Search Documents

By C. A. Heiland

NOT only has the demonstration of progress in all fields of science been characteristic of the Chicago "Century of Progress," but the manner in which the fundamentals of these sciences have been displayed captivated the visitor's eye and ear at the same time. The average individual is interested most in progress which concerns his every-day life. He is fairly well educated in medicine, biology and certain aspects of physics. But how raw materials and chiefly minerals occur, how they are located, taken out of the ground and refined, is something which appears to be more remote from the every-day line of interest, and about which, therefore, the public knows comparatively little. This is particularly true of the oil industry, although it ranks in size second only to agriculture in the United States. In appreciation of the tremendous educational value which a complete exhibit on all phases of the mineral industries would have, both mining and metallurgical as well as oil inter¬ests took steps early to make these exhibits at Chicago a reality. The board of directors of the A. I. M. E. authorized an advisory committee to the Museum of Science and Industry early in 1932. It is divided into four subcommittees - for geology and petroleum, for metal mining, for coal mining, and for metallurgy respectively. The entire committee held its first meeting in Chicago on April 11 and 12, 1932, to advise with the Museum's officials and experts about the most advantageous arrangement of the minerals industries' and geology exhibits.

Jan 1, 1933

By THOMAS LEONBRD WATSON

I. INTRODUCTION. THE results embodied in this paper are based on a careful field- and laboratory-study of the lead- and zinc-deposits of the Virginia-Tennessee district, begun in the latter part of the summer of 1904 and completed in the spring of 1905, preparatory to the publishing of a State report .on them. A separate description of the individual deposits in Virginia is purposely omitted, since I have already described them in considerable detail in a State report. The Tennessee deposits are described here in some detail for the reason that no detailed record of them has yet been published. Practically, this paper summarizes the results obtained from a study of the geology of the ore-deposits of the district as, a whole. (I had the pleasure of visiting the deposits of Virginia and Tennessee with Dr. H. Foster Bain of the U. S. Geological Survey, in April, 1905. Figs. 21 and 22 are from photographs taken by Dr., Bail.) II. HISTORICAL. . The first authentic records of lead-mining .in Virginia date hack more than 150 years; and the old lead-mines at Austinville, on New river in Wythe county, V a., were the first to be worked. Colonel Chiswell, a native of Wales, and one of the earlier adventurers in southwestern Virginia, was one of the first operators of the Austinville mines. Chiswell's operations at Austinville commenced in the year 1750, and closed shortly after the beginning of the Revolutionary War, in the' year 1776, covering a period of about 25 years. From that time to the present, mining has been carried on almost continuously in the Virginia area. For many years after the Virginia mines were operated, mining was confined exclusively to the lead-ores. The zinc-ores

Mar 1, 1906

By P. D. Rao, H. B. Charmbury, D. R. Mitchell

As a result of a changing market pattern for anthracite, there is now an increasing demand for steam size and a decreasing demand for domestic sizes. To help the producer meet this new demand, the authors present the technical aspects of the problem of crushing domestic sizes to steam fineness and size. The market pattern for anthracite coal has changed considerably in recent years. The demand for domestic sizes has been gradually decreasing and the demand for the steam sizes has been increasing. The companies however aim for a maximum production of domestic sizes, since these sizes command premium prices. To meet the market demands, particularly in certain periods of the year, further size reduction of the coarse clean coal is necessary. The present practice of multistage crushing in toothed rolls leads to complicated flow arrangements and is high in cost. Data presented herein indicate that crushers with high reduction ratios could be used with a resulting simplification of crushing flows and an appreciable reduction of capital and operating costs. The different types of crushing equipment investigated included the rotary-type breaker, the jaw crusher, the impactor-type crusher, and the Aerofall mill. CURRENT PRACTICE The standard sizes of anthracite are presented in Table I and market specifications require that any given size be maintained with only a limited amount of oversize and undersize material. The 1958 prices of the various sizes also are presented, so it may be seen that size reduction is only performed when dictated by market demands. At the present time the general practice of crushing anthracite consists of removing the top size and crushing it in a toothed double roll crusher to the next largest size. Consequently, to reduce the domestic egg, stove, and nut sizes to steam sizes of pea, buck, rice, and barley, the original material must be screened to produce the three top sizes and each size must be crushed in three separate rolls to the next largest size. Each crushed product must then be rescreened to remove the oversize for re crush ing. Thus a typical operation would consist of scalping the egg size from a mixture, crushing it to stove size, and rescreening the product. This same cycle would be repeated for the stove and nut sizes requiring three screens and three crushers as well as conveying equipment to handle the crushed products. This results in an expensive series of operations to make a product which sells for a lower price. If the three top sizes are crushed in one operation to the smaller sizes then the yield of steam sizes is low and the production of Nos. 4 and 5 sizes is large. These sizes sell for lower prices than the steam sizes. A typical operation is presented in Fig. 1. From the figure it may be seen that the original cleaned anthracite contains 67.4 pet domestic sizes, 26.4 pct steam sizes, and 6.2 pct fines. After multistage crushing of the domestic to steam sizes the composition of the product is 0.6 pct domestic sizes, 89.6 pct steam sizes, and 9.8 pct fines. From a technical standpoint these results are reasonable but the handling and crushing costs are

Jan 1, 1961

By C. Edwin Nighman

THE following is a description of the methods used in rescuing men and extinguishing the underground fire at the Pennsylvania mine, Butte, Mont. This fire, which cost the lives of 21 men, began about 9 p.m., Feb. 14, 1916, at or near a ventilating fan on the 1,200 air-shaft station. This shaft at that time was downcast, while the main hoisting shaft was upcast. Owing to the proximity of the fire to the air shaft, the air in the latter soon became heated, and as the fan on the level was not running¬the power having been cut off shortly after the outbreak' of the fire-the aim' shaft became upcast to the 300 level. At this point a blanket of cold air from the surface caused the smoke and gases to he drawn in on that level and carried down again through the workings to the 1,200. A short time after the discovery of the fire, water was turned down the air shaft through a series of pipes around the collar of the shaft, which caused the smoke to recede, below the 300, so that within 2 hr. it was possible to search that level for the missing men. From the above it will be apparent why the air shaft was upcast instead of downcast as under normal conditions, and why men were suffocated at considerable distances from the seat of the fire. The smoke and gases that came up the main hoisting shaft did not diffuse through the workings to any extent. There are doors on all levels in the connections to the main hoisting and air shafts, but-in the confusion and running around many of these doors were left open, and this undoubtedly caused the smoke and gases to spread more rapidly than they would otherwise have done. It was necessary for most of the men on the various levels to pass close to the air shaft in going to the hoisting shaft, and when they encountered the smoke and gases in that vicinity a number turned hack and climbed down with the direction of the air currents and were then suffocated, while all those who passed through the relatively short pall of smoke to the main shaft were saved.

Jan 2, 1917

By Voyle R. McFarland, Robert A. Burmeister, David A. Stevenson

The distribution of lead between phases in the Ag-Sb-Te system was studied using microautoradio -graphy. Two compositions were investigated, both containing an intermediate phase Known as silver antimony telluride as the major phase, and one containing AgzTe and the other SbzTes as the minor phase. For both compositions, two thermal treatments were used: nonequilibrium solidification from the melt and long equilibration anneals of the as-solidified structure. For each composition, lead was segregated in the minor phase of the as-solidified structure, but was distributed in the matrix after anneal. The electrical resistivity and carrier type were insensitive to the distribution of lead in the two-phase structure. ThERE has been considerable interest in the Ag-Sb-Te system because of its thermoelectric properties. The major interest has been in compositions on the vertical section between AgzTe and SbzTes, particularly the 50 mole pct SbzTes composition AgSbTez (compositions are conveniently expressed as mole percent SbzTes along the AgzTe-SbzTes section). One of the major problems in the proper evaluation and utilization of this material is the inability to control the electrical properties through impurity additions: all alloys prepared to date have been p-type, even with the addition of large amounts of impurities. It has been shown Wit all the compositions previously studied contain an intermediate phase of the NaCl st'ructure as a major phase (denoted by b) and a second phase, either AgzTe or SbzTe3, as a minor phase.'-3 One explanation for the unusual electrical behavior of this material is that the impurity additions have a higher solubility in the second phase than in the matrix; the impurity would segregate to the second phase, leaving the bulk matrix essentially free of impurity.4 In order to investigate this mechanism with a specific impurity element, the distribution of lead between the two phases was determined using autoradiography. Lead 210 was chosen because of the suitability of its 0.029 mev 0 particle for autoradiography and also because of the interest in lead as an impurity in this system.5'6 EXPERIMENTAL PROCEDURE Two compositions were taken from the vertical section between AgzTe and SbzTes, 50 mole pet SbzTes (Viz. AgSbTez) and 75 mole pct SbzTes, in which AgzTe and SbzTes appear, respectively, as the minor phase. Lead containing radioactive lead (pb210) was added to the above compositions to provide a concentration of 0.1 wt pct Pb. The material was placed in a graphite crucible in a quartz tube which was then evacuated and sealed. The samples were melted and solidified by cooling at a rate of 8°C per min and then removed and prepared for microa~toradiography. After autoradiographic examination of these samples, they were again encapsulated and annealed in an isothermal bath at 300°C for a number of days and prepared for examination. An alternate method of preparation employed a zone-melting furnace; the molten zone traversed the sample at a rate of 1.2 cm per hr and the solid was maintained at a temperature of 500°C both before and after solidification. This treatment had the same effect as solidification at a slow rate followed by an anneal for several hours at 500°C. In order to obtain the best resolution, thin sections of the alloy were prepared by hand lapping to a thickness of approximately 20 p. Other samples were prepared for examination by lapping a flat surface on the bulk sample. The resolution, although somewhat better in the former procedure, was adequate in both instances and the majority of the samples were treated in the latter fashion. A piece of autoradiographic film (Kodak Experimental SP 764 Autoradiographic Permeable Base Safety Stripping Film) was stripped from its backing, care being taken to avoid fogging due to static-electrical discharge. A small amount of water was placed on the sample, the film applied emulsion side down on the surface of the sample, and the sample and the film dipped into water in order to assure smooth contact. After drying, the film was exposed for 2 to 5 days, the period of time selected to give the best resolution. The film was developed on the specimen and fixed and washed in place. Two major factors must be considered in establishing the reliability of an autoradiograph: the in-

Jan 1, 1964

By David A. Summers, John Corwine, Li-King Chen

The results from fracturing plexiglas beams are combined in eight existing equations to determine the surface energy of the material. The reliability of each equation is tested, and the equation in use to determine fracture toughness is found to be the most exact. This equation is then used in determination of the surface energy of Barre Granite.

Jan 1, 1971

By G. A. Parks, C. Kovacs

The xanthate flotation of chrysocolla can be improved by preheating the ore to 500° to 600°C. Addition of water vapor reduces the preheating temperature required. The temperature range of flotation improvement correlates well with the range over which dehydroxylation occurs. This observation is consistent with changes in the structure and properties of the mineral as detected by measurement of solubility, D.T.A., T.G.A., X-ray diffraction, and infrared absorption and with recently proposed explanations of chrysocolla flotation. A brief experiment by one of the authors several years ago showed that exposure of chrysocolla to high temperature water vapor resulted in increased recovery by subsequent xanthate flotation. Recently renewed interest in flotation and thermal properties of chrysocolla1-5 prompted further study of this effect and more detailed reporting.6 This paper explores the response of pure chrysocolla recovery in Hallimond tube flotation tests to the time and temperature of exposure and to changes in the water vapor pressure. Brief attention is paid to the effects of such treatment on accessory minerals. A single experiment with flotation of chrysocolla from an ore is reported. MATERIALS Chysocolla from Inspiration, Gila County, Ariz. was crushed in a porcelain mortar, cleaned of visible and magnetic impurities, and screened to obtain -48 +65 mesh (Tyler) material for flotation test work. The clean material contained 28.5% Cu and was identified as chrysocolla by comparison of X-ray diffraction, D.T.A., and infrared absorption data with that reported for similar materials by others.4,5,7 Samples of malachite and chalcopyrite, prepared in a similar way, were also identified by X-ray diffraction. The sources of these materials are unknown. A sample of chysocolla-bearing oxidized copper ore from Pima, Ariz. was crushed and dry ground for thermal activation and subsequent flotation. PROCEDURES Activation: The apparatus used for exposure of materials to high temperature water vapor is illustrated in Fig. 1. The furnace temperature was controlled to ±5°C Water vapor pressure was controlled by pre-saturating a nitrogen carrier stream with water in an adjustable thermostatted saturator (multiple bubbler). A water manometer and capillary orifice flow meter were used to measure nitrogen flow rates for activation and for subsequent Hallimond tube tests. Gas flow rate and temperature were adjusted prior to introduction of samples. Exposure time was measured from the moment of introduction of the sample to the furnace, hence includes an initial drop below the control temperature. After heating, the samples were removed from the furnace and stored at room temperature in air. Representative samples of activated materials were examined by X-ray diffraction and infrared absorption.

Jan 1, 1967

By A. G. Guy

Thermodynamic activity rather than chemical composition is basic to the analysis of diffusion. This is the essential conclusion reached by Darken1-3 and by Birchenall and Mehl.4 If so, it is reasonable to expect that diffusion calculations should be carried out using activities. This paper will illustrate a method of employing activities in analyzing interstitial diffusion. For interstitial diffusion (of carbon in iron and probably generally) the diffusion of the solvent atoms, volume changes, and other such complexities not explicitly provided for in the usual diffusion equations cause a negligible error of the order of 1 pct. Therefore it is relatively easy to test the validity of an analysis based on activities in the instance of interstitial diffusion. The mathematical treatment of the more complex substitutional diffusion could be simplified once the adequacy of the activity method had been established for substitutional diffusion. Thus the present work has the purpose not only of providing a superior analysis of interstitial diffusion but also of indicating a possible approach to the more important question of an adequate treatment of substitutional diffusion. Development of the Diffusion Equation Although activities are convenient quantities to determine experimentally, they are derived from the more fundamental fugacities.9 Possible confusion in using activities can be avoided by basing equations involving their use on the relationship, dP = -D1d/ax dt [I] where, dP = the number of grams of solute crossing one cm2 in the time dt sec. D, = the diffusion constant for use with fugacities; it is assumed to be constant at a given temperature, and has units of secs. f = the fugacity of the solute in the solid solution; the units are those of pressure, dynes per cm2. x = the distance in cm. Eq 1 can be considered to be the basic form of the first Fick Law for one-dimensional diffusion. In order to convert Eq 1 into an equation involving activities, a choice of a standard or reference fugacity, f°, must be made: then. a = f [2] where a is the activity corresponding to the fugacity f. However, the value of a is also determined by the relation, a = a\c [3] where a is the activity coefficient and c is the concentration. For a given value of a (such as a = 1) it is evident that the units used for expressing concentration will affect the numerical value of a corresponding to a given amount of carbon dissolved in y-iron. Since weight per cent concentration is so widely used, this unit will be adopted as the standard in this paper. When the value off given by Eq 2 is substituted in Eq 1, the first Fick Law becomes, dP= -D,f°dl [4] Since D,f° is constant (at a given temperature), the second form of Fick's Law can be obtained in the usual manner, -dt D'f° dx [5] where c' is the concentration in g per cm3. In terms of weight per cent concentration, c, Eq 5 becomes, dc _ 100 d2a Tt = T /f w [6] where p is the density of the solid solution and will be assumed to be constant. In order to simplify Eq6, it is necessary to consider the standard state, f°. Standard states are chosen for convenience. There appears to be one especially convenient choice for the analysis of interstitial diffusion. If the activity coefficient, a, is set equal to unity at infinite dilution of the solute, 100 then — 100D1fl° is approximately equal P to the usual diffusion constant in dilute solutions. This is true since the activity, a, in Eq 6 can be replaced by the concentration, c, with little error in an infinitely dilute solution.* Here f1° is the standard fugacity necessary to achieve this standard state. It is proposed that a diffusion constant Da' be defined, Da1=100/pD1f1° [7] where A is the metal whose diffusion is * The second derivative of a is equal to the second derivative of c in dilute solution only if -da/dr- is. zero. Although theory does not require this condition, in the systems C in Fe, and Zn in Cu, dc is in fact found to be essentially zero.

Jan 1, 1950

By R. S. Archer

SILICON is one of the most important elements in the metallurgy of aluminum. It is always present in small amounts in the ordinary grades of "pure" aluminum, and hence in all alloys made therefrom. Within the last few years binary alloys containing up to 13. per cent, of silicon have come into extensive use for castings. Silicon is also added, beyond the amount present as an impurity, in alloys containing one or more other elements such as copper, manganese, magnesium and nickel. The binary aluminum-silicon alloys are not yet heat treated to any extent in commercial practice, although, as will be shown, their properties are affected to a very considerable degree by heat treatment. There are other aluminum alloys that develop higher strength, but the special characteristics of the silicon alloys may well lead to the application of heat-treating processes on a commercial scale. The role of silicon in the heat treatment of aluminum alloys is more important than would be indicated by consideration of the binary alloys alone, because many of the alloys that are heat treated in regular commercial practice contain some silicon in addition to that derived from the aluminum ingot as an impurity. Among these may be mentioned the heat-treated 195 alloy castings, and the wrought alloys 258, Special 178 and 51S of the Aluminum Co. of America, and the German wrought alloy, Lautal. It is the purpose of this paper to present the results of experimental work and the conclusions derived therefrom regarding the heat treatment of the binary aluminum-silicon alloys. The products heat treated included forgings, chill castings and both "normal" and "modified" sand castings.

Jan 1, 1927

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.'-' This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,' by the copper-decoration technique,' by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18'19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965

By C. L. Pillar

INTRODUCTION The location, size, character of the ore de- posit and its adjacent formations will deter- mine the mining system best used for its ex- traction. The mining system chosen will have to be engineered to suit the ore deposit and the people that will extract it. What can be done in the Philippines cannot always be accomplished in the upper Northwest Territory of Canada. Mining operations developed under a free enterprise system are planned to achieve a satisfactory return on the capital required to place them into production. Hence, the choices made in planning and developing the mining system must be dictated by sound economics. The mining system planned must favor: 1. Maximum ore extraction of the deposit with minimal grade dilution. 2. The amount of capital expenditure used to develop and equip the mine must be in harmony with the financial policy of the group yet be sufficient to provide a reliable mining system. Excessive frills and extras that are not required for efficient, safe production should not be provided. 3. Mine production costs are determined by the amount of men, material, equipment and energy used in the production process. These must be kept to minimal limits in order to insure dependable, low cost production. Extras that later are needed in the production operation can be added as required by the operator. Basically block caving is a mining system that is normally used to extract deep seated, massive, low grade deposits of copper, molybdenum and iron where stripping ratios for open cast mining are economically prohibited. The caving system is limited in its selectivity. It is a mass production type of underground ore extraction that under favorable conditions is one of the most efficient, low cost mining systems in the world today. Usually block cave mining systems are large. They are capable of producing ore at a rate of 10,000 to 100,000 tons/day from large deposits at costs that are comparable with many open cast mining systems burdened by high waste to ore ratios. Block cave mining systems differ basically in the plan of the area layout, the method of undercutting and the method of draw. The balance of the mining system is the mechanical transportation of the drawn ore to the surface, the mine supply, drainage and ventilation systems. This paper deals mainly with the methods of draw. The method of draw to be used in a block caving system dictates the development plan of the mining area, is highly influential in the method of undercutting to be employed and the supply and ventilation system to be used. There are three basic methods of draw commonly used in today's operations. They are: Gravity draw Slusher draw LHD draw The type of draw planned will have a major affect on: Capital expenditure and time required to bring a deposit into production. Productivity, efficiency and cost of the production operation. Percent recovery of the ore deposit in both tonnage and grade. Degree of production reliability Fundamentally the type-of draw used must be compatible with the physical characteristics of the deposit to be extracted and the financial position of the mining operation. The type of draw chosen must work to advantage with the size, configuration, depth, strength and fracture pattern of the deposit and its adjacent formations. It must favor the financial protection of the planned mining operation. A Gravity Method of Draw requires a finely fragmented, easy flowing product from the caving action of the deposit. To obtain the desired economic advantage the ore deposit must also have sufficient area and height of column to permit minimal development cost on a per ton basis. The gravity system re- quires the maximum amount of development openings and uses the minimum amount of mechanized equipment of all the caving systems. It is unskilled, labor-intensive and is highly sensitive to size of ore fragmen-

Jan 1, 1981

By Ross C. Anderson, William I. Weisman

THE manufacture of anhydrous sodium sulphate or salt cake from natural deposits in the United States has been in general somewhat of a marginal undertaking. Competition from foreign sources and from large quantities of byproduct sodium sulphate produced domestically in the manufacture of hydrochloric acid and other chemicals has existed and continues. For example, most of the sodium sulphate produced is a byproduct or co-product in the manufacture of hydrochloric acid through the reaction of sodium chloride with sulphuric acid. In recent years, many manufacturers of rayon have installed equipment to recover sodium sulphate from waste spin bath liquors; today this is an important source. Before World War II large quantities of sodium sulphate were imported from Germany. In 1949 imported material from Europe again appeared on the domestic market. Natural sodium sulphate from Canada in substantial quantities also enters the United States markets. Despite this kind of competition, numerous attempts have been made to exploit various natural deposits of sodium sulphate in this country, but only a very few of these have survived economically over a period of years. One of these few operations is the plant of the Ozark-Mahoning Co. located 13 miles south of Monahans in West Texas. Several factors contributing to the successful life of this plant may be summarized as follows: 1—Geographical location. Monahans is reasonably close, freightwise, to the Kraft paper mills in Texas, Arkansas, and Louisiana; the Kraft paper industry is the greatest consumer of sodium sulphate in the United States. 2—Availability of natural gas as low cost fuel. Proximity of the natural gas fields of West Texas has been a tremendous asset, as the availability of low-cost natural gas is to all industry throughout the Southwest. 3—The nature of the deposit. The occurrence of sodium sulphate brines in southeastern New Mexico and West Texas has been very well described by Lang,' who writes that the brines are found in the Castile formation of the Delaware basin. Here weathering has altered the anhydrite so that a relatively porous gypsiferous zone overlies a dense impervious mass of anhydrite. This porous zone provides traps where percolating ground waters that have picked up soluble salts may lodge. These traps or pockets are the natural brine reservoirs exploited at Monahans. Although several hundred wells have been drilled, currently some 25 wells serve to supply brine to the plant. All are within 1 1/2 miles of the plant and are conveniently tied together by an electric power system serving electric motors driving the pumps. Having the raw material in the form of a brine which can be pumped from shallow wells makes possible much simpler and more efficient handling than if it were in form of solids. By contrast, other deposits of sodium sulphate, such as those in Arizona, Nevada, and North Dakota, are in the form of the solid minerals, thenardite and mirabilite, which present somewhat more of a mining and mineral dressing problem.' The largest producer of sodium sulphate from natural sources in the United States is at Searles Lake, Cal., and there a brine also is utilized. 4—Water. Substantial quantities are needed for cooling towers and for operation of gas engines. An area underlain with brine is not a promising source of fresh water, but fortunately, after a long search, an adequate supply was found nearly two miles from the plant. It may be appropriate to discuss briefly the grades of sodium sulphate offered on the market. Salt cake is the name usually applied to the grade of sodium sulphate used by the Kraft paper industry. It may be a low analysis byproduct, 95 to 97 pct sodium sulphate, with as much as l 1/2 to 2 pct residual acid, or it may be a natural product. Usually salt cake is considered a low grade product, but a great deal of a higher grade of material is marketed under this name. The specifications for glassmakers' salt cake are somewhat higher than those of the paper industry, usually requiring 98 pct sodium sulphate. Technical anhydrous sodium sulphate is a high grade material and usually exceeds 99 pct sodium sulphate. It finds the biggest market in the textile industry and is used as a builder in some synthetic detergents. Glauber's salt, Na2SO4. 10H20, is usually of high purity. Preferred for some uses, it normally has been recrystallized from an anhydrous salt. A unique manufacturing process has been developed at Monahans. This process results in the production of an exceptionally high grade of salt cake, and qualifies for nearly all uses, including many which specify the technical anhydrous grade. All of the finished product, which is very white, passes a 10-mesh U. S. Standard screen, and is retained on a 200-mesh U. S. Standard screen. It is over 99 pct Na2SO4 with main impurities being sodium chloride and magnesium sulphate. Iron content is less than 0.01 pct. As mentioned, the raw material at Monahans is a brine drawn from wells. Attention was first attracted to this location because a so-called alkali

Jan 1, 1954

By L. L. Gray, D. W. Reed, F. Morgan

A flowMeter has been developed at Gulf Research and Development Co. and tested in the field for measuring the flow of gas in well bores. It has been used in a study of the injection capacity of different horizons in gas injection wells in Oklahoma. The flow sensitive element of the meter is a semi-conductor having a very high temperature coefficient of resistance. Advantages possessed by this meter are the result of that property and the high specific resistance of the element. The instrument possesses a sensitivity considerably higher than any reported previously. In the application described here the element is heated to a temperature considerably above ambient by an electric current, which is supplied by a voltage source at the surface. When fluid flows through the meter the rate of dissipation of heat is increased and the temperature of the element decreases. Because of the negative temperature characteristics of the resistance element such a decrease of temperature will be accompanied by an increase of resistance which, under flow conditions ordinarily found in wells, is of such a magnitude that it can be directly measured or recorded in terms of a change in voltage at the surface. In practice, rate of flow is measured in terms of the drop in voltage in the resistance element. All the metering and control apparatus remains at the surface while the thermal element is lowered into the well on a single conductor cable, consisting of an insulated wire and sheath. The meter is calibrated by passing known quantities of gas through it either at the surface or in the hole at a point immediately above the region in which gas is lost to the formation. In case calibration is made at the surface, the ambient temperature in the hole may readily be obtained by a second resistance element which is operated at a current so low that effectively no heating occurs. The instrument has been adapted to con-tinuous recording, but the velocity of the meter relative to that of the gas must be low unless corrections are made. Curves giving data obtained in actual field tests are shown' The meter can also be used to determine the distribution of flow capacity in a gas producing well. A differential form of the meter has been designed and built in which the local flow or injection capacity of the formation is obtained directly. Introduction When fluid is injected into a well in a secondary recovery or pressure-maintenance operation the question of its most effective use invariably arises. Although the core log, when available, will show the regions of good permeability and oil saturation, there is normally no assurance that the fluid actually enters the formation in zones where injection is deemed desirable. In view of the uncertainties involved in such programs, it is generally conceded that measurements of permeability for a formation in place are more significant than those obtained by the core-sampling technique. A subsurface meter has been developed at the Gulf Research and Development Co. for measuring flow of fluids at different horizons in a well bore, and field tests have been made on the instrument in Cooperation with the Tulsa Division of the Gulf Oil Corp. In this paper the meter is de-

Jan 1, 1948

By F. Morgan, L. L. Gray, D. W. Reed

A flowMeter has been developed at Gulf Research and Development Co. and tested in the field for measuring the flow of gas in well bores. It has been used in a study of the injection capacity of different horizons in gas injection wells in Oklahoma. The flow sensitive element of the meter is a semi-conductor having a very high temperature coefficient of resistance. Advantages possessed by this meter are the result of that property and the high specific resistance of the element. The instrument possesses a sensitivity considerably higher than any reported previously. In the application described here the element is heated to a temperature considerably above ambient by an electric current, which is supplied by a voltage source at the surface. When fluid flows through the meter the rate of dissipation of heat is increased and the temperature of the element decreases. Because of the negative temperature characteristics of the resistance element such a decrease of temperature will be accompanied by an increase of resistance which, under flow conditions ordinarily found in wells, is of such a magnitude that it can be directly measured or recorded in terms of a change in voltage at the surface. In practice, rate of flow is measured in terms of the drop in voltage in the resistance element. All the metering and control apparatus remains at the surface while the thermal element is lowered into the well on a single conductor cable, consisting of an insulated wire and sheath. The meter is calibrated by passing known quantities of gas through it either at the surface or in the hole at a point immediately above the region in which gas is lost to the formation. In case calibration is made at the surface, the ambient temperature in the hole may readily be obtained by a second resistance element which is operated at a current so low that effectively no heating occurs. The instrument has been adapted to con-tinuous recording, but the velocity of the meter relative to that of the gas must be low unless corrections are made. Curves giving data obtained in actual field tests are shown' The meter can also be used to determine the distribution of flow capacity in a gas producing well. A differential form of the meter has been designed and built in which the local flow or injection capacity of the formation is obtained directly. Introduction When fluid is injected into a well in a secondary recovery or pressure-maintenance operation the question of its most effective use invariably arises. Although the core log, when available, will show the regions of good permeability and oil saturation, there is normally no assurance that the fluid actually enters the formation in zones where injection is deemed desirable. In view of the uncertainties involved in such programs, it is generally conceded that measurements of permeability for a formation in place are more significant than those obtained by the core-sampling technique. A subsurface meter has been developed at the Gulf Research and Development Co. for measuring flow of fluids at different horizons in a well bore, and field tests have been made on the instrument in Cooperation with the Tulsa Division of the Gulf Oil Corp. In this paper the meter is de-

Jan 1, 1948

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969

By Franklin G. Pardee

IN 1920 the Minnesota Tax Commission estimated a reserve of 1,341,674,538 long tons of iron ore in Minnesota, the Michigan State Tax Commission report showed 199,092,855 long tons in reserve in that state, and the Wisconsin Geological Survey set the Wisconsin reserves at 21,500,000 long tons. The total reserve that year for the Lake Superior District amounted to 1,562,267,393 long tons. Ten years later the reserves of iron ore in these same districts were Minnesota 1,235,227,510, Michigan 168,349,823, and Wisconsin 23,000,000, or a total of 1,426,577,333 long tons. The decrease in ore reserves in this ten-year period was 135,690,060 long tons, but the shipments were 520,746,975 long tons. In other words, the ten-year depletion in reserves was only 8.68 per cent. If similar conditions carry into the future this calculation would indicate a life for the ore reserves of the Lake Superior region of over 100 years.

Jan 1, 1933

By L. R. van Wert

CAREFUL research into the nature of the metallic state has yet to discover, with any certainty, its essential quality. We do riot yet know, for sure, what it is that makes the metallic elements different from, if not actually unique among, all created things. We do know, of course, that metals have certain more or less characteristic properties-they are hard, strong, and tough, and good conductors of heat and electricity, and these so-called metallic properties provide a definition of a sort. How- ever, it is the structure rather than the behavior of the metals which gives the really fundamental information necessary to the understanding of metallicity. But this information is not easily obtained. Nature has a way of keeping secrets. But happily we do possess some knowledge of how a metal is built up, and it is this matter, rather than the presentation of a formal definition, that will be discussed here.

Jan 1, 1937

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By Tomek Ulatowski

INTRODUCTION In 1974, Industrial Miners Mexico, S.A. (IMMSA), agent for the borrowers, was the largest privately-held mining, smelting, and refining company in Mexico (accounting for 32% of Mexico's nonferrous metal and coal production in 1974), the fourth largest company in terms of sales, and the second most profitable company in Mexico, excluding government wholly-owned and operated industries. The company was engaged in the mining, smelting and refining of coal, copper, fluorite, gold, lead, silver, zinc and related by-products for domestic consumption and export. A combination of favorable factors led IMMSA to propose an investment plan amounting to US$286 million for 1974 through 1978, of which US$150 million was to be financed. These factors included: Substantial profits in 1973 and 1974 Positive near-term outlook for metal prices Success of the reinvestment program in increasing productivity Substantial additions to proved reserves during 1973-1974 and Fiscal incentives provided by the Mexican government to stimulate investment in the mining industry. The primary purpose of the investment program was to construct a new electrolytic zinc refinery and to expand and modernize many of the company's existing mining and refining facilities. THE BORROWER Company History Compania Miners Mexico, S.A. was incorporated in the city of Monterrey in 1918 as a wholly-owned subsidery of ASARCO Inc. (formerly American Smelting and Refining Company, New York) for the purpose of mining and processing non-ferrous metals and related products. In compliance with the Government's Mexicanization program, ASARCO Inc. divested itself of 51% of its equity in Compania Miners Asarco, S.A. on June 30, 1965. Subsequently, ownership in the divested share was apportioned as follows: 15% ownership in Compania Miners Asarco, S.A. to a group of private investors, and 36% in trust for subsequent public sale. The company's name was changed to Asarco Mexicana, S.A. in 1965. Mexican ownership in Asarco Mexicans, S.A. was increased to 51% in 1967, following the purchase of the 36% share ownership held in trust, and then to 66% in 1974 when ASARCO Inc. divested itself of an additional 15% of its holdings in Asarco Mexicans, S.A. Following its 1974 divestiture of 15% of Asarco Mexicans, S.A., ASARCO Inc's ownership in Asarco Mexicana, S.A. was reduced to 34%. In 1974, the company changed its name for the second time to Industrial Miners Mexico, S.A. (IMMSA). Fiscal Agreement IMMSA entered into a fiscal agreement with the Mexican government in 1969. The agreement, which was renewed in 1974, provided for 100% of the production and export tax corresponding to the federal government with a minimum of 50% of the amount refunded to be reinvested in fixed assets. Further, the agreement permitted the company to

Jan 1, 1985

By M. L. Brashears

IN the last 15 years industrial use of ground water has more than doubled, and in 1951 amounted to 5 billion gallons per day. A similar sharp increase in the utilization of ground water for irrigation and public-water supply occurred in the same period. In many areas rapid increase in withdrawal from wells has taken place almost entirely unhampered by regulatory control and with little or no integration of effort. As might be expected, the chief interest in many regions has been maximum production rather than sustained perennial yield. As a result, widespread depletion of underground reservoirs and deterioration of the quality of the water stored in them has taken place in many areas, even though total pumpage in the United States is far below ultimate potential. Of even more concern is the fact that excessive withdrawal has drawn salt water into the reservoirs beneath many heavily populated centers along the Atlantic, Gulf, and Pacific coasts, causing costly abandonment of pumping plants.' Many hydrologists expect that consumption of water will rise rapidly in the near future, and some predict that industrial requirements will more than double in the next decade.2,3 Thus it appears likely that the draft on many already heavily pumped underground reservoirs will be greatly increased and the search for additional sources of usable ground water intensified in years to come. In view of this, industry as a whole will be forced more and more to recognize the potentialities and limitations of ground-water reservoirs and to utilize them more effectively to prevent costly water shortages and disruption of production. Through painful experience, some industries are already well aware of the need for effective water utilization, and have managed individually or through joint effort to check trends threatening to deplete underground reservoirs completely or to impair the quality of the water. Various remedial measures have been used to bring about successful management of local or regional ground-water resources. Of these, replen-ishment of aquifers by recharge wells or basins has played an important role in overcoming some ground water problems. Artificial recharge of underground reservoirs by water spreading has been practiced successfully in the United States for many years. In the West it has become an important method of salvaging flood run-off for irrigation of crops and maintenance of public water-supply reserves, and it is used to some extent in parts of the East. Artificial recharge by means of wells, on the other hand, is a relatively new development. Until recently it was employed in only a few areas, principally along the East coast. For the last few years, in the ever increasing search for additional water supplies, industry has had greater recourse to this method. Utilization of recharge wells to control the temperature and quality of underground water supplies is also being considered seriously. Operation of recharge wells, like water spreading, is governed largely by local conditions. It requires water relatively low in turbidity, whereas in some areas water spreading has been used successfully with water of high turbidity and silt content. However, water spreading must be employed in large areas and can be carried on effectively only where aquifers crop out at the surface. Recharge wells can be used in limited space. Recharge wells are similar to production wells except that the water flows in the opposite direction. Thus any water-bearing bed that will yield water to wells may be recharged by wells. Often, however, the water available for recharge is of a different character and temperature from that existing in the ground-water reservoir and if transmitted directly underground from a recharge well to a production well might require expensive or difficult treatment before it could be used. Fortunately the physical characteristics of reservoir beds, which control the movement and behavior of ground water, are generally not homogeneous. Moreover, the movement of ground water is very slow because of the frictional resistance of the reservoir beds. By taking full advantage of hydrologic and geologic conditions, it is therefore possible in many instances to bring about favorable changes of temperature and dilution as the water moves from the recharge wells underground to the production wells. Furthermore, if the natural quality or temperature of ground water is unfavorable for industrial purposes, recharge wells may be used to introduce water of more favorable quality or temperature into the ground-water reservoir. When water is discharged into a recharge well, the head in the well is increased. Because of this, a cone of elevation is produced on the water table or the artesian pressure surface in the area surrounding the well. The cone of elevation is similar to the cone of depression produced around a pumping well except that the apex of the cone is above the water table or artesian pressure surface. Thus if a recharge well and a production well tapping the same water-bearing bed are close together, as would be the case at many industrial plants, some of the water discharged from the recharge well would be drawn into the production well within a short time. Under such conditions it is apparent that water of unfavorable temperature and chemical characteristics should not be used for recharging. The more important ground-water reservoirs in the United States often consist of alternating layers of impermeable beds and porous material that will yield water readily to wells. Physical characteristics of individual beds in a ground-water reservoir may not persist over great distances, the impermeable layers grading into beds that will yield large quantities of water. Thus the water-yielding material in underground reservoirs, whether large or small,

Jan 1, 1954