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By Alan Stanley

THE MacIntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.' Pigment plant production demands that the MacIntyre mill produce a 44.7 pct TiO, ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the MacIntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from • one level to the next. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO, has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO, has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the MacIntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO, was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiOz a constant gravity would invariably be obtained, and as the TiO, value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct Ti02 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO, value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO, and as the specific gravity increased the trend was for the TiO, assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1953

By Andrew Corry

GEOPHYSICAL investigations based on radioactivity have been applied to the earth's crust for the purpose of discovering bodies rich in radioactive substances, or for the location of solutions with high emanation or radioactive-salt content, or for the detection of oil, which, in virtue of colloidal properties, has strong powers of radioactive absorption. RADIOACTIVE SUBSTANCES Radioactive substances are distributed in all rocks, waters, and gases in the earth's crust in small quantities. Granites and similar acidic rocks are richest in uranium and thorium, two chief radioactive substances; yet the quantities present in such rocks are of the order 10-12g., this concentration being expressed in grams per gram of the whole substance per cubic centimeter. In granites the uranium yields, according to Haddock, 3 X 10-12 g. of radium per gram of rock. In basalts the uranium yields 1.19 X 10-12 g. per gram per cubic centimeter. Of thorium the granites yield -2 X 10-5 g. per gram of rock; the basalts, 0.77 X 10-5 g. per gram. Certain series of alkalis of low atomic weight, like potassium and rubidium, show weak radioactivity; this property has no significance so far for geological research. The uranium is esti-mated indirectly from the electrical properties of one of its derivatives as a -gas (emanation) into which it is transformed. The thorium is expressed directly, though it is measured as a derivative, thorium emana-tion. There is a measure for the gaseous radium emanation, the curie, which is that quantity of radium emanation, or radon, which stands in equilibrium with 1 g. of radium. The concentration of the emanation is the Mache unit corresponding to 3.64 X 10-10 curie per liter. When gases become permeated by alpha, beta, and gamma rays, plus and minus ions are produced in them by the decomposition of neutral gas molecules, and under the influence of an electrical field these ions are given opposite motions. The measurement of the alpha rays and the bisection thicknesses of the beta and gamma rays is a means of analyzing unknown radioactive substances. These rays accompany the disintegration of radioactive substances and arise from "spontaneous internal changes

Jan 1, 1929

By Lawrence F. Rooney

One of Edgar Allan Poe's stories that haunts my subconscious is the Masque of the Red Death. These days, whenever I join a group like this, especially during the cocktail parties, I see myself and others as those mythical swingers seemingly isolated from the plague. The world, but this country especially, has had a ball plundering, spending, and wasting its natural resources for 100 years. And, as in days of yore, it is fitting that we end this ball with spectacular fireworks: trips to the moon, so that our grandchildren, huddled in their caves along the Ohio, will better understand how it all began.

Jan 1, 1970

APPROXIMATELY 3500 people thronged the Hotel Statler from February 18 to 24 for the 173rd general meeting of AIME. It was a technical extravaganza in that 82 technical sessions were held, at which 500 authors presented some 350 papers. Fortunately, Jerry Peirce, outgoing President, didn't have, to preside at all the events although after his year's stint as President, he has more than a nodding acquaintance with some of the latest problems in the mining, metals, and petroleum industries. Although the Welcoming Luncheon on Monday noon was the official opening of the meeting, Local Section Delegates and the Board of Directors convened on Saturday and Sunday, respectively. The large attendance and business like demeanor of these two groups was in accord with the energetic and competent service they have rendered the Institute through the year. To the applause of engineers and their wives who thronged the grand ballroom of the Statler for the Welcoming Luncheon, President Peirce introduced Oliver B. Hopkins, president of the Canadian Institute of Mining and Metallurgy and C. Gerow, secretary of CIM. Dr. Hopkins brought greetings from the CIM and expressed his satisfaction in the splendid spirit of cooperation that exists between the two Institutes. Dr. Hopkins is president, Interprovincial Pipe Line Co., Toronto, and counts as a close personal friend M. L. Haider, who is the 1952 President of AIME and lately of Toronto where he was a director and general manager of Imperial Oil Ltd. Mr. Haider will be known shortly as Mike to thousands of AIME members as he makes his Local Sections presidential tour. There was a pause in luncheon proceedings when Judge Harold R. Medina arrived amid the applause of the audience and somewhat breathless from his trip via motorcade from an antitrust trial against investment bankers at the courthouse downtown. With the Judge at his elbow, President Peirce took the opportunity in his introduction to good humoredly chide the Judge for the vixenish habits of public servants in their treatment of astute businessmen. The successful inventor who patents his inventions is a monopoly; the copper manufacturer who buys his competitors a drink is in collusion; but the business failure need only look to the government for a subsidy, Mr. Peirce pointed out. Judge Medina, quickly captured the admiration of his listeners. He spoke about justice, deploring partisan deals on nominations for judge-

Jan 1, 1952

By AIME AIME

A COMMITTEE, representing a number of the larger oil companies in California, met in San Francisco on Nov. 12, 1919, for the purpose of discussing the depletion deductions to be allowed in computing the Federal income taxes under the Internal Revenue Act of 1918. It was the general sense of the committee that a system based on sound engineering principles should be formulated for estimating the value of oil properties, so that better and more uniform results might be obtained by the various companies in filing their returns with the' Bureau of Internal Revenue. A subcommittee, consisting of five petroleum engineers, was thereupon appointed to collect information and draft a report. The committee consisted of G. C. Gester, Carl H. Beal, J. H. G. Wolf, E. G. Gaylord, and E. D. Nolan; this report is the work of that subcommittee.

Jan 1, 1920

Committee on Reduction and Refining of Copper............ 3 A.I.M.E. Officers and Directors.................... 4 Preface. By C. R. Kuzell....................... 7 Career and Achievements of James Douglas. By Arthur L. Walker. . 9 PAPERS Smelting 1. Reverberatory Smelting Practice History of Reverberatory Smelting in Montana, 1879-1933. By Frederick Laist..............................23 Reverberatory Smelting of Raw Concentrates at the International Smelter, Miami, Arizona. By P. D. I. Honeyman (With Discussion)...... 88 Development of Gun-feed Reverberatory Furnaces at Garfield Plant of American Smelting and Refining Company. By R. A. Wagstaff (With Discussion)........................99 An Experimental Combination of Shaft Roasting and Reverberatory Smelting. By Frederick Laist and J. P. Cooper (With Discussion).... 104 Forms of Copper Found in Reverberatory Slags. By Royal B. Jackman and Carle R. Hayward (With Discussion).............111 2. Converting Practice Development of Copper Converting at Butte and Anaconda. By William Kelly and Frederick Laist...................122 Developments in Converting Lead and Copper Matte at Tooele. By B. L. Sackett.............................132 Messina Stationary Basic Copper Converter. By R. G. Knickerbocker (With Discussion)........................140 Smelting Copper Concentrates in a Converter. By George E. Beavers. 149 Sulfuric Acid from Converter Gases. By George E. Beavers......151 Development of Monolithic Tamped Periclase Converter Linings at United Verde Copper Company Smelter. By F. H. Parsons (With Discussion) . 153 3. Descriptions of Plants The Noranda Smelter. By W. B. Boggs and J. N. Anderson......165 Smelting Operations at Roan Antelope Copper Mines, Limited. By Charles R. Wraith.......................202 4. Waste-heat Boiler Practice Copper-refinery Waste-heat Boilers at Great Falls Reduction Department, Anaconda Copper Mining Company. By E. S. Bardwell......225

Jan 1, 1934

By Oliver Bowles

A HEAVY gel of bentonite clay has been proposed as an effective lubricant to speed down the ways to sea, river, or lake, the mighty cargo ships now hitting the water at the rate of about three a day. Another unusual application of a nonmetallic mineral is in food conservation, for the claim has been made that the next new item on the menu for poultry and rabbits will be vitamin tablets prepared from mont-morillonite clay. These uses have minor importance but illustrate not only the diversity in utilization, but the notable trend in 1942 toward mobilizing nonmetallic minerals for the war program. Although occupying less headline space than iron, steel, copper, aluminum, magnesium, and other metals, the nonmetallics are filling important emergency needs. Mica and quartz crystal are essential to communication; asbestos is urgently needed in fireproof heat and electrical insulation; and strontium minerals are utilized in the manufacture of signal flares and tracer bullets.

Jan 1, 1943

E. T. Dumble, Houston, Texas (communication to the Sec-retary?):—In addition to the list of publications mentioned by Mr. Schorr and those by Prof. Hofman, I call attention to the following references:— Sludi sulle Lignite, by Capacci. Turin (1890). (An excellent work.) Report of Brown Coal Industry in Germany. J. Cosmo New-berry. Department of Mines, Victoria (1892).

Jan 1, 1905

By I. H. Warren, E. Devuyst

A review of the physical and chemical aspects of the direct leaching of metal oxides has been given and com- pared to recent data of the authors and co-workers. The physical aspects, including the anisotropy of the dissolution, the hydration and the zero point of charge of some metal oxides are discussed first and then the kinetics of the dissolution of metal oxides are considered. A general mechanism of the leaching of oxides which describes most of the observed results is proposed.

Jan 1, 1973

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

Mining Methods J. HURRAY RIDDELL,Chariman Guy N. BJORGE, Vice- Chairnan ROLAND D. BANKS, Secretary Alluvial Mining CLINTON BERNARD O. B. PERRY BENERE H. GRANT C. M. ROMANOWITZ Open-Cut Mining Iron G. E. DIERL P. G. HARRISON EARL E. HUNNER

Jan 1, 1939

By Paul M. Tyler

DOES mining pay? Inasmuch as the whining of minerals from Nature is one of the world's principal sources of new wealth, this question is of general economic interest but it is obviously of even more vital concern to investors and those engaged in mining. In a previous article on "Wage Costs in the Mineral Industries,' published in the November issue, I attempted to show that wages paid workers on the job accounted for, roughly, 50 per cent of the mine dollar. Salaries normally range over 5 per cent - lower for large metal mines but higher in stone quarries and minor nonmetallic min. in, industries. Purchases of supplies, materials. fuel, and power generally aggregate within the range of 15 to 25 per cent of total receipts, with the average well under 20 per cent. The total of all such specified expenditures which may he loosely described as

Jan 1, 1934

While the production of this state has not realized the early hopes that this coal would replace eastern coal on the Pacific Coast, it has been steady though small. Nearly all of the tonnages given are from Goodyear's, The Coal Mines of the Western Coast of the U. s., a carefully com- piled and accurate account of the development of the industry along the Pacific. [ ]

Jan 1, 1942

By W. A. Thomas

Steam is, and doubtless always will be, the basic power in the anthracite industry, either directly applied through engines and pumps or electrically. The rapidity with which electric power is being applied to the mining and preparation of anthracite leaves little doubt as to its utility and economy. There is practically no operation, except possibly the drilling of hard rock, that has not been successfully electrified and the matter of drilling is handled economically with electrically driven compressors and the standard compressed-air drills. Conservation and the seemingly ever-increasing cost of production, justify careful consideration of the possible results of the more extensive use of electric power in the industry. It is not planned to discuss, herein, the relative economies of individual applications but to consider the relative economy and flexibility of steam and electric power. The reports available for the year 1920 indicate a production of slightly over 80,000,000 tons of anthracite, of which 8,843,500 tons were used for power and heating purposes; in other words, over 11 per cent. of the production was used at the mines. Some of this was used to generate electric power at the mines, about 160,000,000 kw-hr., while 150,000,000 kw.-hr. was purchased from the public utility companies. One large producer, who is buying some electric power and generating some, used over 13 per cent. of the production for power and heating at the mines. Another producer, where considerable electric power is generated on the properties, is using less than 9 per cent. of the output for power and heating. One of the largest producers has a fuel consumption of over 15 per cent. of the output, besides which considerable power is purchased. A careful study of the field indicates that steam-operated plants use upwards of 13 per cent. of the production for power and heating, while electrically operated plants use about 1 per cent. for heating; so that, for steam-power purposes at least 12 per cent., or 268.8 Ib., are used for power out of each ton produced. In the complete electrification of anthracite mining operations, no set rule can be given for the power requirement, in kilowatt-hours per ton, as conditions vary widely in the matter of pumping, ventilation, and transportation, but the following cases are given as a basis of determining a range and a possible average power requirements:

Jan 1, 1922

By Herbert Hoover

THE time has arrived in our national development when we must have- a definite national- program in the development of our great engineering problems. Our rail and water transport, our water supplies for irrigation, our reclamation, the provision of future' fuel resources, the development and distribution of electrical power, all 'cry out for some broad-visioned national guidance. We must create a national engineering sense of provision for the nation as a whole. If we are to develop this national sense of engineering wand its relations to our great human problems, it must receive the advocacy of such institutions as this. We, together with our sister engineering societies, represent the engineers of the United States. It is our duty as citizens to give voice to those critical matters of national policy which our daily contact with this, the fundamentally constructive profession, illuminates to us. Just as our medical associations voice the necessity of -safeguards to national health; as the bar associations of safeguards to our judiciary, so the engineers should exert themselves in our national engineering policies. We have none; but we need some, or the next generation will face a lower instead of a higher standard of living than ours.

Jan 1, 1920

ALABAMA. Aldrich, Aldrich, W. F. Anniston, Noble, A. E Bessemer, Abbott, C. E., Fer¬gusson, V. Birmingham, Aldrich, T. H., Jr., Bowron, C. E., Bowron, J., Collord, G. L, Crockard, F. H., Davis, F. H, Dimmick, F. D., Hillman, Ludwig, C. P., McCarthy, M. E., McCormack, G B., McCrery, Ramsay, E., Shook, A. M. Car¬bon Hill, Pill, J. R. Coal City, Lydecker, I. S. Gannts Quarry, Hiller, E. Helena, Squire, J. Holt, Shook, J. \V. Huntsmlle, Moss. Lehigh, Toulmin. Oxmoor, Green¬amyer, A. G. Rock Run, Garvin, J. M. Sheffield, Miller, D. I. Woodward, Lodge, J., Woodward, A. H. ALASKA. Ellannar, Stevens, B. Fairbanks, Hamilton, A. L, Robe, L S. Hadley, John¬son, P. Jualin, Hoggatt, W. B. Juneau, Denby, Thane, B. L., Whipple, J. R. Katalla, Hampton, W. H. Ketchihan, Barber, J. C., Geiger, A. \V., Parker, J. L. Niblack, Finck, W. N., Niedling, B. B. Nome, Garfield, C. D. Tin Oity, Fay, A. H. Treadwell City, Kinzie, Stow, H. P. Valdez, Esterly, G. M., Hazelet.

Jan 1, 1910

By Sheldon P. Wirnpfen

AN extensive study of German underground manufacturing experience is being undertaken by the Air Materiel Command. Headquarters officials consider completely underground facilities one of the most effective means of protecting aircraft production against air attacks of the strength and type employed in World War II. Advantages accruing to underground manufacturing installations other than protection are, perhaps, a smaller maintenance problem and the possibility of using gravity flow on some production lines. Offsetting these advantages are the high cost of construction, problems of ventilation, and poor acoustics. Excavation costs might well be less than the cost of enclosing the same area on the surface, as new and better methods of rock drilling and transportation are developed. Certainly the amount of building materials used would be far less than in constructing a surface plant of the same dimensions. A fewer number of skilled workers would be required to perform the labor of excavation. Underground construction would

Jan 1, 1947

By Guillermo Mariaca, Jorge Muñoz Reyer

As far as technology is concerned there has been no development in Bolivia during the year 1936, because the country, just emerging from the war with Paraguay, is only beginning to rebuild its economic foundations. Great steps, however, are being taken in order to secure a rapid and sound development of its oil resources, as follows: 1. The new Petroleum Law, which contemplates the problem of proration and conservation of natural resources, prohibiting the wasteful use of gas, and regulating the number of wells, their spacing and the permissible output per well, for each particular pool according to the conditions prevailing therein. 2. The creation of an official entity with the object of developing and exploiting a large petroliferous area. This entity has been called Yacimientos Petroliferos Fiscales Bolivianos (Y.P.F.B.), and the region assigned to it is all the sub-andean zone, which is approximately one hundred miles wide and borders the eastern part of the Oriental Andean range, from Argentine to Peru. It is said that drilling will be started immediately in various localities. At the present time a wide geological survey of part of the area is being made in order to find out which regions offer the best possibilities of commercial development. Y.P.F.B. has been authorized by the Government to draw up contracts with private companies for the exploitation of limited zones. Production The only company that has been producing in the country in 1936 is the Standard Oil Company of Bolivia, and only from two of its fields: Camiri and Sanandita. New wells were not drilled. During the first nine months of the year 12,762,958 liters (80,275 bbl.) was produced, 34,985 bbl. from the Camiri field and 45,290 bbl. from the Sanandita field. Reports for October, November and December are not yet available. The total for the year 1935 was 25,978,737 liters (163,388 bbl.).

Jan 1, 1937

By W. O. Philbrook, R. S. Kaplan

Rates of oxidation were studied for levitation-melted samples of Fe-C, Fe-Si, Fe-C-Si, Fe-C-P, Fe-C-Mn, and Fe-C-S alloys oxidized by mixtures of either 5 or 10 pct O2, in helium at several temperatures in the range 1850o to 2050°C. The concentrations of the oxidized elements decreased linearly with time. Mass transport in the gas phase was found to be the rate-controlling step. Ilowever, a mulliple -film model was necessary to account for the flux of iron and manganese vapor counter to the oxygen flow. THE advent of the basic oxygen and spray-refining processes of steelmaking has generated considerable interest in the kinetics of reactions between oxygen-bearing gases and liquid iron alloys. The object of this research was the determination of the role of mass transport in the gas and metal phases and of surface chemical reactions in the overall oxidation process. Of the reactions for elimination of elements dissolved in liquid iron, the oxidation of carbon has been investigated most extensively. Studies by Fuji and Ura,1 Fuji,' and Gunji et a1.,3 done with pilot-scale basic oxygen furnaces, indicated that mass transport of gaseous oxygen was rate controlling when the metal carbon content was greater than 0.15 to 0.30 pct. When the carbon content was less than this critical amount, diffusion of carbon dissolved in the iron was thought to be rate limiting. L. A. Baker et a1.4,5 levitated samples of iron-carbon alloys and oxidized them in CO-CO2, CO-C02-He, and O2-He atmospheres at 1660°C. These investigators found that the metal carbon concentration decreased linearly with time and their samples exploded when the carbon content fell below about 0.8 pct. They concluded that the rate-limiting step was the transfer of oxidant to the gas-metal interface. A model based on this rate-limiting step predicted decarburization rates within a factor of two of those experimentally observed. The explosion of the samples was attributed to a shift in rate-controlling step from gas-phase mass transport to transport of carbon dissolved in the metal. L. A. Baker and R. G. ward6 and R. Baker7 used freely falling droplets to investigate oxidation kinetics. In both papers, the authors speculated that flame fronts may have been partially responsible for the lack of better agreement between experiment and theory. Swisher and Turkdogan8 oxidized liquid iron having an initial carbon content of 0.97 pct with CO-CO2 and CO-C02-Ar mixtures at 1580°C. They concluded that a surface reaction was the rate controlling step. Iron-silicon alloys have been oxidized by R. Baker7 and Filipov and Martynov.9 R. Baker 7 also studied iron-carbon-silicon alloys falling as liquid droplets through oxygen. He found that the rate of both carbon and silicon oxidation varied inversely with the drop radius. When the initial silicon concentration was greater than 6 pct, the samples cooled during their fall. Manganese oxidation has been studied by R. Baker,7 and by Filipov and Martynov.9 ward10 investigated the loss of manganese from liquid iron under vacuum. He found that mass transport of manganese vapor was rate limiting in argon atmospheres of 0.02 torr to 700 torr pressure. Iron-sulfur alloys were desulfurized with H2-He and H2-Ar mixtures by Peters et al.11 A model based on the transport of H2S from the gas-metal interface into the bulk gas gave fair agreement between the predictions of the model and the experimental results. EXPERIMENTAL TECHNIQUE Essentially, the technique consisted of using helium-oxygen gas mixtures to oxidize levitated samples of liquid binary and ternary iron-base alloys. The fused silica reaction tube is shown in Fig. 1. The coil design is similar to that of L. A. Baker et al.4'5 A Tef-lon-sheathed, ferritic stainless steel lifter (B) and an alumina pedestal (C) were used to support the sample in the coil prior to levitation and for the recovery of the sample. Samples were inserted into

Jan 1, 1970

By B. F. Oliver, C. W. Haworth

Pure tin and Sn-0.5pct Pb ingots have been frozen unidirectionally from the base. For quiescent melts that were initially undercooled, a transition from lower eqlciaxed structure to an upper columnar structure is found in the alloy ingots. Columnar to equi-axed back to columnar transitions are observed in superheated alloy ingots, but no such equiaxed band is observed impure tin. The reproducible equiaxed band is associated with a thermal undercooling followed by a recalescence. This undercooling is <5"C, whereas the critical (maximum obtainable) under-cooling for both the pure tin and the alloys used is -20°C. A similar undercooling is observed at the same position in the pure tin ingots, although in this case no clear transition in structure can be seen. The structure of the pure tin ingots is either entirely columnar or mixed columnar-equiaxed. A consideration of the detailed thermal history of the ingots indicates that the ingot macrostructures are determined by the occurrence of a local therlnal undercooling in conjunction with nuclei multiplication and transport mechanisrris. GENERALLY it is found that a pure metal ingot solidifies so as to produce an entirely columnar structure. Frequently an alloy ingot is found to have a columnar outer zone and an equiaxed central portion. Early systematic work to examine the factors controlling the formation of the equiaxed structure was reported by Northcott&apos; who showed that, for copper alloys frozen unidirectionally with a given ingot practice, the alloying element influenced the length of columnar crystals and the extent of the equiaxed structure. Northcott showed that alloys with a wider freezing range more readily produced the equiaxed structure. The nucleation process can be important in producing equiaxed structures; frequently an alloy which readily solidifies with an entirely columnar structure will produce an entirely equiaxed structure when a nucleating agent is added to the melt.&apos; The formation of the equiaxed structure was attributed by Winegard and chalmers3 to the presence of constitutional supercooling; that is, a region of liquid in front of the growing solid could have a temperature below its equilibrium liquidus temperature. Thus, with a small enough temperature gradient in the liquid, it was suggested that the presence of constitutional supercooling may be sufficient to bring about the nuclea-tion necessary for the formation of an equiaxed structure. Although this explanation is plausible, and may be relevant in many ingots, Walker has described an experiment&apos; for which constitutional supercooling seems to be an unlikely cause of nucleation. A Ni-20 pct Cu alloy, repeatedly undercooled more than 50"C, was crystallized and found to show the typical colum-nar-equiaxed structure. The separation between the liquidus and the solidus for the alloy is 40°C. Thus, in this experiment the nucleation required for the formation of the equiaxed structure must have come about in some other way than by the nucleation catalysis constitutional supercooling hypothesis. Chalmers has suggested more recently5 that nuclei (in a typical ingot) are present immediately after pouring and are prevented from redissolving by the constitutional supercooling effect. More recently Uhlman, Seward, Jackson, and ~unt&apos; have shown direct evidence using ice and organic materials that freeze dendritically that the "remelt mechanism" may be an extremely effective crystal multiplication process during the freezing of ingots under conditions involving dendritic growth. JSlia" experimentally demonstrated the detachment of dendrite arms. chernov14 has analyzed the dendrite arm detachment process as a coarsening phenomena driven by the minimization of interphase area. Katta-mis and ~lemings" working with undercooled steel melts give evidence supporting this mechanism. Mechanisms of dendrite arm detachment such as those assisted by convection are believed to be the origin of the macrostructures obtained in this study. This study makes no attempt to distinguish the relative contributions of these mechanisms. The object of the present work was to obtain accurate temperature measurements during the solidification of an ingot and to correlate these measurements with the formation of equiaxed grains in the resulting ingot structures. Similar previous work is very limited. The measurements carried out by Northcott are neither sufficiently extensive nor sufficiently accurate for any interpretation. Plaskett and winegard7 carried out experiments on A1-Mg alloys in which they observed values of the temperature gradient, G, in the liquid and rate of freezing, R (for a given alloy solute content Co), at the transition from a columnar to an equiaxed structure. They reported that equiaxed crystals were produced at values of G/G approximately proportional to the solidus composition. Similar experiments using Pb-Sn alloys carried out by £111011" showed a linear relation between G/R and the solidus composition. However, the thermocouples were in the mold wall rather than in the melt and, in one case, ingot surfaces were examined. There is ambiguity in the meaning of the values of G and R measured in all these experiments. APPARATUS AND EXPERIMENTAL PROCEDURE Alloys were prepared by induction melting 99.999 pct Sn and 99.999 pct Pb to form a Sn-0.5 wt pct Pb alloy in air in a graphite crucible and casting into a cylindrical graphite mold 6 in. long, 1 in. in diarn , and with a & in. wall thickness. This mold was mounted on a copper base through which cooling water could be

Jan 1, 1968