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The difficulty of finding new ore bodies, the complexities of patenting them when they are found, and the absence of incentive legislation for exploration have limited mining exploration in the United States mostly to the big companies. This situation, coupled with ECA spending abroad, has caused American capital to look outside our national boundaries for investment opportunities which are further made attractive by some relaxing of restrictions to gain American dollars and patronage.

Jan 1, 1950

By T. Tanaka, H. Kiuchi

The combination of the following two exothermic reactions was studied with the purpose of recovering H2 from H2S formed in acid leaching of sulfide ores, direct reduction of metal sulfides with H2 or desulfurization of crude oils: In the kinetic study of the recovery of H2, the reaction rate was measured by the two methods of single-stage and circulation blowing of H2S through molten Pb in the temperature range of 550 to 750°C. The experimental results showed that the rate determining step is in the chemical reaction itself and also that this reaction is accelerated markedly by the addition of a trace of Ni, which may be responsible for the catalytic action of Ni dissolved in molten Pb. In the experiments where Pb metal was produced, PbS was oxidized in a stream of atmospheric N2 containing 0.5 to 20 vol-% 02 or in the same 02 partial pressures as in N2 though under reduced pressures in the temperature range of 400 to 800°C. It was found from these experiments that the formation of PbSO4, basic sulfates and PbO are suppressable to yield Pb metal alone above 750°C and for 02 concentrations of less than 1 vol-%. Vapor of PbS was thought to take an important part in the Pb formation mechanism, and the probability thereof was demonstrated thermodynamically.

Jan 1, 1978

By H. A. Schlesinger

Various studies have estimated that for the next few decades, about half of all new power plants will be nuclear. The other half will be fueled with coal. Pending legislation on air pollution control would require all new coal-fueled power plants to install stack gas scrubbers or other technology to reduce sulfur oxide (SO,) emissions. These regulations would require flue gas desulfurization (FGD) or other technology for SO, reduction even on lower sulfur western coals. Among the options for FGD are single or dual alkali throw away processes using lime or limestone as the major reagent. These processes are currently more economically attractive than recovery processes, such as magnesium oxide and Wellman- Lord, that produce a salable product such as sulfur or sulfuric acid. One of the major problem areas with the throw away processes is disposal of the thrown away solid wastes, primarily calcium sulfite (CaSO3) and calcium sulfate (CaS04). Coal ash also must be disposed of, even if SOx reduction is not required. This paper addresses the alternatives for handling and disposal of throw away lime, limestone, and dual alkali process solid wastes. Advantages, disadvantages, and the economics of various methods are discussed. Both large central station power plants (500-1000 MW capacity) and smaller industrial power plants (up to 100 MW capacity) are considered. High sulfur eastern coals (53% S) and lower sulfur (3 1% S) western coals are considered.

Jan 1, 1981

By Gustav S. Preller, A. M. Gaudin

For the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2-4 and has now received confirmation as to accuracy by an entirely independent method.' This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8?2 or 16.2?2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8?2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura's results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2?2., with extreme values at 13.7 and 16.9?2. The average of 21 determinations made in connection with this study7 gave a parking area of 14.3 ± 0.27?². In view of this result and of the Harkins and Jura

Jan 1, 1947

By Gustav S. Preller, A. M. Gaudin

For the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2-4 and has now received confirmation as to accuracy by an entirely independent method.' This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8?2 or 16.2?2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8?2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura's results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2?2., with extreme values at 13.7 and 16.9?2. The average of 21 determinations made in connection with this study7 gave a parking area of 14.3 ± 0.27?². In view of this result and of the Harkins and Jura

Jan 1, 1947

By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

By Donald P. Richards, John F. Abel

Geotechnical site investigation for new mine shafts can reduce the level of design uncertainty for shaft linings. The parameters which determine the lining strength required include rock strength and hydrologic properties, the in situ stress conditions, and the concrete strength. These parameters are applied to analytical methods of shaft lining design using the plastic and clastic assumptions of rock response to determine the required lining thickness to maintain the stability of the shaft excavation.

Jan 1, 1982

By Dorsey Hager

NORTH -CENTRAL Texas has recently become a center of interest for the oil men of America. The bringing in of the McClosky well at Ranger, Eastland County, and the shallow pool at Brownwood, Brown County, in 1917, has stimulated interest in this area to fever pitch. Oil men from all over the United States are now investing there. The area of present interest is shown by the accompanying map (Fig. 1). The money spent in leases runs into millions of dollars. It is no exaggeration to say that a strip of country 200 miles (321 km.) long and 125 miles (201 km.) wide, comprising some 15,000,000 acres (6,070,310 ha.)., has been leased practically solid at a cost for rentals and bonuses of at least $1 per acre. The test holes contracted for will certainly number 400, at a cost of at, east $5,000,000. From what has been done in the past six months, $20,000,000 at least will be spent. To pay, returns on this amount of money, new production to the extent of at least 12,000,000 bbl. must be obtained. At present, the production from new fields will not average over 5000 bbl. per (lay; three wells at Ranger are producing 3000 bbl.; 250 wells at Brownwood produce 1000 bbl.; and the Gray well, Coleman County, is as yet an unknown factor. However, at Ranger there is every indication of developing a good pool covering from 1500 to 2000 acres (607 to 809 ha;), more or less, but the wells are deep, 3400 to 3800 ft. (1036 to 1158 m.), and cost $35,000 to $40,000 to drill. Large wells are necessary to pay for such expensive holes. As new wells are drilled, the gas pressure will be lowered rapidly, and large production need not be expected. For those oil men who expect a second Cushing or an Eldorado, Ranger holds little of promise. At Brownwood, Brown County, there are some 250 shallow wells (depths from. 200 to 350 ft.) averaging 4 to 7 bbl. per day. There is a chance of an extensive producing area, for these shallow sands to the southwest, and the opening of several thousand acres of shallow oil territory, and also some promise of deeper oil horizons in the Ranger horizon, but probably all under 2500 ft.

Jan 6, 1918

By AIME AIME

ONE test is worth a thousand expert opinions, say the engineers of the John A. Roebling's Sons Co. of Trenton, N. J. Confronted with the job of building the cables for the new Hudson River Bridge between Fort Lee and upper Manhattan, the Roebling organization, in spite of its long and varied experience in building cables for suspension bridges of various sizes, recognized that old yardsticks would be of little value in estimating safety factors for the immense span across the Hudson.

Jan 1, 1929

By Hsun Hu

NOT much data are available in the literature on textures in cross-rolled metal sheets. Among the body-centered-cubic metals, a few investigators have studied the preferred orientations developed in cross-rolled and in subsequently annealed molybdenum specimens.1-4 Semchyshen and Timmons5 onstructed complete pole figures for the cross-rolled and subsequently annealed arc-cast molybdenum. They used the conventional photographic method. Similar data on cross-rolled iron are still lacking. In view of the fundamental importance of iron as a basic metal for magnetic alloys and many industrial steels, the present investigation was undertaken in an attempt to understand more about its properties. The material selected for the present work was of high purity, and the textures were determined by the Geiger counter spectrometer technique, which permits the construction of quantitative pole figures. Experimental Procedure The material used for this investigation was NRC (National Research Corp.) high-purity, gas-free iron. The total gas content (N2 + O2 + H2) given was less than 0.026 pct, and the carbon content, less than 0.005 pct. Spectrographic analysis of a 2 in. cast ingot showed the percentage of metallic impurities as 0.0004 pct Cu, 0.0002 pct Mg, 0.001 pct Mn, 0.01 pct Ni, and 0.006 pct Si. A 1 in. thick slice was cut off from the 2 in. cast ingot. It was hot-forged at 850 °C to destroy most of the cast structure. Surface scale was removed by milling the forged piece to a size 2 in. long, 1½ in. wide, and ¾ in. thick. After normalizing at 915 °C for 15 min, the piece was alternately cold-rolled 40 pct and annealed at 750°C in hydrogen to a final thickness of 0.165 in., with a resulting uniform grain size of 0.1 mm.

Jan 1, 1958

By Robert W. Zimmerman

POROUS SOLID COMPRESSIBILITIES There are four different compressibilities associated with porous solids, each relating the fractional change in either bulk volume or pore volume with the change in either pore pressure or confining pressure. These will be referred to as Cbc, Cbp, Cpc, and Cpp, with the first subscript denoting the relevant volume, and the second subscript denoting the relevant pressure. They are defined as: [ ] Note that minus signs are included in two of the definitions so that each of the compressibilities will always have a positive value. In general, each compressibility depends on the elastic moduli of the matrix material, the porosity, and the exact geometry of the pores. Taking the latter factor into account calls for separate analysis for each different pore shape, which of course can only be attempted for a few relatively simple cases. But lower bounds for each of the four compressibilities can be found, independant of pore structure, in terms of only the porosity (0) and the elastic moduli of the matrix material (any pair chosen from K, E, G and V). The first step is to find relationships between the four compressibilities, starting with the following observation: If a porous solid made of a linear elastic, isotropic and homogeneous matrix material is subjected to uniform hydrostatic pressure of magnitude P on its external and all of its internal (pore) surfaces, the state of stress in the solid will be exactly the same as that which would occur

Jan 1, 1982

By Robert C. Mackenzie

EXAMINATION by the differential thermal analysis technique of a large number of samples of soil and other clays from various parts of the world has demonstrated that the occurrence of cold-precipitated hydrated ferric oxide (the identification of which in soil clays has previously been reported5) is not confined to any limited locality; e.g., it has been found in varying amounts in clays from Britain, France, South Africa, and Mexico. The conditions necessary for its formation have not yet been elucidated in spite of the number of samples examined, and, since this mineral is so easily prepared in the laboratory, it has been considered that a study of its constitu¬tion and of the conditions under which it could be prepared might. lead to a better understanding of the factors involved. These experiments form the subject of this short paper, and while they do not supply a definite answer to the mode of formation of this mineral in nature, they may, it is hoped, add something to our knowledge in this direction. EXPERIMENTAL WORK Materials Employed The a-Fe2O3.H2O (goethite) and B-Fe2O3.H2O (Weiser and Milligan") were obtained from the Department of Geology, University of Aberdeen, and Rothamsted Experimental Station, respectively. The beta material had been prepared by the method described by Fernelius.1 y-Fe2O3.H2O (lepidocrocite) was prepared at the Macaulay Institute for Soil Research by the method of van Schuylenborgh.6 The method employed for preparation of the cold-precipitated hydrated ferric oxide* was as follows: 1: 1 NH4OH was added (moderately fast with rapid stirring) to a solution of 5 grams FeC13.6H2O in 250 ml distilled water at room temperature (ca. 15°C) until red litmus turned blue, and then 2 to 3 drops in excess. The resultant precipitate was filtered off on a Buchner funnel and washed free from Cl- with distilled water. Previous experiments having shown that drying over P2O5 at room temperature or drying at 105°C in the oven did not significantly affect the thermogram,5 samples were nor-

Jan 1, 1952

By Paul Weir

BLEACHING clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller's earths fall within the general group of bleaching clays and gradually the commercial term "fuller's earth" has been applied to natural clays originating, for the most part, in the south-eastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States.1 Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). TABLE 1.-Physical and Chemical Composition of Different Types of Clays Composition, Per Cent Constituents and Properties Bentonite Fuller's Mud Clay (Wyoming) Earth (P Peak)' (Alluvial) Silica (SiO2) 60.0 69.6 61.67 Alumina (Al203) 19.0 14.3 20.34 Ferric oxide (Fe203) 2.8 3.90 7.70 Titanium oxide (Ti02) 0.13 0.70 1.01 Lime (CaO) 0.5 0.80 0.00 Magnesia (MgO) 2.0 1.00 0.24 Soda (Na2O) 2.4 0.40 0.31 Ignition loss 4.7 6.77 8.51 Moisture content 8.0 10.0 20.0 Isoelectric point, pH 9.2 9.2 6.5 Average swelling volume 15.0 0.0 0.0 Weight per cubic foot, lb 55.0 40.0 65.0 Material passing 200-mesh sieve, per cent 90.0 85.0 50.0

Jan 1, 1939

By Arnlf Muan, Bert Phillips

The quenching technique has been used for- a study of phase velntiorzs within the composition triangle 2CaO.Fe2O3-FeO.Fe2O3 Fe2O3 of the system Ca-Fe-O. Desired total compositions of sanzples were attained by weighing of starting materials in required proportions and keeping them in sealed 80 pct Pt 20 pct Rh tubes during equilibration .runs. The liquidus surface has been delineated. the existence of two ternary compounds has been established, and seven ternary inwariant situations have been determined. ONE unit within the research program on refractory oxides in progress in our laboratories is the study of phase relations in the system Ca-Fe-Si-O. The present paper deals with the ternary system 2CaOFe2O3-FeO.Fe2O3-Fe2O3, which is only a small part of the enormously complex quaternary system. Many of the phases occurring in iron ore sinter products have compositions which can be closely approximated within this ternary system, and a knowledge of stability relations existing among these phases may be expected to be a useful guide for improving sintering operations. Two fundamentally different experimental approach es are commonly used in studies of systems containing iron oxides, both permitting control of the oxidation state of Fe. One method consists in keeping constant the oxygen partial pressure of the gas phase in equilibrium with condensed phases (liquid and crystalline). In the other method, which is the one used in the present investigation, the total composition of condensed phases is kept essentially constant by keeping the samples in a gas-tight container. The details of this experimental procedure will be described in a later section. PREVIOUS WORK Extensive studies of phase relations in the bounding binary system FeOFe2O3-Fe2O3 have been reported by Greig, Posnjak, Merwin, and Sosman,' by Darken and Gurry,2, 3 and recently by Phillips and Muan.4 A diagram summarizing the results of these studies is shown in Fig. 1. Particular attention is

Jan 1, 1961

The report of the Nominating Committee was presented and is given in this same Bulletin. A petition was received for new requirements for membership in the Institute and was ordered to take the statutory course. A petition was received for the establishment of a Tulsa Section of the Institute and was referred to a committee to report on the territory. Thirty-six Members, two Associates, and two Junior Members were elected. The status of two Junior Members was changed to Member.

Jan 12, 1917

By F. C. Hull

The grain size of a metal or alloy is one of the most important factors determining its properties. In steels, for example, grain size affects hardenability, toughness and machinability; in brasses, grain size is related to hardness and deep-drawing quality. In the field of heat-resistant alloys, grain size has a marked effect on ductility, creep and endurance strength. In order to determine these effects, as well as to control the properties of materials, many accurate and rapid measurements of grain size must be made. This paper presents a new and improved method for the estimation of grain size. Usual Methods OF EvaluatiNg Grain Size A frequetly used method of estimating grain size is that of comparing the image of a polished and etched specimen on the ground-glass screen of a metallographic microscope with standard grain-size charts. Several types of standards are available for use with different classes of microstructures. Geometric Grids.—The Metals Handbook' has a series of hexagonal grids ranging in size from ASTM No. I to 8. Idealized Grain Networks.—Idealized grain.boundary networks for ASTM grain sizes I to 8 are included in the American Society for Testing Materials Tentative Standard E 19 - 39 T, standard Micrographs & Metals Handbook and ASTM Tentative Standard E19-3gT contain micrographs of hypo-eutectoid and hypereutectoid steels ranging in grain size from No. I to 8. The grain size of annealed brass (diameter of the average grain in millimeters) is obtained by comparison with 10 micrographs of varying. grain size in ASTM Tentative Standard E 2-39 T. A handicap to accurate evaluation of grain size by this method is the fact that it is difficult to compare photographs in a dimly lighted room with the image on the ground-glass screen, or, if the general illumination is increased so that the printed standards may be clearly seen, the contrast of the image of the unknown is decreased. It is easier to estimate grain size by comparing a micrograph of the unknown with the grain-size standards. However, photographing every specimen on which the grain size is desired is too costly in time and materials to be practicable. For hardened steels, the Shepherd or Jernkontoret fracture grain-size standards are very accurate and useful, but this method obviously cannot be applied to ductile alloys such as brass, stainless steels and austenitic heat-resistant alloys. Jeffries' method for grain-size measurements consists of counting the number

Jan 1, 1948

By F. C. Hull

The grain size of a metal or alloy is one of the most important factors determining its properties. In steels, for example, grain size affects hardenability, toughness and machinability; in brasses, grain size is related to hardness and deep-drawing quality. In the field of heat-resistant alloys, grain size has a marked effect on ductility, creep and endurance strength. In order to determine these effects, as well as to control the properties of materials, many accurate and rapid measurements of grain size must be made. This paper presents a new and improved method for the estimation of grain size. Usual Methods OF EvaluatiNg Grain Size A frequetly used method of estimating grain size is that of comparing the image of a polished and etched specimen on the ground-glass screen of a metallographic microscope with standard grain-size charts. Several types of standards are available for use with different classes of microstructures. Geometric Grids.—The Metals Handbook' has a series of hexagonal grids ranging in size from ASTM No. I to 8. Idealized Grain Networks.—Idealized grain.boundary networks for ASTM grain sizes I to 8 are included in the American Society for Testing Materials Tentative Standard E 19 - 39 T, standard Micrographs & Metals Handbook and ASTM Tentative Standard E19-3gT contain micrographs of hypo-eutectoid and hypereutectoid steels ranging in grain size from No. I to 8. The grain size of annealed brass (diameter of the average grain in millimeters) is obtained by comparison with 10 micrographs of varying. grain size in ASTM Tentative Standard E 2-39 T. A handicap to accurate evaluation of grain size by this method is the fact that it is difficult to compare photographs in a dimly lighted room with the image on the ground-glass screen, or, if the general illumination is increased so that the printed standards may be clearly seen, the contrast of the image of the unknown is decreased. It is easier to estimate grain size by comparing a micrograph of the unknown with the grain-size standards. However, photographing every specimen on which the grain size is desired is too costly in time and materials to be practicable. For hardened steels, the Shepherd or Jernkontoret fracture grain-size standards are very accurate and useful, but this method obviously cannot be applied to ductile alloys such as brass, stainless steels and austenitic heat-resistant alloys. Jeffries' method for grain-size measurements consists of counting the number

Jan 1, 1948

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By J. W. Clark, C. T. Sims

Wrought chromium-base alloys containing yttrium, cubic monocarbides of the Ti(Zr)C type, and similay alloys containing manganese and rhenium have been melted and fabricated. Strength has been studied by hot hardness and elevated-temperature tensile and rupture measurements, low-temperature ductility by tensile testing, and surface stability by oxidation testing. In additiod, studies have been conducted of the carbide stability, and of aging behavior. The carbide dispersion generates effective elevated-temperature strength, which is further enhanced hv strain-induced precipitation. The dispersion exhibits classical dissolution and aging response. The ductile-to-brittle transition temperature of these alloys is above room temperature. The alloys reported show fairly good oxidation resistance, but nitrogen contamination can cause fortnation of a hard Cr2N layer under the oxide scale. Manganese does not appear to be a promising alloying element in chromium. In the years 1945 to 1950, the metal chromium was considered as a possible base for alloy systems due to its considerably higher melting point than superalloys, its low density, its high thermal conductivity, and its apparent capacity for strengthening. However, this interest in chromium was short-lived. It was found difficult to melt and cast, to be exceptionally sensitive to the effect of minor imperfections, to have a lack of ductility at both room and elevated temperatures, and to be subject to a deleterious effect of alloying elements upon the ductile-to-brittle transition temperature.' Since then, chromium, as a practical alloy base, has remained virtually unstudied. Further, purposeful ignoring of chromium has been promoted by statements that its bcc structure would not allow it to be strengthened to useful values, when compared to the "austenitic" alloys.2 Recently, a new look has been taken at chromium-base alloy systems. Study of the literature will show that chromium, providing some of its disadvantages could be eliminated or minimized, actually has a rather attractive potential as an alloy-system base. Analysis of rather scattered data suggests that chromium is quite capable of being strengthened to high levels. Also, significant strengthening of its two sister elements in Group VI-A, molybdenum and tungsten, has been demonstrated in a number of commercial and exploratory alloys. Chromium should be similar. Since chromium does not readily form a volatile oxide like tungsten or molybdenum, it offers a much higher probability of giving birth to alloy systems with useful oxidation resistance. Concerns about possible high elemental vapor pressure have been mitigated by recent data.3 In addition, the physical properties exhibited by chromium are attractive for application as a high-temperature structural material. For instance, its thermal conductivity varies from 49 to 36 Btu-ft/hr-sq ft-°F over its range of usefulness (which is two to four times higher than most superalloys), its density is about 7.2 g per cc (20 pct less than most nickel-base alloys), its coefficient of thermal expansion varies from 4 to 8 x 10-6 per OF, and it has a relatively high modulus of elasticity, approximately 42 x 10' psi.4 Alloying studies on a chromium base in the past have usually encompassed rather sweeping solid-solution alloy additions for strengthening. This is not consistent with contemporary alloying practice in Group VI-A. For instance, molybdenum, also in Group VI-A, is primarily alloyed for strength improvement by use of heat-treatable carbide dispersions.5 Chromium and molybdenum are similar in their chemical activity and other properties. Thus, strengthening of chromium by carbide dispersions was studied. Chromium-base alloys are plagued with room-temperature brittleness, although high-purity unal-loyed chromium can be made ductile.4,8 Use of yttrium as a scavenger has done much to improve ductility and resistance to nitrogen embrittlement in chromium systems,7 so it was utilized in this program. It has also recently been found8 that small rhenium additions (1 to 5 pct) create improvement in the ductility of Type 218 tungsten wire. This is apparently related to the remarkable effect of rhenium additions near its terminal solid solubility in all Group VI-A metals.9'10 Investigation to establish if dilute concentrations of rhenium would also be effective in chromium appeared to be logical for this program. Since rhenium is too expensive to be practical in alloys for application as structural components, ductility improvements through solid-solution alloying were also sought by substitution of manganese for rhenium; manganese, like rhenium, exists in Group VII of the periodic system. The optimum amount of carbide dispersion for chromium-base alloys was obtained by analogy with molybdenum. Strengthening in molybdenum is achieved by use of Ti-Zr carbide dispersions. A

Jan 1, 1964