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By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By C. S. Matthews, W. R. Strickler, M. Prats

To gain an insight into the deviations from normal behavior caused by dip. a mathematical study has been made of single-fluid five-spot floods in dipping reservoirs for flooding techniques likely to be employed in such cases. Streamline patterns and sweep eficiencies are computed for a number of different cases, and the results, where possible, are presented in graphical form. An increase in sweep efficiency can be obtained by moving the central injection well updip, and the opti~num position is found for several cases. The applicnhility of the results is discussed. INTRODUCTION Because of the growing importance of water flooding in California and in other locations where large angles of dip are quite common, it is important to know at least some of the effects of dip on the performance characteristics of water floods in such instances. In the past, only reservoirs having relatively mild dips have been wateflooded. Consequently, little is known today as to the effect of dip on the performance characteristics of a flooding operation from the point of view of field experience; and because of the complexity of the problem, little, if anything, has been done on the problem from the point of view of theory. There are two distinct aspects of the role played by gravity in a flooding operation. The first is that of the preferential segregation of the reservoir fluids at the time when the flood is to commence. The second is the role that it may play in affecting the performance of the reservoir during the course of the flooding operation. In this paper the reservoir is assumed to be filled with only one fluid, so that there is no preferential segregation of reservoir fluids at the commencement of the flood. Moreover, the injected and in-place fluids are assumed to have the same characteristics, so that in effect we consider only a single-fluid problem. Single-fluid results have been used as a guide in the past for predicting and interpreting the behavior of regular five-spot floods in horizontal reservoirs. It is thought that single-fluid results might likewise be used for five-spot patterns in dipping reservoirs as a norm to which the effects of the multifluid problems might he referred.* In confining our attention to the single-fluid case, we therefore do not consider the preferential segregation of injected water in the oil bank, or of the oil bank in the unflooded zone. Instead we consider the deviation from the behavior of a horizontal five-spot which is caused by use of flooding techniques (i.e., the flow potential pattern at injection and production wells) likely to be employed during flooding operations in dipping reservoirs. In other words, we consider effects which are caused by the pattern of injection and production well pressures which we choose to apply. Performance characteristics are given for the five-spot spacing pattern as a function of two parameters; one is the ratio of gravity head to potential difference bctwccn the high updip injection well and the low downdip producer of the same five-spot, denoted by Rg; the second is the orientation of the five-spot pat-

Jan 1, 1956

By C. D. King

The key to maximum production of ingots for the war effort is maximum production of pig iron. For any given furnace and ore, the most important single influence on blast-furnace production is the quality of the furnace coke. It is generally recognized that undoubtedly deterioration of Pittsburgh coking coals will be accelerated by the depletion of some of the better grades of coal; the extension of mine mechanization, with attendant degradation of coal quality; and the opening of new coal fields, some of which are known to be fairly high in sulphur. All of these factors, contributing as they do to higher ash and sulphur, and not infrequently to inferior quality of coke, made it desirable that an extensive study be undertaken to determine the effect of washing some coals that closely approximate the average chemical composition of coking coals to be expected in the future by the subsidiaries of the United States Steel Corporation in the Pittsburgh district. It was deemed advisable to study the improvement obtained by washing such coals and to determine the need for supplementing the existing coal washery at Clairton to assure continued maximum production of pig iron from presently available furnace stacks. The existence of the coal washer at Clairton made it possible to conduct tests on coals used in raw form and on similar coals after washing. This study covers an investigation of the quality of furnace coke as affected by washing coking coals, and is confined to the use of 100 per cent high-volatile Pittsburgh seam coals from Fayette and Greene Counties in the manufacture of furnace coke. It covers the improvement in chemical and physical properties as well as the degree of uniformity in coke obtained by washing these coals, and includes the effect on blast-furnace production and practice. The test period involved is four months; the plants, Clairton by-product coke plant, and the Carrie No. 1 and No. 2 blast furnaces at Rankin, Pa., Carnegie-Illinois Steel Corporation. Clairton By-product Coke Plant and Coal Washer The Clairton by-product coke plant carbonizes 30,800 net tons of coal daily in 22 batteries containing 1482 ovens. Three oven sizes are used, commonly known as wide, medium, and narrow types, recognizing the difference in oven width, These ovens also differ in height and length. The present coal washer has a daily capacity of approximately 14,000 tons, leaving 16,800 tans to be carbonized in raw form. Washed coal is used on all the narrow ovens and on three of the six batteries with ovens of medium width, raw coals being used on all the remaining ovens. The customary arrangement is

Jan 1, 1944

By W. L. Remick

WHEN the senior author of this paper presented an article on Fine Coal Cleaning by the Hydrotator Process,1 at the February, 1927, meeting, that process had been developed in the anthracite region only to clean what is known as "slush" or "silt." This size constitutes all of the material passing the finest screen used at any particular colliery. Some use a 3/32 -in. round-hole screen and others use a 1/16 -in. round hole. Practice varies throughout the anthracite region, but the tendency seems to be toward the finer screen.

Jan 1, 1929

By R. M. Brick

The etched mierostructures of cold-worked alpha brasses, after reductions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonymously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {ill), in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson6 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into symmetry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The high-frequency laboratory induction furnace with a rotating liquid crucible enables research workers to conduct certain investigations heretofore very difficult or impossible to realize because vessels are not obtainable that are capable of resisting the physical conditions or the chemical actions to which they are subjected. Applications for patents covering commercial uses of centrifugal liquid crucibles were filed in the United States in 1919,' in France in 1925, in the United States and Germany in 1926,2 and in France in 1927.3 In 1928, Schuette and Maier,4 of the Bureau of Mines, reported the construction of a whirling table beneath a high-frequency induction furnace. Shape and Size of Centrifugal Liquid Crucibles When a vessel containing a liquid is rotated, the inner surface of the liquid takes the shape of a paraboloid under the simultaneous action of centrifugal force and gravity. The internal dimensions of the paraboloid rotating liquid crucible are governed by the diameter of the container and its speed of rotation. Melted Wood's metal was poured into cylinders 2 1/2 in. in diameter, which were rotated at 180, 300, and 468 r.p.m. When the metal was solid, a slurry of plaster of Paris was added, and rotation continued until the plaster had set. Fig. 1, a photograph of sections of the cylinders, shows the effect of speed of rotation of the containers upon the shape of the inner surface of the rotating liquid crucibles. Types of Furnaces Three types of high-frequency induction laboratory furnaces using liquid-metal crucibles were designed and constructed by the Blast

Jan 1, 1939

By J. B. Murdoch, John G. Jackson

The many mechanical, geological, and economic factors which influence the planning of a directional drilling program are thoroughly discussed and analyzed. It is demonstrated that the planning of a directionally drilled multiple-well artificial island location is a complicated undertaking and that it is imperative that complete planning and engineering analysis be undertaken before the program is started. Complete planning is profitable because all of the factors influencing the directional work are in general interrelated and many time compromises have to be made before a harmonious program results. The engineering control necessary to accomplish a complicated directional drilling program is outlined. Various means by which engineering control can be increased, such as cylinder drilling specifications, are given. A hypothetical example is developed for a complete offshore artificial island of ten wells to demonstrate the more important factors involved in the planning. Included with this example are special charts and tables which make more rapid the drafting of directional drilling proposals and maps. Introduction A petroleum engineer must consider many and varied factors when planning a long range directional drilling program for an offshore or inaccessible location on an oil structure. The basic principles of direc- tional drilling planning and operation must be reconciled with his company's drilling practices, and frequently special concessions to standard drilling and production practices should be made. The field techniques and tools used in directional drilling are well known and widely used, but the deliberate, careful planning of a complete directional program is in the main a recent innovation. This development, plus the increased demand for oil resources and the consequent exploitation of inaccessible structures and offshore locations, has placed this problem before many engineering departments for the first time. Directional drilling programs of a very complex and difficult nature have been successfully carried out in the Mid-Continent and Pacific Coast regions. The planning itself of a directional drilling project, however, has not had the careful analysis it deserves and we can reasonably expect widespread future progress along thesc lines. Data and experience gained in these programs by the directional drilling service companies and the oil producers have been studied with the objective of giving the engineer a better conception of the factors which govern the various steps in planning a series of directional wells. The newest engineering procedures are the result of recent careful analysis of years of directional drilling work accomplished under the supervision of directional drilling service companies working with the oil companies. The purpose of this paper is to illustrate

Jan 1, 1949

M. A. SCHEIL (presented in written form).-Messrs. Franks, Binder and Brown are to be congratulated for the splendid paper that they have presented. We have not made stress-corrosion tests with the cantilever type of specimen which they describe, but it is well known that a uniform stress across a certain portion of the gage length can be obtained with such a specimen. This type of specimen would appear quite expensive to make. The writer was interested in the authors' remarks concerning the erratic results obtained from specimens with cold sheared edges. It might be of general interest to record here some results we obtained with annealed sheet N4 in. thick of type 304 stainless steel. After specimen No. 4 had been exposed 65 days without any signs of cracking we applied a strain gage and measured the stress as 25,810 psi. This value is considerably higher than we find for some of the type 347 stainless alloys and suggests that 18-8 might have a different threshold value for stress-corrosion cracking than 18-8 columbium. The test data in Table I show that strain caused by cold work or polishing has a pronounced effect in lowering the time for failure. In my paper I showed values of 8 hr. and 17 hr. to stress crack cold-rolled type 301 stainless steel stressed beyond the yield point. This steel contained 8.31

Jan 1, 1945

By John L. Burns

The object of this chapter is to present data concerning the effect of the introduction of relatively slight amounts of carbon and nitrogen into supersaturated solution in iron. The study is confined to the alpha temperature range of both the Fe-C and Fe-N systems. The age-hardening characteristics of these two systems are considered. These data are compared to those of other age-hardening alloy systems and a "classification" is essayed. A.—Relation of Lattice Parameter and Electrical Conductivity to Changes in Physical Properties Due to Aging of Fe-C Alloys Since Whiteleyl in 1927 showed that some of the iron carbide that is normally present in slowly cooled low carbon-iron alloys disappears on rapid cooling from just below the A, point, interest has been manifested in the possibilities of age-hardening in these alloys. Masing and Koch,~ and at the same time and independently, W. Koster,~ proved these alloys to be age-hardenable. A. A. Bates4 a little later also published an interesting paper on changes in physical properties due to the aging of low-carbon steels. Many other papers have appeared showing changes in physical properties in specific instances due to this same phenomenon.

Jan 1, 1934

By A. W. Gauger

It is with some trepidation that I approach my subject, for I know that I shall at once incur the suspicion of the mechanical engineer, with his concern for boiler tests and efficiencies; of the mining engineer, with his mechanization problems; and of the chemical engineer with his unit processes. Nevertheless, it must be recognized that the technology of fuels, the systematic body of knowledge relating to the production, processing and utilization of mineral fuels, has grown to such proportions and involves so many widely diverse applications of fundamental science and engineering that it behooves us to stop and consider just what its status is in relation to other technologies, as well as in relation to the present and future needs of the social order. The time has come when technologists, applied scientists and engineers must consider the possible effects that their achievements may have on Society. The development of a machine to - -replace -several hundred men is a fine achievement when considered solely from the point of view of creative endeavor. But what of the men who are displaced by the machine! Does not the responsibility for the development of this machine embrace as well the consequences of obsolescence and technological unemployment resulting from such development? I believe that it does and that we must recognize this fact in our practice of engineering and tech- nology as well as in the training of future engineers and technologists. Magnitude of the Fuels Industry Fuel technology is the body of knowledge that relates to the mineral fuels. The fuels industry is by far the most important of all Our mineral industries. The chart in Fig. I, reprinted from U. S. Bureau of Mines Information Circular No. 6643, indicates the compartive values of metals, fuels and other nonmetallic minerals for the year 1929. Of the grand total of 13¼ billions of dollars in value of minerals at the mines, the mineral fuels contributed 48 per cent. Coal, with 34.4 Per cent, exceeded the value of any other single mineral. In fact, the value of the production of the Pennsylvania anthracite mines alone anand exceeds the value of the gold production of the entire world. Petroleum and natural gas in 1929 contributed 14.3 per cent and 3.3 per cent, respectively, of the total value of world mineral production. So much for the world picture; let us now look at the situation in the United States. Over the 60-year period 1880 to '939, $46,409,727,000 of metal1ic products, $80,788,852,000 of fuels (coal, petroleum, natural gas, natural gasoline) and $27,871,-ooo,ooo of nonmetallic minerals other than fuels were produced. The mineral fuels have contributed 52.7 per cent of the entire mineral wealth produced over this period that has seen such tremendous industrial development in our Our As a matter of fact, our present industrial civilization has been made possible through the use of the

Jan 1, 1942

By P. Hazebroek, M. Prats, E. E. Allen

Well locations in water floods frequently do not coincide with the ideal well locations associated with the flood pattern which is used. A question of importance is. "How much oil is lost because of this?". This is the problem treated in this paper. It is assumed that each pattern in a five-spot flood has the proper number of production and injection wells but that the wells may be off-pattern. The distance by which a well is off-patern is given in terms of the pattern spacing, defined as the length of one side of a five-spot. The influence of off-pattern wells on the performance of a five-spot flood has been investigated mathematically for unit mobility ratio. All production and injection rates are assumed to remain equal. The loss in recovery resulting from pattern irregularitie: has been calculated at a cumulative water injection corresponding to a 98 per cent water-cut in a regular five-spot. Displacing a single production or injection well by about one-third the pattern distance reduces the total field recovery by 4.4/N per cent of the recovery obtainable with regular spacing, where N is the number of five-spots in the flood (assumed large). When off-pattern wells are separated by at least one regular five-spot and are displaced by less than one-third the pattern distance, the total loss in recovery in a large-scale flood is, at most, 1 per cent of the recovery obtainable from that field with a regular five-spot pattern. However, much higher losses may occur if the off-pattern wells are not separated by a regular five-spot, if the rates are imbalanced, or if the mobility of the injected water is higher than that of the crude. Although the loss in oil recovery due to pattern irregularity often may be low, the off-pattern case will always require injection of more water to reach the same final water-cut. The volume of water injected per unit volume of oil displaced has been calculated for each five-spot adjacent to a five-spot containing a single 08-pattern well. The cumulative water injection at the time of 98 per cent water-cut may be increased by as much as 37 per cent when a production well is displaced one-third the pattern distance toward an injection well. The existence of differences between actual subsurface locations and the idealized well patterns used in secondary recovery operations is well recognized. However, the methods commonly used for predicting waterflood behavior ignore such differences, even when subsurface locations are known. The reason for this is simple. The idealized well patterns are highly symmetrical and, as such, the production history of the pattern (and even of the field) can be determined from that of a few production wells—usually from only one. Consideration of the many irregular well spacings found in a specific field would entail a large amount of work, and then the results would be applicable only to that specific field. In an attempt to provide an answer to the more general problem, this paper considers a water flood having an idealized well pattern, except for one well which is not at its regular location. When several off-pattern wells are present, their contributions are assumed to be additive unless the off-pattern wells are close to each other. Only four positions of the off-center well (at x, y. of Fig. 1) are considered in this paper. These are shown

By John Parker

During 1965, a new stoping method was developed at the Bunker Hill Mine at Kellogg, Idaho to enable the profitable mining of a large low-grade zinc orebody. This method, called the Bunker Hill pillar system, incorporates the use of the air-powered Atlas Copco T2GH or CAVO 310 as the prime production component. The method and equipment proved highly successful and was the first step in mechanizing what had been a classic example of a square-set and horizontal cut-and-fill operation. Since that time there has been a realization that the small rubber-tired type of loader could be effectively used to advantage in increasing productivity and decreasing costs in many different stoping and development applications throughout the mine. The net result since 1967 has been that a large and increasing portion of the mine production and an increasing share of the development is being done with small rubber-tired loaders. Presently, ten Atlas Copco T2GH and six CAVO 310 air-operated loaders are in use, having replaced the time-honored slusher which was first introduced into the Bunker Hill Mine in about 1898 in the form of a slip scraper. The recent advent of diesel powered loaders in the one yard size range has in 1970 further accelerated the trend toward rubber-tired mobile equipment at the Bunker Hill Mine. Although The Bunker Hill Company is using small diesel loaders of several different types and manufactures for inclines, declines and level development and will undoubtedly find stoping applications for this equipment, .the bulk of this paper will be confined to the use of the air-operated loader, leaving the diesel equipment to a future presentation. It is sufficient to say that we feel at this time that the Autoloader type air-powered equipment and the small diesel front end-loader

Jan 1, 1970

By N. Marusov, D. K. Lowe, J. C. Karp

This paper considers, from an engineering viewpoint, several factors involved in creating, designing and locating horizontal barriers for controlling water coning. This is an effort to consolidate new concepts with previous information so that a reasonable selection of barrier materials, dimensions and vertical position can be made. Coning theories previously developed are briefly reviewed and an effort i,s made to reduce the results of coning-theory calculations to a point where routine calculations can be made with a desk calculator. It is expected that these simplified calculations will give usable predictions of the amounts of improvement attainable with barriers of various dimensions. Apparatus and procedures used for testing the suitability of commercial cements are described and test results are presented. INTRODUCTION Just about as soon as the phenomenon of water coning was recognized as an oilfield problem, there were suggestions that the production of water coning could be controlled or completely suppressed by means of horizontal barriers. It was also suggested that natural barriers such as shale streaks were helpful in restricting bottom-water production. The implication was that wells not having the benefit of continuous shale streaks to suppress bottom waters should, in some way, be supplied with an artificial barrier. With regard to the selection of barrier materials, there are many references which give the merits of liquid barriers.',' These liquids include surface-active agents," recipitates' and emu1sions. There is no real need to review the merits of these materials again. This paper deals with the use of solid barriers which could be made from various cements. The two major restrictions placed on these barrier cements are that (1) they must be commercially available in large quantities, and (2) they must be applicable by means of standard tools and equipment with techniques that have been fully developed and are in general use at the present time. A schematic drawing of a horizontal barrier in a reservoir is shown in Fig. 1. Two maximum stable water cones are illustrated-—-one for the wellbore diameter and the other for a barrier. A maximum stable cone is one that has attained its maximum volume at the critical production rate and is on the threshold of producing water. The volume displaced by each water cone and the rise in water table are indications of the amount of water-free oil produced. Corrections for porosity, connate water and residual oil, of course, must be applied. The water-oil interface which defines a maximum stable cone is called a free surface. It is a surface over which the pressure is constant. This free surface has the shape of a limiting streamline at and below which there is no movement or transport. The shape of the water cone describes the pressure drop in the reservoir. The effect of a completely impermeable barrier on the cone shape is essentially the same as extending the wellbore out to the barrier radius. The placement of a horizontal barrier requires that a horizontal fracture be created using a single-point entry technique. Two methods may be employed for filling this fracture. One method consists of propping the fracture before filling with cement. The other consists of fracturing with fracture fluid, then immediately following with cement

By H. I. Aaronson

The nucleation of pearlite at proeutectoid ferrite is inhibited, to an increasing extent, at the following locations: At twin boundary-nucleated ferrite, between closely spaced ferrite sideplates, and at intragranular plates. These effects are discussed in terms of the influence of transformation strain energies and of the interfacial free energy of austen-ite:ferrite boundaries on the rate of pearlite nucleation. The growth of pearlite into the interiors of austenite grains from the region of the grain boundaries is markedly restricted when low reaction temperatures and large austenite grain sizes permit the development of interlocking networks of intragranular ferrite plates. PREVIOUS investigators have made extensive studies of the interactions which occur between the proeutectoid ferrite and the pearlite reactions from the viewpoint of the mechanisms through which pearlite interferes with the nucleation and growth of proeutectoid ferrite.1-3 In the present investigation, the processes through which proeutectoid ferrite (hereafter termed simply "ferrite") can reduce the rate of formation of pearlite have been explored in some detail. A steel with a relatively low carbon content, in which the ferrite reaction can compete successfully with the pearlite reaction over a wide range of reaction temperature, and exceptionally coarse-grained specimens, which further emphasize the role of the ferrite reaction, have been employed for most of this work. A brief examination also has been made, however, of the effects of smaller austenite grain sizes upon these processes. Experimental Procedure The steel employed had the following composition: 0.29 pet C, 0.76 pet Mn, 0.25 pet si, 0,007 pet S, and 0.005 pct P. This alloy was homogenized for 48 hr at 1250°C. The investigation was performed

Jan 1, 1959

By W. H. Emmons

INTRODUCTION MINERAL deposits that have formed by the various geologic processes, when exposed to air and water at or near the surface of the earth, break down and form new compounds that are stable under surface conditions. Mechanical disintegration of the ores proceeds along with chemical alteration which generally is attended by oxidation, carbonation and hydration. Essentially all minerals are affected-silicates, carbonates, native metals, sulphides, etc. Where iron sulphides are present, oxidation yields sulphuric acid, and in the presence of oxygen and iron, ferric sulphate, a powerful solvent, is formed. Above the water level, in the vadose or shallow zone, both air and water are present. Below the water level air is excluded and that which is carried down with water is removed from the solution by reactions with reducing materials. Above the water level, solution is the pre-dominating process; below the water level, precipitation generally is equally important. In some deposits, particularly above the hater level, valueless materials are removed from the ore, leaving certain metals in a more highly concentrated state. This type of alteration, which has been termed negative enrichment, is common in ores of iron, aluminum, manganese and certain other metals. Some gold deposits, particularly those in which the environment is unfavorable for solution of gold, have been enriched near the surface by removal of material other than gold. Certain metals are readily dissolved in an oxidizing acid environment. These include copper, silver and, under certain conditions, gold. In the presence of iron sulphides, deposits of these metals are likely to be leached above the water level. The metals are carried downward to depths where air is excluded, and where they may be redeposited, generally below the water level. Such enrichment by addition of metals has been termed positive enrichment.

Jan 1, 1933

By W. M. Weigel

Salt production in Louisiana and Texas at the present time is entirely from salt domes of the interior and coastal groups. Before and during the Civil War salt was recovered from numerous salines and salt springs by evaporation in open kettles. The location of these in nearly every instance was near what is now known to be a salt dome, and the source of the salt in the salines and spring waters was that in the salt core. The tops of many of the shallower domes have been subjected to erosion1. The discovery that the salt occurred as large masses of rock salt in the form of domes was made in May, 1802, at Avery Island, La., by John Marsh Avery, grandson of the original owner, John C. Marsh, who built the old salt works in 18122. The first shaft for mining was sunk on the Avery dome in 1867 by Chouteau and Price. It was 90 ft. deep, about 58 ft. being in solid salt. It was abandoned in 1870. There are three general groups or fields of salt domes; interior Louisiana in northern Louisiana, interior Texas in northeastern Texas, and the coastal domes nearer the Gulf Coast and extending from the Mississippi River to the Rio Grande. This last group contains by far the greatest number of domes. As many of the coastal domes especially are prolific producers of petroleum and a few of sulfur, their geology has been intensively studied and fully covered in the literature. The depth to the top of the salt varies from near the surface, where shallow ground waters have dissolved the salt to just below recent deposits, to several thousand feet, where the depth has been cstimated only by geophysical methods. The diameter of the salt core varies from less than 1/2 mile to over 2 miles. Only domes where the salt is comparatively near the surface have been developed for commercial salt. Three deeper domes, which will be described later, have recently been developed or are in process of development, as a source of brine for chemical use. Fig. 1 shows the location of the domes so far developed for commercial salt and brine. Nos. 1, 2, 4, 7, 8, 9 and 10 are in the Gulf Coastal field,

Jan 1, 1938

By Robert B. Fulton

The objective of this chapter is to discuss the interrelationship between industrial minerals and chemical manufacturing. It is intended to supplement rather than duplicate the commodity chapters. Particular emphasis is given to the pertinent chemical element and to market factors. Condensing this broad subject into a few pages of this handbook permits treating only the most important elements derived from industrial minerals. Hydrocarbons, which quantitatively dominate as raw materials for the chemical industry, are omitted, as are the metallic elements and the minerals covered in other "use" chapters such as phosphorous, potassium and nitrogen for fertilizers, and titanium dioxide for pigments. The remaining six elements of major importance are: boron, bromine, chlorine, fluorine, sodium, and sulfur. These elements are treated individually under separate headings. Table I (Jones, 1973) affords an overview of the main industrial minerals, the chemical products derived from them, and end uses of the products. Salt brines have particular importance as raw material sources for the chemical industry. Table 2 (Anon., 1967) is a chart of the chemical compounds derived from four types of brines: (1) Owens Lake-type brines, which are sources of boron and sodium compounds; (2) Midland-type brines, from which bromine, iodine, and chlorides of calcium, magnesium, potassium and sodium are derived; (3) Searles Lake-type brines, yielding boron, bromine, lithium, magnesium, potassium, and sodium compounds; and (4) Silver Peak-type brines, produced mainly for lithium. Market Attributes Some of the important market traits common to industrial minerals used by the chemical industry are listed below. 1. They are international commodities, such as fluorspar and sulfur, which largely move to foreign consumers. 2. Grade, and freedom from deleterious elements are important factors affecting their usability in chemical processes. An example is salt (NaCl) used in electrolysis where ultrapure evaporated salt is required to meet rigid specifications. 3. Purified products take on the characteristics of specialty items and command a distinctly higher price than the basic commodity from which they are derived. 4. In practically all cases, chemical users require some sort of cleaning or beneficiation of the naturally-occurring mineral to bring it to specification, and individual specifications may vary from user to user for essentially the same use. 5. In some instances it is necessary to strike a balance between what the vendor can supply and what the buyer requires, with the result that specifications have to be eased to afford the needed materials in marginal cases. 6. Because they tend to be bulk commodities, low cost for handling and transportation are important and such costs may limit the area from which a chemical user can draw his supply. For example, fluorspar from China and Thailand normally goes to Japan, while South African fluorspar can go either to Japan or to the US. 7. Shipments are usually in bulk and frequently in multiple-car, full-trainload or full-shipload lots to reduce transport costs, which in turn may require large terminal investment facilities.

Jan 1, 1983

By R. A. Deju, R. B. Bhappu

Further information on the surface characteristics of the silicate minerals was obtained by experimentally correlating the oxygen-silicon ratio of the silicates with their electrokinetic properties. Specifically, the behavior of the minerals in an electric field was investigated using zero point of charge as a parameter. A modified electrophoresis cell was used for the determination of electrophoretic mobilities. It was shown that there is an increase in the zero point of charge with increasing oxygen-silicon ratio in the silicates. Finally, a chemical interpretation was presented to describe the surface phenomena observed in the experiments. In recent years great interest in surface chemistry has produced a number of methods to study the surfaces of minerals and to observe the phenomena occurring at their interfaces. One such method is discussed in this paper. A rather complete review of the surface characteristics of the oxide minerals has been undertaken by parks,' but, a similar study has not been made for the silicate minerals. Two previous papers by the authors2'3 attempted to remedy this situation. In these papers it was demonstrated that the reaction between the silicate mineral particles and acidic water involves mainly an exchange of metal ions for hydrogen ions on the surface of the solid, leading to an increase in pH of the aqueous phase. Also, the degree of reaction was found to depend on the oxygen-silicon ratio of the silicate structure, being least for the quartz and greatest for the olivines. A hypothesis was then set forth explaining that upon the fracturing of a silicate mineral, the oxygen-metal bond (which is almost entirely ionic in character) will break more easily than the stronger oxygen-silicon bond. This results in the exposure of unsatisfied oxygen sites on one hand and active, exchangeable cations on the other. These active sites on the fractured surfaces are then available for reaction with the hydrogen ions in acidified aqueous solution. Thus, an increase in degree of adsorption of hydrogen ions occurs as the oxygen-silicon ratio increases due to the presence of a larger number of active sites on such minerals. A correlation between oxygen-silicon ratio and electrokinetic properties will be further pursued in this paper from both the theoretical and experimental points of view. Efforts will then be made to present a chemical interpretation of surface phenomena observed in the experiments. It is believed that this study may supply pertinent information on the behavior of silicate minerals in froth flotation systems. ELECTROKINETIC STUDIES Equipment: In a previous paper,2 Deju and Bhappu described a simple method for determing the zero point of charge using a potential across a cata-phoresis cell and observing particle movement by means of a Rayoscope* optical system. This setup is simple in design and operation and extremely reliable. With care, reproducible results within 1.5% accuracy may be obtained. A new setup has been developed, based partly on the design by Zeta-Meter Corp.4 and partly on previous cells used at the New Mexico Bureau of Mines. This new, modified cell is shown in Fig. 1. Although

Jan 1, 1967

By George H. Eldridge

The existence of phosphate of lime within the State of Florida has been known for over a decade; but until the spring of 1887, the extent and value of its deposit.;, possibly with one exception, were unsuspected. In that year Col. T. S. Moorehead, induced by a statement made by Mr. J. F. Le Baron, examined the gravels of the Peace river, recognized the importance of the deposits, acquired such tracts as were regarded as desirable, and established the pebble-phosphate industry, making his first shipment in May, 1888, to the Scott Manufacturing Company, of Atlanta, Ga. The establishment of the pebble-phosphate industry upon Peace river was followed, a year later, by the discovery in Marion county of an entirely different class of phosphate, now commonly known as hard-rock phosphate. This discovery was made early in June, 1889, by Mr. Albertus Voght, in a well which he was sinking upon his place near the site of the present town of Donnellon, about 20 miles southwest of Ocala. To it, more than to any other cause, is due the rapid and remarkable development of the present great industry of the State. It was, however, Mr. John F. Dunn, of Ocala, who turned to advantage the accidental discovery of Mr. Voght. After acquiring a knowledge as to the chemical composition and value of the material, Mr. Dunn and hid associates purchased several thousand acres of land and organized the Dunnellon Phosphate Company for active operations. From Dunnellon as a center, prospecting rapidly extended in all directions, until at the present day important mines have been opened over a well-defined tract more than 200 miles long and about 6 miles wide. This tract lies par-

Jan 1, 1893

By B. E. Grant

There are several exceptions from the practical operating viewpoint that might be taken with the paper. The author recommends using a "curve" in plotting safety factors of ropes and suggests that the U. S. Bureau of Mines change its present "step curve" method to the "curve" method. From an engineering theoretical point of view that is possible, but from a practical standpoint it is not possible. Rope manufacturers fabricate their ropes in diameter gradients of 1/16 in. to 1/4 in. which automatically sets up a step pattern gradient. If ropes were manufactured in the diameter gradients of 1/1000 of an inch or thereabouts, the curve method could be used. Also, from a practical standpoint, if an operator is to hoist from a depth of 4000 ft, for example, he will determine the size of the rope necessary for that depth, and it is only natural that he will have safety factor to spare at lesser depths, and in plotting this excess capacity the natural end result is a curve. The U. S. Bureau of Mines tables are set up so that the operator will know what size rope at the required safety factor he will need at his maximum depth. He is not concerned with lesser depths. W. A. Boyer (author's reply)-Mr. Grant states, "Rope manufacturers fabricate their ropes in diameter gradients of 1/16" to 1/4" which automatically sets up a step pattern gradient." There is no connection or relationship between the "size" pattern gradient and the present "factor of safety" step pattern gradient. The inherent factor of safety values for any particular size of rope with a given connected load when plotted for various depths is a curve, and with modern rope material and construction the inherent factor of safety curve is quite far removed from the present recommended factor of safety step curve. This is shown quite clearly in Figs. 3 and 4 of my paper.

Jan 11, 1954