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By AIME AIME

THE report of the united. States Steel Corporation for the' year 1928 gives the, following ,figures of raw materials and' finished products . Raw materials, tons :

Jan 1, 1929

By David R. Mitchell, R. M. Fleming

MANY trends were evident in the coal industry during 1951. Some were favorable for the industry; others were not. Probably those having the most far-reaching consequences are those affecting coal's markets. The rapid dieselization of many railroads and the continued trend toward oil and natural gas for home heating has caused serious dislocations in various mining districts. Mines have been forced to close down or to work on a reduced time basis. Conversely the increased activity in the metallurgical industries has increased the demand for coking and special purpose coals, and the growing production of electric energy has increased the demand in certain areas for steam coals. The increased demand for metallurgical coal and for steam raising by the large utilities is more than equal tonnage-wise to the loss of coal to railroad dieselization and conversions to oil and gas in the domestic market. Since much of the expansion is at captive mines of large corporations, many commercial operators supplying railroad and domestic users have had their markets curtailed without any compensating demand from other sources. Feverish activity was in evidence in many areas by commercial operators attempting to find new markets. The Norfolk and Western Railway is the, only major American railroad committed to the burning of coal. It has an exceptionally good cost record. During 1951, fifteen additional modern coal-burning steam switching locomotives were authorized for construction in the company's Roanoke shops at a cost of about $1,450,000. When the new order is completed the road will own a total of sixty locomotives of the modern-switcher type, including thirty acquired by purchase last year. The Norfolk and Western today is the only American railroad building its own motive power. All of these locomotives burn coal. Production Coal production in the year 1951 will approximate 570 million tons of anthracite, bituminous coal, and lignite. Of this, approximately 7 pet is anthracite. Total production is approximately 30 million tons more than in 1950 and reflects the increase in general industrial activity. Exports are expected to be close to 50 million tons. The industrial stockpile is close to 75 million tons, the highest it has been since 1943. With the exception of the usual local stoppages the year 1951 was unmarked by labor disputes. It was a year of good labor-management relations with a negotiated wage increase unmarred by a work stoppage. This may be the beginning. of an era of sensible negotiations to find agreeable settlements of disputes without the usual protracted bickering and industry-wide strike. The United Mine Workers of America has condemned wildcat strikes, stating that in nearly every, instance proper grievance procedures have not been instituted. Government defense organizations, perhaps profiting by their experiences during World War II, are pursuing a more enlightened program with regard to the fuel requirements of the nation. Many prominent officials have stated that wherever possible coal should be considered the primary source of fuel in all defense expansion. With the increased consumption of steel by defense projects, approval of transportation facilities for liquid and gaseous fuels have been refused where these fuels would enter a coal producing area. Liquid and gaseous fuel producers also have failed to provide satisfactory evidence that they have sufficient reserves and are capable of supplying their product in adequate amounts for the periods of time required. Realization has at last become prevalent that the hydro-electric power installations in several areas are insufficient to handle increased demands.' Steam generating plants are being constructed in these areas and equipped to burn coal. Most notable of these, is the TWA area whose supplemental steam power plants are expected to consume 10 million tons of coal per year when completed. The Pacific Northwest is another area which is expected to follow the same pattern. Nearly all new steam-power generating plants are being equipped to burn coal either as a primary fuel or as an emergency measure. Metallurgical Coal The steel and other metallurgical industries are expanding rapidly to meet increased industrial demands and defense orders. Since these industries are dependent on coke, coke has had a year of high production and can be expected to break all existing records when steel-plant expansions are completed. Most notable of the expansion projects is that of the Delaware River area where the iron ore will be received by ship from Canada and South America. U. S. Steel is only one of several steel corporations that are planning on putting integrated steel producing units in this area. The Defense Solids Fuels Administration announced in December that through. November 30, 1951. 29 projects in eight states, with a total cost of

Jan 1, 1952

By Michael J. Callow

THE PROPERTY of Mount Isa Mines, Ltd., is located at Mount Isa, Northern Queensland, Australia, at roughly 20" south latitude. It is 600 miles from Townsville on the east coast, the port for Mount Isa, 1200 miles from Brisbane and approximately 1600 miles from Sydney in New South Wales. Living conditions in the camp, though wild and crude at the commencement of building, are now excellent and little has been left undone to provide comfort and attractiveness. The climate being warm and dry, many of the buildings are built on posts, 8 to 10 ft. off the ground, with spacious screened-in verandas. Club houses, stores, school, hospital and ice plant have all been provided by the company as well as modern conveniences, such as running water, shower baths, electric lights, septic tank arrangements, tennis courts and amusement grounds.

Jan 1, 1932

By R. W. Diamond

Low-grade ores can be designated by two main classifications: (1) simple low-grade ores, and (2) complex low-grade ores. As a rule the first type has a relatively small metal content, although low- grade iron ores contain a rather high percentage of metal. As the simple type is the one that is ordinarily in mind when the term "low-grade ore" is used, the paper will be devoted mainly to ores in this general category. Cheap treatment is the prime requirement in utilizing low-grade ores of the simple type, although in some cases the value of nonmetallic by-products, such as limestone for fer- tilizer and silica for flux, allows a little more lati- tude than in the usual situation. When the costs are divided under the three headings-mining, milling, and smelting-it is apparent that the last group will not constitute an important factor as a rule because the high concentrating ratio makes the smelting cost per ton of ore fairly low.

Jan 1, 1949

By Ravitz, S. F

76-B Unpublished manuscript. Not available in printed form. An experimental and Theoretical investigation of Quantitative Microscopic Mineralogical Analysis. By S.F.Ravitz and H.A.Steane. Manuscript in Engineering Societies Library.

Jan 1, 1935

By E. A. Cisney

The formula for calculating the crystallographic angles of a tetragonal lattice is: C°S =where $ is the angle between planes (HKL) and (hkl). The angles in Table I have been calculated for indium

Jan 1, 1960

By O. M. Schaus

REDUCED activity of mining, because of the business recession, had the effect of lowering working time, hence of reducing exposure to accidents, so it is probable that 1938 will be found to have had a lesser number (both fatal and nonfatal) though the accident rate may remain about the same as in 1936 and 1937. During periods of re-employment, such as occurred during 1936, 1937, and 1938, the new men entering the industry are less experienced and not as well trained in accident prevention as are the older, more experienced men and are frequently subject to more accidents. This situation should tend to correct itself as the new employees be- come better trained.

Jan 1, 1939

By B. R. Palmer, G. Gutierrez B., M. C. Fuerstenau

Selective flotation in nonmetallic systems is often complicated by the presence of iron-bearing silicates occurring as gangue. Minerals such as augite, diopside, hornblende, and tourmaline respond readily to flotation under the same conditions as ore minerals. Mechanisms by which these minerals respond to flotation with anionic collectors must be established if selective separations are to be made in these systems. It was the objective of this investigation to determine the mechanisms involved in the flotation of two pyroxenes, augite and diopside, with potassium oleate. Experimental Materials and Methods Pure potassium oleate, prepared by neutralization of oleic acid with KOH, was used as collector, while reagent-grade HC1 or KOH were used for pH adjustment. Conductivity water, made by passing distilled water through a mixed-bed ion exchange column, was used in this investigation. Two pyroxenes, [ ], were involved in this work. One member of this class of minerals was augite and was found to contain 3.3% calcium, 4.6% iron, and 9.6% magnesium. The source of this mineral was Tillamook County, Ore. The other pyroxene involved was diopside which contained 8.3% calcium, 2.7% iron, and 7.6% magnesium. The source of this sample was Bancroft, Ont. Microflotation experiments were conducted with a Hallimond cell. Mineral samples were ground dry and sized to 100 x 200 mesh. One-gram charges were conditioned for 3 min in the presence of various additions of potassium oleate. Flotation was conducted for 1 min with a nitrogen flow rate of 50 cm3/min. The electrophoretic mobilities of these two minerals were measured with a Zeta Meter in the absence and presence of [ ] salts and in the presence of an indifferent electrolyte, NaC1, added to maintain ionic

Jan 1, 1978

By C. M. Nickerson

IT is apparent that repressuring of the oil measures is becoming increasingly important to the oil industry, and is a matter that warrants the best efforts of the petroleum engineer charged with applying this method of operation to a producing property. Considerable attention has. been directed to repressuring in various California oil fields, such as Dominguez and Seal Beach, which have served to sell the more progressive operator on this idea and also to keep him sold. The projects that have received most attention are in comparatively young fields where the fluid levels are high, the wells, perhaps, still flowing, where the wet gas production is of considerable volume, and where there is vital need of immediate conservation of gas, which otherwise would be blown to the air. The new State of California Gas Law, which prohibits the waste of gas, has served to interest the oil industry in -means of conserving the gas that is now being blown to the air because of lack of markets. This vitally affects the operator in the older, well-depleted oil fields of the state, because in many cases he has a limited market for gas, on account of the flush production from the more active oil fields. While the waste of gas is relatively small in these older fields, such as the Midway-Sunset area, it now attains considerable importance, since under the new State Gas Law it must be put to some beneficial use. Repressuring in the older fields of California has not received the attention of the petroleum engineers that is warranted by the present situation. This paper was prepared with the view of presenting the salient features connected with repressuring in the well-depleted oil measures of the older fields, and to show what results have already been obtained in these fields by injecting the unmarketable. gas into the sands, particularly in the Midway-Sunset field in the San Joaquin Valley of California. Other projects in the older fields of the state offer some supporting data in this connection, such as the Shields Canyon and the Brea Canyon fields.

Jan 1, 1929

University of Alaska College, Alaska Mining Society (Inactive) H. G. WILCOX, Faculty .Sponsor University of California Berkeley, California Mining Association. OLEG D. SCHERBININ. President CHARLES S. PRATT, Secrctary LESTER C. UREN, Faculty Sponsor

Jan 1, 1944

DAVID THOMAS 1871 R.W. RAYMOND 1872-1874 A.L. HOLLEY 1875 ABRAM S. HEWITT 1876 T. STERRY HUNT 1877 ECKLEY B. COXE 1878-1879 WILLIAM P. SHINN 1880 RICHARD P. ROTHWELL 1881

Jan 1, 1932

By Paul R. La Pointe

GEOTECHNICAL OBJECTIVES OF UCG PROGRAM Underground coal gasification (UCG) is one of several in situ extraction technologies for utilizing deep, otherwise unmineable coal. This technology involves the injection of air or oxygen into the target coal seam, ignition of the coal and recovery of product gases. Geotechnical characteristics of the coal and enclosing rock strata strongly influence the success of this Process. The flame front follows the coal cleats (Hill, 1979), and cleating and bedding control the manner in which coal collapses into the cavity, thereby affecting recovery efficiency (Ramirez and others, 1982). Moreover, coal seams typically behave as fracture dominated aquifers in which cleat orientations govern subsequent contaminant dispersal. For these reasons, the Anaconda Minerals Co. undertook a detailed study of fracturing within the Wyodak-Anderson Coal in the eastern Powder River Basin (PRB) near its Rocky Hill UCG test site (Fig. 1). STRESS HISTORY AND FRACTURING IN THE POWDER RIVER BASIN Vertical jointing, or cleating, in coals may arise from shrinkage shortly after deposition under low confining pressures, or later in time, soon after burial but after the coalification process is well advanced (Ting, 1977). There is much evidence to support the formation of cleating after coalification (e.g. Hawkes and Mellor, 1970; McCulloch and others, 1974), which suggests that the stress state existing at that time strongly influences cleat formation. McCulloch and others (1974) argue that the typically better developed face cleat forms parallel to the plane containing [ol] and [o2]. Where the relation between cleats and stess has been studied (McCulloch and others, 1974; Stone and Snoeberger, 1977; Ward, 1977; Kulander and Dean, 1978), the highly systematic face cleat strongly parallels the [o1] direction. Stone and Snoeberger (1977) report face and butt cleat measurements of N70E and N29W for the Felix Coals 220 m stratigraphically above the Wyodak at the Hoe Creek UCG site (Fig. 1). Structural trends also indicate the past state of stress in the PRB. Glaze and Keller (1963) suggest that the NE-SW regional compression during the late Permian formed major N-S fold lines and basement magnetic anomalies. Mapel (1959) describes folds having N60W and N30W rends in the northern PRB, as well as a large normal fault trending northeast. Glass (1976) also describes normal faults trending northeast. Similarly, Olive (1957) mapped normal faults

Jan 1, 1984

By A. W. Fahrenwald

THE function of the classifier in modern fine-grinding practice is to remove a finished product from the grinding-mill discharge, leaving material that needs further comminution. The classifier, therefore, makes two products: (1) "finished" product, which overflows the rim of the classifier tank, sometimes referred to as "slimes" or as "classifier overflow," and (2) "unfinished" product, which settles to the sloping bottom of the classifier tank and is removed by dragging or raking. This product is generally referred tows "sands" or "oversize." One of the outstanding features of the closed-circuit classifier is its ability automatically to return the unfinished product of the ball-mill discharge to the feed end or scoop box of the ball mill. This is a distinct advantage because it avoids dilution of the ball-mill feed, and, furthermore, the particular method of removing the settled sand, by raking it up the inclined bottom of the classifier, gives a classifier discharge containing a minimum of water. This leads to maximum classifier efficiency, in this type of classifier, because the maximum volume of water is displaced upward by the settling sands. The closed-circuit classifier is required to deliver a finished pulp of closely specified density requirements, therefore added hydraulic water generally is not permitted.

Jan 1, 1930

By ZJ. H. Brophy, A. L. Prill, H. W. Hayden

The effect of Group VIII transition-element additions on the sintering of tungsten powders is shown to be dependent on the phase relationships of the particular tungsten-Group VIII metal alloy system. The acceleration of sintering with nickel additions is diminished by alloying nickel with copper which is known to diminish both the tungsten solubility in nickel and the solid-vapor surface energy. In work previously published on the effects of additions of Ni, Pd, Pt, Rh, Ru, and Ir, which form solid solutions or intermediate phases of wide composition width with tungsten, sintering behavior is independent of element concentration beyond that concentration necessary to form a continuous layer on the surface of the tungsten powders employed. The sintering behavior of tungsten with additions of iron or cobalt, which form intermetallic compounds with tungsten, is highly dependent on addition-element concentration. Additions in excess of amounts necessary to form continuous layers lead to successively decreased sintering rates. The effects of certain Group VIII transition metals on the sintering rates of tungsten at temperatures below those at which a liquid phase would be predicted have recently been investigated by the present authors1-4 It was found that small additions of palladium, nickel, rhodium, platinum, and ruthenium accelerate the rate of tungsten sintering. Additions of iridium decelerated the rate of densification compared to that of pure tungsten in the same temperature range. In all cases the rate of densification changed with increasing amounts of these additions, up to those compositions at which a continuous layer was formed on the surfaces of the tungsten-powder particles. The rate of densification was then independent of further increases of the compositions of any of these addition elements. These observations were consistent with a sintering model in which the addition element formed an interface with tungsten in which tungsten dif-fusivity was either greater or less than its grain boundary self-diffusivity. Kinetic analysis of this model indicated that linear shrinkage should vary according to the relation:

Jan 1, 1964

NEW YORK SECTION Executive Committee DAVID H. BROWN, Chairman JOHN H. JANEWAY, Vice-Chairman F E. PIERCE, Secretary, 35 Nassau St., New. York, N. Y. P. A. MOSMAN, Treasurer LEWIS W. FRANCIS BENJAMIN B. LAWRENCE At the meeting of the New York Section held at the Machinery Club on Dec. 8. 1915, the subject was "The Engineer in Modern Warfare, with Especial Reference to the Present European Conflict." Dr. Henry S. Drinker, who is Chairman of the Institute committee on the Engineer's Reserve Corps movement, opened the evenings' talk with a short statement of the aims and advantages of the Students' summer military camps, fostered by the Society of the National Reserve Corps, he being a member of the Advisory Committee of University Presidents. The speakers of the evening were Col. William M. Black and Col. John Biddle, both of the Corps of Engineers, U. S. Army. Col. Black is the

Jan 1, 1916

By R. C. Thompson

THE lead-zinc mill of Phelps Dodge Corporation, Copper Queen Branch, Mines Division, Bisbee, Arizona, is about 3 miles from the main hoisting shafts of the Junction and Campbell mines at Lowell. All the ore treated in the mill is obtained from these two mines. The mill was designed for an all-flotation treatment of 450 tons of lead-zinc ore per day, and has been operated at that capacity since the start of milling operations on Nov. 17, 1945. An expansion program is underway whereby the mill capacity will be doubled, but this article describes only the original program and presents results of the 45o-ton operation. GENERAL DESCRIPTION The milling plant consists of an ore-receiving bin and three steel-constructed buildings housing, respectively, the primary crushing equipment, the secondary crushing equipment, and the ore-storage bins, grinding, flotation, and filtering equipment. The mill site is the one that was used for a previous copper-concentrating plant, which was operated over a period of years and then dismantled. There remained from this operation some milling equipment, a reservoir for mill-water supply, railroad tracks, tailings-disposal ponds, and a steel-constructed building, all of which were incorporated in the design of the present lead-zinc mill. The location plan of the plant layout is shown in Fig I. The flowsheet of the mill is based on the conventional scheme for lead-zinc treatment, however, several innovations were made necessary in order to utilize the existing building. Placing of equipment also was governed by the design of the building; thus making the mill unique in many respects. The following brief description of the mill building as adapted to the flowsheet points out the compactness of the installation and some of its unusual features. The first floor (Fig 2) houses the grinding equipment, with connecting conveyors for ore feeding, also an air compressor, two vacuum pumps, bins for lead and zinc concentrate storage with individual conveying systems for loading the two kinds of concentrates. Filtering of concentrates is done on the second floor, the concentrates discharging directly into the concentrate-storage bins. On this floor are the lead and zinc filters, two diaphragm pumps, sample-filtering equipment, sample-preparation room and a change room for the mill employees. The flotation machines are on the third floor, at elevations allowing a gravity flow of the lead and zinc concentrates to the thickeners. The annex to the building contains a freight elevator and provides space for all reagent mixing and feeding, also storage of reagents and grinding balls. All the water used for milling purposes is pumped from the Junction mine and

Jan 1, 1947

By John Hays, Hammond

IT is both a pleasure and an honor to be a guest of the Institute and I thank you, Mr. President and fellow-members, for giving. me the opportunity of meeting you this evening. My esteemed friend, President Smith, has requested me to do a bit of "reminiscing" as to the earlier years of my career as a mining engineer, which has now covered a period of fifty years. Let me reassure you by promising that my narrative will not include all the experiences I have had over that long period. You will, I trust, pardon what might seem egotistical but I do not see how a personal narrative could well be otherwise.

Jan 1, 1928

By G. H. F. Gardner

The boundary conditions F = 1.0 and 4 = 1.0 (100 per cent) are dictated by the definition of F in the equation 1/F = aFp. These conditions have physical significance as the "limiting conditions" for the observed behavior in systems of dispersed particles. The other boundary conditions, cited by Gardner in his Eq. 3 as applying to this system, have no significance in the systems we studied. Maxwell's equation (Eq. 2) cited in Gardner's comments was developed for and limited to a regular, rather than random, dispersion of spheres which are sufficiently removed from each other so that they do not interfere with current flow about their neighbors. These restrictions also apply to Rayleigh's analysis. The title of Rayleigh's paper cited by Gardner is "On the Influence of Obstacles Arrayed in Rectangular Order upon the Properties of a Medium". He is not discussing randomly dispersed spheres. It might be inferred from Gardner's comments that Rayleigh specifically considered the differential equation (Gardner's Eq. 3). This is not the case. Mathematically, Gardner's Eq. 3 is exactly true for the system to which it applies, however, as both Rayleigh and Maxwell note that their equation for F in terms of F is not for randomly dispersed spheres. At the time we wrote our paper, we were aware of the work of Wyllie and Gregory as cited by Gardner. We cited their work in Ref. 5 of our paper. Our comment on page 287 of the paper about the validity of an m value of 1.3 for spheres with a porosity of 38 per cent remains as our answer to Gardner's question on this point. Our data, at 38 per cent porosity, show that the condition a = 1 and m = 1.3 holds for spheres near 40 per cent porosity.

By K. D. Sheffler, R. W. Hertzberg, R. W. Kraft

The Ni-Ni,Ti lamellar eutectic alloy responds to unidirectional solidification by alig-nment of the platelets of the two phases roilghly perpendicular to the moving solid-liquid interface. X-ray diffraction and zetallographic experimenls show that the following cryslallographic relationships exist in the directionally solidified ingots: lamellar interface w [0001] Ni3Ti 11 (111 }Ni local growth direction (1120) Ni3Ti n (110) Ni These relationships are rationalized on the basis of the crystallography of the constituent phases. In recent years researchers in several laboratories have shown that an aligned or "controlled" micro-structure can be produced in many binary eutectic alloys by forcing the alloy to solidify unidirectionally in an elongated crucible.'-3 It also has been found that a unique crystallographic relationship often develops between the two phases in such a structure.4, 5 Since a parallel arrangement of phase particles in an alloy should, and, in many cases, does, produce unique and highly anisotropic properties, the alloys so produced are of potential interest in a variety of applications. Studies of these alloys are also of interest at the academic level because they help to improve our basic understanding of the way in which metals solidify. This paper reports the metallographic and crystallographic structure of another of these alloys—that between nickel and Ni3Ti. In a separate paper, hot tensile and stress rupture properties as well as deformation and fracture behavior of the same alloy are discussed.19 EXPERIMENTAL DETAILS AND RESULTS General Characteristics of the Eutectic Reaction. Several small exploratory Ni-Ti melts were made to resolve a conflict in Hansen6 over the eutectic composition. The alloy containing 16.4 at. pct Ti, Fig. 1, appeared metallographically to be closest to the eutectic composition, although small dendritic patches of proeutectic nickel are present. The eutectic morphology is lamellar and appears quite sharp and angular, indicating a strong influence of crystallographic factors upon the microstructure. Some of the eutectic nickel platelets are continuous with the primary phase, whereas in hyper eutectic melts a "halo" of nickel generally surrounded the proeutectic inter-metallic platelets, indicating that nickel is the nucleating phase in this eutectic reaction. Extensive precipitation of Ni3Ti has occurred in the primary nickel phase in a Widmanstatten pattern which makes the dendrites difficult to differentiate from the eutectic mixture. This phenomenon may account for discrepancies among the eutectic compositions reported in the literature. The sloping solvus line bounding the nickel primary solid solution explains the presence of the intermetallic precipitate. Poole and Hume-Rothery7 report that the solubility of titanium in nickel drops from 13.8 at. pct at the eutectic temperature (1304°C) to approximately 9 at. pct at 700°C (Ni3Ti, on the other hand, melts con-gruently and exhibits essentially no solubility for nickel or titanium). Lever rule calculations based upon Poole and Hume-Rothery's phase diagram indicate an increase from 21 vol pct Ni3Ti in the eutectic mixture at the eutectic temperature to 61 pct at room temperature. Selective point count measurements of the volume fraction of eutectic Ni3Ti platelets in the eutectic microstructure yielded a value of 46 i 2 vol pct, which required extensive precipitation of Ni3Ti from the nickel solid solution onto the eutectic intermetallic platelets during cooling from the solidification temperature. Influence of Directional Solidification. Nickel bar and titanium sponge of 99.9 pct purity were induction-melted in zirconia crucibles under argon in the proportion of 13.8 wt pct (16.4 at. pct) Ti to produce 14-lb master heats which were cast into investment molds yielding 5/8-in.-diam pins approximately 10 in. long. These pins were remelted under argon in horizontal zirconia boats and unidirectionally solidified to produce 1/2-in.-sq ingots approximately 44 in. long. Details of the experimental techniques and apparatus are described elsewhere.'

Jan 1, 1970

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4'6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969