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By Harrison Schmidt

Since the U. S. Geological Survey published the data on the Central Mining District collected by Lindgren and Gratonl and by Paige2 much new information has been obtained by development and mapping, but none of it had been published until recently when Kniffin3 published on Fierro, Lasky4 on the Ground Hog mine, Thorne5 on Santa Rita and Landon6 filed a thesis on the Fierro-Hanover-Santa Rita area at the University of Chicago. During the years 1927-1930 much of the writer's time was spent in mapping the geology and ore deposits of this district, particularly in the area of the zinc deposits at Hanover. Some of the data collected are presented here. Previous publications have been freely drawn upon and additional data used that were generously supplied by L. M. Kniffin, Wilfred Wright and Gerald Ballmer. Thanks are due Augustus Locke, Samuel G. Lasky, Kniffin, Wright and Ballmer for suggestions and critical readings of the manuscript, and to the Empire Zinc Co. (a subsidiary of the New Jersey Zinc Co.) for the privilege of publishing material compiled largely at its expense. The relation of the Central or the Santa Rita-Hanover-Fierro district to the Silver City district is shown on Paige's geologic map in the Silver City folio.7 Granodiorite porphyry and quartz-monzonite porphyry

Jan 1, 1935

By B. Stoughton, H. O. Hofman

Before examining a fire-clay in the labori~tory for its resistance to heat or to fluxes, the sample is always ground to an impalpable powder. But when the clay is actually used for the manufacture of bricka, blocks, pots, etc., it is not ground to a uniform size, the particles varying from coarse grains to the finest slimes. The natural inference is that the tests with finely-ground substances mill give lower results than if the materials are tested just as they are going to be used. The, following experiments were made to find out how far this inference is justified. The method employed for fusion was Seger's direct method,* and, for fluxing, the modified Bischof method, described in the paper on that subject presented at the present meeting, The first question to be decided was, how large the test-cones ought to be made, to include representative proportions of the diflerentrsized particles colnposing the mixture. This was subjected to a screenanalysis with the following results :

Jan 1, 1899

By R. H. Jacoby, M. J. Rzasa

Experimental equilibrium vaporization ratios (K values) were obtained for nitrogen, methane, carbon dioxide, ethane and hydrogen sulfide in two natural gas-absorber oil mixtures and in two natural gas-Elk Basin crude oil mixtures. For each mixture of constant over-all composition, data were obtained at 100°, 150° and 200°F and at various pressures in the range 200 to 5,000 psia. Some effects of composition on the K values were obtained to serve as a guide in choosing K's for engineering calculations on other mixtures. The pressure cell used to obtain the data is a new type and is described here for the first time. INTRODUCTION The phase equilibria of complex hydrocarbon mixtures such as natural gases, crude oils and their mixtures have been studied previously for the purpose of finding equilibrium vaporization ratios for the hydrocarbon constitutents. In a few cases, such non-hydrocarbon.: as nitrogen, carbon dioxide, and hydrogen sulfide were included in the mixture. studied because they occur. in the fluids obtained from petroleum reservoirs. The increasing occurrerce. of these non-liydrocarbon.; antl their growing economic importance. make it necessary to account for them more accurately in engineering calculation.: than is now possible using the meager published data. The available data for non-hydrocarbons may he classified into two groups: namely, binary mixtures of a hydrocarbon and a non-hydrocarbon. and mixtures containing three or more components, only one of which is a non-hydrocarbon. Amon: the former. phase analyses are available for two nitrogen-HC mixtures, tve carbon dioxide-HC mixtures and three hydrogen sulfide-HC mixtures. Data for more complex mixtures are available as follows: Nitrogen-Methane-Pentane'; Nitrogen-Methane-Hexane,'; Nitrogen-Methane-Heptane'; Carbon dioxide-Natural Gas-Natural Gasorline": Carbon dioxide-Natural Gas-Crude Oil". These data have been used generally lor engineering calculations, often with little regard for their precise applicability because data for the non-hydrocarbons in the complex mixtures being dealt with were not available. The use of K values from binary data for calculation:; involving complex mixtures is open to criticism because such K's are not a function of composition and very often show large differences from the K's for the same components in a complex mixture. Thus the effects of composition must be evaluated when obtaining K's for components in complex mixtures. Poettmann and Katz " varied the carbon dioxide content of their mixture.; from about five to ten mol per cent and found substantially no effect on the K values due to this change. This was not surprising since one might expect that changing a minor com-ponent by * three mol per cent would have little effect. It is more important to find the composition change which have the largest effect on the K values. For example. varying the methane or heptanes — plus compositions over a wide rangr may have a large effect on the K'. of all components in the mixture. Interesting data to this effect were obtained by Eilerts and Smith." It was toward these problems that the experimental data presented here were directed. EQUIPMENT The pressure cell used to obtain the data i:. somewhat dif-ferent from those which have been described in the past. Photographs of the equipment are shown in Figs. 1 and 2. Fig. 1 Shows. the front panel: from a .rated position at the right the

Jan 1, 1952

By George R. St. Pierre, John Chipman

METALLURGISTS have been studying the chem-ical behavior of sulfur in steelmaking for many years in order to have a better control of the sulfur content of finished steel. During the refining period in the open hearth, molten steel is separated from a gas phase by molten slag. Chemical reactions occur principally at the slag-metal interface and at the slag-gas interface. A need for physical-chemical investigations of reactions between sulfur-bearing gases and steelmaking slags was recognized some time ago.'.' From the early work, it can be qualitatively concluded that increased sulfur content and low partial pressure of oxygen in the gas phase favor the passage of sulfur from gas to slag. Using radioactive sulfur S Koch and Fink' have demonstrated the rapid rate of exchange of sulfur between gas and slag in an open hearth furnace. Gurry and Darken and Darken and Shields (as reported by Derge and Marshall') have equilibrated lime-iron oxide slags with SO—O2 gas mixtures. The major conclusion from the reported results is that sulfur content increases with increasing lime content in lime-iron oxide slags equilibrated with a gas of high oxygen pressure (10-2). The data were interpreted as indicating the presence of SO, and S,O, ions. Richardson and Fincham' have conducted the most extensive experimental study of sulfur equilibria between gas and slag. Their results confirmed many of the conclusions drawn from calculations of Richardson" and Withers. Richardson and Fincham's data fitted very well into the sulfur scheme represented by the reactions 1/2 s2 (g) + (0) melt - 1/202(g)+ (S) melt [II 1/2 S, (g) + 3/2 O (g) + (0) melt - (SO,) melt. [2] At oxygen pressures greater than 10 to 10 they found that reaction Eq. 2 was predominant while reaction Eq. 1 was controlling at oxygen pressures less than 10." to 10.". The slag compositions and gas mixtures used in their investigations were different from those used in the present study. Wherever possible, comparison has been made between their results and these, and agreement is excellent. It is evident that the distribution of sulfur between slag and gas depends upon the oxygen pressure of the gas. In FeO slags, a change in oxygen pressure produces a change in ferric oxide content, and a knowledge of this equilibrium is a prerequisite to studies of sulfur distribution. The data are found in the work of Darken and Gurry" on the FeO system and the more recent experiments of Gurry and Darken" and of Larson and Chipman" on FeO slags containing lime and silica. The effect of oxygen pressure on the ratio Fe /(Fe" + Fe ), the so-called j-ratio, reported by these investigators will be used in interpreting the results which follow. Experimental Method The purpose of the experimental program was to determine the equilibrium sulfur content in slags exposed to gases of known oxygen and sulfur pres- sures. The slag compositions selected for study were from the lime-silica-iron oxide system. Additions of magnesia were made to some of the slags. Apparatus—The apparatus used by Larson and Chipman was modified slightly to accommodate the addition of SO2 to the gas mixtures. As in their work, slag samples of 0.5 to 2.0 g were held at temperature (lcc) in platinum crucibles under a steady stream of gas, 100 to 200 ml per min, for several hours and then rapidly lowered to the bottom of the furnace where they were quenched in mercury. Preparation and Analysis of Gas Mixtures—Mixtures of SO,-CO were prepared from Virginia Smelting Co. Extra Dry liquid SO, and Pure Co. CO,. After removing traces of water vapor with an-hydrone, the CO, was passed over graphite at 1200°C, at which temperature the conversion to

Jan 1, 1957

By W. O. Philbrook, K. M. Goldman, G. Derge

THIS is the third in a series of papers from the Metals Research Laboratory dealing with the transfer of sulphur across the iron-slag interface in a carbon-saturated system. The first paper' showed that the transfer obeyed first-order kinetics. The second' presented detailed evidence in support of the three-stage mechanism: FeS(Fe) FeS(slag) FeS(slag) + CaO(sing) ? CaS(slag) + FeO(slag) FeO(slag) + C ? Fe + CO. This emphasized the role of an iron-sulphur complex as the transfer agent across the interface and as an essential intermediate in the overall process. The present paper shows the influence on the process of the individual elements, carbon, silicon, manganese, and phosphorus, the alloying elements normally present and of interest in commercial blast furnace operations, aluminum, which has a pronounced accelerating influence, and nickel and copper, which are common minor impurities in the raw materials. The experimental methods and procedures for interpretation of data are the same as described earlier.1,2 Induction heated, graphite crucibles were used, and sulphur-free slag was added to the molten iron containing sulphur and the selected alloy. Slag samples were taken at regular time intervals and analyzed for sulphur and other components of interest. The authors wish to state specifically that these experiments were not intended to simulate industrial blast furnace operations. However, they do represent a study of the kinetics and mechanism of sulphur transfer at the slag-metal interface under specified laboratory control of the major variables in the system. It is believed that the results can be usefully applied to the blast furnace if consideration is given to the differences which are known to exist between the two conditions. A rigorous evaluation of the accuracy of rate studies is difficult. Recognized sources of error include sampling and analysis of both slag and metal, temperature measurement and control, selection of zero time, composition of the gaseous atmosphere over the reaction system, and extraneous sources of sulphur from the graphite crucible and reagent materials. In this study carefully standardized procedures were followed consistently in order to minimize the errors. It is believed that the reproducibil-ity of duplicate runs indicates that errors have been rendered negligible relative to the observed effects from intentional variables. For example, original experimental points for duplicate runs are shown in Figs. 1, 2, 7, etc. In most cases in this paper the drawn curves represent an average of at least two heats. The spread in sulphur values at a given time ranges from 0.02 to 0.08 pct, which is a small frac-tioi of the total values ranging up to 2 pct S in slag. In the systematic study of the influence of alloy additions, each element was added over a range of concentrations. The two slags used in this study were designated as "acid" or 1530 and "basic" or 1545. They had the nominal compositions given in Table I. Rates were measured in the temperature range 1500" to 1650°C. Data will now be presented to illustrate the various features of the study. Silicon The first alloying element examined was silicon, because its presence is unavoidable in any silicate slag system through the reaction y/2SiO2(slag) + xM?y/2Si(liq.Fe) + MxOy where M is any reducing agent such as iron or carbon. It is known that the attainment of equilibrium by this reaction is extremely slow and probably not reached in the blast furnace." The influence of silicon on the final stages of the sulphur reaction has also been studied.' It has been shown5 hat silicon increases the activity of sulphur in iron. For such reasons silicon may also be expected to influence the kinetics of the reaction. The observed effects will now be described. The general procedure was to melt 530 grams of ingot iron in a graphite crucible, 3 in. OD, 2 1/4 in.

Jan 1, 1955

By H. Ries

In the marketing of mineral products, it is always highly desirable for both the producer and the consumer to be able to discuss things in a common language, and this can only be done if there are standard methods for expressing the properties of the raw materials. Having developed such a form of expression, the next step would be the making of specifications, which may serve as a basis for selecting raw materials. Considering the large number of non-metallic minerals that are used, there are not a few for which there are no standard laboratory tests to be used in determining their properties, or even standard specifications on which grades or market price may be based. Indeed in many cases the consumer simply requests the producer to submit samples, and rejects or accepts them without any explanation. Could the producer know in advance just what the consumer needed, time and money might often be saved. It appears to the writer that it is of the highest importance to devise standard laboratory tests wherever possible, as this enables the consumer to state definitely what he needs, and is of great assistance to the producer. It should also work to reduce misunderstandings and disputes. In the case of sands, we find that they show a wide variation in their character, ranging from those that are so coarse as to be of gravelly nature to those that are so fine that they might be classed as silt; and from very clayey ones to those that are practically free from clay. For this wide range of sands, we have a corresponding variety of uses, which are based mainly on the physical properties of the sand, although these are not always very definitely stated. The chemical composition need rarely be considered, if the sand is of siliceous nature. To determine and express these properties there should be standard tests, which are to be followed in all cases where the material is tested in the laboratory. The use of sands for foundry work (making molds or cores) is old, and it has been recognized for some time that the important properties to be

Jan 1, 1926

By Brian F. Dyson

The surface tensions at 1550°C of some Fe-S alloys (in the range 0.008 to 0.052 wt pct S), Fe-Sn alloys (0.31 to 48.4 wt pct Sn), Fe-P alloys (0.038 to 2.38 wt pct P), Fe-Cu alloys (2.15 to 22.8 wt pct Cu), and Fe-1 pct C-S alloys (0.005 to 0.076 wt pct S) along with the surface tension of the base iron have been measured by the sessile-drop method. A mean value of 1754 dynes per cm was found for the surface tension of the base iron. Sulfur was found to be highly surface-active, the surface-tension results being in quantitative agreement with existing data. Tin and copper were found to be less surface-active than sulfur while phosphoms was completely nonsurface-active. The surface tensions of Fe-1 pct C-S alloys were found to be lower than those of the Fe-S alloys containing the same sulfur content. This was shown to be a mmzifestation of the increase in the thermodynamic activity of suZfur by carbon. It is only in recent years that attempts have been made to measure the surface tension of liquid iron of known high purity.1-3 Earlier measurements4-7 were made on liquid iron containing variable amounts of what are now known to be surface -active solutes. The exact value of the surface tension of liquid iron is still, however, open to some doubt. Halden and Kingery' reported a value of 1720k 34 dynes per cm at 1570°C, Kozakevitch and Urbain8 gave 1790k 25 dynes per cm at 1550°C, while Van-Tszin-Tan et al. obtained a value of 1865k 37 dynes per cm at 1550°C. The first systematic investigation into the effect of controlled solute additions on the surface tension of iron was made by Halden and Kingery.' They showed that sulfur and oxygen were highly surface-active, whereas nitrogen was only slightly active, and carbon inactive. A subsequent investigation by Kingery indicated that two other group-6B elements, selenium and tellurium, were also surface-active. This highly surface-active nature of sulfur and oxygen has recently been substantiated by Kozakevitch and Urbainla and Van-Tszin-Tan et al. l1 Kozakevitch and Urbainl2 have also conducted an experimental survey of the effects of a number of metals on the surface tension of liquid iron. Their surface-active nature was, in all cases, less than that of the group 6B elements. The present investigation was undertaken to study in more detail the surface tensions of dilute Fe-S alloys and to measure the surface tensions of binary alloys of iron containing phosphorus, copper, and tin. The effect of sulfur additions on the surface tension of Fe-1 pct C alloys was also determined. EXPERIMENTAL PROCEDURE The sessile-drop method was employed in the present investigation. An apparatus was built similar in principle to that described by Humenik and Kingery.lS It consisted of a horizontal silica tube, which could be evacuated to pressures less than 10-5 torr, with its central portion surrounded by a water jacket within which was a high-frequency coil. This generated heat in a tantalum susceptor placed inside the silica tube, which in turn radiated heat to the specimen mounted on a recrystallized alumina plaque. Temperatures were measured by an optical pyrometer and photographs of the molten drop were taken on a fixed-focus plate camera giving a magnification of X2. Surface-tension values were determined from the resultant drop using the method described by Baes and Kellogg.l4 The high vapor pressure of molten iron made it necessary to conduct all the experiments under a 1/4 atm of argon (greater than 99.995 pct purity). The analysis of the base iron used in the investigation is given in Table I. Each sample was approximately 3 g in weight and had a hemispherical base to ensure a uniform advancing contact angle on melting. The iron alloys were prepared individually in the sessile-drop apparatus by drilling a hole in the top of each sample and adding the required amount of solute, the drops being analyzed after the experiment. This method of preparation had the advantage of ensuring a consistent minimal contamination by oxygen due to refractory attack and also allowed surface tension to be measured at the same time. Every precaution was taken to ensure that the specimen was not contaminated by grease when it was introduced into the apparatus, the samples being cleaned in acid, dried in alcohol, and rinsed in petroleum ether. All handling was done with tweezers. Once the specimen had been placed inside the susceptor, the furnace was evacuated and the Sample leveled. The furnace was then degassed at approximately 1000"C before the argon was introduced. In every case the surface tension was determined at 1550" C.

Jan 1, 1963

By W. B. Plank

I HAVE been asked by the Chairman of the Engineering Education Committee to outline what the engineering colleges would like the mining companies to do with the young engineer just, out of college. It has been suggested that, because my own personal experience has been almost entirely within the coal industry, I handle this subject from that view- point. Many thoughtful engineering educators are today wondering what effect the present employment policies of many industrial companies are going to have on the young man just starting out in his profession. Since before the World War large industrial concerns, such as those in the electrical and mechanical industries, have gone to the colleges to interview 'likely graduates until today there has developed in most of our engineering colleges, especially in the eastern part of the country, what appears to be a lively competition on the part of these companies in bidding for the young graduate engineer. The employers of mining engineers, with one or two exceptions, have not yet begun to enter this competition. It remains to be seen how serious this situation will become, how it will affect the training of other engineers, and what effect, if any, it will have on the mind of the young man about to enter college who may be inclined to take up mining engineering, but who gains the impression from this well advertised employment service just mentioned that there is no opportunity for him in the mineral industry as com- pared with the opportunities offered in say civil, mechanical, and electrical engineering.

Jan 1, 1929

By C Gunther

The term metamorphism as commonly used means any change in a rock in either form or composition, from whatever cause. By metasomatism, according to Lindgren, is meant a metamorphism that involves a change in the chemical composition of a rock by the addition or subtraction of substance. Certain types of metamorphism are due to the action of mineralizing solutions, and are closely connected with ore deposition; they form, therefore, valuable guides in the exploration for ore-deposits. Other types of metamorphism are due to regional processes, and are not connected with ore deposition. By dynamo-regional metamorphism is meant a primary alteration of rocks over large areas under conditions of pressure, flow- age, and heat. This process produces schists and gneisses from either sediments or igneous rocks. It is thought that there is little migration of minerals or of elements in dynamo-regional metamorphism, and that the changes are due chiefly to recrysallization and rearrangement of original minerals in bands with their major axes oriented normal to the direction of greatest pressure. Under these conditions limestones are commonly altered to marble, and sandstones to quartzite, basic igneous rocks to greenstone or serpentine, while rocks of normal or acid com- position commonly yield the usual types of schist or gneiss. Dynamo-regional metamorphism, extending over large areas, has no connection with mineralizing processes, and is, therefore, no guide to ore deposits; while this process has certain features, such as characteristic mineral associations, in common with contact metamorphism, the results of the two processes may usually be distinguished without difficulty.

Jan 1, 1932

By David R. Mitchell

THE mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during war-time, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for separating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concentrating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435,000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PYRITE PRODUCTION According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By David R. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during wartime, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for sepa- rating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concen-trating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435.000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PyRite Production According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By David R. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during wartime, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for sepa- rating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concen-trating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435.000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PyRite Production According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

The term metamorphism as commonly used means any change in a rock in either form or composition, from whatever cause. By metasomatism, according to Lindgren, is meant a metamorphism that involves a change in the chemical composition of a rock by the addition or subtraction of substance. Certain types of metamorphism are due to the action of mineralizing solutions, and are closely connected with ore deposition; they form, therefore, valuable guides in the exploration for ore- deposits. Other types of metamorphism are due to regional processes, and are not connected with ore deposition. By dynamo-regional metamorphism is meant a primary alteration of rocks over large areas under conditions of pressure, flowage, and heat. This process produces schists and gneisses from either sediments or igneous rocks. It is thought that there is little migration of minerals or of elements in dynamo-regional metamorphism, and that the changes are due chiefly to recrystallization and rearrangement of original minerals in bands with their major axes oriented normal to the direction of greatest pressure. Under these conditions limestones are commonly altered to marble, and sandstones to quartzite, basic igneous rocks to greenstone or serpentine, while rocks of normal or acid com- position commonly yield the usual types of schist or gneiss. Dynamo-regional metamorphism, extending over large areas, has no connection with mineralizing processes, and is, therefore, no guide to ore deposits; while this process has certain features, such as characteristic mineral associations, in common with contact metamorphism, the results of the two processes may usually be distinguished without difficulty.

Jan 1, 1932

By B. V. P. Rao, H. L. Lovell, G. Simkovich

In the study described here, flotation tests were conducted on pure CaF2, on CaF2 doped at several concentration levels with either NaF or YF3, and on natural fluorite samples containing various amounts of impurities in an effort to extend previous knowledge of the influence of crystalline point imperfections on the flotation properties of solids. The results of these tests showed that although recoveries generally decreased as impurities increased, the differences in recovery were not nearly as striking as those detected in earlier experiments. A number of experimentalists have shown an interest in the way in which crystalline point imperfections affect the flotation properties of solids. As long ago as 1953, Welch hypothesized that it might be possible to control surface imperfections and thereby also control the flotation of solids.' A few years later, in some rather extensive work, Plaksin and his coworkers varied the surface imperfections of a number of compounds by oxidation or reduction processes and found that significant variations in flotation properties resulted.2-4 More recently, Simkovich showed that the recovery of both AgCl and PbS could be markedly varied by adding solid-solution impurities, which acted as doping agents, to these compounds.5 Then Mular studied the flotation of ZnO as a function of the doping agents Al2O3 and Li2O.6 Once again, it was found that these impurities, even in very low concentrations, had profound effects upon flotation recoveries. From an imperfection point of view, the defect structures of the compounds tested previously are as follows:7 PbS — amphoteric semiconductor with a Frenkel-type defect structure in the cation sub-lattice.8 AgCl - ionic conductor-Frenkel type defect structure? ZnO — n-type semiconductor, zinc ion interstitials and quasi-free electrons.10 All of these works undoubtedly bear some relation to the findings that the flotation properties of seemingly identical minerals from different ore deposits often exhibit extreme variation in flotation behavior, i.e., that small amounts of analytically undetectable impurities often have a great influence upon flotation

Jan 1, 1969

By R. L. Skaggs, R. A. Molsberger

DARKEN1 has pointed out that in most binary liquid metal systems the thermodynamic behavior is relatively simple in the terminal regions. Between the terminal regions. the thermodynamic behavior is more complex. To describe this behavior. he has defined the stability and the excess stability as shown: Qualitatively, an inflection in the free energy of mixing curve results in a change in sign, from positive to negative, of the stability function and is associated with a phase separation. Conversely, a large, positive stability over a narrow composition range is indicative of compound formation. Darken has shown a number of binary systems where the excess stability is constant in the terminal regions and varies sharply in between. The work described in this communication was undertaken to study the variation of stability and excess stability in a binary system as a function of temperature. In addition, this work provides means for the direct comparison of previously existing equilibrium (activity) and calorimetric (molar heat of mixing) data on the Hg-Sn system. Hildebrand2 measured the vapor pressure of mercury over Hg-Sn alloys at 595°K. Calorimetric studies were made by Kawakami3 at 523°K and by Kleppa4 at 423°K. In this work, the equilibrium vapor pressure of mercury was measured over a series of Hg-Sn alloys at 453" and 503°K by use of fused salt manometer with one arm exposed to mercury vapor. Deflections of the fused salt manometer were balanced by argon pressure on the other arm. Argon pressure was subsequently measured with a dibutyl phthalate manometer. Tin activities were determined by graphical integration of the Gibbs-Duhem equation making use of the familiar Darken5 a function. The activities of mercury and tin showed positive deviation from Raoult's law at 453 and 503°K as Hildebrand observed at 595 K. In Fig. 1 are plotted log activity of mercury and tin vs reciprocal temperature. The plot contains activities obtained from calorimetric studies. Hult-gren6 has calculated activities from Kleppa's4 data, and Kubaschewski7 has similarly treated Kawakami's7 data. Presumably. in each case a regular solution was assumed. For regions where a two-phase field

Jan 1, 1970

By W. J. Helfrich, R. A. Dodd

Binary aluminum solid-solution alloys containing various amounts of silver, magnesium, and zinc were prepared by careful directional solidification, and the hydrostatic and X-ray densities were compared. With the exception of the Al(Ag) alloys, the X-ray densities were consistently greater than the hydrostatic measurements, in agreement with earlier observations by Ellwood. In contrast to Ell-wood's interpretation in terms of vacant lattice sites associated with Brillouin zone effects, a tentative explanation based on the existence of solidification microshrinkage was favored. This hypothesis was confirmed by an examination of Al(Zn) alloys prepared by vapor diffusion of zinc into aluminum. The hydrostatic and X-ray densities were now in very close agreement, and it was concluded that the filling of Brillouin zones in aluminum solid-solution alloys does not necessarily result in the formation of defect structures containing an excess of vacant lattice sites. ThE existence of defect structures of the vacancy type in alloys in which the excess vacancies have an electronic rather than a thermal or mechanical, and so forth, origin is well recognized. Examples of incomplete lattices of this type are to be found in the Ni-Al,1-3 Fe-Ni-A1,4 c~-Ni-Al,5 Fe-Cu-Al,= and Co-A17 systems. These defect structures are of a special kind in that the intermediate phases possess an ordered atomic arrangement or superlattice, and in some instances the vacancy concentration may be unusually large, e.g., at 45.25 at. pet Ni in NiA1, approximately 8.8 pet of the lattice sites are unoccupied. Ellwood8-10 has reported similar defect structures in the aluminum solid solution alloys of the Al-Zn and A1-Mg systems and in alloys of the Au-Ni system." In Al(Zn) the (apparent) vacancy concentration rose, somewhat irregularly, to a maximum of about 2 pet vacant sites at 25 at. pet Zn, while in Al(Mg) the (apparent) vacancy concentration increased continuously to 1.7 pet at 15 at. pet Mg. An explanation in terms of Brillouin zone overlap was attempted, although Pearson12 has pointed out the difficulty of reconciling the observations with zone theory. However, the possibility of the effect being caused by the Fermi surface just touching a plane of energy discontinuity inside a prominent Brillouin zone has, in general, been accepted. In fact, Massal-ski13 has interpreted Ellwood's8 observations as confirmation of Leigh's14 theoretically predicted zone overlap occurring at approximately 2.67 electrons per atom. Unfortunately, Massalski was apparently unaware that Ellwood9 had revised his earlier results considerably, and the revised data did not confirm Leigh's analysis. Ellwood's clata were reexamined by the present authors who noted a possible correlation between the percentage defects as a function of alloy composition and the temperature interval of solidification measured from the respective equilibrium diagrams. This suggested an explanation in terms of shrinkage porosity rather than vacant lattice sites, and pointed to the desirability of reexamining appropriate alloy systems using: both Ellwood's method of specimen preparation (casting followed by wrought fabrication) and alternativ'e methods, i.e., diffusion, which might be expected to minimize, or even completely obviate, microporosity. ALLOY PREPARATION 1) Cast Allolys and Aluminum Single Crystals. Al(Ag), Al(Mg;l, and Al(Zn) alloys of various compositions up to 20 at. pet silver, 13.5 at. pet mg, and 30 at. pet Zn were prepared by melting under helium and casting into graphite molds. In the first two systems, the maximum alloying addition was quite close to the limit of solid solubility, but the possibility of transformation to a' during quenching somewhat restricted the suitable Al(Zn) composition range. The alloys were prepared from high-purity aluminum, a lot analysis showing 0.002 wt pet Cu, 0.002 wt pet Fe, and 99.996 wt pet A1 by difference. The silver, magnesium, and zinc were of 99.99+, 99.98+, and 99.998 wt pet respectively. Each composition was analyzed chemically. The as-cast ingots measured 7/16 in. diam and 5 in. length. One in. was removed from the top of the ingot, and the bottom 3 in. was machined to 0.275 in. diam; a point was also machined on the smaller diameter end. The remainder of the original ingot served as a top riser during subsequent remelting and controlled solidification. The machined ingots were now remelted using a Bridgman soft-mold technique to ensure directional solidification and, therefore, a minimum of micro-shrinkage. Alumina powder was used as mold material contained in an alundum thimble, and this crucible was placed in a helium-filled Vycor tube. The assembly was lowered through a suitable temperature gradient at approximately 0.5 in. min-l, and the risered portion of the casting was subsequently removed by sawing.

Jan 1, 1962

By A. E. Lee

THE Blackwell Zinc Co., Inc., a subsidiary of the American Metal Co., Ltd., operates a horizontal retort zinc smelter at Blackwell, Okla. The plant has 14 furnace blocks of 800 retorts each, fired with natural gas on a 48 hr cycle. Over 13,000 tons of zinc-bearing material, chiefly sulphide flotation concentrates, are treated monthly to produce slab zinc and high lead-cadmium fume. In 1942 a program of rebuilding and modernizing the smelter was started. By 1947 furnace smelting capacity had been increased to a point where roasting and sintering facilities were inadequate, and it was necessary to purchase oxidized materials to supplement sinter production. The seven 210 ft Ropp roasters and three 42 in. x 44 ft Dwight-Lloyd machines then in use had been in service at least 20 years and were in need of major rebuilding. Thus it was entirely practical to consider all new equipment and a change of method rather than rebuilding and repairing obsolete units. A study of the problem indicated that roasting as such could be eliminated and roasting and sintering accomplished in one step by a modification of the Robson process,' which had been used since the early 1930's by the National Smelting Co., Ltd., at their plants at Avonmouth, England, and Swansea Vale, South Wales. Francis P. Sinn, General Manager, Zinc Smelting Operations, The American Metal Co., Ltd., who was familiar with the practice in England, suggested the use of one large machine for the entire operation from concentrate to sinter. One step sintering appeared to best meet Blackwell's plant requirements and indicated substantial savings in labor, gas, coal, and repair costs. Choice of Machine Size The sinter machine size was set at 12x168 ft for a rated capacity of 540 tons per day. This tonnage, produced on a five day week, would meet the seven day requirements of the 14 furnace blocks. The one large machine was quoted at a lower cost than two or more 6 ft wide machines of similar total capacity. Further, the larger machine could be housed in a smaller structure and only one set of equipment for charge preparation and delivery and for disposal of sinter cake was needed. One machine on a five day week made possible a concentration of the skilled operating personnel and required less men than a plant including two or more machines and related equipment circuits. Fewer units of equipment meant less maintenance, and the two down days weekly allowed ample time to repair and, if necessary, to make up lost production. Experience had indicated better sintering quality and rates with larger masses of material, not only on wider machines, but also in deeper beds. The ratio of windbox perimeter to area for the 12x168 ft machine is 0.179, compared to 0.353 for a 6x102 ft machine and 0.617 for a 42 in. x 44 ft machine. This meant less air leakage with resulting fan power savings and less spoilage of charge along the pallet sides. Performance Initial operation of the new sinter plant was made in November 1951 and regular production attained late in December. The average product sinter output during 1952 and the first half of 1953 has been 18.2 tons per hr. The average for one month has been as high as 22.4 tons per hr. Considerable experimenting with varied operating conditions accounts in part for the below capacity — 24 tons per hr — average output, and work to further improve production rate continues. A typical sinter analyses is 66.0 pct Zn, 0.3 pct Pb, 0.1 pct Cd, 0.3 pct S, 8.0 pct Fe, 2.0 pct SiO,, 0.8 pct CaO, and 0.2 pct MgO. Use of this material has made possible increases in furnace burden and improved furnace operation over the former practice using sinter made from Ropp roasted concentrates. Better lead and cadmium elimination in sintering has permitted the furnace production of slab zinc lower in lead and cadmium. Anticipated economies of operation have largely been gained. The sinter plant is operated by seven men per 8 hr shift — one head operator, three equipment operators and three sweepers — plus one oiler on day shift only. While it has been necessary at times to operate seven days a week to produce the required sinter tonnage, the five day work week usually has been adequate. Consumption of natural gas for sinter bed ignition is 200,000 to 300,000 cu ft per day. Green Ore Sintering Practice The 30 to 31 pct sulphur content of the —200 mesh zinc concentrates is the fuel used to sinter the charge, no coal addition being required. In the feed to the machine, sufficient concentrates are added to crushed return sinter fines containing 0.3 to 0.5 pct sulphur to produce a charge averaging 5.0 to 6.5 pct sulphur. Since the return sinter used in Blackwell's practice is varied from — 1/2 to — 1/8 in., the actual sintering mixture of fine sinter and concentrates is somewhat higher in sulphur. The coarser sinter particles are too large to resinter and merely aid porosity in the sinter bed. The ratio of concentrates to return sinter in the charge ranges from about 1:4 to 1:5.5. Variations are based on the appearance of pried up bed sections, bed exit gas temperature trends, windbox suctions, and return sinter size. Sufficient sulphur must be used to obtain fritting of the charge into a soft sinter cake and to aid in the elimination of lead and cadmium. Excessive feed sulphur will result in partial slagging of the cake impairing porosity and prolonging sintering time.

Jan 1, 1954

By J. E. Hilliard, H. E. Cook

It is shown that for systems having a miscibility gap the spinodal composition (c,) in the vicinity of the critical temperature (Tc) is related to the equilibrium composition (c,) by where cc is the critical composition. This expression is exart for the limit T — Tc and is a good approximation down to (T/Tc) - 0.9. If the miscibility gap meets the composition of the pure components THE recent theoretical treatment by cahn1,2 on spinodal decomposition of solid solutions has revived interest in methods of estimating the chemical spinodal, * i.e., the locus on a binary phase By use of the appropriate expression, the spinodal can be drawn on the Phase diagram almost by inspection with an accuracy comparable to that of lengthy calculations in which a free-energy function is fitted to the phase diagram. Satisfactory agveemenf is also obtained with spinodals comPuted from experimental free-energy curves. where G is the Gibbs free energy of the homogeneous solution and c the atomic fraction of component 2, the derivative being evaluated at constant temperature (T) and pressure (P). (These subscripts will hereafter be omitted from the partial derivatives.) If experimental measurements of G as a function of c and T are available in a single-phase region above the spinodal, then these can be extrapolated to obtain a series of metastable free-energy isotherms in the two-phase region, and from these isotherms a series of spinodal compositions can be calculated. Because the value of is very sensitive to experimental errors, an elaborate analytic procedure is required for

Jan 1, 1965

By D. E. Ranta, M. W. Ganster, A. D. Ward

An ore zoning technique developed by Climax geologists during the past forty years has been used to contour drill-hole assay values on cross-sections for fourteen porphyry molybdenum deposits in western North America, including the Climax and Henderson orebodies. Detailed geological studies of these large, complex deposits are essential in determining ore controls, which are the factors most critical to the zoning of MoS2 and to conceptualizing geologic model s. The technique provides a detailed representation of the size, shape, grade distribution, and geologic continuity of the individual deposits. It demands a disciplined approach and adheres to rigorous rules while maintaining flexibility for adaptation to widely varying geologic conditions. By defining the limits that guide and control manual, computer-assisted conventional, and geostatistical reserve estimates, it exerts a strong geologic influence on the estimation process. A combination of ore zoning and geostatistical analysis of molybdenum deposits produces a significantly more accurate, precise, and defendable geologic reserve estimate than other methods.

Jan 1, 1984

By J. W. Downey, J. B. Darby, L. J. Norton

THE only previous investigation of the phase equilibria in the Ta-Pd system was reported by Greenfield and Beck.1 Their work (actually a portion of a much broader survey) was limited to the composition range 50 to 75 at. pct Ta and to a single temperature, 1000°C. The results indicated that no intermediate phases were present at this temperature. They pointed out that this was an unexpected result in view of the fact that niobium, which belongs to the same group in the periodic table as tantalum and has essentially the same atomic size, forms a o phase with palladium.' Also, tantalum in combination with rhodium,' iridium,' or platinum' stabilizes the s phase. By analogy, the Ta-Pd system would also be expected to contain a s phase. The present investigation was therefore undertaken to explore more fully the phase relationships in this system. Alloys were prepared by arc melting on a water-cooled copper hearth in an argon-helium atmosphere. The purity of the starting materials was greater than 99.9 pct. The weight losses on melting were less than 1 pct and therefore the alloys were not analyzed chemically. Specimens were wrapped in molybdenum foil, encapsulated in quartz capsules under a vacuum of at least 1 x 10-5 mm of Hg, annealed as indicated in Table I, and water quenched. Optical and X-ray metallography were used for identifying the phases present in the annealed and quenched alloys. The alloys were resistant to attack by several acids; however, a sodium cyanide electroetch and an immersion etch containing 1 part HF, 1 part HNO3, 2 parts H2SO4, and 5 parts H2O by volume were found satisfactory. The X-ray diffraction patterns were taken with a Straumanis-type Debye-Scherrer camera and filtered copper or chromium radiation. A summary of the phases found in this investigation is presented in Table I. No attempt was made to determine the composition limits of the various phases. The present results indicate that this system consists of two terminal solid solutions separated by at least four intermediate phases at the approximate compositions Ta3Pd, -TaPd, TaPd,, and TaPd3. The Ta-rich solid solution, containing less than 10 at. pct Pd at 1150°C, is in equilibrium with a o phase which is stable in the vicinity of 25 at. pct Pd. The latter phase is also in equilibrium with a bct phase at the equiatomic composition. At high temperatures it appears that the Pd-rich solid solution extends to at least 66.6 at. pct Pd and is in equilibrium with the bct phase. When annealed at 900°C, a sample containing 66.6 at. pct Pd transformed to an unidentified phase designated as X. An X-ray diffraction pattern of this phase contained sharp low-angle lines while the high-angle lines were characteristically diffuse. The observed d-spacings and relative intensities for lines in the low-angle region are presented in Table 11. In the vicinity of 70 at. pct Pd an intermediate phase having the TiA13-type structure is formed. It is stable to at least 1100°C, and presumably dissolves congruently into the ter-

Jan 1, 1963