AADDVVAANNCCEESS IINN XX--RRAAYY AANNAALLYYSSIISS VVoolluummee 99 ADVANCES IN X-RAY ANALYSIS Volume 9 Edited by Gavin R. Mallett, Marie Fay, and William M. Mueller Proceedings of the Fourteenth Annual Conference on Applications of X-Ray Analysis Held August 25-27, 1965 Sponsored by University of Denver Denver Research Institute g:> SPRINGER SCIENCE+BUSINESS MEDIA, LLC ISBN 978-1-4684-7635-4 ISBN 978-1-4684-7633-0 (eBook) DOI 10.1007/978-1-4684-7633-0 Library of Congress Catalog Card Nurnber 58-35928 Copyright 1966 Springer Science+Business Media New York Originally published by Plenum Press New York in 1966 Softcover reprint of the hardcover 1 st edition 1966 PREFACE The papers presented in this volume of Advances in X-Ray Analysis were chosen from those presented at the Fourteenth Annual Conference on the Applications of X-Ray Analysis. This conference, sponsored by the Metallurgy Division of the Denver Research Institute, University of Denver, was held on August 24,25, and 26, 1965, at the Albany Hotel in Denver, Colorado. Of the 56 papers presented at the conference, 46 are included in this volume; also included is an open discussion held on the effects of chemical com bination on X-ray spectra. The subjects presented represent a broad scope of applications of X-rays to a variety of fields and disciplines. These included such fields as electron-probe microanalysis, the effect of chemical combination on X-ray spectra, and the uses of soft and ultrasoft X-rays in emission analysis. Also included were sessions on X-ray diffraction and fluor escence analysis. There were several papers on special topics, including X-ray topography and X-ray absorption fine-structure analysis. William L. Baun contributed considerable effort toward the conference by organizing the session on the effect of chemical combination on X-ray spectra fine structure. A special session was established through the excellent efforts of S. P. Ong on the uses and applica tions of soft X-rays in fluorescent analysis. We offer our sincere thanks to these men, for these two special sessions contributed greatly to the success of the conference. We also extend our thanks to those who chaired the sessions. Through their diligent efforts the conference ran on a smooth and efficient schedule. The chairmen were Sheldon H. Moll, Advanced Metals Research Corporation, Burlington, Massachusetts; William L. Baun, Air Force Materials Laboratories, Wright-Patterson Air Force Base, Ohio; S. P. Ong, Philips Electronics, Mount Vernon, New York; A. F. Berndt, Argonne National Laboratory, Argonne, Illinois; W. J. Wittig, Union Carbide Stellite Company, Kokomo, Indiana; Frank Bernstein, General Electric Company, Milwaukee, Wisconsin; and W. V. Cummings, General Electric Company, Pleasanton, California. Sincere thanks and appreciation go also to Mr. Frank Rivera, who took charge of the meeting aids and audio-visual equipment during the conference, andto Mrs. Mildred Cain, who so effectively transcribed the discussion sessions which then required only a small amount of editing to make them readable. G. R. Mallett M.J.Fay W. M. Mueller CONTENTS A Camera for Borrmann Stereo X-Ray Topographs . . . . . . . . . . . . . . . . . . . . . . . . . . 1 F. W. Young, Jr., T. O. Baldwin, A. E. Merlini, and F. A. Sherrill A Modification of the Scanning X-Ray Topographic Camera (Lang's Method) . . 14- Mitsum Yoshimatsu, Atsushi Shibata, and Kazutake Kohra Lattice Defect Research by the Kossel Technique and Deformation Analysis. . . . . 23 Masata,ka Umeno, Hideaki Kawabe, and Gunji Shinoda The Crystalline Perfection of Melt-Grown GaAs Substrates and Ga(As, P) Epitaxial Deposits. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 J. K. Howard and R. H. Cox The Application of Cylindrical Geometry for the Determination of Crystal Orien- tation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 Robert D. Forest, Richard J. Barton, and N. C. Schieltz Observations of G-P Zone Reversion in AI-Zn-Mg Alloys by Small-Angle X-Ray Scattering and Transmission Electron Microscopy. . . . . . . . . . . . . . . . . . . . . . . . 59 R. W. Gould and E.A. Starke, Jr. Substructure Measurements by Statistical Fluctuations in X-Ray Diffraction Intensity. . . . . . . . . . . ... . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74- E. F. Sturcken, W. E. Gettys, and E. M. Bohn Analysis of the Broadening of Powder Pattern Peaks Using Variance, Integral Breadth, and Fourier Coefficients of the Line Profile. . . . . . . . . . . . . . . . . . . . . . . 91 N. C. Halder and C. N. J. Wagner Lattice Strain Measurements on Deformed fcc Metals....................... 103 Eckard Macherauch X-Ray Study of Wire-Drawn Niobium and Tantalum. . . . . . . . . . . . . . . . . . . . . . .. 115 R. P. 1. Adler and H. M. Otte The Structure of the y'-Phase in Nickel-Base Superalloys . . . . . . . . . . . . . . . . . . . . 131 S. Rosen and P. G. Sprang Generation of a Two-Dimensional Silicon Carbide Lattice.................... 14-2 R. L. Prickett and R. L. Hough An X-Ray Diffraction Study of the Phase Transformation Temperature of MnO.. 152 Charles P. Gazzara and R. M.· Middleton Crystallographic Studies of NH4CI-NH4Br Solid Solutions. . . . . . . . . . . . . . . . . . . . 159 Sister Jane Edmund Callanan and Norman O. Smith Rotational Polymorphism of Methyl-Substituted Ammonium Perchlorates. . . . . . . 170 M. Stammler, R. Bruenner, W. Schmidt, and D. Orcutt Oriented Crystallization of Urea in Membranes ............. ~ . . . . . . . . . . . . . . .. 190 Edwin H. Shaw, Jr. High-Intensity Rotating Anode X-Ray Tubes............................... 194- A. Taylor A Dual Counter X-Ray Analyzer for the Rapid Quantitative Analysis of Two- Phase Systems. . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 202 B. S. Sanderson and L. E. MacCardle vB viii Contents Correction for Non-Linearity of Proportional Counter Systems in Electron Probe X-Ray Microanalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 208 Kurt F. J. Heinrich, Donald Vieth, and Harvey Yakowitz A Combined Focusing X-Ray Diffractometer and Nondispersive X-Ray Spectrom- eter for Lunar and Planetary Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 221 K. Das Gupta, Herbert W. Schnopper, Albert E. Metzger, and Rex A. Shields Two-Crystal X-Ray Spectrometer Attachment. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 242 Leonid V. Azaroff Plane-Polarized, Two-Crystal X-Ray Spectrometer. . . . . . . . . . . . . . . . . . . . . . . . .. 251 Raymond J. Donahue and Leonid V. Azaroff Evaluation of Quantitative Electron Microprobe Analyses of Multiphase Micro crystalline Refractory Materials................. . . . . . . . . . . . . . . . . . . . . . . .. 259 David H. Speidel A Method for Trace Analysis with an Electron Microprobe .................. 265 L. A. Fergason The Application of the Ziebold Correction Procedure for Probe Data to Three Ternary Copper-Base Alloys ................................' ............ 273 Richard M. Ingersoll, Jack E. Taylor, and Donald H. Derouin Homogeneity Characterization of NBS Spectrometric Standards II: Cartridge Brass and Low-Alloy Steel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 289 H. Yakowitz, D. L. Vieth, K. F. J. Heinrich, and R. E. Michaelis Electron Probe Microanalysis of Zinc-Bearing Hexagonal Ferrites. . . . . . . . . . . . .. 304 J. R. Shappirio Electron Microprobe Analysis of Highly Radioactive Samples. . . . . . . . . . . . . . . . .. 314 V. G. Scotti, J. M. Johnson, and R. T. Cunningham Effect of Chemical Combination on the K X-Ray Spectra of Silicon. . . . . . . . . . .. 323 Donald M. Koffman and Sheldon H. Moll The Effect of Chemical Combination on Some Soft X-Ray K and L Emission Spectra.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 329 David W. Fischer and William L. Baun Land M Spectra in the Region 2-85A..................................... 344 Franklin D. Davidson and Ralph W. G. Wyckoff Cheniical Bonding and the Sulfur K X-Ray Spectrum ........................ 354 D. W. Wilbur and J. W. Go/man Determination of Electron Distribution and Bonding from Soft X-Ray Emission Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365 J. E. Holliday Chemical Effect on X-Ray Absorption-Edge Fine Structure. . . . . . . . . . . . . . . . . .. 376 E. W. White and H. A. McKinstry The Effect of Chemical Combination on X-Ray Spectra: Open Discussion...... 393 Determination of Interatomic Distances from X-Ray Absorption Fine Structure 398 F. W. Lytle X-Ray Techniques in the 1 to 400 A Range................................. 410 Andrew A. Sterk Contents A Blazed-Grating Scanning Spectrometer for Ultrasoft X-Rays Suitable for Use in an Electron Microprobe......................................... 420 1. B. Nicholson and M. F. Hasler Application of Multilayer Analyzers to 15-150 A Fluorescence Spectroscopy for Chemical and Valence Band Analysis.................................... 430 Burton L. Henke Matrix and Particle Size Effects in Analyses of Light Elementll, Zinc Through Oxygen, by Soft X-Ray Spectrometry. . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . .. #1 K. W.Madlem The Characteristic X-Rays from Boron and Beryllium........................ 456 R. C. Ehlert and R. A. Mattson The Application of a Soft X-Ray Spectrometer to Study the Oxygen and Fluorine Emission Lines from Oxides and Fluorides............................... 471 R. A. Mattson and R. C. Ehlert Use of the Soft X-Ray Spectrograph and the Electron-Probe Microanalyzer for Determination of Elements Carbon Through Iron in Mineral and Rocks. . . . .. 487 A. K. Baird and D. H. Zenger A "Windowless" X-Ray Fluorescence Tube and a High Resolution Diffractometer 504 George Walker On the Primary X-Ray Analyzer. ......................................... 508 Shizuo Kimoto, Masayuki Sato, Hitoshi Kamado" and Takuzi Ui Some Observations on the Use of Certain Analyzing Crystals for the Determination of Silicon and Aluminum ............................ ;................. 515 Frank L. Chan X-Ray Spectrographic Analysis of Automotive Combustion Deposits Without the Use of Calibration Curves. . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528 1. C. Wagner and F. R. Bryan Author Index 533 Subject Index 539 A CAMERA FOR BORRMANN STEREO X-RAY TOPOGRAPHS F. W. Young, Jr., T. O. Baldwin, A. E. Merlini,* and F. A. Sherrill Oak Ridge National Laboratory Oak Ridge, Tennessee ABSTRACT A relatively inexpensive camera which was designed for taking Borrmann topographs with standard X-ray diffraction equipment is described. This camera has been used to take stereo pairs of Borrmann topographs by rotating the crystal around an axis normal to the diffraction planes. Topographs have been taken of nearly perfect copper crystals up to 0.2 em thick using silver, molybdenum, copper, and chromium radiation, and comparisons have been made with topographs obtained with crystal monochromated radiation. Geometrical factors affecting the resolving power of the technique are briefly reviewed. In addition, the resolution inherent in the diffraction phenomenon is analyzed on the basis of the theory of anomalous transmission. Comparisons are made between calculated and observed image widths of a few dislocations. INTRODUCTION A number of X-ray diffraction techniques are available for the study of individual dislocations in crystals; these techniques and the advantages of X-ray diffraction topo graphy were recently reviewed.1,2 Topography in anomalous transmission (Borrmann topography) is the one which has been least applied and studied, probably because of its limited application to the few perfect crystals until recently available such as silicon and germanium. In the past few years anomalous transmission was found in crystals of zincS and in nearly perfect crystals of copper,4 and the interest in Borrmann topography for the study of dislocations in metal crystals was increased. It was believed that anomalous transmission topographs could show with a sufficient degree of sharpness only those imperfections lying very close to the crystal surface from which the diffracted X-rays exited. Experimental evidence and theoretical estimates of the projected size of the dislocation image have shown that this is not the case if the proper choice of the character istic radiation is made (for example, Ag Ka. and Mo Ka. for copper crystals). The possibility of seeing dislocations lying at a depth of 0.06 to 0.08 cm from the exit surface5 is a definite advantage of the technique for the study of thick crystals. Finally, it was believed im possible to obtain satisfactory stereo pairs if a strong Borrmann effect were present. In Lang topography stereo pairs can be obtained from the hkl and khZ reflections and have proved to be very useful for the study of the spatial arrangements of dislocations.6 Even this objection has been eliminated since Noggle et aU showed that Borrmann stereo topographs could be taken by rotating the crystal a few degrees around the normal to the diffraction planes. This method, which can also be used with thin crystals,8 has the advantage of versatility with respect to the stereo angle. • Guest scientist from Euratom, Ispra, Italy. 1 References are at the end of the paper. 1 2 F. W. Young, Jr., T. o. Baldwin, A. E. Merlini, and F. A. Sherrill A camera for Borrmann topography was briefly described and some examples of topographs were presented in an earlier paper.5 A camera of improved vertical resolution was subsequently designed .. Good quality topographs can be taken with standard X-ray diffraction equipment and a relatively inexpensive camera. The purpose of this paper is first the description of such a camera and of some of the results obtained, and then the presentation of simple rules for the evaluation of the diffraction resolution in Borrmann topography. PRINCIPLES OF BORRMANN TOPOGRAPHY The conclusions of the theory of anomalous transmission9,10 as they apply to X-ray topography can best be discussed with the aid of Figure 1. Suppose an X-ray beam is incident at the Bragg angle with respect to crystallographic planes which are normal to the crystal surface (symmetrical case, Laue geometry). Provided the crystal is nearly perfect, two standing wave fields for each polarization direction of the incident radiation are generated inside the crystal. One wave field has nodes at the atomic planes and is transmitted almost undiminished in intensity, while the other wave field has antinodes at the atomic planes and is highly absorbed. If the crystal is thick [p.t (absorption co efficient x crystal thickness) ,.., 10 or greater], the net energy flow is very nearly parallel to the diffraction planes, and only the wave field with polarization perpendicular to the plane of incidence and with nodes at the atomic planes is transmitted with appreciable intensity. Only this latter wave field will be considered in the remainder of the paper. At the exit surface the wave field splits into two beams of nearly equal intensity, which we will denote as the anomalously transmitted beam T and the anomalously reflected beam H. The anomalously transmitted beam has the same direction as the incident or direct beam D, but is displayed toward the reflected beam a distance which is proportional to the thickness of the crystal. Whenever the lattice is disturbed from its perfect periodicity, such as is the case for dislocations and other imperfections, the intensity of both beams in Borrmann transmission is normally reduced, and regions of reduced intensity or white images of the imperfections appear on a photographic plate placed near the exit surface a£ the crystal. CRYSTAL AND PLATE TRANSLATED SYNCHRONOUSLY Figure 1. Principles of the Borrmann o DIRECT BEAM PLATE technique for X-ray topographs. Stereo r topographs are taken by rotating the TRANSMITTED BEAM crystal around the [111] axis. H REFLECTED BEAM