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By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly i00 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi¬tion is accompanied by a change in volume of as much as S per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potters have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to g0 per cent Mn. is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to ½ in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By E. E. McGinley, L. D. Woodworth

DURING the past several years has occurred what, in the light of future events, may aptly be called the rebirth of the acid Bessemer process. The increased attention given to the technical and metallurgical details involved in the production of Bessemer steels has been exceedingly fruitful, and indicates the value of further research and plant development. In times like these, when the steelmaking capacity of the country is operating at a maximum rate to supply materials for the national defense program, it behooves the Bessemer operator not only to strive to increase production but also to maintain a high standard of quality. The opportunity is ripe, it seems, to recapture fields of application once considered the birthright of Bessemer steels, but supplanted in recent years by open-hearth grades. This involves cooperation all along the line, from the blast-furnace operator to the metallurgical contact man and salesman. The metallurgist's part in this program involves the study of the many steelmaking variables and the measures necessary to ensure constancy in the finished product. It is equally important that the knowledge gained be disseminated widely to ensure the wise application of Bessemer steels in new fields. The merits of Bessemer steels for certain work are well understood. The combined properties of good weldability, machinability and stiffness are unique and fully explain the strong entrenchment of Bessemer steels in certain fields; e.g., skelp for small butt-weld conduit, screw steels machined in automatics, and certain tinplate applications. It is the purpose of this paper to review briefly the physical properties of Bessemer steels as contrasted with those of open-hearth steels, to discuss control measures now employed in the making of Bessemer steel, and to consider the advantages derived from the use of these control measures. PHYSICAL PROPERTIES OF BESSEMER VS. OPEN-HEARTH STEELS A number of Bessemer blows and open-hearth heats were tested for tensile strength, ductility and impact strength. The steels selected were confined to sections from ¾ to 1 ¼ -in. diameter, inclusive, and the carbon content covered was sufficient to yield parallel ranges in ultimate strength for the comparison. Other factors, such as the extent of deoxidation of the steel and variations in chemistry, were kept as comparable as possible. Machined test pieces of 0.505-in. diameter with an 8-in. gauge length were pulled. The data obtained are shown in Fig. 1, ultimate strength being plotted against carbon content. This graph shows that for equivalent carbon content Bessemer steel has on the average 15,000 lb. per sq. in. greater tensile strength and, conversely, for the same tensile strength Bessemer steel requires on the average 0.14 per cent less carbon. The average phosphorus content for the Bessemer steel was 0.090 per cent,

Jan 1, 1941

By E. R. Atkins, G. H. Smith

Results of laboratory tests are presented to show that lire value of "m", in the Archie expression dernlined by the shapes of the particles in the system. Tile value of m "the shape factor", is constant for a system of particles of a given shape for a range of F - + values. Applying this concept, one can predict F - + relationships for mixtures of particles with different shapes, and these predicted relationships are useful in electric log interpretation. It is suggested that an equation of the form 1/F -10mcan be used to describe the properties of natural formations containing varying amounts of sand and clay. From this work and values of "a" and "m" reported in the literature, it appears that in many cases rocks in the same geological horizon have a common primary porosity but contain varying amounts of a particular clay. It is concluded that the equation can be applied to a rock-water system only when values of "a" and "m" have been established for the particular system. INTRODUCTION The petroleum literature contains many reports of the results obtained by determining formation resistivity factor F and porosity + of rock samples from oil fields all over the world. The usual practice is to use data from a large number of samples from a number of fields to find an average relationship between F and +. Several such average relationships have been advanced. In the absence of data on a particular formation or field, it has been the practice to use the average relationships to give a rough approximation of the F - + relationship. The purpose of this paper is to report on basic relationships that exist between F and + for naturally occurring particles in water solutions. Other workers' have found the same relationships apply to the diffusion of hydrogen through packed beds of dry particles. In the work discussed here, relationships for application to unconsolidated sands or shales containing mix- tures of particle shapes are derived. These relationships, developed for unconsolidated formations, may apply to consolidated formations. EXPERIMENTAL To evaluate F- relationships for unconsolidated rocks, the results of laboratory measurements on simple slurries of clay or sand will be used. Such laboratory studies are concerned with the electrical behavior of water-containing rocks. The wet rock constituents are electrically similar in slurries and in rocks. Archie2 defined formation resistivity factor as All resistance measurements were made using a 1,000-cycle impedance bridge with an oscilloscope as the null detector." The accuracy of this bridge was better than * 0.15 per cent. For the particular apparatus employed, no additional reactance was required to achieve balance for samples with resistances between

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufliciently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion .4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. "I hey believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They (lid not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (1) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led hint to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed (luring the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (AS208)

Jan 1, 1942

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly 100 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposition is accompanied by a change in volume of as much as 5 per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson' found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter5 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to 90 per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced 90 per cent when forged to ½ -in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By Richard Hodgson

FMC Corporation, at their mine and soda ash refinery near Green River, Wyoming, currently mines in excess of 3 million tons per year of trona. Upon completion of the current expansion, the mine will be producing in excess of 4.0 million tons per year. The single level mine, approximately 1,500 feet in depth, is currently serviced by five (5) concrete lined circular shafts varying in diameter from 12 ft. to 24 ft. A sixth shaft is complete, but not yet operational and the seventh is currently being sunk. Two of the shafts are equipped with single drum hoists. The original production shaft is equipped with a double drum hoist. The newest production shaft and the main service shaft are both equipped with ground mounted friction hoists. These friction hoists have given excellent service and another will soon be installed as a man and material hoist at No. 7 Shaft. There are a number of advantages that the ground mounted hoist has over a tower mounted hoist. There are also operating problems common to both. FMC's original experience with ground mounted friction hoists began in 1962 with the conversion of a single drum hoist to a friction hoist. The converted hoist was an Ottumwa with a 5 ft. diameter drum and a 4 ft. face. This hoist had been installed at the No. 3 Shaft for some years prior to its conversion to a friction hoist. At the time the conversion of this hoist was made, there were no friction hoists in service in Wyoming. Wyoming mining laws required that all conveyances carrying men be equipped with safety dogs. Since it was desired that wire rope guides be used, safety dogs were impractical. Agreement was reached with the State Mine Inspectors that safety dogs would not be necessary provided that recommended rope safety factors for hoisting men would still be maintained if one hoisting rope was broken. Since-the shaft is approximately 1,500 ft. deep, the recommended safety factor is 6.0 so that this installation has a safety factor in excess of 8.0 for hoisting men when new ropes have been installed. The hoist conversion was engineered by Lake Shore, Incorporated. The friction ring was made in halves and bolted over the original drum face which had been machined to remove the grooves. The ring provided for four 3/4 in. diameter ropes on 8 inch center to center spacing. The pitch diameter of the modified drum was 72 inches. The grove liners are hald in place by hard-wood wedges bolted to the drum. The other modification required by the conversion was an increase in size of bearing caps and the hold-down bolts because of the increased force tending to lift the drum.

Jan 1, 1975

By Jules E. Jenkins

IN the past quarter century the seismograph has played an increasingly important role in evaluating vibratory effects transmitted to adjacent communities by industrial blasting operations. In this period research has advanced through two major phases—from falling pin seismometers to three-component recording seismographs. The initial phase of this research is now regarded as the era of recording, during which the seismograph merely recorded occasional events. It has emerged from this stage into the era of control and analysis and in this later period has been recognized as a full-fledged industrial tool. Although the falling pin machines of earlier years indicated probable amplitudes of industrial blasting vibrations, they gave no reliable measure of such displacements, nor did they provide essential information concerning direction or frequency of motion. The first contribution of the three-component recording seismograph was the weight-for-distance formula developed by the U. S. Bureau of Mines. This empirical formula enabled users of commercial explosives to determine beforehand the probable vibratory effects of a blast when the weight of the explosives charge and the distance from the shot point were known. This formula has withstood the test of time and is still applicable for blasts detonated by instantaneous methods. The second major contribution of the three-component recording seismograph followed the introduction in 1945 of short period or millisecond delay detonation. This might be described as a two-stage contribution, the first of which revealed a 50 pct reduction in the vibration magnitude when millisecond detonation was used rather than instantaneous discharge. This second part of this double contribution led to the discovery of the vibration dip phenomena, see Fig. 1. In Fig. 1 the horizontal coordinates indicate the displacements amplitude in inches, and the vertical coordinates, the explosive weight in pounds. The top curve is that of the U. S. Bureau of Mines for instantaneous detonation. Its curvature conforms to the two-thirds power of the explosive weight as provided in the weight-for-distance formula; hence the vibratory effects increase in proportion to an increase in the explosive charge. If the other curves shown below are temporarily disregarded, it may be considered that the entire area below this top curve represents both useful and waste energy. As mentioned previously, when millisecond delay detonation was first investigated it was found that in general the U. S. Bureau of Mines curve could be decreased by about 50 pct, or to the position of the middle curve. At the outset it was assumed that this curve would likewise increase in some proportion to the explosive charge, as did the top curve, that is, the curve would indicate a continuous upswing. As seismographic data accumulated this assumption was found to be erroneous in part. It was discovered that

Jan 1, 1957

By John P. Bryant

Plant nutrients are obtained by plants from both the air and the soil. Carbon dioxide, a gaseous form of carbon and oxygen, supplies the carbon which usually makes up 50% or more of plant structure. Plants are capable of absorbing carbon dioxide directly from the air. Most of this nutrient comes from the air, although some carbon dioxide is absorbed by soil water and taken into the plant as liquid. Growing plants use more water than any other substance. Plant nutrients in the soil dissolve in soil water; soil water entering the plant carries nutrients into the plant structure. Water is then given off into the air as the plant breathes or transpires. The inorganic or mineral portion of the nutrients which plants require comes from the soil. Inorganic or mineral composition of plants is usually less than 5% of their weight, and this mineral requirement, usually lacking in the soil, must be provided by fertilizers. Proper fertilization of a soil to improve its mineral level and productivity is the basis for the fertilizer industry (Thomas, 1960). There are 13 essential plant nutrients which often must be added to soils or plants and are generally considered as fertilizer minerals. These nutrients are divided into the categories: primary minerals (nitrogen, phosphorus, potassium); secondary minerals (calcium, magnesium, sulfur); and micro or trace minerals (boron, iron, manganese, copper, zinc, molybdenum, chlorine). Further, cobalt is often added to fertilizers. Although it is not considered to be an essential plant nutrient, it is essential to animal health and is often applied to forages as a fertilizer constituent. One point of major significance to the fertilizer industry is that not all nutrient carriers supply that nutrient in a chemical form which will be available to the plant. Thus, a product which may be considered a fertilizer mineral may require substantial processing or treatment before it becomes useful as a nutrient carrier. Fertilizer Industry Scope Until about 1900 demands for higher crop yields were met simply by bringing new agricultural lands into cultivation. Since that time great progress has been made in increasing yields through fertilization and improved varieties and cultural practices. The importance of the fertilizer industry to the economy and welfare of the U.S. is widely recognized. [Fig. 1] illustrates the relationship of lime and fertilizers to crop yields. In terms of tons of fertilizer products, the growth of the industry has been phenomenal, particularly between 1950 and 1970. Table 1 shows the increase in fertilizer usage. Primary Plant Nutrients in Fertilizers Primary minerals (nitrogen, phosphorus, potassium) are designated as such because of their significance to plant growth. Practically all soils are deficient in both nitrogen and phosphorus, and most of them are also deficient in potassium. Consequently, these nutrients

Jan 1, 1975

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By J. F. Wolff, Anson A. Betts

The following correspondence relating to a paper bearing the above title, presented by J. F. Wolff, at the New York meeting in February, 1917, and published in the Transactions, Volume LVI, page 142, has passed between the author of the paper, and Mr. Anson G. Betts, and is interesting, although it was received much too late for incorporation in its proper place in Volume LVI. Anson G. Betts, Asheville, N. C.—1. I should like to ask Mr. Wolff if he finds from analysis of the iron formation and of the iron ore, and from the relative amounts of each in each unit area of the formation, unleached and after leaching, that the iron remains entirely insoluble and the total quantity still remains present; or whether he finds that some of the iron is removed, or possibly even added by deposition from the water passing through the formation. 2. The water that passed into the iron formation had to go somewhere; was it absorbed by underlying formations through hydration, or, after passing through the ore formation, did it come to the surface in springs at a lower elevation, or how did it escape from the ground? 3. I should like to ask Mr. Wolff whether he finds that the iron formation in the sedimentary series does not come next to the quartzites and generally between the quartzites and slates. J. I?. Wolff, Duluth, Minn.—1. In common with others, you appear to have some hesitancy in accepting the fact of the removal, by solution, of the enormous quantity of silica which has been leached out of portions of the Biwabik iron formation, thus forming orebodies of merchantable iron ore. I believe that even Dr. Waldemar Lindgren once hesitated to accept this fact. However, the evidence is so simple and absolutely conclusive that the fact is established beyond all question. At the contact of orebodies with their rock walls, the bands of iron ore in the orebody can be seen in contact with the corresponding bands of original iron oxide in the rock wall, and the chert layers in the rock wall can be seen to give place to fine granular material (fine silica and iron oxide) and pore space. This is especially noticeable where slumping at the rock walls has not been so great as to displace the layers in the orebody from their contact with their corresponding layers in the rock wall. Although complete analyses of the entire original rocks in the iron series have not been made in any place, to my knowledge, from the best data at hand as to the average analysis of the Biwabik series and the

Jan 1, 1920

By D. Turnbull

RECENTLY it has been shown that aggregates of small liquid droplets of tin,' mercury' or gallium' kept from intercommunicating by suitable films do not solidify at an appreciable rate unless the supercooling is very much greater than that usually necessary to cause a large continuous mass of the metal to solidify. For example oxide-coated tin droplets1 (1 to 10 micron diam) must be supercooled 100" to 110°C before their rate of solidification becomes rapid, although large continuous masses of liquid tin usually begin to solidify when supercooled 30" or less." These experiments have been interpreted' on the hypothesis that nucleation of crystals in large continuous metal samples is almost always catalyzed by accidental inclusions. Therefore, if the metal is dispersed into a number of isolated droplets large in comparison with the number of inclusions, most of the droplets should not crystallize until a temperature sufficiently below the thermodynamic melt- ing point, T0, has been reached to permit an ap-preciable rate of homogeneous (noncatalyzed) nu-cleation. In general this temperature is very much less than the temperature at which the rate of heterogeneous (catalyzed) nucleation is appreciable. If this interpretation is correct then investigation of the kinetics of crystallization of small droplet aggregates should be one of the most fruitful methods of obtaining information about the homogeneous formation of crystal nuclei in liquids. In this paper the results obtained on gallium and mercury are reported more fully. In addition, results on the supercooling of aggregates of liquid bismuth and lead droplets are included. Experimental Procedure Some care must be exercised in the choice of a barrier to prevent the liquid droplets from coalescing lest the barrier itself catalyze the formation of crystal nuclei. From this standpoint, the most desirable barrier is vacuum or inert gas, but, because of the difficulty of experimental arrangement, solid compounds and adsorbed films have been selected. There are two guiding principles in the selection of compounds as barriers in addition to the requirement that they prevent coalescence of liquid droplets. First, the compound should be almost insoluble in the liquid metal and second, its lattice structure should be quite unlike that of the forming metal crystal. Even so, there is no a priori assurance that the solid compound film will not catalyze to some extent the formation of metal crystal nuclei. An adsorbed protective monolayer is less likely to be catalytic than a crystal compound film, but it is not often possible to find a monolayer that is stable under the experimental conditions. Also, it is desirable, though not generally essential, that the aggregate of droplets be prepared by breaking up the massive metal rather than from a powdered compound of the metal.

Jan 1, 1951

By R. E. Caffrey, S. K. Tung

This paper reports some of tile results obtained from the vapor-phase reaction of a volatile metal halide with a hydrogen and carbon dioxide mixture in an epitaxial-deposition chamber. Tile oxides deposited were silicon di oxide, aluminum oxide, mix-12tves of silicon di oxide and aluminum oxide, and titanium oxide. Tile deposited silicon di oxide was transparent and amorphous and had a density and index of refraction similar to that of thermally grown silica. The vote of etching was determined. The thickness uniformily of the oxide was found to he related to the aerodynamics of the system employed for deposition. A clear silicon di oxide layer was found to be dependent upon the quality of the surface prior- to aside deposition. The process parameters affecting the vale 0f deposition were studied. The deposited aluminum oxide was transparent, holy-cl-ysttrlliile, and possessed remarkable resistance to hydrofluoric acids. By measurements it has been shown that the deposited aluminum oxide is both insulating and continuous. ThE cleanness of an epitaxial silicon surface both immediately after growth and during device processing is thought to be one of the major factors contributing to the electrical properties of a final device. The advantage of protecting an epitaxial silicon wafer surface with an oxide grown immediately following epitaxial deposition is obvious. The successive growth of silicon and silicon diox- ide in epitaxial apparatus was studied by Steinmaier and loem.' They formed silicon dioxide films on a silicon substrate by adding water vapor to the silicon tetrachloride-hydrogen mixture in an epitaxial system. They also showed that, when a gaseous mixture of carbon dioxide and hydrogen is injected, water is formed only at elevated temperatures. Thus the reaction of water vapor and silicon tetra-: chloride will be limited to a relatively small reaction zone near the substrate. This paper reports some results of oxide films obtained from a vapor-phase reaction of a volatile metal halide with a hydrogen and carbon dioxide mixture in an epitaxial-deposition chamber. EXPERIMENTAL APPARATUS The system employed for the oxide deposition is a modification of a vertical system used to produce high-resistivity silicon layers by the hydrogen reduction of silicon tetrachloride.' The modification shown schematically in Fig. 1 consisted of an additional carbon dioxide gas stream which entered the reaction chamber with a hydrogen stream saturated with metal halide vapor and a diluting hydrogen stream. Silicon dioxide layers made from a mixture of silicon tetrachloride, hydrogen, and carbon dioxide gases will be discussed first. EXPERIMENTAL RESULTS 1) Factors Affecting the Rate of Oxidation. An epitaxial silicon layer was deposited by the hydrogen reduction of silicon tetrachloride on an n-type,

Jan 1, 1965

By A. A. Smith, J. S. Smart

THE controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modem copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range 0 to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously.1-2-3 Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,1, 2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of 3/8-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 850°C. from a surface scale. Test wires were drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at o.3125, 0.257, o.204 and o.162 in., and a final cold reduction of 95 per cent t0 0.081 in. Oxygen-bearing slugs made by remelting were hot-rolled to 5/16 in., drawn to 0.162 in., annealed for 30 min. at 600°C. and cold-drawn 95 per cent to 0.081inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 5/16-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700° to 800°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals were of one hour duration followed by a rapid quench in 10 per cent H2SO4. EFFECT OF PHOSPHORUS The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1945

By P. M. Robinson, M. B. Beaer

The heat of formation at 0°C of the intermetallic compound AgMg as a function of composition has been determined by tin-solution calorimetry. In this technique, the heat of formation is determined as the difference in the heat effects, at infinite dilution, on dissolution of the compound and a mixture of its components added alternately to liquid tin from a reference temperature, such as 0°C. The experimental technique and method of calculation have been described elsewhere.' The compound AgMg is a 0 electron compound with a CsCl structure.2 In nonstoichiometric compositions of the compound, atoms of the excess component are substituted on the AgMg lattice.3,4 The homogeneity range is approximately 43 to 52 at. pct Mg at room temperature and 38 to 65 at. pct Mg at 500Oc.2 Single-phase alloys outside the homogeneity range at room temperature can be prepared by quenching. The specimens used in this investigation contained from 39.0 to 54.8 at. pct Mg. They were made available, together with analyses, by the Research Laboratory of the General Electric Co. Metallographic examination of the quenched specimens containing 39.0 and 54.8 at. pct Mg gave no indication of the presence of a precipitated phase. The measured heats of formation are listed in Table I. In a calorimetric run, four to six additions each of a specimen and the corresponding mixture of the components were made. One or two calorimetric runs were carried out with each composition depending on the amount of samples available. The limits stated in the table represent the experimental precision and not the absolute accuracy of the measurements. Thermodynamic investigations of the compound AgMg have been made by Trzebiatowski and Terpilowski 5 and Kachi.6,7 The heats of formation at 500°C derived from the combined electromotive-force values of these investigators8 are more exothermic than the heats of formation at 0°C reported here, Fig. 1. The differences cannot be explained by the difference in temperature. This is shown by the published heat capacity of the stoichiometric compound, which obeys the Kopp-Neumann rule from 0" to 500oC.9 The heats of formation derived from equilibrium data are generally considered to be less accurate than those determined by calorimetric methods because small errors in the change of the equilibrium values with temperature have a large effect on the calculated value of the heat of formation. The heats of formation derived from the combined published electromotive-force values reach a maximum at 56.0 at. pct Mg.8 Kachi reports a maximum of -4.7 kcal per g-atom at the stoichiometric composition.7 The present results also indicate a maximum at or near the stoichio metric composition, Fig. 1.

Jan 1, 1964

By E. F. Johnson, F. H. Brinkman, H. J. Welge, A. L. Hicks

A method is presented for predicting the character of gas or water displacement in a radial system, which can be either horizontal or inclined. The latter case would comprise cone-shaped or dome-shaped symmetry. The method conriders the one dimension of radial distance, taken parallel to the bedding planes. Approximate allowance can be made for segregation of the two fluids perpendicular to the bedding planes. A complete saturation history can be obtained in about a day's time with the use of a desk calculator. Results of an example calculation agree well with the performance of simulated gas drive in a large model representing a section of a cone. This pie-shaped, sand-packed model was 8-ft long and 4-in. thick. The method of solution is useful in handling other partial differential equations of first order and first degree. INTRODUCTION A new analytical method has been developed for predicting the performance of gas or water drive in a reservoir having radial or cone-shaped symmetry (see Fig. 1). In addition, this new development offers a general method of handling partial differential equations of first order and first degree. This work extends those methods developed previously'- "or predicting the displacement of oil by gas or water in linear systems. The method of calculating oil recovery in a radial system involves two major parts. The first part is a calculation of the distribution of saturations at various times of depletion. The second part is the calculation of oil recovery and producing gas-oil or water-oil ratios through volumetric balance on the saturation distributions obtained in the first part. This second part differs only slightly in principle from similar calculations made with linear systems, for instance. The basic assumptions used in the calculations are as follows. 1. One-dimensional radial flow. An approach is explained later for approximating a second vertical dimension. (With- drawals of oil, and of the driving fluid after breakthrough, are assumed uniform around the periphery of the dome.) 2. Constant-volume fluid flow. Thus, in a gas drive there is no change in gas solubility, or in oil or gas volume due to viscous and gravity pressure drops. 3. Capillary forces are negligible. 4. Constant rate of injection. A program has been written for carrying out the calculations needed on a digital computer. However, a prediction can also be arrived at using a desk calculator; this latter method of work requires about a day's time for each prediction made. CALCULATION OF SATURATION DISTRIBUTION For definiteness, we describe the development of our method for the case of gas drive from the crest of the structure. The reader will note, however, that the method is just as applicable to an advancing radial water drive. The equation describing gas flow over an infinitesimal

By L. C. De Jong, J. F. Shirley, M. L. Campbell

At the Southern Peru Copper operation in Toque-pala, Peru, a new process flowsheet for the recovery of byproduct molybdenite has proved successful in dealing with complex and highly variable ores. This paper describes the process and the functions of each of the chemicals used. The Toquepala concentrator of the Southern Peru Copper Corp., located approximately 720 miles southeast of Lima near the Chilean border, processes a daily 36,500 tons of ore containing between 0.50 and 3.00% copper. The molybdenite content in the ore also varies greatly ranging from essentially nothing to as high as 0.15%. The 1966 yearly averages were approximately 1.20% copper and 0.03% molybdenite. The Toquepala porphyry deposit is a mushroom-shaped ore body consisting of a flat-lying enriched zone of predominant chalcocite with a stem-like extension of hypogene chalcopyrite ore in depth within and around a large breccia pipe.1 The underlying chalcopyrite ore has not been reached; however, due to the presence of a major post orebody fault, predominantly chalcopyrite ore is present in the north side of the pit. Most of the molybdenite occurs either as small, fine granular, pulverulent masses in vugs or empty voids of breccia, or as thin foliated masses and narrow thread-like filling in rock joints and fractures. The normal occurrence of quartz gangue with the molybdenite gives some basis for correlating the molybdenite mineralization to some later periods of silicification. On April 18, 1962, the molybdenite recovery plant at Toquepala went on stream, approximately 27 months after the copper concentrator had been in production. The plant was designed and built by Southern Peru Copper Corp.'s engineering and mechanical departments. The basic method chosen for separating the molybdenite from the copper concentrate was the sodium hypochlorite-sodium ferrocyan-ide process. The selection of this process was based on the results of an extensive testing program performed by the Colorado School of Mines Research Foundation, Inc. and the economic conditions of the area. The originally designed process could never be fully implemented due to a lack of sodium hypo-chlorite and has had to be continually modified to satisfy the requirements of the kaleidoscope of ores from the mine. The three basic problems that plague the operation of any molybdenite recovery plant are all present at Toquepala in large measure. Both the quantity of plant feed and the quantity of molybdenite contained in the plant feed are continuously changing. Even more detrimental to an efficient operation is the fact that the copper mineralization in the feed frequently changes once in every 24 hours and occasionally once a shift. From the point of view of the molyb-

Jan 1, 1968

By D. H. Davis

HAND picking was the earliest form of coal preparation, first practiced to improve the outward appearance of the coal being loaded and to remove any pieces that might appear objectionable to the buyer. It is still extensively practiced on the plus 1-in. sizes and particularly on the plus 4-in. and larger sizes. The percentage of ash reduction that can be obtained by hand picking depends entirely upon the amount of free impurity occurring in the coal. In a particularly dirty seam, where a considerable quantity of rock occurs with the coal as mined, hand picking produces sizable reductions in ash. If the coal is prepared clean at the working face hand picking is a final check; in some cases, on the smaller sizes, it is practiced only to show that an effort is being made to prepare a clean product. Because of the variety and different methods of handling coal, the early plants were not always adapted for e5cient hand picking. At most mines an attempt is made to - remove the visual impurities at one or more of the following places in the surface plant: (1) in the tipple during screening; (2) on picking band, belt, or shaking conveyors; (3) during the loading of the coal as it goes into the railroad car. Whatever the physical arrangements of the plant may be, the usual practice is to run the coal over the screen, picking table or boom at such a rate that each piece of impurity is exposed to the view of the picker. Coal should be uniformly sized and spread out on the table so as not to exceed one particle in depth. The flow should be even in tonnage and the speed of travel should be from 30 to 60 ft. per minute and not exceed 80 ft. per minute. The dirtier the coal, the slower the speed required for a fixed number of pickers. Actually, picking capacity depends on the number of particles per minute that can be picked out and rejected. The percentage of impurity removed is determined by this and the average weight of piece rejected. Handling a mixture of sizes from nut to the largest lump over the same picking table or conveyor is not conducive to efficient separation by hand picking because the lump hides the smaller impurities. Picking tables should not exceed 5 ft. in width, so that a picker on either side will be able to remove impurities from the center of the table. Guards usually are placed at the side of the screen, boom or table, to allow the pickers to stand close enough to remove the impurities without too long a reach.

Jan 1, 1950

By Walter R. Hibbard

ALTHOUGH extensive pole figure studies have been reported by Brick1 and others2,3 showing preferred orientations in rolled and annealed 70-30 alpha brass, and by Hermann and Sachs4 in 70-30 alpha brass cups, comparatively little information has been published on textures in drawn 70-30 alpha brass tubes. Crampton5 reported a (110), [III] texture in drawn brass tubes based on selected individual X ray photograms following the method of Norton and Hiller,6 but the extent and ease of developing this texture and the annealing texture have not been reported and pole figures of these structures were not found in the literature. The present investigation was further stimulated by the possible influence of textures on the mercury stress-corrosion cracking of brass tubes. According to Snoek,7 iron-nickel alloy sheet with a strong cubic texture was more resistant to corrosion than a randomly oriented sheet. Crampon5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr s in a standard mercurous nitrate test. Edmunds 12 found that single crystals of 70-30 alpha brass did not crack in a standard mercurous nitrate test but did crack when subjected to ammoniacal vapor. Wassermann reported a similar failure of a single crystal of brass in ammonia. A tube with a strong texture might approach single crystal behavior and tend to resist mercury cracking if the differences in orientation between adjacent grains were sufficiently slight. PREPARATION OF SPECIMENS Crampton's5 tubes drawn 28 pct reduction in area developed a slight degree of preferred orientation while in tubes drawn 48 pct it was more marked. Based on this information, in order to obtain specimens with markedly different degrees of preferred orientation but with the same final draw, two sets of 70-30 alpha brass tubes were made following the mill schedules shown in Table I. The final draw involved a large reduction in outside diameter, and a ratio of reduction in area to reduction in outside diameter similar to that reported by Crampton,5,10 to cause mercury cracking of brass tubes. The brass contained 71.31 pct copper, 0.01 pct lead, 0.01 pct iron and zinc by difference. DETERMINATION OF POLE FIGURES A 6-in. length from each tube was rotated rapidly by an electric stirrer in 25 pct nitric acid until the gauge was reduced to 0.003-0.005 in. The tubes were carefully cut longitudinally and the walls gently flattened. They were further etched in 25 pct nitric acid to 0.0015 in. thickness and (III) pole figures were determined using copper K-alpha radiation in the manner described by Brick.1 The three general types of pole figures

Jan 1, 1947

By R. Scot Clark

The reactively sputtered silicon dioxide capacitor -was developed for use in the monolithic integrated circuit, thereby requiring the capacitor to be fabricated on an oxidized silicon slice. The silicon dioxide film is formed by reactively sputtering silicon in a 50 pct Ar-50 pct 0, atmosphere and the physical properties are indistinguishable from silica. A practical upper limit of capacitance per unit area of 0.25 pf per sq mil is reached with the capacitors fabricated from the Si0, film. Methods shown to enhance this value are double stacking the thin-film capacitors and addition of aluminum to the silicon cathode during sputtering to form an aluminosilicate dielectric. A major contribution to the field of diffused integrated circuits would be the addition of auxiliary passive devices for replacement of diffused passive devices which are currently being fabricated for many integrated circuits. This accomplishment would increase the flexibility of the diffusion process in order to concentrate more on transistor parameters rather than on fabricating diffused resistors and capacitors. To pursue this technique, a thin-film SiOz capacitor was developed which has _ proven applicable to many integrated circuits. Although the SiOl capacitor has an application, the major deterrent from extending the integrated circuit into many useful areas such as low-frequency linear application is the low dielectric constant of SiO, and the low usable capacitance in an integrated circuit. This paper will cover the sputtering techniques used for forming the SiO, film, the physical and electrical properties of sputtered SiO,, and yield information concerning the application of these capacitors to integrated circuits. REACTIVE SPUTTERING Reactive sputtering is simply the sputtering of a metal or semiconductor in glow discharge in the presence of a reactive gas. The material to be sputtered is seen in Fig. 1 as the cathode of the system and is bombarded with positively charged ions of the ambient gas. In this investigation, the ambient gas is composed of 50 pct Ar and 50 pct O2 at a pressure of approximately 2.5 X l0-' Torr. The ions are accelerated toward the cathode in the cathode dark space by the electric field and upon striking the cathode effect a momentum energy transfer to the surface atoms. The transferred energy is sufficient to dislodge a surface atom or atoms and these particles diffuse through the glow discharge to the collector or anode. Several mechanisms of oxidation in the reaction chamber can be considered during reactive sputtering. 1) The surface of the cathode is oxidized and the oxide is subsequently sputtered. 2) Oxidation and sputtering occur simultaneously. 3) Sputtering of the cathode material is followed

Jan 1, 1965

By Herbert H. Kellogg

In 1930, Taggart, Taylor and Knoll1 found that addition of various electrolytes to suspensions of ground minerals resulted in the stopping or starting of Brownian movement of the suspended particles. On the basis of the many new facts found, they rejected the " classical"† theory of Brownian movement and proposed an "ioniza-tion " theory. This new theory was further supported in later publications by Taggart.3,4 The acceptance of the ionization theory by men in the field of flotation may be judged by the mention given this theory in Gaudin's "Principles of Mineral Dressing,'16 Wark's "Principles of Flotation,"8 as well as in a recent paper by Fitt, Thomas and Taggart.7 The proponents of the ionization theory have gone further than the mere statement of the new theory. A parallelism between the Brownian movement of mineral particles and their behavior in flotation was reported.1,3,4 Likewise, the correlation between flocculation-dispersion of mineral particles and the Brownian movement of these particles has been investigated.' Bankoffl5 has suggested that "slime-coating" can also be directly correlated with the Brownian movement of the slime particles. In each of the instances mentioned it is the ionization theory of Brownian movement that has been used to "explain" the correlations that were found. The essential conflict between the kinetic theory and the ionization theory can be understood best by a brief description of each. The kinetic theory* proposes that Brownian movement is caused by the impacts of liquid molecules against the solid particles. At any instant of time, the molecular impacts on all sides of the solid particle will not balance, and the particle will receive a push in some direction. According to this theory, dl particles suspended in a liquid are in Brownian movement. However, if the particle is very large, the impacts on all sides will very nearly balance and the motion will not be noticeable. Another factor, besides the size of the particle, that affects the magnitude of the Brownian movement is the viscosity of the liquid—the greater the viscosity, the less the displacement of particles by Brownian movement. This theory has been verified experimentally by measurement of the velocity of Brownian movement, and by measurement of the compacting of suspensoid particles under the influence of gravity.2 The originators of the ionization theory found that he addition of various electrolytes to slime pulps caused cessation or commencement of Brownian movement, depending upon the chemical nature of the particle and the electrolyte. The Brownian movement of quartz particles was observed to stop upon the addition of Certain electrolytes, where the conditions of the experiment prevented flocculation

Jan 1, 1947