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By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..' and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young's modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen's5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967

By Samuel Taylor

IF I LIVE another fourteen months and am still con-nected with the coal industry, I shall then have com-pleted a half century with it. Since May, 1874, when .I first entered the bituminous workings as a miner, I think I have held almost every position connected with a mine except possibly that of mule driver, for which I was unfitted by reason of my religious upbringing. We are all agreed, at least I have not heard it contra-dicted, that there is serious over-production in the bituminous industry. This has come about in various ways and is easily explained. During the Fuel Admin-istration, I recall making an estimate of the possible output of the bituminous mines of the country provided they were given a full force of men and a full-car supply; my estimate was a little over a billion tons a year. A few months ago, the late Francis H. Peabody, of Chicago, made a practically identical estimate. If, however, both of these conditions should happen con-currently, there would very soon be no market for the coal, and many of the mines would close down. Even today, if 10 per cent. more cars were furnished, to the bituminous mines, market prices would drop very seriously.

Jan 4, 1923

By Martial P. Corriveau

Almost everyone agrees that coal and oil shale are the only fossil fuel resources in which the United States is self-sufficient. Of the two, only coal has a technology sufficiently developed to be of intermediate term benefit. Since it takes at least 20 years to bring advanced technology into practice, it seems logical that the major focus on energy developments should be aimed at coal. Meanwhile, we need to trade-off between actions to meet our immediate needs and the various political regulations and social demands that are disrupting the coal industry and the industries dependent upon it. The largest single user of coal is the electric power generation industry. Over 300 million tons of coal are presently being consumed each year. In view of the 5-to 7-years lead time to bring in a base-load fossil-fuel fired generating station, our requirements for double this tonnage in 1980 are already well forecast; that is, if the coal companies are allowed to mine and the utilities are allowed to burn the coal.

Jan 2, 1974

By Harry H. Power

WORK of the Committee on Education of the Petroleum Division has been under way for approximately-one year. Although some progress has been made, further activities of the Committee are necessary in order to discuss mutual problems more thoroughly by a unified group interested primarily in this field of specialization.

Jan 1, 1944

By Donald D. Smythe

Tars paper describes briefly the topography and geology of the region where the mica-bearing pegmatites are found and discusses prospecting, the quality of the mica, its preparation, and evaluation of the deposits. Muscovite mica occurs in a number of widely separated localities in Brazil, but production has come largely from deposits in the southeastern and eastern part of the State of Minas Gerais (Fig. I). There the deposits form a discontinuous zone, which starts at a point 90 km. north of the city of Rio de Janeiro and extends north for some 500 km., roughly parallel to the coast. A maximum width of 180 km. is reached along the Rio Doce. To the west in Minas Gerais, and extending east into the states of Espirito Santo and Rio de Janeiro, the mica zone proper is fringed by areas in which there are scattered occurrences of mica-bearing pegmatites. A few of these outlying deposits have produced commercial mica, but most of them are unimportant. To the southwest, in the State of São Paulo, there are a number of mines, which at one time produced a very considerable amount of sheet mica, largely as a by-product of kaolin mining. These deposits, and, a few others lying between them and the main productive areas to the northeast, appear to be the southwestern continuation of the strong Minas Gerais mica zone. In the vicinity of Conquista, just north of the Minas Gerais boundary in the State of Bahia, and still farther north, near Jacobina, there are several known mica deposits. Their location indicates that they may be the northern continuation of the main mica zone. The major part of Brazilian mica production has come from four areas within the mica zone proper; from north to south, Governador Valadares, Raul Soares, Espera Feliz, and Muriaé. The first is 190 km. from north to south and reaches a maximum width of 180 km. The Raul Soares area extends 135 km. from northeast to southwest, and in places is 80 km. wide. The Espera Feliz area is 100 km. from north to south, and reaches a width of 35 km. The Muriaé area extends 150 km. from northeast to southwest and its width reaches 40 kilometers. Between the known productive areas, and in the areas directly to the southwest and to the north of them, little mica has been produced. These gaps, as well as certain irregularities in the outline of the mica zone itself, are to be ascribed either to lack of prospecting or to conditions preventing the discovery of mica, rather than to its nonexistence. Elsewhere in Brazil mica has been reported from eastern Goiaz, Ceará, Pernambuco, Rio Grande do Sul, Matto

Jan 1, 1946

By H. J. Donnell, B. C. Parks, O&apos

In 1930 the late Dr. Reinhardt Thiessen set up a method of microscopic analysis and type classification of coal that has since been followed as standard practice in the coal-petrography laboratory of the Bureau of Mines. Thiessen's terminology which designated the constituent parts of coal in terms of botanical origin was introduced in 1920.1 The technique, however, of preparing a completely representative series of thin sections from a column sample of coal for use in making quantitative determinations of coal components with a microscope was developed about 10 years later by Thiessen and coworkers G. C. Sprunk and H. J. O'Donnell.2 Complete thin-section analyses subsequently have been made of 126 column samples of various ranks and types of American coals. The data and information were assembled from these thin-section studies and published in a large number of reports dealing chiefly with investigations of the coking and hydrogena-tion properties of certain American coals. In the years following adoption of Thies-sen's method, a considerable amount of work was done in collecting column samples of many coals, making routine thin-section analyses of these, interpreting the results, and finding practical application for the information in other fields of coal research. The many reports and papers covering the work in coal petrography, however, offer very little discussion that can be considered as critical appraisal of the technique. Criticism outside the Bureau most often has voiced questioning opinions concerning the accuracy of the method used of measuring coal components microscopically and classifying the coal into arbitrary types on the basis of the quantitative determinations. The principal purpose of this paper is to discuss in some detail and present data showing the results of certain investigative work done in the petrography laboratory on the accuracy of the Bureau's method of microscopic measurement of components in coal thin sections. Data from microscopic analyses on file made by G. C. Sprunk and H. J. O'Donnell were freely used in the investigation, and a table of columnar analyses from an unpublished manuscript by Sprunk is included in this paper for reference. In the course of the experimental work a method was developed for measuring in-strumentally with a planimeter the components shown in micrographs of selected thin sections. Measuring coal components with a planimeter furnished useful information for studying the accuracy of microscopically measuring the same components in thin sections. Petrographic Components and Type Classification of Coal Thiessen considered coal to be composed of two visibly different major components present in various types of coal in greatly varying proportions. He named

Jan 1, 1949

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

By H. J. O’Donnell, B. C. Parks

IN 1930 the late Dr. Reinhardt Thiessen set up a method of microscopic analysis and type classification of coal that has since been followed as standard practice in the coal-petrography laboratory of the Bureau of Mines. Thiessen's terminology which designated the constituent parts of coal in terms of botanical origin was introduced in 1920.l The technique, however, of preparing a completely representative series of thin sections from a column sample of coal for use in making quantitative determinations of coal components with a microscope was developed about 10 years later by Thiessen and coworkers G. C. Sprunk and H. J. O'Donnell.2 Complete thin-section analyses subsequently have been made of 126 column samples of various ranks and types of American coals. The data and information were assembled from these thin-section studies and published in a large number of reports dealing chiefly with investigations of the coking and hydrogenation properties of certain American coals. In the years following adoption of Thiessen's method, a considerable amount of work was done in collecting column samples of many coals, making routine thin-section analyses of these, interpreting the results, and finding practical application for the information in other fields of coal research. The many reports and papers covering the work in coal petrography, however, offer very little discussion that can be considered as critical appraisal of the technique. Criticism outside the Bureau most often has voiced questioning opinions concerning the accuracy of the method used of measuring coal components microscopically and classifying the coal into arbitrary types on the basis of the quantitative determinations. The principal purpose of this paper is to discuss in some detail and present data showing the results of certain investigative work done in the petrography laboratory on the accuracy of the Bureau's method of microscopic measurement of components in coal thin sections. Data from microscopic analyses on file made by G. C. Sprunk and H. J. O'Donnell were freely used in the investigation, and a table of columnar analyses from an unpublished manuscript by Sprunk is included in this paper for reference. In the course of the experimental work a method was developed for measuring instrumentally with a planimeter the components shown in micrographs of selected thin sections. Measuring coal components with a planimeter furnished useful information for studying the accuracy of microscopically measuring the same components in thin sections. PETROGRAPHIC COMPONENTS AND TYPE CLASSIFICATION OF COAL Thiessen considered coal to be composed of two visibly different major components present in various types of coal in greatly varying proportions. He named

Jan 1, 1948

By AIME AIME

UNDER the auspices of the Institute's Committee on Industrial Preparedness, a symposium was arranged for the Annual Meeting on the subject "Ores, Metals, and the War," with many well-known Government men and industrialists participating. Wilfred Sykes, president of the Inland Steel Co., of Chicago, presided, with C. K. Leith and Clyde Williams as vice-chairmen, Mr. Williams presiding over the latter part of the meeting. On the Auditorium stage in the Engineering Societies Building was a formidable corps of "experts," with an audience of several hundred to hear what they had to say and to ask questions.

Jan 1, 1942

By Walter Miller

BY the beginning of 1945 the output of petroleum products for war had reached a volume and a rate of growth which practically assured all requirements so long as war continued. The programs for making gasoline, lubricating oils of required quality, toluene for T.N.T., and chemicals for manufacture of synthetic rubber, as well as numerous other lesser petroleum products, were all well in hand, and unless catastrophic developments occurred there was no doubt of the ability of the industry to meet all demands. The end of the fighting found the refining industry working at top capacity on war commodities, but also in position to convert quickly into peacetime civilian production. 100-octane Aviation Gasoline Production of the vital 100-octane aviation gasoline, starting with approximately 44,000- bbl. daily capacity at our entry into the war, reached a top of 525,000 bbl. a day in the United States by the end of hostilities. With 75,- bbl. from other Allied sources, the grand total was 600,000 bbl., or 25,000,000 gal. each 24 hr. available to the armed forces had fighting continued. At times it was a close race between requirements and production, but never were any important military operations involving the use of high-octane aviation gasoline held up or delayed for lack of sufficient output of such material. The undivided effort of the entire refining industry in full cooperation with the Government made this record possible. Little diminution in output followed the German surrender on May 7. Plans called for a correspondingly greater activity for the Japanese war and possibly for well into 1946. But when the Japanese sued for peace on Aug. 10 most contracts were quickly canceled. Substantial stocks, reputed to be somewhere between 20,000,000 to 30,000,000 bbl., built up largely between V-E and V-J day pending organization of the larger Japanese war program envisaged after Germany gave up, were in the Government's hands in this country, in addition to working stocks in the war areas. Toluene and Lubricating Oil Requirements for toluene for T.N.T. increased rapidly as bombing speeded UP with increasing control of the air by the Allies in Europe and Asia. Production in excess of T.N.T. requirements which had been going into 1000-Octane aviation fuel blending during 1943 and 1944 was again drawn into explosive manufacture early in 1945. In anticipation of the war continuing into 1946, two new plants were ordered constructed, the decision being announced in April, plans calling for one of them to get into production about the end of 1945, the other in the first quarter of 1946. Both of these projects were later canceled as victory made it evident that the additional supplies would not be needed. Production was

Jan 1, 1946

By Walter Miller

BY the beginning of 1945 the output of petroleum products for war had reached a volume and a rate of growth which practically assured all requirements so long as war continued. The programs for making gasoline, lubricating oils of required quality, toluene for T.N.T., and chemicals for manufacture of synthetic rubber, as well as numerous other lesser petroleum products, were all well in hand, and unless catastrophic developments occurred there was no doubt of the ability of the industry to meet all demands. The end of the fighting found the refining industry working at top capacity on war commodities, but also in position to convert quickly into peacetime civilian production. 100-octane Aviation Gasoline Production of the vital 100-octane aviation gasoline, starting with approximately 44,000- bbl. daily capacity at our entry into the war, reached a top of 525,000 bbl. a day in the United States by the end of hostilities. With 75,- bbl. from other Allied sources, the grand total was 600,000 bbl., or 25,000,000 gal. each 24 hr. available to the armed forces had fighting continued. At times it was a close race between requirements and production, but never were any important military operations involving the use of high-octane aviation gasoline held up or delayed for lack of sufficient output of such material. The undivided effort of the entire refining industry in full cooperation with the Government made this record possible. Little diminution in output followed the German surrender on May 7. Plans called for a correspondingly greater activity for the Japanese war and possibly for well into 1946. But when the Japanese sued for peace on Aug. 10 most contracts were quickly canceled. Substantial stocks, reputed to be somewhere between 20,000,000 to 30,000,000 bbl., built up largely between V-E and V-J day pending organization of the larger Japanese war program envisaged after Germany gave up, were in the Government's hands in this country, in addition to working stocks in the war areas. Toluene and Lubricating Oil Requirements for toluene for T.N.T. increased rapidly as bombing speeded UP with increasing control of the air by the Allies in Europe and Asia. Production in excess of T.N.T. requirements which had been going into 1000-Octane aviation fuel blending during 1943 and 1944 was again drawn into explosive manufacture early in 1945. In anticipation of the war continuing into 1946, two new plants were ordered constructed, the decision being announced in April, plans calling for one of them to get into production about the end of 1945, the other in the first quarter of 1946. Both of these projects were later canceled as victory made it evident that the additional supplies would not be needed. Production was

Jan 1, 1946

By Tommy Wilson

OIL well drilling fluids have become a vital part of the drilling industry during the past 25 years. From chance usage of drilling mud at the fabulous Splindletop field in 1901, drilling fluid control has become an extremely technical and exacting science. Drilling for oil today involves exploration at depths ranging to 21,000 ft, nearly 4 miles. Geological formations encountered at these depths offer a tremendous challenge to the production, research, and service facilities of any drilling mud company.

Jan 5, 1954

By R. H. Pemberton

The principle of airborne electromagnetic prospecting is well-known. The basic geophysical texts in most cases discuss the main elements involved in electromagnetic prospecting. However, there is certainly little information available to the public concerning the present types of airborne electromagnetic systems being flown today by both contracting companies and some of the mining companies which have their own instruments. This is unfortunate since it is difficult for those people not conducting such operations to understand thoroughly the large variation in the electromagnetic instruments available.

Jan 1, 1961

By C. H. Mathewson

MY first reflection on the subject assigned to me by the officers of this symposium was that a critical description of these lesser characters in the cast of inanimate actors now before us under the title "The Role of Metals in New Transportation" would be about as well received as the description of a horse race in terms of harness buckles and jock-ey's buttons. The word "new" in the title of this symposium seems to shout strong aluminum and stainless steel, unless we transfer our attention to transpor-tation on another planet where the strength-density ratios may require very different engineering treatment. To load a speaker with the "heavier nonferrous metals" amidst the airy consideration of flying or 20th century gliding along the earth and through water, like Hermes, the messenger of the immortals, and expect an instructive or enlivening flight into the area of current exploitation and popular interest in transportation would, of course, require the performance of a miracle or at least the exhibition of genius to which I can lay no claim. But copper and nickel, headliners in other classifications, are also indis-pensable as components of the important new structural materials of transportation, and together with lead, tin and zinc perform many minor or contributory functions in this field that may indeed be con-sidered well-nigh indispensable. A complete and well planned fabric of classification, explanation and critique of even these secondary functions would take much time, and I cannot hope in the 25 minutes or so alloted for the purpose to offer more than a rambling treatment, in which a thread of continuity will be sought by anchorage to one after another of the following attributes or appurtenances of the moving vehicle: 1. The machinery and accessories. 2. The framework and superstructure, and the line or travelway. 3. Light, heat, power, water, sanitary and housekeeping services. 4. Embellishment, or style.

Jan 1, 1936

By W. C. Hagel, J. H. Westbrook

Usittg a sectioning technique with Agl10 as the tracer, the diffusion of silver in silver-excess (45.8 at. pct Mg), near-stoichiometric (49.8 at. pct Mg), and magnesium-excess (52.0 at. pct Mg) cylinders of CsCl-type AgMg was determined from 500" to 700°C. Diffusion coefficients conform to the expression D = Do exp (-q/RT) where the respective Do values are 1.53, 0.280, and 0.134 sq cm sec-I and the Q values are 41.3, 40.6, and 38.0 kcal g-atom-'. Lnttice-parameter and density measurements were performed on a more numerous assortment and wider range of compositions. Substitutional defects were found on both sides of stoichiometry. Activation energies for other rate processes in these alloys show related trends with changing composition, although silver may not be the rate-detemining species. KNOWLEDGE of diffusion coefficients is necessary for a quantitative understanding of the many rate processes (e.g., grain growth, precipitation, sintering, oxidation, or mechanical deformation) occurring in solids. Although these data are available for most metals and common alloys, they are quite limited for intermetallic compounds—a group of materials whose unique physical and mechanical properties are presently attracting great interest. From a fundamental viewpoint, diffusion in intermetallic compounds also offers several engaging aspects owing to: their ordering, the possibility of introducing large, stable concentrations of lattice defects, and the variety of bonding types and crystal structures which can be found. In the case of CsC1-type compounds, some previous work has been directed at examining the role of vacancy defects by changing their concentration compositionally. The diffusion of Co60 was measured in 0 NiAl1- and in P COA., Except for the results of Smoluchowski and Burgess, isothermal diffusion coefficients were found to pass through a minimum at the stoichiometric composi- they decreased sharply on what was reported by Bradley and co-wrkers' to be the vacancy-rich (aluminum excess) side of stoichiometry. This investigation of the diffusion of Agl110 in AgMg was undertaken both as an adjunct to a concurrent study of its deformation behavior and for the purpose of obtaining information on the influence of lattice defects and temperature on diffusion in another CsC1-type intermetallic compound. Bcc AgMg remains ordered up to and melts congruently at 820°C. Solubility limits at 300°C are about 41 at. pct Mg and 53 at. pct Mg. It is one of the Hume-Rothery electron compounds with a 3/2 electron-atom ratio. Previous investigations of its properties include hardress,' tenile,'-' electrical reistivity, and thermodyna-mic1',14 studies. Indications of a high bonding strength may be found in the large heat of mixing1' and in the 6-pct vol contraction on compound formaticp, as calculated using atomic radii of l.40 and l.55a for Ag and Mg. EXPERIMENTAL PROCEDURE Alloys were prepared by the induction melting of selected fine silver (99.95) and low-iron magnesium (99.95) in magnesia crucibles under 1 atm of A. Supplied by the Handy and Harmon and Dow Chemical Cos., respectivelv. Melts were poured under argon into graphite molds providing 1 1/8-in.-diarn. by 4-in.-long ingots. These were homogenized in evacuated and argon-filled fused-silica capsules by heating for 16 hr at 750'. Three 1 in.-diam. by 3/4-in.-long cylinders were machined from the mid-portion of each ingot for diffusion measurements. Three alloys, analyzing 45.8, 49.8, and 52.0 at. pct Mg were taken as representing the extremes of interest, with 49.8 at. pct Mg being very close to the stoichiometric composition of 50.0 at. pct Mg.

Jan 1, 1962

By P. A. Beck

ACCORDING to the traditional definition,1 re-x crystallization is a process taking place upon annealing of cold worked metals, characterized by the appearance of new strain-free grains, growing at the expense of the cold worked grains until ultimately the new crystals completely replace the cold worked structure. In metals like brass this process was observed long ago to take place simultaneously with the return of the mechanical properties to those characteristic of well annealed material. The above definition implicitly assumes that the matrix in which the new grains are growing is essentially still in the cold worked condition at the time it is absorbed by the new grains, i.e., that the energy stored in the metal during cold working is not greatly decreased by recovery, prior to recrystallization. Accordingly, the bulk of this energy is assumed to serve as the driving force for the process of recrystallization. Recently, a great deal of evidence accumulated, indicating that the traditional concept may be considerably in error. Suzuki' found that by far the largest portion of the stored energy of cold work in compressed polycrystalline copper is released in the early stages of annealing, well in advance of recrystallization. Thus, the new recrystallized grains are undoubtedly growing in a matrix which is, at least energetically, no longer in the cold worked condition, but has nearly returned to the annealed state. It is true that in Suzuki's experiments the major hardness changes due to annealing were observed to take place concurrently with the formation and growth of the new grains, but this process apparently involved the release of only a minor residual fraction of the stored energy of cold work. Confirming in this respect the views of Wood," several recent investigations by various techniques lead to the conclusion that the grains of many, if not all, metals in the cold worked condition consist of small, slightly disoriented "crystallites" or "sub-grains".* (After appreciable deformation at room temperature, the subgrain size in copper appears to be about 7.104 cm and in high purity aluminum about 2.10-4 cm.) Recent investigations which demonstrated this phenomenon most convincingly are those of Heidenreich8 with hammered high purity aluminum, of P. B. Hirsch and collaborators7,8 with cold worked polycrystalline aluminum, copper, nickel, iron, gold, etc., and of Warren and Averbach9 with a rolled copper plus 2 pct Si single crystal. In addition to the existence of slightly disoriented sub-grains, the cumulative evidence from these investigations also shows that in the cold worked condition the subgrains themselves are severely strained. With regard to the early stages of annealing, Heiden-reich's results indicate that within the subarains of hammered high purity aluminum the strain gradually disappears, without discernible migration of the subboundaries. This recovery process presumably accounts for the major portion of the energy release

Jan 1, 1953

By G. L. Oldright

THE upper limit of richness of concentrates that can be smelted by means of the blast furnace without added diluents is fixed by the opera-tion of sintering. A sinter feed with normal gangue constituents, con-taining more than about 50 per cent of lead, tends to fuse; as a result, air does not come sufficiently into contact with the sulphides at roasting temperatures, and sulphur elimination is poor. Since most lead con-centrates now contain 55 to 80 per cent lead, it is necessary to add diluents to lower the grade of such sinter feed to about 50 per cent or less. This not only entails the expense of providing barren diluents when adequate diluents containing precious metals are not available but also appreciably lowers the capacity of the blast furnace to produce lead and increases slag losses. Attempts to desulphurize rich lead concentrates by methods other than sintering have not proved successful. Flash roasting, for example, converts much of the lead sulphide to lead sulphate rather than to oxide. However, this suggested the possibility that deliberate flash roasting of the concentrates to sulphate, followed by sinter roasting of the resulting product, might prove promising, particularly inasmuch as the elimination of sulphur from lead sulphate requires heat alone and not contact with atmospheric oxygen. The sintering of lead sulphate products has additional interest because important amounts of such products are now treated by lead smelters. Considerable quantities of lead sulphate are present in rich lead flue dusts and other by-products; lead-chamber sulphuric acid plants and other

Jan 1, 1940

By F. R. Brotzen, L. D. Whitmire

Single crystals of high-purity molybdenum were de-formed at temperatures from 195°to 473°K, and the effect of deformation on the electrical resistivily was deler-mined. To separale the resislivity components of point and line defecls some cryslals were annealed at 473°K. The vale of resislivily increase wilh strain was nearly linear and was strongly dependent upon the deformation temperature. Point dejects are annealed out without any effect on the flow stress. At low temperatures the flow stress is a linear function of the square root of the resistivity increase attributable to dislocations. ELECTRICAL-resistivity measurements have been used successfully to gain information on structural changes in metallic materials. During plastic deformation the electrical resistivity rises because of electron scattering from newly created lattice defects. Such measurements lend themselves, therefore, to corroborating results from direct observation of lattice defects and, to a certain extent, to correlating defect densities and distribution with mechanical properties. Published information on research with single crystals of the bcc metals of Group VI, particularly molybdenum, is still limited. Yet, molybdenum single crystals of relatively high purity can be readily prepared by electron-beam-melting techniques. Furthermore, some valuable information on the defect structure of deformed crystals by direct observation is available. Lawley and Gaigher,1 for example, have examined dislocation configurations in deformed molybdenum crystals by means of transmission electron microscopy. Their results revealed that the dislocation density and distribution were strongly dependent upon the deformation temperature. These findings differed from those by Keh and weissmann,2 who found that the average dislocation density in polycrystalline iron deformed between 138° and 298°K depended only on the degree of strain and not on the deformation temperature. Martin3 and peiffer4 showed that point defects introduced in polycrystalline molybdenum by cold work can be eliminated by annealing at a relatively low tempera-ture. In view of their work it became apparent that resistivity measurements of suitably annealed crystals could disclose changes in their dislocation structure and contribute to the understanding of the work hardening of molybdenum crystals. EXPERIMENTAL PROCEDURE Crystals were grown by electron-beam zone melting5,6 of 0.062-in.-diam molybdenum rods (99.99 pct) supplied by General Electric Lamp and Wire Division, Dover, Ohio. The crystals, about 4 in. long, were prepared by using five zone-refining passes at a speed of about 6 mm per min in a vacuum of about 5 X l0-6 Torr. The resistivity ratio of the crystal, p(4.Z°K)/p(273°K), was generally near 10-3. These crystals were used as tensile specimens of uniform diameter in the "as-grown" condition. They were oriented for maximum shear on the (011)[111] slip system (Schmid factor >0.49). The specimens were held in spherically seated Templin-type grips so as to minimize bending. Samples were deformed on an Instron machine at a strain rate of about 5 X 10-5 sec-1 in an isopentane bath with dry ice at 195°K, in ice water at 273°K, and in a vegetable-oil thermostat at 373° and 473°K. The temperature in the latter was maintained constant within +2°K. Resistance measurements were carried out with a Kelvin double bridge. The resistance of the potential leads was kept low by using large-diameter wires outside the low-temperature bath. Many of the resistance data were checked by measurements made with an ac bridge. Current and potential leads were spot-welded to the specimens. The distance between the potential leads, about 3 in., was also considered to be the gage length for the strain measurements. Diameter and gage length of the samples were measured optically with an error of less than 2 pct. These measurements were used also to insure that the deformation had been uniform over the gage length of the specimen. Resistivity changes were then determined from the resistance measurements at 4.2°K assuming constancy of volume. In the course of a test, the crystal diameter, gage length, and resistance at 4.2°K were determined first in the initial state and subsequently for various amounts of elongation.

Jan 1, 1968

By Evan Just

DIRECT subsidies for mine production in this country began as an outgrowth of wartime 'price regulation. The price-fixing authorities realized that the volume of production to be required from domestic copper, lead, and zinc mines would invoke costs of production considerably higher than the established ceiling prices. Accordingly, beginning Feb. 1, 1942 the Premium Price Plan was set up, which undertook to pay premiums to mines for production in excess of quota, of 5¢ per lb of copper and 2Y4¢ per lb of zinc or lead. Quotas, except for small mines, were initially established at the average rate of production in 1941, but were later reduced arbitrarily on an individual basis. Subsequently, additional "B" premiums were set for lead and zinc of 2Y40 per lb and a further "C" zinc premium of 2%¢. Additional copper premiums were negotiated on an individual basis, mainly with small mines. Quotas under each of these successive categories were the production obtained at the next lower premium level. In other words, under ceiling prices of 12¢ for copper, 6,14¢ for lead, and 83¢ for zinc, it was possible for high-cost operations to receive prices plus premiums of 17¢ or more for copper, 12¢ for lead, and 16% 0 for zinc on a portion of their production. On the other hand, some of the larger operators received only slight premiums and in at least one instance none at all. The average price plus premium for copper was 12.25¢ in 1942 and rose to 13.65¢ in 1945. That for lead was 6.99¢ in 1942 and 8.73¢ in 1945, and for zinc it was 9.06¢ in 1942 and 11.200 in 1945.

Jan 1, 1948

By Prince Gelasio Caetani

PRESIDENT DWIGHT'S invitation to be a guest of the American Institute of Mining and Metal-lurgical Engineers was the first of the subsequently very numerous invitations to dinner I have received from my American friends. When I received his telegram I had not yet been even formally appointed Ambassador. I cannot tell you how deeply I appreciated it. It was a hearty welcome in returning to your country which has been for me a second home and it came from the American mining brotherhood which has been my second family.There are two distinct periods of learning in life. The first one are the years spent in school where we learn many things we after-wards forget; the second one are the years of prac-tical apprenticeship which engrave indelible signs in a man's character and shape his life. These latter years I spent in the United States and they have influenced the whole course of my life. I owe very much to my American friends who trained me. The earliest was Prof. Robert Peele, of Columbia University. At the Daly West mine, in Park City, Utah, he curbed my futuristic English spell-ing and had a hard time at it. Prof. James F. Kemp taught me that geology is a guess work just as unre-liable as the prediction of international events; he taught me also that a frank, honest and loyal character will lead a man equally straight through a mining report and through public life.

Jan 3, 1923