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By Thomas L. Kesler

IF all of the 14 million tons of kaolin produced in Georgia through 1949 had been mined from a single deposit 20 ft thick, it would represent a mined-out area of less than 1 sq mile. This measure of depletion is in such strong contrast with the large size of the area shown in Fig. 1, from which most of the output has come, that there has developed an optimistic outlook concerning future supplies of kaolin equal in grade to that already mined. Dozens of mines are widely but not evenly distributed within this area, which consists mostly of parts of Twiggs, Wilkinson, and Washington counties. There are scarcely half a dozen kaolin mines elsewhere in the state that have been appreciably productive, although the areas in which they occur may have good possibilities. Most of the efforts to find new deposits, therefore, will be confined to the area shown in Fig. 1, for it is here that the industry has established its facilities, and prospecting is encouraged by relatively numerous outcrops and opened deposits of kaolin.

Jan 10, 1951

By D. Harrington

One of the main functions of the United States Bureau of Mines is to obtain and disseminate information that will promote safety in and around mines, and the health and safety of employees engaged in mining. Serious health and safety conditions arising out of contamination of air in metal mines by dust, fumes from explosives and fires, and absorption of oxygen by timber and other causes, led the Bureau of Mines to cooperate with the United States Public Health Service in the study of dust occurrence and ventilation in metal mines in various parts of the country. A. J. Lanza, of the U. S. Public Health Service, and Edwin Higgins, mining engineer of the U. S. Bureau of Mines, in 1915, made a detailed study in the mines around Joplin, Mo.; their reports1 are now available. In 1916, 1917, and 1918, a similar study was made in the Butte, Mont., region by Doctor Lanza and D. Harrington, mining engineer of the Bureau of Mines; the reports of this investigation will be available soon. In 1919, the study was continued in some of the Arizona mines by D. Harrington, of the Bureau of Mines, and G. E. McElroy and R. A. Koronski, of the U. S. Public Health Service, the underground work being completed in June, 1920; these reports are now being prepared for publication. In the spring of 1920, the scope of the work was extended, with D. Harrington in charge as supervising mining engineer, and short studies were made in the mines of the Coeur d' Alenes in Idaho and around Oatman, Ariz. It is hoped soon to extend the work into mines of California, Nevada, Colorado, Michigan, and Minnesota, and ultimately to other states should the mining companies be willing to coöperate. While the coöperation of the mining companies is necessary, the companies are put to practically no expense other than supplying a guide to accompany the investigators underground, the length of time spent

Jan 1, 1922

By Jerome Strauss

IN his review of developments in 1943, Gilbert Seil, Chairman of this Committee on Reduction of the Ferroalloy Ores, tabulated the consumption of the alloying metals in relation to the steel production of that year. In the year just closed the approximate tonnage was of the same order, differing only to a minor degree or suffering some correction with more precise figuses available, as indicated in the following estimates: Consumption Metals in Tons Steel 92,000,000* Manganese 700,000 Silicon 200,000 Chromium 200,000 Nickel 75,000 Molybdenum 20,000 Tungsten 8,000 Vanadium 1,700 Titanium 1.600 Boron 10 `Production figure. The technologic studies instituted during 1942 and carried forward with such great vigor during 1943 continued into 1944 although in some instances were brought to a close either by completion of the specific development

Jan 1, 1945

By E. H. Hamilton

THE furnace on which the following investigation was based had dimensions 48 by 160 in., and was in continuous operation during the three days of the test. The average charge consisted of PER CENT. LB. PER HOUR Bed ore?14.5?2,980 Roast from Dwight-Lloyds?44.5?9,160 Siliceous ore?3.5?720 Iron flux?2.1?430 Battery plates?0.5?103 Lime rock?23.9?4,925 Briquettes?4.0?825 Scrap iron?2.1?430 M. P. slag?4.2?865 L. P.speiss?0.7?142 Total 100.0 THE furnace on which the following investigation was based had dimensions 48 by 160 in., and was in continuous operation during the three days of the test. The average charge consisted of PER CENT. LB. PER HOUR Bed ore?14.5?2,980 Roast from Dwight-Lloyds?44.5?9,160 Siliceous ore?3.5?720 Iron flux?2.1?430 Battery plates?0.5?103 Lime rock?23.9?4,925 Briquettes?4.0?825 Scrap iron?2.1?430 M. P. slag?4.2?865 L. P.speiss?0.7?142 Total?100.0?20,580

Jan 1, 1924

By C. O. Lee, R. H. Feierabend, Z. W. Bartlett

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By L. C. Brown, J. S. Kirkaldy

Measurements have been made of carbon diffuswn in the five ternary austenites Fe-C-Si, Fe-C-Ni, Fe-C-Co, Fe-C-Mn, and Fe-C-Cr in which the carbon (component 1) diffuses through interstitial sites and the ternary addition (component 2) diffuses substitutionally. Values of the diffusion-coefficient ratio, D12/D11 were determined for each system with finite couples using the transient equilibrium method. The effect of temperature and of concentrations of both the carbon and substitutional component upon D12/D was examined and was found to agree with the theoretical predictions. It is concluded that within an experimental uncertainty of 10 to 15 pct, it is possible to calculate the ratio D12/D11 from purely thermody-namic data. Difficulties of measuring the other off-diagonal coefficient, 4,, are discussed. Any quantitative attack on the fundamentals of the hardenability problem in steel must begin with the multicomponent diffusion formalism and with the accumulation of data pertaining thereto. In a recent paper Kirkaldy and purdy 1 employed the formalism derived from irreversible thermodynamics to treat the problem of diffusion in ternary austenites. In the latter solutions, carbon diffuses through interstitial sites and the substitutional component diffuses through the lattice. Examples were given of diffusion in the systems Fe-Mn-C and Fe-Si-C. In the present paper, we present new results on and discuss their agreement with the thermody-namic theory. Since the theory has been slightly modified from the original presentation of Kirkaldy and Purdy, their results on Fe-Si-C and Fe-Mn-C have been recalculated and are presented here for completeness. The flux of the interstitial component with respect to a fixed lattice framework can be written as a linear expansion in the independent concentration gradients, where X1 and X2 are the independent thermody-namic forces in the lattice fixed frame of reference. These forces can be obtained from the general statement for forces in a volume fixed frame2 if the partial molar volume of carbon atoms is set equal to zero and that of the substitutional component 2 is set equal to unity, viz where the are the chemical potentials and the N's are mole fractions. Introducing into [3] and [4] the function If, as suggested by statistical arguments, the off-diagonal interaction L12 is sufficiently small, [6] reduces to i.e., the coefficient ratio becomes purely thermo-dynamic. The activity of components 1 and 2 in a dilute ternary system (standard state at infinite dilution) may be represented by the expansion3

Jan 1, 1964

By R. M. Hudson, P. E. Perry

Weight-gain data obtained by nitriding low-carbon sheet steel in an amrnonia CNH,) atmosphere indicated that the process obeyed a parabolic rate law. The calculated actization energy for nitriding in the range 964" to 1268°F agreed reasonably well with published data. At 1358"F, rate data indicated that the activation energy decreased. Weight-gain data obtained by uszng mixtures of NH3 -Nz at 1268°F containzng jrom 10 to 100 zol pct NH3 also obeyed a parabolic rate law. The rate of 'nitriding increased with an increase in the NH3 content of the gas Mixture. It is well-known that steel heated in gas mixtures containing ammonia (NH3) takes up much larger quantities of nitrogen than steel heated in nitrogen, both gases having a total pressure of 1 atm;' this phenomenon can presumably be attributed to the catalytic decomposition of NH3 on the steel surface to furnish nascent (monatomic) nitrogen. This process was studied bv Brunauer. Jefferson, Emmett, and Hend-ricks at furnace temperatures of 752" and 831°F2 using mixtures of NH3 in Hz. Englehardt and wagner3 reported that, at a furnace temperature of 914°F and under their experimental conditions, both nitriding and denitriding were controlled by the rate of gas-metal reactions at a steel surface rather than by the rate of diffusion of nitrogen in iron. The present study was undertaken to obtain information on the kinetics of nitriding low-carbon steel strip at higher temperatures so that practical rates for short-time strip-annealing treatments could be estimated. Variables studied included time: temperature, and NH, content in the annealing atmosphere. Mechanical and chemical characteristics of steel nitrided in this manner will not be considered in the present article. MATERIALS AND EXPERIMENTAL WORK The samples used were from a commercial low-carbon steel, 0.0244 cm thick, in the cold-reduced condition. The chemical composition of this steel is given in Table I. Panels were cut to 5.1 by 17.8 cm, degreased in toluene, and weighed just before treatment. Four specimens were nitrided under each of the experimental conditions. A study was made of the nitriding rate of steel in a 100 vol pct ammonia atmosphere, 740 mm pressure, at five specific temperatures within the range 964" to 1358°F. The nitriding rates of steel in ammonia-nitrogen gas mixtures containing 10, 18, 26, 50, and 100 vol pct ammonia, 740 mm total pressure, at 1268°F were also determined. All atmospheres used were dried by successively passing them through drying towers packed with soda lime and with Linde Molecular sieve Type 4A. Quoted gas compositions refer to those entering the furnace. Specimens were held in the constant-temperature zone of a vertical annealing tube furnace for times of 14, 3, 5, 10, or 15 min. Gas flow rates were maintained at 3.8 cu ft per hr, which was nineteen volume changes per hour for the system used. The rate of flow was selected to provide a high level of free NH3 for cracking on the steel surface where the ammonia gas is most effectively used as a nitriding agent. The vertical annealing tube furnace consisted of a Hevi-Duty tube furnace with a 2 1/2-in.-ID mullite ceramic high-temperature tube. The constant-temperature zone (controlled within 10°F) was about 10 in. long. After each specimen was degreased, a hole was punched in one end, for attaching the specimen by hook to a chain so that it could be lowered into or raised from the high-temperature portion of the tube by means of a power-driven winch. A stainless-steel access port with O-ring seals was connected by suitable glass-to-metal seals to the cool upper portion of the furnace tube. After the weighed specimen was placed in the access port, the furnace tube was evacuated to approximately 10"3 torr, and then the system was flushed thoroughly with the atmosphere under study. When the gas flow rate and constant-temperature zone of the furnace were established, the specimen was lowered into the constant-temperature zone. The atmosphere flowed from the top to the bottom of the vertical furnace tube and was then vented. For all these runs, during the first 3 min of the time the specimen was in the constant-temperature zone of the furnace the specimen was heating up to the tempera-

Jan 1, 1970

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;'-' and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By C. F. Smart

THE heat treatment of the bronze composed of 88 per cent. copper, 10 per cent. tin, and 2 per cent. zinc, has been investigated by H. S. and J. G. S. Primrose,1 and also by the U. S. Bureau of Standards.2 The results obtained by H. S. and J. G. S. Primrose on dry-sand castings subjected to reheating followed by air cooling, or by quenching in water, are shown in Figs. 1 and 2. The values for tensile strength have been FIG. 1.-EFFECT OF QUENCHING ON DRY SAND CASTINGS (H. S. AND J. G. S. PRIMROSE.) converted from tons per square inch to pounds per square inch. Figs. 3and 4, have been plotted from values obtained by the Bureau of Standards on material of the same composition and treatment. Both investigations show that the ductility of the cast bronze is improved by heating to 700° C. and cooling in air, the strength not being impaired by this treatment. They are not in agreement, however, as to the effect of quenching, Messrs. Primrose reporting a decrease, and the Bureau of Standards an increase, in both strength and ductility when the cast bronze is heated to 600° or 700° C. and quenched.

Jan 9, 1919

By J. S. Marsh, T. B. Winkler

THE past year, the first full one of peacetime production, proved that the process of beating swords into plowshares has increased in complexity in step with civilization. Further, judging by various remarks of our distaff departments, the crystal balls of certain radio and magazine oracles must have been cloudy, because we have been in formed from time to time that coveted items such as automobiles and refrigerators did not appear in great abundance. This seemingly extraneous matter is really not out of place here, however; the steel producer and the fabricator exist in a sort of symbiosis: the making of consumer goods produces scrap which is returned to the steelmaker who makes more steel, and so on and so forth. Thus, no abundance of automobiles, no abundance of scrap from this normal source; and other sources had been picked pretty clean during the war. To be short, so was scrap. Since the economy of the steel industry lean; as heavily upon iron from scrap as upon iron from ore, the statement on transformation of swords to plowshares follows. But this is not the whole story: after all, ingot production was a record for a peace year!

Jan 1, 1947

By S. S. Clarke

ABOUT two years ago some of my friends were discussing the amount of drill-steel breakage that was permissible or not excessive, per month, per rock ton, per ton of steel or any unit of measure or output that would give a comparison between different kinds of drill steel. No one seemed to know what life to expect of steel, or what percentage of breakage might be termed excessive. In fact there were no operating data available to guide one in selecting the best steel for our mines, nor could any ideas or information be secured from the steel manufacturers. One was merely told that so and so used their steel and it was very satisfactory; or else one was given a highly technical lecture on their specific heat-treatment. Any estimates on expected breakage were just guesses, ranging from a fraction of a per cent to as high as ten per cent per month.

Jan 1, 1933

1. Healthy and active Local Section organizations are vital factors in promoting the vigor and growth of the Institute. 2. Activity on the part of Local. Sections should be recognized and stim¬ulated by appropriation of funds from the Institute's treasury; and these appropriations should be as large as is consistent with the relative needs for other activities. 3. As between different Sections, the amount of such appropriations should be based primarily on the extent of activities as reflected in the number and character, of meetings held and the attendance of the members at such meetings. 4. In making a request for funds for any year, the officers of a Local Section should submit a report on the printed form approved by the Directors at their meeting on November 19, 1937. 5. A . standing Committee on Local Section Appropriations, consisting of one past chairman of a Local Section, one member of the Institute's Executive Committee, and one member of the Finance Committee, shall be appointed by the President and shall pass upon requests for appropriations and authorize payments within bounds of the budget. The committee will be guided by the principles herein outlined, always having in mind the vital importance of healthy, active sections to the welfare of the Institute as a whole.

Jan 1, 1938

By AIME

TO say that Milton Fies has been active in promoting the Southern Research Institute is a masterpiece of understatement. He is a director and trustee who was in on the ground floor when plans were first made for the Institute and since it became an actuality early in 1945 his interest and efforts continue. He talked about it at the last regional meeting of the Birmingham Section of the A.F.A. and has talked all over the South-and when he makes a speech he has really prepared it. He does not try to rival a political spellbinder, but his careful, concise English is always well thought out and to the point. Southern Research might be called his present hobby as it has been for the past two or three years. Another major interest has been his encouragement and training of engineering students. Active in the formation of the Student Chapter of the A.I.M.E. at the University of Alabama, for several years he saw to it that the students had a prominent engineer at each monthly meeting, usually taking them down to Tuscaloosa from Birmingham in his own automobile. He has also been keenly interested in the mining engineering activities at Tuscaloosa, both in the Bureau of Mines and the University.

Jan 1, 1946

By E. T. Turkdogan, P. Grieveson

It is shown experimentally that, by making use of the coupled S-O reaction in ionic melts, it is possible to transfer slclJur or oxygen from a lozv to a high chemical potential through an ionic nzenzbrane. This uphill transfer of sulfur is accompanied by a counter downhill transfer of oxygen and vice versa. The Materials balance shows that the amoulits of sul -fur and oxygen lost or gained by one system are the same as those gained or lost by the other systenz — the two systejns being separated by an iofzic membmne. The systems used in these experi?nents were solid Mn-MnS-Mno and liquid Fe-S-0. Sufficient results were obtained Lo study the kinetics of the transfer and the indications are that the counter diffusion of sulfide and oxide iojzs in the membrane is the rate controlling process. WHEN an ionic oxide-melt reacts with an atmosphere containing sulfur and oxygen-bear ing gases the following reaction occurs: 1/2 S2 (gas) +O2- (melt) = S2- (melt) + 1/2 0, (gas) [1] Under the restrictions that i) electric conductance in the melt is purely ionic and ii) each constituent element in the melt does not change valence, the solution of an atom of sulfur in the melt will result in the evolution of an atom of oxygen, so that the electric neutrality is maintained. For a given temperature and melt composition, the equilibrium concentration of sulfur in the melt is determined by the ratio, po2 /ps2 , in the gas phase and not by the individual partial pressures of oxygen and sulfur. This has been demonstrated by a number of investigators, for example by Richardson and withers', Fincham and Richardson,la by St Pierre and Chipman,' and by Turkdogan and Darken.3 In his Howe Memorial Lecture for 1961, Darken discussed the possibility of uphill pumping of sulfur through an ionic membrane at the expense of oxygen. TO test the validity of this concept associated with coupled reactions, experiments were carried out in the following manner. A presintered mixture of Mn-MnS-MnO and prefused mixture of Fe-S-0, contained in platinum and iridium crucibles, respectively, and separated by a thin layer of soda-glass (to act as an ionic membrane), were placed side by side in an evacuated silica capsule and sealed. This was then kept at 1400°K for a required time to allow Reaction [11 to occur via the ionic membrane. When partial equilibrium is reached, the ratios Po2 /pS2, for systems on either side of the membrane, are equal and the flux of sulfur and oxygen through the membrane becomes zero, although the individual partial pressures po2 andp,, in these two systems may differ considerably.

Jan 1, 1962

By JOHN R. SUMAN

TONIGHT I want to speak of the current problems and the postwar difficulties facing American industry. American industry has done an outstanding job in adjusting its operations to wartime necessity. The national income for 1942 was nearly $120,000,090,000 and of this outlay approximately $55,000,000,000 went for war material. The enormity of the expenditures for war material is indicated by the fact that the expenditures for war purposes alone were greater than the annual gross national income in the period 1931-34. This tremendous production job in turning out a record output of war products was accomplished by industry in spite of a large number of restraining and hampering influences, and I want to mention several of the more important problems.

Jan 1, 1943

By David J. Mack, Dennis R. O’Boyle

The mechanical properties of three polycrystalline intermediale Phases that have the y bvass structure were measured in compression between 400° and 900°K. At the lower testing temperatures— termed Region I— no plaslic deformalion occurred prior to brittle fracture. A1 higher temperatuves— lermed Region III—the three phases deformted plaslically for all strain rules from 1.5 to 36.0 x 10-4 sec-1. The homologous temperature for the inilialion of plaslic flow increased in the same order as tile atomic size difference between atoms in each plmse (0.50Tmp for y AgZn, 0.62Tmp for y CuZn, and 0.76 Tmp for y CuCd). The increased flow resistance oj. y CuCd above 0.50Tmp is explaitzed in terms of the more random arrangement of copper and cadmiwn atoms on the laltice sites of&apos; the y bvass slrilctlire. Plaslic deformation of the three intevmiediate phases in the smooth plaslic flow region appears to be controlled by oacancy-induced dislocation climb. RESULTS are reported in this paper on the mechanical properties of three binary intermediate phases having the complex cubic y brass structure (D82, 143m) containing fifty-two atoms in the unit cell. The structure of the prototype y brass phase, y CuZn, was first analyzed by Bradley and Thewlis&apos; based on the X-ray work of Westgren and Phragmen.2 The y brass structure can be visualized as an arrangement of twenty-seven body centered cubes (3 by 3 by 3) into a unit cell containing fifty-four atoms. From this cell the center atom and the four corner atoms are removed and the remaining fifty-two atoms are slightly displaced, resulting in the y brass structure. Approximately thirty-five binary intermediate phases that have an electron to atom ratio of 21:13 have been reported to form the y brass structure. The three y brass intermediate phases selected for this study are formed from elements in groups IB and IIB of the first and second long period. Each compound exists over a composition range that includes the stoi-chiometric composition A5BB (Cu5Zn8, Ag5Zn8, Cu5Cd8). y CuZn (a0 = 9.944A) has solubility limits extending from 57 to 67 at. pct Zn at 500°C apd melts peritecti-cally at 834°C; y AgZn (a0 = 9.326A) has a solubility range from 58 to 63 at. pct Za and melts peritectically at 661°C. y CuCd (a, = 9.596A) melts congruently at 563°C and has a maximum range of solubility extending from 58 to 64 at. pct Cd. In order to minimize coring and microporosity during solidification, the composi- tion of the compounds that form peritectically (y CuZn and y AgZn) was chosen so that the temperature difference between the liquidus and the solidus is only a few degrees centigrade. In selecting y brass compounds for this study, phases were avoided that contained a transition element or that had an electron to atom ratio greater than 1.70. Hume-Rothery et a1.3 has observed that, when the electron to atom ratio of y brass intermediate phases exceeds 1.70, atoms begin to drop out of the unit cell to maintain a constant electron to unit cell ratio. EXPERIMENTAL PROCEDURE Each of the three intermediate phases was prepared from elements having a purity >99.999 pct. Only trace quantities of impurities (<0.0001 pct) were detected by spectrographic analysis of the four elements. A master alloy of each compound weighing approximately 130 g was prepared by melting the elements in evacuated sealed quartz tubes heated in an electric furnace. Specimens having the desired diameter for the mechanical property measurements were obtained by remelting the master alloy in a Vycor tube under argon and drawing specimens from the melt into 4-mm-diam quartz tubes. To obtain a smooth surface on specimens drawn from the melt, the inside of the quartz tube was coated with a thin layer of graphite formed by thermally decompositing acetone. All specimens were imbedded in sealing wax and cut to the proper length with a diamond-impregnated cut-off wheel. The individual specimens (4 mm diam by 8 mm long) were then sealed in evacuated Pyrex tubes and homogenized at 500°C for 72 hr. Chemical composition, variations over the length of the rod (10 cm long) were generally less than 0.2 pct and the analyzed composition differed from the desired composition by less than 0.5 pct.4 Metallographic evaluation of the specimens after homogenization showed no evidence of a second phase in any of the compounds. The average grain size of the specimens after homogenization was 1 to 2 mm. All mechanical property measurements were carried out in an argon atmosphere using a compression apparatus described previously.5 Prior to applying the load to the specimen, the test apparatus was evacuated, back-filled with argon, and heated to the test temperature for 20 min to establish thermal equilibrium. EXPERIMENTAL RESULTS Mechanical properties measured as a function of temperature and strain rate for each of the three y brass phases were similar. From room temperature to the ductile-to-brittle transition temperature, only elastic deformation was observed prior to fracture.

Jan 1, 1968

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,&apos; but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By Allen V. Heyl

This old district is a major zinc and lead source and minor copper and barite source. Ores are chiefly in the Galena Dolomite and in limestones and dolomites of the Decorah and Platteville Formations, all of Middle Ordovician age. Locally, deposits have been mined from Lower Ordovician dolomites and Upper Cambrian sandstones. Small deposits of lead, zinc, and iron sulfides have been found in Upper Ordovician Maquoketa Shale and in Lower and Middle Silurian Edgewood, Kankakee, and Hopkinton Formations. No post-Precambrian igneous rocks are known in the region, and the granitic and metasedimentary Precambrian basement rocks unconformably underlie the district at depths of 1500 to 2000 feet. The strata are gently flexed and faulted, probably largely the result of gentle compressive and rotational adjustments in the underlying crystalline basement, especially along lineaments between basement blocks. Folds of three orders ·of magnitude are recognized, and many related reverse, strike-slip, and normal faults of small to moderate displacements are present. Zinc-lead deposits are commonly linear, arcuate, or elliptical in plan. Most ore occurs as vein fillings in fractures and as breccia fillings and lining vugs, but some is in bedded replacements and impregnations of wall rocks. The ore is in shears, small reverse and bedding- plant faults, joints, and solution-slump structures related to intermediate and small folds. The main primary minerals in their general sequence of deposition are quartz, illite, dolomite, pyrite, marcasite, cobaltite(?), sphalerite, galena, chalcopyrite, millerite, barite, and calcite. Wall-rock alterations include solution of the carbonate rocks, silicification, dolomitization, clay alteration, and sanded dolomite. Oxygenisotope, trace-element, lead-isotope, and sphalerite- stratigraphy studies are in progress. Fluid inclusions in sulfide and gangue minerals are filled with concentrated brines at 120° to 40°C. Sulfides are directly replaced by supergene minerals above the water table at 50 to 100 feet in depth. In this relatively cool climate and limestone environment, smithsonite is in pseudomorphs after sphalerite; solution transport and redeposition of supergene minerals are rare. Ore genesis is postulated by rising hot-water solutions-a mixture of heated connate, magmatic, and meteoric waters.

Jan 1, 1968

By W. A. Backofen, A. T. English

The kinetics of re crystallization were determined metallographically for a 3-1/4 pcl Si-Fe rapidly compressed at temperatures of 710° to 911°C, and held for various times at the working temperature. As in re crystallization following cold wwk, the time for re crystallization was reduced by increased temperature and strain. Nucleation occurred chiefly at grain edges, although other pre-existing interfaces, notably inclusions, also served as nucleation sites. The importance of intragranular nucleation to grain refinement in hot working is pointed out, together with some possible techniques by which nucleation might be induced within the grains. The observed isothermal growth rates are quite accurately described by the equation G = 4 x 10-&apos;/t (cm per sec), independent of temperature and strain at all but the shortest times. Changes in G during recrystalliza-tion can exceed two orders of magnitude. It is argued that release of stored energy associated with lattice defects cannot adequately explain the time dependence. A suggested alternative involves processes of solute segregation and desegregation in the unrecrystallized matrix and at the moving boundary, respectively. EFFORTS to improve hot-working practice are hampered by an incomplete understanding of the fundamental metallurgy involved. Research directed at establishing the required basic foundation falls into two categories, the first concerned with measurement of mechanical properties under the conditions of high temperature and strain rate which characterize such processing, the second focused on structure and its relation to the deformation conditions. Rossard,&apos; Rossard and Blain,2 and Hardwick and Tegart have conducted many high-speed, high-temperature torsion tests on various metals. One of their objectives was interpretation of stress-strain curves in terms of the structures of specimens rapidly quenched following interruption of twisting. They showed that appreciable hardening occurred in the early part of the test, and that this hardening reflected the concurrent development of an increasingly dense substructure within the grains. The detailed nature of this substructure was observed to depend on the ease of polygonization which, at least in fcc metals, varies with the stacking-fault energy.= By holding specimens after interruption but before quenching, the nucleation and growth of new grains could also be studied. Some success has been realized in relating the microstructure of hot-rolled steel to its temperature:strain rate:strain history with such testing.&apos; The same general observations have been made by others investigating rolling4f5 and drop-hammer forging.~-~ Incident to these experiments, some efforts were made to determine the kinetics of re-crystallization as well as the velocity of the migrating boundaries. The results have been largely qualitative, owing to difficulties of interpreting hardness measurements5 and microstructures. The work described here was undertaken to obtain more quantitative information from tests on a material having suitable metallographic properties, and, in this way, to provide further insight into the fundamentals of this practically most important kind of deformation processing. I) MATERIALS AND EXPERIMENTAL TECHNIQUES Materials. Electrolytic etching of a Si-Fe alloy reveals dislocations and substructure in unrecrystallized grains.8&apos;9 This unique characteristic makes possible a precise determination of the extent of recrystallization. For that reason, it was the material selected for all experiments in the present work. The two particular alloys that were used are identified in Table I. A major difference between "A" and "B" is the number of inclusions, as noted in the table. Most of the experiments were made with material "A". It was received as hot-rolled plate 1 in. thick, sawed to 2-in. widths, hot-forged at 1200°C to 5/8-in. rounds, and finally annealed in a mechanical vacuum at 1000°C for 24 hr. The result was substructure-free grains of mean diameter 0.05 cm.*

Jan 1, 1964