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By David Keys

THE actual procedure in estimating depth of overburden from mag-netic observations made on the surface will vary with the form of the deposit and any theoretical discussion will apply only so far as the form of the deposit conforms to the mathematical premises on which the theory is based. Since the shapes of natural deposits in the field cannot be expressed rigorously in mathematical form, the best that can be done is to assume some simple form and deduce results. Fortunately many small variations in form produce only slight changes in the estimated depth of overburden, therefore the methods have a definite practical value. For the theoretical treatment, magnetic ore deposits may be divided roughly into three classes, depending upon whether the magnetic anom-alies may be considered to arise from (1) a single magnetic pole, (2) a dike or (3) a magnetic doublet. Particular cases, falling under one or other of these classes, have been discussed by different authors.1-4 In general, it may be stated that when the magnetic effects as measured on the surface are due only to one pole of the body, the other pole being so remote that its effect may be neglected, the resultant anomaly F at any point will vary as the inverse square of the distance r of the point from the pole, which may be expressed mathematically by F = k/r2, where k is a constant. When the deposit occurs in the form of a long, thin dike, the resultant anomaly will be of the form F = k'/r and when the deposit is in the shape of a lens, so that both poles have an appreciable effect on the surface, the result will be similar to that caused by a magnetic doublet, and the form will be F = k'/r3. The particular class under which a deposit falls may be deduced from the results of the magnetic survey. The second class is readily found, but there may be difficulty in deciding between the first and third. Isody-namic contours of both the vertical and horizontal anomalies will often be a good guide in making a correct decision.

Jan 1, 1937

By J. H. Swisher

When an Fe-Mn alloy is internally oxidized, the inclusions formed are MnO which contains some dissolzled FeO. In the internal oxidation reaction, not all of the manganese is oxidized; some remains in solid solution as a result of the high Mn-0 solubility product in iron. Taking these factors into consideration, the rate of internal oxidation of an Fe-1.0 pct Mn alloy is computed as a function of temperature, using available thermodynanzic data and recently published data for the solubility and diffusivity of oxygen in iron. The predicted and experimentally determined rates for the temperature range from 950 to 1350°C are in good agreement. ThE rates of internal oxidation of austenitic Fe-A1 and Fe-Si alloys have been studied extensively.1"4 Schenck et al. report the results of a few experiments with Fe-Mn alloys at 854" and 956C, and Bradford5 has studied the rate of internal oxidation of commercial alloys containing manganese in the temperature range from 677" to 899°C. When Fe-Mn alloys are internally oxidized, the inclusions formed are solutions of FeO in MnO, the composition depending on the experimental conditions. Since the thermodynamics of the Fe-Mn and FeO-MnO systems have been investigated,6"9 and since the solubility and diffusion coefficient of oxygen in y iron have been determined recently,' it is possible to predict the rate of internal oxidation from known data. The calculations used in predicting the rate of internal oxidation will first be outlined, then the results of the prediction will be compared with the experimental results of this investigation. PREDICTION OF PERMEABILITY FROM THERMODYNAMIC AND DIFFUSIVITY DATA Oxygen is provided for internal oxidation in these experiments by the dissociation of water vapor on the surface of the alloy. The dissociation reaction is: + H2(g) + [O] [1] where [0] denotes oxygen in solution. The equilibrium constant for this reaction is known as a function of temperature:' log As oxygen diffuses into the alloy, oxide inclusions are formed which are MnO with some FeO in solid solution. The reactions occurring are: [Mn] + [0] = (MnO) [31 and [Fe] + [0] = (FeO) [41 where [ Mn] is manganese dissolved in iron and (FeO) is iron oxide dissolved in MnO. The overall reactions may be written as follows: [Mn] + HOte) = (MnO) + H2(£) [5] and [Fe] + H20(g) = (FeO) + Hz(R) [61 The standard free-energy changes and equilibrium constants for Reactions [5] and [6] are known.6 Therefore the equilibrium constants for Reactions [3] and [4] may be obtained by combining known thermodynamic data for Reactions [I], [5], and [6]. For Reactions [3] and [4]: K = and For the present purpose, both the Fe-Mn7,8 and FeO-~n0' systems can be considered to be ideal, i.e., [amn] = [NM~] and (aFeO) = (NM~~) = 1 - (NFeO) where the Ns are mole fractions. These relations, together with Eqs. [I] and [8], permit us to compute both the oxide and metal compositions as a function of temperature and oxygen potential at any point in the specimen. For cases where the oxygen concentration gradient between the surface and the subscale-base metal interface is linear, the kinetics of internal oxidation is an application of Fick's first law: where dn/dt is the instantaneous flux of oxygen into the specimen, g-atom per sq cm sec; 6 is the instantaneous thickness of the subscale, cm; Do is the diffusion coefficient of oxygen in iron, sq cm per sec; p is density of iron, g per cu cm; h[%O] is the oxygen concentration difference between the surface and sub-scale-base metal interface, wt pct. B6hm and ~ahlweit" derived an exact solution to the diffusion equation for systems in which there is a stoichiometric oxide formed. They showed that the oxygen concentration gradient is given by a rather complex error function relation. For the Fe-Mn-0 system and for most other systems that have been studied, however, variations in oxide compositions are small and rates of internal oxidation are sufficiently slow that the deviation from linearity in the concentration gradient of oxygen is negligible. The mass of oxygen transported across a unit area of the specimen for the total time of the experiment is given by the mass balance equation:

Jan 1, 1969

By William E. Ford, Edward Salisbury Dana

URANINITE. Cleveite. Broggerite. Nivenite. Pitchblende. Isometric. In octahedrons (o), also with dodecahedra1 faces (d) ; less often in cubes with o and d. Crystals rare. Usually massive and botryoidal; also in grains; structure sometimes columnar, or curved lamellar. Fracture conchoidal to uneven. Brittle. H. = 5'5. G. = 9'0 to 9'7 of crystals; of massive altered forms from 6'4 upwards. Luster submetallic, to greasy or pitch-like, and dull. Color grayish, greenish, brownish, velvet- black. Streak brownish black, grayish, olive-green, a little shining. Opaque. Comp. -A uranate of uranyl, lead, usually thorium (or zirconium), often the metals of the lanthanum and yttrium groups; also containing the gases nitrogen, helium and argon, in varying amounts up to 2'6 p. c. Calcium and water (essential?) are present in small quantities; iron also, but only as an impurity. The relation between the bases varies widely and no definite for- mula can be given. Radium was first discovered in this mineral and it has been shown that it and the helium present are products of the breaking down of the uranium.

Jan 1, 1922

By Elmer A. Jones

Development work in mines of St. Joseph Lead Co., Southeast Missouri, using trackless loading equipment shows definite advantages: Speed of cleaning, ability to work on steep grades and sharp crosscuts, good later tracking conditions, and possibility of wasting rock in old abandoned stopes. THE Desloge mine is one of a group of mines owned by the St. Joseph Lead Co., in the so-called Lead Belt of Southeast Missouri. It has been operating approximately 40 years producing a daily tonnage ranging from 1600 to 3800, depending on various factors. On an average, the present mine is 300 ft deep with an extreme extent of 2.7 miles by 1.7 miles. Most of the present mining is in the lower horizons of the Bonne Terre dolomite, a fairly soft rock requiring no support except occasional channel iron and roof pins. Due to the contour of the underlying sandstone and porphyry, some development work has been through short stretches of these different formations. In some areas the lower part of the dolomite is quite sandy and generally is considered abrasive. Sizes and Methods of Drifting Have Changed: Development work has, like other phases of mining, changed considerably in the last 20 years, from cleaning by hand to the use of a mechanical method. The conception of a standard drift has also changed. Before the advent of mechanical loading in stopes there were many pieces of main line drift averaging 7 ft high x 9 ft wide. With the coming of the St. Joe shovel the drift was increased to 8 ft high x 10 ft ELMER A. JONES, Member AIME, is Assistant General Mine Superintendent, St. Joseph Lead Co., Bonne Terre, Mo. AIME Columbus Meeting, September 1949. TP 2859 A. Discussion (2 copies) may be sent to Transactions AIME before July 31, 1950. Manuscript received Sept. 16, 1949. wide. Now with the Joy loader and shuttle car, a 9x11 ft drift is coming to be standard size. Methods of cutting drifts have changed considerably over the last few years. Some changes in drilling equipment have been made such as reducing the weight of column, clamp, air feed, and fittings to go with the HC10 Cleveland jackhamer. Other changes have been made in drill steel such as the use of detachable bits; throw-away variety, screw type, and the tungsten-carbide insert bits. Later developments have introduced spiral-welded pipe with victaulic couplings, millisecond exploders, bulky powder, and the use of electric cap lamps. Experimental work is going on continually in various phases of development work, some to be tried and discarded, others gradually to become standard practice. To sum up, the standard method of development now in use at Desloge is as follows: The work is done on a two-shift cycle 7:00 p.m. to 3:00 a.m. and 7:00 a.m. to 3:00 p.m. Two men known as development drillers comprise a crew on each shift. These two men arrive at their work about 7:30 to find a round blasted by the previous shift. After scaling down back and walls they proceed to the cleaning operation, using either a Joy loader and shuttle car, a drag hoist mounted on a slide ramp, or an Eimco Finlay to load into a 21/2 ton mine car. Cleaning may take from 2 to 4 hr depending on conditions such as length of round broken, length of haul, and other variables. After fitting up pipe and setting up columns and drills they are ready to drill a round which should measure 9 ft high x 11 ft wide and break from 5 to 7 ft advance. This may also take from 2 to 3 hr. Then they are ready to charge and

Jan 1, 1951

By Elmer A. Jones

Development work in mines of St. Joseph Lead Co., Southeast Missouri, using trackless loading equipment shows definite advantages: Speed of cleaning, ability to work on steep grades and sharp crosscuts, good later tracking conditions, and possibility of wasting rock in old abandoned stopes. THE Desloge mine is one of a group of mines owned by the St. Joseph Lead Co., in the so-called Lead Belt of Southeast Missouri. It has been operating approximately 40 years producing a daily tonnage ranging from 1600 to 3800, depending on various factors. On an average, the present mine is 300 ft deep with an extreme extent of 2.7 miles by 1.7 miles. Most of the present mining is in the lower horizons of the Bonne Terre dolomite, a fairly soft rock requiring no support except occasional channel iron and roof pins. Due to the contour of the underlying sandstone and porphyry, some development work has been through short stretches of these different formations. In some areas the lower part of the dolomite is quite sandy and generally is considered abrasive. Sizes and Methods of Drifting Have Changed: Development work has, like other phases of mining, changed considerably in the last 20 years, from cleaning by hand to the use of a mechanical method. The conception of a standard drift has also changed. Before the advent of mechanical loading in stopes there were many pieces of main line drift averaging 7 ft high x 9 ft wide. With the coming of the St. Joe shovel the drift was increased to 8 ft high x 10 ft ELMER A. JONES, Member AIME, is Assistant General Mine Superintendent, St. Joseph Lead Co., Bonne Terre, Mo. AIME Columbus Meeting, September 1949. TP 2859 A. Discussion (2 copies) may be sent to Transactions AIME before July 31, 1950. Manuscript received Sept. 16, 1949. wide. Now with the Joy loader and shuttle car, a 9x11 ft drift is coming to be standard size. Methods of cutting drifts have changed considerably over the last few years. Some changes in drilling equipment have been made such as reducing the weight of column, clamp, air feed, and fittings to go with the HC10 Cleveland jackhamer. Other changes have been made in drill steel such as the use of detachable bits; throw-away variety, screw type, and the tungsten-carbide insert bits. Later developments have introduced spiral-welded pipe with victaulic couplings, millisecond exploders, bulky powder, and the use of electric cap lamps. Experimental work is going on continually in various phases of development work, some to be tried and discarded, others gradually to become standard practice. To sum up, the standard method of development now in use at Desloge is as follows: The work is done on a two-shift cycle 7:00 p.m. to 3:00 a.m. and 7:00 a.m. to 3:00 p.m. Two men known as development drillers comprise a crew on each shift. These two men arrive at their work about 7:30 to find a round blasted by the previous shift. After scaling down back and walls they proceed to the cleaning operation, using either a Joy loader and shuttle car, a drag hoist mounted on a slide ramp, or an Eimco Finlay to load into a 21/2 ton mine car. Cleaning may take from 2 to 4 hr depending on conditions such as length of round broken, length of haul, and other variables. After fitting up pipe and setting up columns and drills they are ready to drill a round which should measure 9 ft high x 11 ft wide and break from 5 to 7 ft advance. This may also take from 2 to 3 hr. Then they are ready to charge and

Jan 1, 1951

Jan 1, 1882

By N. S. Greensfelder

THE firing of explosive charges by electricity dates back to 1745 when a Doctor Watson is said to have used an electric spark for igniting gunpowder. His method failed in practical application because, to ignite blasting powder, heat must be applied for a period longer than the duration of an electrostatic spark; Wheatstone found that this does not exceed 14000 sec. The usual result, therefore, of an electrical discharge in gunpowder is to scatter the grains, without igniting them. Benjamin Franklin partly overcame this difficulty by confining the powder and crushing grains that lay in the line of discharge. In 1822, after the primary cell had been discovered by Volta, Robert Hare, professor of chemistry at the University of Philadelphia, noticed the heating of a short piece of wire placed in the circuit of a voltaic battery. Later work by Oersted, Faraday, Wheatstone, and Henley resulted in the development of the magneto blasting machines. Fulminates of gold and silver are thought to have been discovered by Cornelius Drebbel, about 1600. Pepys, in his diary for November 11, 1663, recounts a conversation with Doctor Allen, who told him about aurium fulminans "of which a grain ... . put in a silver spoon and fired, will give a blow like a musquett and strike a hole through the silver spoon downward, without the least force upward.1," This fallacious belief that explosives act downwards only, is still held by many who should know better. Fulminate of mercury was discovered by Howard in 1799. J. Shaw of Philadelphia is said to have invented a fulminate-of-mercury cap in 1814; his idea was later adopted by gunmakers in England and France. The principal advantages of

Jan 9, 1922

By N. J. Themelis, A. W. Last

Autogenous grinding, broadly defined as the self-comminution of ore in a cylindrical tumbling mill without using auxiliary grinding media, was first applied in the early 1930s in the so-called Hadsel mills (Hardinge, 1955) as seen in [Fig. 1], mainly used in gold mines on the US West Coast. A number of these mills were built in sizes of 6.1 to 7.3 m (20 to 24 ft) in diameter and 1.5 to 1.8 m (5 to 6 ft) in length but were later abandoned because of operating and maintenance problems. Further development of autogenous grinding led to the Hardinge wet grinding mill, the Aerofall dry grinding mill, and others. A tabulation of all known autogenous and semiautogenous installations around the world was sent recently to the authors by G. J. Kushner of Koppers Metal Processing Division. In the size range of 7.3 to 9.8 m (24 to 32 ft) in diameter, it lists a total of thirty mills used in the processing of copper ores. An additional 120 units are listed in the same size range for the processing of iron ores and other minerals. The largest mills in existence are 11.1-m-diam X 4.6-m-long (36-ft-diam X 15-ft-long) mills in Minnesota, powered by 8950 kW (12,000 hp) motors and used in taconite beneficiation. It is indicative of the phenomenal growth of this technology that none of the above 150 mills was in operation prior to 1964. Grinding rates in autogenous mills are very sensitive to variations in ore breakage characteristics and even with fairly constant ore type can exhibit large fluctuations in throughput. Autogenous grinding also depends on availability of a fraction of the ore to be ground in the form of "competent" rock which can withstand to a certain degree the tumbling and impact action within the mill. If the ore is uniformly "soft", it will soon be crushed into small size particles and further grinding, which depends on the existence of large size rocks in the mill, becomes impossible. This apparently is the case with most copper ores, as discussed by Bachman, Last and Nabbs (1970) who described pilot testing of a large number of ore samples from Kennecott 's Chino Mines. Under circumstances where autogenous grinding is impractical, it is possible to realize most of its benefits by utilizing large grinding balls in place of the "competent" rock and practice what has become known in the mining industry as semiautogenous grinding. In semiautogenous grinding (SAG), a grate discharge tumbling mill is fed the product of a primary crusher or run-of-mine rock. Forged steel or alloy grinding balls, in proportions ranging from 3.10% of the total volume in the mill, are used to complement the self-grinding ability of the ore. Semiautogenous circuits can be either designed for single-stage closed-circuit grinding which produces a final product for recovery processes, or for two-stage operation in which the SAG mill product is fed to a second stage of grinding in a conventional ball mill.

Jan 1, 1981

By R. G. Grieves, G. Thodos

A method is presented for the accurate calculation of the cricondentherm and cricondenbar pressures of multicomponent hydrocarbon mixtures of known composition. The mixtures may contain six and quite possibly any number of components including paraffins, isoparaffins, olefins, acetylenes, naphthenes and aromatics. The approach is similur to that used for calculating critical pressures and cricondentherm and cricondenbar temperatures. The critical pressure, the normal boiling point and the approximate vapor pressure behavior of each component are all that art required. A stepwise culculation procedure is necessary for mixtures containing more than two components. From an analysis of 22 binary systems and 118 mixtures, the average deviation of calculated cricondentherm pressures from reported values is 2.4 per cent. For nine multicomponent mixtures the average deviation is 1 per cent. Considering 19 binary systems and 108 mixtures, the average deviation of calculated cricondenbar pressures from reported values is 1.7 per cent. For 15 multi-component mixtures, the average deviation is 2.2 per cent. INTRODUCTION A knowledge of the phase behavior in the critical region of multicomponent hydrocarbon mixtures is of value both in industrial processing operations and for the optimum operation of gas condensate reservoirs. Accurate methods of calculating the critical temperatures and critical pressures4,6,7,8,9,23 and cricondentherm and cricondenbar temperatures6p10 of multicomponent hydrocarbon mixtures are available in the literature. If the cricondentherm and cricondenbar pressures could be calculated with equal accuracy, the entire phase diagram of a multicomponent hydrocarbon mixture could be well approximated. The work of Etter and Kay6 is limited to systems containing the normal paraffins and has not been tested on systems containing a heavier component than heptane. In addition, the development of their multicomponent equations is based upon a limited number of mixtures containing from three to six components. Silverman and Thodos have considered systems containing both paraffinic and non-paraffinic hydrocarbons, but their correlation is limited to binary systems and is highly inaccurate for methane systems. Eilerts has done extensive work on the cricondenbar pressure; he has produced an excellent correlation for binary systems. However, his procedure for multicomponent mixtures is chiefly useful for highly complex mixtures requiring a knowledge of the vapor-liquid equilibrium behavior of the mixtures; he has not considered the cricondentherm pressure. The objective of this study was the development of an accurate and rapid method for the calculation of the cricondentherm and cricondenbar pressures of multicomponent mixtures containing all types of hydrocarbons and having a wide volatility range. The approach that was adopted is similar to that used by Grieves and Thodos for cricondentherm and cricondenbar temperaturesl0 and for critical pressures.9 However, methane systems had to be considered separately and a modified stepwise calculation procedure was utilized for the cricondertherm pressure. The correlations were developed in a manner similar to those for critical pressures and cricondentherm and cricondenbar temperatures. Based upon binary data reported in the literature it was observed that the ratios of cricondentherm and cricondenbar pressure to the pseudocritical pressure (molar average), pt/ppc and pp/ppc, respectively, in two-component systems depended upon the mole fraction of the low-boiling component and upon the diversity in properties of the two components. A dimensionless boiling-point parameter Tb,/Tb was chosen to represent the diversity in properties of the components. For a binary system, Ti,'is the molar average of the normal boiling points of the two components involved. For a multicomponent system it is either the molar average of the normal boiling points of all of the components involved or the molar average of the normal boiling point of the pure low-boiling component and of the atmospheric boiling point of the low-boiling-free mixture of

Jan 1, 1965

By J. C. Reed

CINNABAR was discovered in southwestern Arkansas on Little Missouri River in sec. 1, T.7S., R.26W., in April, 1930, and near Antoine Creek in sec. 28, T.6S., R.23W., some 15 miles farther east in May of the same year. It was not, however, until June, 1931, that cinnabar was identified as such in a specimen from the original discovery area sent to W. M. Weigel1 by Walter F. Hintze of Murfreesboro. Almost simultaneously2, in July, 1931, Moritz Norden of Hot Springs identified specimens from the Antoine Creek area as cinnabar. Immediate interest in the district followed the identification of cinnabar and by January, 1932, the district was known to extend as a mineralized belt about one mile wide trending east-northeast from sec. 13, T.7S., R.27W., in Howard County-across central Pike County and into Clark County to sec. 19, T.6S., R.23W., thence extending southeast into sections 33 and 34 of the same township. Since then, cinnabar has been found in sec. 6, T.7S., R.22W., thus giving a total east-west length to the district of approximately 30 miles. Interest focused mainly on the two discovery areas, with the result that mining development has progressed most rapidly in those localities. In the Antoine Creek area the Arkansas Quicksilver Co. has done con-siderable exploration work and has retorted the high-grade ore so .obtained. In the Little Missouri area the Southwestern Quicksilver Co. has had a 12-ton rotary furnace in more or less continuous operation since April, 1932, and has been the largest producer in the district.

Jan 1, 1935

By G. H. Edmunds, C. H. Mathewson

About fifty pages of Henry M. Howe's profound treatise, "The Metallography of Steel and Cast Iron," are devoted to twinning with special reference to the origin, nature and general significance of the Neumann bands in ferrite. Howe believed with Osmond and Cartaud1 that the Neumanns are mechanical twins and his careful observations leave no doubt that these straight-sided narrow bands habitually occur parallel to trapezohedral planes of form {211). Attempts to develop the structure of the bands by various methods SO that their identity could be established beyond question have not been conspicuously successful. Howe thought that they deflected slip bands. Some of the etching figures which have been developed within and adjacent to Neumann bands support the contention that they are twins. A good example of this effect in ferrite containing 0.6 per cent, of niekel and 1.3 per cent. of phosphorus, originally due to Harnecker and Rassow,2 was reproduced in the 1928 lecture before the Institute of Metals Division on twinning in metals.3 In this case, the sides of the figures might represent the traces of cubic planes laid bare by etching a properly oriented grain of ferrite, twinned along a plane of form (211). Our own observations in this direction may be represented by Fig. 1 which shows in a deeply etched cavity in the boundary region between a Neumann band and the original crystal two small crystal surfaces which resemble the faces meeting at a reentrant angle in the simple cube twinned along a bisecting plane of form (211) as sketched in Fig. 2. Rosenhain and McMinn4 in 1925, after a careful study of slip bands in ferrite containing Neumanns previously produced by shock, concluded

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

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

Jan 1, 1969

By Ralph Hultgren, David W. Mitchell

Magnesium alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600" to r 7o0°F.; the casting temperature, which depends upon the mold shape, is usually 200° to 300°F. lower. The process of superhcating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported1 that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results? As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted' project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. Materials and Methods The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesiun used in these alloys was of both carbothermic3 and electrolytic' origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200° to 1250°F., portions of approximately one pound each, were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21 † covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F. for 15 min., then . cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By R. I. Jaff, H. R. Ogden, D. J. Maykuth

A phase diagram for alloys containing from 0 to 66.9 pct Mn was determined. Two compounds, tentatively labeled 6 and y, were found in this range. The 6 compound is located at about 66.9 pct Mn and melts congruently at 1330°C. The ? compound has a composition near 53 pct Mn and originates in a peritectic reaction at 1200°C between liquid and 6. ß and Y enter into a eutectic reaction at 1175°C. The ß phase field terminates in a very sluggish eutectoid reaction between a and ? at 550°C. MANGANESE is one of the important alloying addition elements to titanium. As a ß-stabiliz-ing addition for a-ß and ß alloys, it provides high strength with adequate ductility.' Two of the earliest commercial alloys contain manganese as a major alloying component.' The earliest published data on the constitution of Ti-Mn alloys was that of Wallbaum,~ who reported the existence of the compound TiMn2. The transformation range of commercial-purity Ti-Mn alloys was investigated by Craighead, Simmons, and Eastwood' who found limited a solubility and a lowering of the ß transus to about 790°C at 7 pct Mn. Preliminary work by the authors of this paper, using high-purity titanium, confirmed the ß-stabilizing action of manganese and showed the existence of several intermediate phases in the Ti-Mn system." More recently, McQuillan3 determined the ß transus temperatures for high-purity Ti-base alloys containing up through 4.4 pct Mn. These data are given in Fig. 1. The present investigation covered alloys made with a high-purity base. The constitution of titanium-rich alloys made with commercial titanium has been reported4," by Holladay, Kura, and Jackson. The alloy range covered in the present investigation was from 0 to 69.5 pct Mn. This alloy range extends slightly beyond the composition of the first congruent-melting compound encountered on proceeding from the titanium end of the system. A description of the materials and methods used in the determination of the diagram is given in the Appendix. The partial phase diagram determined for the Ti-Mn system is shown in Fig. 2. Details on equilibria in the titanium-rich alloys are given in Fig. 3. Liquid-Solid Relationships Observations on the cast structures of the arc-melted ingots showed that the terminal solid solution of manganese in ß titanium enters into a eutectic reaction with an intermetallic compound labeled ?. As will be shown later, this compound has a composition around 53 pct Mn. The eutectic reaction temperature was determined as 1175°C by thermal analysis which also showed that the ? phase originates in a peritectic reaction at 1200°C. Fig. 4 shows typical eutectic structures for alloy compositions on both sides of the eutectic composition which is located at 42.5 pct Mn. In alloys over the range of 45.4 through 69.5 pct Mn, a second intermetallic compound, labeled 6, was identifield as the primary phase. This phase consistently increased in amount as the manganese content approached 66.9 pct, and, as shown in Fig. 5, an alloy structure containing 66.9 pct Mn consisted essentially of the 6 compound. Thermal-analysis data indicate a melting point of about 1330°C for the 6 intermediate phase. At 67.0 pct Mn, small quantities of a new, higher manganese-content phase were observed in the form of Chinese-script eutectic particles. Comparison of Fig. 6a and b shows an increasing quantity of this phase as the composition was increased to 69.5 pct Mn. The formation of peritectic ? in arc-melted alloys containing 45.4 pct Mn and above appears to be almost entirely suppressed, as shown in Fig. 7a and b. This is because of the narrow freezing range available for its formation by peritectic reaction and because of the very high cooling rates obtained in

Jan 1, 1954

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins' and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer' type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By J. Lewis, J. Harper, M. F. Ashby

A grain boundary in a metal interacts with second-phase particles, which exert a pinning force (first estimated by Zener) on the boundary opposing its motion. We have computed the shape of boundaries which interact with more or less spherical second-phase particles and have constructed a soap-film model to reproduce the shape of the boundary surface. An important result is that measurement of this shape allows the pressure, or driving force, on the boundary to be measured. We hare applied this technique to grain boundaries in two alloys and hate measured the pinning force exerted by single second-phase jwrticles on the boundaries. It is in good agreement with Zener's estimate. J\. boundary between two grains, or two bulk phases, interacts with small inclusions or particles of a second phase, whether they are gas or solid. This interaction means that the boundary, forced to migrate by a difference in free energy between the material of the two grains or phases which it separates, exerts a force on a particle which it touches, tending to drag it forward. (The movement of inclusions through metals under the influence of this force, has, in fact, been observed. 1-3) Equally, the particle can be thought of as exerting a pinning force on the boundary, tending to hold it back. Zener (in a celebrated private communication4) first realized that this interaction, and the resulting pinning force, existed. His calculation of its magnitude was crude but adequate: a spherical inclusion of radius r blanks off an area nr2 of the boundary on which it sits; since the boundary has an energy of rMM x per unit area, the blanlung-olf decreases the energy of the system by MM: this energy is returned to the system if the boundary is pulled free from the inclusion— a forward movement of the boundary by a distance r will do this—so that the maximum pinning force is Trrym.M- A similar argument can be made for inter-phase boundaries. The nature of the particle itself did not enter this, or two subsequent treatments.5,6 When it is considered, tic leifthe energyoftheb a) The boundary may enter and pass through the particle if the energy of the boundary is lower within the particle than in the matrix. Fig. l(r/). Certain coherent precipitate particles behave like this. h) More usually, the boundary will bend round the particle, enveloping and bypassing it. Fig. l(b). In doing so, it changes the structure and energy of the interface between the particle and its matrix. This means that the boundary does not touch the particle surface at right angles, as early treatments assumed,5'9 but at some angle a which depends on this change in surface energy of the particle, and can be calculated from the equilibrium of surface tensions. Most precipitate particles and inclusions behave like this. Gas bubbles or liquid drops can be regarded as belonging to either group. The progress of bypassing is conveniently measured by the angle shown in Fig. 1. When the nature of the particle is ignored, its maximum pinning force is exerted when - 45 deg. When it is considered, this critical value of is found to depend on a and thus on the nature of the particle. The maximum pinning force lies between nryMM and 2jtjMM (Appendix 1). not very different from Zener's result. In reality, a boundary between crystals has a specific energy and tension which varies with the orientation of the boundary. Furthermore, recent experiments7 indicate that such a boundary is not atom-ically smooth, but has steps on it: migration of the boundary corresponds to the sweeping of these steps across the boundary surface, like the Frank model of crystal growth from the vapor. This means that the interaction of a boundary with particles should really be considered in terms of the way in which particles hinder the movement of these steps. To suppose a grain boundary or interphase boundary to be smooth, and to ignore the variation of its energy with orientation, is to liken it to a soap film. The advantage of this soap film approximation, which we have used throughout this paper, is that interaction energies and boundary shapes can be calculated easily. We have done this by numerical computation and by using a soap film model, and have compared the results with grain boundaries in an aluminum-based and a copper-based alloy. It turns out that the shape of the boundary which bulges between particles allows the pressure an it to be calculated; that is, the local driving force an the boundary can be measured. This has allowed us to check the Zener relationship experimentally.

Jan 1, 1970

By R. F. Shurtz

R. Duval (Mining Engineer, Ancien eleve de PEcole Polytechnique, Paris, France) I do not agree with the Eq. 3, reading: m =1/100- [(0.214x30.4) + (0.7B6 x0.00)] =6.5pct CaO If 0.214 and0.786 were proportions by weight, the equation would represent the well known mixtures law of the conventional arithmetics and 6. 5 pct CaO would be the correct average content. But it is not the case as the author states: "In samples consisting of single grains of mineral, those grains must, as already mentioned, be either of dolomite or magnesite. Since 78.6 pct of the deposit consists of magnesite and 21.4 pct of dolomite (excluding for present purpose the presence of other minerals), for any single grains picked at random the probability will be 0.214 that is it dolomite and0.786 that is it magnesite. In 1000 such samples the expected numbers of dolomite and mapesite grains will be 214 and 786 respectively." 0.214 and 0.786 would be proportions by weigbt under the necessary condition that all grains of dole mite and magnesite should have an identical weight. Obviously it is not the case, as the specific gravities are not the same for mapesite and dolomite and the volumes of the grains are different. Furthermore, because of these differences the conditions for a random sampling are not fulfilled and we are not authorized to state that the probabilities are, respectively, 0.214 and 0.786. The author however makes a simple application of Eq. 1: M = 1/n— ? fi x i . n Should we deduce that this relation is wrohg? Not at all, but when applying Eq. 1 you must not overlook what it actually. means. Eq. 1 gives a definition of the arithmetic mean of a total of n observed values Xi and nothing else. But the average conteht of a deposit has not the same significance. It is the ratio between the weight of concerned mineral in the deposit and the total weight of the deposit. As from 1000 particles the 214 of dolomite and the 786 of magnesite have not the same weight, the two definitions do not concur, and when applying Eq. 1 the result is an arithmetic mean of figures which has no connection with what is named average contentof a deposit. The situation is similar to the calculation of an average velocity. If a car travels a first mile over at 30 miles per hr and a second mile over at 60 miles per hr, when applying formula 1 you find as average velocity for the 2 miles: 30+60 ------- - 45 miles per hour. Many people calculate in this way and they do not realize that a mistake is involved. In fact the definition of he average velocity for the 2 miles is the quotient of the distance of 2 miles by the time (in hours) necessary for 2 miles travel, i.e.: 2 ---------- = 40 miles per hr. 1 + 1 30 60 In other words, the average volocity wanted is not the arithmetic but the harmonic average of the two velocities. The above mentioned bias in the calculation of the average contents of deposits is frequent, even in the assessments made by experienced engineers and is independant of what is named the sampling error. In order to supress the bias and to be able to use Eq. 1, you must apply a correction. An example on the subject can be found in an article by Duval et al. in the January 1955 issue of the ''Annales des Mines" (French), page 19. R. F. Schurtz (Author's Reply) Mr. Duval's position is quite correct. The proportions shown for dolomite and magnesite., respectively, of 0.214 and 0.786 are, in fact, proportions by weight uncorrected for specific gravity. In our day to day operation of producing magnesite from these mines at a very substantial rate, we do not normally make corrections for the difference between the specific gravity of dolomite and that of magnesite. If these corrections are made in Eq. 3 as shown in my article, then the numbers of grains turn out to be in proportions of 0.226 dolomite and 0.774 mapesite instead of the values actually shown in the equation. For the purposes of our work, and in view of the inherently low accuracy of the data, this correction was not deemed worthwhile making.

Jan 1, 1961

By Raymond D. Sloan

Retaining third place in crude-oil production among the nation's oil-producing states, Oklahoma's output in 1942 totaled 137,792,000 bbl., a decline of 9.4 per cent from the previous year's total of 152,117,000 bbl. Production declined from an average of 403,000 bbl. daily in January 1942 to an average of 355,000 bbl. during December, a reduction of 48,000 bbl. daily (11.9 per cent) during the year. At the end of 1942 it would appear inevitable that the downward trend in production will continue in 1953 unless halted in the immediate future by greater than normal discoveries and development. To Jan. I, 1943, Oklahoma has produced 5,067,013,000 bbl. oil crude oil. Development and Exploration Development dropped abruptly in 1942, reflecting the lack of any sizable discoveries and the effect of the provisions of Federal Well Spacing Order M-68, which became effective in December 1941. In all, 1210 wells were drilled in 1942. This represents a decrease of 42.7 per cent from the 1941 total of 2110. Of the total wells completed, 553 (45.7 per cent) were oil wells with an average initial production of 443 bbl.; 102 (8.4 per cent) were gas wells with an average initial of 3,359,000 cu. ft.; and 555 (45.9 per cent) were dry. Although the number of completions declined sharply, the total of 320 wildcats completed (26.4 per cent of all wells) repre-sents a decrease of only 2.7 per cent from the previous year's figure of 329. Of the wildcats drilled, 44 (13.8 per cent) were oil wells, 13 (4.0 per cent) were gas wells, and 263 (82.2 per cent) were recorded as failures. Reconditioning of wells throughout the state resulted in a total recompletion of 355 wells. Of these, 234 were oil wells with a combined initial production of 96,808 bbl., 32 were gas wells with a total initial of 381,488,000 cu. ft., and 89 were abandoned. None of the 26 pools found in 1942 has developed into a major discovery. The Pauls Valley pool, Garvin County, is the most outstanding. Since its discovery in April, 14 wells with an average initial of 1898 bbl. have produced 803,000 bbl. of 42' gravity oil from the Bromide zone. Development in this pool is believed to be almost completed. Other of the more important discoveries are the East Watchorn pool, Pawnee County; Guthrie Townsite and West Navina, Logan County; Brooksville and Macomb, Pottawatomie County, and the Liberty and Northeast Lucien discoveries in Noble county. The East Watchorn pool, at the close of the year, had 14 completed oil wells with an average initial of 989 bbl. from the Wilcox sand at 3930 it.; Guthrie Townsite, one well with an initial of 840 bbl. from dolomite at 5600 It.; West Navina, six wells with an average initial of 284 bbl. in the Lay ton sand at 5050 ft., Brooksville, eight wells in the Hunton at 4800 ft. with an average initial 01 355 bbl.; Macomb, one well with an initial of 160 bbl. in the IIunton at 4700 ft.; the Liberty pool, one well with an initial of 1268 bbl. in the second Wilcox at 4500 ft., and two wells in the Tonkawa sand at 2500 ft., with an average initial of 230 bbl. In the Northeast Lucien pool, four wells were completed in the Wilcox at 5380 ft. for an average initial of 1164 bbl., and one well was completed in the Viola lime at 5255 ft. for an initial of 55 barrels.

Jan 1, 1943

By Raymond D. Sloan

Retaining third place in crude-oil production among the nation's oil-producing states, Oklahoma's output in 1942 totaled 137,792,000 bbl., a decline of 9.4 per cent from the previous year's total of 152,117,000 bbl. Production declined from an average of 403,000 bbl. daily in January 1942 to an average of 355,000 bbl. during December, a reduction of 48,000 bbl. daily (11.9 per cent) during the year. At the end of 1942 it would appear inevitable that the downward trend in production will continue in 1953 unless halted in the immediate future by greater than normal discoveries and development. To Jan. I, 1943, Oklahoma has produced 5,067,013,000 bbl. oil crude oil. Development and Exploration Development dropped abruptly in 1942, reflecting the lack of any sizable discoveries and the effect of the provisions of Federal Well Spacing Order M-68, which became effective in December 1941. In all, 1210 wells were drilled in 1942. This represents a decrease of 42.7 per cent from the 1941 total of 2110. Of the total wells completed, 553 (45.7 per cent) were oil wells with an average initial production of 443 bbl.; 102 (8.4 per cent) were gas wells with an average initial of 3,359,000 cu. ft.; and 555 (45.9 per cent) were dry. Although the number of completions declined sharply, the total of 320 wildcats completed (26.4 per cent of all wells) repre-sents a decrease of only 2.7 per cent from the previous year's figure of 329. Of the wildcats drilled, 44 (13.8 per cent) were oil wells, 13 (4.0 per cent) were gas wells, and 263 (82.2 per cent) were recorded as failures. Reconditioning of wells throughout the state resulted in a total recompletion of 355 wells. Of these, 234 were oil wells with a combined initial production of 96,808 bbl., 32 were gas wells with a total initial of 381,488,000 cu. ft., and 89 were abandoned. None of the 26 pools found in 1942 has developed into a major discovery. The Pauls Valley pool, Garvin County, is the most outstanding. Since its discovery in April, 14 wells with an average initial of 1898 bbl. have produced 803,000 bbl. of 42' gravity oil from the Bromide zone. Development in this pool is believed to be almost completed. Other of the more important discoveries are the East Watchorn pool, Pawnee County; Guthrie Townsite and West Navina, Logan County; Brooksville and Macomb, Pottawatomie County, and the Liberty and Northeast Lucien discoveries in Noble county. The East Watchorn pool, at the close of the year, had 14 completed oil wells with an average initial of 989 bbl. from the Wilcox sand at 3930 it.; Guthrie Townsite, one well with an initial of 840 bbl. from dolomite at 5600 It.; West Navina, six wells with an average initial of 284 bbl. in the Lay ton sand at 5050 ft., Brooksville, eight wells in the Hunton at 4800 ft. with an average initial 01 355 bbl.; Macomb, one well with an initial of 160 bbl. in the IIunton at 4700 ft.; the Liberty pool, one well with an initial of 1268 bbl. in the second Wilcox at 4500 ft., and two wells in the Tonkawa sand at 2500 ft., with an average initial of 230 bbl. In the Northeast Lucien pool, four wells were completed in the Wilcox at 5380 ft. for an average initial of 1164 bbl., and one well was completed in the Viola lime at 5255 ft. for an initial of 55 barrels.

Jan 1, 1943

Admissions: Joseph C. Gordon, Chairman K. F. Anderson Allen B. Gibson H. J. Gruy R. F. Madera Dan H.-McLendon K. W. Robbins Aurel E. Smith W. F. West Advertising: John. D. Wisenbaker, Chairman Bernard F. Klein Henry N. Lyle R. E. Howard Clark R. Edgecomb, Jr. [ ]

Jan 1, 1961