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By M. C. Udy, C. H. Lorig

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By Bernard Kopelman

The particle size of tungsten metal powder used to make tungsten wire for use in radio tubes and incandescent lamps must be closely controlled if the highly desirable feature of nonsagging is to be achieved. Our knowledge of factors affecting the particle size of tungsten powder has been limited by lack of any extensive literature on the subject. There are no publications in the English language discussing this problem in any but the most general terms. In this paper the published experimental information on this subject is reviewed. Based on the published data and some experimental data obtained by the author, a general theory of factors affecting the particle size of tungsten metal powder obtained by reduction of the oxides in hydrogen is offered. The various forms of the tungsten oxides and tungsten metal used in the experiments described were those prepared by commercial processes, so that the experimental results obtained on a laboratory scale would be more directly applicable to actual commercial reduction conditions. The effects of time of reduction, temperature. and concentration of water vapor in the hydrogen were observed by counting microscopically the particle distribution obtained. Such a method is very time-consuming, but the data obtained by this method are more reliable and more fundamental than those obtained by any of the several instruments available for measurement of particle size. Review of the Literature Until the year 1912, tungsten powder was prepared commercially by reducing tungstic oxide in the presence of carbon or one of its compounds (such as glycerin or ethylene glycol), usually by firing the mixture in a closed fire-clay crucible. The resultant powder contained about 95 per cent tungsten.' When reduction of tungsten oxides by H² was introduced Commercially,²,³ several investigators became concerned with the equilibria between tungsten metal and its several oxides in an atmosphere of hydrogen and water vapor.4-l3 While these many investigations were in fair agreement on the equilibria WO³ + H2 = WO2 + H2O and WO2 + 2H2 = W + 2H2O there arose considerable controversy as to the chemical composition of the oxide between WO³ and WO², because of very poor agreement on the equilibrium constant of this intermediate oxide reduction reaction. The controversy on this intermediate oxide has been in progress for more than 100 years. Thus Malguti,14 in 1835, decided it was WO2.56 In 1857, Riche15 proposed the formula W³O8. Usler,16 in 1865, confirmed the existence of WsO8 and further proposed W1O1l. In 1897, Desil7 agreed upon W²O8 but also found W5O14.

Jan 1, 1947

By K. A. Johnson, F. H. Ellinger, C. C. Land

The Pu-In phase diagram has been determined by thevmal, filtvation, micrographic, and X-ray diffraction methods. This alloy system is characterized by 1) limited solubility of indium (-2 at. pet) in 6 and e plutonium, 2) one eutectic, and 3) fizte intermediate phases. Of the latter, PuIn and PuIn3 melt con-gruently, and Pu31n, Pu31n5, and the high-temperatuve 7 solid solution are formed peritectically. The n phase decomposes eutectoidally into Pu3In and PuIn at 865°C. Although the 6 phase can readily be retained to room temperature, it is not thermo-dynamically stable below 300°C. The Pu-In system has been investigated at Los Alamos as part of a study of the alloys of plutonium with the group 111-B elements. Constitutional studies of the Pu-A1 and Pu-Ga systems have been reported earlier.'9' To date, published information on the constitution of Pu-In alloys covers only the identification of the intermediate phases Pu3In and PuIn3.3,4 EXPERIMENTAL The alloys were prepared from five different lots of plutonium and three different lots of indium. The principal impurities in the plutonium differed from lot to lot within the following limits (in ppm): iron, 30 to 80; nickel, 30 to 60; aluminum, 15 to 30; silicon, 20 to 145: thorium, 50 to 300; carbon, 75 to 335; and oxygen, 20 to 135. Spectroanalysis of the indium showed that two of the lots were 99.9 wt pct pure, and the third was 99.98 wt pct pure. The alloys, in the form of about 5-g buttons, were prepared by arc melting in conventional equipment. The components for each alloy were weighed to the nearest 0.1 mg. In most instances the weight losses during melting were negligible; therefore confirmatory chemical analyses were usually not made. A few results are given in Table I. Density measurements of the arc-cast buttons were made by the liquid displacement of bromoben-zene. Heat treating was done in muffle furnaces controlled to +2°C. The alloy buttons were wrapped in tantalum foil before being enclosed in evacuated clear silica capsules. As a precaution against breakage, each capsule was in turn placed in a silica tube closed with a refractory wool plug prior to being charged into the furnace. For a moderately fast quench of the alloys, the outer protection tubes containing the capsules were plunged into cold water. Differential thermal analyses (DTA) in racuo were performed at heating and cooling rates of about 1.5°C per min. Tantalum crucibles having inverted thermocouple wells were used for most of the analyses. It was found micrographically, however, that the liquid alloys containing more than about 35 at. pct In reacted with the tantalum, resulting in contamination of the surface of the alloy. A search for a more satisfactory crucible material was not successful: tungsten and yttria behaved comparably to tantalum; thoria, vitrified magnesia, and vitrified alumina severely contaminated the alloys. So as to minimize the contamination by the crucible mater-

Jan 1, 1965

By Bernard Kopelman

The particle size of tungsten metal powder used to make tungsten wire for use in radio tubes and incandescent lamps must be closely controlled if the highly desirable feature of nonsagging is to be achieved. Our knowledge of factors affecting the particle size of tungsten powder has been limited by lack of any extensive literature on the subject. There are no publications in the English language discussing this problem in any but the most general terms. In this paper the published experimental information on this subject is reviewed. Based on the published data and some experimental data obtained by the author, a general theory of factors affecting the particle size of tungsten metal powder obtained by reduction of the oxides in hydrogen is offered. The various forms of the tungsten oxides and tungsten metal used in the experiments described were those prepared by commercial processes, so that the experimental results obtained on a laboratory scale would be more directly applicable to actual commercial reduction conditions. The effects of time of reduction, temperature. and concentration of water vapor in the hydrogen were observed by counting microscopically the particle distribution obtained. Such a method is very time-consuming, but the data obtained by this method are more reliable and more fundamental than those obtained by any of the several instruments available for measurement of particle size. Review of the Literature Until the year 1912, tungsten powder was prepared commercially by reducing tungstic oxide in the presence of carbon or one of its compounds (such as glycerin or ethylene glycol), usually by firing the mixture in a closed fire-clay crucible. The resultant powder contained about 95 per cent tungsten.' When reduction of tungsten oxides by H² was introduced Commercially,²,³ several investigators became concerned with the equilibria between tungsten metal and its several oxides in an atmosphere of hydrogen and water vapor.4-l3 While these many investigations were in fair agreement on the equilibria WO³ + H2 = WO2 + H2O and WO2 + 2H2 = W + 2H2O there arose considerable controversy as to the chemical composition of the oxide between WO³ and WO², because of very poor agreement on the equilibrium constant of this intermediate oxide reduction reaction. The controversy on this intermediate oxide has been in progress for more than 100 years. Thus Malguti,14 in 1835, decided it was WO2.56 In 1857, Riche15 proposed the formula W³O8. Usler,16 in 1865, confirmed the existence of WsO8 and further proposed W1O1l. In 1897, Desil7 agreed upon W²O8 but also found W5O14.

Jan 1, 1947

By R. H. Doremus, E. F. Koch

The first carbide phase that precipitates at 120°C from a iron containing about 0.02 wt pct, C was studied with the electron microscope. In both strained and unstrained material the carbide particles appeared to form on the dislocations in the iron, in agreement with the results of the kinetic study in part II. The structure of the carbide was tentatively identified as an expanded a-iron lattice (body-centered tetragonal) with about 0.7 wt pct C. This phase appeared to be metastable and apparently transformed into cementite or epsilon carbide when the iron was over-aged. WhEN a iron containing less than about 0.025 wt pct C is quenched from 700°C to room temperature the carbon is retained in solid solution and precipitates out slowly with time. The morphology and structure of the precipitating phase are still in doubt, two different carbide phases, epsilon carbide and cementite, have been identified, but there is considerable disagreement about the time and temperature at which they appear.1-4 Epsilon carbide seems to form at lower temperatures than cementite, although one group of investigators4 found only the latter phase over a wide range of aging temperatures. Usually these two phases have been identified after aging times much longer than needed to drain the carbon from supersaturated solution, at least for aging temperatures below 200oC. The precipitated carbides have been observed with the electron microscope,'-5 but again most results have come from samples aged much longer than necessary to reduce the carbon concentration in solution to a low value. In this study the carbide phases were observed in earlier stages of precipitation with the electron microscope, in order to learn more about the shape, size, and distribution of the carbide particles. Samples strained small amounts before aging, as well as unstrained samples, were studied, and the structure of the carbide phase was tentatively identified. EXPERIMENTAL "Ferrovac E" vacuum-melted iron, from which the wires for kinetic studies were also made (Refs. 6 and 7 and the following paper) was used for this work. An analysis of this material is given in Table I; it agrees well with the manufacturer's values. The number of inclusions in the iron was very small, as can be seen in the optical micrograph in the following paper. Pieces of iron about 1 mm thick and 5 to 10 mm in diam were used for all the studies except for those in which the sample was strained before aging; then the specimen was a rod 3 to 6 mm in diam and 20 cm long. The samples were held at about 700°C in wet hydrogen for at least an hour to remove residual carbon and nitrogen, after which they were heated to 950" (in the y region) and cooled to room temperature in the furnace. This treatment gave an average grain diam of more than 1 mm, so that the effect of grain boundaries on the precipitation process was negligible. The samples were carburized at 710°C for about 2 hr in hydrogen that had passed over toluene held at -30°C; then they were rapidly quenched into water. From chemical analysis this treatment gave a carbon concentration of from 0.012 to 0.016 wt pct, which is less than the solubility of carbon at this temperature. After quenching, the samples were aged at 120 "C in an oil bath for vari-

Jan 1, 1961

By P. W. George

This paper presents geological data regarding deposits of over 7,500,000 tons of fine-grained sulphide ore in barite gangue. A series of pyroclastics and arkoses was intruded by sills of quartz porphyry in connection with batholithic intrusions of granite 3 miles from Buchans. Gentle folding, with fracturing and shearing of tuff beds and intruded quartz porphyry, accompanied and followed the intrusion of granite and porphyry. The sulphide-barite mineralization is localized primarily in fractured and sheared tuff beds, but also in the sheared quartz porphyry. Two structures have proved particularly favorable for mineralization-one, the center of an anticline; the other, a series of weak, incompetent tuff beds intruded by thin sills of quartz porphyry and located between strong beds of arkose. During the folding the weak tuff with intruded quartz porphyry was intensely sheared and contorted and subsequently mineralized by sulphides and barite. INTRODUCTION Buchans is 5 miles north of Red Indian Lake, in Central Newfound- land, at an elevation of 900 ft. above sea level and 400 ft. above Red Indian Lake, and is reached by a 37-mile private railway from Miller- town Junction. The first ore body found at Buchans was discovered some 30 years ago in the bed of Buchans River, by Matty Mitchell, an Indian woodsman employed by the Anglo-Newfoundland Development Co. Ltd. In the years following the discovery the ore was developed by shaft-sinking and drifting, with results indicating a lenticular ore body in a shear zone, containing about 100,000 tons of extremely fine-grained sulphide ore in barite gangue averaging about 0.05 oz. Au, 4 oz. Ag, 1.5 per cent Ch, 10 per cent Pb, 18 per cent Zn. Because a profitable metallurgical treatment for the ore was not found, the mine was closed down in 1911. In 1915, Mr. H. A. Guess, Vice President of the American Smelting & Refining Co., learned of the Buchans River ore body, and after metallurgical tests had been carried on from time to time in his company's testing plant a satisfactory separation of the sulphides by selective flotation was finally effected in 1925. Prospecting for additional ore bodies was begun in 1926, utilizing geophysical methods under the direction of Hans Lund-

Jan 1, 1937

By W. H. McFarland

The mechanical properties have been determined for a large number of alloy-free martensitic steels with carbon contents ranging from 0.08 to 0.20 pct and with manganese contents of about 0.4 to 0.5 pet. These steels were tested 1) as water-quenched, 2) after quenching, temper rolling, and tinning, and 3) after tempering treatments which involved temperatures from 400o to 1300oF and times from 1 min to 8 hr. The majority of these tests represent steel from commercial-size coils, i.e., strip 32 in. wide, coil weights up to 20,000 16, and steel thicknesses from 0.0055 to 0.024 in. As a result of these treatments, it has been shown that as-quenched low-carbon alloy-free steels can be produced with tensile strengths ranging from 140,000 to 220,000 psi and tensile elongations from 3.0 to 4.0 pet in 2 in. The tensile strength of the as-quenched martensites can be represented by the equation, tensile strength (ksi) = 119 + 560 (wt pet C). The response to tempering of these steels is related to previous work by Muir, Averbach, and Cohen and by Grange and Baughman. Strain aging of low-carbon martensite has also been investigated. If low-carbon steels are defined as those steels with a maximum carbon content of 0.2 pet, it is found that the literature on low-carbon, alloy-free martensites contains little data on the mechanical properties of these steels. However, the following facts concerning low-carbon alloy-free martensites seem firmly established:'-' 1) The major factors in controlling the strength of the martensite appear to be a) fine structure, b) the internal strain resulting from the transformation, and, particularly, c) the amount of carbon in solid solution. 2) In low-carbon steels, the martensite is auto-tempered and is in the form of needles with only minor amounts of internal twinning, whereas the martensite in high-carbon steels forms as plates which are internally twinned on a fine scale. 3) Care must be taken in comparing the results of work that has been done on low-carbon steels with varying amounts of alloying elements to data on plain carbon steels. As has been noted by Irvine, Pickering, and Garstone,6 alloying elements generally lower the martensite start temperature and, thereby, decrease the amount of auto tempering obtained during the quench. This makes it difficult to

Jan 1, 1965

By Rex B. McLellan

Studies of the eyuilibrzum between ferrite and austenite with gas mixtures (CO + CO2 and H2 + CHe) have been used as a means of deducing the energy and vibrational entropy of carbon atoms in dilute interstitial Fe-C solutions. A simple model for dilute interstitial solutions is given which enables a solubility equation for the equilibrium between the gas mixtures and the solid to be deduced. This solubility equation is used to estimate the partial In this work measurements of the equilibrium between dilute solid solutions of carbon in iron and gaseous mixtures of CO2 + CO and CH4 + Hp have been analyzed using theoretical solubility equations deduced from a knowledge of the thermodynamic parameters of the gas mixtures and an appropriate model for the solid solution. The solubility equations are deduced by equating the chemical potential of carbon atoms in the gas thermodynamic functions of dilute Fe-C solutions from the measured equilibrium between the solid and the gas mixtures. It is shown that the vibra-tional entropy of a carbon atom in a and y iron is smaller than the corresponding entropy 01. a nitrogen atom in solid solution inferrite or austenite and that there is little difference between the vibrational entropies of both nitrogen and carbon atoms in ferrite and austenite. and solid phases. The chemical potential of carbon in the gas is found from a simple statistical mechanical analysis of the gas mixtures utilizing spec-troscopic data while that for carbon in the interstitial solution is found from a model in which the carbon atoms act as bound oscillators distributed in a random fashion in the solution. The solid solution is dilute enough to enable solute-solute interactions to be ignored. Thus the configurational entropy of the solution is ideal but the mixing entropy contains additional excess terms due mainly to the vibrational changes occurring on solution formation. The partial excess entropies (and the partial energies) do

Jan 1, 1965

By W. A. Ver Wiebe

UNder the impetus of new demands caused by the defense program, the oil and gas industries of Kansas established new records during the year 1941. In all, 2113 wells were drilled, which compares favorably with the record total drilled in 1937. These 2113 tests resulted in 1446 oil wells, 76 gas wells and 592 dry holes. In all three categories there was an increase over the previous year, but unfortunately the most marked increase was in the dry holes. Nearly 80 per cent of the increase must be allocated to the drilling 01 unsuccessful tests. This was partly because of the increasing difficulty of finding new reserve areas and partly because of the erratic character of the production in the Arbuckle dolomite, which is now the main producing zone. Closer analysis of the totals reveals that western Kansas accounted for 1634 tests, of which 1186 were oil wells, 34 were gas wells and 415 were dry holes. The total potential initial daily production uncovered by the successful wells amounted to 1,691,000 bbl. of oil and 508,000,000 cu. ft. of gas. Both figures indicate a considerable decrease when compared with the proceeding year; in 1940 the respective figures were 2,128,000 bbl. and 1,289,000,000 cu. feet. In eastern Kansas a total of 479 wells were drilled. Among these, 260 were oil wells accounting for a daily initial potential production of 45,662 bbl. The new gas wells numbered 42 and added 290,438,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 177 in number, were dry. It is interesting and significant that almost half (791) of the total wells drilled in western Kansas were drilled by the independent operators. Among the large companies the Cities Service Oil Co. drilled 169 wells; the Stanolind Oil and Gas CO., 101; the Skelly Oil Co., 80; the Continental Oil Co., 99, and the Shell Petroleum Co., 63 wells. In eastern Kansas the independent operators drilled 406 out of the total of 479 wells. Among the major oil companies the Cities Service Oil Co. drilled 38; the Phillips Petroleum Co., 13, and the Sinclair-Prairie Oil Co., II wells. The figures on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas approximately one third of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 844 wells in western Kansas, of which 678 were successful in finding either oil or gas. It thus appears that the major companies fared much Getter than the independents. In eastern Kansas the major companies drilled 73 wells of which 63 were successful in finding commercial quantities of oil or gas. No less than 286 wildcat tests were put down in western Kansas and 72 in eastern Kansas, or 358 in all, during 1941. Considerably more than half of these were drilled by independent operators; zoo in western and 66 in eastern Kansas. An exploratory hole % mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, approximately 75 per cent of all wildcat wells were failures; only 25 per cent found oil or gas in western

Jan 1, 1942

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By George E. Moore, B. K. Miller

The Missouri fire clays are here divided into plastic and semiplastic clays occurring as widespread bedded deposits in east central Missouri and flint and diaspore clays occurring as isolated "sink-hole" deposits in the north central Ozark region. Visual inspection was the first method used in clay prospecting. Thin overburden, hard sandstone "rimrocks," and the occurrence of diaspore float made this method particularly applicable in the flint and diaspore fields. The first drilling tool used was a hand auger. One man can drill 25 to 50 ft. per day at a cost of about 35 cents per foot. Holes can be drilled to a depth of 150 feet. Spud drills are often used where the overburden is hard. This drill uses a slotted earth socket bit. A two-man crew can drill about 100 ft. per day at a cost of about 35 cents per foot. Mechanically powered auger drills have been used extensively in wildcat drilling in the past few years. This type of drill furnishes a continuous set of cuttings. The practical depth limit with this drill is 50 to 60 ft. Two men can drill 300 ft. per day at a cost of about 20 cents per foot. Core drilling is used mainly to prove a known 'lay deposit. A A crew with a No. 22 Sullivan drill can drill about 30 to 40 ft. per day in soft clay, at a cost of about $1.25 per foot. Introduction Because of the geological variations in the Occurrence of the several types of fire clay mined in Missouri, it is necessary, when discussing the prospecting methods used for discovering and proving these clays, to divide these operations into two classes, one including plastic and semi-plastic fire clays, the other flint and diaspore clays. The plastic and semiplastic fire clays in the east central and St. Louis districts are generally classified as Cheltenham clays. This formation is a more or less continuous deposit and is found Over a large area in east central Missouri. There are variations, however, in the quality and thickness of the clay, which necessitate detailed prospecting in order to determine deposits of economic value. The nature of the overburden (Fig. 1), which consists of Pennsylvanian limestone and shale beds of varying thicknesses, and a mantle of glacial drift, regu1ates the methods and equipment used in prospecting for these clays. The district in which these clays occur is a gently rolling upland region, characteristic of most of northern Missouri. Along the southern fringe of this area there are numerous deposits of flint clay lying as masses or lenses in depressions at the base of the continuous and widespread Cheltenham formation, or as outlying "sink-hole" deposits in the area marginal to that formation. South of the Missouri River in the north central Ozark region, there are high-grade flint and high-alumina clays, commonly referred to as burley and diaspore clays in sink-hole type deposits. The overburden On these deposits is thin, consisting chiefly of soil and hard-pan, which varies from a plastic

Jan 1, 1948

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By W. A. Ver Wiebe

UNder the impetus of new demands caused by the defense program, the oil and gas industries of Kansas established new records during the year 1941. In all, 2113 wells were drilled, which compares favorably with the record total drilled in 1937. These 2113 tests resulted in 1446 oil wells, 76 gas wells and 592 dry holes. In all three categories there was an increase over the previous year, but unfortunately the most marked increase was in the dry holes. Nearly 80 per cent of the increase must be allocated to the drilling 01 unsuccessful tests. This was partly because of the increasing difficulty of finding new reserve areas and partly because of the erratic character of the production in the Arbuckle dolomite, which is now the main producing zone. Closer analysis of the totals reveals that western Kansas accounted for 1634 tests, of which 1186 were oil wells, 34 were gas wells and 415 were dry holes. The total potential initial daily production uncovered by the successful wells amounted to 1,691,000 bbl. of oil and 508,000,000 cu. ft. of gas. Both figures indicate a considerable decrease when compared with the proceeding year; in 1940 the respective figures were 2,128,000 bbl. and 1,289,000,000 cu. feet. In eastern Kansas a total of 479 wells were drilled. Among these, 260 were oil wells accounting for a daily initial potential production of 45,662 bbl. The new gas wells numbered 42 and added 290,438,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 177 in number, were dry. It is interesting and significant that almost half (791) of the total wells drilled in western Kansas were drilled by the independent operators. Among the large companies the Cities Service Oil Co. drilled 169 wells; the Stanolind Oil and Gas CO., 101; the Skelly Oil Co., 80; the Continental Oil Co., 99, and the Shell Petroleum Co., 63 wells. In eastern Kansas the independent operators drilled 406 out of the total of 479 wells. Among the major oil companies the Cities Service Oil Co. drilled 38; the Phillips Petroleum Co., 13, and the Sinclair-Prairie Oil Co., II wells. The figures on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas approximately one third of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 844 wells in western Kansas, of which 678 were successful in finding either oil or gas. It thus appears that the major companies fared much Getter than the independents. In eastern Kansas the major companies drilled 73 wells of which 63 were successful in finding commercial quantities of oil or gas. No less than 286 wildcat tests were put down in western Kansas and 72 in eastern Kansas, or 358 in all, during 1941. Considerably more than half of these were drilled by independent operators; zoo in western and 66 in eastern Kansas. An exploratory hole % mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, approximately 75 per cent of all wildcat wells were failures; only 25 per cent found oil or gas in western

Jan 1, 1942

By B. K. Miller, George E. Moore

The Missouri fire clays are here divided into plastic and semiplastic clays occurring as widespread bedded deposits in east central Missouri and flint and diaspore clays occurring as isolated "sink-hole" deposits in the north central Ozark region. Visual inspection was the first method used in clay prospecting. Thin overburden, hard sandstone "rimrocks," and the occurrence of diaspore float made this method particularly applicable in the flint and diaspore fields. The first drilling tool used was a hand auger. One man can drill 25 to 50 ft. per day at a cost of about 35 cents per foot. Holes can be drilled to a depth of 150 feet. Spud drills are often used where the overburden is hard. This drill uses a slotted earth socket bit. A two-man crew can drill about 100 ft. per day at a cost of about 35 cents per foot. Mechanically powered auger drills have been used extensively in wildcat drilling in the past few years. This type of drill furnishes a continuous set of cuttings. The practical depth limit with this drill is 50 to 60 ft. Two men can drill 300 ft. per day at a cost of about 20 cents per foot. Core drilling is used mainly to prove a known 'lay deposit. A A crew with a No. 22 Sullivan drill can drill about 30 to 40 ft. per day in soft clay, at a cost of about $1.25 per foot. Introduction Because of the geological variations in the Occurrence of the several types of fire clay mined in Missouri, it is necessary, when discussing the prospecting methods used for discovering and proving these clays, to divide these operations into two classes, one including plastic and semi-plastic fire clays, the other flint and diaspore clays. The plastic and semiplastic fire clays in the east central and St. Louis districts are generally classified as Cheltenham clays. This formation is a more or less continuous deposit and is found Over a large area in east central Missouri. There are variations, however, in the quality and thickness of the clay, which necessitate detailed prospecting in order to determine deposits of economic value. The nature of the overburden (Fig. 1), which consists of Pennsylvanian limestone and shale beds of varying thicknesses, and a mantle of glacial drift, regu1ates the methods and equipment used in prospecting for these clays. The district in which these clays occur is a gently rolling upland region, characteristic of most of northern Missouri. Along the southern fringe of this area there are numerous deposits of flint clay lying as masses or lenses in depressions at the base of the continuous and widespread Cheltenham formation, or as outlying "sink-hole" deposits in the area marginal to that formation. South of the Missouri River in the north central Ozark region, there are high-grade flint and high-alumina clays, commonly referred to as burley and diaspore clays in sink-hole type deposits. The overburden On these deposits is thin, consisting chiefly of soil and hard-pan, which varies from a plastic

Jan 1, 1948

Discussion of the paper of Archer E. Wheeler and Milo W. Krejci, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 1831 to 1880. BRADLEY STOUGHTON, New York, N. Y.:-I would like to ask Mr. Krejci whether they have tried mixing coke dust with the lime in those converters and, if so, if any advantage has been found. It has been a very great advantage in the steel converters where coke dust has been mixed with the lime near the tuyeres. Of course the agent that causes the corrosion at that point is oxide of iron, and coke seems to prevent the formation of the oxide of iron and so protect the tuyeres. It would be interesting to know if it had the same effect in the copper converters. MILO W. KREJCI:-We have never tried it here. At Anaconda the tuyere section was formerly put in by mixing magnesite with tar and ramming that into the tuyere section, but they have abandoned that. Might I ask how you would apply the coke dust? How get it into the tuyere section ? How hold it there ? BRADLEY STOUGHTON :-The coke dust is mixed with silica and clay and then rammed in and burned. I suppose in your converters it would be mixed with the magnetite or magnesite and then agglomerated with the material in place. MILO W. KREJCI:-We never tried it here. PROF. JOSEPH W. RICHARDS, South Bethlehem, Pa.:-I would like to ask how thick this deposit of magnetite is on the lining. How thick a layer would be practical ? MILO W. KREJCI:-About 21 in. would be sufficient. SOLOMON LE FEVRE, Mineville, N. Y.:-I was interested to hear of the use of magnetite in connection with the copper smelter. I am interested in the mining of magnetite, but was not aware that it had been used at all' by the copper metallurgists.

Jan 11, 1913

By L. Albert, A. M. Cameron, J. W. Gullick

International Nickel has 15 operating mines in Canada, and. 3 mines which are being maintained on a standby basis. Annual production is about 20 million dry short tons of ore, most of which is from underground mines, the remainder from open pit mines. Although some of the underground mines are served by ramps for trackless vehicles, most men, materials and ore are hoisted in vertical shafts. In addition to shafts and raises for ventilation and service purposes which are not equipped with hoisting plants, there are now 28 vertical shafts at Inco mines served by 47 hoists. Of these, 22 shafts and 36 hoists are located in the Sudbury District of Ontario, one shaft and two hoists are at the Shebandowan mine in Western Ontario, and 5 shafts with 9 hoists are located near Thompson, Manitoba. This paper describes the components of Inco hoisting plants-which have been applied at different times and under different conditions, and indicates the rationale for the various designs. Some engineering and maintenance practices, considered advantageous, are also described. MINE SHAFTS Many of the shafts sunk in the early days of the Sudbury District, on what are now Inco properties, were inclined shafts. Of the identifiable shafts sunk between 1885 and 1920, thirteen were inclined and at least four were vertical. Since 1920, thirty vertical and two inclined shafts have been sunk. All of the inclined shafts have been abandoned for hoisting purposes but the majority are still in use as service or ventilation ways. Shafts at Thompson- and Shebandowan are all vertical. The vertical shafts range from 2 or 3 compartment exploration and development shafts to 6 compartment shafts for ore, man and material hoisting. They vary in depth from 1,050 to 7,137 feet and in addition to hoisting compartments all contain manway and service compartments. Prior to 1948, unlined rectangular shafts with timber sets and guides were used. The rectangular cross-section was favoured since the rock is competent, the shape compatible with timber set framing, and since available shaft space could be used efficiently. Resistance to air flow was not of prime importance. Concrete linings were introduced for the first time at the Creighton No. 7 Shaft which was collared in 1948. All major shafts since that date have been concrete lined. Vertical set intervals were increased in steps, with the introduction of structural steel sets secured to the concrete linings. Whereas 7 foot set intervals were used with timber framing, this increased to 10 feet 6 inches with steel sets and more recently to 15 feet with steel and steel backed wood guides. With the advent of deeper shafts, or shafts which are expected to be deepened, the trend is to circular concrete lined shafts. The majority of shaft guides in service are of select Douglas Fir. This practice commenced as a component of timbered shaft design but continued as a

Jan 1, 1975

By John Johnston

WHEN I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in 1916-that is, about 25 years ago-in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father ¬Dr. Samuel Gridley Howe, his mother-Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature. is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-carbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable, tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass . . . by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half-initiated from misusing it and the uninitiated from being misled by these misuses," he writes-and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. It tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works "f the watch was the best butter. If the reader learns no more than to beware of attempts to decipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By J. W. Spretnak, G. W. Powell, J. H. Bucher

Tlze room-temperature tensile fracture oj smooth, round specitnens of three ultrnhigh- strength steels tempered to a wide range of strength levels was studied by means by light and electron-microscopic examination of the fracture surfaces. The fracture of AISI 4340 and 300 M at all the strength levels studied, and H-11, except after tempering at 1200° and 1300°F, occurs in three stages. The initiation of fracture is internal (except in some lightly tcmpeved specimers in which fracture is initiated at surface flaws), and is nucleated largely by separation at metal-second phase intevjaces. TIze voids grow and, coalesce to form a crack. When the crack has reached a sufficienl size, rapid propngutio~z ensues. Failure in this stage of fracture usually occurs by dimpled rupture of inicroshear stefis. In the case of H-11 tempered in the 1125° to 1300°F range, fracture in the shear steps is predominantly by concentrated deformation without void formation. The termination of fracture is usually occomplished by the formation of a shear lib in which fracture occurs by shear dimpled rupture. In the case of H-11 tempered at 1200° and 1300°F, no shear lip was obserued, and the radial elelments extend to the surface—a true termination slage does not exist. ThE tensile fracture of several metals and alloys has been investigated.2-4 In the case of polycrystal-line materials, cup-cone fracture usually results. The mechanism of cup-cone fracture may be summarized as follows.5 Cavities are formed in the necked region of the specimen. They usually are initiated by inclusions or second-phase particles. The cavities extend outwards by means of internal necking, and a crack lying about perpendicular to the length of the specimen is formed in the necked region. Subsequent crack growth occurs by the spread of bands of concentrated plastic deformation inclined at an angle of 30 to 40 deg to the tensile axis. Cavities are formed in the bands of concentrated deformation. The deformation bands zigzag across the bar with the net result that mac-roscopically the crack extends about perpendicular to the specimen axis. The final separation, or cone formation, appears to occur by continued crack propagation along one of the deformation bands out to the surface of the specimen. The micromechanics of the tensile fracture of ultrahigh-strength steels have not been thoroughly investigated. Larson and carr6,7 studied the tensile-fracture surfaces of AISI 4340 with a low-power microscope and reported that three stages of fracture could be observed in general. A centrally located region characterized by circumferential ridges, an annular region characterized by radial surface striations, and a peripheral shear lip were found. It was first pointed out by 1rwin8 that the central region is very probably one of fracture initiation and slow growth, and that the annular, radially striated region is one of rapid crack growth. Presumably the crack grows slowly, assuming roughly a lenticular shape, until it is large enough for the initiation of rapid propagation. In this investigation, it was attempted to determine the fine-scale aspects of the room-temperature tensile fracture of some ultrahigh-strength steels, and to relate the variation in fracture mode with microstructure. The steels studied were AISI 4340, 300M, and H-11 tempered to a wide range of strength levels. I) EXPERIMENTAL PROCEDURE The compositions of the steels studied are given in Table I. The steel was received in the form of hot-rolled bar stock 5/8 to 1 in. in diameter from which oversized specimens were machined and heat-treated. The heat treatments employed are given in Table 11. Subsequent to heat treatment, the specimens were ground to the final dimensions and stress-relieved by heating for 1 hr at 350°F (with the exception of the as-quenched steel). Standard smooth round specimens of 0.252-in. diameter and 1-in. gage length were tested in a Tinius Olsen Universal Testing Machine using a cross-head speed of 0.025 in. per min. The relatively coarse aspects of the fracture topography were determined by light-microscopic examination of sections through the fracture surface of nickel-plated specimens. A direct carbon-replication technique9 was used in the electron-microscopic study of the fracture surfaces. The replicas were examined in the electron microscope, and stereo pairs of electron micrographs were taken. The stereo pairs were then examined using a Wild ST4 Mirror Stereoscope. Carbide and inclusion particles extracted in the replicas were analyzed by selected-area electron diffraction. II) EXPERIMENTAL RESULTS The mechanical testing data are summarized in Table 111. The values reported are the average of

Jan 1, 1965

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the frothability of pine oil is governed by: 1-rate of aeration, 2-time of aeration, 3-height of liquid column, 4-chemical composition of pine oil, 5-pH value of solution, 6-temperature of, solution, and 7-concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.1 The results also show that the relative frothabilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of reproducibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1-compressed air and its regulating system, 1-3, are eliminated; and 2-a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be .either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifing and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.2 Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 ± 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1952

By D. W. G. White

The surface tension of zinc has been determined by the sessile-drop method in a progvam emphaszzing detailed experimental care. The surface tension oj. the pure metal was measured over a range of ternperature from the melting point (419.6"C) to 540°C. At the melting point, the suvface tension of zinc was found to be: 1) 99.99+ pct Zn - 757.0 5 dynes per cm 2) 99.999+ pct Zn - 761.0 5 dynes per CI 3) 99.9999 pct Zn - 76'7.5 5 dynes pev cna From experiments carried out in a closed, isothermal cell, the temperatuve coejyicient of the surface tension (6y/6T)p, , of zinc xas found not to be negative but to be postiue. A positive tenzperatre coefficient indicates a greater depee of order in the surface than in the body of the lquid. Houlezer, by delibevately inducing continuous zaporization, a temperature coefficient of su)face tension with a negative slope can be produced. The work reported herein was undertaken as part of a larger program of fundamental research on the properties of molten zinc and zinc alloys. This program grew out of a continuing interest at the Mines Branch in the behavior of liquid metals in the foundry and of a desire on the part of the zinc industry for reliable basic data. The work was originally begun in cooperation with the Consolidated Mining and Smelting Co. Ltd., Trail, B.C., and was subsequently continued from 1960 to date in association with the Canadian Zinc and Lead Research Committee and the International Lead and Zinc Research Organization. Although the surface tension of liquid zinc has of course, been measured before, as Table I and Fig. 1 demonstrate, there is not good agreement among the existing values. Such disparities arise because sources of experimental error are insufficiently controlled. This situation places the reader in doubt. One result may be correct within narrow limits—even fortuitously—yet, because there is not agreement between several values, none can be accepted with conviction and all become suspect. It seemed, therefore, in the circumstances, that there was room for further work embodying considerable emphasis on experimental care in order that, within a small margin of error, an accurate value might be obtained. It was in this spirit that the work was undertaken. METHOD The sessile-drop method -as adopted for this work. In this method, when applied to liquid metals at elevated temperatures, the outline of the meridional section through a drop resting freely on a horizontal surface is recorded photographically. Certain parameters

Jan 1, 1967