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By W. 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) , [111] 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. Crampton5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr in a standard mer-curous nitrate test. Edmunds12 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. Wasserman11 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 pet nitric acid to 0.0015 in. thickness and (111) pole figures were determined using copper K-alpha radiation in the manner described by Brick.' The three general types of pole figures

Jan 1, 1949

By S. F. Urban, G. Derge

At the time this investigation was initiated variations were observed in the quality of different heats of basic electric-furnace steels, although they had been made under purportedly similar conditions. This indicated that these variations were related to normally unobserved variations in the character of the bath, especially during the "refining" period. Although the slags used for this operation are commonly referred to as "reducing" slags, and are regarded as having a "deoxidizing" action on the bath, no reliable measurements of this action were available. It was decided, therefore, to study the behavior of oxygen in the metal for ' large enough number of heats to learn its normal variations and to relate these variations to regularly observed conditions of operation. The most important general conclusion reached was that the time a heat is held under a reducing 'lag should be reduced to a minimum, which was about an hour and a half under the conditions studied. Beyond this time no observable beneficial effects are obtained from the reducing slags, insofar as oxygen and sulphur content of the bath are concerned. It is likely that added time may increase hydrogen content as well as heat costs. The oxygen content of the bath is never reduced below the amount in equilibrium with the carbon. Concurrently with this work, J. S. Marsh1 presented data that supplement and support many of the results of this paper. Procedure The work was done in two different electric-furnace shops of the same plant. The selection of heats was made primarily with regard to the convenience of heat schedules. companion slag and metal samples were taken just prior to slag-ofi and throughout the refining period for an initial set of 17 heats, and before slag-off and near tap for an additional I3 heats. slag Sampling presented no particular problem; a spoonful of slag was poured onto a metal plate and when sufficiently cool was sealed in an airtight container. Sampling the metal for oxygen presented a more complex problem. Because of the lack of previous experience in sampling electric-furnace baths, a number of methods were compared. Chilled Wedge Samples2 An unkilled metal sample is removed from the furnace in a well-slagged car-bometer spoon and poured immediately into a heavy copper mold designed to provide rapid freezing. Three different types of molds were used to determine the optimum for electric-furnace hats. The Big wedge Mold (a) was a 4 by 4 by 4-in. split copper mold, yielding a wedge-shaped casting I in. wide, 1 1/2 in. long, and 34 in. maximum thickness, and was finally adopted as the most satisfactory design.

Jan 1, 1948

By S. F. Urban, G. Derge

At the time this investigation was initiated variations were observed in the quality of different heats of basic electric-furnace steels, although they had been made under purportedly similar conditions. This indicated that these variations were related to normally unobserved variations in the character of the bath, especially during the "refining" period. Although the slags used for this operation are commonly referred to as "reducing" slags, and are regarded as having a "deoxidizing" action on the bath, no reliable measurements of this action were available. It was decided, therefore, to study the behavior of oxygen in the metal for ' large enough number of heats to learn its normal variations and to relate these variations to regularly observed conditions of operation. The most important general conclusion reached was that the time a heat is held under a reducing 'lag should be reduced to a minimum, which was about an hour and a half under the conditions studied. Beyond this time no observable beneficial effects are obtained from the reducing slags, insofar as oxygen and sulphur content of the bath are concerned. It is likely that added time may increase hydrogen content as well as heat costs. The oxygen content of the bath is never reduced below the amount in equilibrium with the carbon. Concurrently with this work, J. S. Marsh1 presented data that supplement and support many of the results of this paper. Procedure The work was done in two different electric-furnace shops of the same plant. The selection of heats was made primarily with regard to the convenience of heat schedules. companion slag and metal samples were taken just prior to slag-ofi and throughout the refining period for an initial set of 17 heats, and before slag-off and near tap for an additional I3 heats. slag Sampling presented no particular problem; a spoonful of slag was poured onto a metal plate and when sufficiently cool was sealed in an airtight container. Sampling the metal for oxygen presented a more complex problem. Because of the lack of previous experience in sampling electric-furnace baths, a number of methods were compared. Chilled Wedge Samples2 An unkilled metal sample is removed from the furnace in a well-slagged car-bometer spoon and poured immediately into a heavy copper mold designed to provide rapid freezing. Three different types of molds were used to determine the optimum for electric-furnace hats. The Big wedge Mold (a) was a 4 by 4 by 4-in. split copper mold, yielding a wedge-shaped casting I in. wide, 1 1/2 in. long, and 34 in. maximum thickness, and was finally adopted as the most satisfactory design.

Jan 1, 1948

By Rollin Farmin

Rock pressure against the supports for underground workings in certain mines becomes sufficiently severe to crush sound timbers. The cost of maintenance of these mines increases critically as the workings are extended. "Heavy ground " and "swell-jng ground" are terms commonly applied to a condition of excessive pressure from the wall rock. Defined for the purposes of this paper, "heavy ground" delivers gravi-tative pressure on the supports of a mint opening; "swelling ground" delivers pressure arising from expansion of the wall rock. Mining problems created by heavy ground have been studied extensively by mining engineers, as in the recent Symposium on Block caving.' A parallel study of rock bursts2 attacks the field of ground that ruptures under strain. The problem of swelling ground, which has received less current attention, is the subject of this paper. An ExaMPLe of Swelling Ground Severe cases of swelling ground are found in the gougy shear zones in mines along the western Sierra Nevada, where the veins are accompanied by faults through altered serpentine, schist and slate. For example, along troublesome stretches in the ldaho Maryland mine, Grass Valley, California, swelling ground continues to crush drift timbers, with diminishing intensity, for 3 to 10 years after entry. During this period, from five to nine generations of crushed timber sets must be replaced and a large additional tonnage of scaly rock and wet gouge must be removed from the drift to make room for this succession of new timbers. After "the squeeze has been taken out of the ground" the timbers will stand for years, until they collapse from decay. Heaving of floor and footwall along drifts develops soon after the timber sets are placed and frequent grading down of the track is necessary to keep it serviceable and to maintain headroom. If sills are placed under the drift posts, the sets break more quickly and the track becomes impassable at once. When the floor is left Open? and the bottoms of posts and stulls are pencil-pointed, the scaly ground of the fault zone swells up around the timbers (Fig. I) instead of breaking them (Fig. 2). A foot or two of this encroaching ground is trimmed from the floor and lower sides of the drift several times before complete retimbering is necessary. when a set of timber fai1s under the Pressure of swelling ground, there is no immediate fall of timber and broken rock to fill the drift, as is customary in heavy, caving ground. Instead, ground swelling from sides, top and bottom gradually closes the opening, over a period of weeks or months, and no especial hazard to workmen is present while they have room to walk through the narrowing drift. Most

Jan 1, 1946

By Walter E. Duncan

The ores treated at the concentrating plant of the Mahoning Mining Co. at Rosiclare, Ill., come largely from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately inter-grown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four coyentrates: (I) lead, (2) zinc, (3) acid-grade fluorspar and (4) metallurgical-grade Auorspar.2-3 Although fluorspar had been floated in Canada in 19214 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Alines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1948

By Walter E. Duncan

The ores treated at the concentrating plant of the Mahoning Mining Co. at Rosiclare, Ill., come largely from the blanket replacement deposits of the northeastern part of Hardin County, Illinois, and consist of complex mixtures of galena, sphalerite and fluorspar in a gangue of quartz, limestone and sandstone. The several minerals are so intimately inter-grown that they are not liberated at the sizes usually treated by gravity concentration in the usual fluorspar plant. For this reason, an all-flotation method of concentration was developed in cooperation with the station of the U. S. Bureau of Mines at Rolla, Mo.1 This flotation separation made possible the commercial production of four coyentrates: (I) lead, (2) zinc, (3) acid-grade fluorspar and (4) metallurgical-grade Auorspar.2-3 Although fluorspar had been floated in Canada in 19214 and a plant at Rosiclare had been floating fluorspar since March 1929, fluorspar flotation was given considerable impetus by the Mahoning developments, since some features of the separation were quickly adopted by other fluorspar companies. The Bureau of Alines5 reports that in the 10 years preceding 1938 only 50,552 tons of fluorspar flotation concentrates were produced in the United States. The rise from this almost nominal figure to 153,750 tons (largely acid grade) in one year (1944)6 is indicative of the activity in fluorspar flotation occasioned by the war. The industry thus proved to be in a position to expand and keep up reasonably well with the requirements imposed upon it by such developments as occurred in high octane aviation gasoline alkylation, in the use of Freon as a refrigerant and as carrier in the Aerosol "bug bomb," and in the atomic bomb project as well as in the expansion of other activities requiring hydrofluoric acid; for example, the aluminum industry. Despite the fact that the greater portion of acid-grade fluorspar produced in the last few years went directly into war uses, the future of the acid-grade field still appears bright. As a result of the activity in fluorine chemistry during the war, it seems likely that in the relatively near future almost every phase of human endeavor will find some fluorine compound involved. The other three concentrates produced deserve some attention in these introductory remarks. The lead concentrates first produced contained both zinc and fluorspar but these did not interfere with their marketing. As will be pointed out later, the quality has steadily improved until today it is a relatively high-grade product. Although some zinc smelters accept concentrates containing limited quantities of fluorspar, it is a very objectionable impurity. Since flotation methods fail in the complete removal of the fluorspar, chemical methods were developed for

Jan 1, 1948

By James Pollock

SUMMARY THE possibility of colloidal deposition of cinnabar has been neglected. In opalite deposits cinnabar exists in particles within or near the colloidal size range. Colloidal processes have been admitted to be operative in hot springs and low-temperature deposits similar to most cinnabar deposits. Mercuric sulphide sols are stable to elevated temperature and pressure, and in nature probably are chiefly affected by the electrolytes in solution, dilution of colloid, and presence of protective colloids as silica. The stability of mercuric sulphide sols to electrolyte is measured, and shown to be greatly increased by dilution and by the protective action of silica. Mercuric sulphide sols follow the Schulze-Hardy valency rule, therefore the precipitating power of complex mixtures of electrolytes can be computed roughly. The stability of mercuric sulphide sols is shown to be greater than the equivalent precipitating power of the electrolytes in a hot spring depositing mercuric sulphide. It is concluded that finely divided or earthy types of cinnabar are colloidally deposited. POSSIBILITY OF COLLODIAL DEPOSITION While colloidal solution has been suggested as a means of transport for a number of minerals, such as the sulphides of antimony, arsenic, and iron, it has been neglected in connection with mercury. This is surprising because there exists positive evidence that cinnabar is present in certain deposits in particles of colloidal or near colloidal size. Colloidal transport could result from either the rapid dilution or neutralization of alkaline sulphide solution bearing mercury coming in contact with deep ground waters, or from colloidal solution near the original source and subsequent flow to the point of deposition unchanged. That the dilution of a mercuric alkaline sulphide solution will precipitate mercury sulphide in colloidal form has been demonstrated a number of times and is easily confirmed. The dilution hydrolyzes the alkaline sulphide Na2S to the corresponding hydroxide and hydrosulphide NaOH and NaHS, and the diminution of the concentration of alkaline sulphide reduces the solubility. It is not the contention of this writer that colloidal deposition is the mode of transport of mercuric sulphide in all mercury deposits, but that the stability of a mercuric sulphide sol, as demonstrated below, in waters that are similar to those that have deposited mercuric sulphide necessitates consideration of this possibility in many deposits, especially those of the hot-spring and so-called opalite type. EVIDENCE OF COLLOIDAL DEPOSITION Ross1 has shown that most deposits of quicksilver are formed at low temperatures and pressures, and probably by solutions that have relatively simple chemical compositions. In most cases the solutions are probably similar to those observed in hot springs, and in two instances-at Steamboat Springs, Nevada, and Sulphur Bank, California-hot springs have been reported by Becker as actually depositing cinnabar.2 Opalite deposits were believed by early investigators to be surface phenomena

Jan 1, 1944

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 Simon D. Strauss

INTRODUCTION The changes in ownership, management, and operation of the non-fuel minerals industry since the Second World War have been dramatic. World-leading enterprises have lost their identity; host countries have taken over operations from multi-national firms; marketing practices have been drastically altered - and yet the world industry is supplying minerals on a scale far greater than had been anticipated in projections made at mid-century. The world's known mineral resources have been enormously expanded, despite the doom sayers who for decades have been predicting that depletion of non-renewable resources would impose limits to growth. PALEY REPORT One can set the stage by reviewing how the minerals outlook was regarded in a thoughtful and comprehensive analysis made in the years 1950 and 1951. During the War years, President Harry Truman of the United States had come to appreciate the decisive role played by minerals resources through his chairmanship as a U.S Senator of a committee that investigated the procurement and allocation of natural resources. In 1950, in the Cold War era that resulted in actual military conflict in Korea, he appointed a prestigious five-man commission to study the problems of Materials Policy over the following quarter century. Their findings, published in five impressive volumes in early 1952, became known as the Paley report. The text was prepared by expert scientists and economists who spent 18 months assembling statistics, making projections of future demand, and interviewing leaders in industry, academia, and government. [ ] The Commission had correctly foreseen that aluminum would replace copper as the largest volume non-ferrous metal, but it had fallen short of reality by a wide margin indeed for all three materials. Even though the Commission's expectations for growth proved to be extremely understated, it had concluded its report with grave foreboding about the effect of its estimates of demand in relation to supply, as follows: "Consumption of almost all materials is expanding at compound rates and is thus pressing harder and harder against resources which, whatever else they may be doing, are not similarly expanding. This materials problem is thus not the kind of 'shortage' problem, local and transient, which in the past has found its solution in price changes which have brought supply and demand back into balance. The terms of the materials problem we face today are larger and more pervasive." With respect to some minerals, the Paley Report expressed scepticism that, in fact, supplies would be forthcoming regardless of price. Because the Paley demand forecasts understated the actual growth in demand for virtually every mineral, one could logically have expected frequent and protracted shortages in the years since 1950.

Jan 1, 1985

By W. R. Seyfried

THE -problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations, An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper, The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reaent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp, became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant, By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1492°F). (b) The roasted ore would then be leached .with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1948

By R. I. Jaffee, J. G. Dunleavy, W. Hodge, H. R. Ogden

Early in 1946, at the instigation of the U. S. Army Signal Corps, the authors made an extensive survey of the available literature covering high-strength, high-conductivity alloys. For the purposes of the Signal Corps, the minimum tensile strength to be considered was 150,000 psi, together with at least 50 pct IACS conductivity. No single alloy was found to be in production, or mentioned in the literature, which had this combination of properties. The constitution diagram for the iron-copper alloys is not well established in the respect to the two-liquid region. Fig I, taken from the 1939 Ed. of the ASM Metals Handbook, shows a two-liquid system existing above the liquidus temperature, but disconnected from it. Although Ruer and Fickl and Ruer and Goerensz definitely established the fact that two liquid layers could occur in the system, Ruer3 was not convinced that the line of immiscibility was closed in the center. Maddocks and Claussen4 found no liquid immiscibility at temperatures up to 157oOC in alloys containing almost no carbon. Although the diagram would indicate age hardening of the copper-iron alloys is possible, Hanson and Fords found that little hardening effect could be obtained. However, Gordon and Cohen6 reported that the response is better if the quenching is very efficient. Although iron has a potent effect on the conductivity of copper, Hanson and Fords have shown that, when hot-rolled copper-iron alloys are aged at 1200°F, the electrical conductivity decreases sharply with iron contents up to 0.2 pct Fe, and then levels off at conductivities between 60 to 70 pct IACS with compositions to 2.1 pct Fe. They also found that aging did not increase the tensile strength, although increasing iron content gave a moderate improvement in strength. High-strength copper-iron alloys, usually containing about 60 pct iron, had been reported by Smith and Palmer.7 They found that an alloy containing 56.4 pct copper, 0.21 pct magnesium, balance iron, would give a maximum tensile strength of 170,000 psi and an electrical conductivity of slightly over 35 pct IACS. The alloy could also be processed to have I50,000 psi tensile strength, and about 41 pct I.\CS conductivity. Decreasing the iron content increased the electrical conductivity, but the long mushy range during freezing of the alloy containing 10 to 20 pct iron made the production of good castings difficult. In spite of the difficulty encountered by Smith and Palmer with alloys of around 20 pct iron, it was decided to make a rather complete investigation of this type of alloy. As a result of this investigation, a method of alloying and fabricating copper alloys containing 10 to 15 pct iron was developed

Jan 1, 1949

By Walter Miller

Petroleum refining, like other industries in the United States in 1940, focused much attention on its duties and opportunities in the field of national defense. In crdiiter-distinction to the situation during the World War, the industry is well constituted as to existing equipment, processes, and capacity, together with planned additions, to handle any demands that may be made upon it by the defense program needs. Evident throughout was the growing sense of ability to manipulate oil molecules for the production of materials not hitherto considered as being available commercially from petroleum. The development and application of catalytically induced reactions on a broad front is one of the distinguishing characteristics of refining progress during the year. In the hands of the refiner, catalysis has developed into a most important means to secure higher antiknock motor fuels and 100-octane fighting grade aviation gasoline in greatly increased quantity. One illustration of the importance being assigned to catalytic refining is the construction by the Houdry group of an experimental laboratory at a cost of $7'307'30'3, to be staffed with over 100 research men7 solely for the purpose of studying catalytic reactions. In the aviation gasoline picture a modification of specifications by the Government widened the field from which acceptable fuel can be secured, and the continued expansion of the alkylation process in itself promises to go far in filling the demands expected from 50,000 fighting planes. It is conservatively estimated that eyen now the industry can turn out 1,300,000 gal. of 100-octane aviation gasoline daily. The upper limits of octane numbers for regular grades of motor gasoline reached in 1939 were not exceeded, but the average octane number approached the upper level more closely. A survey made of the 1940-model cars showed no rise in average octane requirement of the engines. The trend throughout the year was for greater reliance on the A.S.T.M. method for octane determination. The "1939 Research Method" is less widely used, although still considerably in evidence; the older L-3 method seems to have lost considerable ground and to be on the way out. Re-forming Capacities Increased Interest continued to grow apace in re-forming low-octane naphthas into high-octane gasolines. Some additions, although not great, were announced in thermal re-forming capacity. Interest in catalytic re-forming was greatly stimulated by the technical success of the operation of the converted hydrogenation unit at the Bay-way, N. J., rehery of the Standard Oil Company of New Jersey, mentioned in last year's review, and also by the knowledge that recoverable proportions of toluene are present in the hydroformed (catalytically

Jan 1, 1941

By Walter Miller

Petroleum refining, like other industries in the United States in 1940, focused much attention on its duties and opportunities in the field of national defense. In crdiiter-distinction to the situation during the World War, the industry is well constituted as to existing equipment, processes, and capacity, together with planned additions, to handle any demands that may be made upon it by the defense program needs. Evident throughout was the growing sense of ability to manipulate oil molecules for the production of materials not hitherto considered as being available commercially from petroleum. The development and application of catalytically induced reactions on a broad front is one of the distinguishing characteristics of refining progress during the year. In the hands of the refiner, catalysis has developed into a most important means to secure higher antiknock motor fuels and 100-octane fighting grade aviation gasoline in greatly increased quantity. One illustration of the importance being assigned to catalytic refining is the construction by the Houdry group of an experimental laboratory at a cost of $7'307'30'3, to be staffed with over 100 research men7 solely for the purpose of studying catalytic reactions. In the aviation gasoline picture a modification of specifications by the Government widened the field from which acceptable fuel can be secured, and the continued expansion of the alkylation process in itself promises to go far in filling the demands expected from 50,000 fighting planes. It is conservatively estimated that eyen now the industry can turn out 1,300,000 gal. of 100-octane aviation gasoline daily. The upper limits of octane numbers for regular grades of motor gasoline reached in 1939 were not exceeded, but the average octane number approached the upper level more closely. A survey made of the 1940-model cars showed no rise in average octane requirement of the engines. The trend throughout the year was for greater reliance on the A.S.T.M. method for octane determination. The "1939 Research Method" is less widely used, although still considerably in evidence; the older L-3 method seems to have lost considerable ground and to be on the way out. Re-forming Capacities Increased Interest continued to grow apace in re-forming low-octane naphthas into high-octane gasolines. Some additions, although not great, were announced in thermal re-forming capacity. Interest in catalytic re-forming was greatly stimulated by the technical success of the operation of the converted hydrogenation unit at the Bay-way, N. J., rehery of the Standard Oil Company of New Jersey, mentioned in last year's review, and also by the knowledge that recoverable proportions of toluene are present in the hydroformed (catalytically

Jan 1, 1941

By John A. Emery, Frank G. Snyder

MINING geology has a threefold objective: to guide prospecting for new ore, to evaluate known orebodies as development risks, and to supply the detailed knowledge of ore structures necessary for more economical extraction. The role of geology in exploration is well established. This article will deal solely with orebody evaluation and the application of geology to development and mining problems as practiced by St. Joseph Lead Co. in the southeast Missouri district, which for many years has supplied approximately 30 pct of U. S. lead production. The primary concern of the present discussion is geology in the district, not geology of the district. The southeast Missouri district, locally called the Lead Belt, includes parts of St. Francois, Madison, and Washington counties. The first recorded mining was about 1720 at Mine La Motte in Madison County on surface showings of lead ore. Later discoveries near Bonne Terre, twenty-five miles to the north, led to extensive prospecting and underground mining. To date the district has yielded well over 8 million tons of pig lead, valued at more than $1 billion. By far the greater part of the lead production has come from an area of 50 sq miles, centering on the city of Flat River, as shown in Fig. 1. Role of Geology in Metal Mining The history of the use of geology in the older metal mining districts follows a simple consistent pattern that may be considered in terms of four distinct phases. Each geologic phase is a response to the economic status of the mining district; each has definite characteristics setting it apart from other phases; and each passes into the succeeding phase as the mining operation gradually exhausts the large, rich, easily discovered deposits and lives upon increasingly smaller, lower grade orebodies that are less easily found. The geologic phases and their major characteristics are as follows: Period of No Organized Geologic Program: During the early history of a great metal district ore is easily found by random prospecting and wildcat drilling. Many small operators are active, as profitable mining can be done with a relatively small capital outlay and a minimum of technical staff. Mining practice consists largely of sinking a shaft on an ore showing and following the ore in sight. When the ore is exhausted or becomes unprofitable to mine, the process is repeated on a new ore showing. The miners become familiar with certain ore habits and use this practical geologic knowledge to guide mining. The method is successful as long as large tracts of virgin mineralized area are available. This phase ends when small-scale mining methods are no longer profitable and the mines become consolidated into the hands of a few operators.

Jan 1, 1957

By A. A. Jr. 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 modern 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 o 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. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 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 %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-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 8o0°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 wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946

By Lloyd R. Jackson

In the past 15 years there has been a great deal of interest in the fundamentals of plastic flow and rupture in metals and a number of papers have presented substantial advances toward a fundamental insight into the mechanism of these two processes. This paper is an appraisal of the present position with respect to the following: 1. The relative importance of shear and hydrostatic stresses in controlling the plastic flow of metals. 2. The relative importance of shear and hydrostatic stresses in determining the amount of flow before rupture in metals. 3. The use of generalized strains in determining the effect of plastic flow on the work-hardening of metals. FundamentalS Involved in Plastic Flow In attempting to devise a quantitative description of plastic flow in metals, it has been customary to assume that metals are homogeneous and isotropic. The fact that neither of these assumptions is correct complicates the experimental appraisal of relations developed. Nevertheless, as will be shown, metals are close enough '0 being isotropic and homogeneous so that considerable insight into the mechanism of plastic flow can be obtained. The assumptions of isotropy and homogeneity allow both the elastic and plastic behavior of metals to be described in terms of 12 variables—six being stress variables, and six being strain variables. From this viewpoint, it should be possible to represent the stress-strain relations in the plastic range for metals by a surface in 12 dimensions. One boundary of this surface would be the surface of transition from elastic to plastic behavior; the other would be the surface of rupture. These two surfaces would be joined by the surface of plastic flow. The shape of this composite surface would depend on the test temperature and speed of straining This paper is concerned only with results obtained at constant temperature and constant speed of straining. While such a representation is conceivable, the demonstration of such a surface would present almost insurmountable obstacles. The most fruitful simplification of this concept has been the recognition that the behavior of metals in the plastic region is primarily a result of shear stresses and strains. Based on this viewpoint, it is possible to utilize stress and strain invariants that are independent of hydrostatic components to define an effective stress and strain. In effect, this amounts to reducing the task of representing stresses and strains in 12 dimensions to one of representation in two dimensions. The two invariants (one for stresses and one for strains) that have received most attention are the following: q2 = ½[(Txx= - Tyy)2 + (Tyy - Tzz)2 + (Tzz - Txx)2 + 3(Txy2 + Tyz2 + 7xx2) [1]

Jan 1, 1947

By Lloyd R. Jackson

In the past 15 years there has been a great deal of interest in the fundamentals of plastic flow and rupture in metals and a number of papers have presented substantial advances toward a fundamental insight into the mechanism of these two processes. This paper is an appraisal of the present position with respect to the following: 1. The relative importance of shear and hydrostatic stresses in controlling the plastic flow of metals. 2. The relative importance of shear and hydrostatic stresses in determining the amount of flow before rupture in metals. 3. The use of generalized strains in determining the effect of plastic flow on the work-hardening of metals. FundamentalS Involved in Plastic Flow In attempting to devise a quantitative description of plastic flow in metals, it has been customary to assume that metals are homogeneous and isotropic. The fact that neither of these assumptions is correct complicates the experimental appraisal of relations developed. Nevertheless, as will be shown, metals are close enough '0 being isotropic and homogeneous so that considerable insight into the mechanism of plastic flow can be obtained. The assumptions of isotropy and homogeneity allow both the elastic and plastic behavior of metals to be described in terms of 12 variables—six being stress variables, and six being strain variables. From this viewpoint, it should be possible to represent the stress-strain relations in the plastic range for metals by a surface in 12 dimensions. One boundary of this surface would be the surface of transition from elastic to plastic behavior; the other would be the surface of rupture. These two surfaces would be joined by the surface of plastic flow. The shape of this composite surface would depend on the test temperature and speed of straining This paper is concerned only with results obtained at constant temperature and constant speed of straining. While such a representation is conceivable, the demonstration of such a surface would present almost insurmountable obstacles. The most fruitful simplification of this concept has been the recognition that the behavior of metals in the plastic region is primarily a result of shear stresses and strains. Based on this viewpoint, it is possible to utilize stress and strain invariants that are independent of hydrostatic components to define an effective stress and strain. In effect, this amounts to reducing the task of representing stresses and strains in 12 dimensions to one of representation in two dimensions. The two invariants (one for stresses and one for strains) that have received most attention are the following: q2 = ½[(Txx= - Tyy)2 + (Tyy - Tzz)2 + (Tzz - Txx)2 + 3(Txy2 + Tyz2 + 7xx2) [1]

Jan 1, 1947

By A. A. Jr. 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 modern 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 o 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. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 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 %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-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 8o0°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 wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946

By Frank C. Appleyard

Gypsum, the dihydrate form of calcium sulfate, has a history of usefulness to man dating back several thousand years, and a worldwide industry has been built on the mining and processing of this versatile industrial mineral. However, anhydrite, the other principal calcium sulfate mineral has very limited use, so much so that separate statistics for it are not always kept, but are usually included with those for gypsum. Although often found in close association, the two minerals have important chemical differences in that anhydrite is the anhydrous form of calcium sulfate (CaSO,) whereas gypsum is the dihydrate (CAS0;2H20). These two molecules of combined water result in significant differences in hardness, density, and solubility of the two minerals. However, of most importance is the difference in thermal properties wherein gypsum, upon the application of a modest amount of heat, can be converted to the hemihydrate of calcium sulfate (CaS0;Vi H,O) or plaster of paris, an intermediate product upon which is based over 90% of the value of all calcium sulfate end products. Anhydrite, on the other hand, is inert at these temperatures and its uses have been limited to only those few cases where calcium sulfate in the anhydrous form may have an advantage. The earliest known use of gypsum plaster dates back some 5000 years to the time of the Pharaohs of Egypt who had discovered that gypsum rock, when exposed to fire, broke down into a powder which when mixed with water would form a putty that could be "plastered" on a rough mud brick or stone wall to make a smooth finish. It was used down through the centuries in a limited way for ornamental purposes, but did not achieve wide acceptance because of its quick (25 to 30 min) setting or hardening time which made it difficult to use. The first real understanding of gypsum chemistry was developed in France about 1755, and the gradual growth of its present utilization dates from that time. In the United States, the first utilization of gypsum was to grind it to a fine material for use as a soil conditioner at about the time of the Revolutionary War, and the term "land plaster" for ground gypsum has remained in use. Another cementituous material-lime or calcium oxide-had become the usual plastering material, but by about 1870 a method for retarding the set of gypsum plaster was discovered and it has today almost completely replaced lime as a plastering material. In recent years, gypsum products sold in the United States have reached a total valuation of approximately $500 million per year as illustrated in [Table 1].

Jan 1, 1975

By A. G. H. Andersen, A. W. Kingsbury

SILICON bronzes containing iron are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith' and of A. G. H. Andersen .2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 determined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at 1100°C. Hanson and Ford," using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. Of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West7 have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,1,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. PREPARATION OF SAMPLES Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates h in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1942