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By John E. Lanning

During the last decade, since most smelters have included Cottrell plants as standard equipment for the removal of dust from furnace gases, it has become apparent that smeltermen have had a new problem slowly developing. This problem has manifested itself in accelerated destruction of, or serious injury to, the masonry of flues and chimneys. The masonry either spalls, if the material is of low strength, or acquires large major cracks, either of which conditions attains such proportions that renewals or reinforcing become necessary to maintain the structure in satisfactory condition. This paper describes the failure of a large modern brick chimney to such an extent that its safety was vitally impaired; the investigation of its condition; the methods of restoring satisfactory strength to the structure; and the installation of an acidproof lining. Plant History The Clarkdale smelter of the United Verde Copper Co., which was put in operation in 1915, was primarily a blast-furnace plant. The smelter at Jerome had utilized blast furnaces exclusively, and in the design of the new (1915) plant, blast-furnace smelting evidently was considered of major importance, the smelting equipment consisting of four blast furnaces 48 in. by 26 ft. 8 in. and three reverberatories, each 19 by 101 ft. The latter, supplemented by roasters, were intended mainly for handling dust and fine ore resulting from the crushing operations. The original roasting equipment consisted of six six-hearth Wedge roasters, six more being added in 1917. All gases from blast furnaces, reverberatories, roasters and converters were conducted by means of suitable flues and dust chambers to one central chimney. This chimney, 30 ft. inside diameter by 400 ft. high, is a self-supporting steel structure, lined with 4-in. brick supported on steel shelf angles, riveted to the shell, spaced about 15 ft. vertically. The bricks were of local manufacture, not particularly hard-burned, and were laid in ordinary cement-fireclay-sand mortar. No record is available to indicate that any particular effort was made to secure an acidproof mortar. The same materials were employed in the construction of the reverberatory and roaster flues, and the roaster dust chamber. Parenthetically, it may

Jan 1, 1934

Extractive Metallurgy Division Institute of Metals Division Iron and Steel Division OFFICERS AND COMMITTEES John Chipman, President W R Hibbard, Jr, Past President C C Long, Vice-President T D Jones, Treasurer R W Shearman, Secretary AIME, 29 West 39th Street New York 18, N Y

Jan 1, 1959

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman EDGAR RICHARD, Vice-Chairman D. M. LIDDELL, Secretary, 7 Wall St., New York, N. Y. C. A. BOHN, Treasurer JOHN V. N. DORR LEWIS W. FRANCIS Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman JAMES G. CARLETON, Vice-Chairman E. E. BUGBEE Secretary-Treasurer, Mass. Inst. of. Technology, Cambridge, Mass. W. E. C. EUSTIS G. A. PACKARD Columbia Holds four sessions during year. Annual meeting in September or October. W. H. LINNEY, Chairman OSCAR LACHMUND, Vice-Chairman LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON S. SHEDD Puget Sound Meets second Saturday of each month SIMON H. ASH, Chairman I. F. LAUCKS, Vice-Chairman PERCY E. WRIGHT, Secretary-Treasurer, 2012 L. C. Smith Bldg., Seattle. Wash. GLENVILLE A. COLLINS JOHN N. POTT

Jan 11, 1917

By William E. Ford, Edward Salisbury Dana

The monoclinic Wolframite Group and the tetragonal Scheelite Group are included here. Wolframite Group WoIframite (Fe,Mn)W04 a : b : c = 0.8300 : 1 : 0.8678 B = 89' 22' Hiibnerite MnW04 048362 : 1 : 0.8668 89' 73' WOLFRAMITE. Monoclinic. Axes a : b : c = 0.8300 : 1 : 0.8678; B = 89' 22'. mm"', 110 A 1TO = 79" 23'. ay', 100 A 101 = 62' 54' at, 100 A 102 = 61" 54'. $', 011 A 011 = 81" 54'. Twins: (1) tw. axis c with a (100) as comp.-face; (2) tw. pl. k (023), Fig. 449, p. 171. Crystals commonly tabular (1 a (100); also prismatic. Faces in prismatic zone vertically striated. Often bladed, lamellar, coarse divergent columnar, granular. Cleavage: b (010) very perfect; also parting (1 a (100), and 11 t (102). Fract,ure uneven. Brittle. H. = 5-5.5. G. = 7.2-7.5. Luster submetallic. Color dark

Jan 1, 1922

By J. Winlock

To have been chosen by you to give the Howe Memorial Lecture is the greatest honor I have ever had and I should like to have you know that I appreciate it deeply. Many years ago I had the privilege and the pleasure of working with Professor Howe in the private laboratory which he had established in his home at Bedford Hills, New York. Without doubt he was one of the world's greatest metallurgists and so you can imagine what a difficult task it has been for me to live up to his teachings. Every morning Professor Howe would outline the work he wanted done and the recollections of those conferences are clear to me to this day. Sometimes he would ask me to ride in his automobile and the chauffeur had full instructions to go no more than fifteen miles an hour. If he did so, Professor Howe was sure to rap upon the man's shoulder with his cane. I assure you, however, Professor Howe's thinking was not at that rate. His homely advice, his patience and his perfect control of the English language still impress me. Many times I heard him dictate a complicated paper on metallurgy and never find it necessary to change a single word. There are no better words to describe the character of Professor Howe, in my opinion, than those used by Professor Sauveur when he presented the John Fritz Medal to him in 1917: "Lover of justice and humanity Public servant and public benefactor, Master of the English Language, Loyal and devoted friend, Untiring and unselfish worker in an important field of science." I hope you will bear with me with the same patience and understanding which he used to give to me. The peculiar behavior of steel at the yield point has long been known and has been the subject of much research, both in this country and abroad.',' Many theories, including some of mine and my colleagues, have been suggested, but none of them, in our opinion, fully explains to our satisfaction why the phenomena occur. Of particular importance has been the work of Nadai,3 Siebel and Pomp,' Sachs and Fiek,5 Rawdon,0 Kenyon and Burns,' Gensamer," Gensamer and Meh1,0 Davenport and Bain,'" Fell," Deutler,12 Brinkman,13 MacGregor,14 Hollomon,15 Cot-trell,16 and Palm." The question of what is occurring during this singular behavior is not only of interest from an academic point of view, but is of great practical importance for at least two reasons: 1—The highly localized plastic flow which occurs during the deep drawing of light-gage steel gives rise to surface markings which seriously mar its appearance, Fig. 1. If the forces causing the deformation are primarily tensile forces, these surface markings occur as depressions in the surface. Whereas, if the forces causing the deformation are primarily compressive, irregular lines of elevations occur. These surface markings are known as Luder's lines, Hartmann lines, the Piobert affect, and, in the shop, as "stretcher strains." 2—The steel is in the most suitable condition for deep drawing after the yield point phenomena have been removed. When this is done, the steel may be deep drawn more easily and to a greater extent.' It should be mentioned that steel is not the only metal which shows this peculiar behavior at the yield point. Stretcher strains occur, also, during the deformation of some copper-nickel-zinc alloys." The purpose of this paper is not an attempt to describe what causes the steel to behave in this peculiar manner, but an attempt: l—to describe what is taking place at the yield point; and 2—to show the influence of the rate of deformation on the tensile properties of some plain carbon steels. As is well-known, there are two methods of deforming a metal in tension: 1—by actually hanging an increasing amount of dead weight on the metal; or 2—by deforming the metal at some given rate or rates by means of oil pressure cylinders, screws, etc. With the first method, the load is always present and, clearly, no drop in load can ever occur while the steel is deforming. With the second method, the registered load is the resistance of the steel to the deformation being imposed upon it. The second method is the one most widely used, and is the one referred to throughout this paper. In order to describe clearly what is occurring at the yield point in steel, it will help, I believe, if a description is first given of what occurs when alumi-

Jan 1, 1954

At the annual meeting of Southern California Section, held on May 28, the following officers were elected: Chairman, W. F. Staunton, vice-chairman, L. C. Mott, secretary-treasurer, A. B. Carpenter; executive committee, J. W. Neill, C. Colcock Jones, Mead Goodloe. ALVIN B. CARPENTER, Secretary-Treasurer.

Jan 8, 1919

By K. R. Price, M. Gauna

A high seam geologic condition exists at Jim Walter Resources No. 4 mine that requires immediate rib support after a continuous miner cuts a place. High seam mining heights are typically 2.4 to 2.6 m (8 to 9 ft) and a thick rock layer is present in the upper portion of the coal rib side. The 610-m (2000 ft) mining depth at No. 4 mine induces horizontal rib line movement after excavating an entry. Horizontal rib movement greater than 305 mm (12 in.) have been noted. When lateral movement occurs in the high seam areas, the thick rock layer, and the coal above the rock layer, become fractured and tend to roll into the entry. If not adequately supported, large rib rolls develop in the place being bolted as well as in previously mined areas that endanger men and equipment. To control this, rib support must be installed in the roof bolting operation as the bolting crew works toward the face. A rib control system has been developed for this high seam mining condition using a mechanical anchor bolt placed at an angle in the rib and installed with a modified Fletcher DDM-15 bolting machine. More than 120 km (75 miles) of entry have been supported with angle rib bolts. These angle bolts constitute 43% to 60% of the total roof and rib bolt footage in the high seam portions of No. 4 mine. The angle rib bolting system has proven safer, more effective, and more efficient than the earlier support method using bolts installed horizontally into the rib. No rib roll accidents have occurred since the angle drill bolting machines were placed in service in 1981. By securing the broken rib material with an angle bolt anchored above the coal pillar, a more effective means of rib control is achieved. Angle rib bolting does not interfere with continuous miner productivity. In addition, bolting crews are now reduced from three to two people. Total drilling supply costs are about 60% the previous cost, when compared to the previous support method using horizontal rib bolts:

Jan 1, 1985

By R. W. Smith, M. E. Brookes

The temperature at which th: quenched 0' (ordered bcc) phase transfo.rms to the ( (complex hexagonal) phase on heating has been examined for certain Ag-Zn and Ag-Au-Zn alloys using an electrical resistivity method. The transition temperature decreases by approxinzately 7°C as the zinc content is reduced by 1 at. pct. The critical temperature, Tc, for long-range order has also been measured for a number of Ag-Au-Zn alloys. Extrapolation to zero gold content suggests that Tc decreases by approximately 5°C per 1 at. pct reduction in zinc content. The 0 phase of the Ag-Zn system exists over a narrow range near the composition Ag zn,' Fig. 1, and has a bcc structure which is disordered above 272°C. Slow cooling to temperatures below the range 274"/258"C allows the complex hexagonal phase, r° to form.2 This is the stable structure at room temperature.3 Upon quenching 0 -phase alloys from high temperatures, it is found that the 0 — (' transformation is suppressed; but ordering takes place (i.e., 0 -0'). This ordered structure can also be obtained by the room-temperature aging of cold-worked (0.4 Deformation of the 0' phase gives rise to a fur- ther hexagonal phase ( (of nearly ideal axial ratio) which reverts to b' within a few hours.= In view of this, it has been suggested that the equilibrium struc-

Jan 1, 1969

MEMBERS, JUNIOR MEMBERS, ASSOCIATES AND JUNIOR ASSOCIATES LIST OF MEMBERS ALPHABETICALLY ARRANGED EXPLANATION OF SYMBOLS ** Junior Member. t Associate. || Junior Associate. Members are not marked. Capital letters signify Honorary membership. Student Associate and Rocky Mountain members on pages 165-167. Abadilla. Quirico A Catanawan. Tayabas, P. I. Abbey. Robert Graham. District Mgr The W. W. Sly Mfn. Co., 60 Church St New York. N. Y. Abbott. A. N Mines Supt Mazapil Copper Co Ltd . .Conception del Oro. Zac., Mexico. Abbott. Ckrence E Mgr Mines & Quarries, Tenn. Coal. Iron & R. R. Co 1242 Brown Marx Bldg Birminrham. Ala. Abbott. Louie Benjamin. Chief Enar Consolidation Coal Co Elkhorn Div .Jenkins, KY. Abeel. Gsorge H Jr., Cons. Min. Enar .Box 427. Santa Monica. Cal. Abel. Albert E Asst. to Pres Valley Mould & Iron Corp Hubbard. Ohio. Abel. Raymond L. Asst. Prof., Dept. of Pet. Refin Univ. of Pittsburgh Pittsburgh. Pa. Abernathy. George Elmer. Prof. of Geol. & Min Kansas State Teachers College. Pittsburg. Kans. IlAbernethy. D. Carl, Jr. Min. Engr Hudson Coal Co .Scranton. Pa. Abey, Hiroshi. Min. & Met. Engr., Min. & Met. Dept., The Higher Technical School, Osaka. Japan. tAbarn, Robert H Instructor in Met Harvard University Cambridge, Mass tAbozeid,Mahmood. Pet. Production E r . . Marland Oil Co. Ponca City, Okla. Abraham. Arthur W Geol., Richfield Oil Co Box 788. Bakersfield, Cal. Abraham, W. E. V Member, Staff of Burmah Oil Co Ltd. Nyaunghla. Upper Burmz, India. Abrahams. Alexander I Gen'l Mgr., Racon Electrical Co Slough, Bucks England. tAbrahammn. C. W Min. Engr The Mond Nickel Co Ltd . Coniston, Ont Canada. IlAbmn. Guy W., Asst. Metallographist, Youngstown Sheet & Tube Co., Research Dept., Youngstown. Ohio. Abstein. Henry T., Engr. & Mgr Profile-Tamarack Mines Co . .Yellow Pine, Idaho. tAcker. E. O'C Met I28 East Washington Lane. Germantown, Philadelphia. Pa. Ackerman. D. E Met. Research Lab International Nickel Co Inc Bayonne. N. J. tAbckerman. Ernest R Pres., Lawrence Portland Cement Co . .Plainfield. Union Co N. J. ||Ackerman. George F Jr. Min. Engr El Potosi Min. Co. .Apt. 13. Chihuahua, Chih Mexico. Acres, T. H Geol. Dept Valuation & Pet. Engr., Richfield Oil Co. 655 S. Flower St Los Angeles. Cal. Adachi. Jinzoo Address Wanted. Adair. Arthur C Valuation Enar., Internal Revenue. Treasury Dept., Washington, D. C. Adam. John. Min. Ennr., The Zinc Corp. Ltd., Box 4 C. Broken Hill, N. S. W Australia. Adami. Arthur E V. P Montana State School of Mines.Butte, Mont. Adami. Charles J Min. Ensr St. Joseph Lead Co 4540 Lindel Blvd., St. Louis, Mo. Adams. C. W.729 South Normandie St LaGranada Apt Los Angeles, Cal. Adams. Cmyler Geerwwd. Minn. Adams. F. J Gen'l Anent. Gulf Production & Pipa Line Cos .Fort Worth. Tex. ADAMS. FRANK DAWSON. Logan Prof. of Geology and Dean, Faculty of Applied Science, McGill Univ Montreal. Que Canada. Adama, Gale L Research Enar., General Pet. Corp. of California, Higgins Bldg Los Angeles. Cal. Adams. George I, Prof. of Geol. & Mineralogy Univ. of Alabama, Tuscaloosa, Ala. Adams. H. H Cons. Geol Room 416, W. T. Waagoner Bldg Fort Worth. Tex. Adams, Henry. Cons. Min. Ennr 1050 Edgewood Ave., Plainfield, N. J. Adams, Henry H.285 Madison Ave., New York. N. Y. Adams, Henry Farnum. Engr., Charge. Experimental Work. Inspiration Concentrator, Inspiration Cons. Copper Co Box 354. Inspiration. Ariz. Adams. Huntington. Min. Enar I41 Broadway, New York. N. Y. Mama, Leland D., V. P., Leslie-California Salt Co 166 Montgomery St., San Francisco, Cal. Adams, Louis W., Illinois Steel Co .Gary. Ind.

Jan 1, 1929

By Shiro Ban-ya, John Chipman

Using the same experimental method previously described, the activity of sulfur in a number of quaternary and more complex liquid iron alloys at 1550oC is determined. A "cross-product term zj.zk is determined for each of the quaternary alloys to take account of the mutual effects of the combinalion on the indi-vidual contributions to In 5 The interactiotl coefjicienls delermined for ternary solutions and cross-pvoducl coefficierlts from the quaternary systems are used to estimate the activity coefficient of sulfur in more complex alloys. OUR recent papers 1,2 have described new determinations of the activity of sulfur in Fe-S binary and Fe-S-j ternary solutions, but the practical applications of these data require the estimation of activity of sulfur in more complex systems. Previously, Sherman and chipman3 devised an approximate method for calculating the activity of sulfur in complex systems by summing the contributions to the logarithm of the activity coefficient of each element in the alloy. This procedure is more successful, as one of us has pointed out,4 when the concentration variable is taken as zs = ns/(nFe — nS t CLJ~ nj) rather than the conventional atom fraction x~ = nS/(nF, + nS + Enj). In the former definition, which is based on analogy to interstitial solutions, the value assigned to uj is normally +1 for metallic and -1 for nonmetallic elements." In addition, however, the effects of mutual interaction between alloying elements must be considered for the accurate estimation of the activity of sulfur in more complex systems. The purpose of this investigation has been to devise a more reliable method for estimating the activity coefficient of sulfur in nmIticomponent iron alloys. The measurements were carried out on some quaternary systems Fe-S-j-k for combinations of silicon, chromium, nickel, cobalt, molybdenum, and tungsten. Manganese was not included since the experimental method has been found unsatisfactory for volatile, sulfide-forming elements. The experimental method was the same in every detail as described previously. 1,2 The concentrations of sulfur, silicon, chromium, and copper in the quenched metals were determined by chemical analysis but those of nickel, cobalt, molybdenum, and tungsten were calculated from charged amounts. Iron sulfide was included in the charges in amounts estimated to furnish approximately the final sulfur content. CALCULATION W2 have shown2 that when zs and zj are the concentration variables in a ternary Fe-S-j solution the logarithm of the activity coefficient S = a~/zg is a linear function of the variables as and aj defined as follows:

Jan 1, 1970

By C. G. Dunn

WITH respect to theories of recrystallization in metals plastically deformed, it has been said that the present status of this subject is far from satisfactory.1 It may also be said that before any mechanism of recrystallization for metals and alloys can be set forth in a satisfactory manner, there must be made available considerable data on orientation changes that occur during the deformation and recrystallization processes. Although extensive data have been published on recrystallization in single crystals and in polycrystalline specimens, more results of a type that can be classified according to simple orientation changes would be desirable in this complex field. It might even be said that before classifications are made according to types of orientation changes, it may be possible to classify a considerable amount of data into certain kinds of orientation states if groups of common or nearly common orientation occur. Methods for computing the probability of occurrence for various types of groups have been published2 and it has been pointed out in particular that it should be possible to analyze orientation data for high-order twin relationships between old and new grains even when agreement is not at all exact. In this connection, work on recrystallization in silicon ferrite reported in a paper concerned with complex groups of annealing twins' indicated that some data were consistent with primary nucleation occurring according to a second-order or a third-order twin transformation. However, further work in this latter direction was definitely needed. It is, therefore, the purpose of the present paper to report data and analyses for primary nucleation in silicon ferrite following small deformations that have been carried out at the Pittsfield Works' Laboratory of the General Electric Co. Analyses have been made with the aid of standard groups of twins that are reported elsewhere .4 PREPARATION OF SPECIMENS AND EXPERIMENTAL PROCEDURE The material used in the present investigation was taken' from the same heat of steel as that used in a prior report.3 The finished strip in both cases was made by the Allegheny-Ludlum Steel Corporation according to methods that produce a high degree of preferred crystal orientation. Samples with large grains had the following composition: 3.45 per cent Si, 0.003 C, 0.008 P, 0.020 S, 0.075 Mn, 0.031 Al and 0.072 Cu. Thickness of specimens was 0.012 inches. Plastic deformation was produced by cold-rolling the samples on a mill with

Jan 1, 1945

By Paul L. Cloke, S. R. Titley

Paul L. Cloke (Assistant Professor, Dept. of Geology and Mineralogy, The University of Michigan, Ann Arbor, Mich.) - On examination of the paper by S. R. Titley it appears that several errors have been made, many of them of a fundamental nature. It is the intent of this discussion to point out these mistakes, and, insofar as possible with the data at hand, to correct them. EXPERIMENTAL WORK Ferrimolybdite-Limonite-Water: The results of the experiments described are very difficult to interpret; nevertheless, a correct interpretation is essential as is pointed out subsequently. The difficulties become apparent when reasons are sought for the continuing change of pH after conversion of ferrimolybdite to ferric hydroxide and for the change of pH when -stirring is stopped after a steady value has been reached. In seeking an explanation of this experiment it seemed to this writer that the (temporarily) steady pH values might be due to kinetic rather than equilibrium effects. In this view the steady pH on stirring might be explained as a balance of several reactions proceeding simultaneously. The first of these would be the slow solution of ferrimolybdite,

Jan 1, 1964

By J. L. Lamont, W. Crafts

Studies of the effect of composition of steel on hardenability by Grossmann,' and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0'65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc' The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By W. Crafts, J. L. Lamont

Studies of the effect of composition of steel on hardenability by Grossmann,' and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0'65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc' The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.'.' It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.' Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By Cyril Smith

IN the study of the structure or the properties of a series of alloys or nonmetallic compounds, it is often advantageous to express the com-position not as percentage by weight, according to which the material is always made up and analyzed, but as the atomic percentage of the two constituents. The conversion from the one to the other is repre-sented by the formulas: 100A 100x Y x 100 ? x/A A [1] A+ B x + A/B(100-x) X _ 100yA 100y [2] yA+(100-y)B or y+A(100-y) where x and y are the weight and atomic percentages respectively of the element of atomic weight A, and (100 - x) and (100 - y) are the per-centages by weight and by atoms respectively of the element of atomic weight B. While calculations according to these formulas are simple, they are' time consuming if several conversions have to be made. In 1931 Water-man' constructed a nomograph for performing the conversion, but this did not permit an accuracy greater than about 1 per cent to be obtained in the neighborhood of 50 per cent. Olander2 has proposed a graphic method simpler than Waterman's and one that gives a uniform precision throughout the entire scale. The possible accuracy is about 0.5 per cent of the whole, depending on the size and accuracy of the coordinate paper used. Recently, Hermann3 has described a slide rule for making the calculations. These devices make use of the simple rearranged equation:

Jan 1, 1933

By Michel Elle, John Chipman

The equilibrium of gaseous H20-H2 mixtures with liquid iron-columbium alloys in the range 0.2 to 2.4 pct Cb shows that the activity coefficient of oxygen is strongly diminished by Cb. The oxide in equilibvium with the melt is identified as CbO2. The equi-librium constant at 1600 deg C is [%Cb][fo. % 0]2 = 2.9 x 10-4 where log fo= —0.14 [%Cb]. The deoxidizing power is comparable to that of vanadium, COLUMBIUM (niobium) is finding increasing use as an alloying element in steel. It forms several stable oxides and is removed from the steel bath by oxidizing slags. The specific oxide formed in steel-making is not known although Sazanov snd Shvarts-man,' in their study of its partition between slag and metal, have assumed this to be Cb2O5 It is the purpose of this study to determine its deoxidation equilibrium at 1600°c, the nature of the oxide formed and the interaction between columbium and oxygen in the melt. The investigation was based on the reaction H2 + O=H2O; Kl=ph2o/(pH2[%O]) [1] in which 0 signifies oxygen dissolved in the liquid Fe-Cb alloy. The method and equipment of recent studies2,3 were utilized. In brief, the molten alloy, contained in a small crucible, is held in a controlled mixture of steam, hydrogen, and argon until equilibrium is reached. It is then cooled quickly in a stream of helium and analyzed for columbium and oxygen, the latter by vacuum fusion.4 The solubility of the oxide in liquid iron is determined by visual observation of scum formation on the surface of the melt. Crucibles of MgO proved unsatisfactory because of partial reduction at the metal interface. Pure A12O3 crucibles were heavily blackened by the melt and could not be used at high concentrations of columbium. Silica crucibles were more satisfactory but these introduced some silicon into the melt thus necessitating an uncertain but small correction for its effect on the activities of the other solutes. In silica it was possible to observe the scum formation when the melt became saturated and there was no apparent reaction between scum and crucible. The procedure for saturated melts was as follows. The alloy charge composed of electrolytic iron and columbium grain was melted and held at constant temperature. The gas ratio H2O:H2 was progressively increased by raising the saturator temperature until a point was reached at which a bright film appeared on the surface and covered it completely. This film could be dissolved by raising the temperature of the melt and it reappeared when the temperature was lowered. Under a partial film covering, utilizing bare areas for temperature measurement, the melt was brought to equilibrium with the atmosphere by holding at temperature for about 1 hr as suggested by Dastur.5 INTERACTION IN THE MELT Several experiments were made without columbium to establish a base in silica crucibles. The results are shown in Table I. Except for one run, they agreed well with Floridis1 comparable results in other crucibles. The value of log K1 is taken from Table I as 0.58. This is slightly larger than Floridis' result, probably because of less elaborate safeguards against thermal diffusion. Results obtained in the Fe-Cb-0 series in which no scum formed are shown in Table 11. The equilibrium ratio Kl is defined as ph2o/(ph2[%O]). It is related to the equilibrium constant K1 as follows:

Jan 1, 1962

The Secretary : The work of Mr. A. E. Outerbridge, Jr., of Philadelphia, first made known in his paper on " The Mobility of Molecules of Cast-Iron," read at the Pittsburgh Meeting of the Institute, in February, 1896, has been reviewed by the Committee on Science and the Arts of the Franklin Institute, whose report, dated May 5, 1897, is accompanied with a table of tests made by the Committee, and amply confirming the statements of Mr. Outerbridge. Concerning the originality and novelty of his investigation, the Committee says: " The fact that a certain molecular change takes place in cast-iron in the course of time has been known and recognized by many persons for a long time, and that this change tends to relieve the internal strains and render the casting tougher has often been noticed and acted on, although in a very crude way; but, so far as the sub-committee has been able to learn, Mr. Outerbridge has been the first to make a careful study of this, and to note that the change may be hastened by impact, and the whole effect produced in a short time, and also to make a scientific study of the phenomenon. We believe great credit is due him for the initial observation and the careful work dependent thereon. The results were first given to the public in a paper read before the American Institute of Mining Engineers, on February 20, 1896. This aroused a wide-spread interest and discussion among users of cast-iron, and so far as the sub-committee has been able to determine, it has not been shown that anyone, either in this country or abroad, has antedated Mr. Outerbridge in his work in this line. The Franklin Institute therefore recommends the award to him of the John Scott Legacy Premium and Medal." This report has not been published, hut I have had the opportunity to read it in manuscript. The table of testa accompanying it comprises 91 tests of " rumbled" and an equal number of " not rumbled" companion-bars of cast-iron, 26 by 2 by

Jan 1, 1898

By L. V. Pirela, S. M. Farouq Ali

Some interest has been expressed recently in the application of solvents in conjunction with a thermal drive, such as a steamflood. At least one field project of this type has been reported. This paper makes the first attempt to provide some of the basic information necessary for choosing a solvent for such an application. Results of displacements conducted at elevated temperatures are also discussed. This paper shows that, in the case of alcohol-hydrocarbon-water or brine ternary systems, the system miscibility may increase, decrease, or both increase and decrease within the same system when the temperature increases. The distribution coefficient was consistently found to increase in favor of the oleic phase with an increase in temperature, which is advantageous from the standpoint of oil recovery. Results of solvent displacements in a sandstone core showed that even a relatively small temperature effect in the favorable direction (increase in miscibility and distribution coefficient) can lead to a 50 percent increase in oil recovery. On the other hand, if the system miscibility decreases with the temperature, even though the distribution coefficient increases, the oil recovery at the higher temperature may not increase. INTRODUCTION Miscible displacement has been the subject of many investigations. Miscible-phase solvent flooding, employing solvents such as alcohols that are miscible with both oil and water, has received considerable attention. Investigations conducted by Gatlin and Slobod,l Taber, Kamath and Reed,2 Holm and Csaszar,3 and Farouq Ali and Stah14 have helped in understanding the mechanism of solvent flooding. While the use of alcohols and similar solvents as oil recovery agents is economically unattractive, these solvents nevertheless provide a means of understanding the mechanistic aspects of important miscible-phase oil recovery processes such as the Maraflood process (discussed by Gogarty5). As shown by Taber et a1.,2 the phase behavior of a solvent-oil-water system is of .utmost importance in determining the efficiency of the oil displacement. This paper makes the first attempt to obtain the ternary phase behavior data for nine alcohol-hydrocarbon-water/brine systems at elevated temperatures. Results of core tests at elevated temperatures are also presented which corroborate the effect of temperature on oil recovery, as judged on the basis of phase-behavior data. The use of solvents at elevated temperatures has been suggested earlier by Farouq Ali.6 At least one field test of this type has been reportedO7 With the widespread use of thermal recovery techniques, it is possible in some situations (especially in steamflooding) that the use of a suitable solvent in conjunction with the heat carrier may be economically feasible. This paper attempts to provide some of the basic information needed for judging such feasibility. LOCATION OF THE PLAIT POINT The phase behavior of a typical ternary system consisting of a solvent, hydrocarbon and brine (or water) can be represented by a triangular diagram such as the one shown in Fig. 1 (for temperature TI). Point Pon the binodal curve represents the plait point, being the limit of tie lines such as Y1 Y2 The compositions of the coexisting oleic and aqueous phases are given by points Y2 and Y1, respectively, for any mixture composition along Y1Y2. The characteristics of ternary diagrams have been discussed by Findlay8 and others. Taber et aL3 have shown that the position of the plait point in a particular ternary system plays the decisive role in determining whether or not theoleic phase would be displaced in a continuous manner during an alcohol displacement. The area above the binodal curve also is important, since it represents

Jan 1, 1969

By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman' and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965