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By J. S. Bowles

THE martensite transformation in lithium, dis- covered by Barrett,' has been studied extensively by X-ray techniques by Barrett and Trautz,² and Barrett and Clifton.V he present paper reports the results of an investigation into the metallographic characteristics of lithium martensite. Such an investigation has not been carried out before. The spontaneous transformation in lithium consists of a change from a body-centered cubic to a close-packed hexagonal structure with the hexagonal layers in imperfect stacking sequence." As far as is known at present, this transformation can be regarded as being crystallographically equivalent to the body-centered cubic to close-packed hexagonal transformation that occurs in zirconium,5 although stacking errors have not been reported in zirconium. From a study of the orientation relationships in zirconium, Burgers5 as proposed that the martensite transformation, b.c.c. to c.p.h., occurs by a heterogeneous shear on the system (112) [111]. The crystal-lographic principle underlying this proposal is that the configuration of atoms in the (112) plane of a b.c.c. structure is exactly the same as that in the (1010) plane of a close-packed hexagonal structure based on the same atomic radius. The pattern in 2v2 both these planes is a rectangle d X 2v2d where v3 d is the atomic diameter. Thus a close-packed hexagonal structure can be built up from a body-centered cubic structure by displacing the (112) planes relative to each other.* This mechanism leads to orientations that can be described by the relations: (110)b.c.e. // (0001)c,p.h.; [111]b.c.c. // [1120]c.p.h Observations confirm these relations. In zirconium, Burgers' measurements indicated an angle of 0" to 2" between the close-packed directions, while Barrett's measurements on lithium indicated an angle of 3". According to the Burgers' mechanism, the martensite habit plane for this transformation would be expected to be the (112)b.c.c. plane, for this plane would not be distorted by the transformation. One of the purposes of this investigation was to find out whether the observed lithium habit plane agrees with this prediction of the Burgers' mechanism. Experimental Procedure Materials: The lithium was from the same purified ingot used by Barrett and Trautz.² The Bridgman technique was used to produce single crystals. To maintain a temperature gradient in the melt, during the production of these crystals, it was necessary to use a steel mould with a wall thickness of only 0.015 in. Metallographic Techniques: Lithium specimens could be given an excellent metallographic polish by swabbing them gently with cold methyl or ethyl alcohol.? The best results were obtained with methyl alcohol saturated with the reaction product, lithium alcoholate. With higher alcohols the reaction became progressively slower and the attack became an etch pit attack rather than a polish attack. Butyl and amyl alcohols were used for macroetching. After polishing, it was necessary to remove all traces of alcohol from the specimens; otherwise, on subsequent quenching in liquid nitrogen, the alcohol froze to a glassy film. The alcohol was removed with dry benzene. The benzene in turn had to be removed before quenching, but since it does not react with lithium it could be allowed to evaporate. The specimens could then be quickly quenched before they began to tarnish. This operation could be carried out in air on all but excessively humid days when it was advisable to use an atmosphere of dry nitrogen or argon. For examinations at room temperature, the specimens could be transferred directly from the benzene bath into a bath of mineral oil. In mineral oil the specimens oxidized slowly by the diffusion of oxygen through the oil but the structure remained visible for about an hour. Lithium Martensite: Specimens prepared in the manner described above transformed spontaneously to martensite with an audible click when quenched into liquid nitrogen; i.e., M, was above the boiling point of nitrogen (77°K). The disparity between this result and the M, temperature of 71°K, found by Barrett and Trautz, is probably to be attributed to the large grain size and freedom from mechanical deformation of the specimens used in the present work. The relief effects produced by the transformation did not disappear when specimens were quenched from liquid nitrogen into mineral oil at room temperature. This permitted the microstructures to be studied at room temperature where, of course, the martensitic phase was no longer present. Typical micrographs of lithium "martensite" made at room temperature are reproduced in figs. 1, 2, and 3. As anticipated by Barrett and Trautz, the microstruc-

Jan 1, 1952

Discussion of the paper of GEORGE S. RICE and H. H. CLARK, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2563 to 2571. NORMAN V. BRETH,* Pittsburgh, Pa.-It was my privilege to visit in the last two months on behalf of the U. S. Bureau of Mines 10 mines where electric shot-firing systems controlled from outside the mine are installed. I will describe briefly what I saw in some of these mines, which are located in Utah, New. Mexico, Oklahoma, Alabama, and Kansas. At a mine in Utah, 230-volt alternating current is used to fire the shots, which is taken from a small transformer in the substation. The shot-iring circuit is independent of all other wires and is tested for grounds every day. There are no lightning arresters on the firing circuit. Porcelain insulators are used inside of the mine, and glass outside. The switches are situated as follows: One in the substation, one in, the shot-firer's cabin, two at each cross entry; where the shot-firing circuit crosses the trolley wire a switch is placed on either side of the entry in series with the shot-firing circuit. The miners are checked in and out of the mine. The coal is undercut and is shot down with permissible explosive, the shots being connected in multiple. There are 75 to 110 shots fired each day. A great many times there are no missed shots. If not more than two or three are missed they are left until next day. The fan is kept running at full speed when the shots are fired. The shot-firing switch is closed only once and the whole mine is shot at once. At another mine in Utah, power wires are used for shot-firing circuits; 500-volt, direct current is used to fire the shots. The only sizes of wire used outside of the power wires are Nos. 8 and 14 B. & S. gauge. The return is connected to the pipe lines and track. Porcelain insulators are. used inside of the mine.

Jan 4, 1915

Jan 1, 1922

Jan 1, 1922

By K. K. Kohli, S. S. Peng, R. E. Thill

Introduction Since the adoption of the Surface Mining Reclamation and Control Act of 1977, which mandates that surface subsidence be an intergral part of the underground coal mine design, there has been a sudden rise of demand on guidelines for minimizing surface subsidence and its associated structural damages. Unfortunately there is no sufficient amount of systematic subsidence data to fill such a gap, although considerable research has been devoted to the subsidence induced damages of surface structures in the past. However, it was said that many surface subsidence surveys have been performed and monitored by coal companies during the past twenty years, and that it will be a great source of information for subsidence engineering design if they can be collected and assembled together. An effort was therefore initiated in the Department of Mining Engineering, West Virginia University, under contract with the U. S. Bureau of Mines in December 1978 to contact each individual coal company in the Northern Appalachian Coal Field for any surface subsidence survey data. After 10 months' survey, the data collected include: 17 longwall panels and 2 room and pillar sections. The data in each panel and section cover the complete set of subsidence survey raw data, underground mine layout maps, surface topo maps, geological loggings showing the stratigraphic sequences and thickness of the overburden, and if available, locations and types of surface structures. On-site visits were followed to study the surface terraines and structures. Interviews were conducted with the owners of the surface structures in most cases about, if any, the history and characteristics of damages. Most subsidence surveys started with the first panel and ended with the second or sometimes, but rarely, the third panel. The first panel may be located in a virgin area but frequently it was adjacent to (on the tailentry side) a mined-out room and pillar section. It must be noted that all of the subsidence data is restricted only to the amount of vertical subsidence and that the horizontal displacement measurement was completely ignored. Primarily due to the fact that vertical subsidence is the most striking feature in a subsidence trough, which is mistakenly considered to be the only critical contributor to surface structural damages, and that a horizontal displacement survey is much more complicated and time-consuming.

Jan 1, 1981

By T. Egleston

THE materials containing copper which are refined in the United States, are, for the most part, the native, coppers of Lake Superior. Until quite recently but little pig copper was made for sale, and that came principally from the pure sulphurous ores of New England and the South, and was generally sold to refineries not far from the ore furnaces. A small amount found its way into the market which was produced either as the by-product of the treatment of gold and silver ores, or as the result of the treatment of impure copper ores; but both these grades, on account of the impurities they contained, were looked on with suspicion, and were not sought for. All the grapes of pig copper are sold by the unit of copper contents, a great reduction being made in the price when impurities are present. There are at the present time only three works which treat native copper, the two of the Detroit and Lake Superior Copper Company, and the works of C. G. Hussey & Co., in Pittsburgh. There are a few works which smelt sulphurous ores and refine their pig; besides these there are a few small works where pig copper is refined only. Some of these purchase black copper, refine scrap, or simply refine such grades of ingot copper as are found in the market, but mostly that from Lake; Superior, for the purpose of getting it into such shapes that can be handled commercially to advantage, such as in making large plates or high grades of wire for electrical purposes. A number of such works are situated in the Naugatuek Valley and elsewhere in New England. The recent discovery, of valuable ores in Arizona makes it probable that within a few years the refining of copper in the United States will make great developments. Up to the time of the discovery of the mines on Lake Superior, only a very small quantity of native copper had ever been found, not sufficient to justify the erection of works for its special treatment. It had, besides, never been found in very Large masses, so that the discovery of great-blocks of it presented serious difficulties, not only in mining it,† but in bringing it into a merchantable condition. It seemed a very simple process to melt these large masses, * Road at the Lake Superior Meeting, August, 1880. †Transactions American Institute Mining Engineers, vol. vi, page 2S2.

Jan 1, 1881

By S. S. Clarke

LATE in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls Were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1947

By J. S. Marsh

The student of steelmaking is all too well acquainted with the fact that in many instances he must deal with data that in graphical representation exhibit the property most desirable in bird shot. This is scarcely mystifying, since the effort to establish one variable as a function of another is usually hampered by the simultaneous operativeness of two or three other factors that may be important. A large part of arriving at relationships that have the pleasing self-consistency of, say, precise measurements of thermal expansion, consists of determining what factors must be held constant-—an even larger part usually consists of collecting data for which those factors have been so maintained. It is not intended to imply that functional relationships in the physical chemistry of steelmaking are hopelessly obscure; on the contrary, it is merely necessary to be undisturbed by marked deviation of some points from a curve that otherwise makes sense. A reaction mechanism suggested by such a curve may call attention to hitherto unsuspected factors operative in the origin of the deviating points, and thus permit another step to be taken in the direction of fuller understanding. It is proposed, therefore, to suggest several empirical relationships. Even though the approach is not always rigorous, deviations caused by simplifying assumptions appear to be too small to obscure a provisional It has been appreciated for some time that the carbon-oxygen reaction in liquid steel is highly important. For example, Körber et al.,' in introducing a summary of their extensive work on steelmaking reactions, said: "... the far-reaching and truly dominating action of carbon upon the metallurgical reactions will be especially stressed ..." In "Basic Open Hearth Steelmaking"2 (hereafter BOHS, for simplicity), it is accepted repeatedly that the various slag-metal interactions are nearly always controlled by the carbon-oxygen reaction. Before further discussion of this reaction, however, it will be worth while to consider briefly the carbon-oxygen equilibrium. In BOHS (p. 483) it is stated that: When liquid iron is brought into contact with gases containing carbon monoxide it absorhs carbon and oxygen. Conversely the carbon and oxygen in the metal unite to form carbon monoxide which is evolved from the bath during the open-hearth boil or while rimming ingots are solidifying. . . . When the equilibrium pressure is one atmosphere the equilibrium-constant equation simplifies, on the assumption that the activity of each element is equal to its percentage, to a constant which has been so much used that it has acquired a special symbol m. where m = %C X %O

Jan 1, 1945

By Eugene McAuliffe

The management of The Union Pacific Coal Co., which operates a group of coal mines in Southern Wyoming, believes in the value of applied psychology as a productive factor in the work of getting out coal. Operating almost wholly through the medium of mechanical loading machinery, the company has for some years paid a bonus, equivalent to one-half the labor saving made above a determined average output per shift worked, on a given machine. No penalty is attached where the established output is not obtained, but in 1933 the men on one class of machines earned an average premium of $0.633 per shift on 56.4 per cent of the tonnage loaded. On another class of machine, the men earned an average premium of $0.686 per shift on 28.4 per cent of the tonnage loaded An increase of 36 per cent in tons loaded per man-shift has resulted since the program was instituted. This coal company has also been very successful in reducing mine accidents through prizes awarded in an unusual way. At the close of the year, every man whose particular mine section passes through the year without a lost-time accident is given a ticket entitling him to participate in a safety drawing where an automobile is awarded as first prim.. There are also a number of cash safety prizes which are similarly awarded. Some 1500 persons attend the drawing, which excites much interest and attention. The particular plan employed, the payment of production bonus awards and safety prizes, is foundationed upon collective. rather than individual effort, and, once gotten under way, has proved to be substantlally self-cnforcing.

Jan 1, 1934

By A. R. Denison

The Permian Basin as it appears in the title of this article refers to three rather widely separated areas of production. It includes what are commonly known as the "Panhandle" fields of the northwest part of Texas; the West Texas fields, in the southwest part of Texas; and the New Mexico fields, in the southeast corner of New Mexico. These three areas are all included in a single province and produce the majority of their oil from limestones or dolomites of Permian age. The manner of accumulation of oil in the three areas is somewhat diverse. In the Panhandle, production is found on the flanks of an enormous structural ridge, the core of which is granite. In southwest Texas and New Mexico oil is produced from both gentle and steep folds and from lenticular areas of porosity. Production in Texas During 1927 Texas produced a total of 216,306,000 bbl. of oil of which the Permian Basin contributed 89,797,000 bbl., or 42 per cent. During 1928, Texas produced 255,021,000 bbl. of oil of which the Permian Basin contributed 145,955,000 bbl., or 57 per cent. The increase in total production is entirely due to the West Texas fields. All other districts in Texas declined during the year while the west Texas fields registered an increase of more than 71,000,000 bbl. West Texas daily average production increased from 260,752 bbl, at the beginning of 1928 to a maximum of 406,318 bbl. per day the first week in May. Due to prora-tion agreements, the production was held at a fairly constant level around 340,000 bbl. during the remainder of the year, having 345,660 bbl. the last week in December. Daily average production of the Panhandle fields decreased from 80,178 bbl. at the beginning of the year to 59,025 bbl. at the close of the year. The combined daily average production of the Panhandle and West Texas fields at the beginning of the year was 341,138 bbl. and at the close of the year was 405,408 barrels. Fig. 1 gives a comparison of the production in the Permian Basin in relation to the production of the entire state. It is clearly shown that

Jan 1, 1929

By Forrest K. Pence

BENTONITE deposits are known to occur in Texas within the Jackson group of formations. This group represents the uppermost Eocene age sediments found in the coastal plain area of Texas. It outcrops across this area of the state in a narrow band of some 4 to 20 miles width. The outcrop pattern roughly parallels the present Gulf of Mexico shore line and is some 100 miles inland from the Texas shore, Fig 1. The principal bentonite deposits are found in the areas where this outcrop pattern cuts across the south-central Texas counties of Karnes, Gonzales, and Fayette. In these deposits, the better quality bentonite is found in the lower or bottom layers of the volcanic ash deposits in which they occur. Some of these better quality bentonites develop very light colors upon firing and therefore justify their being classified as "white firing." The deposits in Karnes and Gonzales Counties apparently occur in commercial quantity, whereas the white firing strata so far uncovered in Fayette County have been too thin to be classified as yet as "commercial." A study of the ceramic properties of the weathered ash in Gonzales and Karnes Counties was reported in 1941.1

Jan 1, 1949

By V. H. Wilhelm

Greater stabilization in the petroleum industry was effected during 1934 through stricter compliance with curtailment measures and the establishment of the Pacific Coast Petroleum Agency. Various estimates of individual, company and state reserves revealed the fact that they were inadequate to sustain the present rate of production over a lengthy period, therefore drilling operations were increased during the year both in proved and wildcat territory. This greater activity resulted in the addition to reserves at Mountain View, Mount Poso and Edison in Kern County, Santa Barbara in Santa Barbara County and Playa del Rey in Los Angeles County. Additional reserves were also established in the Long Beach and Santa Fe Springs fields, in Los Angeles County, due to operators being successful in isolating small prolific sand bodies, formerly disregarded during the flush production periods.

Jan 1, 1935

R. G. BROWN, Bodie, Cal.: Mr. Rickard's paper, with its valuable illustrations, brings into fresh clearness the game of hide-and-seek which the miner must play with his ore-deposit; but, more than this, it goes far towards classifying those perplexing idiosyncrasies which, while unclassified, constitute a labyrinth almost without clue. Probably every engineer can add to the list by the mention of at least one fresh detail from his own experience, and I for one would like to comment on two of Mr. Rickard's divisions. To what he has written about " walls within walls" and " walls without walls," the accompanying Figs. 1 and 2 may be appropriate, the more so as they represent conditions obtaining in a part of the Butte copper-belt more typical of the copper-veins as a whole than the Gagnon, which, in some respects the most interesting mine in the camp, stands almost alone in many particulars. (See nuns., xvi., 62.) Fig. 1 was sketched in January, 1895, in the stopes above the 700-foot level of the Colusa-Parrot mine, east of the Parrot and southwest. of the Anaconda. The stope, the commercial foot-wall of which is shown at A, was 30 feet wide at this section, the pay-ore being massive chalcocite, jumbled with bornite, pyrite, quartz and thoroughly broken-down granite. A and At are inch-thick seams of black talc; B, B' and B" are also talc, possibly 1/8-inch thick. In the plane of the section the "banded quartz " and " quartz and pyrite " were both of too low grade for extraction, but 5 feet back along the stope had been of fair value. The granite with quartz and bornite between Bt and A' was pay-ore, but that to the right of B" was not. In both cases the ferro-magnesian minerals had been removed, leaving, where not obscured by ore, faint, dark patches. Between A'

Jan 1, 1897

By Robert H. Richards

OF the several professions-the chemist, the civil engineer, the mining engineer, the mechanical engineer-the courses of instruction, as arranged at the scientific schools, differ considerably as to the amount of practical information which the student is able to gain. The analytical chemist has facility for a very thorough review of the processes which he will be called upon to perform. The student in civil engineering by his field practice learns the use of his tools and the art of taking field-notes. The mechanical engineering student is in the vicinity of machine-shops, which he can visit, and at which he can work. The student in mining engineering has no such advantages. The mines are at a distance, and the railroad fare to get to them is oftentimes an insuperable difficulty. The aim of these laboratories is essentially to give to the student in mining and metallurgy a chance to study on a small scale the practical parts of his profession. We cannot, in a small laboratory, build a mine to timber, to work, and to survey; we cannot make artificial quicksands and other impediments to mining. In short, we cannot study exploration; but we can study the mechanical preparation and the subsequent smelting of ores. Before presenting the plan of these laboratories it may be interesting to indicate the progress of the idea from its beginning. During the summer of 1870 President Runkle visited the mines of Colorado, and while there, conceived the idea of making an expedition with the mining students to some of the Western mining regions. He talked over the scheme with many railroad and mining men, and everywhere received encouragement. In the summer of 1871 the Institute party visited the mines of Colorado, and spent six weeks in taking notes of them. President Runkle here conceived the idea of building up a mining and metallurgical laboratory ; and by the aid of Booth & Co. of San Francisco, a stamp-mill was obtained, with the Washoe silver-working apparatus. During the year

Jan 1, 1873

By J. B. Clark

An exploratory study of the 60 wt pct Mg and 80 wt pct Mg sections of the solid constitution in the magnesium-rich region of the Mg-Al-Ca-Zn system was undertaken. The objective of the investigation was to determine the general configuration of the phase fields with respect to the magnesium solid solution in this complex system. The 335°C (635°F) tetrahedron was selected for study because the solid constitutions of the bounding ternary systems—Mg-Al-Zn,1 Mg-A1-Ca,2 Mg-Ca-zn3—were well known and, at least in these ternary systems, diffusion was rapid enough at 335°C for equilibrium to be reached fairly rapidly. Metallography and powder X-ray diffraction were selected as the best corroboratory methods for determining the solid phase equilibria. A total of forty-six quaternary alloys on the 60 wt Mg and 80 wt Mg sections were prepared, annealed to equilibrium at 335°C, and the phases present identified. Singly sublimed (99.99 pct) magnesium, electrolytic (99.99 pct) zinc, high-purity (99.99 pct) aluminum, and USP calcium were alloyed in graphite crucibles under a chloride flux and chill cast into a split graphite mold. Alloy samples were sealed under argon in Pyrex vials and annealed at 335°C ± 1/2° for a minimum of 500 hr. At the conclusion of the anneal, the alloy samples were quenched rapidly in ice water. Standard metallographic procedures for magnesium alloys were used. Powder X-ray diffraction patterns were taken on a G. E. Camera with a diameter of 14.32 cm using nickel filtered copper radiation. The phase equilibria in the 60 wt pct Mg section of the 335°C (635°F) tetrahedron is shown in Fig. 1. The complex equilibria in the zinc-rich region were not accurately determined and are shown only tentatively with dotted lines. The equilibria of the three bounding ternary 335°C sections from pure magnesium to 60 wt pct Mg are also shown as though folded away from the tetrahedron. The 80 wt pct Mg section has the same configuration of phase fields as that shown in Fig. 1. Thus it is reasonable to conclude that in higher magnesium sections, the same relative configuration of phase fields is maintained though the relative proportions of the individual phase fields may change slightly as the magnesium solid solution is approached. Note that all the ternary phases present in these ternary diagrams enter into the quaternary equilibria with the exception of the phase of the Mg-Al-Zn system which becomes unstable with the addition of as little as 1/2 pct Ca. No quaternary intermetallic phases were found. No liquid phase was detected in any of the quaternary alloys annealed at 335°C suggesting that if a quaternary eu-tectic exists, it must lie between 335°C and 339°C, the temperature of the ternary eutectic in the Mg-Al-Zn system.

Jan 1, 1962

By Charles Will Wright

THE HIGHLY SPECIALIZED heavy air transport services to mining regions, such as exist in the New Guinea gold fields and in northern Canada, have been even more essential in the development of mines in Peru. Few nations have been con- fronted with greater natural obstacles to transport than has Peru, and without the plane it would have been impossible to get the machinery and supplies for the construction of power plants and mills to many of these interior mines, situated as they are over high mountain ranges, with muleback the principal means of transportation. As the mines within a district become important producers and warrant the expenditure, the mule trail is being replaced by automobile roads to connect with the railway stations and with the airports.

Jan 1, 1940

By Otis M. Clarke

The Eufaula bauxite-kaolin district in southeastern Alabama is an important source of raw material for the refractory industries in the United States. At the present time, five companies are mining and processing bauxite and kaolin from this district and a sixth company is holding substantial reserves. Mining operations are expanding, but finding new ore reserves is a major problem. The Geological Survey of Alabama sponsored geologic research in the Eufaula district to: (1) investigate the

Jan 1, 1973

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By M. J. Marcinkowski, E. N. Hopkins

An investigation has been made of the ß(fcc) — a(hexagonal) transformation which occurs in lanthanum using both electrical resistivity and transmission electron microscopy techniques. It has been shown that the ß phase can be retained below the transformation temperature by rapid quenching but that the sample immediately begins to transform to the a phase. The transformation is observed to nucleate in the vicinity of inclusions. Based on the above observations, a detailed model of the transformation has been advanced which involves the nucleation of an extrinsic stacking fault bounded by a pair of Shockley partial dislocations in the vicinity of some heterogeneity, i.e., an inclusion. The stress field of the resultant dislocation pair acts to nucleate extrinsic faults in adjacent planes and leads quite naturally to the B-a conversion with a minimum of strain energy induced in the crystal. LANTHANUM possesses an fcc structure ß) (8) upon cooling transforms to a hexagonal modification (a) in much the same way as cobalt. The one exception, however, is that the stacking sequence of the closest packed planes in a La is ABAC ABAC, and so forth,1 whereas in cobalt it is ABAB, and so forth, i.e., hep. Mainly on the basis of transmission electron microscopy techniques, there seems to be little doubt that the 0 — a transformation in cobalt involves a dislocation mechanism2 although its exact nature still remains obscure. Although the ß - a transformation in lanthanum is somewhat more complex than that occurring in cobalt, it was thought that its very uniqueness would be helpful in understanding fcc — hexagonal transformations in general. Such a general understanding of these transformations is important since they represent what are perhaps the simplest of the martensitic class of transformations. The experimental techniques used were those of electrical resistivity and transmission electron microscopy. EXPERIMENTAL PROCEDURE The lanthanum used in this investigation was prepared by the calcium reduction of lanthanum fluoride in a tantalum crucible under an argon atmosphere as described by Spedding et al. The residual calcium was removed by vacuum remelting in a tantalum container. Portions of the metal were then analyzed by emission spectroscopy as well as vacuum fusion. The amounts of the various impurities that were found are listed in Table I. A portion of the lanthanum ingot was swaged at room temperature into 0.030-in.-diam rod for the resistivity samples while the remainder was rolled into 0.010-in.-thick sheet for the transmission electron microscopy phase of this investigation. In order to eliminate the plastic deformation induced in the samples during fabrication, they were sealed in evacuated tantalum lined quartz capsules and annealed for 1 hr at 700° C. Specimen resistances were measured using the conventional "four-wire" technique described by MacDonald, 4 employing a type K-3 Universal Potentiometer and a standard 0.001-ohm resistor, both manufactured by Leeds and Northrup Co. By taking into account all of the possible errors in the apparatus, it was felt that the absolute resistivities of the approximately 0.87-in.-long specimens measured are reliable to 3 pct. Resistances from room temperature to 700°C were measured using a vacuum furnace. In order to avoid sample contamination by the thermocouple, chromel-alumel leads were spot-welded into a tantalum shield which in turn was welded to the lanthanum specimen. Resistances below room temperature were obtained by transferring the sample to a helium gas-filled quench tube and slowly dripping liquid nitrogen into a surrounding dewar flask. A steady reduction of temperature to about —190°C was completed in about 23 hr, and the resistances were measured at various temperature intervals. As will be shown shortly, rapid quenching from above about 350°C was sufficient to suppress the B -a transformation initially but subsequent annealing at lower temperatures leads to a partial ß --a conversion. To investigate this aspect of the transformation, the samples were suspended in the hot zone of a helium-filled furnace from which they could be rapidly dropped into the quench tube mentioned previously which was now

Jan 1, 1969

By J. B. Darby

In an investigation of various equiatomic alloys of transition elements, Dwightl did not find evidence for the CsC1-type ordered structure in VMn. More recently waterstrat2 has reported the occurrence of this structure in the alloy his sample had been homogenized at 1150°C and subsequently reannealed at 725°C after crushing to powder. The purpose of this note is to confirm the existence of the CsC1-type ordered structure in VMn and to report a lattice parameter. An equiatomic alloy was prepared by arc-melting under an argon atmosphere vanadium and electrolytic manganese having a purity of at least 99.9 pet. The composition was obtained by charging an excess of manganese and monitoring the weight loss until the stoichiometric composition was achieved; the assumption that the loss during melting was due to the vaporization of manganese appears to be a valid one.' The calculated composition of the sample prepared was 49.85 at. pct V and 50.15 at. pct Mn. Specimens taken from the fractured as-cast buttons were wrapped in molybdenum foil and encapsulated in quartz capsules under vacuum; there was no evidence of a reaction between the alloy and foil. The X-ray patterns were obtained using filtered copper or chromium radiation with a Straumanis-type Debye-Scherrer camera having a diameter of 114.6 mm. The CrKa radiation is best suited for detecting the superlattice lines since it overcomes the slight difference in scattering powers of the components by making use of the anomalies in atomic scattering factor which occur when the frequency of the radiation is close to the characteristic absorption frequency of one of the elements.394 A specimen in the as-cast condition, as well as one which had been annealed for 1 week at 900°C and water-quenched, gave a diffraction pattern for the disordered bcc solid solution. However, when samples were homogenized at 900°C for 3 weeks followed by a subsequent anneal at 700°C for 6 to 7 weeks and then water-quenched or furnace-cooled, the (loo), (1111, and (210) Ka superlattice lines were observed in films taken with chromium radiation. An ao = 2.904 * 0.001 was determined by a Nelson-Riley extrapolation from a film taken with CuKa radiation. The author wishes to thank Mr. J. W. Downey and Mr. L. J. Norton for carrying out the experimental portion of this investigation. This work was performed at the Argonne National Laboratory under the auspices of the U.S. Atomic Energy Commission.

Jan 1, 1963