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By J. A. M. van Liempt

SINCE the discovery, of von Laue, that a crystal forms a natural grating for X-rays, our knowledge of the structure of solids has gone forward with rapid strides. This progress is not only of purely scientific interest, but has also yielded direct technological results. One of the most valuable results is the broadening of our knowledge of the structure of pure metals and alloys. To promote these studies it is often desirable to have at our disposal pieces of metal consisting of one single crystal. As is so often the case in the natural sciences, we obtain the best results by making our earliest experiments on pure, simple materials and avoiding unnecessary complications. The Cryogen Laboratory at Leyden followed this method with much success, because the work was done at such low temperatures that the heat movement of the atoms was almost' absent. Similarly we can simplify the studies of metals by leaving out of consideration the influence of the grain boundaries and the mutual influence of the crystals by using unicrystalline instead of polycrystal-line metal. Methods of making single crystals have been scientifically studied during the past few years. Some methods were already known in the arts, but these have been improved and new methods have been developed. The methods for making metallic single crystals may be divided into the following groups: A. From the liquid state B. From the gaseous state C. Electrolytically D. By recrystallization in the solid state

Jan 1, 1927

By H. C. Brown

SINCE 1934 the steel industry has been utilizing the spectrograph for supplementing wet chemical analysis in the production control of electric and open hearth furnaces. This means of control made great strides during the war years because of the general acceptance of the spectrograph and the increased emphasis that was placed on rapid control methods. However, in the post war era, with the demand still on increased production, it became apparent that a still more rapid and economical means of production control was needed. Since the spectrograph had been used mostly in the analysis of low alloying and residual elements, it also became apparent that equipment was needed to extend the spectrographic technique to the analysis of the high alloying elements in stainless steel. For these reasons, companies manufacturing spectrographic equipment were prompted to start development work on direct reading instruments. In June 1949, the Applied Research Laboratories of Glendale, Calif., announced that a direct method of spectrochemical analysis for stainless type steels had been developed. This paper will describe the use of the Applied Research Laboratories Production Control Quantometer in the quantitative control of stainless, silicon, and plain carbon steels being made at the Butler Pennsylvania Div. of the Armco Steel Corp. The Armco Butler Div. has one 70-ton electric furnace and six 150-ton open hearth furnaces. The electric furnace is employed in the making of all types of stainless steel and the open hearth furnaces are used for the production of silicon, wheel, and plain carbon steels. The ARL quantometer was purchased primarily for the purpose of controlling the steelmaking in the electric furnace, but its use has been extended for the analysis of final tests (ladle tests) on a number of different types of stainless, silicon, and plain carbon steels. Because of this additional work by the quantometer, substantial savings in manpower and time have been realized by the laboratory. In the analysis of a set of preliminary tests from the stainless steel furnace, approximately 40 min in laboratory time are saved due to quantometric analyses. Despite the fact that more specialty grades of stainless steel are being made in the electric furnace, the average tons per hour have been increased since the quantometer was put into operation. Specialty grades require more furnace time than regular commodity grades of stainless steel. The installation of the ARL production control quantometer was completed on March 13, 1952. By May 1, 1952, the instrument was calibrated for nickel, chromium, manganese, silicon, and molybdenum, which are the elements necessary for the production control of the stainless steel furnace. Within the following month, training of personnel on the quantometer was achieved and a study of the accuracy of the instrument showed that the results obtained were sufficiently accurate for control purposes. Therefore, on June 11, 1952, the quantometer was placed on production control for all types of stainless steels. Starting September 11, 1952, the instrument was gradually placed on ladle analysis (final tests) as the analytical curves were refined and additional curves were drawn. The quantometer has been relatively free of breakdowns since placing it on production control. The samples from only one stainless steel heat have had to be analyzed by wet chemistry because of instrument trouble. The previously existing heat-time record was also bettered by 15 min on a commodity grade of 18-8 stainless steel. Scope of Control In general, the quantometer determines all elements necessary for the production control of all types of stainless steel heats and for the ladle analysis of various types of stainless steel heats. It is also used in reporting final results for silicon, manganese, chromium, nickel, molybdenum, tin, copper, and aluminum on all silicon steel grades and manganese, chromium, nickel, molybdenum, tin, and copper on several plain carbon steel grades. Table I shows the elements and the concentration ranges of these elements in the various types of stainless, silicon, and plain carbon steel that are determined on the quantometer. A study of the results obtained on ladle test samples of stainless steel types 410, 430, 430 Ti, 446, 301, 302, 304, 304L, 305, and 17-7 PH will be discussed. Also included in the study are the results obtained on ladle test samples of a number of silicon steels. Apparatus In order to take full advantage of the potentials of the production control quantometer, the unit has been placed in an air-conditioned room with relative humidity control. The temperature is maintained at 73'22°F and the humidity at 45&5 pct. The air conditioning serves as a precaution to minimize the amount of adjustment and calibration needed during operation. It also reduces contaminating fumes and dust and thereby lessens the necessity for maintenance on the equipment. The quantometer is composed of three units: the high precision multisource unit, the 1.5 meter vertical spectrometer, and the console. The source unit supplies excitation conditions varying from spark-like discharges to arc-like discharges. The voltage to the source unit is supplied by a motor-generator

Jan 1, 1955

By A. G. Taylor, H. P. Ehrlinger, U. C. Tainton

FOR the last 15 years lead has been the standard material for anodes in electrolytic zinc production and it has been generally accepted that this lead should be as free as possible from impurities. Laistl says, "Next in importance to the purity of solution is the purity of the electrodes and tank lining material. The purest lead obtainable should be used for anodes." The same conclusion is expressed by Ingalls2 and by two German investigators who say that experiments have demonstrated that the purer the lead, the greater is its resistance to corrosion during electrolysis.3 Pure lead, however, while the best material hitherto available for anodes, is not entirely free from objection. The plain lead anode gradually disintegrates under electrolysis, so that the life of an anode, say 1/4 in. thick, is frequently not more than two years. Part of the lead from the anode finds its way to the cathode, lowering the purity of the deposited zinc and decreasing the hydrogen overvoltage. The rest of the lead that comes from the disintegration of the anode goes into the manganese dioxide which is precipitated in the cells, rendering unsaleable what might otherwise be a valuable by-product. Yet a further disadvantage of plain lead anodes comes from their tendency to bend or buckle during electrolysis, as a result of intercrystalline oxidation. This makes it necessary to use a fairly aide spacing between anode and cathode to avoid short circuits, and thus leads to a higher power consurnption than would otherwise be necessary. The power consumption is also affected by the high decomposition voltage at a lead peroxide surface.

Jan 1, 1929

By Nelson P. Hulst

To those who have had the happy privilege of friendship with George W. Goetz, the announcement of his death has brought great sadness. He was born in Milwaukee, Wisconsin, February 17, 1855, and died January 15, 1897. In his boyhood days, when I first came to know him, his frank, trustful manner; his eyes brimming with truthfulness; his eagerness, never obtrusive, to gain knowledge from all whom he met; and his equal readiness to give without ostentation of his store, constituted a personality which at once commanded confidence and won friendship. I am told that as a scholar of five years he was conspicuous for brightness, a show-pupil, who was called on to recite when visitors were present at school. Yet this in no way spoiled him. His modesty was too strong a trait in his character to be overcome by any attention which might, be expected to arouse vanity. In his simple-heartedness he was pleased then, as he always was in his maturer years, to give of his knowledge for the gratification of his listeners, with never a thought of himself. So strong was this characteristic that in a brief autobiography, in the form of a letter to his wife and children, found among his papers, he excuses himself to them for recounting what he had accomplished in his life-work. As a preface to this autobiography (which, it seems, was prepared on the eve of a sudden journey to California, taken February, 1895, for his health) he says: " I am writing this rather hastily, and I

Jan 1, 1898

The paragraphs quoted, regarding Mr. Hoover's appointment as chairman of the newly organized food board of the United States, are taken from the editorial page, of the New York Times for April 13: ?The country is fortunate in commanding the services of Herbert C. Hoover as Chairman of the newly established Food Board. This is n, problem of first importance. Few realize the extent to which American food stuffs will enter into the decision of the war, and it is doubtful if it has occurred to many minds as yet that we shall have to deny ourselves what we have regarded as necessaries in order to keep our European allies supplied. " Mr. Hoover is one of the leading mining engineers of the country. At the outbreak of the war he put his private affairs aside to become the head of the American Commission for Relief in Belgium. He has had an experience that perhaps no other man has ever had, covering the raising of money and the purchase and distribution of supplies on a large scale; He has been brought into close relations with the neutrals and the belligerents on both sides. By them all he is recognized is one of the best executives brought to the fore by the mar. Mr. Hoover is in a position now to place abilities and experience at the service of his country. He will come back with comparative data that will enable him to measure resources and deficiencies accurately. This appointment gives renewed assurance of our Government's grasp of the problems of war and its resolve to apply, business principles to their solution."

Jan 5, 1917

By Frank Corwin

It is the purpose of this article to give a brief account. of the experimental work and to show how the increase in efficiency was brought about. Part of the experimental work described in this paper was carried out by the writers, while in the employ of the Anaconda Copper Mining Co., under the direction of M. W. Krejci, Metallurgist, and Arthur Crowfoot, Chief Sampler. Complete records of all of the MacDougall testing work have been placed at our disposal through the courtesy of A. E. Wheeler, Superintendent. II. BRIEF HISTORY OF PRESENT MACDOUGALL PLANT. The first change from the Brueckner cylinders used for roasting concentrates at Great Falls was the construction of a MacDougall roaster of the Herreshoff type. This furnace was first started on June 15, 1898. It bad eight hearths, was lined with fire brick, and had an air-cooled central shaft, but no provision was made for cooling the rabble arms. It was operated for a while, and accomplished the work of roasting, but ran so hot that the rabble arms became twisted and distorted out of shape. To prevent the furnace from becoming too hot a device was then installed to draw the heated gases away from the hearths. This consisted of a pipe connected to alternate hearths of the MacDougall furnace and also connected to the flue. It was equipped with dampers, 'so that the hot gases could be drawn away from any one of the alternate hearths directly into the flue.

Jan 7, 1913

By J. E. Johnson

The description of the machine which coilstitutes the subject of this paper is best iutroduced by a statement of the conditions which led to its construction, which may be briefly given as follows : The ore handled at the plant to be here described* is of the variety sornetimes called by those familiar with the brown ores of the South, " Mountain," as distinguished from the " Lime-

Jan 1, 1899

H. D. HIBBARD, Plainfield, N. J. (written discussion *).-While this valuable and timely paper may not go to the root of the matter, it deals with many of the elements and factors involved. It might be taken as the engineer's solution of the case, starting with the assumption that steel is steel, while the tendency for a rail to have transverse fissures may, and probably does, depend, in part at least, on conditions met before it reaches the track. Admitting with the author that "brittleness of fracture in all grades of steel is characteristic of fatigue tests" we may yet look farther back to find out, if possible, why some rails and some steels are more prone to have transverse fissures than others, for it has been found that rails from certain heats of steel developed these fissures under a service which

Jan 3, 1918

By CHARLES F. RAND

PRESIDENT CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N.. Y. FIRST VICE-PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER. W. RAYMOND, NEW. YORK; N. Y. SECRETARY BRADLEY- STOUGHTON NEW YORK, N. Y.

Jan 2, 1914

By A. O. Bartell

Do you know that valuable clues to the geology and mineralization of a district can be found in a handful of sand from a stream bed draining the area? This handful of sand has a story to tell to those who have a little patience. The handful of sand may contain tiny specks of valuable minerals (gold, scheelite, cinnabar, chromite, tourmaline-to mention a few), that will lure you upstream with the hope of uncovering a new deposit. More practically, this handful of sand can indicate the type of rocks that are exposed by the drainage system. Any mineral that has a specific gravity of 3.5 or higher can be separated from soil by panning. Garnet and pyrite, for example, can indicate an outcrop of metamorphic rock. In one district where the writer prospected, small boat-shaped orthorhombic crystals of topaz always indicated the presence of andesite outcrops.

Jan 1, 1948

By Albert Sauveur

THE senior author of this paper has expressed the belief that when gamma iron transforms into alpha iron on reaching the A3 point, each gamma grain does not change bodily into one or more alpha grains but that the alpha phase forms first at the boundaries and along the crystallographic planes of the austenite grains.1 To quote: On cooling through the point A, at about 900° C., iron passes from the gamma condition to a. new allotropic form generally designated as alpha. This transforma¬tion, however, is not instantaneous. There are good reasons for believing that it begins at the grain boundaries and along the octahedral planes of the crystals and that it progresses until each grain of gamma iron is changed into a grain of alpha iron, the resulting structure being similar to that of gamma iron. Were it possible to retain at room temperature pure iron but partially transformed, it seems probable that a Widmanstättian structure, or rather, as later explained, a martensitic structure would be observed (Fig. 1), consisting of alpha iron at the boundaries and at the octahedral planes, and of a groundmass of gamma iron. In order to confirm, if possible, the accuracy of that view, a number of experiments were conducted. Polished samples of electrolytic iron were heated in a vacuum, maintained in the gamma range for several hours and quenched in different media. It was hoped by such means to produce and retain on the polished surfaces a pattern which would reveal the mechanism of the allotropic transformation. The samples were placed in evacuated quartz tubes, heated to 1000° C. and held 2 hr. at that temperature. The tubes were then immersed in the quenching bath. Iced brine and liquid air were used first. The polyhedral austenitic structure existing at the time of immersion was very clearly revealed (Fig. 2). This is generally ascribed to iron volatilizing at the grain boundaries.

Jan 1, 1929

By J. B. Newkirk, A. H. Geisler

The alloy Cu4Pd has a disordered face-centered-cubic structure when quenched from temperatures between 478ºC and the melting point (about 1100°C). Below 478ºC an ordered phase is stable. The results of a Debye-Scherrer X-ray analysis indicate that the ordered phase has a tetragonal unit cell described by the space group C24h — P42/mt with 2 Cu in 2a, 2 Cu in 2f, 4 Cu in 4j (x = 0.2, y = 0.6), 4Pd in 4j (x = 0.4, y = 0.2), and 8 Cu in 8k (x = 0.1, y = 0.3). The orientation relationship between the face-centered-cubic phase and the ordered tetragonal phase is given by: [100],,. // [130]al,. COO1Ia.d.//COO1I,,.. • The behavior of Cu,Pd is typical of ordering alloys except that the transformation is very sluggish. The increase in hardness and the microstructural and X-ray diffraction effects are interpreted in terms of coherency strains caused by the ordering. AN anomalous construction in the Cu-Pd phase diagram (Fig. 1) was reported in 1939 and has been allowed to stand without further published attention since that time. The odd figuration about the composition 10 to 27 atomic pct Pd is derived mostly from the work of Jones and Sykes.1 Evidently several features of this binary system require further study if the constitutional forms are to be well understood. The present paper includes a study of one of these features, that is, the crystal structure of a single ordered alloy containing nominally 20 atomic pct Pd. This choice of composition was suggested by the work of Harker and associates who determined the structure of Ni4Mo2 and Ni4W.3 The nature of the ordering process in Cu4Pd was studied also by observing the hardness, microstructure, and Debye-Scherrer patterns of specimens which had been aged at various temperatures after quenching from an initial disordering treatment. Experimental Methods A 20 gram ingot of Cu4Pd was made by melting spectrographically standardized copper from Johnson, Matthey, and Co., and commercially pure (99.5 + ) palladium in an argon-filled quartz tube. Chemical analysis showed that the ingot contained 80.0 atomic pct Cu. The ingot was rolled about 60 pct to a strip 0.060 in. thick and was homogenized for 16 hr at 950°C in low pressure argon. Rods cut from the rolled strip were worked into wire 0.015 in. in diameter, and specimens for hardness and microscopic examination were cut from the remaining strip. All specimens, with the exception of some of the wire, were given an initial disordering treatment by heating for 16 hr at 950°C, followed by water quenching. A 10 cm length of as-drawn wire was water quenched after being held in a temperature-gradient furnace4 for 89 days. Room-temperature Debye-Scherrer photograms were then made at points along the wire to determine the temperature below which the ordered phase was stable. Although the accuracy of temperature determination in the gradient was only about ±10 °C, the temperature gradient was sufficiently gradual that the sensitivity was much better and locations which had differed by as little as 1°C could be distinguished. An analysis of the crystal structure of the well ordered alloy was made by X-ray diffraction using a specimen cut from this wire. The change of Debye-Scherrer pattern as ordering progressed was studied by using isothermally aged samples of initially disordered wires. The wires were sealed under low-pressure argon in small quartz tubes for heat treatment. After the aging treatment, the tubes were quenched in water and photograms were made at room temperature in a 10 cm diam camera using filtered Cu kX. (A = 1.540511) Hardness was measured on a Vickers hardness tester using a 10 kg load and 2/3 in. objective lens. Reported values are the average of at least three impressions made on flat specimens 0.060 in. thick. After the hardness of a heat-treated sample had been measured, it was resealed in low-pressure argon and returned to the furnace for continued aging at the same temperature. In this way, two samples served for all aging times at each temperature. Hardness specimens which had been aged 500 hr or more were used for metallographic examination after the final aging treatment. A dilute potassium-dichromate etching solution was used.

Jan 1, 1955

By Paul Billingsley

WHEN I was an undergraduate at the Columbia School of Mines, the mining curriculum was subdivided into two major branches's known respectively as the Metallurgical and the Geological Options, which diverged rather widely as the course progressed. When I duly elected the Geological Option, I believed, I am sure, that this divergence would continue throughout the years. The facts have proved otherwise. The mining industry is a closely knit entity in which the search for its raw materials, called mining geology, cannot be separated from the conversion of these raw materials into marketable form, called metallurgy. The mining geologist searches for materials which the metallurgist can utilize, and only such; and whenever an advance in metallurgy opens the gates for new materials, the geologist's problem is correspondingly modified. No better instance of this relationship can be given than that seen in the Salt Lake region in recent years. Our mineral industry here is of long standing. The three principal tributary districts, Bingham, Park City and Tintic, were discovered in the 1860's and have been vigorously and intelligently developed for many decades. Their production has made the Salt Lake valley one of the world's great smelting centers. The maintenance of this industry has for years depended upon the continual development of new orebodies to take the place of those being extracted. Intensive exploration in the old districts has been supplemented by prospecting in outlying districts of lesser prominence. . Many new orebodies have been discovered, such as those of the Daly West, Silver King, and Judge mines in Park City, the Utah Apex in Bingham, and the Sioux, Colorado Chief Consolidated and Tintic Standard in Tintic. New mines in other districts have been discovered also, but without affecting the dominance of the three major districts. In all cases discoveries, to be of value, had to be of ore amenable to treatment in the available metallurgical plants. This meant that, for the most part, zincy ores, both oxide and sulfide, must remain untouched, and also that ores high in iron and ores high in silica had a fictitious value, either high or low, set by the balance of these

Jan 1, 1928

Note by the Secretary.-—In the preceding communication of Mr. Rickard, in the present discussion, as printed in Trans., xxiii., the loss of quicksilver at Pestarena, reported on p. 569, as 230 and 234 grammes per metric ton, is stated as equivalent to about 74 pounds per short ton avoirdupois—an obvious error, which escaped correction in my reading of the proofs, and was not discovered until after Vol. XXIII. had left the press. The true equivalent is 0.46 pound or about 7 1/2 ounces (instead of pounds) per short ton.— R. w. R. Philip Argall, Denver, Colo. (communication to the Secretary) : Mr. Rickard's last contribution to this discussion* calls for some reply from me, if only by way of defending myself against the charge (p. 569) that my criticisms of his paper were "unnecessarily hypercritical and occasionally unfair." At the same time I am fully aware that our Transactions are not the place for mere personal controversy, and that the sole object of discussion is to define differences of opinion, and defend opposing views as a means of eliciting the truth. Mr. Rickard disclaims the statement, which he says I attributed to him, that in the slow-crushing Gilpin county mills the pyrites remain longer in the mortar than the other portions of the ore. My understanding of his statement was based on the following passages in his paper: " Particles of ore, which have heen pulverized to a fineness which would permit of their exit through the screen, are enabled to settle towards the bottom of the mortar. It would he expected that the heavy metallic minerals occurring in the ore would, because of their greater specific gravity, be most affected by this feature of the treatment. In practice this is found to be so. The fine slimes contain a large proportion of metallic sulphides, generally valuable on account of their close association with the precious metals, while the coarsest particles to be found in the tailings usually consist of quartz and other minerals forming the less heavy gangue (Trans., xxiii., 139).

Jan 1, 1895

James W. Malcolmson died suddenly on Dec. 26, 1917, at Kansas City, Mo., where he had made his home for the past ten years. He was born at Dover, Kent, England, on Oct. 6, 1866. He graduated from the Royal School of Science, London, England, in 1889, and almost immediately after graduation came to Mexico, accepting a position with the Michoacan Railway and Mining Co., as mining and mechanical engineer. His work in the mining profession was carried on principally in Msxiac and the United States. • In 1888, he married Katherine Haden Krause, of Woolwich, Kent, England, and leaves, besides his wife, five sons and one daughter. During Mr. Malcolmson's long and successful career as a mining engineer, he was connected with the following companies: from 1889 to 1893, with the Michoacan Railway and Mining Co., as mining and mechanical engineer; from 1893 to 1898, in various capacities with the Kansas City Smelting & Refining Co.; after the consolidation of the Kansas City Smelting & Refining Co. with the American Smelting & Refining Co., he remained as manager of the mining department in Mexico of the American Smelting & Refining Co. until 1902. In 1902, he located in El Paso, and took up the practice of his profession as a consulting engineer. While there, he was consulting engineer for the famous and rich Pedrazzini mines at Chispas, in the State of Sonora. He was instrumental in organizing the La Republics mine in Chihuahua, and for a time acted as consulting engineer for the property. He remained in El Paso until 1907 and then moved to Kansas City and became associated with the United States & Mexican Trust Co., as consulting engineer. In 1909, he became connected with The Lucky Tiger Combination Gold Mining Co., as its consulting engineer, and continued in this connection and in the general practice of his profession as consulting engineer until his death.. His general policy in connection with the Lucky Tiger company was always a progressive one and the success of the enterprise can be largely attributed to him and his good judgment. Mr. Malcolmson contributed several articles to the Institute at different times, one of them being on the ore deposits of the Sierra Mojada Mining District, in 1901. Much of his work was in Mexico, and during his long residence in that country he acquired a very thorough knowledge of the Mexican people and their customs. During the revolution, from 1910 to 1916, this knowledge was of great value in connection with his work for the Lucky Tiger company, and often assisted greatly in keeping the property going. Mr. Malcolmson was one of the very widely known men in his profession; he was everywhere held in the very highest regard, and his position among men in the mining profession was an enviable and honorable one. At the time of his death, besides being consulting engineer for the Lucky Tiger company, he was interested in mines in the Miami zinc fields and was acting as consulting engineer for two of the operating properties there. He invested to quite an extent in real estate when he moved to Kansas City in 1907 and his investments in this line proved successful.

Jan 1, 1920

By C. B. Post, G. V. Luerssen

It is generally recognized that non-metallic inclusions in steel come from two principal sources. First are the chemical reactions in the furnace, or in subsequent deoxidation, resulting in slag which does not free itself from the metal. Much information has been published concerning these chemical reactions and their control through proper attention to slag viscosity, composition of deoxidizers, and other qualities. The studies of this subject by C. H. Herty, Jr. and others through the medium of physical chemistry have yielded much information for the steelmaker. The second source is erosion of ladle refractories, such as lining brick, stoppers, nozzles and runners, causing entrapped particles of globules of fluxed silicate material. In contrast with the large amount of information available on the first source, relatively little has been published on the subject of erosion which, in the case of basic electric melted steel, is the principal source of nonmetallics. This is probably due to the fact that the problem was assumed to be one of simple mechanical erosion, which could be solved primarily by modification of ladle practices. Good improvements have been made by elimination of slurries in the ladle, better ladle and runner refractories, and more attention to pouring temperatures. It is doubtful, however, that this problem has been recognized in its true light since it is not one of simple mechanical erosion but rather one of chemical reaction between the metal and the refractories; and in this sense is as much a problem of physical chemistry as the reactions involved in the actual steelmaking process. The influence of ladle refractories on the resulting cleanness of steels was early recognized by A. McCancel who examined large inclusions in steels made by both acid and basic practices. His chemical analyses showed the large influence exerted by the manganese content of the steel on erosion of the ladle and nozzles used in those days. The presence of MnO in such inclusions led McCance to the hypothesis that both basic and acid steels react chemically with the ladle refractories so that small globules of fluxed refractories are carried in the stream into the molds. This early work of McCance was checked by one of the present authors on basic electric bearing-steel, and it was found that on steels containing as low as 0.40 pct manganese the fluxed surface of the ladle lining after delivering such a heat showed as high as 25 pct MnO by actual analysis. Furthermore, by lowering the manganese content of the steel to 0.20 pct, ladle erosion was decreased with a corresponding decrease in silicate inclusions in the steel. Limitations placed on the manganese content for the required inherent properties made it impossible to pursue this line further, and subsequent attention was concentrated on improved ladle refractories, care in keeping the ladle clean and free from loose refractories up to the time of tapping, and pouring the steel at optimum temperature. Our study of the chemical reactions at the metal-brick interface between steel and ladle refractories was revived in 1939 as a result of an experimental observation made on the cleanness of alloy steels of the SAE types. This observation showed that the relative cleanness of such steels made in basic electric arc furnaces of 12 ton capacity and poured in ingots ranging from 1100 to 2200 lb weight was determined to a large extent by the ratio of the manganese and silicon contents, provided other steelmaking variables such as tapping temperature, pouring temperature, pouring time, amount of aluminum added for grain size control, and degree of deoxidation in the furnace were kept reasonably constant. Detailed studies made on the deoxidation and slag practice during the refining period of basic electric furnace practice showed that these two variables exerted some influence on the resulting cleanness of steel in the form of bars and forgings. The important variable, the manganese-silicon balance, was not apparent until heats were made in succession by the best furnace practice kept under fairly rigid metallurgical control. Another observation pertinent to this work concerned the similarity in the microscope of slag particles causing magnaflux or step-down indications in subsequent rolled bars, and the patches of slag frequently seen on the surface of ingots. These patches are generally believed to come from the glassy metal-brick interface in the ladle and represent an entrapment of such glass (both from the ladle brick and nozzle) in the metal as it flows over the refractories in the neighborhood of the nozzle. These glassy particles are carried down into the mold with the liquid steel, and gradually coalesce into a slag "button" which floats on the surface of the steel as it rises in the molds. Periodically the button is washed to the side of the ingot where it is trapped between the surface of the ingot and the mold, later appearing as a slag patch on the surface of the ingot after stripping. Even though most of the small glassy particles coalesce into a slag button while the ingot is being poured, it is logical to suspect this step in the steelmaking process as being a source of slag lines large enough to cause trouble

Jan 1, 1950

By J. Chipman, G. G. Hatch

T. ROSENQVIST*—It is a pleasure to see the excellent way in which the experimental part of this work has been handled. There seems to be little doubt that the distribution data obtained corresponds most closely to thermodynamic equilibrium under the prevailing reducing conditions, namely equilibrium with graphite and one atmosphere CO pressure. The desulphurization curves in Fig 10 show the same general feature as the curves given by Holbrook and Joseph, but the distribution ratios are from 20 to 40 times greater—undoubtedly due to a closer approach to true equilibrium. In the theoretical discussion, the authors calculate a theoretical distribution (S) ration -jg-. which they find to be about 50 times greater than the experimental. The deviation is so great that the basis for their calculation needs a more thorough examination. The authors base their thermodynamic calculation on free energy expressions where diluted solutions of FeS and CaS are used as standard states. (The activity coefficient in diluted solutions is taken to equal unity.) Such a standard state will change when the nature of the solvent is changed. Taking the free energy of the reaction [FeS] ? (FeS), Eq 2, which is derived from the distribution of sulphur between an iron and a FeO-melt, it is very unlikely that the free energy of this reaction will be the same for a distribution between pig iron and a calcium silicate slag. Therefore a more fundamental basis for the thermodyuamic calculations seems needed, where all thermodynamic equations are referred to unambiguously defined standard states. The most natural standard states for CaO and CaS are the pure solid substances at the same temperature. As standard state for sulphur in iron, pure liquid FeS can be used. This rules out Eq 2 [FeS] ;=s (FeS) because ?F° = 0. The standard equation will then be: FeS, + CaO6 + Cgraph ?Fei + CaS8 + CO. vFo1773 = 25,000 cal It would be more universal and also simpler to refer the escaping tendency of sulphur in liquid iron to the corresponding H2S/H2 ratio which can readily be determined experimentally. As standard state a gas mixture H2S/H2 = 1/1 can be used. (This corresponds at the temperature of liquid iron closely to one atmosphere S2 vapor.) Thus the standard equation for the sulphur reaction can be formulated as follows: H2S0 + CaO3 + Cgraph ?H2o + CaS8 + COg The standard free energy of this reaction has been calculated from the best available data to AF°m3 = —35,000 cal. This gives for the equilibrium constant at 1500°C Now, the solubility of CaS in blast furnace slags has been determined by McCafferey and Oesterle* and corresponds at 1500°C to about 10 pet S (varying somewhat with the composition of the slag.) If the activity of CaS is assumed linear between 0-10 pet as curve 1, (see Fig 11), then acaO = 0.1 (S); (S) being wt. pet sulphur in the slag. For a diluted solution of sulphur in an iron melt saturated with carbon, the ratio H2S/H2 is, according to Kitchener, Bockris and Liberman,f about 0.01 [S], [S] being wt. pet sulphur in iron. Substituting these values in the expression for Kp we find The value 2.103 is only 4 times greater than the experimental coefficient found by Hatch and Chipman, but the value is very sensitive to a small error in AF°. A better agreement with the experimental distribution coefficient can be obtained if one assumes the activity of CaS to run like curve 2 (Fig 11). This (S) will give a lower theoretical W, value, a value which varies with (S) exactly as Hatch and Chipman learned. Such a shape of the activity curve, which corresponds to a positive deviation from Raoult's law, is actually to be expected from the fact that liquid silicate and sulphide phases usually show incomplete miscibility. A closer agreement between experimental and theoretical data can not be expected before we have more complete data for the individual activities of CaS and CaO in the slag. The activities acaS and Ocao referred to the solid phases as standard states, are exact defined quantities contrary to the somewhat undefined expression "free lime," and they are independent of any theory for the constitution of liquid slag. J. CHIPMAN (authors' reply)—The authors wish to thank Mr. Rosenqvist for his very interesting and useful thermodynamic addition. Curve 2 of his figure offers the needed basis for explaining the increase in the ratio (S)/[S] with increasing sulphur content. Attention is called to an error in the printed paper: Fig 2 and 3 are reversed. M. TENENBAUM*—In the figures showing the relationship between excess base and sulphur distribution (Fig 6, 7 and 9) the slope of the curve tapers off in the negative basicity range. Somewhat the same thing is observed with open hearth slags. In that case, the fact that some sulphur distribution between slag and metal is obtained with negative basicity is interpreted as indicating some dissociation of the lime silicate compounds whose existence in oxidizing basic slags has been used to explain various observed phenomena with regard to other slag-metal reactions. In the case of the blast furnace slags, the reduced slope of the sulphur distribution curve with decreasing excess base is attributed to the amphoteric effect of alumina. Has the possibility of other explanations been investigated ?

Jan 1, 1950

By AIME AIME

WEDNESDAY night, by long tradition, is al- ways set aside for the annual dinner, even when, as it was this year, it is Ash Wednesday. Whether the somewhat smaller attendance than last year is attributable to that cause, the unexpectedly long persistence of business depression, or whatever may have been the reason, it was a joyous occasion, and the grand ball-room of the Commodore Hotel was as completely filled With diners as * was consistent with com- fort. In the half hour before the dinner was actually served the guests assembled in an adjoining room and not only exchanged greetings but proceeded along the receiving line to greet the guests of honor. The number present was so large that hardly more than half of them had been able to do this before the summons to the dining room sounded and a hearty and immediate response was made to it. Toy balloons at each plate, inflated and directed at the heads of companions or nearby friends, but which were just as likely to carom from the nose of a hurrying waiter, successfully broke the ice as well as not a few plates. It would be interesting to know whether the pleasure the guests derive from these de- vices is in part based on the all-too evident annoyance of the waiters, and what the relative quantitative relationships are.

Jan 1, 1931

By David V. Ragone, James A. Craig, Richard E. Balzhiser

The Gibbs free energies of formation of UC2 and UC were measured by equilibrating two-phase mixtures of UC2 + C and UC, + UC with liquid bismuth. The measured equilibrium concentrations of uranium in the bismuth combined with available activity coefficient information yielded uranium activities in these two-phase regions. Measurements on UC2 were performed over the range 1015 to 1160 K and on UC over the range 1115° to 1165°K. The values obtained for UC2 are in excellent agveement with values determined using combustton calorimetry and low-temperature heat capacity measurements. The UC values are in fair agreement with the calorimetric values, differing by about 10 pct from the calorimetric determination. MUCH interest has been shown in the uranium carbides in recent years because of their potential as nuclear fuels. As nuclear reactor operating temperatures have been raised to increase thermal efficiency, new fuels have been required. The uranium carbides are of interest because of their high melting points, >2000°C, high thermal conductivity, and resistance to irradiation damage. The manufacture and use of uranium carbides are aided by a knowledge of their stability and reactivity under various conditions. In this regard the thermo-chemical properties of the carbides, i.e., heat capacity, heat of formation, free energy of formation, and so forth, are particularly important. A great amount of work has recently been done on the thermodynamics of the U-C system. Unfortunately, however, there has not been good agreement among the various investigations. This study of the free energies of formation of uranium monocarbide and uranium di-carbide in the temperature region 1100°-1200° K was undertaken to help clarify the situation. It should be noted that in the temperature range of this investigation, 1100°- 1200° K, the thermodynam-ically stable phase in equilibrium with graphite is U2C3, not UC2, Fig. 1. However, U2C3 is reported to be stable only under extremely low oxygen and nitrogen pressure. Although UC2 is metastable below 150O°C, it exists under most experimental conditions. It should also be noted that "UC," never exists as UC2 but with compositions near UC1.9. However, "UC2" will be used to designate the dicarbide phase except when the stoi-chiometry is necessary for clarity. METHOD The approach taken in this study of the free energies of formation of UC and UC2 was to determine the thermo- dynamic activities of uranium in the two-phase regions UC, + C and UC + UC, by equilibrating the two-phase mixtures with the liquid bismuth. When a mixture of solid UC2 + C is brought to equilibrium with liquid bismuth, the reaction that occurs is: Neither carbon nor UC, could be detected as dissolved material in the bismuth. The standard free energy for this reaction may be written: In the two-phase region UC, + C, Fig. 1, the thermo-dynamic activities of UC2 and carbon are unity. The activity of uranium in this region was determined by measuring the concentration of uranium in a liquid bismuth melt in equilibrium with the two-phase mixture. This concentration was then used in conjunction with the activity coefficient data of uranium in bismuth reported by Tien et al.' to determine the activity of uranium in the two-phase region, UC, + C. All of the quantities in Eq. [2] were then known, and the AG; (uc,) was evaluated. UC + UC2. For the studies involving UC + UC,, the reaction taking place when the two-phase mixture is brought to equilibrium with liquid bismuth is: The standard free-energy change for this reaction is given by:

Jan 1, 1969

By H. S. COOLEY

TO talk about a "factor of economy" in connection with the wire ropes used in mining practice may be coining a new phrase. If such be the case it needs no other apology than that economy in wire rope usage is so bound up with the factor of safety as to justify a similarity in naming that makes one suggest the other. At the latest Wire Rope Research Conference, held under the auspices of the A. S. M. E., Re- search Committee and Engineering Foundation, data were introduced covering mine ropes working under

Jan 1, 1930