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By C. O. Swanson

In the iron ranges of northern Michigan, magnetic data have been used as an aid in geologic field work since the time of the earliest surveys. The presence of complex structures containing magnetic formations, and the general scarcity of exposures, guided the early work into this line of attack, and later field studies tended to place more and more emphasis upon this geophysical relationship, until, at present, the collection of magnetic data is a matter of routine in any areal survey. At first, horizontal deflections of the compass needle were the only data collected. In subsequent surveys, greater dependence was placed on dip-needle readings, which record variations in the intensity and inclination of the earth's magnetic field. Recently the trend has been toward adjusting the instrument so as to reduce the influence of changes in inclination, and using a more sensitive modification, called the Superdip,' in weakly magnetic areas. To a minor extent, the magnetometer has also been employed. The object of this paper is to present the writer's experience with magnetic data in this region. The conclusions are based on work covering a period of 10 years, and spread over nearly all of the iron ranges and a large part of the intervening areas. The viewpoints expressed are purely geological ones. In other words, any opinion as to the usefulness of a certain relationship is based upon the writer's experience with it as a guide in interpreting the structures of this region, and not upon its soundness theoretically, nor its usefulness under other conditions. A very brief summary of the conclusions is as follows. The most important step is that of collecting the magnetic data. This requires a suitable adjustment of the dip needle, and sufficient readings to accurately portray the variations in the magnetic field, which are apt to be irregular. Once the readings are taken and plotted in some clear fashion, the interpretation of them is usually merely a matter of observing their relation-

Jan 1, 1934

By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.' Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.' For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

Jan 9, 1951

By A. H. Rhoades, D. T. King, R. J. Gray

Tests and methods of detecting oxidized coal are studied. Particular emphasis is placed on the microscopically discernible changes that accompany the chemical and physical changes affecting the technological properties of coal during oxidation. Coal samples were used from the low-volatile Pocahontas No. 3 Seam, McDowell County, W.V., and from the high-volatile Cedar Grove Seam, Mingo County, W.V. Tests conducted include: carbonization, free-swelling index, phase inversion, froth flotation, Gieseler plasticity, oxygen by difference and by neutron activation, volatile matter, pH of coal slurries, alkali solubility, and electrostatic charge.

Jan 1, 1977

By A. M. Gaudin

A great number of hypotheses has been advanced to explain the complex phenomena that are encountered in flotation. In the days of bulk-oil flotation, when a large quantity of oil was employed, it was observed that the oil-mineral aggregate floated above the ore-pulp because of its lesser density. With the advent of froth-flotation this phase of the theory had to be modified to take into account the presence of air bubbles. The reason why the mineral-bearing froth of today rises to the top of flotation cells is, of course, because the air-mineral aggregate, with whatever reagent may be associated with it, is lighter than the pulp. In an attempt to explain froth-flotation the fact has been emphasized that certain minerals are wetted and therefore remain in water; while others are not wetted and therefore become associated in preference with air. Such an "explanation" does not explain facts, it merely states them; for instance, it does not explain why minerals are wetted under some circumstances and not wetted under others. Going somewhat further, the wetting or nonwetting of minerals by water has been ascribed' to differences in the angles of contact between oil droplets and mineral surface at the surface of the minerals. This explanation, however, was abandoned when soluble flotation reagents came to replace the so-called "insoluble" reagents. Another theory, sponsored about 10 years ago by Ralston,² involves the effects of electric charges at the surface of the mineral particles and air bubbles. This theory, unfortunately, was not developed as fully as it seems desirable. The belief that adsorption phenomena might play a preponderant role in flotation3 has been rather widespread for the last 10 years. Unfor-

Jan 1, 1928

By R. A. Meussner, C. T. Fujii

Chromium solution in wustite depresses the oxygen activity in a nonideal manner and expands the lattice slightly. Gravimetric measurements of the equilibrium compositions of wustite containing 0.00 to 1.38 wt pct Cr define the oxygen potential (CO2-CO atm) and the limits of the phase field at 1000°C. These data extrapolate to a maximum solubility of 2 wt pct Cr. The lattice parameter data, room-temperature measurements of quenched samples, differ significantly from those in the literature. Both pure and chromium wus-tites contract at uniform and equal rates as the oxygen content (metal deficit) increases. The a. US metal deficit relationships are straight lines showing none of the curvature previously reported. At constant metal deficit, the a. expands by 0.002? on alloying with 0.4 to 0.5 wt pct Cr but is insensitive to further chromium additions: a small expansion rather than a marked contraction. These results require a modification of the accepted alloying mechanism. IN the high-temperature oxidation of Fe-Cr alloys in Ha-H,and CO2-CO atmospheres the vapor transfer of oxygen from the continuous wustite outer scale to the porous inner scale/alloy interface sustains the high oxidation rates.1"3 The driving force for this transport is the difference in the oxygen activity of the outer wustite and that at the inner scale/alloy interface. In pure CO2, as well as in CO2-CO atmospheres, carburization of the alloy accompanies this oxidation. Current efforts to evaluate the parameters controlling this carburization have shown that the process is not simple; i.e., the carbon concentration in the alloy initially increases rapidly, reaches a maximum, and then decreases slowly as the oxidation time is extended. This is the same pattern reported by McCoy for the more complex oxidation-carburization of stainless steels and an Fe-Cr alloy in CO2 at lower temperatures.4 These changes in the carburization process occur while the overall oxidation rate and the lattice parameters of the scale layers remain constant. If this invariance of the lattice parameter is assumed to indicate a constant scale composition and thus a constant oxygen potential, the carburization results are not easily explained. Electron microprobe traces across the thickness of these outer scales, however, have revealed distinct chromium gradients penetrating 10 to 50 µ from the inner surface where the chromium concentrations were estimated at a few tenths percent. The variation of the chromium cmcentration on the inner surface of the scale, and the resulting change of the oxygen activity, during the oxidation process is considered to be important in defining the carburization process. Thus, to gain an understanding of the complex oxidation-carburization proc- ess, it was necessary to measure the properties of wustite containing known amounts of chromium (chromium wustite). Although the general features of the Fe-Cr-0 equilibrium diagram between 900° and 1300°C have been fairly well established by Richards and white: Wood-house and White,6 Seybolt,7 and Katsura and Muan,8 there have been no detailed studies of the limits of the chromium wustite phase field or the properties of these alloyed wustites. The recent results of a limited study of chromium wustite by Levin and wagner9 indicate that more than 0.67 wt pct Cr is soluble in wustite above 850°C and that this alloying is accompanied by a substantial lattice contraction. This change in the lattice parameter was not evident in the X-ray diffraction patterns of wustite layers from the oxidation experiments;1,3 the lines were sharp even though a chromium gradient existed in the scale. The present paper describes gravimetric equilibrium experiments which delineate the boundaries of the chromium wustite single-phase field at 1000°C and define the changes in the oxygen activity and the lattice parameter of wustite as functions of chromium and oxygen contents. The lattice parameter data of chromium wustite obtained from these equilibrium and special quenching experiments differ considerably from those reported.9 Those for pure wustite show significant differences from the widely accepted data of Jette and Foote.10 Since the causes of these differences are not easily assignable, and since the literature contains many sets of data on wustite which if not in conflict are at best not in harmony, the experimental procedures are discussed in the present paper. EXPERIMENTAL Oxide Preparation. The specimens used in these studies were porous pellets compacted from high-purity (Fe,Cr)2O3 or Fe2O3 powders. These powders were prepared from electrolytic chromium (99.8 pct purity) and electrolytic iron purified by consumable-electrode, vacuum arc-melting processing (299.9 pct purity).11 The oxides were produced by standard analytical procedures: solution of the metals in acids (HC1, then HNO3 added), coprecipitation of the hydroxides (NHaOH), and filtering and washing these precipitates. Initial dehydration of the coprecipitated hydroxides was done in a porcelain evaporating dish heated by a Meker-type burner, final dehydration by firing in a recrystallized alumina crucible at 1000" to 1050°C for 20 hr in an electrically heated furnace. Spectrographic analysis detected the following impurities: silicon, 0.01 pct or less; aluminum, 0.001 pct to trace; manganese and copper, 0.0001 pct to none. Each of these levels is at least one order of magnitude lower than in commercially available CP grade ferric and chromic oxides. Fluorescence analy-

Jan 1, 1969

By Dwight E. Woodbridge

DuriNg April, Max, and June, 1910, I was in charge of an examination of the greater part of the Moa iron-ore area in Oriente Province, Cuba, on the north coast, near the east end of the island. My instructions, on arrival at the properties, were to check former estimates of tonnages and grades, and to re-examine the ore comprised in claims covering 44,727 acres. This work included the running of lines dividing the properties into co-ordinate planes, the boring of many thousand feet of holes spaced at the intersections of these co-ordinates, the taking of samples of the ore penetrated, the analysis of these samples for their various constituent minerals, and the determination of the results as to tonnages, depths, and grades, both for individual properties and for the entire group. Each section of every one of the thousand holes drilled was to be compensated for depth and grade with every other, a series of simple arithmetical calculations of no slight magnitude, the mere mechanical labor of which consumed much time, but finally resulted in giving a complete average of all the essential facts for the entire area of 18,000 hectares, Had it not been for the more than willing, active, and able co-operation of the officers of the Spanish-American Iron Co., from Charles F. Rand, President, and Jennings S. Cox, General .Manager, down to the most humble water-carrier, the work would have consumed far more time than it did. The lands thus systematically explored by me were comprised in the following denouncements: Punta Gorda, Yaminiguey, Baracoa secunda, Sagua, Moa, Yajrumaje, Lirio, and Cabanas, all of which were massed as the Moa group, so called, and cover an area of 13,832 hectares, or 34,179 acres. Some 10,000 acres additional to this was included in neighboring properties, lying between Moa and the east end of the island, the Buena Vista,

Jan 1, 1912

By Franklyn Oatman

IN order that the conditions which obtain in an oil well may be readily understood, a brief description of a typical California well and. a number of the phenomena accompanying same will be given. That the necessity for the exclusion of water be realized, the effects of water intrusion, a description of methods of prevention, and a discussion of causes of failure will be presented, followed by a summary and recommendations. Fig. 1 shows a section of a typical well which illustrates the relation of oil sands to overlying strata. It indicates a deep water sand separated from the oil sand by shale, and the proper place for the final shutting off of water. In this well a comparatively thick stratum of compact shale protected the oil from overlying water so that the operation of landing the water string was a simple matter. In some wells the protecting stratum may be only from 3 to 5 ft. thick and very careful operation is necessary in order to land the water string of casing properly and not puncture through to the oil sand. The cases just cited are common, but occasionally, after excluding overlying water, productive oil sands are drilled through in the expectation of finding more productive underlying sand, and a water-bearing stratum is tapped. In this case the problem is the reverse of the normal; water must be prevented from ascending rather than descending. A discussion of well-drilling methods is not within the scope of this paper, except such operations as pertain to shutting off of water. A brief outline of the several conditions which may accompany drilling follows. Some or all may be present in any particular case. The direct relation of these to prevention of intrusion will he discussed in detail further on. In drilling, the hole. becomes more or less irregular in shape, and rough, and as the casing follows the bit into the well it does not fit snugly against the walls. As a result, water may descend between the casing and walls of the well. If a circulation pump is not used during drilling, the hole is simply punched through and the pulverized material removed from the well by means of a bailer. If circulation is maintained there is a continual flow of water down inside the casing and up around the outside between the pipe and the walls of hole. This keeps an open. space around the pipe.

Jan 3, 1914

By Robert M. Jimeson, James M. Grout

The competitive market potential for solvent-refined coal is estimated and the market advantages are enumerated. Markets are possible in combustion, railroad locomotion, and carbon electrodes. The combustion characteristics are consistent with expected air pollution restrictions on the emission of sulfur and particulate matter. A market potential of sufficient size exists to support the initiation of solvent refining in the United States. The market analysis should help fuel producers determine the advisability of their undertaking solvent refining of coal.

Jan 1, 1972

By M. Cohen, R. T. Howard

It has long been realized among metallurgists that a fast, reliable method for the quantitative determination of the percentage of microconstituents in an alloy would be of great benefit in studies of equilibrium and transformation in the solid state. For example, Polushkinl has shown that the compositions of two coexisting phases in a binary system at a given temperature may be calculated very simply with the aid of two alloys lying in the two-phase field if the relative amounts of the two phases in each alloy can be determined. Recently, Grange and Stewart2 have traced the course of the austenite-martensite reaction in a series of commercial steels by making visual estimates of the percentage of martensite formed as a function of cooling temperature. The correlation of mechanical properties with structure, a subject of wide-spread current interest, is likewise dependent upon quantitative microanaly-sis. Yet, there are very few investigations described in the metallurgical literature, wherein methods of quantitative microscopy are employed. Usually, the relative amounts of the microconstituents are estimated in a qualitative or semiquantita-tive way. The authors were faced with this problem some time ago in studying the kinetics of austenite decomposition. Several aspects of this research could not be treated satisfactorily by other quantitative tools, such as specific volume,' magnetic,6 dila-tometric, electrical resistance7 or x-ray measurements.a It became necessary to find an impersonal quantitative method that could be applied to microstructures. Fortunately, it was noted that geologists and petrographers had coped with quantitative microscopy to a considerable degree in their attempts to evaluate the mineral contents of rocks. A number of excellent articles were found on this subject, and since they appear to be unknown generally to many metallurgists, the first part of the present paper is concerned with a review of the literature in some detail. With this survey as a background, the authors have adapted the so-called methods of point-counting and lineal analysis to metallography, as described in the second part of the paper. Austenite-martensite structures were selected for illustration not only because they are important in many ways, but because such fine intermixtures are notoriously difficult to estimate visually. Literature Survey Perhaps the earliest work on quantitative microscopic analysis goes back to Delesse9 (1848) who proved mathemati-

Jan 1, 1948

By M. Cohen, R. T. Howard

It has long been realized among metallurgists that a fast, reliable method for the quantitative determination of the percentage of microconstituents in an alloy would be of great benefit in studies of equilibrium and transformation in the solid state. For example, Polushkinl has shown that the compositions of two coexisting phases in a binary system at a given temperature may be calculated very simply with the aid of two alloys lying in the two-phase field if the relative amounts of the two phases in each alloy can be determined. Recently, Grange and Stewart2 have traced the course of the austenite-martensite reaction in a series of commercial steels by making visual estimates of the percentage of martensite formed as a function of cooling temperature. The correlation of mechanical properties with structure, a subject of wide-spread current interest, is likewise dependent upon quantitative microanaly-sis. Yet, there are very few investigations described in the metallurgical literature, wherein methods of quantitative microscopy are employed. Usually, the relative amounts of the microconstituents are estimated in a qualitative or semiquantita-tive way. The authors were faced with this problem some time ago in studying the kinetics of austenite decomposition. Several aspects of this research could not be treated satisfactorily by other quantitative tools, such as specific volume,' magnetic,6 dila-tometric, electrical resistance7 or x-ray measurements.a It became necessary to find an impersonal quantitative method that could be applied to microstructures. Fortunately, it was noted that geologists and petrographers had coped with quantitative microscopy to a considerable degree in their attempts to evaluate the mineral contents of rocks. A number of excellent articles were found on this subject, and since they appear to be unknown generally to many metallurgists, the first part of the present paper is concerned with a review of the literature in some detail. With this survey as a background, the authors have adapted the so-called methods of point-counting and lineal analysis to metallography, as described in the second part of the paper. Austenite-martensite structures were selected for illustration not only because they are important in many ways, but because such fine intermixtures are notoriously difficult to estimate visually. Literature Survey Perhaps the earliest work on quantitative microscopic analysis goes back to Delesse9 (1848) who proved mathemati-

Jan 1, 1948

By Paul Giesecke

SINCE most modem metallurgical plants are operated continuously and on a large scale, successful operation at maximum efficiency demands that an accurate knowledge of the performance at each stage of the process be available at all times. Quantitative analyses provide the most practical process guides, and it is essential to have analytical procedures that combine accuracy and speed. In continuous plant operations, large losses may occur if the time interval between the development of trouble at any stage and its recognition and correction is great. Many metallurgical plants are using rapid colorimetric and spectrochemical methods of analyses for control purposes. So-called "color coppers" may be cited as an example of the colorimetric methods, in contrast with the routine use of the ultraviolet spectrograph for the analysis of steels.42 By means of this more refined spectrochemical procedure, a complete quantitative analysis of the molten metal is obtained every few minutes. During the past two years the Physics Division and the Ore Dressing Laboratory of the American Cyanamid Company's Stamford Research Laboratories have collaborated in a study of the use of spectrochemical methods for the analysis of various metallurgical products. New methods have been developed, which have proved of practical value in plant operation. The following pages give a general review of the principles of spectrochemical methods and also the details of several specific analyses. PRINCIPLES OF SPECTROCHEMICAL ANALYSIS In general, it can be said that a visible light spectrochemical analysis can be performed for any ion or molecule that is naturally colored, or that can be made to react with another to produce a colored salt or complex. Whereas transmission measurements in the ultraviolet and infrared portions of the spectrum are most useful for the analysis of organic molecules, visible light measurements are of particular value for metal salts. Such elements as copper, manganese, cobalt, nickel, iron, molybdenum, vanadium, chromium, phosphorus, mercury, zinc, lead, and a great many others, can now be determined with a high degree of sensitivity, accuracy and dispatch. From the simplest of qualitative determinations, color analyses have been improved to such an extent that, at the present time, through the use of recording spectrophotometers, hundreds of accurate quantitative analyses can be performed by a single analyst during an 8-hr. day after the standardization curves have been established for the ions to be determined.

Jan 1, 1944

By William G. Pariseau

The flexure of geologic strata, a phenomenon of interest to geologists and mining engineers alike, is examined as a sheet bending problem in Coulomb plasticity. Fonnulae for the distribution of stress, strain, and displacement increments; volume change; change in the length of the central surface; and power of dissipation, as well as for the neutral surface shift are given. Strains of any magnitude are considered. The analysis shows that deeply buried strata may bend and develop "tensile" cracks under generally compressive states of stress. It is also shown that bed separation and high capacity props are desirable in mechanized longwall mining, a result in keeping with operating experience. Although speculative at this time, the analysis provides a rational working hypothesis as regards the problem of strata flexure and control. | he purpose of this paper is to present an analysis of the flexure of geologic strata as a problem in the bending of a sheet of material failing in accordance with a Mohr-Coulomb criterion. The flexure of strata has an obvious academic interest to the geologist concerned with the mechanics of folding. It is of interest to the economic geologist as it relates to the structural control of certain types of ore deposits. It has an intimate association with mine subsidence phenomena, and is of concern to the mining engineer. Strata flexure is also the dominant feature of roof behavior about longwall workings. An improved understanding of strata flexure through a rational mechanical analysis thus appears desirable not only from the academic view but from the economic one as well. In the field, the most commonly observed feature of folding, subsidence, and longwall roof behavior is the permanent and therefore inelastic nature of the strata movement. Fig. 1 illustrates the physical disposition of strata in the vicinity of a longwall face. Inasmuch as most rocks (with the possible exception of certain evaporites) do not exhibit significant viscoelastic behavior, at least not over time spans of engineering interest, a plastic analysis is indicated. The analysis is meant to apply to strata whose deformation is dominantly that of bending such as might be expected in the remote roof about a longwall face.

Jan 1, 1970

By J. Szekely, J. W. Evans

A formulation is given for radiant heat loss from the surface of molten steel held in a ladle and numerical solutions are presented for the resultant integrodif-ferential equations. The results are shown on plots of the net rate of heat loss against time, with the geometlry, emissivities, thermal properties of the walls, and Preheat as parameters. It was found that the rate of the vadiant heat loss from the exposed metal surface was comparable to the conductive losses from the Portion of the metal in direct contact with the walls. The radiant heat loss was markedly affected by the geometry and by the thermal properties of the walls the net radiant heat loss from the steel could be drastically reduced by providing a top cover and also by the provision of preheat. The results of this work are thought to be relevant to heat loss calculatious concerned with vacuum degassing and with operatzons in which molten metals are held in ladles. WhEN molten steel is held or transferred in ladles heat losses inevitably occur. The accurate assessment of these heat losses is of importance in process design considerations, as the temperature of the metal may have to meet rigid specifications in certain stages of the processing sequence. As shown in Fig. 1, the principal mechanisms responsible for heat loss are: i) Conduction into the walls and ii) Thermal radation from the top metal surface (possibly augmented by natural convection) The conductive heat loss may be readily calculated as much information is available in the literature on both the general theory1'' and on its particular applications to ladle heat loss calculations. Evaluation of the radiant component of the heat loss is less straight-forward. In two recent papers it has been shown that the presence of a slag layer 2 to 3 in. thick would prevent any significant heat loss for periods up to an hour,5'" however, should bare metal be exposed, constituting the radiant surface, substantial heat losses could occur. This latter case is of considerable practical interest in various degassing operations and in the vacuum processing of certain specialty steels, where the top surface of the metal is not covered by a protective slag layer. Under these conditions a substantial radiant flux is emitted by the top metal surface; part of this flux leaves the system, part of it falls in the ladle walls. The radiant flux incident on the ladle walls is in part absorbed and conducted away, and in part reflected and re radiated. The purpose of the paper is to present a general formulation of the problem, the resultant solution of which should enable computation of the net radiant heat loss from the metal surface. The principal variables, the effect of which will be investigated, include initial metal temperature, geometry, thermal and radiative properties of the wall, and various modes of preheat. FORMULATION Consider a cylindrical enclosure, shown in Fig. 2, with a diameter D, height H, and wall thickness W, the cover at the top of the cylinder having a wall thickness L. If the temperature of the base (representing the top surface of the metal) is kept constant, say, Tb, the problem is to calculate the net rate of heat loss from the base as a function of time, geometry, the initial temperature distribution, and the thermal properties of the system. As customary, the formulation will consist of the mathematical statement of the conservation of thermal energy within the system.

Jan 1, 1970

By H. H. Hausner, H. S. Kalish

IN recent years zirconium and beryllium have become of great interest because of their special properties. Zirconium is known for its remarkable ability to absorb the gases oxygen, nitrogen and hydrogen, has extensive use as a getter in electron tubes and has indeed become the primary metal in the manufacture of photoflash bulbs. Beryllium is of interest because it is light metal and as such could supplement aluminum and magnesium in light metal applications. The late development of zirconium ductile at room temperature produced by both the iodide and calcium reduction methods has stimulated frequent articles on this metal in the recent literature. Beryllium is so closely akin to zirconium crystall-ographically that some investigators are of the opinion that beryllium should be ductile at room temperature if it were pure enough. The crystallographic relationship of beryllium and zirconium, the interest created in Be-Zr alloys where the zirconium is believed to function as a remover of solid solution gas in beryllium and thus increase the ductility of the beryllium rich alloy, and the amenability of these metals to powder metallurgy methods stimulated this approach to an investigation of the system Be-Zr. Preliminary work showed that a zirconium compact melted when pressed in contact with a beryllium compact and sintered at 1250°C, without any apparent final bond between the two. A search of the literature revealed nothing pertinent about the Zr-Be system or about any zirconium - beryllium alloys. In 1936 Misch³ vaguely identified the compound ZrBe2 and reported that it has a deformed cubic structure. Two patents," , were issued to Mach-lett Laboratories in 1943 and in 1946 regarding the addition of small amounts of zirconium to beryllium in order to improve the ductility of beryllium so that it may better be used for X ray windows. In considering the alloy formation of beryllium with other metals Raynor thought it unlikely that zirconium would have any solid solubility in beryllium. From this indefinite information nothing could be ascertained about the possible use of Zr-Be alloys or the use of these metals intimately. A brief preliminary study of the system Zr-Be by powder metallurgy methods was undertaken to provide regions for more intense studies of Zr-Be alloys and as a guide to a formal phase diagram determination. The investigation described in the following pages was completed in less than three weeks. The usefulness of this rapid method to facilitate phase diagram studies and new alloy investigations will be shown. Materials and Procedure Zirconium powder was produced from crystal bar stock of high purity supplied by Foote Mineral Co. The crystal bar was converted to hydride at 730°C, crushed, and the hydride decomposed in purified argon at 850°C. 60 pct of the powder passed through a 325 mesh screen, 40 pct of the powder was —140 mesh, +325 mesh and the average particle size of the total was 8 to 12 microns. The beryllium powder was used as re-

Jan 1, 1951

By Frank Tolonen

IRON-ORE beneficiation is becoming of vital importance to the Lake Superior region, since only a few decades will be needed to exhaust the direct shipping ores even if generous allowances are made for discoveries of new orebodies. If the region is to continue as the chief source of ore to the steel industry of the United States, it must concentrate or otherwise beneficiate the enormous tonnages of available iron formations. A beginning along this line has already been made. About one-fifth of the total shipment, even now, is the product of some sort of concentrating process, while another fifth is improved in physical structure by crushing, screening, drying, sintering, or some other similar method. The amount of material amenable to these processes is limited, however; and, in order to be able to utilize the billions of tons of iron formations that cannot be so beneficiated, an intensive study of their nature and concentration possi-bilities is necessary. As long as high-grade ores are available in ample quantities, ore dressing is economically impossible, but as soon as the supply nears exhaustion it becomes necessary. At first the products of ore dressing must meet as nearly as possible the same specifications as the rich ores in order to be adapted to the reduction processes already established. The future requirements as to quality will depend on the one hand upon the ability of the ore dresser to eliminate undesired constituents and charac-teristics in the material, and on the other upon the adaptation of the reduction processes to the product that can be economically supplied. A better understanding of the blast furnace and other reduction reactions, and improvements in the preparation of raw materials, should enable the Michigan districts to continue to supply ore for a long time to come. The study and testing of the iron formations necessary to bring a utilization of the low-grade ores, though requiring time and effort on the part of all concerned, should not be postponed, especially since the economic situation forces the use of the highest grade ore in preference to the leaner material.

Jan 1, 1933

By Charles A. Ashburner

At the Philadelphia meeting of the Institute, held in February, 1881,I had the honor of reading a paper on "A New Method of Mapping the Anthracite Coal Fields of Pennsylvania."* At that time the State appropriation for the Second Geological Survey had just expired, and, as a new appropriation was not assured, no detailed plan had been adopted by Professor Lesley, State Geologist, for the practical examination of the mines, and the solution of the geological structure of special localities, or the representation in sections, vertical and columnar, of the general structure of the coal basins and coal beds. I had merely proposed a plan of mapping, as the material for the construction of maps was most available, and it was at that time uncertain what money the Survey would have to enable it to extend the surface and underground explorations, in order to make the examinations complete. After a continuation of the Survey was authorized until January, 1884, by the legislature, in May, 1881, the Anthracite Survey was regularly organized, and a plan adopted for a systematic and exhaustive geological and mine examination of the region. This plan provided for such work, other than that of mapping, as was necessary for a complete and practical geological and mining survey of a coal field. To do any geological work, of however general a character, it was absolutely. necessary that the members of the Survey Corps should obtain unrestricted access to all the mining records of the operators, which have been made with great care and accuracy and at an enormous expense during the past thirty years and more. The unanimous and generous support of the individual and corporate coal operators, of the plan of carrying on the Survey, was promptly assured, on condition that the results should be of such a character as to render them of practical utility to the property-owners and those directly interested. It was hoped

Jan 1, 1883

By Adrien Berton

FOR nearly a century, the Corocoro deposit has been renowned among geologists from the fact that it shares with the Lake Superior deposits of the United States the distinction of being the only important copper districts where native copper is worked commercially. The Corocoro district, named after the city of Corocoro, the capital of the Province of Pacajes (Department of La Paz, Bolivia) is situated towards the western edge of the Bolivian high plateau, at an altitude of a little over 13,000 ft. The most interesting part of the district is that immediately surrounding the city of Corocoro, at a distance, by railway, of 65 miles from La Paz and 210 miles to the Chilean port of Arica on the Pacific Coast. The climate of the region is that of the semi-desert, dry and relatively cold, with big differences of temperature between day and night. The rainy season begins in December and ends in March. The cupriferous lodes of Corocoro have not attracted as much interest as the silver mines of Potosi but they have been known for a long time. In the precolonial period the Indians were using the charquis, or natural native copper sheets, to make small brass objects, and the beautiful pale green brochantite of the outcrops as a source of green pigments. During the colonial period, the oxidized ores of the outcrops were worked for copper, which was used by the mint at Potosi for making currency. The native copper ores were neglected because the Spanish miners were at a loss how to concentrate and smelt them. About 1830, work by rudimentary processes, which were improved little by little, was begun on the native copper ores. The total production of native copper in the following hundred years amounted to 100,000 tons. This native copper, which was remarkably pure, was much appreciated on the European markets before the introduction of electrolytic copper. It was useful for making special ornamental brass or bronze and the granular concentrates of native copper, called barrilla, containing 80 to 85 per cent copper were suitable for making copper sulfate by direct oxidation and subsequent leaching with sulfuric acid.

Jan 1, 1936

By E. P. Abrahamson II

The effect of transition element binary solid-solution additions upon the recrystallization temperature of vanadium has been investigated. Cr, Fe, Co, Ni, Mo, Ru, Rh, Os, and IY lower the recrystallization temperature, while Ti, Mn, Zr, Cb, Pd, Hf, Ta, W, Re, and Pt raise it. The majority of elements have their greatest effect in less than 0.15 at. pet. Both the rate of change of recrystallization temperature with atomic percent solute and the limit of initial linearity are found to Correlate with the free atom grozdnd state outer electron configuration of the sollte element. THE work of Abrahamson and Grant1 and Abraham-son and Blakeney2 has shown that the solute's elec- tron configuration appears to be a prime determinant of both brittle-to-ductile transition and recrystallization temperature in dilute binary alloys. It has also been shown by Abrahamson3 that the limit of linearity, i.e., the limit of initial linear change of recrystallization temperature with atomic percent solute, is also a function of the electron configuration of the solute in iron base alloys. Because of the systematic nature of the solute electron configuration correlation, it is to be expected that some systematic variation might be observed upon changing the solvent. Thus, this study of recrystallization in vanadium base alloys is the first of a series aimed at defining the role played by the electron configuration of solute in determining the recrystallization characteristics of dilute transitional alloys. PROCEDURE All alloys were made using 99.8 pct V containing 0.011 C, 0.024 N, 0.08 0, 0.006 H, 0.035 Ta, and

Jan 1, 1962