists by various American universities. The teaching of microscopy was also discussed by Mason (190) who describes three levels of knowledge of microscopy which should be considered. He also describes how persons a t these levels should be taught and lists a series of “minimum facts for microscopists.” FranGon’s new book, ‘‘Modern Applications of Physical Optics,” (83) contains much of interest to microscopists concerned with the optics of image formation. The theory of microscopy is presented by Michel in his new book (197). He is concerned with the geometrical and physical optics of transmission microscopy. He describes 50 instructive experiments on the theory of the image formation which can be carried out using a modernized version of Abbe’s diffraction plate and accessory apparatus available from Carl Zeiss (Oberkochen). A very interesting survey of microscopy including some history of the development of microscopy, its current status and future outlook is presented by Meyer-Arendt (196). He discusses not only general light microscopy, but also microspectroscopy, interference microscopy, and electron and x-ray microscopy. Slater ( n 6 )describes new microscopy techniques, including the laser microscope, Dyson’s image splitting eyepiece, the hypodermic microscope, a polarizing vertical illuminator for reducing glare, and microscopes for space applications such as studying moon surface materials.
Crystallography has always been of interest to chemical microscopists. TWOgeneral books on this subject are Bunn’s book entitled “Crystals, Their Role in Nature and Science” (38), and Wood’s book “Crystals and Light” (317 ) . Bunn writes for the beginner or interested student or layman who wants to find out, in a general way, about crystals. Wood’s book is also written for people with no training in crystallography. She tells what crystals are, how they are classified, and something of their physical properties, and goes on to describe some of the interactions between crystals and light, particularly polarized light. There are chapters on the polarizing microscope and its use in optical crystallography. “Introduction to Dynamic Morphology” is the title of a book by &layer (191) designed to explain to the physical scientist how the biologist derives and interprets morphological information. It supplies a background on the morphology of biological structures for physical scientists mho have a need for this kind of information in their research programs. Biek (22) has written a book on “Archaeology and the hIicroscope.” However, its subtitle, “The Scientific Examination of Archaeological Evidence,” is more indicative of its contents. The book is not confined to microscopical examinations and it is not concerned with instructing the reader on how to use the microscope to examine objects of archaeological interest. BenedettiPichler (17) has published a book entitled “Identification of Materials via Physical Properties, Chemical Tests and Microscopy,” which should prove useful to the chemical microscopist. Another book which may be of general interest because of the variety of microscopical techniques described is the ASTM publication “Symposium on Resinographic Methods” (6). It contains papers on specimen preparation, highspeed cinematography in photoelasticity studies, fluorescence microscopy, dispersion staining, phase microscopy, ultraviolet microscopy and light scattering techniques as well as papers on the microscopical examination of polymers and resins. A “1964 Yearbook” (111) published by the New York Microscopical Society contains a number of papers and abstracts of talks given before the Society as well as describing the activities of the Society. OPTICS
Two of the books mentioned above (83, 197) mere concerned with the broad aspects of microscopical optics. I n this section of the review papers dealing with specific optical phenomena will be cited. White (312) derives expressions for the transmission function of a microscopical object. He relates the optical absorption and the refractive index (n) of an
object to the concentration of matter within it. Both the amplitude and phase of the transmitted waves are shown to carry information about concentration per unit area. Charman (46) compares the diffraction images given by holes in an opaque film under incident illumination with thnse given by opaque discs in transmitted illumination. Some differences are noted. Annular stops in the substage condenser and their effects on the microscopical image were examined experimentally by Lau and Weide (170) and Rienitz (235). Lau and Weide claim that optimum image quality is obtained by using an annular diaphragm and they discuss the theoretical considerations which elucidate their experimental results. Rienitz shows that multiple image planes, in addition to those known t o be found in image forming optical systems, are present when annular illumination is used. White (311) gives a good discussion of the exit pupil in visual microscopy and relates it to magnification, numerical aperture of the objective, and to position of the eye. Resolution beyond the limits indicated by theory is dealt with by several authors. Lohman and Paris (179) discuss the theory of super-resolution in mathematical terms. They show that superresolution is possible only when something is known about the specimen, for example, that it is not birefringent and that it is not changing with time. Attainment of super-resolution using polarized light microscopy is described by Lohman and Paris. Bouyer (28, 29) uses a microscope, in which the polarizer and analyzer rotate in synchronism, which makes it possible to use full aperture and obtain improved resolution with isotropic specimens. A special case of resolution (spurious) involving gratings moving behind fixed apertures is discussed by Barlow (13) and by Palka (215). Cargille (42) discusses the optical function of immersion oil, its ideal properties, and its application. A simple method of measuring numerical apertures greater than one is proposed by Hewlett (124). This method does not apply to objectives having numerical apertures less than one. Bradbury and Turner (SO) have examined one of Norbert's ten-band test plates in the electron microscope. They show that the spacings on this plate are substantially correct. They also discuss the history of test objects briefly. An elaborate and apparently highly accurate method of measuring microscope magnification is given by Freeman (87). Interferometers for testing objectives are proposed by Steel (278) and Burch (39). Claussen (49) discusses the development of the plano-objective during the last two decades. The theory of this
type of objective is given, and illustrated with micrographs showing results obtained. Diagrams and optical data for many plano-objectives are included. Terrell (289) describes the design of 16mm. and 8-mm. interference objectives manufactured by Watson. These are 2-beam interferometers which can be attached to ordinary microscopes. Aspheric reflecting objectives for a Cassegrain-type microscope have been designed and evaluated by means of a computer program (59). This lens is aplanatic in the infrared and is to be used for infrared multireflectance spectrophotometry. A computer was also used by Rosch (242) to compute the sequence of polarized light interference colors (Korrenberg colors) and thin film colors (Yewton's colors) through the third order. The results are tabulated and shown in graphical form. The Mach effect associated with microscope images has been studied by Charman and Watrasiewicz (48) and by Watrasiewicz (307). They measure and compare the distribution of subjective brightness in microscope images of an opaque straight edge with the corresponding physical luminance distributions. A method of enhancing contrast between grains in thin sections of polycrystalline minerals was proposed by Deffeyes (61). A pair of right and left handed optically rotatory plates are placed between the polarizers and before and after the specimen. The thickness of the plates is such that the rotatory dispersion of the first plate spreads the visible spectrum over a 90" sector, and the second plate compensates this dispersion if no sample is present. This device gives color contrast even t o sections which ordinarily produce only low order grays. The relationships between coverglass thickness, its refractive index, and the tube length of the microscope are shown on a series of graphs worked out by Uhlig (299). The sources of errors in reflectivity measurements made with a vertical illuminator are described and the effects of these errors on measurements of refractive index and absorptivity are set forth by Piller and Gehlen (925). Equations for the exact determination of these errors are given. A very interesting paper on the significance of Becke line refractive indices in synthetic fibers has been published by McLean (186). He concludes, among other things, that the Becke line test does not necessarily measure the refractive index of the surface layer in contact with the standard liquid. Saylor (255) has made a valuable study of the errors which occur in the measurement of microscopic spheres. These studied were concerned with the influence of indices of refraction of the specimen, focus, aperture, and resolution on these errors.
INSTRUMENTS
Microscopes. Sippel and Glover (275) describe the results of examining the structures of carbonate rocks using a new type of luminescence microscope. The luminescence is excited by electron irradiation. Details of the instrumentation are to be published by the Rev. Sci. In&. Microscope optical systems designed for observing surface topography by frustrated total internal reflection and by interference are presented by XlcCutchen (184). Lau (169) has continued and expanded his work on the doppelmikroskop. Peppers (221) has developed a laser microscope which is essentially a ruby laser attached to a microscope in such a manner that a given tiny area of the specimen can be selected and irradiated with the focused laser pulse. It is possible to concentrate 1000 joules per mm.* in a spot 1 micron in diameter. Long, Brushenko, and Pontarelli (180) have designed and built a fiber-optics hypodermic microscope which can be inserted into living tissue to observe structures within the tissue. Vialli (303) describes a histophosphoroscope which he has had built and uses to study the relationship between histophosphorescence and histofluorescence. Vialli also outlines other fields of histofluorescence research which have received little attention. A suggestion for an apparently similar instrument has been put forth by Szent-Gyorgyi (285). This latter instrument makes it possible to separate fluorescence from phosphorescence. Stereomicroscopy is the subject of two papers (132, 287). The first of these discusses the method of using a divided polarizing filter in the substage and cap analyzers over the eyepieces. The second paper concerns the displacement of an annulus in the substage to provide oblique illumination which results in a pseudoscopic, plastic, image. Barron (14) shows how to attach a Jackson tubelength corrector to a Zeiss GFL microscope. He also describes the testing of the apparatus and gives calibration curves. Stages. As is usually the case there were several reports of hotstage designs (62, 108, 110, 195). Hallbauer (110) has developed a stage for studying crystal growth in silicate melts. This stage is suitable for transmission microscopy using polarized light. The highest temperature reported was 1650' C. Temperatures were read with an optical pyrometer. Dodd (62) uses a wire loop as a microfurnace, the wire loop serving as a resistance thermometer for measuring the temperature to & 3 O C. Temperatures to 2000' C. are attained. Mercer and Miller (195)have modified a thermocouple microfurnace to allow continuous monitoring and recording of cooling curves for melt droplets quenched a t rates up to 20,000° C. per VOL. 38, NO. 5, APRIL 1966
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second. Another thermocouple type microfurnace is described by Gutt (108). This microfurnace is used for x-ray diffraction work as well as microscopy. Gutt reports temperatures to 2150" C. Combinations of hot stages with tensiometers are reported by Feltham ('79) and by Kirchner and Ripling (151). Feltham's stage is a vacuum chamber while the other stage provideq for a controlled atmosphere. Both stages can be used to observe flow and fracture of metal specimens. .I review of high temperature surface microscopy was published by Rlitsche and Jeglitsch ($03). They also pointed out the possible disturbing influences, particularly selective evaporation of the sample constituents. Direct observation of the sintering process in metal powders was reported by Torkar and Weitzer (295). Fehrenbacher and Jacobson (78) observed the monoclinic to tetragonal phase transformation in Zr02. Stages designed to cover a lower temperature range are also reported. Hay (119) used a simple thermistor bridge thermostat in a hot stage for a polarizing microscope. This thermostat gave control to =k0.02" C. over a range from 50" to 200" C. This stage maintained temperature stability over periods of several days and \\-as used to study crystallization kinetics of stereoregular polymers. Hooss (128) has built a thermoelectric stage which can be used for cooling as well as heating. Fluids can also be circulated through the cell. Temperatures in the range -3" C. to $50" C. can be maintained to zk0.05" C. Another thermoelectric stage was reported by Markussen and McCrone (189). The range of this stage is -50" to $100" C. A selected temperature can be attained in 4-5 minutes. A different approach to control of the temperature of microscopical specimens can be used if the temperatures are low enough. The entire microscope and its surroundin,vs can be warmed. Although this is usually done by enclosing the microscope in some type of box (269), Gordon (105) describes an air wall incubator which uses a heat gun to direct a flow of heated air over the stage. Temperature can be controlled to 37" ==I 0.05" C. The history, development and applications of warm stages is presented by Schmidt (261) Designs for a variety of special stages, for purposes other than controlling temperature, have appeared in the literature. Rikmenspoel (236,237)described a chamber for the simultaneous measurement of motility and respiration of spermatozoa, and an electronic analyzer to be used in connection with the cell. Crisler (57) placed a microscope in a gloved dry box for very careful control of the atmosphere around the specimen. This arrangement was used to study highly toxic materials. Crisler found I
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that the melting points for some compounds as measured in the drybox differed from those measured in ordinary laboratory atmosphere>. Foster (82) has built a hydraulic device for applying a measured undirectional force on a microscopical specimen. The effects of pressure on the electronic structure of solids is the subject of a paper by Drickamer (64). Petriconi (222) describes a cell chamber suitable for interference and ultraviolet microspectrophotometry while nutrient media flows through the chamber. Kretschmann (159)had built a special cell and a dipping cone for objectives suitable for studying changes in the birefringence of tissues which result from imbibition of various liquids. Mosebach (210) shows how the optical properties of an unstable compound can be obtained using a polarizing microscope equipped with a universal stage. Miscellaneous Accessories. -in easily built micromanipulator which achieves reduction in amplitude of motion by a novel use of springs is reported by Bailey and Bailey (11). This micromanipulator is quite small and a number of them can be mounted on one microscope. Piezoelectric micromanipulators were proposed by Ellis (73), and two very simple, easily made at home, micromanipulators were described by Horwitz and Wood (129) and by Schoenmakers (265). Zanotti (321) described a translating table (mechanical stage) which is particularly useful for histophotometry. It has both coarse and fine motions and the position of the specimen can be set to less than one micron. kings (134) has studied the influence of stress and deformation on the structure of cotton fibers using microtorsion, microstretching and ion etching apparatus. A cutting and notching device was described by Prevorsek, Coe, and Lyons (230) in a paper concerned with the behavior of notched textile fibers in longitudinal tension. "Foot Operated Continuous Focusing Attachment for Dissecting Microscopes" is the title of an article by Fulford and Slater (92). Micrometer eyepieces of the image-splitting variety are discussed in two papers, one by Houston (130) and one by Payne (218). Stadelmann (277) described an apparatus, to be attached to a screw micrometer eyepiece, which reads out and records, via automatic typewriter, the measurements made. Kiss (152) suggests a condenser designed to produce a plastic three-dimensional appearance of the specimen. Such a condenser, called by the author a mobilisierter filter-kondensor, has a filter consisting of a central opaque spot surrounded by concentric opaque rings.
All of these spots and rings as well as condenser lenses and mirrors are adjustable and moveable. This arrangement provides great flexibility in the illuminating system. A very interesting apparatus is dealt with by Clegg (50). With it selected cells in a specimen can be irradiated with a microbeam of (Y particles. A method of mounting the irradiated cell and cutting it with a microtome so as not to lose track of the cell is included in the article. A variable color filter consisting of a series of crystal plates can be made to supply any polarization color on demand ( 8 ) . Colors are changed by relative rotation of the plates. Another variable color filter of the interference type is proposed by Jones (140). A device for tilting the specimen so as to produce stereophotomicrographs is described by McCrone (183), and Hartshorne (115) tells about his single axis rotation apparatus for studying the optical properties of crystals. He also tells how t o use a manipulator he has built to mount the crystal on the rotation apparatus (116). Multiple beam interferometers built to hold the specimen and the interferometer plates are reported by Klute and Fajardo (154) and by Gould and Pick (106). Both of these instruments use differential screws to establish and adjust the fringe patterns. A reversible microscope slide is described by Sims and Lyon (274). This slide makes possible the examination of both sides of a specimen. POLARIZED LIGHT MICROSCOPY
The sequence of polarized-light interference colors (Norrenberg colors) and the sequence of thin film interference colors (Newton's colors) were calculated by computer (842). The results through three orders are tabulated and shown in graphical form. These colors are also listed in the T-S-D system according to DIN 6164 (a German standard). This last representation gives an idea of the visual impression created. Missmahl (201) proposes a method of testing the optics of a polarizing microscope using a stained tissue which is dichroic because the stain is deposited in a preferred orientation within the tissue. Such a preparation is useful for setting the polarizers exactly crossed and for observing strain birefringence in the optics. Slater in his general article on new microscopy techniques (276) describes a polarizing vertical illuminator having minimal glare. Reed-Hill, Smeal, and Lee (232) have examined four polished and etched face centered cubic metals with the polarizing microscope and with the electron microscope. These specimens were found by electron microscopy to have surface grooves as predicted by Jones. From these data it was deduced that the extinction directions on such specimens could not be
used to determine directly the crystallographic orientation. On the other hand, Eales (68) has used polarization figures as an aid in the identification of polished isotropic minerals. If plane polarized light of known azimuth of vibration is reflected from a polished isotropic surface it generally becomes elliptically polarized and the axis of the ellipse is rotated. From measurements of these changes the refractive index and absorptivity of minerals can be calculated. Measurements of the ellipticity of polarized light were accomplished through the use of compensators. Gahm (97) has published an article on this subject entitled “Quantitative Measurements by Compensators in Polarized Light.” Frey-Wyssling (91) has concerned himself with the quantitative determination of form dichroism. He shows that ultraviolet dichroism and the dichroism of fibers stained with noble metals are essentially form effects. The Nakamura plate was used by Vogel (304) for the precise determination of orientations using a universal stage. He also uses this plate to determine the position of minimum birefringence for objectives and hemispheres. The sign of birefringence of a textile fiber may change with changes in temperature. If such a change occurs the point a t which the birefringence is zero is characteristic of the fiber. Sieminski ($71) has examined a series of fibers and has recorded their temperatures of zero birefringence. ULTRAVIOLET AND INFRARED MICROSCOPY
I n his introductory remarks a t a symposium on the ultraviolet microscope, Caspersson (44) gave a brief historical review of the subject. At the same symposium Williams (314) spoke on the “Applications of the Vidicon and Image Converter in Ultraviolet Microscopy.” Montgomery, Bonner, and Cook (206) reviewed briefly the development of flying spot ultraviolet microscopy, discussing the advantages and disadvantages of this type of microscope. They suggest a stepping spot television microscope in which the scanning beam would stop at each specimen point until a given flux of ultraviolet light has passed through the specimen. The intensity of each spot of the image viewing screen would then be made proportional to the time required to attain the given flux. Forty (81) has continued his work on the ultraviolet transmission microscopy of the alkali metals. The nature of the optical contrast between molten and solid potassium was investigated. Cuthrell (59) has reported on the design of aspheric reflecting optics for a Cassegrainian microscope for infrared multireflectance spectrophotometry. The design and evaluation of this microscope were carried out on a computer,
INTERFERENCE MICROSCOPY
Interference microscopy has received considerable attention in the past few years. A new book by Krug, Rienitz, and Schulz (162) entitled “Contributions to Interference Microscopy” has been translated from the German by Dickson. This is the most comprehensive book available on this subject. FranGon’s book (83),on physical optics, devotes a chapter to the optics of the interference microscope. He has also published an article (84) on polarization interference microscopes in which the principles are set forth and various microscope designs are described. Richards (234) discusses the precision, instrumental errors, and observer errors which should be considered when making measurements with the AOBaker interference microscope. Gahm (95, 96) discusses quantitative measurements with interference microscopes for both isotropic and anisotropic preparations. The Leitz interference microscope for transmitted light was described by Walter (305), and Terrell (289) reported on the design of 16-mm. and 8mm. interference objectives manufactured by Watson. In a paper entitled “Some Applications of Equidensitometry in Interference Microscopy” (54), Cosslett described a photographic technique for producing very sharp fringes which are the contours of equal exposure on the photographic plate. This technique increases the accuracy to which two-beam interferograms can be read. Goldstein (104) has investigated the Relation of Effective Thickness and Refractive Index to Permeability of Tissue Components in Fixed Sections. Galjaard and Szirmai (99) have used interference microscopy to determine the dry mass of tissue sections. Coackley and Kliger (51) have devised a compression technique to study the water : solid relation in activated sludge flocs. They compress the floc to a measurable thickness in a cell and determine the concentration of water and solids using interferometry. Peck and Carter (219) have written a general paper on interference microscopy in polymer research. The interferometric determination of the refractive indices and birefringence of mohair wool fibers has been reported by Barakat and Hindeleh (12). Ross and Galavazi (2.46) measured the size of bacteria using an interference microscope equipped with a special half-shade device. The use of this device apparently eliminated systematic errors which occurred in earlier mork of a similar nature. Surface replicas aluminized and examined by interference microscopy were used by Medellin, Wendell, and Ang (192) to investigate epitaxial films. Thornton (291)
used an interference microscope to measure the surface contour of droplets on a surface and from these measurements he calculated the interfacial tension. Two authors (106, 154) have designed multiple beam interferometers intended for use with a microscope, and Tolansky (294) used multiple beam interferometry to examine the craters produced when a micro-drop or sphere strikes a surface. He compared the microcraters with craters caused by the impact of great meteorites upon the earth. A new kind of interference microscopy is the so-called wavefront reconstruction microscopy. In principle, a wavefront reconstruction microscope needs no lenses. There are a number of articles in the recent literature on wavefront reconstruction imaging. Of these, three (176, 177, 194), are directly concerned with microscopy. FLUORESCENCE MICROSCOPY
Fluorescence microscopy continues t o be used primarily in the biological sciences and no attempt has been made to review biological microscopy. However a few articles on fluorescence microscopy seem to be of general interest. Sansoni (253) has made a study of the use of luminescence analysis in ore dressing and in the quantitative or semiquantitative determination of the components of raw mined materials. Morgenroth (209) has studied the fluorescence of recent marine plankton and compared these rewlts with the results of a similar study of fossils. The application of fluorescence microscopy to research on the genesis of petroleum is pointed out. Eder and Fritsche (69) discuss the color photography of fluorescent microscopic objects. Gabler and Herzog (93) have combined phase microscopy with fluorescencemicroscopy. They describe the equipment which they used and point out the advantages and disadvantages as well as the potential applications of this device. Sippel and Glover (275) report an investigation of structures in carbonate rocks made with a special microscope. In this microscope, the luminescence is excited by an electron beam. The possibility of building a phosphorescence microscope is discussed by Szent-Gyorgyi (285). Vialli (303) describes a histophosphoroscope which can be used to study the relationship between phosphorescence and fluorescence. MICROSPECTROPHOTOMETRY AND MICROPHOTOMETRY
The measurement of reflectivity of the components of a specimen can be used to characterize the component. Ehrenberg (72) surveys the method and describes the newer instruments which VOL. 38, NO. 5, APRIL 1966
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can be used. He is particularly concerned with mineralogy and petrology. Roblin (238) describes an apparatus for measuring reflection factors, and Piller and Gehlen (225) discuss the errors in the measurements of reflectivity factors and the calculation of index of refraction and the absorptivity from these measurements. Trojer (296) uses reflection measurements to identify transparent inclusions in metallurgical products. Mitsche and Scheidl (204) apply reflection measurements to the identification of both metallic and nonmetallic phases. Pflug (223) has investigated lamellar geological structures by reflection photometry. He shows that replicas of the polished and etched surfaces can also be studied by this means. In some of his examples the specimen was treated with a reagent and the reaction products were stripped off with the replica and examined. Transmission microspectrophotometers are described by Liebman and Entine (174) and by Duecker, and Lippincott (66). A highly sensitive low light level microspectrograph is described by the authors of the first paper (174). They used this apparatus to detect the photosensitive pigments in retinal cones. The second paper (66) describes the assembly and performance of a double-beam microscope spectrophotometer from commercial instruments. A sliding photometer head for the microspectrophotometer has been reported by Evans (’75). Altman (1) describes a nonrecording microdensitometer of simple design. Altman (1) describes a nonrecording microdensitometer of simple design. Hartman (114) has designed an attachment which fits over the ocular of an ordinary microscope converting it t o a scanning microdensitometer. The specimen can be viewed a t the same time that it is being scanned. Walter (306) has published a description of the Leitz microspectrograph for the visible and ultraviolet range. This instrument can produce an image of the specimen using any wavelength between 2000 and 7000 A. It also produces a spectrogram of selected areas of the specimen along with a comparison spectrum of the source using a rotating sector. By intercomparing these spectra and images, quantitative measurements can be made. Television technology can be used to advantage in the field of microspectrophotometry. Hovnanian, et al. (131) have reported “UV-TV Microscopy and Microspectrophotometry.” Mitrani, et al. (202) describe a diskriminator-cytoplanimiter which produces an image on the television screen in which all areas of the image brighter than some selected value are white and all other areas are black. Boev, et at. (25) have modified this instrument so that only areas of the
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image having a brightness lying between limits selected by the operator are displayed on the screen. Practical testing of microdensitometers is dealt with by Charman (47). Gahrton (98) reports a quantitative study of the periodic acid-Schiff (PAS) reaction in human neutrophil leukocytes. This paper is of interest because the author uses a model system for comparison and standardization. Zanotti (320) describes tests involving the use of different type condensers and varying illumination, and shows how these factors affect histophotometric and histofluorometric measurements. Mira (100) uses a Loquin band photometer to follow quantitatively the melanophor reaction in isolated cells. A somewhat different method of measuring the transmissivity of living cells is reported by Pomerat, Rounds, and Huff (227). They have built an optical scanning device which measures and records the optical density of a phase contrast cinema film. DARKFIELD AND ULTRAMICROSCOPY
An improved optical arrangement for ultramicroscopic studies is reported by Heilmann (121). He claims that performance can be improved by a factor of 200 and that thermal scattering of very pure single crystals can be observed. Lark (165) describes a simple sample cell for orthogonal darkfield illumination. Uhlig (298) has designed a special condenser which makes it possible to change continuously from brightfield to phase contrast or from brightfield to darkfield illumination. Miles (199) reports on the observation of impurity precipitates in MgO single crystals by ultramicroscopy. iimelinckx (2) uses darkfield microscopy as well as other forms of microscopy to observe dislocations directly. SPECIMEN PREPARATIVE TECHNIQUES
Embedding and Replication. DuFresne, Rosa, and Campbell (67) describe a high pressure impregnator suitable for embedding friable samples. Savdir (154) has published an article describing a simple method of preparing replicas for light and electron microsCOPY.
Staining. The staining of thin sections of rocks to reveal the location of iron is described by Babel (9). Microtomy. A new microtome in which the knife is vibrating parallel to its edge during cutting is described by Bergstedt (20). A holder, which replaces the spring back usually used when sharpening microtome knives, is described by Tighe-Ford (292). He also discusses the sharpening of microtome knives. A technique for preparing longitudinal sections of entire single wood cells is described by Exley (76). Hennig and
Elias ( 1 M ) have published a seventh article in their series on the geometry of sectioning. This article deals with the sectioning of elliptical cylinders. Miscellaneous Techniques. Jones and Hawes (145) have worked out semiautomatic methods of preparing ultrathin sections of ceramic or petrologic materials. They have produced sections 6 inches square. Seal (266) uses an etching technique for studying various types of diamonds. Copeland (53) describes a simple apparatus for trimming specimens of minerals prior to polishing them. TECHNIQUES FOR SPECIMEN EXAMINATION
Petrography. A brief review entitled “The Microscope in Petrology” by Freere (88) is concerned with explaining to beginners the things that can be done. Friday (85) discusses some new methods in the preparation of pyritic fossils for microscopical examination. Eales (68) discusses polarization figures and their use in the identification of polished isotropic minerals. Blaschke (24) has used reflected polarized light for quantitative texture analysis of fine grained minerals. Photomicrography. Several recent books (15, 153, 173, 245, 258) are either concerned entirely with photomicrography or have sections devoted t o this subject. Two of these treat specialized subjects; the one by Rose (245) is concerned with cinemicrography, and that by Kivenson (163) deals with stroboscopy. An article by Sabine and Vaselekos (252) explains how a 35-mm. single lens reflex camera can be used for photomicrography. Several possible optical adapters to fit between the microscope and a cinecamera are discussed by Mollring (205). Schneebeli (261) shows how to use a Wild split-beam prism for the same purpose. Postlethwait, RIills, and Lohmann (229) have described a technique of cinephotomicrography of sequential serial sections in which a cinecamera and microscope are mounted in alignment with a microtome to photograph the sections as they are cut. The principal problem in this technique is to obtain accurate registration of adjacent sections. The determination of exposure for photomicrography appears to be a continuing problem. Designs for new exposure meters or explanations of how to use meters t o determine exposure are given in several articles (109, 265, 308-310, 318). A survey of different exposure meters is given by Tchacarof and Stomonyakov (288) who also give a brief discussion of cameras, and describes a camera which they designed. Schrader (264) describes a transistorized automatic exposure timer which measures the light flux and closes the shutter when the proper exposure has been attained.
The use of flash illumination in photomicrography was the subject of several papers. Courtney-Pratt (55) gives a brief review of methods and problems in high speed photography and micrography. Gabler, Kropp, and Schodl (94) describe a new electronic flash lamp, housing, and plot lamp especially designed for photomicrography. Brokaw and Wright (35) have used multiple flash illumination to study the bending waves of the flagellum of an organim. The use of flash illumination in cinemicrography is the subject of two papers (%$,YO). Koritnig (157) has published an article on taking color photoniicrographs through crossed polarizers. McCrone (183) describes a tilting stage which can be used to take stereomicrographs a t magnifications up to 2500. Two authors, McLachlan (186) and Simon (273), considered the problem of limited depth of field and arrived a t the same solution. They illuminate the specimen with a planar light beam. The objective is focused on the plane of the beam and the specimen is moved through the plane in a direction parallel to the optic axis of the microscope. Bird and Emerson (23) discuss photographic materials for recording color and low-light intensity through the microscope. Kornmann and Steinbach (168) have published a brief article on the use of Polaroid films in photomicrography. Refractometry. RIcLean (186) has written a very interesting article reporting his research on the significance of the Becke refractive indices in synthetic fibers. H e shows that the Becke line test does not necessarily give the refractive index of the surface in contact with the standard liquid. Wilcox (313) has devised a series of immersion liquids of strong dispersion ranging from n = 1.46 to n = 1.52. These liquids are useful for dispersion staining. Other less stable mixtures having indices of refraction up to 1.619 are mentioned. Jones (140) describes the use of an annular wedge interference filter in measurements of refractive index and dispersion. The filter, which serves as a monochromator, is supported over the eyepiece, and can be rotated to change the wavelength of the light as needed, Jones also gives dispersion curves for a number of liquids ranging from n = 1.40 to n = 1.76. Lawless and DeVries (171, 172) have reported a refinement of the Duc de Chaulnes’ method of measuring refractive index. They have used this method to determine accurately the ordinary ray refractive index of BaTiOa. Lacourt and Delande (164) have used a range of constants related to refractive index for the identification of 39 amino acids. Glover and Goulden (103) have discussed the relationship between refractive index
and concentration of solutions. Crisler (67, 58) has compared the refractive index of liquid sodium with that of silicone oil. This comparison shows the index to be greater than 1.37 a t 98” C. All the values reported in the literature were measured by reflection methods and ranged from 0.0045 to 0.048. Particle Size Measurement. Experiments concerning the limitations and errors in size measurements of small objects by visual microscopy have been reported by Charman (45). He used holes in an opaque film, opaque discs, and transparent spheres as objects. Saylor (265) has made a study of errors in the measurement of microscopic spheres. Kritzinger, Linhart, and van der Westhuyzen (160) discuss the human factor in projection microscope readings of wool fiber diameter. Bach (10) shows how to determine the frequency distribution of the radii of spherical particles from the frequency of their circular cross-sections in random sections of known thickness. He also gives formulas for the calculation of mean spherical volume and the total volume of the spheres as well as examples of the application of his methods. The shape of irregular particles can be expressed in geometrical or dynamical terms. Davies (60) gives a method of making alternative descriptions consistent with one another. An apparatus for automatically reading and recording length measurements made with a screw micrometer eyepiece is described by Stadelmann (277). Karasimham, et al. (211) have built a counter which records the number of particles in each size class as read from a projected image of a micrograph. Boguth and Goertz (26) have described a diffractometric method of measuring erythrocyte diameters using a microscope and a photoelectric measuiing device. The determination of the magnification of the microscope is of great importance in particle size work. Freeman (87) gives a procedure for calibrating a ruled scale. He discusses the measurement of magnification for microscopes equipped with moveable hairline micrometers, image splitting oculars, or photoelectric scanners for the image plane, and also for photoelectric scanners of photomicrographs. Ross and Galavazi (246) have used interference microscopy to measure the size of bacteria. The systematic errors which can creep into these measurements are discussed, and a special halfshade device, which seems to eliminate the errors, is described. A series of articles, published in booklet form and edited by Johnstone (139), deal with the applications of counting and sizing in medicine and biology. Included in this booklet are articles on automatic counters of various types. Sybenga
(284) describes a scale which he uses for measuring the sizes of chromosomes. Dispersion Staining. Brown, et al. (36) have published Part I1 of their article on dispersion staining. This is concerned with the systematic application of the method to the identification of transparent phases. They describe methods of identifying isotropic, uniaxial, and biaxial crystals. Data for a number of compounds are tabulated in an analytically useful form. McCrone (182) describes the application of dispersion staining t o the study of biological tissue. Kirchgessner and Gaisser (150) apply the technique to the examination and identification of fibers and plastics. Kantz (146) uses dispersion staining to enhance the contrast of clear crystals as an aid in studying crystal geometry. Miscellaneous Techniques. A method of evaluating the dispersion of carbon black in rubber or plastics is described by Stumpe and Railsback (281). They prepare a photomicrograph of a cut surface of the specimen, and compare the photomicrograph with a series of ten standard micrographs showing graded dispersion. Electrophoresis of particles such as cells is the subject of a report by RuhenstrothBauer (250). Frieden (86) presents a method of measuring the thickness of transparent films which are greater than 12 microns thick. Laskowski (167) tells how to treat microscope slides with silicone rubber so that liquids which wet glass too well can be used easily as solvents in chemical microscopical operations. APPLICATIONS OF CHEMICAL MICROSCOPY
Crystallography. A number of recent books on crystallography are of potential interest to the chemical microscopist. Some of these (38, 136, ,924) are concerned with crystallography in general. One of them (193) is “Crystallographic Book List.” Three of the books deal with crystal chemistry. Evans (74) has written “An Introduction to Crystal Chemistry.,’ Bennett, et al. (19) have entitled their book “Crystals: Perfect and Imperfect,” and Kroger’s book (161) is “The Chemistry of Imperfect Crystals.” Wood (317) is concerned with the interaction of crystals and light. She has included chapters on the polarizing microscope. Hartshorne and Stuart (117) have written “Practical Optical Crystallography” which is directly concerned with the microscope. Both Wood’s and Hartshorne and Stuart’s books are written for beginners in optical crystallography. Three books are compilations of crystallographic data. Vol. I11 of “Barker Index of Crystals” on “Crystals of the Anorthic System” has been published by Porter VOL. 38, NO. 5, APRIL 1966
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and Codd (228). The third edition of (‘The Microscopical Character of Artificial Inorganic Solid Substances,” by Winchell and Winchell (315) has been published. Winchell (316) has also published a new book entitled “Optical Properties of Minerals.” This book consists primarily of determinative tables although there are some introductory notes. A report on the optical properties of semiconducting crystals (300) has been published by the Office of Aerospace Research, CSAF. The use of the universal stage in conjunction with the polarizing microscope to obtain the optical properties of an unstable organic compound has been reported by Mosebach (210). He demonstrates how the universal stage is indispensable for determining the crystal properties of such unstable compounds. Joel and R‘Iuir (138) give several alternative procedures for calculating the optic axial angle 2V from extinction measurements made with a universal stage. Vogel (304) discusses the use of the Kakamura Plate for accurately determining extinction position and subsequently crystal orientation. Hartshorne (115) describes a single axis rotation apparatus which he has developed and shows how it is used for studying the optical properties of crystals. Koble (213) presents “Rapid Conoscopic Method for Measurement of 2V on the Spindle Stage.” Tocher (293) proposes a simple stereographic solution of general application to the calculation of 2V from extinction data. Ehinger (71) explains how dichroic reflections can be used t o orient birefringent highly absorbing materials such as Se. LlcCrone (181) presents plots of: angular aperture vs. numerical aperture, optic axial angle US. numerical aperture, and angular aperture us. d / D where d is the distance between melatopes of the isogyres in a biaxial crystal interference figure and D is the diameter of the back aperture of the objective. He also plots optic axial angle us. d / D . He tells how the curves can be used. Cameron (41) has conducted an investigation, the results of which indicate that the optical symmetries of many anisotropic ore minerals can be partly or wholly determined from reflectivity measurements in monochromatic light. Crystal Nucleation and Growth. The anomalous behavior of some amino acids as nucleation agents for ice was discussed by Barthakur and Maybank (16), and a paper on carbon particles and ice nucleation was published by Garten and Head (100). Bernal, Knight, and Cherry (21) have investigated the growth of crystals by random close packing using, as a model, solid balls in a box with roughened interior walls. The box was a parallelogram the edges of which mere hinged so that the shape of the box could be 204 R
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changed. This model is interesting as a teaching device for demonstrating the behavior of regular crystals, dislocation movements, twinning, and grain boundaries. Seltzer, et al. (268) have measured, microscopically, step movements during the growth of Ge crystals by chemical vapor deposition. Keith and Padden (148, 149) have studied the spherulitic crystallization of polymers from the melt. They were concerned with the influence of fractionation and impurity segregation on crystal morphology and the kinetics of crystallization. Penfold and Hellawell (220) report on the structures of the eutectics NiF-XaF and NaF-NaC1. They investigated directional freezing and the effects additives on these structures. Brandstatter-Kuhnert (31) has carried out a very interesting study of systems in which both isomorphism and polymorphism exist. Very complex systems can occur, for example, there are 11 polymorphic forms of phenobarbital and six of these were discovered by thermal analysis of mixtures of phenobarbital with other materials. Deformation and Defect Structures. Amelinckx’s book ( 2 ) on the direct observation of dislocations discusses decoration and etching techniques for light microscopical preparations, however, most of the book is devoted to electron microscopical and diffraction techniques. Sturner and Bliel (282) have used conventional light microscopy as well as phase interference, polarizing, and electron microscopy to study defect structures in cadmium sulfide and cadmium selenide. Light and Wolfstirn (178) have used infrared microscopy to observe directly the precipitation of Li a t dislocations in GaAs crystals. Thomas, Renshaw, and Roscoe (290) report a study of the production of dislocation etch pits on calcite using optically active etchants in which they show that the shape of the etch pit depends on the configuration of the stereoisomer used. Sasaguri, Yamada, and Stein (251) have investigated the deformation of poly(butene-1) spherulites by measuring the variation in birefringence with strain for different angular positions within the spherulite. Polymers and Resins. Two important books on polymer crystallization have been published recently; “The Crystallization of Polymers” (188) by Mandelkern and “Polymer Single Crystals” (101) by Geil. A symposium volume on resinographic methods (6) has been published by ASTM. This book contains 17 papers on various aspects of resinography such as sample preparation, the use of various techniques of microscopy in polymer research, and studies of various polymer systems. Rochow (240) has written an article on the ways and meaning of
resinography. This article also discusses the organization and activities of ASTM Committee E-23 on Resinography. The papers presented a t meetings of the Division of High Polymer Physics of the American Physical Society have been published in special sections of the J . App2. Phys. (4, 5 ) . Papers appearing in these special sections which were of special interest to chemical microscopists have been noted in the appropriate sections of this review. Sullivan (283) has discussed the interference microscopy of crystalline linear polymers. He describes interference microscopes, discusses crystalline polyethylene, and reports his experimental results on the morphology of melt grown and solution grown crystals of polyethylene. Hay (119) describes a thermostat unit which controls a microscope hot stage to 10.02” C. This degree of control is necessary for measuring the crystallizations kinetics of stereo-regular polymers. The unit covers a range from 50’ to 200’ C. and is stable for several days. A symposium volume entitled “The Morphology of Polymers” has appeared under the editorship of Rochow (239). Keith and Padden have published two papers (148, 149) on spherulitic crystallization from the melt. They discuss the influence of fractionation and impurity segregation on morphology and the kinetics of crystallization. Rochow (241) reports finding what he thinks are macromolecular and micellar domains in poly(methy1 methacrylate) samples from various sources. Padden and Keith (214) report a light and electron microscopical study of the morphology of synthetic polypeptides. Keith (147) describes the habits of polyethylene crystals grown from paraffinic solvents and from the melt. This is a light and electron microscopical study of linear polyethylene. The superheating of linear high-polymer polyethylene crystals is discusped by Hellmuth and Wunderlich (122). They used heating rates up t o 3000’ C. per minute. Sasaguri, Yamada, and Stein (251) have investigated the relationship between morphology and deformation mechanisms in polyolefins in particular poly(butene-1). They prepared uniaxially crystallized films and followed the effects of mechanical deformation using x-ray defraction and birefringence measurement techniques. Moore and Gieniewski (207) describe microscopical and light scattering studies of deformed ringed spherulites. Giuffria, Carhart, and Davis (102) have investigated the effects of microstructure on the gloss of high impact polystyrene. Various methods of producing glossy surfaces were studied and the best method was selected. The degradation of surfaces by heat and O2was examined briefly.
Textiles and Fibers. Two books concerned with general textile microscopy have been published recently : “Microscopic and Chemical Testing of Textiles” (155) by Koch, and “Methoden der Textilmikroskopie” (166) by Laske. Several more specialized books of interest to microscopists have appeared. “Wollkunde” (63) by Doehner and Ruemuth is really a third edition of “Die Leistungen des Schafes.” Much of this book is devoted to the microscopy of wool. Hearle and Peters (120) have compiled a book on fiber structure. Chapters 6 to 11 are concerned with the fine structures of fibers and contain many micrographs. The rest of the book covers the chemistry and physical properties of fibers and fiber materials. Haussner (118) has published a fiber atlas. It contains longitudinal and cross-sectional views of plant, animal, and synthetic fibers, as well as information on dyeing characteristics which are useful for fiber identification. Morehead (208) has written an article on the development of textile microscopy and its contribution and potential in textile research. Jayme (136) describes a number of light and electron microscopical techniques which have been applied in studies of cellulose fibers. These technique3 are: staining, sectioning, swelling and dissolving, surface replication, and stereoniicrography. Peck and Carter (219) discuss interference microscopy in polymer research. They used a Baker interference microscope to study and measure the optical properties of external skin layers on cellulose acetate, modified acrylic, and polyester fibers. The rubber phase in ABS plastics was compared with that in emulsions. Barakat and Hindeleh (12) have used interferometry to measure the indices of refraction and birefringence of viscose rayon and mohair wool. Nettelnstroth (212) has used the polarizing microscope to study the surface structure of cotton fibers. Prevorsek, Coe, and Lyons (230) have investigated the behavior of notched fibers in longitudinal tension. The effects of both chordal and circumferential notches were studied. Isings (It%$) has studied the effects of stress and deformation in torsion and tension on the structure of cotton fibers. Farrow and Ford (77) have examined the transverse markings which appear on various polymeric fibers vhen they are strained below the breaking point. A mechanism for the formation of these markings is proposed. The mechanism of the fracture of wool fibers under tension has been studied by Andreivs ( 7 ) . He used fractographic methods to show that such fractures originate a t the fiber surface. Grabar (107) has measured the changes in birefringence
with temperature for Creslan type 63 fibers. At about 180” C. the birefringence becomes zero above 180” C. the sign of birefringence is reversed. This temperature of zero birefringence (TZB) is characteristic of the particular material, and Sieminski (271) has determined the TZB of spun Arne1 cellulose triacetate, Acrilan, Creslan, Fiber T, Orlons 21, 42, 72, and 81, Verel, and Zefran. Hine and hlcPhee (125) have used light microscopy to study the effectiveness of treating wool with polymers to reduce felting and shrinkage. Takahashi, Nukushina, and Kosugi (286) have systematically investigated the effect of fiber forming conditions on the microstructure of arylic fibers. They examined various samples microscopically and by measurements of moisture retention, density and small angle x-ray scattering. Bucher (37) has investigated the structure of natural cellulose fibers microscopically using staining and swelling methods. Rollins, et al. (2.45)report a comprehensive study of the ultrastructure of mercerized cotton fibers by light and electron microscopy. Paper. “A Photomicrographic Atlas and Woody, Non-Woody and Man-Made Fibers Used in Papermaking” has been published by Carpenter, et al. (43). It contains 77 tables of data with numerous micrographs. A 2nd edition of “Microscopy of Pulp and Paper Bibliographic Series No. 177” has been published by Roth and Weiner (248). It covers the period from 1939 to 1964 and deals with light microscopy only. Jayme and HardersSteinhauser (137) have investigated the relationship between the fine structure and the state of preservation of coniferous wood pulp tracheids using the new cellulose solvents Cadoxen, E W S N , and Nioxam. Ceramics. The American Ceramic Society (3) has published the proceedings of a symposium on the “hlicrostructure of Ceramic Materials” which was held in 1963. A report of a conference on ceramics held a t Noordwijk aan Zee in hiay 1963 has been published in book form (279). It has sections on the properties of raw materials, the processing of materials, behavior during firing and the structures and properties of products. A number of the papers are of interest to microscopists. Trojer (297) has written a book on the crystalline oxides of inorganic industrial products. He deals with OH-- and HzO-free oxides only and gives optical and x-ray diffraction data and physical chemical properties. Hallbauer (110) describes a hot stage which is suitable for observing crystal growth in silicate melts. Fehrenbacher and Jacobson (78) report on the microscopical observation of the monoclinic to tetragonal phase transformation in ZrOs.
Minerals. As already stated no attempt has been made to review the field of microscopical examination of minerals. The papers reported here were thought to have general interest for the chemical microscopist. The origin of anomalous etch pits in minerals was investigated by Fleischer, Price, and Synies (80). Apparently the tracks of fission fragments provide points of attack for the etchant. Benedict and Berry (18) have reported a quick microscopic method for determining the degree of oxidation of coal. The reflectance of a sample of coal, changes in the calorific value of the coal, and the swelling of coal when it is heated can reveal the extent of oxidation which has taken place. Harrison and Tolansky (112) have made a study of the growth history of diamonds using polished and etched sections of a variety of natural diamonds. They use several microscopical techniques such as interferometry, to study etch pits, ultraviolet transmission to determine type, and polarized light to reveal strain patterns. Seal (266) has also studied natural diamonds from a wide variety of sources using an etching technique. Pate1 and Agarwal (216) have examined the microstructures on the natural faces of diamonds from the Panna mines in India. They suggest that etching occurs in the natural environment. Metals. “The Interpretation of Metallographic Structures,’ is the title of a recent book of Rostoker and Dvorak (247). As the title indicates this book is concerned only with the interpretation of structure and does not deal with techniques of sample preparation or examination. Polushkin (226) has written a book entitled “Structural Characteristics of hietals.” However, Polushkin’s book has chapters on light and electron microscopy, etching, and photomicrography. Kirchner and Ripling (151) have designed a hot stage tensiometer for observing the flow and fracture of metals. The atmosphere in the stage cell is controlled. This apparatus has been used to investigate hot salt stresscorrosion cracking of Ti alloys. Another arrangement for studying the deformation of metals in tension is described by Feltham (79). He has mounted a vacuum chamber on a Hounsfeld Tensometer and used it to study the deformation of Cu strips up to 700” C. Torkar and Weitzer (295)have used a hot stage to observe the sintering of metal powders. Forty (81) has observed the melting and freezing of films of potassium by means of transmitted ultraviolet light. Miscellaneous. Paulssen (217) has written a book on the “Identification of Active Charcoals and Wood Charcoals.” Vand, Dachille, and Simons VOL. 38, NO. 5 , APRIL 1966
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(301) have proposed a qualitative method for dating of glasses by etching fossil fission tracks and examining the resulting etch pits microscopically. They used this technique to show that tektite-like objects from the Ries-Kessel meteroic crater were not tektites. Simkiss (272) has investigated the variations in the crystalline form of calcium carbonate precipitated from artificial sea water.” Quinlan ($SI) has examined the microscopic structure of small arms propellants. The microstructures of LiF-KaF and NaF-NaC1 eutectics is described by Penfold and Hellawel (220). They discuss the variations in interphase separations and the effects of added impurities on the eutectic structure. Miles (199) has examined l I g 0 crystals containing impurity precipitates by ultramicroscopy. Unusual dislocation configurations were observed. The composition of the precipitate particles was discussed. Holzl and Bancher (166, 127) have studied the penetration various liquids into starch grains. Starch from a variety of sources was tested. The reaction between starch grains and a chloroxinciodide (Chlorzinkjod) reagent was also tested. Seidemann (267) has written on the use of optical methods in starch research with particular emphasis on colorphotography of starch grains in polarized light. Various starches and their properties are discussed. ANALYTICAL MICROSCOPY
Many of the articles cited in previous sections of this review were concerned with techniques or apparatus which could be used to identify materials. This section is concerned primarily with articles reporting data or properties by means of which specific materials can be identified. However, a few books and articles on methods of chemical microscopical identification of materials are mentioned. BenedettiPichler’s book (17) on the identification of materials via physical properties, chemical tests and microscopy describes various ways in which the microscope can be used to identify materials. Kofler (156) describes the system of identification developed by L. Kofler, namely, measurement of the melting point of the material, measurement of the melting points and characteristics of two eutectics formed by mixing the unknown with standard reference compounds, and measurement of the refractive index of the molten unknown. She also discusses what can be done with unknowns for which these four measurements cannot be made. Jones and AleCrone (144) apply microscopical fusion methods to determine the relationship between three forms of 2-amino-5methylthiazole hydrochloride. Two of the three forms were shown to be polymorphs and the third a hemihydrate of
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the compound. Brandstatter-Kuhnert (31) has made an extensive study of a series of systems in which both isomorphism and polymorphism exist. Very complex systems can arise under these conditions. It was shown that there are 11 polymorphs of phenobarbital, eight of Medomin, six of dipropyl barbital, six of Dormin, six of Alphenol, and six of barbital. Schmid, Mangold, and Lundberg (259, 260) have published a series of three articles on the critical solution temperatures of aliphatic compounds. They point out that the critical solution temperature (CST) of a pair of liquid phases can be used to characterize small amounts of liquids under the microscope. One of the two phases is a standard liquid, such as nitromethane or acetonitrile for identification of alcohols, ethers, and esters. The CST is used in conjunction with melting point and refractive index. The authors give data for homologous and vinylogous fatty acids, methyl esters, triglycerides, alcohols, ethers, and esters. Schaeffer (266) reports on the chemical microscopy of the platinum metals in particular their reactions with 4bromoisoquinoline and .i-(p-nitrobenzyl) pyridine. The first compound is a suitable reagent for P t , Au, and I r ; the second is useful for Pd, Os, Ir, Pt, and Au. Previous work has shown that isoquinoline is a reagent for Rn, Ir, Pt, and Au. Van Ligten and van Velthuyxen (302) have investigated violuric acid as a reagent and have found that it forms insoluble salts with Cs, Rb, Li, T1, Ca, Ba, Sr, Pb, UO?, Cd, Zn, and Co ions, Micrographs of the crystalline precipitates, formed when these ions react with violuric acid, are shown. Leipziger, Croft, and Roberts (175) suggest that a mixture of formic acid and ammonium formate produces a characteristic precipitate with the cerium group of rare earth elements from La to Gd. The reagent characterizes the entire group, and not the individuals within the group. Jones (149) discusses the identification of the double salt of aspirin and potassium aspirin by means of optical crystallography and fusion methods of analysis. Chemical analyses are also given. Lacourt and Delande (164) use a range of constants related to refractive index for the identification of amino acids. These constants are determined microscopically. Combined with eutectic melting temperatures they permit identification of 39 amino acids. Bradstatter-Kuhnert and Junger (32) describe thermoanalytic studies of the steroid hormones including the formation of molecular compounds, mixed crystal formation, isomorphism, and melting point data. BrandstatterKuhnert, Junger, and Kofler (33) have carried the study of the steroid hor-
mones further giving detailed information for the characterization of 77 steroid hormones. In addition to melting point, eutectics, and index of refraction they give ultraviolet absorption spectra. Laskowski (168) has developed a scheme for the identification of cystine, uric acid, urates, hydroxyl apatite, carbonate apatite, CaHP04.2H20, NgNH4PO4.6Hz0, and calcium oxalate monoand dihydrates in urinary calculi. He used morphology, optical properties, and appearance under dispersion staining conditions as criteria for identification. Kuhn and Peterson (163) show how calcium oxalate monohydrate and 1-cystine can be identified in human tissues by observing their morphology, refractive index, birefringence, and extinction angles. Jones and Sfasri (1.62) report the optical and crystallographic properties of racemic allantoin, comparing allantoin isolated from urine with synthetic allantoin. Jones, et al. (141) give the optical, crystallographic, and x-ray diffraction data on cycloalliin hydrochloride monohydrate. Cady (40)gives optical crystallographic and x-ray diffraction data on 1,3,5triamino - 2,4,6 - trinitrobenzene. Yee (319) has developed a photomicrographic and microradiographic method for qualitative analysis of solid propellants. LITERATURE CITED
(1) Altman, J. H., A p p l . Opt. 3, 153 (1964).
(2) Amelinckx, S., “The Direct Observation of Dislocations,” Academic Press,
New York, 1964.
(3) Am. Ceram. Soc., “Microstructure of Ceramic Materials,” Natl. Bur. Stds. Mist. Pub. 257 (1964). (4) Am. Physical Soc., “Special Section
on High Polymer Physics,” J . A p p l . Phys. 35, No. 1 (1964). (5) Am. Physical Soc., “Selected Papers in High Polymer Physics,” J . A p p l . Phys. 36, No. 10 (1965). (6) Am. Soc. Testing Mater., “Symposium on Resinographic Methods,” Am. SOC.Testing Mater., Spec. Tech. Publ. 347 (1964). (7) Andrews, AI. W., Textile Res. J . 34, 831 11964). (8) Appelt, H . , AppZ.,Opt. 4, 136 (1965). (9) Babel, U., Leztz-Mitt. Wiss. u. Techn. 3, 12 (1964). (10) Bach, G., 2. Wiss. Mihroshopie 66, 193 (1964). (11) Bailey, E. M., Bailey, D. I., Microchem. J . 9, 134 (1965). (12) Barakat, N., Hindeleh, A. M., Textile Res. J . 34, 357 (1964), Ibid., 34, 581 (1964). (13) Barlow, H. B., Science 149, 553
I 1 F)A.5\
1965.’ (16) Barthakur, N., Maybank, J., Nature 200,866 (1963). (17) Benedetti-Pichler, A. A., “Identifica-
tion of Materials Via Physical Proper-
ties, Chemical Tests and Microscopy,” Academic Press, New York, 1964. (18) Benedict, L. G., Berry, W. F., Chem. Eng. News, Dee. 14, 41 (1964).
(19) Bennett, A., et al., “Crystals: Perfect and Imperfect,” Walker and Co., Kew York, 1965. (20) Bergstedt, J. E., 2. W i s s . Mikroskopie 66, 218 (1964). (21) Bernal, J. D., Knight, K. R., Cherry, I., 1Yature 202, 852 (1964). (22) Biek, L., ‘[Archaeology and the Microscope,” Butterworth, London, 1963. (23) Bird, G. R., Emerson, E. S., J . Boy. Micros. SOC.83, 221 (1964). (24) Blaschke, R., 2. Wiss. Mikroskop. 67, 1 (1965). (25) Boev, K., et al., Mikroskopie 19, 199 (1964). (26) Boguth, IT,,Goertz, L., 2. Wiss. Mikro~lzop.66, 24 (1964). (27) Booth, A. D., J . Roy. Micros. SOC. 83, 119 (1964). (28) Bouyer, R., J . Microscopic 3, 225 i 1964) \----,
(29) Bouyer, R., Zbid., 4, l(1965). (30) Bradbury, S., Turner, G. L’E., J . Rou. Micros. SOC.84, 65 (1965). (31 Brkdstatter-Kuhnert. AI., Micro-
XI., J . Opt. doc. Am. 54,791 (1964).’ (4!3) Claussen, H. C., A p p l . Opt. 3, 993 (1964). (50) Clegg, AI. D., J . Roy. Micros. SOC. 83, 433 (1964). (51) Coackley, P., Kliger, B., Nature 203, 77 (1964). (52) Cocks, G. G., ANAL. CHEM. 36, 163 R (1964). (X3) Copeland, D. A,, A.m. Mineralogist 50, 1128 (1965). (54) Cosslett, A., J . R o y . Micros. SOC. 84, 385 (1965). (55) Courtney-Pratt, J. S., A p p l . Opt. 3, 1201 (1964). (56) Cowan, ‘G. S. M., “1964 Yearbook,” Sew York Microscopical Society, No. 9, 59. (57) Crisler, J. P., Microscope 14, 152 (1964). (58) Crisler, J. P., Zbid., 14, 363 (1965). (59) Cuthrell, R. E., A p p l . Opt. 4, 473 (1965). ~
(60) Davies, C. N., Nature 201, 905 (1964). (61) Deffeyes, K. S., Am. Mineralogist 49, 165 (1964). (62) Dodd, J. G., Microscope 14, 302 (1965). (63) Doekner, H., Remuth, H., “Wollkunde, T erlag Paul Parey, Berlin, 1964. (64) Drickamer, H. G., Science 142, 1429 (1963). (65) Duddington, C. I., “The RIicroscope,” Museum Press, Ltd., London, 1964. (66) Duecker, H. C., Lippincott, E. R., Rev. Sci. Znstr. 35, 1108 (1964). (67) DuFresne, E. It., Rosa, F., Campbell, D. L., Microscope 14, 354 (1965). (68) Eales. H. V-.- A&. h-lineralooist 50. 942 (1965). (69) Eder, H., Fritsche, H., Leitz-Mitt. Wiss. u. Techn. 2, 143 (1963). (70) Edgerton, H. E., Carson, J. T., A p p l . Opt. 3, 1211 (1964). (71) Ehinger, H., 2. Krist. 117, 301 (1962). ( 7 2 ) Ehrenbere, H., Z. Wiss. Mikroslio;oie 66, 32 (19647.‘ ‘ (73) Ellis, G. W., Science 138, 84 (1962). (74) Evans, R. C., “An Introduction to Crystal Chemistry,” 2nd ed., Cambridge Univ. Press, Cambridge, Eng., 1964. (75) Evans, R. L., Rev. Sci. Znstr. 35, 305 (1964). (76) Exley, It. R., J . Roy. Jficros. SOC. 83, 479 (1964). (77) Farrow, B., Ford, J. E., Nature 201, 183 (1964). (78) Fehrenbacher, L. L., Jacobson, L. A., J . Am. C h e m SOC.48, 157 (1965). (79) Feltham. P.. J . Sci. Znstr. 41. 176 (1964). (80) Fleischer, R. L., Price, P. B., Symes, E . AI., Am. Mineralogist 49, 794 (1964). (81) Forty, A. J., Phil. M a g . 9,673 (1964). (82) Foster, A. D., J . Sc. Instr. 42, 172 (1965). (83) Francon, &I., “Modern Applications of Physical Optics,” Interscience, (Riley), New York, 1963. (84) Franqon, RI., A p p l . Opt. 3, 1033 (1964). (85) Friday, A. E., Microscope 14, 403 (1965). (86) Frieden, B. R., A p p l . Opt. 3, 395 (1964). (87) Freeman, D. H., Zbid., 3,1005 (1964). (88) Freere, R. H., Zbid., 3, 1023 (1964). (89) Freund, H., Berg, A,, “Geschichte der Mikroskopie: Leben und Werk Grosser Forscher, Band 11, Medizin,” Umschau Verlag, Frankfurt am Main, 1964. (90) Frey-Wyssling, A,, Mikroskopie 19, 2 (1964). (91) Frey-Wyssling, A., 2. W i s s . Mikroskopie 66, 45 (1964). (92) Fulford, R. M., Slater, C. H. W., J . Sci. Znstr. 40, 368 (1963). (93) Gabler, F., Herzog, F:, A p p l . Opt. 4, 469 (1965). (94) Gabler,,F., Kropp, K., Schodl, O., Makroscopae 19, 149 (1964). (95) Gahm, J., Zeiss-Mitt. 2, 389 (1962). (96) Gahm, J., Zbid., 3, 3 (1963). (97) Gahm, J., Zbid., 3, 153 (1964). (98) Gahrton, G., E x p . Cell Research 34, 488 (1964). (99) Galjaard, H., Szirmai, J. A., J . Roy. Micros. SOC.84, 27 (1965). (100) Garten, V. A., Head, R. B., Nature 201, 1091 (1964). (101) Geil, P. H., “Polymer Single Crystals,” Interscience (Wiley), New York. 1963. (102) Giuffria, R., Carhart, R. O., Davis, D. A,, Microscope 14, 106 (1963).
(103) Glover, F. A., Goulden, J. D. S., Nature 200, 1165 (1963). (104) Goldstein. D. J., J . Rov. Micros. SOC.84, 43 (1965). (105) Gordon, H. P., iyature 202, 1035 (1964). (106) Gbuld, P. A., Pick, U., J . Sci. Instr. 41, 474 (1964). (107) Grabar, D. G., Microscope 14, 209 (1964). (108) Gutt,. W.,, J. Sci. Znstr. 41. 393 ‘ (1964). (109) Hall, H. J., J . Quekett Micros. Club 29. 283 f19641. (110) HallbauG: D., Neues Jahrb. M i n eral. 1963, 1. ( i l l ) Harrington, P. A., Bartels, P. H., “1964 Yearbook,” The New York Microscopical Society, h’ew York. 1112) Harrison. E. K.. Tolanskv. S.. ‘ Proc. Roy. Soc. Series A 279,4907f964): (113) Hartley, W. G., “How to Use a Illicroscope,” Am. ed. translation by Lee, J. J., Friedman, B., Natural History Press, Garden City, L. I., Sew York, 1964. (114) Hartman, A. W., Rev. Sei. Instr. 36. 31 (1965). ( l l 5 j Hartshorne, N. H., Microscope 14, 81 (1963). (116) Hartshorne, N. H., Zbid., 14, 282 (1964). (117) Hartshorne, N. H., Stuart, A;: “Practical Optical Crystallography, Elsevier. New York. 1964. (118) HaLksner, W.; “Faseratlas-Das Erkennen der textilen Faserstoffe,” VEB Fachbuchverlag, Leipzig, 1962. (119) Hay, J. N., J . Sci. Znstr. 41. 465 (1964).‘ (120) Hearle, J. W. S., Peters, R. H., “Fiber Structure,” Butterworth, RIanChester and London, 1963. (121) Heilmann, G., A p p l . Opt. 4, 1201 (1965). (122) Helmuth, E., Wunderlich, B., J . A p p l . Phys. 36, 3039 (1965). (123) Hennig, A., Elias, H., 2. Wiss. Mikroskopie 66, 226 (1964). (124) Hewlett, P. S., J . Sci. Instr. 42, 127 (1965). (125) Hine, R. J., McPhee, J. R., Textile Res. J. 34, 659 (1964). (126) Holzl, J., Bancher, E., Mikroskopie 18, 345 (1964). (127) Holzl, J., Bancher, E., h t e r r . Bat. Zeitscher. 111, 69 (1964). (128) Hooss, E., Mikroskopie 18, 269 ’
\ - -
~
i 1964) - - - -,. \
(129) Horwitz, C., Wood, S., J . Sci. Instr. 41, 518 (1964). (130) Houston, J. K., Zbid., 40,373 (1963). (131) Hovnanian, H. P., Botan, E. A., Brennan, T. A., Neurath, P. W., Microscope 14, 141 (1964). (132) Huber, P., Mikroskopie 18, 231 (1963). (1963). (133) Hughes, A., J . R o y . Micros. SOC. 83, 25 (1964). (134) Isings, J., Textile Res. J . 34, 236 (1964). (135) Jaswon, &I. A., “An Introduction to Mathematical Crystallography,” Elsevier, New York, 1965. (136) Jayme, G., J . Roy. Micros. SOC.82, 127 (1963). (137) Jayme, G., Harders-Steinhauser, &I., 2. Wiss. Afikroskopie 66, 54 (1964). (138) Joel, N., Muir, I. D., Am. Mineralogist 49, 286 (1964). (139) Johnstone, M. C., Ann. N . Y . Acad. Sci. 99, 231 (1962). (140) Jones, F. T., Microscope 14, 440 \ - - - - / .
(196.5) \----,.
(141) Jones, F. T., Lee, K. S., Black, D. R., Palmer, K. J.,Zbid., 14,379 (1965). (142) Jones, F. T.. Masri. M. S.. Ibid.. ‘ 14, 271 (1964). ’ (143) Jones, M., “1964 Yearbook,’’ New York Microscopical Society, No. 9, 39. VOL. 38, NO. 5 , APRIL 1966
207 R
(144) Jones, &I.,bfccrone, W. C., Mzcroscope 14,264 (1964). (145) Jones, T., Hawes, R. 1%’. M., Ibzd., 14, 200 (1964). (146) Kantz, A I . R., Zbzd., 14,422 (1965). (147) Keith, H. D., J . A p p l . P h y s . 35, 3115 (1964). (145) Keith, H. D., Padden, F. J. Jr., Ibzd., 35, 1270 (1964). (149) Keith, H. D., Padden, F. J. Jr., Ibzd., 35, 1286 (1964). (150) Kirchgessner, W.G., Gaisser, A. R., Teztzle Res. J . 35,78 (1965). (151) Kirchner, R. L., Ripling, E. J., Rev. Scz. Instr. 36, 1599 (1965). (1.32) Kiss., F.,, Xzkroskovze 18, 288 (1963). (153) Iftvenson, G., “Industrial Stroboscopy, Hayden Book Co., Xew York, 1965. (154) Klute, C. H., Fajardo, E. R., Rev. Sei. Instr. 35, 1080 (i864). (155) Koch, P. A., Microscopic and Chemical Testing of Textiles,” translation by Hooper, C. W., Textile Book Service, New York, 1063. (156) Kofler, A., Mzcroscope 14, 239 (1964). ( l j 7 ) Koritnig, S., Zeiss Information, KO. 53, 75. (158) Kornmann, H., Steinbach, K., Leitz-Mitt.Wiss. u. Techn. 3, 48 (1964). (159) Kretschmann, H. J., Z. Wiss. Mikroskopze 65,449 (1964). (160) Kritzinger, C. C., Linhart, H., van der Westhuyzen, A. W.G., Textile Res. J . 34,518 (1964). (161) Kroger, F. A., “The Chemistry of Imperfect Crystals,” Interscience (Wiley), New York, 1964. (162) Krug, W., Rienita, J., Schulz, G., “Cont,ributions to Interference Microscopy,” translation by Dickson, J. H., Hilger and Watts, London, 1964. (163) Kuhn, 12. J., Peterson, B. J., Microscope 14, 411 (1965). (164) Lacourt, A., Delande, K., Mikrcchim. Acta 1964,No. 2-4, 547. (165) Lark, P. D., Jficroscope 14, 301 (1965). (166) Laske, T., “liethoden der Textilmikroskopie,” Kosmos-Gesellschaft der PIJ aturfreunde Franskh’sche Verlagshandlung, Stuttgart, 1964. (167) Laskowski, D. E., ANAL.CHEM. 37, 174 (1965). (168) Zbid., p. 1394. (169) Lau, E., Jenaer Rundschau 1964, ,\ - -
45.
(170) La,, E., Weide, H. G., Optik 21, 119 I,1964). (171) .Lawless, W. N., DeVries, R. C., J . A p p l . P h y s . 35, 2638I (1964). (172) Lawless, W. N., DeT’ries, R. C., J . Opt. SOC.Am. 54, 1225 (1964). (173) Lawson, D. F., “The Technique of Photomicrography,” Macmillan, New York-, 1Qfil (174) 1Liebman, PLA:;Entine, G., J . Opt. *-I-’
‘
Skc. Am. 54, 1451 (1Y64).
(175) Leipziger, F. D., Croft, W. J., Roberts, J. E., AXAL.CHEM.36, 314 (1964). (176) Leith, E. N., Upatnieks, J., J . Opt. SOC.Am. 55. 569 (1965). (177) Leith, E:N., Upatnieks, J., Haines, K. A,, Ibid., 55, 981 (1965). (178) Light, T. B., Wolfstirn, K. B., J . A p p l . P h y s . 35, 1649 (1964). (179) Lohman, A. W., Paris, D. P., A p p l . Opt. 3, 1037 (1964). (180) Long, C., 11, Brushenko, A,, Pontarelli, D. A., A p p l . Opt. 3, 1031 (1964). (181) RIcCrone, W.C., Microscope 14,60 (1963). (182) ?rlcCrone, W. C., J . R o y . Micros. SOC.83, 217 (1964). (183) McCrone, W. c., IZlicroscope 14, 429 (1965).
208 R
ANALYTICAL CHEMISTRY
(184) McCutchen, C. W., Rev. Sei. Instr. 35. 1340 (1964). (185j LicLachlan, D. Jr., A p p l . Opt. 3, 1009 (1964). (186) AlcLean, J. H., Textile Res. J . 35, 242 (1965). (187) Malies, H. >I., Microscope 14, 257 (1964), Ibid., 14, 351 (1965). (188) blandelkern, L., “Crystallization of Polymers,” AicGraw-Hill, New York, 1964. (189) Markussen, J., McCrone, W. C., Mzcroscope 14,395 (1965). (190) Mason, C. W., “1964 Yearbook,” Kew York Microscopical Society, KO. 9j 67. (191) Mayer, E., “Introduction to Dynamic Morphology,” Academic Press, New York, 1963. (192) Riedellin, D., Wendell, &I., Ang, C. Y., J . Am. Ceram. Soc. 48, 381 (1965). (193) hiegaw, H. D., “Crystallographic Book List,” Int. Union of Crystallographers, Polycrystal Book Service, Brooklyn, N. Y., 1965. (194) Meier, R. W.,J . Opt. Soc. Am. 55, 987 (1965). (195) Mercer, 12. A., Miller, R. P., J . Scz. Znstr. 40. 352 (1963). (196) RIeyer-Arendt,‘ J. R., A p p l . Opt. 4, 1 (1965). (197) M,ichel, K., “Die Grrindzdge der Theorie des Mikroskops in elementarer Darstellung,” 2nd ed., Wissenschaftliche Verlagsgesellschaft, Stuttgart, 1964. (198) Micro ’65, “A Symposium on Applied RIicroscopy,” University of Sheffield, England, July 6-9, 1965, Sponsor, RicCrone Research Institute, unpublished work. (199) Miles, G. D., J . A p p l . P h y s . 36, 1471 (1965). (200) Riira, ’E., Mikroskopie 18, 216 (1963). \ _ _ . _
(201) liissmahl, H. P., Z. Wiss. Mikroskopze 66, 81 (1964). (202) Mitrani, L., et al., Mikroskopze 18, 222 (1963). (203) Mitsche, R., Jeglitsch, F., Rades Rundschau 2, 405 (1963). (204) Mitsche, R., Scheidl, H., Mzkrochim. Acta 1965,No. 3, 551. (205) Mollring, Fr. K., Zeiss-Information 12, 126 (1964). (206) Rlontgomery, P. O’B., Bonner, W. A.. Cook. J. E.. J . R o v . Micros. SOC. 83: 73 (1964). ’ (207j hioore, R . S., Gieniewski, C., J. A p p l . P h y s . 36, 3022 (1965). (208) Morehead, F. F., “1964 Yearbook,” New York RiicroscoDical Society, No. 9, 55. (209) Morgenroth, P., Mikroskopie 18,193 (1963). \__..
(210) hiosebach, R., Z . Wiss.Mikroskopie 66,85 (1964). (211) Narasimham, P., Yaseen, M., Kolatkar, P. S., Aggarwal, J. S., J . Colloid Sci. 20. 473 (1965). (212) Ne’ttelnstroth,‘ K., Leitz-Mitt. Wiss. u. Techn. 2, 238 (1964). (213) Noble, ‘D. C.’, Am: Mineralogist 50, 180 (1965). (214) Padden, T. J., Jr., Keith, H. D., ,J. A T J WP~h.v s . 36. 2987 (1965). (215) Pilka, ,f.,Science 149, 551 (1965). (216). Patel,,A. R,,Agarwal, ;If. K., Am. Mzneralogzst 50, 124 (1965). (217) Paulssen, L. M., “Identification CI$ Active Charcoals and Wood Charcoals, Scandinavian Univ. Books, Universitetsforlaget: Munksgaard, Copenhagen, 1964. ~. (218) Payne, B. O., Microscope 14, 217 (1964). (219) Peck, V. G., Carter, W. L., Textile Res. J . 34, 4 (1964).
(220) Penfold, D., Hellawell, A., J . Am. Ceram. SOC.48, 133 (1965). (221) Peppers, S . A., A p p l . Opt. 4, 555 (1965). (222) Petriconi, J-., Z. IVzss. Jfikroskopte 66, 213 (1964). (223) Pflug, H. D., Ibzd., 66, 123 (1964). (224) Phillips, F. C., “An Introdiiction to Crystallography,” 3rd ed., Wiley, Sew York, 1964. (225) Piller, H., Gehlen, K. Y.)Am. Nzneralogzst 49, 867 (1964). (226) Polushkin, E. P., “Structural Characteristics of Metals,” Elsevier, New York, 1964. (227) Pomerat, C. M.,Rounds, D. E., Huff, IT., J . Roy. Mtcros. Soc. 8.3, 265 (1964). (228) Porter, 11. IT., Codd, L. W., “Barker Index of Crvstals. Yol. 111: Crystals of the Aiyorthic System,” IT. Heffer and Soni, Ltd., Cambridge, England, 1965. (229) Postlethwait, S. N., liills, R., Lohmann, K. B., Jr., J . Soc. Motion Pzcture Engrs. 73, 629 (1964). (230) Prevorsek, D. C., Coe, A. B., Lyons, IT. J., Teztzle Res. J . 35, 878 (1965). (231) Quinlan, J. B., Mzcroscope 14, 385 (1965). (232) Reed-Bill, R. E., Smeal, C. R., Lee, L., Trans. J i e t . Sac. AZME 230, 1019 (1964). (233) Richards, 0. W.,J . R o y . Jlzcros. Soc. 83, 123 (1964). (234) Richards, 0. IT.,A p p l . Opt. 3, 1027 (1964). (235) Rienitz, J., Optzk 21, 631 (1964). (236) Rikmenspoel, R., Itev. Sci. Instr. 35, 49 (1964). (237) Ibzd , p. 52. (238) Roblin, G., Rev. d’0ptzpue 42, 401 (1963). (239) Roch:y, T. G., “Morphology of Polymers, J . Polymer Scz., Part C, Polymer Symposia, S o . 3, Interscience (Wiley), Yew York, 1963. (240) Rochow, T. G., Jizcroscope 14, 246 (1964). (241) Rochow, T. G., J . A p p l . Polymer Sei. 9, 569 (1965). (242) Rosch, S., Z . Wiss. Nikroskopie 66, 136 (1964). (243) Rollins, M. L., Rloore, A. T., Degray, I. V.. Dearav. V., Govnes. Goynes, W.R.. R., J . Rou. Roy. Micros. SOC.84, 111965). Mi;rob.’Soc. l(1965). (244) Ronkin, R. R., “1964 Yearbook,” The New York Microscopical Society, No. 9, 72. (245) Rose, G. G., “Cinernicrography in Cell Biology,” Academic Press, Few York. 1963. (246) Ross, K. F. A., Galavazi, G., J . R o y . Micros. SOC.84, 13 (1965). (247) Rostoker, W., Dvorak, J. R., “Interpretation of Rletallographic Structures,” Academic Press, New York, 1964. (248) Roth, L., Weiner, J., “Microscopy of Pulp and Paper, Bibliographic Series,” N o . 177, 2nd ed., Institute of Paper Chemistry, Appleton, Wisc., 1964. (249) Royal Alicroscopical Society, “Symposium on the hlicroscopy of Fibrous Materials,” Manchester College of Science and Technology, April 6-8, 1964. J . R o y . Micros. SOC.83, 340 (1964). (2i0) Ruhenstroth-Bauer, G., Zeiss-Mitt. 3, 253 (1964). (251) Sasaguri, K., Yamada, R., Stein, R. S.,J . A p p l . P h y s . 35, 47 (1964); Ibid., 35, 3188 (1964). (252) Sabine, D. B.. Taselekos, J., Microchem. J . 9., 42 11965). . (253) Sansoni, G., Jenaer R u n d s c h a u 8, 170 (1963).
(254) Savdir, S., Mikroskopie 19, 112 (1964). (255) Saylor, C. P., A p p l . Opt. 4, 477 (1965). (256) Schaeffer, H. F., ANAL.CHEM.36, 169 (1964). (257) Schaeffer, H. F., Microscope 14,464 (1965). (258) Schenk, R., Kistler, G., “Photomicrography,” translation by Bradley, F., Franklin Pub. Co., Palisade, N. J., 1963. (259) Schmid, H. H. O., Mangold, H. K., Liinrlhwe. N. 0.. Microchem. J . 7. 287
soc.79,119 (i95~/60j. (262) Schneebeli, G. L., Zbid., 84, 393 (\ -1966 1. - - - ,
(263) Schoenmakers, G. A., Microscope 14, 101 (1963). (264) Schrader, M.,2. Wiss. Alikroskopie 65, 409 (1964). (265) Schrader,, M., . Mikroskopie 19, 92 (1964). (266) Seal, M., Am. Mineralogist 50, 105 (1965). (267) Seidemann, J., Phot. Korrespondenze 100, 85 (1964). (268) Seltzer, 31. S., Albon, N., Paris, B.. Himes, R. C., Rev. Sci. Instr. 36, 1423 (196g). (269) Sharp, J. A., J . Roy. Micros. SOC. 82. 217 (1963). (270j Sheridan,’ J. W., Zbid., 83, 115 (1964). (271) Sieminski, hl. A., Textile Res. J . 34, 918 (1964). (272) Simkiss. K.. Nature 201. 492 (1964). i273j Simon, h . , ’ R e v . Sei. Znstr. 36, 1654 (1965). (274) Sims, A. L., Lyon, A. G., J. Sci. Instr. 40, 370 (1963). (275) Sippel, R. F., Glover, E. D., Science 150, 1283 (1965). ’
(276) Slater. P. N., Industrial Research, May 1964, 82. ’ (277) Stadelmann, E., Mikroskopie 19, 135 (1964). (278) Steel, W. H., J. Sci. Instr. 42, 102 (1965). (279) Stewart, H., “Science of Ceramics. Vol. 2. Academic Press, New York, 1965. ’ (281) Stumpe, N. A,, Jr., Railsback, H. E., Rubber World 151,41 (1964). (282) Sturner, H. W., Bliel, C. E., A p p l . Opt. 3, 1015 (1964). (283) Sullivan, P. K., M.S. thesis, Cornell University, Ithaca, N. Y., 1963. (284) Sybenga, J., 2. Wiss. Mikroskopie 65, 437 (1964). (285) Szent-Gyorgyi, A., A p p l . Opt. 4, 137 (1965). (286) Takahashi, M., Nukushina, Y., Kosugi, S., Teztile Res. J . 34,87 (1964). (287) Tchacarof, E. L., Dokov, V. K., Vankova, S. A., Natchef, T. K., Mikroskopie 18, 210 (1963). (288) Tchacarof, E. L., Stomonyakov, V. Ch., Mikroskopie 18, 263 (1963). (289) Terrell, A. C., Microscope 14, 174 (1964). (290) Thomas, J. ?*I., Renshaw, G. D., Roscoe, C., Nature 203, 72 (1964). (291) Thornton, B. S., Zbid., 200, 1000 (1963). (292) Tighe-Ford, D. J. T., J . Roy. Micros. SOC.83, 239 (1964). (293) Tocher, T. E., Am. Mineralogist 49, 1622 (1964). (294) Tolansky, S., Nature 202,75 (1964). 1295) Torkar. K.. Weitzer. H. H.. Zeit. ‘ Metullkunde 55,‘ 142 (1964). (296) Trojer, F., Radex Rundschau 1962, No.1, 43. (297) Trojer, F., “Die oxydischen Kristallphasen der anorganischen Industrieprodukte,” Schweizerbart’sche Verlagsbuchhandlung, Stuttgart, 1963. (298) Uhlig, M., Mikroskopie 19, 107 (1964). (299) Zbid., p. 161. ~
,I”.
(300) U. S. Air Force, Report ARL 64-98 (unclassified), Office of Aerospace Research, USAT, June, 1964. (301) Vand, V., Dachille, F., Simons, P. Y., Nature 201, 597 (1964). (302) van Ligten, J. W. L., van Velthuysen, H., Mikrochim. Acta 1964, No. 5, 759. (303) Vialli, M., 2. W i s s . Mikroskopie 66, 164 (1964). (304) fJogel; T. A., Am. Mineralogist 49, 406 (1964). (3(15) Walter, F., Microscope 14, 156 (1964). (306) Zbid., p. 185. (307) Watr,asiewicz, B. M., Optica Acta 10, 209 (1963). (308) Weston, R. MeV., J . Roy. Micros. SOC.82, 211 (1963). 19) White, G. W., Microscope 14, 34 p. 149. G. W., J . Quekett Micros.
?,
(313) Wilcox, R. E., Am. Mineralogist 49, 683 (1964). (314) Williams, G. Z., J . Roy. Micros. SOC.83,69 (1964). (315) Winchell, A. N., Winchell, H., “The Microscopical Characters of Artificial Inorganic Solid Substances,” 3rd ed., Academic Press, New York, 1964. (316) Winchell, H., “Optical Properties of Minerals,” Academic Press, New York, 1964. (317) Wood, E. A., “Crystals and Light,” Van Nostrand, New York, 1964. (318) Woolard, L. D., J . Quekett Micros. Club 29, 217 (1964). (319) Yee, T. B., ANAL.CHEM.37, 772 (1965).
(320) Zanotti, L., 2. Wiss. Mikroskopie 66, 180 (1964). (321) Zanotti, L., Mikroskopie, 19, 191 (1964).
Electron Microscopy Clinton D. Felton, FMC Corporation, American Viscose Division, Marcus Hook, Pa. Marie
79061
H . Greider, Department o f Pathology, The State University, Columbus, Ohio
HE REVIEW PERIOD extending from T J a n u a r g 1964 to ,January 1966 witnessed marked progress in the instrumental field with regard to image improvement and the ability to examine specimens within the microscope under dynamic conditions. Instrumentation has been devised that permits the direct study in the electron microscope of morphological features such as the nucleation and growth of thin metal films, motion of domain walls, and the effects of ultrasonic waves on solid state materials. Correction of instrumental defects such as lens aberrations, source size, high voltage and lens current instabilities, stray fields and vibration of the optical system, coupled with no\-el operational modes, have resulted in measurable improvement in the quality of the electron microscopical image and higher resolution of structural de-
tails. Along with these corrections, devices have been produced to drastically reduce aperture and specimen contamination. Of course, the actual performance of an electron optical system depends in large part on the specimen preparation examined as well as the mierascope. A high performance instrument is worthless if the specimen preparation is poor. Therefore, electron microscopists have devoted a major part of their efforts to designing preparative techniques that reduce the basic diffuseness of the interaction of electrons with matter. The desire to improve image quality and electron transmission in specimens has led to the development of techniques for preparing very thin substrates or completely eliminating them. Shadowing techniques have been exhaustively studied to reduce the grain size in the speci-
men structure due to the deposited layer. Concurrently, microscopists have significantly increased the quantity of information retrievable from microscopical images by the simple expedient of becoming more thoroughly acquainted with the theoretical aspects of wave mechanics and image formation. X o longer do microscopists think only in terms of descriptive properties, such as size, shape, and number. Interference and phase contrast images and diffraction contrast images, resulting from dislocations, strain displacements, double diffraction from structures or combinations of structures, lattice defects, etc., have been extensively studied. The interpretation of such images has resulted in structural arrangement determinations practically on the interatomic distances level. Image interpretation has also progressed to the VOL. 38, NO. 5 , APRIL 1966
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