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By W. R. McMillan, E. A. Gulbransen, K. F. Andrew

Annealed and electrolytically polished pure iron was oxidized between 650° and 850°C at oxygen pressures of 0.1 to 2 microns Hg. Electron optical studies showed that oxidation occurs discontinuously over the surface and orients crystallographically with the substructure of the metal grains. IN previous papers', " the authors described the formation of oxide films on high purity iron at norrnal pressures and at temperatures below 300°C. Electron optical studies showed that the oxide film consisted of many individual oxide crystallites having nearly random orientation on each metal grain. The size of the oxide crystallites depended upon the temperature and upon the extent of oxidation. In these studies the crystallite size varied from 250 to 1800Å. Recently, Bardolle and Benard3 studied the crystal habit of the oxide crystallites formed on Armco iron between 650" and 850°C in what might be defined as a "poor vacuum" atmosphere in which the pressure could be varied between 10-1 to 10-3 mm of Hg. Their results showed that, at 850°C and a vacuum of l0-2 to 10-3 mm of Hg, a few well oriented nuclei of oxide were formed on the metal grains. At pressures between l0-1 to 10-2 mm of Hg, many oriented nuclei of oxide were formed. At 750°C the metal surface was bright although an oxide was present. Unfortunately, the extent of oxidation, the oxygen pressure, and the influence of carbon in the metal were not determined, and it was, therefore, impossible to give a theoretical interpretation to the very beautiful light micrographs. Bardolle and Benard used the light microscope to determine the crystal habit of the oxide and X-ray diffraction to determine the orientation relationships. It was believed that the use of controlled amounts of oxidation at high temperature is an important method for the study of the initial stages of oxidation of metals at high temperatures. This paper presents the first results of an electron optical study of this problem for iron. Since the electron microscope and electron-diffraction methods using stripped oxide films and surface replicas yielded finer details of the crystal habit and structure of oxide film, these methods were used in this study. Two types of iron having different carbon contents were used: Puron and Armco* iron. A com- parison of the results for these materials made possible a study of the influence of the surface oxide-carbon reaction on the initial stages of oxidation. Before discussing the experimental results, the thermodynamic equilibria of 1—the oxidation reaction, 2—the surface oxide-carbon reaction, and 3—the solubility of oxygen in iron, will be considered. In addition, it is important to consider the kinetic-theory predictions on the rate of collision of oxygen with the iron surface. Thermodynamic and Kinetic-Theory Calculations Only one type of reaction is usually considered in the oxidation of iron at normal pressures at high temperatures: Fe(a) + 1/2O2(g) = FeO(s) 3Fe(a) + 2O2(g) = Fe3O4(s) 2Fe(a) +3/2O2(g) = a-Fe2O3(s). [11 However, two other reactions may occur: FeO(s) + C (solid solution in Fe) + Fe(a) + CO(g) [2] and Fe(a) + O2(g) e Fe(a) (solid solution of 0,). [ 3 ] In addition, iron will react with the higher oxide at certain temperatures to form FeO. For a complete interpretation of the oxidation of iron at low pres-

Jan 1, 1955

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

Discussion of the paper of L. O. HOWARD, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin No. 91, July, 1914, pp. 1785 to 1790. E. P. MATHEWSON, Anaconda, Mont.-I would like to add a few words of praise on Mr. Howard's work at the Old Dominion. Mr. Howard has given this particular converter shell his personal attention, and the results are shown in the figures given. Similar converter shells, a little different in shape and of about the same size, have been tried in many plants throughout the United States. The results have been highly satisfactory, but there is no shell of the size of the one described by Mr. Howard that has given anything like the results that Mr. Howard's shell has given. I know of larger shells that have given very good service, and are still in operation, and require very little repair. The main thing about the whole process of using the basic lining in copper converting is to keep the temperature within reasonable bounds, particularly not to get the furnace too hot. If it is overheated a little bit, for say half an hour, an entire lining may be ruined. It is very easy to keep the temperature regulated 'if the mass is large. If you have a large mass in your converter you can easily prevent it from getting over-heated, and that is the big argument in favor of the extra large converters. Of course, there is a limit to what a plant can turn out in the way of matte. Very few plants can supply matte sufficient to keep a converter of 20 ft. in diameter in operation constantly, but the 20-ft. converter is very much superior to the 12-ft. converter in easy handling and absolute control of the temperature. I think Mr. Howard is to be congratulated on the excellent showing he has made.

Jan 12, 1914

By R. S. Dean

ALTHOUGH it is obvious that in any flotation process we must have a froth, in recent years the development of collecting reagents has caused the possibilities of better frothing agents to be overlooked. Some investigators have even gone so far as to say that the number of satis-factory frothing agents was sufficient. A little consideration will show, however, that the reagents available in the past were far from ideal frothers. The properties of an ideal frother for flotation work may be set down as follows: 1. It. must form in low concentrations a copious but not too persist-ent froth. 2. It must be insensitive to hydrogen-ion concentration of the pulp; that is, it must froth equally well in an acid or alkaline medium. 3. It must be insensitive to salts, even in high concentration. 4. It must be absolutely noncollecting to both sulfides and nonsulfides. 5. Its frothing properties must not be affected by collecting reagents, including soap, the most generally used nonsulfide collector. 6. It must readily emulsify and disperse any insoluble collecting agent that is likely to be used. Clearly the existing frothers do not qualify. Pine oil, for example, is an acceptable frother for many purposes but if used in soap flotation a delicate balance between pine oil and soap must be struck because, as pointed out by Coghill1, these two reagents are incompatible in certain concentrations. The objections to soap itself as a frother are obvious, and the cresols and their substitution products all have some collecting Dower and very little emulsifying power.

Jan 1, 1935

By Willard L. Cumings, Benjamin L. Miller

The Camaguey brown iron-ore deposit covers the top of Sari Felipe hill, the nearest point of which lies 14 miles NW. of the city of Camaguey. While there are several low flat-topped hills in the vicinity covered with a more or less continuous mantle of brown iron-ore, the deposit of San Felipe hill is the only one of any size and importance, and the name " San Belipe district" is proposed for the region. The deposit extends in a NW-SE. direction for a distance of about 10 miles, with an average width of 5 miles. The location is shown in Fig. 1, a sketch-map of the eastern part of Cuba. Fig. 2 is a map of the San Felipe district. 2. Description. The district is mentioned by Spencer,' who says: " The Cubitas iron-ore fields are situated from 12 to 15 miles north of Camagueg City, in the province of Camagueg.....Within an area measuring roughly 10 miles east and west and 4 miles north and south, there are several flat-topped mesas rising 300 to 400 ft. above the level of an almost featureless plain which extends for many miles in all directions except toward the north." With the exception of the discrepancy in his statements .as to the distance from Camaguey and the area of the hill, which is over 50 sq. miles, his description is a very good one. Kemp2 has the following to say of ores in Camaguey Province:

Jan 1, 1912

By R. B. Adair, J. S. Browning

The laboratory batch and continuous flotation pilot plant tests demonstrated the technical feasibility of recovering high grade mica concentrates from weathered mica pegmatite ores of Alabama and Georgia. The research indicated that combinations of anionic and cationic collectors may be used effectively for flotation of fine size mica from weathered pegmatite ores. In continuous tests, concentrates containing 98.5% mica were obtained from the Georgia pegmatite ore; the Alabama pegmatite ore concentrates contained 98.4% mica. The recoveries were 91 and 89% respectively. INTRODUCTION The principal uses of fine ground mica are as a filler in wallboard joint cement, as a filler and surface coating for roofing, as an ingredient in paints, and in oil well drilling mud. The mineral has other uses in the manufacture of rubber, wallpaper, plastics, welding rods, electric insulation, house insulation, and textiles, and as an annealing agent in metal treatment. In recent years, more than 99% of the domestic mica produced has been scrap and flake mica (mica which does not meet specifications for sheet mica and is used for producing fine ground mica). There has been a continued increase in mica production for several years, the 1963 production of scrap and flake mica totaling 117,251 tons.1 Ground mica is obtained primarily by crushing and milling pegmatites and schists. To a lesser extent, mica is produced as a byproduct of kaolin washing and feldspar and spodumene flotation operations. The processes used in recovering mica by crushing and milling pegmatites are generally simple, consisting of various combinations of alternate roll crushers and trommel screens that separate the mica and gangue at screen sizes coarser than 6-mesh. As these processes are designed to recover only coarse mica, high losses in the plant rejects are common. Large tonnages of tailings from the crushing and screening plants have been accumulated in a number of areas. Methods for treating such products were developed by the Bureau of Mines in 1941,2 but have not been generally applied. More recently, mica flotation research has been completed and published by the Bureau of Mines.3 These methods required complete removal of 150- to 200-mesh materials from the flotation feed with consequent fine mica losses. Later, the Bureau of. Mines investigated methods for-recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials, but not so drastically as to remove the fine sands. This report summarizes the results of these studies. The process developed was effective on pegmatite ores from two locations and should be applicable to the commercial treatment of other mica-bearing pegmatite ores and fine rejects that have been accumulated at various mica-milling operations. DESCRIPTION OF ORES The ores used in the investigation were obtained from the Dixie Mines, Inc., Heflin, Alabama, and the Ruberoid Corporation, Hartwell, Georgia. The sample from Alabama contained muscovite and quartz, with a high percentage of clay, and minor amounts of biotite, kaolin, limonite and tourmaline. The mica in the ore was essentially all minus 4-mesh in size and was free of attached mineral grains. The Georgia sample contained muscovite and quartz, with minor amounts of biotite, kaolin, and limonite. The mica in the ore, which was essentially all minus 4-mesh, was liberated. Petrographic analyses of the two samples are given in Table I. THE ANIONIC-CATIONIC MICA FLOTATION METHOD Previous investigators2,3 have reported that complete desliming of mica ores at 150- to 200-mesh was required prior to flotation with cationic collectors to obtain satisfactory selective separation of the mica from the other mineral components. Numerous tests were made at the Tuscaloosa Metallurgy Research Center to determine if some reagent combination could be used to selectively float finer size mica without complete desliming. The investigation led to development of a process using a simple reagent com-

Jan 1, 1967

By N. Brown, M. Herman

IT has been pointed out by Cottrell' and Fisher that long-range order would produce superdis-locations, consisting of two partial dislocations separated by an out-of-phase region. The mutual repulsion of the partial dislocations is balanced by the surface tension of the out-of-phase domain boundary joining the dislocations (Fig. 1). The calculation of the equilibrium spacing of the dislocations has yet to be made. The argument uses the Bragg and Williams theory of long-range order." The metal under consideration is the A-B, body-centered type, such as ß brass. The slip system is taken to be [Ill], (110). Since nearest-neighbor interactions are considered, only the atoms position in the two (110) planes adjoining the slip plane have to be labeled. Corner sites are called a and a' in the top and bottom (110) planes, respectively. Similarly ß and ß are the body-centered sites. Thus, a and ß and 0 and a sites are nearest neighbors. Assume that the bottom plane moves and the top plane is fixed during slip; the atoms in a and ß sites exchange sites but atoms in a and ß sites remain fixed. Fraction of A atoms in a sites, for example, is given by fa and fa. for the un-slipped and slipped condition, respectively. Similarly number of A atoms in the a sites is given by n, and n'a for the unslipped and slipped condition, respectively. As the dislocation moves into the ordered region the change in number of A-A bonds is given by

Jan 1, 1957

By F. S. McNicholas, M. S. Walker, V. C. Rogers

During the year of 1944 and the first half of 1945, the Climax Molybdenum Co. made a study of some of the problems in block and panel caving, with the use of a scale model. The experiments dealt essentially with the type of rock and conditions at Climax, but some experiments were carried out to simulate conditions found in other mines. Most of the previous experiments on the caving characteristics of rock have dealt with sedimentary or broken igneous material. The series of experiments described here was designed to show the caving action of unbroken igneous rock. Con- siderable difficulty was experienced in duplicating unbroken material in the model. The results obtained are believed to be relatively correct, but verification must necessarily come from future mine operation. Observations in the mine and glory hole, together with statistical data, were used as criteria for creating similar conditions in the model. In 1913, George R. Lehman' experimented with broken material in a model for the Inspiration Consolidated Copper Co. and, more recently, P. B. Bucky2 experimented with broken material with a capping of mill tailings. Mr. Lehman's model represented a maximum ore height of 70 ft. capped by 55 ft. of waste. He varied the draw-hole spacing from 6¼ ft. to 8? ft. and 12½ ft. The material used graduated from fines to 30-in. maximum size. Some of his conclusions were: "(I) The less the distance between chute centers, the greater the extraction (Fig. I); (2) the higher the ore column, the greater the extraction; (3) the less the amount drawn at a time from each chute, uniformly, the greater the extraction of clean ore before the capping appeared, but not the greater the total extraction to a I per cent copper final product." (Fig. 2.) Professor Bucky concluded, in part: "(I) Drawing of ore may take place at any time from any finger and in any amount without affecting materially: (a)

Jan 1, 1946

By John Tyssowski

IN 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temper-atures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several parti-cles had become one unit. From this dis-covery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the appli-cation of about 30c0 tons pressure on a 10-in. piston. Stout decided that cathode copper pro-duced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H, Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable form, and to them must be given the greater part of the credit for this phase of the development program as well as for that relating to the gas cleaning of the cathode particles.

Jan 1, 1940

By Walter McDermott

This machine is an improvement on the well-known endless travelling belt used for dressing slimes in many mills; the chief point of difference, and constituting the essential advantage of the present over the old form, is the application to the machine of a secondary agitating or shaking motion, in addition to the ordinary progressive motion of- the belt. In the machine as heretofore made, the inclined belt or apron moved slowly up against a thin stream of water and ore, depositing the concentrations carried over in a tank placed below, through which the belt travelled, of course, in a reversed position. By reference to the accompanying drawings, it will be seen that in this main principle the new modification does not differ materially; but the means by which it is carried out are essentially different. The machine consists of a substantial frame of mood, F, Figs. 41, 42, and 43, within which hang the shaking frame and rollers, B B, A, Endless apron ; B, Apron frame and rollers ; C, Driving drum ; D, pulleys; B, Shaft and connecting rods; F, Wooden frame; G, Shaft of regulating Pulley; H, Yokes. supporting the upper half of the travelling apron, A, which passes below around the driving drum, C, in the water-tank, J. On leaving the water-tank, the belt passes over the guiding and tightener pulley, G. The ends of the shaking-frame, B, are provided with iron yokes, H H, bored to admit the shafts of the end rollers, and carrying a lug, by which attachment is made to the connecting rods,

By R. W. Raymond

(Pittsburg Meeting, March,1910.) THE Giroux Consolidated Mines Co. is equipping a five-compartment shaft at Kimberly, Nev., which will serve the Alpha mice. The depth of this shaft, January, 1910, is 963 ft., and of this depth 948 ft. was opened by raising, 15 ft. of sinking was done so that the bearers, collar-set, and three shaft-sets might be installed and concreted, and with this done it was possible to erect the necessary surface-equipment for resuming shaft-timbering on the completion of the raise. The arrangement of the shaft-timbering is shown in Fig. 1. At the 1,000-ft. level of the Alpha, and 750 ft. SW. from the Alpha shaft, a 14- by 18-ft. station was cut, and a 25-h-p. air-hoist *as installed. From here the raising commenced on July 5, 1909. The raise was cut approximately 13 by 21. ft. in area, and supported by timbering with square sets, illustrated in Fig. 2, which shows the division into four compartments. The end compartments, which were used as chutes, had the center girts heavier than in the others on account of the wear from falling rock. The chute-lining was braced by inserting 8- by 8-in. stiffeners parallel to and half way between successive caps. Similarly, the lagging on the wall sides of the cage-way and the compartment for pipes and ladder was stiffened with 4- by 6-in. timbers. In the pipe-and-ladder compartment the chute-stiffeners were reinforced with 8- by 8-in, struts, and as the cage-way was partitioned off by braced lining, there was practically no chance of rock entering the ladder-way in case a chute burst into the cage-way. Over the two center compartments the last two, sets were always bulkheaded with 8- by 12-in. timbers, shown in Fig. 3, and from the lower bulkhead the cage sheave-wheel was suspended. After a round of holes had been blasted and the loose

Jun 1, 1910

By B. M. Loring, I. R. Krame, F. M. Walters

NO observations on the mechanical properties of man-manganese alloys have been published since pure manganese became readily available, either distilled manganese or electrolytic manganese. The purpose of this investigation was to determine whether iron-manganese alloys are essentially brittle, as reported by Hadfield,' or whether the lack of ductility observed was due to impurities in the alloys that he studied. Experimental Methods The alloys were melted in a roo-lb. high-frequency induction furnace with a magnesia crucible, using ingot iron and electrolytic manganese. The heats were split, the first giving six 18-lb, ingots and the second three. Each successive heat was higher in manganese and about 0.3 per cent silicon was added as ferrosilicon. The alloys forged without difficulty and were given a 9' per Published by permission of the Navy Department. Manuscript received at the office of the Institute June 28. 1941. Issued as T.P. 1369 in Metals Technology. September 1941. * Division of Physical Metallfirgy Naval Roscarch Laboratory. Anacostia Station Washington. D. C. 1 References are at the end of the paper. 4 cent reduction to ¾-in. rounds. The chemical analysis of the alloys is given in Table I. The forged rods were homogenized for 224 hr. at r150°C. (2100°F.) and air-cooled. The alloys were tested in two conditions of heat-treatment: (I) as normalized from 870°C. (1600°F.) and (2) normalized from 870°C. and tempered for I hr. at 540°C. (Iooo°F.) and air-cooled. The tensils specimens were 0.505 in. in diameter with a 2-in. gauge length, and the impact specimens were v-notch Charpy. The proportional limit and yield strength were taken from the stress-strain diagrams drawn by a Peters recorder. The data obtained from the tensile test and the hardness measurements are given in Table 2. Specimens that were normalized are designated by N; those that were normalized and tempered by T. Alloy G was tempered after forging (D).

Jan 1, 1942

By B. M. Loring, I. R. Krame, F. M. Walters

NO observations on the mechanical properties of man-manganese alloys have been published since pure manganese became readily available, either distilled manganese or electrolytic manganese. The purpose of this investigation was to determine whether iron-manganese alloys are essentially brittle, as reported by Hadfield,' or whether the lack of ductility observed was due to impurities in the alloys that he studied. Experimental Methods The alloys were melted in a roo-lb. high-frequency induction furnace with a magnesia crucible, using ingot iron and electrolytic manganese. The heats were split, the first giving six 18-lb, ingots and the second three. Each successive heat was higher in manganese and about 0.3 per cent silicon was added as ferrosilicon. The alloys forged without difficulty and were given a 9' per Published by permission of the Navy Department. Manuscript received at the office of the Institute June 28. 1941. Issued as T.P. 1369 in Metals Technology. September 1941. * Division of Physical Metallfirgy Naval Roscarch Laboratory. Anacostia Station Washington. D. C. 1 References are at the end of the paper. 4 cent reduction to ¾-in. rounds. The chemical analysis of the alloys is given in Table I. The forged rods were homogenized for 224 hr. at r150°C. (2100°F.) and air-cooled. The alloys were tested in two conditions of heat-treatment: (I) as normalized from 870°C. (1600°F.) and (2) normalized from 870°C. and tempered for I hr. at 540°C. (Iooo°F.) and air-cooled. The tensils specimens were 0.505 in. in diameter with a 2-in. gauge length, and the impact specimens were v-notch Charpy. The proportional limit and yield strength were taken from the stress-strain diagrams drawn by a Peters recorder. The data obtained from the tensile test and the hardness measurements are given in Table 2. Specimens that were normalized are designated by N; those that were normalized and tempered by T. Alloy G was tempered after forging (D).

Jan 1, 1942

By C. Everard Arnold

The Giroux Consolidated Mines Co. is equipping a five-compartment shaft at Kimberly, Nev., which will serve the Alpha mine. The depth of this shaft, January, 1910, is 963 ft., and of this depth 948 ft. was opened by raising; 15 ft. of sinking was done so that the bearers, collar-set, and three shaftrsets might be installed and concreted, and with this done it mas possible to erect the necessary surface-equipment for resuming shaft-timbering on the completion of the raise. The arrangement of the shaft-timbering is shown in Fig. 1. At the 1,000-ft. level of the Alpha, and 750 f't. SW. from the Alpha shaft, a 14- by 18-ft. station was cut, and a 25-h-p. airhoist was installed. From here the raising commenced on July 5, 1909. The raise was cut approximately 13 by 21 ft. in area, and supported by timbering with square sets, illustrated in Fig. 2, which shows the division into four compartments. The end compartments, which were used as chutes, had the center girts heavier than in the others on account of the wear from falling rock. The chute-lining was braced by inserting 8- by 8-in. stiffeners parallel to and half way between successive caps. Similarly, the lagging on the wall sides of the cage-way and the compartment for pipes and ladder was stiffened with 4- by 6-in. timbers. In the pipe-and-ladder compartment the chute-stiffeners were reinforced with 8-by 8-in. struts, and as the cage-way was partitioned off by braced lining, there was practically no chance of rock entering the ladder-way in case a chute burst into the cage-way. Over the two center compartments the last two sets were always bulkheaded with 8- by 12-in. timbers, shown in Fig. 3, and from the lower bulkhead the cage sheave-wheel was suspended. After a round of holes had been blasted and the loose

Jan 1, 1911

By R. G. Jones, W. L. Kinney, R. E. Schilson, R. S. Wilson, G. A. Clark, H. Suralo

This paper discusses the results of the Fry conventional or cocurrent in situ combustion test, which was conduct-ed in a 3.3-acre inverted five-spot. The depth of the formation was between 880 and 936 ft; the oil had a specific gravity of 28.6° APl and a viscosity of about 40 cp at the reservoir temperature of 65°F. Preceding the combustion test, air injection tests were conducted which, in conjunction with geological studies, were used to evaluate the characteristics of the reservoir. Combustion was initiated on Oct. 13, 1961, with ignition being accomplished by a 40 kw electrical heater. The test phase of the project ended on Oct. 1, 1963. During the test, the average air injection rate was 1,520.-000 scf/D. Throughout the test, production of all fluids— gas, oil, and water—was monitored. Cumulative oil production credited to the project was 100,586 bbl. The cumulative air-oil ratio was 11,500 scf/bbl oil, and the oxygen uti1ization efficiency was 87 per cent. INTRODUCTION The Marathon Oil Co. conducted a successful in situ combustion test, beginning Aug. 22, 1961, at the Fry unit, Crawford County, 111. The purpose of the project was to test the feasibility of cocurrent in situ combustion as a means of oil recovery in the Fry type reservoir. Interest in in situ combulstion as an oil recovery tool has been stimulated mostly by the existence of large reserves of heavy viscous crudes with low expected recovery, usually less than 10 per cent. These are the so-called unrecoverable reserves, and most combustion tests to date have been conducted in this type of reservoir.1-4 In contrast, the Fry combustion test was conducted in a reservoir with a relatively high gravity oil having a relatively low viscosity. This paper discusses the performance of the test. The geology of the reservoir and the field operations are discussed in separate papers.5 TEST SITE The Fry combustion test was carried out in a 3.3-acre inverted five-spot portion of a lenticular body of Robinson sandstone. Net sand was 50 ft thick, porosity averaged 19.7 per cent, oil saturation was 68 per cent of pore volume, and water saturation was 20 per cent of pore volume. The oil in place was estimated at 1,040 bbl/acre-foot, or 171,600 bbl within the 3.3-acre pattern. The water in place was 326 bbl/acre-foot, or 53,800 bbl. The oil has a specific gravity of 28.7° API and a viscosity of 40 cp at the reservoir temperature of 65°F. AIR INJECTION PERFORMANCE Air injection took place in two phases, the phases separated by ignition of the reservoir. In the pre-ignition phase, air injection tests were conducted in the summers of 1960 and 1961. These indicated that the Fry reservoir was confined, and a high return rate of injected air could be expected. This proved to be an outstanding characteristic of the project, as cumulative gas production was 95.3 per cent of the air injected. The difference between the cumulative air injected and the total gas produced can be largely accounted for by the quantity of air stored in the reservoir. An estimated 16 X 10 cf of air remained in the burned-out portion of the reservoir and an indeterminate amount of gas was stored in the unburned but pressurized reservoir. Hence, a complete material balance of gases would account for nearly 100 per cent of the air injected. At times during the test, the daily gas production rate was 98 per cent of the daily air injection rate. Fig. 1 presents the air injection history of the Fry com-

Jan 1, 1966

By Marcel R. Daly

In a preceding paper1 the writer has pointed out some apparent relationship between the distribution, on the surface of the globe,, of the known hydrocarbon deposits and the disposition of the principal zones of deformation of the earth's body (geosynclines). He wishes to present some further remarks on this subject. Petroleum deposits, or their derivatives or descendants, are found through the whole range of sedimentary strata, from the pre-Cambrian to the Quaternary. For instance, the prc-Beltian (Shuswap) series of the Canadian Cordillera are interbedded with limestones which are sometimes rich in carbonaceous matter (Sicamous limcstone); and the Beltian system of the same region contains layers of argillitcs and dolomitic limestones which are equally high in carbon content.2 This carbon may be interpreted as the last remnant of hydrocarbons previously contained in the rocks. On the other hand, the actual formation of hydrocarbons under conditions that would eventually permit their deposition in modern sediments is conceded by some geologists.3 Between these two extreme limits, bitumens are found indifferently in all sedimentaries. Thcy constitute a continuous series, some kind of a large family, whose individual members may be entitled to a community of origin and probably represent the different stages of evolution of the primitive, parent matter. The kinship between petroleum and such substances as asphalt, ozocerite, manjak, grahamite, albertite, etc., is well known; and E. H. Cunning-gam-Craig has recently shown how intimately shale fields and oil fields are connectcd.4 For this reason, no distinction is made in the present

Jan 1, 1918

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

By R. W. Raymond

At the Pittsburg meeting of the Institute, in March, 1910, the death of Mr. Metcalf was announced, and Col. H. P. Bope, of Pittsburg, delivered in memory of him a brief but eloquent address, which, though expressing the Norrow of Mr. Metcalf's friends, and, in general terms, the debt of gratitude which his country and his profession owed to him, was not intended to be a complete survey of his life and work. With Colonel Rope's permission, and with the aid of some of the statements in his address, I substitute for it, in our Transactions, this more cletailed, yet still inadequate memorial. As Colonel Rope justly remarked, the men who could do justice to this theme—such men as Jones, Chalfant, Bennett, Oliver, and Park—passed away before Metcalf, leaving him almost the last of the generation of great steel-makers who made Pittsburg the Sheffield of America, and who discharged a double function, as the rearguard of the old metallurgical practice and the ran-guard of the new. I knew many of them; would that I were better qualified to celebrate their achievements. William Metcalf was born Sept. 3, 1838, at Pittsburg, Pa., where his father, Orlando Metcalf, was an eminent member of the bar. At the age of sixteen, he entered the Rensselaer Polytechnic Institute, at Troy, N. Y., from which he was graduated in June, 1858: Returning to his native city, he became an assistant engineer in the Fort Pitt Foundry, of which he was made Superintendent in 1859. This famous establishment produced the largest castings and heaviest machinery then knolrn in the United States; and Mr. Metcalf's intense, intelligent and incessant study of his business prepared him as a manufacturer for a patriotic service to his country more valuable than, as a soldier, he could have rendered in the field. The call came in 1862, when the government needed, above all things, a supply of field, naval and siege artillery. The

Jan 1, 1911

By Edward Steidle

THAT veterans are crowding the colleges is no longer news; 78 per cent of the 1916-47 enrollment in mineral industries curricula in the United States were veterans, but the rapid comeback from an estimated 1262 total mineral industries students in 1944-45 to 11,422 in 1946-47 is almost astonishing. The figure, which includes 1008 graduate students, is a substantial increase over the previous top record of 9619 in 1938-39. A small part of the increase is caused by the larger number of women entering the field, of whom there were c 9 in 1916-47. Petroleum leads the curricula with 34.5 % of the enrollment, metallurgy is second with 28%, and mining is third with 18%. Table 1. shows all curricula offered and those accredited by ECPD. Using the Mississippi River as a dividing line, 31 colleges in the East and 27 in the West offer curricula in the mineral industries.

Jan 1, 1948