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By 0. H. ESCHHOZ

HARMON F. FISHER,* New York, N. Y. Mr. Eschholz discusses the particular case of large precipitators installed in connection with large metallurgical operations, and receiving their high-potential energy through the conversion of alternating current to direct current by means of the mechanical rectifier. He classifies these mechanical rectifier installations, according to source of power, as follows: System A.-Applications utilizing individual alternating-current generators, either single-phase or polyphase, installed exclusively for furnishing energy to one or more transformer-rectifier-precipitator units. System. B.-Applications having no special alternating-current generators, but utilizing the existing alternating-current industrial or lighting mains to supply the energy to one or more transformer-rectifier-precipitator units. System C.-Applications receiving their energy from high-tension power circuits supplied directly to potential regulator-rectifier-precipitator units. I do not intend here to enter upon a detailed technical discussion of the foregoing classes, which would really interest only the manufacturers of electrical apparatus and the electrical engineers. A brief general discussion follows:

Jan 11, 1918

By Rex B. McLellan, M. L. Rudee, T. Ishibachi

A modelfor dilute quasi-regular interstitial solid solutions is proposed in which the solute atoms can occupy both the octahedral and tetrahedral interstices in the bee solvent lattice. The distribution function, according to which the solute atoms are apportioned between the two kinds of sites, is calculated. The partial thermodynamic functions of the solution are calculated from the distribution function. It is shown that such a solution model can explain the deviation from linearity of the Arrhenius plot of the temperature variation of the diffusivity of carbon through a iron. The published difiusivity data is analyzed to obtain numerical values for the distribution function. Finally it is shown from the numerical values of the distribution function that the possibility of dual-site occupancy will have a negligible effect on the solution thermodynamics for this system. DeSPITE the large amount of experimental data available on the thermodynamics and diffusion kinetics of dilute solid solutions of carbon in a iron, many of the elementary properties of these solutions are not understood due to real or apparent discrepancies in the experimental data. Basically there is a lack of agreement between the solubility and diffusion data obtained by anelastic damping techniques and by bulk chemical thermodynamic methods. SPecifically the heat of solution of cementite in ferrite estimated from thermodynamic measurement1, 2 is about twice as high as that determined from anelastic damping measurements.3 Furthermore the diffusion coefficient D of carbon in a iron in the range -40" to about 150°C (covering about ten orders of magnitude) determined from anelastic damping techniques is such that an Arrhenius plot of In D vs 1/T is linear. However in the range of about 300o to 850°C where mass flow measurements of D have been made (covering about four orders of magnitude), although the data merges with the low-temperature data, the Arrhenius plot departs from linearity. The object of this paper is to present a more refined model of dilute ferrite solutions in which the solute atoms can occupy two kinds of interstitial sites. The experimental data is analyzed in the light of this model and it is believed that thereby some of the anomalies can be resolved. snoek4 explained the room-temperature internal-friction peak (usually referred to as the Snoek peak) in iron as the stress-induced ordering of interstitial carbon and nitrogen atoms occupying the octahedral (0, 0, 1/2) interstices in the bee lattice. From the consideration of a hard-sphere lattice model the (0, 1/4, 1/4) tetrahedral interstices are larger than the octahedrons but their symmetry would not produce the strain dipole necessary to give rise to the Snoek peak. Thus the presence of the Snoek peak is direct evidence that the octahedrons are occupied. Since the publication of Snoek's explanation, most workers have assumed that all of the carbon and nitrogen in the a solid solution was located in the octahedral sites. This assumption of universal octahedral occupancy has been implicit in the theory of wert5 for interstitial

Jan 1, 1965

By L. S. Castleman, L. L. Seigle

IN a recently reported investigation, J. B. Clark and F. N. Rhines1 used a diffusion couple technique to determine the number of intermetallic phases which should be present in the Al-Mg equilibrium phase diagram. Their method was an application of the following generally accepted principle. If a diffusion couple made up of two metals is annealed at a given temperature for a long time, all the phases of the binary system which exist under equilibrium conditions at the diffusion temperature will form intermetallic layers. It is important that the diffusion temperature be high enough and the diffusion time be long enough to permit the nuclea-tion of all thermodynamically stable phases at the interface of the couples and their growth to observable thicknesses. These simple time-temperature criteria are at times difficult to satisfy, and it is the purpose of this note to point out a situation in which this is the case. The authors are currently studying diffusion bonding in the Al-Ni system." It is well established

Jan 1, 1958

By R. T. Gallagher

FOLLOWING recent precedent, the Mineral Industry Education Division opened its first session on Sunday afternoon at the Columbia University Men's Faculty Club with an unexpectedly large attendance. The first session was presided over by the Division Chairman, A. F. Greaves-Walker. The first paper, a preliminary report on college enrollments in mineral technology curricula, by W. B. Plank, though incomplete, pointed to a general over-all reduction of 38 per cent in enrollment in mineral industry curricula. Following that, A. C. Callen's paper elicited many comments. It presented the results of a survey (no direct questions asked) addressed to officials in the mining industry. J. L. Bray spoke on war production drive methods and results and his slides gave visible evidence (and much laughter) of the success of the drive. C. L. Wilson's able presentation covered not so much present status but the future status of accelerated mineral technology programs after the war. The last paper of the first session by Edward Steidle, was handed out in mimeographed form.

Jan 1, 1943

By AIME AIME

MATTERS pertaining to mine ventilation were, taken up at the annual meeting Wednesday morning with E. A. Holbrook in the chair. In the absence' of its author, G. E. McElroy, the first paper, entitled "Economic Size. of Metal Mine %Airways," was read by title by the chairman. The second paper, "Intermittent Mine Ventilation," by Oscar A. Glaeser, was 'abstracted by Dan Harrington. It related to metal-mining practice, being inapplicable to coal mining, of course. B. F. Tillson asked how the ,quantity of air was measured and con- trolled in the different splits and Mr. Harrington stated that an anemometer presumably was used and that split- ting was controlled by adjusting the steel doors to the desired position by means of screws. George 'S. Rice asked if the fan were underground, and Mr. Harrington replied that it was. Although he had at, one time recommended that it be placed' on the surface, certain factors led the management to keep it underground, a. location that has several advantages in this particular case.

Jan 1, 1932

By L. R., McLeod

NO important changes in metallurgical practice are exhibited in the smelter that has been erected for treating the Morenci concentrate: the material is charged to reverberatory furnaces without roasting, and the matte subsequently blown in Peirce-Smith converters to separate the iron and sulphur from the copper. In fact the process is essentially the same, except for preliminary roasting of the concentrate, that was adopted in the new smelter that was built for the Arizona Copper Co. at Clifton, a few miles away, to treat Morenci concentrate just before the start of the first World War, and which went into service in October, 1913.

Jan 1, 1942

By E. T. Turkdogan, Klaus Schwerdtfeger, P. Grieveson

The rate of growth of "Fe4N" on a iron was measured by nitriding purified iron strips in flowing am -monia -hydrogen gas mixtures at 504" and 554°C. It is shown that a dense nitride layer is formed when a zone -refined iron is used in the experiments. With less pure iron, the nitride layer is found to be porous. Through theoretical treatment, the self-diffusivity of nitrogen is evaluated porn the parabolic rate constant, and found to be essentially independent of nitrogen actirlity, e.g., D* = 3.2 x l0-12 and 7.9x l0-12 sq cm per sec at 504" and 554?C. Some consideration is given to the mechanism of diffusion in the nitride phase. THERE is a great deal of background knowledge on the solubility and diffusivity of nitrogen in iron, and on the thermodynamics and crystallography of several phases in the Fe-N system. Although case-nitrided steels have many applications in practice, no work seems to have been done on the diffusivity of nitrogen in the iron nitride, ?', phase. The only work reported on the related subject of which the authors are aware is an investigation by Prenosil,1 who measured the growth rate of the e phase on iron by nitriding in ammonia-hydrogen gas mixtures. EXPERIMENTS Purified iron plates of approximate dimensions 1 by 0.5 by 0.03 cm were nitrided in flowing mixtures of ammonia and hydrogen, in a vertical furnace fitted with a gas-tight recrystallized alumina tube. After a specified time of reaction, the sample was cooled to room temperature by withdrawal to the water cooled top of the reaction tube. The furnace temperature was controlled electronically in the usual manner within *l°C; the temperature was measured using a calibrated Pt/Pt-10 pct Rh thermocouple. For each experiment the iron strip sample was cleaned with fine emery cloth and degreased with tri-chloroethylene prior to the experiment. The ammonia-hydrogen gas mixtures were prepared from anhydrous ammonia and purified hydrogen using constant pressure-head capillary flowmeters. The gas mixture flowed upward in the furnace with flow rate of 400 cc per min at stp. The composition of the gas mixture was checked by chemical analysis at regular intervals. In most cases, the compositions of the exit gas and metered input gas agreed within about 0.3 pct, indicating that cracking of ammonia did not pose a problem at the temperatures employed. Two series of experiments were carried out using two different types of purified iron samples. In the first series of experiments at 550°C, vacuum carbon deoxidized "Plastiron" was used. The main impurities present in this iron were, in ppm: 4043, 50-Cr, 20-Zr, 40-Mn, 20-P, 20-S, 20-C, 50-0, and 10-N. In these experiments the rate data were obtained by measuring the change in weight of the iron specimen suspended in the hot zone of the furnace by a platinum wire from a silica spring balance. The nitride layer formed in these experiments was found to be porous, particularly near the outer surface. In other experiments, high purity zone-refined iron (prepared in this laboratory) was used. The total impurity content of this iron was 30 ppm of which 20 ppm was Co + Ni, 4 ppm 0, other metallic impurities were less than 1 ppm. The zone-refined iron bar, -2.5 cm diam, was cold rolled to a thickness of about 0.03 cm and the specimens were prepared for the experiment as described earlier. After the nitriding experiment, the sample was copper plated electro-lytically and mounted in plastic for metallographic polishing. After polishing, the thickness of the ?' layer was measured using a metallographic microscope. The nitride layer formed on the zone-refined iron was essentially free of pores. RESULTS The different morphology of the nitride layers grown on "Plastiron" and zone-refined iron is shown in Fig. 1. Both samples were nitrided side by side for 55 hr. The holes in the less pure iron, Fig. l(a), are confined to a region about one half thickness from the outer surface. The dense layer grown on zone-refined iron, Fig. l(b), is thinner than the porous layer on the "Plastiron". The impurities in the iron are believed to be responsible for the formation of a porous nitride layer. The pore formation may be due to the high nitrogen pressures existing within the nitride layer, e.g., the equilibrium nitrogen pressure is 1.2 x l05 atm in the 38.6 pct NH3-61.4 pct H2 and 6.6 x l03 atm at the Fe-Fe4N interface at 554°C and 0.96 atm. It is possible that the oxide inclusions present in the electrolytic iron may facilitate the nuclea-tion of nitrogen gas bubbles within the nitride layer. Support for this reasoning is the fact that pores are only encountered in the outer range of the layer where nitrogen pressures are largest. The photomicrographs in Fig. 2 show the effect of reaction time on the thickness of the dense nitride layer formed on zone-refined iron. These sections are from samples nitrided in a stream of 29 pct NH3-71 pct H2 mixture at 554°C for 22, 70, and 255 hr. In all the sections examined the nitride-iron interface was noted to be rugged. These irregularities are be-

Jan 1, 1970

By J. VAN DEN BERC

Tin production and export from the Far East are still a long way off from the prewar figures. The Malayan Peninsula, which had a rather good start directly after the war largely because of stock piles found in Singapore and elsewhere, has since been hampered in the rehabilitation of its tin mines and dredging operations by material shortages and, more recently and more severely, by revolts and attacks of communist elements and gangster bands. These hindrances make working in the mines dangerous and form a daily threat against the valuable and highly vulnerable dredges. Contrary to the conditions in Malaya are those on the tin islands of Billiton, Banka, and Singkep-all in the Netherlands East Indies-where the Dutch have re-established peaceful relations with the population. Dutch efforts since the fall of 1945 have been rewarded by continuously increasing production, extension of production facilities, and return of moderate prosperity, complete safety, and all-out co-operation among the population ? native and Chinese ? to the benefit of all concerned.

Jan 1, 1949

THE Howe Memorial Lecture, in memory of Henry Marion Howe, Past President of the Institute, was authorized in April, 1923, as an annual address to be delivered by invitation under the auspices of the Institute by an individual of recognized and outstanding attainment in the science and practice of iron and steel metallurgy or metallography, chosen by the Board of Directors upon recommendation of the Iron and Steel Division. The following were the Howe lectures and lecturers for the years indicated: 1924 What is Steel? By Albert Sauveur. 1925 Austenite and Austenitic Steels. By John A. Mathews. 1926 Twenty-five Years of Metallography. By William Campbell. 1927 Alloy Steels. By Bradley Stoughton. 1928 Significance of the Simple Steel Analysis. By Henry D. Hibbard. 1929 Studies of Hadfield's Manganese Steel with the High-power Microscope. By John Howe Hall. 1930 The Future of the American Ironand Steel Industry. By Zay Jeffries. 1931 On the Art of Metallography. By Francis F. Lucas. 1932 On the Rates of Reactions in Solid Steel. By Edgar C. Bain. 1933 Steelmaking, Processes. By . George B. Waterhouse.

Jan 1, 1946

By C.F. Pascoe, H.J. Roast

The object of this investigation was to compare the arsenical antimony-lead alloy with some of the regular bearing-metal alloys. With this end in view, the following tests were made: 1. Chemical analyses to show the composition. 2. Thermal analyses. 3. Macroscopic examination of fractures. 4.Microscopic examination. 5. Tensile tests. 6. Crushing tests. 7. Scleroscope tests.' 8. Brinell tests, at temperatures from 80' to 400' F. Tests 3 to 8 were conducted on both sand-cast and chill-cast specimens. For the purposes of this paper the alloys have been numbered from 1 to 6; their composition is as follows: Lead. ' Antimony, Tin, CoppeR ARSEnic, NumBeR PeR CENT. PER CENT. PeR Cent. PeR CeNt. PeR Cent. 1 82.64 12.95 4.40 0.01 none 2 27.54 9.04 59.87 2.65 none I 3 none- 0.13 ------------1.47 4 82.95 16.85 none 0.20 none 5 83.78 15.35 none 0.05 0.82 6 0.15 7.87 . 84.13 7.85 none The analysis, in the case of the antimony, was made by solution in sul-furic acid and titrated with permanganate. For tin, the ferric-chloride method was used; for copper, the alkaline separations, and the thio-cyanate methods; for arsenic, volatilization of arsenic and titration with iodine. The lead, with the exception of alloy 6, was taken by difference. With the exception of No. 5, the alloys were taken as received from the manufacturer. About 40 lb, were melted in a graphite crucible and recast into small ingots to insure uniformity of composition; samples

Jan 1, 1923

By C. F. Pascoe, H. J. Roast

The object of this investigation was to compare the arsenical antimony-lead alloy with some of the regular bearing-metal alloys. With this end in view, the following tests were made: 1. Chemical analyses to show the composition. 2. Thermal analyses. 3. Macroscopic examination of fractures. 4.Microscopic examination. 5. Tensile tests. 6. Crushing tests. 7. Scleroscope tests.' 8. Brinell tests, at temperatures from 80' to 400' F. Tests 3 to 8 were conducted on both sand-cast and chill-cast specimens. For the purposes of this paper the alloys have been numbered from 1 to 6; their composition is as follows: Lead. ' Antimony, Tin, CoppeR ARSEnic, NumBeR PeR CENT. PER CENT. PeR Cent. PeR CeNt. PeR Cent. 1 82.64 12.95 4.40 0.01 none 2 27.54 9.04 59.87 2.65 none I 3 none- 0.13 ------------1.47 4 82.95 16.85 none 0.20 none 5 83.78 15.35 none 0.05 0.82 6 0.15 7.87 . 84.13 7.85 none The analysis, in the case of the antimony, was made by solution in sul-furic acid and titrated with permanganate. For tin, the ferric-chloride method was used; for copper, the alkaline separations, and the thio-cyanate methods; for arsenic, volatilization of arsenic and titration with iodine. The lead, with the exception of alloy 6, was taken by difference. With the exception of No. 5, the alloys were taken as received from the manufacturer. About 40 lb, were melted in a graphite crucible and recast into small ingots to insure uniformity of composition; samples

Jan 1, 1923

By AIME

BORN in 1899, in Bridgeport, Conn., E. A. Anderson grew up in a center of the nonferrous metal industry. Perhaps that had something to do with his selection of mining as a career while an undergraduate in Yale. After securing his Ph.B. in mining he worked for a year at Handy & Harman. By this time physical metallurgy had supplanted his interest in mining and he entered the Yale graduate school where he secured his M.S. degree in metallography under C. H. Mathewson. After completing his graduate work he entered the employ of The New Jersey Zinc Co. in their research division where he has remained ever since. The transition from graduate study to industry involved no disruption of technical interests. Academic research relating to the zinc-aluminum alloys, then coming into use for die-casting, was followed by extensive and productive industrial research in the perfection and commercialization of these alloys. Research on rolled zinc and rolled zinc alloys, corrosion and stress corrosion, dry cells, electroplating on zinc, and electrodeposition of zinc followed in overlapping succession as time passed.

Jan 1, 1947

The following is am incomplete list of members and guests who called at Institute headquarters during the period May 10, 1918 to June 10, 1918. Arthur K. Adams, Potrerillos, Chile. J. M. Mahoney, Wilkinsburg, Pa. John Carter Anderson, Tucson, Ariz. Benjamin L. Miller, South Bethlehem, Pa. George S. Blair, Camp Cordon, Ga. Wilbur A. Nelson, Nashville, Tenn. W. A. Deane, Summitville, N. Y. Miles G. Nixon, Chicago, Ill. Charles H. Fulton, Cleveland, Ohio. Walter G. Perkins, San Francisco, Cal. Rudolf Gahl, Inspiration, Ariz. G. M. Ponton, Ottawa, Canada. C. C. Griggs, Eureka, Utah. D. A. Powell, Columbus, Ohio. J. F. Hanst, Potrerillos, Chile. H. W. Reed, Salt Lake City, Utah. Stanley C. Herold, Pittsburgh, Pa. J. C. L. J. Seelig, Padong, East. Indies. Floyd D. James, Boston, Mass. Oberlin Smith, Bridgeton, N. J. Charles Janin, San Francisco, Cal. Harrison Souder, Cornwall, Pa. E. Horton Jones, Copper Cliff, Ont. Stanley A. Spellmeyer, Camp Meade, Md. William Kelly, Vulcan, Mich. Roger S. Sperry, Waterbury, Conn. Ichiro Kitsunezaki, Tokyo, Japan. D. R. Thomas, Toronto, Canada. P. K. Lucke, San Antonio, Tex. Thor Warner, Phoenix, Ariz. E. Francis McCrossin, Birmingham, Ala. L. Douglass Anderson, formerly superintendent of the United States Smelting Co., Midvale, Utah, is now manager of smelters, Intermountain District, United States Smelting, Refining & Mining Co., Salt Lake City, Utah.

Jan 7, 1918

C. H. MATHEWSON, New Haven, Conn. (written discussion *).-In a recent discussion of Dr. Jeffries' paper on tungsten,1 J. C. W. Humfrey,2 after taking exception to certain of the author's ideas relative to the cohesion of A and C metal, expresses the opinion that future research is likely to develop a method of preparing tungsten possessing "mechanical properties in line with those of other metals." The present paper by Dr. Jeffries begins with a determination of comparative properties of tungsten, copper, and iron, in which much dissimilarity is apparent, and ends with a coherent explanation as to why much of this dissimilarity is natural and inevitable, thereby supplying theoretical means for visualizing the changing properties of metals in general, once certain fundamental facts are known. The author's reasoning is primarily from the standpoint of the amorphous theory and his principal achievement is the development of an idea f differential cohesion according to conditions of temperature, etc., between A and C metal (which was first plainly suggested by Rosehain and Ewen, in their papers on Intercrystalline Cohesion of Metals) along with associated ideas, so as to give us a really useful working theory. I have come rather reluctantly to believe in the amorphous theory, or some theory admitting a modification of the ordinary crystalline phase so as to permit differential properties within the conglomerate, mainly because in no other way does it seem possible to account for observed changes of properties with temperature, etc. The very best illustration f the competency f the amorphous theory in this respect is seen in this and other recent papers by the author. All fractures through normal or healthy metal that have been preceded by deformation are supposed, by Dr. Jeffries, to take place either through the amorphous phase or at certain boundaries between amorphous and crystalline material; his reference to fractures, both members of which are similar in appearance and do not reveal a preexisting coarse-grained structure because of a coating of amorphous metal, indicates his preference for the former interpretation.

Jan 5, 1919

By AIME AIME

WHEN H. I. Smith joined the Institute back in 1908, he was an instructor in mining and metallurgy at Penn State the college from which he had graduated the year before with a B.S. degree. He had not gone far afield for his education, for he was born, February 15, 1984 at Finleyville, Pa., a small village some fourteen miles south of Pittsburgh and without doubt famous chiefly as H. I.'s birthplace. The summer that he graduated he took a trip to the copper mines Arizona and Mexico and en route worked for four weeks for the Portland Gold Mining Co. at Cripple Creek, Colo., as a mucker and trammer. The next summer he roamed farther afield mines and metallurgical works in Europe. Wishing to see more of Arizona, he left the Penn State faculty early in 1909 and went out to Wenden in that State to become mining engineer and assistant superintendent of something called the Corona Copper Co., with 72 mining claims and a one-mule-powered whim for a hoist. When that job folded he helped build the Santa Fe railroad from Parker. Ariza., to Danby Cialif., and then came back to Pennsylvania to enter Government services as a junior mining engineer with the Bureau of Mines.

Jan 1, 1943

By H. P. Allen

The Achotla mill of the Cia. Minera de Penoles is of special interest in that it is one of the few still employing the chloridization process. The ore milled comes from the Suriana mine and consists of both oxide and sulphide, from neither of which can the gold or silver be extracted by a simple cyanide treatment. The mill was built in 1927, after several years of study in the development of the process1, and operated from December of that year until October 1930. Operations were resumed in February 1935, and have been continuous since, treating approximately 5000 tons per month, while the mine is getting up to full tonnage of 6500 tons per month. Transportation of Supplies The property is in Guerrero, Mexico, some 175 km. by airline southwest of Mexico City. The mill site is at Temisco (Fig. I), 8 km. from the Balsas River and 4.8 km. by aerial tram from the mine. At Temisco are the general office, shops, warehouses and laboratory serving both mine and mill. Here sufficient water is available either from a small creek running through the property or from the Balsas River, also convenient and ample storage space for the tailings. With the exception of the mine timber and a few native building materials which may be obtained locally, all supplies for both mine and mill are brought down the Balsas River from Balsas, the terminal of a Mexican National Railway line out of Mexico City. The method of transportation on the river is interesting. Rapids with very fast water are numerous, prohibiting the use of mechanically propelled boats. Those used resemble large, flat-bottomed rowboats some 22 ft. long by 8 ft. wide (Fig. 2). They are manned by two oarsmen sitting in the bow, each handling one large oar, and usually another man in the stern who, with his oar, assists in steering the boat, especially when the rapids are run. From 3 to 7 tons of freight are carried on each boat, depending upon the stage of the water, which governs also the time

Jan 1, 1939

By H. P. Allen

The Achotla mill of the Cia. Minera de Penoles is of special interest in that it is one of the few still employing the chloridization process. The ore milled comes from the Suriana mine and consists of both oxide and sulphide, from neither of which can the gold or silver be extracted by a simple cyanide treatment. The mill was built in 1927, after several years of study in the development of the process1, and operated from December of that year until October 1930. Operations were resumed in February 1935, and have been continuous since, treating approximately 5000 tons per month, while the mine is getting up to full tonnage of 6500 tons per month. Transportation of Supplies The property is in Guerrero, Mexico, some 175 km. by airline southwest of Mexico City. The mill site is at Temisco (Fig. I), 8 km. from the Balsas River and 4.8 km. by aerial tram from the mine. At Temisco are the general office, shops, warehouses and laboratory serving both mine and mill. Here sufficient water is available either from a small creek running through the property or from the Balsas River, also convenient and ample storage space for the tailings. With the exception of the mine timber and a few native building materials which may be obtained locally, all supplies for both mine and mill are brought down the Balsas River from Balsas, the terminal of a Mexican National Railway line out of Mexico City. The method of transportation on the river is interesting. Rapids with very fast water are numerous, prohibiting the use of mechanically propelled boats. Those used resemble large, flat-bottomed rowboats some 22 ft. long by 8 ft. wide (Fig. 2). They are manned by two oarsmen sitting in the bow, each handling one large oar, and usually another man in the stern who, with his oar, assists in steering the boat, especially when the rapids are run. From 3 to 7 tons of freight are carried on each boat, depending upon the stage of the water, which governs also the time

Jan 1, 1939

By K. L. Komarek, P. F. J. Landler

Synthetic polycrystals of wustite were reduced ilz H2-H2O mixtures over limited roncentration ranges wiltun the wustite. field and the weight changes were continuously followed with a McBain quartz spiral balance. The reduction was. found to be controlled by a combined surface plus solid-state diffusion reaction. The solid-state diffusion had an activation energy of 38 kcal. Self--diflusioities of iron decreased with itzcreasing vacancy concentration. The activation energy of. the surface reaction runs different tor- different samples. The surface reaction-rate constan increased with increasirzg vacancy concentration. THE reduction of the oxides of iron has been studied for many years. Edstroem' has summarized the early work and has provided much information on the reduction of magnetite and hematite by hydrogen and carbon monoxide. More recent summaries are those by smeltzer2 and Themelis and Gauvin.3 Most investigators have reported that the iron metal which forms the outer layer during gaseous reduction is rather porous. According to Kohl and Engel14 the formation of such a porous iron layer depends on the properties of the underlying wiistite layer, on the reaction of the gas with the wustite surface, and on the transport of matter through the wustite layer. McKewan, Quets, Wadsworth, and Lewis, and Knacke 10 have found that, if a porous iron layer is formed, a surface reaction between gas and wustite at the bottom of the pores controls the rate of reaction. Seth and ROSS 11 and Warner 12 have pointed out that the influence of the gaseous pore diffusion through the porous iron layer cannot be neglected. It has further been shown that the wiistite layer formed during reduction is dense and that transport of matter across the layer occurs only by solid-state diffusion of iron ions.13,14 The solid-state diffusion rates observed by Edstroem and Bitsianis 14 and the surface reaction rates observed by Quets eta1.' show that an interaction of the two steps in controlling the reaction rate has to be considered. In this investigation the reduction of wustite was studied with respect to the interaction of the two steps, isolated from any other effects, by reducing wustite within the wustite field from higher to lower oxygen concentrations with H2-H2O gas mixtures. A similar study with CO-CO2 mixtures has been performed by Levin and wagner.15 Fused synthetic wustite polycrystals were reduced in steps of 0.4 wt pct from 24.4 to 23.2 wt pct 0 and over a temperature range from 700" to 1050°C. A few tests were also conducted with reduction steps from 24.4 to 23.6 wt pct 0 and 24.5 to 23.2 wtpct0. The Fe-O phase diagram is shown in Fig. 1 where the composition of the gas phase in equilibrium with the condensed phases is plotted as pct H2 vs the temperature. A careful study of the literature led to the conclusion that the fully drawn equicomposition curves (in wt pct O) in the wustite field used by Edstroem 1,16 and other authors needed some correction. Based on results by Darken and Gurry17 (shown as open circles) and on some of our own data, four corrected curves for 23.2, 23.6, 24.0, and 24.4 wt pct O were calculated (drawn as dashed lines in Fig. 1) which should replace the fully drawn equicomposition curves. MATERIALS AND APPARATUS Materials and Specimen Preparation. Wustite was prepared from iron sulfate (Fisher Scientific Co., New York) which had a purity of over 99.92 pct, with small amounts of manganese, copper, and zinc adding up to 0.03 pct. From the aqueous solution iron oxalate was precipitated and decomposed to magnetite according to Economos. 18 The magnetite powder was pressed into cylinders and sintered in vacuum at 900°C for several hours. The sintered compacts were placed in a platinum crucible of 2.5 cm diam which was fitted into a high-purity alumina crucible and then inserted into the center of the graphite heating element of an electric resistance furnace.lg The furnace was evacuated to below 1 p Hg and the magnetite sample was slowly heated. The evolution of gases during heating deter-

Jan 1, 1967

By Charles Prasky, Robert K. Zahl, John C. Nigro

Bench scale and pilot plant research was conducted using dolomitic (CaO - MgO) lime as the basic additive in the preparation of self-fluxed pellets from a typical magnetic taconite concentrate (5.5% SiO2). The specific objective of this investigation was to ascertain the viability of the magnesia lime pellets in high temperature oxidizing and reducing atmospheres. Pellet basicity and induration temperature were major parameters affecting fired pellet quality; temperatures ranging from 1200° to 1250°C appeared to be the most favorable for production of self-fluxed pellets with basicities (B) above 1.0. Comparison of the mechanical and metallurgical properties of regular (acid) and self-fluxed pellets (B = 1.55) produced under similar conditions in a modified grate pelletizing machine showed that the selffluxed pellets were more resistant to abrasion and to high and low temperature reduction disintegration, an important consideration in commercial application. The +3 mesh Linder index increased from 68% (regular pellets) to over 90% (self-fluxed pellets). The reducibility and swelling indices of the self-fluxed pellets were found to be comparable to the regular pellets.

Jan 1, 1974

By M. B. Bever, A. K. Jena

In the investigation reported here, calorimetric measurements have been made to determine the heat of formation of the compound AuSb2 and the partial gram-atomic enthalpies of antimony and gold in dilute solution in liquid tin and their enthalpy interaction coefficients. In order to interpret the behavior of antimony and gold in dilute solution in tin, nonzero values are assigned to the energies of bonds between like solute atoms relative to the pure solute state. Sa.mples of the compound AuSb2 were prepared by melting stoichiometric amounts of antimony and gold (99.999 pct pure) in evacuated and sealed Vycor tubes, which were shaken vigorously and quenched in water. The ingots were annealed in evacuated and sealed tubes at approximately 700°K for 2 weeks. Metallo-graphic and X-ray examinations gave no indication of second phases or microsegregation. The samples were added from 273°K to tin-rich solutions in a solution calorimeter1 maintained at 623°K. The calorimeter was calibrated with tin; the heat content of tin, H623°K- H273°K, was taken as 4.08 kcal per g-atom.2 In each calorimetric run at least four additions were made. The total concentration of solutes in the bath at the end of any run did not exceed 1 at. pct. The measured heat effect of an addition was plotted against the average of the atom fractions x of Sb + Au in solution before and after that addition. From this plot the heat effect at infinite dilution h,,, and the composition dependence of the heat effect dh/dx in the composition range 0 < x < 0.01 were obtained. The results for the additions of antimony, mixtures of antimony and gold, and the compound AuSb2 are listed in Table I. The heat effect h on addition of a sample of the compound AuSb2 or a mechanical mixture of antimony and gold at 273°K to a tin-rich solution at 623°K can be expressed as:

Jan 1, 1969