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By A. J. Boynton

THIS paper is not the result of recent research with regard to any particular feature of iron metallurgy, blast-furnace practice or mechanical engineering. It is rather a series of notes with regard to contemporaneous progress in blast-furnace construction and operation, together with some suggestions as to changes and improvements that seem to be desirable. On April 1, 1930, a committee of the Chicago District Blast Furnace and Coke Association presented to that association a rather ambitious study of blast-furnace equipment, together with recommendations for the design of construction of a complete blast-furnace unit for the production of 1000 tons of pig iron per day. This report represented the result of months of study by members of the committee, all of whom were actively engaged in operation or design of blast-furnace plants. It is natural, therefore, that comments on the present state of the art should take this 1000-tons furnace, as recommended by the Association, as a basis for comparison with corresponding features of construction or design. See Table 1. In looking through this report at the present time, the significant difference is in the nature of the gas-washing equipment that today would be specified. In other respects, the installation would remain generally very much as it was outlined in 1930. The change in furnace dimensions would be very slight and of no especial significance, except with respect to changes in stock-line diameter, of which more will be said hereafter. The high-efficiency stove as developed by various designers is thoroughly described within this report, and few changes have taken place since. Blowing equipment shows refinement and reflects the improvement in steam engineering. Hoisting and charging equipment and ladles for the conveyance of iron and slag remain, in general, as they were in 1930. In accordance with a general tendency

Jan 1, 1935

By Charles E. Wait

HAVING had some experience in the use of gasoline-gas in a laboratory, I have been induced by frequent inquiry to present a few hints concerning it, which I hope may be of some value to those who are out of the reach of coal-gas, and who contemplate using this gas. While I will not delay to describe the method by which this gas is made, it may not be out of place to note that, unless frequent charges are put into the carburetter, the gas is variable in richness. This may be partially avoided, it is said, by repeatedly pumping from one cell in the carburetter to another. If a machine is in constant use for many months without re charging, the gas becomes rather poor for illuminating purposes ; but in this condition it may be burned in a Bunsen burner with advan tage. Could the gas be used always in this condition, no difficulty would be experienced, and it would be quite satisfactory for general laboratory purposes. Considerable annoyance, however, is experi enced whenever the machine is filled with gasoline. The Bunsen and other burners then produce a flame too smoky to be used with com fort, and, in fact, with most of them, a full supply of air; turned on at the base of the burner, will not suffice to completely burn off all the carbon. Finding it necessary to adopt some method by which I could get a flame free from unconsumed carbon, I adopted a plan which has in every way proved satisfactory. In addition to the pipe conveying the gas to the table, and ar ranged with a stopcock, there is brought to the table, within a fern inches of the gas-pipe, another pipe, conveying air direct from the pump. This pipe is also arranged with a stop-cock. The air- and gas-pipes are now connected with one pipe by a T joint; and to this last pipe is attached, by rubber tubing, the Bunsen or other burner. I have successfully used this simple system in connection with both small and large Bunsen burners, a burner with three tubes, arid a Fletcher burner; and recently I have added a new still to our equipment, and have been tising with it a Fletcher special high power burner No. 6, to which this system has been applied. With

Jan 1, 1886

By L. W. McKeehan

THE occurrence of twins in large ferrite crystals, made by a new process, was reported in a recent note. This paper describes a typical case of such twinning and suggests, on the basis of the observed facts, why smooth slip-planes are rarely observed in this metal. METHOD OF PREPARATION The material In which the crystals here dealt with were grown was made from 1/8 -in. Armco iron welding rod containing C, 0.04; S, 0.037; P, 0.003; Si, 0.008, and Mn, 0.02 per cent. This rod was cold drawn into wire about 1 mm. dia. A piece of this wire was supported vertically and was locally heated in hydrogen at atmospheric pressure to about 1400° C. by an alternating current (60 cycles per sec.) of about 35 amp., passed through it between a pair of travelling contacts about 8 cm. apart. The rate of travel for the case in hand was 12 cm. per hr. After some 30 cm. of the length of the wire had been heated and cooled in this manner the whole wire was immersed for a few seconds in dilute nitric acid, not restrained by alcohol. Etching was continued until, as nearly as could be judged by eye, the original smooth cylindrical surface of the wire was no longer capable of specular reflection.

Jan 1, 1927

By Charles H. Fulton

FOR some time it has been thought that there should be > closer relationship between the members' of the Institute engaged in education in the mining schools, the mining, metallurgical, ceramic, and geological departments of universities, and the members of the Institute actually engaged in the production of mineral products and the operation and direction of works. The American Society of Chemical Engineers and the American Ceramic Society have for some years past devoted especial attention to the educational matters of their respective fields. The Engineering Foundation, representing the great engineering societies of the country, is deeply interested in technical education and maintains a Committee on Educational Research.

Jan 1, 1932

By W. C. McClain

In the design of underground excavations, rock mechanics considerations are nearly always based on an elastic behavior of rock. Most rocks do exhibit a certain amount of elasticity, and the application of principles and concepts of elasticity to rock mechanics problems has been largely responsible for progress in the field over the past 10 or 15 years. No doubt the theory of elasticity will remain the most useful analytical tool available for both the design of underground openings and the interpretation of phenomenological data.

Jan 1, 1967

By A. W. Hahn

USE of gold leaf goes back to biblical and even to prehistoric times. Both gold and silver, as well as other metals, were employed in illustrating or illuminating manuscripts. The medieval monks also used bronze powders. Metals were subdivided as finely as possible by mechanical methods, or by granulation and then were pounded into finely divided flakes. Substances such as honey have also been employed, since early times to keep the flakes of metal apart during grinding. Stearic acid is a more modern agent used in flaking aluminum and other metals. Finely divided "blue powder" is a by-product in retorting zinc ores, and contains from 78 to 90 per cent of zinc metal. This has been used as a precipitant for precious metals in the cyanide process and for chemical reduction processes. The making of zinc dust by atomizing is a step well known in electrolytic zinc plants. The Thermit process of Goldschmidt also requires the use of finely divided aluminum.

Jan 1, 1937

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

By Hollis Peacock

THE Bingham area in the West Mountain mining district on the eastern slope of the Oquirrh range, some 28 miles southwest of Salt Lake City, has been the most consistent producer for the United States Smelting Refining and Mining Company, production having been continuous, except for minor interruptions, since the organization of the United States Mining Co. in 1899. This production has come from fissures and mantos largely within limestone members aggregating something less than 10 per cent of a thick quartzite sequence of Pennsylvanian age which has been warped into an open syncline plunging northwesterly. Bedding on the easterly limb dips 10°-45° but steep-ens to 90° and even overturns on the westerly limb. Ore bodies cluster about the more northerly of two elongate interconnecting stocks of monzonite which have risen in an axial position within this syncline. Largely within the more northerly of these stocks is the low-grade copper ore body exploited in the Utah Copper open cut of the Kennecott Copper Corp. The values, in seams, minute fracture fillings, and disseminations of pyrite and silica, pervade not only the stock but adjacent sediments, and form a nebulous, sprawling mass which both mineralogically and geographically is the center of the district. The more southerly of the twin stocks appears to be comparatively inert and without obvious relation to mineralization. which

Jan 1, 1948

By William P. Prof. Blake

WHEN we consider the efforts made in Europe to promote the physical and moral well-being of the working classes, the question is suggested whether in this country, where, theoretically, every man is peculiarly the arbiter of his own destiny, we may not be too prone to expect every man to take care of himself, and neglect to make those provisions for the welfare of the employed, demanded alike by enlightened economy and humanity. In the older countries, where the disproportion between capital and labor is greater, and the working classes are more dependent, their welfare largely occupies the attention of employers. The subject is involved in the problem of the just relations of capital and labor, and we are rapidly approaching the time, if we have not already reached it, when a generous paternal interest in the welfare of the employed should be more generally manifested. It is a subject which is of special importance to mine-owners and engineers in this country, especially to those located in the coal regions. My own attention has been particularly directed to it by a visit made to the Hassard collieries, a few miles from Liege, Belgium, under the direction of M. Andrimont. This celebrated engineer has established a comfortable home for the miners near the mouth of the shaft of the mine. It has been highly successful and beneficent in its results, and may to a great degree be regarded as a, model for such undertakings. It is known as "Hotel Louise," this being the name of Madame d'Andrimont, who laid the corner-stone of the building April 4th, 1871. The structure is of brick, upon three sides of a square, and

Jan 1, 1875

By William P. Blake

When we consider the efforts made in Europe to promote the physical and moral well-being of the working classes, the question is suggested whether in this country, where, theoretically, every man is peculiarly the arbiter of his own destiny, we may not be too prone to expect every man to take care of himself, and neglect to make those provisions for the welfare of the employed, demanded alike by enlightened economy and humanity. In the older countries, where the disproportion between capital and labor is greater, and the working classes are more dependent, their welfare largely occupies the attention of employers. The subject is involved in the problem of the just relations of capital and labor, and we are rapidly approaching the time, if we have not already reached it, when a generous paternal interest in the welfare of the employed should be more generally manifested. It is a subject which is of special importance to mine-owners and engineers in this country, especially to those located in the coal regions. My own attention has been particularly directed to it by a visit made to the Hassard collieries, a few miles from Liège, Belgium, under the direction of M. Andrimont. This celebrated engineer has established a comfortable home for the miners near the mouth of the shaft of the mine. It has been highly successful and beneficent in its results, and may to a great degree be regarded as a model for such undertakings. It is known as ((Hotel Louise," this being the name of Madame d' Andrimont, who laid the corner-stone of the building April 4th, 1871. The structure is of brick, upon three sides of a square, and

By James V. Thompson

ENGINEERS from industrialized countries are frequently called upon to examine mining operations in primitive areas and make recommendations regarding mechanization and modernization. They often set forth with self-confidence, knowing full well that all that is needed is their experience and several shiploads of mining machinery, and at times they mentally provide the answers before the problems have been clearly stated. In primitive areas it is absolutely essential that the examining engineer spend enough time at the site to acquire a thorough understanding of what is being done now and why it is done the way it is. The objective here is to state in simple terms some of the problems that may be encountered, in- as much as solutions, if they can be found at all, will differ with each experience.

Jan 8, 1958

By J. Gordon Parr, D. H. Polonis

The formation and subsequent decomposition of metastable phases in Ti-Ni alloys containing up to 11 pet (atomic) Ni have been studied. The decomposition of a completely retained ß phase and of a completely transformed 8 phase in a 6 pet alloy has been followed by X-ray diffraction and metallographic methods and by hardness determinations made during the process. The possible mechanisms of the reactions are discussed. PREVIOUS investigations of the Ti-Ni system have usually been limited to phase diagram studies; but little attention has been given to metastable phases and tempering processes. These are important, however, since equilibrium conditions are rarely achieved—nor, perhaps, are they desired—in practice. Up to the present time the available transformation data for titanium alloys appear to be restricted to isothermal transformation curves for selected binary and ternary systems. No quantitative studies have been made of the mechanism by which equilibrium is approached. Several independent investigations have been carried out to determine the Ti-Ni phase diagram. Early work by Wallbaum' and later by Long et al.' produced tentative phase diagrams which were not representative of true binary conditions, since the alloys were contaminated with oxygen and nitrogen. The most recent diagram (Fig. 1) is due to Margolin et al.," and a slight modification of the a + ß/ß boundary (shown dotted) has been proposed by McQuillan.' The structure of the phase Ti,Ni was shown by Duwez and Taylor" to be face-centered-cubic, with 96 atoms per structure cell. The formation of a martensitic ß phase (close-packed-hexagonal) in Ti-Ni alloys has generally been observed when specimens of low nickel content are rapidly cooled from the 0 (body-centered-cubic) range. Margolin et al. reported an increasing tendency for P to be retained in lump specimens as the nickel content increases. McQuillan' has studied the effect on the microstructure of delay time in quenching, and has reported the formation of pro- eutectoid a precipitate in a quenched hypoeutectoid alloy. In a previous study of Ti-Fe alloys," experiments were made on powder specimens produced by filing alloy ingots. Techniques were devised for the preparation and heat treatment of alloys, and X-ray diffraction methods were used both for structure determinations and phase ratio estimations. A similar approach has been made in this study of Ti-Ni alloys. Experimental Methods Ten alloys ranging from 0.25 pet to 18 pet Ni* * All compositions are in atomic percentages unless otherwise stated. were prepared from iodide titanium bar stock (hardness Rf 72) and Johnson-Matthey spectrographic standard nickel by levitation melting.' As a check

Jan 1, 1957

By David White

ATTENTION has been given to the sources and supply of the raw vegetal matter and. the conditions of its submission to the process of sedimentation. An original and most valuable review has been made of the more important or significant chemical compounds originally contained in the organic debris, and of the biochemical changes-undergone by the latter during deposition. Consideration also has been given to the factors controlling the selective biochemical decomposition, in whole or in part, of :this debris, and the deposition, as, sediments, of the undecomposed plant structures and compounds, together with more or less of the so-called "ulmic," or "humic," organic decomposition products in colloidal solution.1 BIOCHEMICAL CHANGES END IN PEAT FORMATION The biochemical process terminates in the peat stage of coal formation, and with the cessation of this process organic sedimentation is completed. All subsequent changes result from geological causes and conditions. The deposits are in the form of peats of different types, organic muds, oozes, etc. They are essentially uncompressed and are wholly unconsolidated, and their water content is great, amounting to over 85 per cent. near the surface of the deposit. Many of the chemical compounds remain as in the once living organisms; others are biochemically broken down and new ones formed.

Jan 2, 1925

The University of North Dakota, State Geological Survey, Grand Forks, N. D A G. Leonard, State Geologist. Two publications of the State Geological Survey are of interest Fourth Biennial Report, The clays and clay industries of North Dakota, and Bulletin 4, Lignite deposits and lignite industries of North Dakota. Bulletin 11 of the University is of interest: Geology and natural resources of North Dakota For further information, address the above

Jan 1, 1933

Jan 2, 1976

THE decades immediately before and after the end of the nineteenth century (1890-1910) were a period of increased activity in mineral industry education. One reason for this, undoubtedly, was the rapid increase in mineral production in the decade 1880-1890; pig iron and copper production tripled; coal, lead, and zinc output more than doubled. Most of the other mineral substances followed the same general trend. Aluminum production began in 1886; petroleum output, which in 1888 was less than it was in 1882, almost doubled in the next three years. Gold alone showed no appreciable change until its discovery at Cripple Creek in 1891, followed by the Klondike in 1896, brought to boiling a public interest in minerals that had been simmering for some years previously. The first cyanide plant in the United States was erected at Bodie in 1892, and the first chlorination plant at Cripple Creek* the next year. Silver- lead smelting had already greatly developed, and the metallurgy of copper was almost transformed. The hearth area and smelting capacity of copper reverberatory furnaces more than quadrupled between 1878 and 1894; matte converters were first erected at Butte in 1884. Copper production of the United States in 1899 was 20 times that of 1872. While it was the increased technology used in mineral production that really made the field attractive for educated young men, undoubtedly they did not realize that, and were impressed mainly by the quantitative increase in output. Another factor was the increased general interest in engineering education; three times as many men took engineering degrees in the United States in 1890 as in 1880; 1892 showed almost a 56 per cent increase over 1890. Industry had come to recognize that technical training was worth while. The mineral industry lagged somewhat at first; the total number of mining degrees

Jan 1, 1941

By J. J. Jonas, G. Gagnon

SHG zinc was extruded in the temperature range 110" to 350°C and the strain rate range 0.05 to 5 sec-1 The strain rate/flow stress/temperature results were analyzed using a power sinh stress relationship. When temperature changes due to the heat of deformation and to heat losses are neglected, the exponent of the sinh function of the stress is 5.6, and the apparent activation energy of deformation is 28 kcal per mole. When these changes are taken into account, the exponent decreases to 4.7 and the activation energy to 23 + 2 kcal per mole. The corrected stress exponent and activation energy are in very good agreement with published values obtained from creep experiments, and suggest that the hot extrusion of zinc is controlled by a mechanism involving self-diffusion. When the extrusion and creep data are compared using a Zener-Hollomon parameter and either a sinh or an exponential stress term, an appreciable offset is observed, which may be due to the difference in impurity content. For a given set of extrusion conditions the ram speed, maximum pressure, and initial temperature can also be correlated using a Zener-Hollomon parameter and a sinh pressure term. THE deformation of metals at temperatures over about one-half the absolute melting temperature has been extensively studied at creep strain rates. By contrast, relatively little work has been carried out on the behavior of metals at hot working strain rates. Most of the latter investigations have been performed using simulative methods, such as hot torsion and hot compression, in which the friction conditions and temperature rise during deformation may differ appreciably from those existing under industrial conditions. Recently, however, Wong and Jonas1 used a scaled-down industrial process to determine the stress and temperature dependence of the strain rate during the extrusion of aluminum. In such tests, the effects of friction and adiabatic heating are closer to those produced in industrial operations. Also, with regard to the testing of materials of limited ductility such as zinc, hot compression and hot torsion do not permit the attainment of true strains as large as the deformations usually applied commercially. The present study was undertaken to investigate the extrusion behavior of Special High Grade (SHG) zinc. The detailed objectives were: 1) to establish the stress and temperature dependence of the strain rate with and without a consideration of adiabatic heating, 2) to study the pressure and temperature dependence of the ram speed, and 3) to investigate the microstruc- tural changes occurring during the deformation. The last aspect of the investigation will be covered in a separate paper. The treatment described below differs from that of Wong and Jonas in that the adiabatic temperature rise during deformation is taken into account, and the calculation of the mean equivalent strain rate is based on the redundant as well as on the homogeneous work. EXPERIMENTAL PROCEDURE Rods from two shipments of continuously cast SHG zinc* were used in the investigation. The composition *Supplied by courtesy of Cominco Ltd. range of the impurities present, as given by the supplier, was: Pb: 0.0013 to 0.0023 pct, Fe: 0.001 pct max Cd: 0.0001 to 0.0006 pct, Cu: 0.0002 to 0.0005 pct, Ti: 0.0001 pct max; thus, by balance, zinc valued from 99.9963 to 99.9966 pct. The as-received rods were machined into billets having a nominal diameter of 1.56 in. and a nominal length of 1½ in.; longer billets up to 4 in. in length, were also used to investigate special aspects. The as-machined rods were annealed at 400°C for 24 hr and slowly cooled. This treatment produced a columnar grain structure, with a grain size of about $ by 2½ cm which was appreciably larger than the as-cast one. A 150-ton, direct extrusion, vertical press was used. Ram displacement and force were recorded continuously against time. A constant flow control valve permitted the maintenance of a range of preselected ram speeds up to in. per sec. The selected speed was held constant, irrespective of the required force, as long as the load developed was below the maximum available. Strain gages were used to determine the force; the gages were calibrated before and after each testing period with a 200,000-lb capacity load cell. Further details of the experimental equipment can be found in Ref. 2. The billets were preheated for 90 min in the extrusion container, which was well insulated so as to minimize temperature gradients. This period was sufficient for the billet to reach a uniform temperature at all temperatures between 110" and 350°C. A square-shoulder die having a 0.290-in. diam central hole was used. The extrusion ratio was 30 to 1. This is equivalent to a reduction in area of 96.7 pct, an elongation of 2900 pct, and a true strain of 3.4. The ram speed was varied over two orders of magnitude from 0.0027 to 0.26 in. per sec. The ram was water-cooled during most of the tests, although some experiments were conducted with a preheated, uncooled ram. All extrusions were run without lubricant, which resulted in conditions of sticking friction. EXPERIMENTAL RESULTS Stress Dependence of the Strain Rate Neglecting Adiabatic Heating. The maximum force required to extrude is given in Table 1 for each of the five initial

Jan 1, 1970

By M. G. Corson

INFORMATION regarding the use of manganese alloys has hitherto been incomplete and available only from widely scattered sources. This paper attempts a systematic description of properties and uses of alloys other than manganese bronze, manganin and duralumin, which are probably the only non-ferrous alloys associated with manganese in the minds of most metallurgists.1 PROPERTIES OF MANGANESE Manganese can react either acid or basic; it is hard to obtain in the pure state; it has two different crystalline lattice structures, both of the cubic system, one stable above 850° C. and the other below 650° C., both coexisting in the intermediate range. Although the commercial product is hard and brittle, the pure metal seems to be ductile. In fact Zhemchuzhny, in Russia, was able to obtain ductile manganese and draw it to fine wires by the simple expedient of adding about 3 per cent. copper to the alumino-thermic product. Copper most probably brings the sili-cides, aluminides, nitrides and carbides present in the commercial product into a much less harmful form of distribution. One industrial use that can be foreseen for wrought manganese articles is as anodes for electrolytic processes in sulfate and nitrate solutions, particularly with high voltages. A practically insoluble skin of manganese peroxide is likely to form in such cases and an insoluble and strong anode material will be available.

Jan 5, 1927

By L. T. Larson

The spectral reflectivity of zirconium in light of 441 to 668 nanometers (nm) wavelengths and air immersion has been determined. Bireflectance and apparent-angle -of-rotation measurements show zirconium to be optically isotropic when examined in light of approximately 484 nm wavelength. There is a direct relationship between bireflectance and the tilt of the basal pole of zirconium from the surface normal. This relationship allows the determination of the spatial orientation of the basal pole of an individual single crystal within a coarse-grained poly crystalline section to within± 2 to 3 deg for angles of basal pole tilt from 0 to 90 deg. In recent years considerable attention has been given to the quantitative determination of optical properties of opaque minerals by use of vertically incident, plane-polarized light. In particular, Cameron' and Cameron et a1.2 have developed criteria for the identification of a large number of anisotropic ore minerals based upon measurement of the apparent angle of rotation and the ellipticity or phase difference of the reflected light. It was shown by Larson and Pickle-simer3 that apparent-angle-of-rotation measurements may also be used to determine crystallographic orientations of grains of noncubic metals. In particular, it was shown that the basa.1 pole orientation in space of zirconium grains can be determined to ±3 deg for those grains with basal pole tilts of 10 to 90 deg from the plane of the section. Another, even more widely studied, optical property is reflectivity. cameron4 has commented upon measurement of the reflectance of plane-polarized, vertically incident light and Bowie and Taylor5 have made such measurements an integral part of their system of ore-mineral identification. Leow6 has reported on the spectral reflectivity of molybdenite and has used reflectivity values to calculate refractive indices and absorption coefficients. Cameron7 has made use of reflectivity values to ascertain aniso-tropic ore mineral symmetry and Piller and v. Gehlen8 have evaluated sources and importance of errors in reflectivity measurements as applied to calculation of optical constants. cambon9 has shown that reflectivity measurements using vertically incident, plane-polarized light are useful in the investigation of metals and in the identification of phases present in alloys. Bronson10 has made preliminary measurements on the optical anisotropy of beryIlium and Mott and Haines11 have published qualitative data on the intensity of light reflected from sections of bismuth, tin, and aluminum when these metals are microscopically examined under crossed polarizing plates. Koritnig12 has correlated the reflectivity of homogeneous solid solutions with their chemical compositions. From the above work and investigations in progress by this author, it is apparent that accurately determined values for the reflectance of vertically incident, plane-polarized monochromatic light from carefully polished surfaces of noncubic metals can prove useful in identification, composition determinations, and crystallographic orientation applications. Finally, reflectivity values, when measured in two media of differing refraction index and related to standards whose spectral reflectivities in these media are known, can be used to calculate optical constants such as refractive index and absorption coefficient. These constants may prove of use to those concerned with problems of electron band configuration. This paper reports the spectral reflectivity of zirconium measured in light of 441 to 668 nanometers (nm) wavelengths and air immersion. It also gives maximum bireflectance values for a prism section of zirconium in these wavelengths and shows how bire-flectance may be used to determine the crystallographic orientation of zirconium single crystals. Because of the lack of information on the reflectivities of the standards in oil immersion, no attempt is made to calculate the refractive indices or absorption coefficients although it is recognized that such values may be of fundamental importance. METHOD Single crystals of zirconium were cut by electro-discharge machining from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.13 The crystal sections were mounted in cold-setting epoxy resin and mechanically polished to a plane, uniform, bright surface. Each crystal was then chemically polished in a 26/26/43/5 mixture (by vol) of water, nitric, lactic, and hydrofluoric acids to remove the mechanically damaged and smeared surface layer. Final polish was obtained by electropolishing at 30 v in a bath of methyl alcohol and perchloric acid (98/2 by vol) at -70oc.14 Reflectivity measurements were made using a photometer system designed and developed at Oak Ridge National Laboratory and described in detail by Larson.15 Briefly, the reflectivity measuring system consists of a reflecting microscope; a double-beam, null-balancing photometer array; a mechanically driven microscope stage; and a direct X-Y readout of the reflectivity of the specimen relative to its orientation on the microscope stage. The measuring photometer receives its signal from the specimen through a slotted Wright occular placed on top of the photovisual head of the microscope. The reference photometer receives light through a flexible glass "light pipe" from a mirror in the reflecting system of the microscope. Monochromatic light is attained through use of interference filters (15-nm half-peak width pass bands) placed in front of a stabilized Vickers 12 v, 100 w, tungsten-filament, quartz-iodide lamp.

Jan 1, 1970

By C. H. P. Lupis, Henri Gaye

There are m -I conditions for the stability of a solution of m components with respect to infinitesinzal flucturations. However, in most cases, only one of these conditions has to be considered to determine the domain of instability and the existence of this more restrictive condition greatly simplifies the calculations. It may be used advantageously for the prediction of miscibility gaps and the method is illustrated in details for the case of the Ag-Pb-Zn system. THE thermodynamic conditions for the formation of a miscibility gap may be viewed as a necessary consequence of the conditions for spinodal decomposition. A previous article1 has examined in detail the form of these conditions for multicomponent systems. There is only one condition for the stability of a binary system (with respect to infinitesimal fluctuations), but there are two conditions for a ternary system, and m — 1 conditions for an m-component system. The probability of violating a stability condition, and thus forming a miscibility gap, obviously increases with the number of components, a result which is rather intuitive since the atoms of the solution have now many more ways of redistributing themselves and introducing complexities in the form of the free energy hy-persurface. It is of interest to take advantage of this possibility of precipitating new phases and to examine which stability condition is the likeliest to be violated, that is, which stability condition is thermodynamically the most restrictive. The finding of such a condition would greatly simplify the application of the stability criteria since only one condition could then be considered, instead of m - 1. In Ref. 1, coherency strain energy terms were neglected, thus restricting the applications of the treatment to solutions where they are negligible, such as liquid alloys. In the following study the same assumption will be made. To generalize the treatment to systems where the strain energy terms are sizable, the reader is referred to Cahn's classical article on spinodal decomposition.2 Let us designate by Gij the second derivative of the Gibbs free energy with respect to the number of moles ni and n j. There are several equivalent sets of m — 1 stability conditions.' The one considered here expresses that the successive diagonal determinants of order 1, 2, ... m — 1, associated with the symmetric Gij matrix (for 2 5 i, j 5 m) are positive.' For a binary solution 1-2, the condition for stability is: O(u=G22^0 [1] For a ternary system 1-2-3, the condition [I.] is re- tained (the value of G22 will differ, of course, according to the concentration of 3) and another condition is introduced: £>(21 = G22G33 - Gl3 ^ 0 [2] In a composition diagram, these two conditions define two domains of instability. Starting at a point where the solution is stable (for instance at a point where the solution is very dilute) we gradually change the composition until the condition [I] or [2] is violated. As already noted in the literature, e.g., in the work of Prigogine and Defay,3 it is the boundary of the domain (2) which is first crossed. For if we assume that the boundary of the domain (1) is reached first, at this point G22 = 0 and the second condition is necessarily violated (D(2) = -& 5 0), in contradiction with our original assumption. An exhaustive study of the ternary regular solution case may be found in the work of Meijering.4 Moreover if the boundaries of the two domains have a common point, they also have a common tangent. For if the two lines were to cross each other as is illustrated in Fig. 1(a) any point M in the line QP would be such that £> = 0 and 0"' > 0 which, as shown above, are incompatible results. Thus, the two lines must be tangent at their common point Q as illustrated in the example of Fig. l(b). The reasoning of Fig. l(a) implies that the point Q is not a "singular" point for either boundary line. This singularity may be of two types. First, the lines meet without crossing each other and without being tangent. Second, the tangent at Q for D"' or 0"' is not single-valued. Other types of singularity are unlikely because of the usual analytical forms of D"' and 0"'. The exception to the common tangent requirement due to the first type of singularity was pointed out by John Morral;5 it occurs when the common point, Q' or (3" in Fig. l(b), is located at a boundary of the composition diagram, e.g., at the line X3 = 0. It may also be noted that at the common nonsingular point Q of D(1) and D(2), Fig. 1(b), G23 is necessarily equal to zero, whereas at a point such as Q' or Q", this conclusion is no longer valid because the product G22G33 is now indefinite (of the form 0. a). The exception to the common tangent requirement due to the second type of singularity occurs when two branches of the same boundary line intersect, for example when D(1)or D(2) decomposes into a product of functions, at a point which belongs to the boundary of the other condition. It is possible to show by a simple analytical calculation that, in this case, if Q is a singular point of D(1), then it is necessarily a singular point of D(2), and that the reciprocal is true except if G33 = 0 at Q. For the present article, however, more elaboration on these singularities appears to be unwarranted. To generalize the previous results to an m -component system, we use the mathematical theorem stating that if the diagonal determinant D(r) = 0, then

Jan 1, 1970