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By Charles H. Jacoby

In 1774 a Swedish chemist, C. W. Schule, first recognized manganese as an element. That same year Schule's associate, J. G. Gahn, isolated the element manganese for the first time. In 1856 the Bessemer process of steelmaking gave birth to the economic importance of manganese. Later, in 1882, Robert Hadfield discovered high manganese steels. Although the primary use of manganese is in the ferroalloy industry, two additional important uses for manganese are making chemicals and dry cell batteries. Manganese is also vital to plant and animal life. Various chemical compounds of manganese are used in fertilizers, feeds, glass manufacture, paints, varnishes, and for numerous medicinal and chemical purposes. For the study of industrial minerals and rocks, only the chemical and battery grade material is of concern, but for the sake of comparison, metallurgical aspects are included in this presentation. Although currently the world's largest consumer of manganese, the United States is producing only minor amounts of ore at the present time. This is due primarily to the fact that although huge deposits of manganese occur within our borders, all are of such low grade as to be economically unfeasible to mine. For many years various government agencies and segments of private industry have devoted sizable sums of money and time in an attempt to upgrade ores from the various deposits, and also in an attempt to recover manganese from blast furnace slags. In view of current world prices, and the quantity of high grade material available, there is little likelihood that any of these approaches will be found to be economically feasible in the near future. Geology and Mineralogy Mineralogy There are over one hundred minerals that contain manganese. These minerals vary from those with compositions that are predominantly manganese to those having only minor percentages. [ ] Geology From a geological standpoint most manga¬nese deposits are complex. In general, it can be said that all primary deposits of manganese are carbonates or silicates. The most productive and profitable have been those of sedimentary origin and residual concentrations. Examples of these residual types of deposits are associated with the metamorphosed lodes of Madhya, Pradesh, India, and the lateritic deposits of Orissa and Bihar, India; nodules in the residual clays of the Philippine Islands, U.S. southern Appalachians and Arkansas, Ghana, and Brazil. Sedimentary manganese deposits are best exemplified by the Nikopol district of Russia and the Tchiatouri area of Georgia, USSR. Hydrothermal replacements are characterized by the rhodochrosite deposits of Butte and Phillipsburg, Mont. In general, the hydrothermal type deposit has not resulted in any large tonnages being produced, but may have given

Jan 1, 1975

By John F. Knudsen

Following the flowsheet from the primary crushing plant of Ray mines division through the final products sample mill, there are eight exhaust systems ranging in size from 12,000 to 30,000 cfm. Where possible, hood face velocities are kept around 500 ft per min, permitting branch velocities of 2500 ft per min. Tight-fitting enclosures are provided over all ore drops, crushing operations, and vibrating screens. All enclosures are exhausted either primarily or secondarily, except those around conveyor head-pulleys where the ejector effect of the falling ore creates sufficient indraft to abate dust dissemination. IN 1947 an Industrial Hygiene Department was organized to represent and assist the four western mining divisions in industrial hygiene problems. Department headquarters are located at the Utah Copper Division, Magna Plant, Magna, Utah, with a branch office at the Chino Mines Division, Hurley, N. M. The headquarters staff includes a director, a department secretary, an industrial hygienist, a supervising ventilation engineer, and two ventilation designers. To be in closer association with work at the Southwest properties, a field engineer at the branch office conducts field studies which include ventilation problems at the New Mexico and Arizona properties;i.e., the Chino and Ray mines divisions. Functions of the department are to discover and evaluate existing hazards and to develop protective measures, either by personal protective devices or by proper ventilation, depending on the nature of the contaminant. Other than dust counting, all air samples collected at the four properties are processed at the home office. If through plant surveys or by suggestion of management some type of ventilation or air conditioning is required, the problem is usually handled by the ventilation section of the headquarters department, where general arrangement or line drawings are prepared, showing hoods, ducting, and equipment. Some hood and special parts detailing is done at headquarters; otherwise, required detailing is done by the respective plant engineering departments. Prior to the design of industrial ventilation, either new projects or the revamping of old ones, a thorough survey is made of existing conditions. In so far as possible weighted average exposures are determined and adequate ventilation provided on the basis of maximum allowable concentrations of the contaminant in question, as well as medical case histories, if these are available.

Jan 1, 1954

By James S. Foster, Paul G. Shewmon, Frank V. Nolfi

Analytical expressions are developed for the kinetics of dissolution or growth of a spheroidized, solute rich stoichiometric Precipitate in the surrounding matrix. There are two limiting cases; in one the rate of dissolution or growth is limited by long range solute diffusion through the matrix and in the other by the transfer of atoms across the mrdrix-precipitate interface. In the former case local interfacial equilibrium exists while in the latter it does not and the rate of dissolution or growth is controlled by an interfacial reaction. The analysis treats both limiting cases as well as mixed control in a single development, where it is found that the thermodynamic state of the interface is completely specified by a single parameter, o, defined by where K is the reaction rate constant, D is the matrix solute diffusivity, and R, is the precipitate radiz~s. If K is infinite then a is zero and local equilibrium prevails; if K deviates infinitesimally from zero, then a is very near unity and an interfacial reaction is rate controlling. Mixed control occurs for intermediate values of o. From the analytical results, numbers are computed which are useful in determining the duration of interfacial reaction or mixed control; following this time period, long range diffusion is rate controlling. THE rate controlling process or processes governing phase boundary migration has been the subject of much speculation and investigation. Traditionally, the most widely assumed boundary condition in quantitative treatments of this problem has been that of local interfacial equilibrium. This condition implies that long range diffusion of one or more elements controls the migration and is referred to as "diffusion controlled migration" (herein DCM). In contrast to the above view is the proposition that local interfacial equilibrium does not exist and that transport of atoms across the interface is rate controlling. Consequently, this mechanism is referred to as "interface controlled migration" (herein ICM). In processes of the latter type, the activity, a, of one or more elements is discontinuous at the phase bound- ary and the flux, J, across the boundary of a given element is some function of its activity discontinuity, a. One of the most comprehensive contributions to a mathematical description of phase boundary migration is due to am.' His analyses are applicable to precipitation in binary systems in which a) the precipitates are spherical* solute rich compounds of constant

Jan 1, 1970

By John G. Hall

The pumping operations at the Chief mine have been unique in the respect that for many years the entire flow of water into the mine has been disposed of by pumping into natural underground "caverns" or "sinks." Volumes up to 4000 gpm have been pumped into these caverns with no apparent tendency for the caverns to fill with water, and it has never been proven that any of the water returns to the mine workings. Major pumping operations have been carried on during two periods, the first from 1918 to 1927, and the second from 1942 to the present time. Early Pumping Operations CHIEF MINE The Chief Consolidated Mining Co. was organized in 1909, and for the following nine years ore was developed and mined from the 600 level down to the 1800 level, all above the permanent water table, the 1820 level. The ore occurs as extremely-irregular pipes of replacement ore in limestone, and to date a total of approximately 2 1/2 million tons of ore has been produced. The ore was highly oxidized down to the permanent water level, and some highly-oxidized ore runs occur beneath the permanent water table. In 1916, with extensive mining being done on the 1800 level, 20 ft above the water table, there were indications that a zone of secondary enrichment might exist below the water, and in order to follow the ore runs to greater depth, it was realized that arrangements would have to be Made to pump water to the surface. The original pumping installation was designed to pump 350 gpm in five stages against a 1900-ft head to the surface. By January 1919, the water had been lowered to the 1900 level and an excellent grade of silver-lead ore was being produced from the zone of secondary enrichment. At this point. the flow of water equalled the capacity of the pumps, and pumps of an additional 1000 gpln were installed to supplement the original system. By January 1920, the water had been lowered approximately 100 ft, and the total flow of water was 1000 gpm. The water was being pumped from many different places in the mine where ore was being followed downward, with 27 different pumps operating below the 1800 level, mainly Cameron air-driven sinker pumps. These first sinking pumps were cumbersome and inefficient, and each of the larger pumps weighed approximately three tons and required tremeridous volumes of compressed air. During this period, an exploration drift being extended north and west from the Chief shaft on the 1600 level encountered a large natural cavern some 2000 ft from the shaft. This cavern in places measured 60 ft in diameter. Sometime later the disposing of water into this cavern was suggested, and as an experiment to determine the results of such an operation, an attempt was Made to fill the cavern by pumping in a small volume of water, but the water disappeared as fast as it was discharged into the cavern. It was decided then to try the cavern as a drainage outlet for the entire volume of water being pumped to the surface, and the water apparently did not return to the mine workings. Subsequently water up to 3000 gpm was pumped into this cavern. An attempt was made to determine whether any water was being returned from the cavern to the lower workings, and 100 lb of sodium fluorescein salt was added to the water discharged into the cavern, but no trace of it was found in the drainage water in the mine. Results of another such test will be described later.

Jan 1, 1950

By D. N. Dietz

A method for determining average reservoir pressure is presented, which is simpler to apply than that devised by Matthews. Brons and Hazebroek. For bounded reservoirs, identical results are obtained if stabilized-flow conditions prevail. The present method yields inferior results in the transient state. The method can, with a slight modification, also be used for water-drive reservoirs. INTRODUCTION In the method proposed by Matthews, Brons and Haze-broek' for determining average reservoir pressure in a multi-well reservoir, the cumulative production (the production time of each well) enters twice: once when the buildup is plotted against In (t + t)/At to arrive at p*, and a second time when the correction, p*-p is determined with one of the several formulas for differently shaped drainage areas. Once a steady state has been attained, however, the previous production history should be immaterial. The same pressure distribution could have been arrived at after different cumulative productions of the individual wells. In principle, therefore, it should be possible to determine average pressures without referring to cumulative productions. In the following paragraphs an expression is presented for the difference between the pressure in a producing well and the average pressure of its drainage area. Then the build-up time needed to overcome this difference is indicated. CASE OF A CIRCULAR DRAINAGE AREA AND A CENTRAL WELL PRESSURE DISTRIBUTION BEFORE SHUT-IN The general differential equation of radial flow (see Muskat, Eq. 10.2) may be written In the steady state, the rate of production of the well is equal to the rate of expansion of the fluid contained in the the drainage area; thus

Jan 1, 1966

By Elmer W. Pehrson

The term "survival" in the title means the preservation of a society in which men are free from the political and economic restraints that characterize totalitarian systems, be they communist, socialist or facist. It means the ability to withstand the enemy's offensives in the fields of propaganda, commercial competition and, if necessary, war. The temptation to substitute "victory" for "survival" is great but a realistic appraisal of the creeping socialism and demagoguery that pervade our time indicates that we may have to be content with survival in status quo. "Mineral strength" means assurance that adequate supplies will be available to meet all the contingencies of cold and hot wars. The overall mineral position of the U. S. viewed in the light of these premises is far from secure. It is true that we are the leading producing and consuming nation of the world, but the Soviet Union is gaining and the Sino-Soviet Bloc confronts us with a sobering potential. The emergence of the Common Market in Europe as an economic and political unit places a third independent entity into the competition. Our total mineral output continues on an up- ward trend but the reverse is true in certain strategic commodities. Moreover, consumption is moving ahead faster than production so that there is increasing dependence on imports which has significant adverse geopolitical connotations. There is widespread belief that our resources can at least maintain present levels of self-sufficiency during this critical period in world history, but social dreamers, the labor monopoly, and trade and taxation policies have discouraged aggressive activity in exploration and development, and access to essential foreign sources is threatened by a variety of circumstances. Our stockpiles, belatedly built up to achieve minimum protection against shortages in time of war, are under. political attack and threatened with partial destruction on the basis of what are at best uncertain assumptions regarding the new: look of global warfare.

Jan 11, 1962

By N. Standish

Heat transfer coefficients have been measured in beds of various packings irrigated with mercury and molten fusible alloy countercurrent to hot gases. The measured coefficients for both systems were found to increase with gas velocities and liquid rates. Correlations were determined which show this dependence and also indicate that heat transfer in these systems is influenced by the liquid flow characteristics and the thermal conductivity of the gas and the solid packings. A heat transfer model has beer2 proposed which explains the various features of the experimental results. On the basis of this study, which gives an insight into the heat exchange in the melting zone of the blast furnace, it was concluded that by comparison with the furnace stack heat transfer coefficients are about 1.5 times higher in the melting zone. EACH year large tonnages of metal are produced in operations which, in part, involve liquid metal irrigation of "packings" countercurrent to hot gases. The melting zone in blast furnaces and in cupolas is a good example of packings irrigated with a liquid melt countercurrent to gases. In all instances of this kind large amounts of heat are exchanged and it is desirable to have some knowledge of heat transfer phenomena involved in these systems. So far the most common method of analyzing furnace efficiencies, fuel requirements, and the general thermal state of the furnace has been through the use of heat balances. As heat balances are essentially statements of the first law of thermodynamics they give no real indication of the factors which govern heat transfer between phases in the various zones of blast furnaces. Hence, rational improvement in production efficiency and the development of theoretical models is only possible if the heat transfer characteristics are known at every stage of the process and related to the important variables involved. This has been generally recognized for some time but it was only recently that Kitaev et al.' have produced a comprehensive treatment of heat transfer in solid-gas countercurrent systems such as the blast furnace stack and the packed bed regenerator. Using their treatment it is now possible to predict the effect of particle size, thermal conductivity, bed porosity, and the flow rates of both the gas and the solid material on the heat transfer in the blast furnace stack. However, the stack of a blast furnace is only one part of an integral unit for which the heat transfer analysis cannot be complete without also considering the heat exchange in the melting zone. The complexity of heat transfer processes in this region of the furnace has so far escaped quantitative description. Yet, the melting zone accounts for a greater amount of heat exchange than all the other zones of the furnace put together. Moreover, if the reduction of oxides in the melting zone proceeds in part in the liquid state the importance of heat transfer on furnace productivity and on the metal and slag temperatures is obvious. THEORY Heat transfer for two-phase flow in packed beds is a complex problem involving a number of heat exchange paths for which interphase areas are not known with any degree of certainty. Analytical solution is, therefore, difficult. This difficulty is emphasized by noting that Rabinovich~ and Luck have only recently solved the steady-state heat transfer for simplified two-phase heat exchangers of known area. However, useful progress can be made for the system considered by making a not unreasonable assumption that the usual heat transfer considerations apply and restricting treatment to the steady state. For these conditions the rate of heat transfer dq in a height dz of a packed bed of unit area is: dq = UaATdz [I.] Integration of Eq. [I] then gives the total heat transferred: assuming both U, the overall heat transfer coefficient, and a, the interphase area, to be independent of bed height. Since a, in these systems, is unknown it is convenient to combine this term with U. The group U, then represents the overall heat transfer coefficient on a volumetric basis. If AT is linear with q, then for a bed of unit volume Eq. [Z] can be integrated to give: is the log mean of terminal temperature differences. From Eq. [3] U, can be readily calculated as q and {AT)im are experimentally obtained quantities, but a difficulty arises in interpreting its meaning. Two approaches are possible depending on whether the effect of packing in the transfer of heat is neglected or not. If the packing is thermally decoupled then the resistance concept gives the relationship: which states that the overall resistance is the sum of the gas phase and the liquid phase resistances (assuming areas are equal throughout). Because the resistance to heat transfer in liquid metals is negligible by comparison with that of the gas,4 Eq. [4] can be simplified, i.e.:

Jan 1, 1969

J: H. POLHEMUS, New York, N. Y. (written discussion*).-The Joplin .mining and milling practice has largely influenced operating methods in the Wisconsin district. Milling equipment is essentially of the same type with the notable exception that no tables are used. The treatment of the flue 'sands has been attempted several times but without commercial success. Table material coming from any one mill is low both in tonnage and zinc content. The iron is comparatively high as the pyrite-line "chat" is much more prevalent than the zinc-lime attached particle. In the finer sizes the zinc occurs mainly as free mineral. These condi-tions make the production of good-grade table concentrates very diffi-cult. The accompanying tabulated results from several mill tests indi-cate the character of the mill tails. I think the average mill tails in the district assay nearer 1.5 per cent. zinc than under 1 per cent., as stated by Messrs. Boericke and Garnett.

Jan 10, 1919

By Harold M. Mooney

RESISTIVITY measurements for determining depth to bedrock, water table, and other geologic discontinuities have had only limited success. Many of the difficulties can be attributed to complex geology and to basic limitations of the method; current flow through a continuous medium is a diffusion phenomenon, emphasizing irregularities near the source and smoothing out those at a distance. Some of the failures, however, are due to careless field work and incompetent interpretation. A forthcoming publication1 may help to reduce difficulties of this sort. The writer here attempts to bring order into the multiplicity of interpretation methods and, to a limited extent, to evaluate them. For all methods, the field data to be interpreted consist of apparent resistivity values plotted against electrode separation, Fig. 1. The interpretation should give depths to one or more geologic horizons. Direct currents and the Wenner four-electrode configuration will be assumed, since these are widely used, although the interpretation problems remain essentially the same for other electrode configurations. Alternating currents higher than, say, 20 cycles per second introduce complications beyond the scope of this paper. Three approaches to the interpretation problem have been used. These may be called empirical, theoretical curve matching, and direct. Many techniques have been proposed, but each can be reduced to one of these approaches and to a single geologic idealization. This idealization rests on the following assumption: the earth in the limited volume of interest can be approximated by a horizontal sequence of layers, each homogeneous and isotropic in its electrical properties. This seemingly restrictive assumption has proved to have practical value, although future work should aim at removing some

Jan 1, 1955

By F. D. George, M. J. Salkind

Al3Ni whisker-reinforced aluminum was found to exhibit good Charpy impact toughness and little notch sensitivity even though its room-temperature tensile elongation parallel to the whiskers is only 2 pct. This impact behavior was maintained d liquid nitrogen temperature (-196"C). It is postulated that this behavior is due primarily to the presence of the continuous aluminum matrix which provides sufficient 10calized ductility in the vicinity of the crack tip to absorb considerable energy from the advancing crack. The impact behavior of Al-Alni was found to be quite anisotropic. Of six orientations studied, the transverse orientation having the notch normal to the whisker axis was found to exhibit the lowest impact energy, whereas the transverse orientation having the notch parallel to the whisker axis was found to exhibit the highest impact energy. A significant differnce was noted between the impact behavior of material containing needlelike whiskers and that containing bladelike whiskers. Only two of the six orientations studied exhibited complete fracture for the material containing needlelike whiskers. On the other had, most of the specimens containing bladelike whiskers exhibited complete fracture. It was postulated that the bladelike whiskers block transverse flow, thus reducing the amount of plastic deformation ahead of the crack tip. One of the more significant advantages of composite materials is the prospect of combining high strength with toughness. In general, toughness is associated with materials which exhibit considerable ductility and can deform plastically in the presence of a stress concentration. Very strong materials which resist plastic deformation generally exhibit low toughness. At first glance, then, it would appear as though strength and toughness are mutually incompatible so that useful engineering materials would have to be a compromise between the two. One approach to the problem of combining the high intrinsic strength of ceramics with the toughness of metals was to mix them together to form a cermet. Unfortunately, the toughness of cermets was found to be rather disappointing. Whisker reinforcement of metals, however, appears to be a more promising approach. It has been demonstrated that whisker-reinforced metals produced by unidirectional solidification exhibit enhanced strength due to the presence of high strength nonmetallic whiskers. The total strain capacity of these composites in the direction of fiber alignment is limited to that of the fibers, the matrix being unable to carry the load once the fibers have failed. A characteristic, then, of whisker composites is low ductility in the direction of whisker alignment, on the order of a few percent elongation. This low elongation, which is usually associated with brittle behavior, should not be taken as an indication of low toughness. Such a material can exhibit significant ductility in directions other than parallel to the fibers7 and can therefore possess significant intrinsic toughness. Toughness in a fiber-reinforced metal is derived from several mechanisms. The first is due to the toughness of the matrix itself. A continuous ductile metal matrix can act as an effective crack arrest medium by undergoing localized plastic deformation. Cracks initiated from the surface of the composite or from a brittle fiber failure must travel through the matrix before reaching another brittle phase particle. A second crack arrest mechanism peculiar to fiber composites is due to the fact that, as a crack travels through the matrix and approaches a fiber, the plastic deformation ahead of the crack tip will result in loading of the fiber. This causes the matrix shear strength in the plastic zone to be apparently higher, thus extracting more energy from the crack and diverting the crack at an angle to the original direction of propagation. A third crack arrest mechanism occurs in fiber composites which exhibit a weak bond between fiber and matrix. The idea was proposed by Cook and Gordons that if a crack propagating transversely in a fiber composite were made to turn and run along the fibers by decohesion of the fiber-matrix bond, then toughness would be imparted by the blunting of the crack tip and the creation of new surfaces. The last mechanism, interfacial decohesion, is commonly noted in naturally occurring fiber composites such as wood, bone, and bamboo, and has been observed in man-made composites such as glass fiber-reinforced resins,g silica fiber-reinforced aluminum," laminated steel," and tungsten and silica fiber-reinforced electroplated copper.'' The first mechanism, crack arrest by plastic deformation in the matrix, has been noted in tungsten wire reinforced cast copper." The purpose of this investigation was to quantitatively assess the toughness of a whisker-reinforced metal as a function of orientation. Previous investigation considered only cracks propagating nominally perpendicular to the reinforcement. In this investigation, crack propagation in three mutually perpendicular directions as well as three intermediate orientations was investigated. The system chosen for study was the unidirectionally solidified A1-A13Ni eu-tectic alloy which has a microstructure consisting of 10 pct by volume of A13Ni whiskers in a matrix of aluminum This material exhibits two different kinds of whisker morphology, depending upon the rate at which it is solidified.' At low rates of solidification (less than 2 cm per hr) the whiskers are bladelike, whereas at higher rates of solidification they are

Jan 1, 1969

By K. K. Clark

Excessive injection pressures in water injection wells may create deeply penetrating fractures, or may open up existing reservoir fractures. If these fractures are oriented toward offset producing wells, oil recovery at injected water breakthrough and ultimate recovery will be impaired. A method of calculating fracture lengths from pressure fall-off test data is presented. The method is based on a linear flow model that simulates conditions present during the early-time period after shutting in an injection well. Fracture lengths can be calculated directly if formation permeability is known. A graphical technique is presented that provides fracture lengths based on permeabilities calculated from normal fall-off tests, where those permeabilities are adjusted for flow geometry. Test data from four injection wells and results obtained from applying the method to these wells are discussed. Introduction Rates of water injection into nonstimulated wells in low permeability reservoirs frequently fall below economically desirable levels. Therefore, some form of stimulation such as hydraulic fracturing often is performed on these wells. Usually these fractures penetrate a short distance from the well — short as compared with interwell spacing — and therefore should not create problems of water channeling to offset producing wells. In the past, some operators have been tempted to increase injection pressures continually to maintain a specified injection rate. But pressures cannot be increased indefinitely. Field data indicate that continued injection above fracture opening pressure can cause excessively long fractures to approach between well distances. If these long fractures intersect or closely approach offset producing wells, premature water breakthrough can result. It is difficult to seal effectively these fractures by various workover procedures after premature water breakthrough has occurred. This paper describes testing procedures that are potentially capable of detecting premature water breakthrough before it occurs. Knowledge of fracture lengths and fracture opening pressures can assist field engineers in selecting optimum operating conditions for water injection wells. Fracture lengths should be calculated from pressure fall-off tests on injection wells, and maximum permissible iniection pressures should be determined from step-rate injectivity tests. Equipped with this information, the field engineer is in a better position to recommend for a particular injection well the optimum operating conditions that will lessen the chances of channeling to offset producers. Historically, pressure transient tests have been conducted primarily on producing wells and analysis procedures have been based on radial flow concepts. Several authors have suggested that these same procedures be applied to tests conducted on water injection wells. This application is justified for wells that are not connected to extensive fracture systems. However, if the formation is severely fractured, the interpretation methods must be modified. Several authors have presented the pressure response of various systems that are intended to simulate reservoir conditions. A paper by Russell and Truitt* on vertically fractured svstems is probablv the most useful from the standpoint bf the fieid engineer. Russell and Truitt presented the pressure-vs-time behavior of a well connected to vertical fractures with various fixed lengths. Their permeability adjustment technique is used in this paper to refine methods of calculating fracture length and interwell permeability. Theory and Definitions Three flow-system geometries are considered in analyzing injection well test data. These various geometries are applicable during specific time intervals of transient pressure tests. Schematic drawings of the flow models, and the time intervals over which they are applicable, are shown in Fig. 1 in the chronological order that they are applied to the pressure response of water injection wells in fractured formations. The very early response is simulated by an infinite linear system as shown in Fig. 1A. This representation permits the calculation of matrix surface area exposed to the fracture. The model shown in Fig. 1B is identical with the one studied by Russell and Truitt. They evaluated the transient pressure response of this vertically fractured system by finite difference techniques. The results were presented as tabulations of dimensionless pressure drop functions for a range of fracture lengths. A semilog plot of these data shows that the apparent matrix permeability can be related to the true matrix permeability by a simple exponential function. Their adjustment factor is used in this paper to improve the accuracy of matrix-permeability and fracture-length calculations.

Jan 1, 1969

By R. V. Whetsel, V. R. Garfias

It is estimated that during 1936 world consumption of petroleum, its products and related fuels reached an all-time peak of 1,757,778,000 bbl., an increase of 143,000,000 bbl. over 1935. As indicated in Table 1, world output of petroleum and related fuels exceeded demand by 92,510,000 bbl. during the year, as compared to an excess output of 88,000,000 bbl. during 1935. Production within the United States exceeded domestic demand by approximately 51,000,-000 bbl. in 1936, as compared to an excess output of 53,000,000 bbl. in the previous year. Outside the United States, production exceeded demand by 41,510,000 bbl. in 1936 and by 35,000,000 bbl. in 1935, indicating that foreign output is making no progress toward curtailment in line with demand. Table 1 also combines excess production in the United States with the favorable balance of exports over imports, showing that stocks in the United States were reduced by 23,400,000 bbl. in 1936, as compared to 22,447,000 bbl. in the previous year. In the rest of the world, excess output over demand combined with the excess of imports over exports from the United States indicates an unfavorable balance of approximately

Jan 1, 1937

ASIDE from the John Fritz Medal, in which the Institute participates through its representation on the John Fritz Medal Board, the Institute itself has five major awards to make annually for excellence in technical papers, as follows: The Robert W. Hunt Medal and Prize, The J. E: Johnson, Jr. Award, The Lewisohn Platinum Prize to senior members, and the James Douglas Medal. ROBERT W. HUNT MEDAL AND PRIZE The partners of Robert W. Hunt established a fund which was presented to the Institute at a fitting ceremony on May 27, 1920, to' establish an annual medal and a sum of money to be awarded under the following rules: 1. The award shall consist of two prizes; first of a gold medal, second of a sum of money; a certificate to accompany each prize. The money prize shall not be awarded to a member over 40 years of age, but under unusual circumstances, both prizes may be allotted to one person provided that he is not over 40 years of age. In general it will be understood that the Committee shall award the money prize to the younger men, rather than the medal. 2. The awards shall be made not oftener than once a year to that person or persons contributing to the Institute the best original paper or papers on iron and steel. The scope of the term" iron and steel" shall be determined by the sub-committee considering the awards. In general, papers dealing with the practical side of the subject have preference over those dealing with the theoretical side in recognition. of the fact that Captain Hunt's main contributions to the industry have been in the improvement of production and quality of material. 3. A sub-committee of three to five, including the Chairman of the Iron and Steel Committee, shall be appointed by the Iron and Steel Committee annually to adjudge the award subject to approval. 4. The awarding committee shall submit its report to the Iron and Steel Committee at its October Meeting, and the award be certified to the Secretary of the Institute in time to permit the presentation to be made at the Annual Meeting of the Institute. 5. The recipient of the award shall be ,designated "The Hunt Medallist." This prize is administered by the Iron and Steel Committee. J. E. JOHNSON, JR. AWARD This award is made from the income of a fund of $3000 donated by Mrs. Margaret Hilles Johnson in memory of her husband, J. E. Johnson, Jr., who was a prominent engineer, author of two valuable volumes on iron blast-furnace construction and practise, vice-chairman of the Institute's Iron and Steel Committee, and a frequent contributor of papers to the Institute's Transactions. This prize is administered by the Iron and Steel Committee. The intent of the donor is to encourage young men in creative work in branches of the metallurgy or manufacture of pig iron with which the professional activities of Mr. Johnson were chiefly concerned. The control of the fund and distribution of the awards having been vested in the Board of Directors of the Institute, this Board has made 'the following regulations concerning it:

Jan 1, 1925

Discussion of the paper of O. P. Hood, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2607 to 2611. R. V. Norris, Wilkes-Barre, Pa.-I have had a little experience with gasoline locomotives and I want to indorse very strongly Mr. Hood's point with regard to the danger of carbon monoxide poisoning. I think .the terrible danger is not fully realized. I was foolish enough some time ago, in investigating a gasoline locomotive, to attempt to walk out of the mine entry behind it, and for several days I felt very seriously the carbon monoxide effects. The use of gasoline locomotives ought to be confined to mine entries where there is a very large amount of air. One of the grave dangers is their great convenience and the temptation to run them into chambers for just a few moments to get a car or two. GEORGE S. RICE, Pittsburgh, Pa.-Apparently one of the great dangers is in the style of the gasoline engine. When my attention was. first directed to the type of gasoline locomotives which I saw in the foreign mines-France, Belgium, and Germany, I was most favorably impressed with them, and they have given no trouble on account of fumes, so far as I could learn. Large numbers of them were being used, but all were of small capacity, and of a kind in which the speed control is by a governor of the hit-or-miss type, the engine running continuously. Their power capacity was very low, if I remember correctly it was not over 4 or 5 h.p., but they were used under favorable conditions where the grades in the mines were slight, since the entries or tunnels bad a slight grade in favor of-the load, making about the same pull for the empties against the grade as for the load with the grade. I understand the hit-or-miss valve arrangement enables a setting that will give more perfect combustion than can be insured with the valve controlled by the operating man, as in the automobile type of valve and engine used in this country. Apparently the European type of locomotive does not have the capacity to permit use under the conditions existing in this country, where most of our entries or tunnels have variable grades and long heavy trips of mine cars are used.

Jan 4, 1915

By Douglas Ashmead

In his paper Mr. Braley makes no mention of the bacteriological aspects of the problem. It is now quite well established that certain bacteria play a major role in formation of acid mine waters, and it is a simple matter in the laboratory to show that under sterile conditions the rate of acid production from a pyrites suspension is only about one quarter of that obtained from a similar suspension inoculated with drainage from a mine producing an acidic pit water. Under sterile conditions the oxidation is due to direct chemical action and, from the evidence just given and from much other evidence, this increase under nonsterile conditions is due to certain bacteria. Experiments recently completed, and shortly to be published, have shown that this bacteriological oxidation can be prevented by the maintenance of pH conditions above 4. It was found that to raise this pH above 4 at the beginning of the experiments was not sufficient but that, due to the continuing chemical oxidation, alkali had to be added daily to maintain the pH conditions above 4. The amount of alkali added, however, over a fixed period, was only about one quarter of the alkaline equivalent of the acid produced when pH conditions were not controlled over an equal period. The opinion expressed by Mr. Braley that sodium hydroxide has little or no effect on the rate of oxidation of pyrites is not substantiated by the above experiments. The writer does not claim that these results show a practical solution to the problems, especially in abandoned workings, but feels that the application of an alkaline coating, such as lime wash, to exposed accessible workings might be well worth trying. S. A. Braley (author's reply)—In 1919 Powell and Parrl suggested that bacteria, or some catalytic agent, hastened the oxidation of pyritic or marcastic sulfur in coal. Carpenter and Herndon (1933)' attributed the action of Thiobacillus thiooxidans. Colmer and Hinkle (1947)3 observed an organism similar to T. thiooxidans and another organism that oxidized iron. Leathen and Braley 9rst discovered this organism in 1947 in a sample of water from the overflow of the Bradenville mine (Westmoreland County, Pennsylvania). They characterized the organism in 1954" and gave it the name Ferrobacillus ferrooxidans. Although Temple and Colmer (1951)' had suggested the name Thiobacillus ferrooxidans, since they claimed it oxidized both ferrous iron and thiosulfate, we have found that pure cultures of the organism do not oxidize thiosulfate, hence the name F. ferrooxidans. In 1955 Ashmead7 isolated an organism, similar to the one called Thiobacillus ferrooxidans by Temple and Hinkle, from acid mine water in Scotland. It is probable that this organism was F. ferrooxidans. In 1954 Bryner, Beck, Davis, and Wilsonh reported microorganisms in effluents from copper mine refuse. These organisms appeared to be similar but were not in pure culture. In view of this history of bacterial investigation of acid mine water and our own ten years of experience, we do not agree with Mr. Ashmead that bacteria play a major role in acid formation. We do not find that any of these bacteria will directly oxidize pyritic material. They do, however, augment the chemical formation of sulfuric acid by atmospheric oxidation. In two papers in 1953% eathen, Braley, and McIntyre discuss the role of bacteria in acid formation and postulate the mechanism through which they operate. Mr. Ashmead in his discussion of my paper has assumed that this work was carried on in the presence of acid mine water in which bacteria would be present. This was not the case. Strictly sterile conditions were not maintained, but the organisms present in mine drainages were definitely absent in these experiments. We believe that we have demonstrated that alkalis do not inhibit the chemical oxidation of pyritic material. This is also indicated by Mr. Ashmead's discussion in which he says that alkali must be added daily due to the continuing chemical oxidation. It is interesting to note that Mr. Ashmead finds that maintenance of pH above 4.00 decreases the activity of the bacteria. We have found also that a decrease in pH below 2.8 also inhibits its activity. Table XIII of published data'" illustrates the decrease in activity with increased acidity, although pH values are not given. These values are in comparison with uninoculated controls and show the marked increase in acidity up to 22 weeks but a decline at 29 weeks, at which time the experiment was terminated. It is probable that after a longer period only chemical oxidation would have continued. From our studiesv we have postulated that the iron oxidizing bacterium (Ferrobacillus ferrooxidans) oxidizes the ferrous iron, resulting from chemical oxidation, to ferric iron. The ferric iron then aids the atmospheric oxidation of the sulfuritic material and is itself reduced to ferrous iron, which in turn acts as food for the autotrophic bacteria. Study of the physiologic properties of F. ferrooxidans shows that its preferred pH is about 3.00 and its activity decreases with variation in either direction. It is extremely inactive above pH 4.00 and below 2.5. This inactivity above 4.00 is indicated by Mr. Ashmead's observations. These properties of F. ferrooxidans then correlate perfectly with our hypothesis. Ferrous iron is oxidized very slowly by atmospheric oxygen in highly acid sohtion and since the bacteria become inactive, acid is formed only by atmospheric oxidation. At a pH of 4.00 or above iron is more readily oxidized by atmospheric oxygen, but the bacterial activity is decreased. However, with a pH above 4.00 the ferric iron is removed from the field of activity since its soluble sulfate hy-drolyzes and precipitates the iron as ferric hydroxide or a basic sulfate. As we have shown in the paper under discussion, the alkali does not inhibit the chemical oxidation, and thus the acid formation continues. This

Jan 1, 1957

By H. B. Goodrich

In considering historically oil development in Oklahoma, it must be recognized that basic evolutionary factors interlock and have an effect in common throughout the whole oil industry, regardless of locality or minor problems. Oklahoma, as the third in rank of oil-producing states (Texas being first and California second in production for 1929) has, like the rest, advanced to at least a partial recognition of the words, "Conservation," "Unitization," "Curtailment," "Prora-tion," and especially "Cooperation." Whether through altruism (of which there have been examples) or by exercise of good business common sense, Oklahoma operators realize that the oil business can run itself by cooperative action for the good of all. In this long-continued period of overproduction, Oklahoma has brought the advancing output down to limit of market requirements at least temporarily. Sources of Statistical Data For this paper, figures published by four recognized authorities were consulted. Between themselves these vary only a negligible per cent, in their totals. To be consistent, and on account of earlier availability the estimates published by the Oil and Gas Journal are mainly used herein, supplemented from other public and private sources. General Oil ProdCction in Oklahoma In 1927 Oklahoma's peak of all years was 276,022,024 barrels. In 1928 Oklahoma's total production was 247,500,851 barrels. In 1929 Oklahoma's total production was 252,229,474 barrels. The efforts of proration and curtailment programs on flush and semi-flush districts such as Greater Seminole, Oklahoma City, Logan County and others, with the natural decline of older pools, kept 1929 below 1927, but still the total was greater than in 1928. The total United States production for 1929 is herein taken as estiiated at 1,004,266,723 bbl.† Oklahoma produced 25.1 per cent. Of

Jan 1, 1930

By B. W. Veal, B. S. Chandrasekhar

THE Laue method of orienting single crystals requires the use of tables of angles between crystal-lographic planes, and between zone axes. Such tables have been published for cubic crystals, and some rhombohedra12 and hexagonal3 crystals. A table of angles between planes in ß-tin has also been published;4 these angles refer to only low-index planes, and are not particularly helpful in the actual indexing of spots on a Laue photograph. Furthermore, it is often useful to know the angles between zones which share a common low-index plane. We have calculated such tables of angles for ß-tin and indium, both between planes in principal zones, and between zones passing through principal planes. The results are given in Tables I and 11. The standard formulas were used, with c/a = 0.54554 for 0-tin, and 1.07586 for indium.

Jan 1, 1962

By W. H. Andrews

The constantly increasing consumption of Portland cement in the State makes the above subject of particular interest at this time. The increasing demand is due to the rapid settling of the country and the fact that new uses are being found frequently for the above named commercial article. The industry is one that is bound to grow as the population increases, and this being the case it may be well at this time to consider briefly the matter of the chemical and physical composition of proper raw materials. A cement mixture is one that contains approximately 75 per cent, carbonate of lime, 15 per cent. silica, and 5 to 7 per cent. alumina and iron oxides; the other elements being magnesium carbonate and mall quantities of the rarer elements generally associated with limestone deposits. It can be readily seen from the above composition that it is possible to build up this mixture from a number of different materials. First.—A rock high in carbonate of lime can be mixed with clay or shale in such proportions as to bring about the desired composition ; the chief difficulty in the building up of such a mixture is that it is hard to find a clay or shale in which the silica-alumina ratio lies between 4 to 1 and 3 to 1 and at the same time shows physical characteristics which will make certain its adaptability to the practical manufacture of Portland cement. Very often clays or shales are found which are right chemically but contain large quantities of grit or free silica. Such clays or shale must be ground to extreme fineness in the mixture in order to make the silica and alumina combine with the lime when the mixture is burned. On the other hand, clays or hales are often found that have the proper physical characteristics but in which the amount of alumina is too great. Second.—A mixture can be built up of different limestones some of which run above the 75 per cent. requirement and others below;

Jan 1, 1914

By R. S. Sherwin

The extractive metallurgy of primary aluminum from its ores is discussed with special attention to the production of alumina from high grade ores by the Bayer process, including differences between American and European practice and a brief description of some processes for lower grade ores and the electrolytic reduction of the oxide to aluminum. METALLIC aluminum is not found in nature, but the oxides, hydroxides, and especially the silicates are plentiful. The estimated percentage of in in the crust of the earth is about 8 pct while that of iron is about 5 pct. By far the larger portion of this is combined with silica in the form of various clay minerals and igneous silicate rocks. From the point of view of extractive metallurgy of aluminum, these are low grade ores while the better qualities of bauxite are the high grade ores. There have been various definitions of bauxite but perhaps the best definition at the present time is that bauxite is a rock or earth commonly used as an ore of aluminum or its salts in which the aluminum is present predominantly as a hydrate or a mixture of hydrates and hydrous oxides. It contains varying amounts of oxides of silicon, iron, and titanium and traces of compounds of some of the less common elements. The silica is mainly combined with alumina as clay or clay minerals which are hydrous aluminum silicates, although a part of it may be present as quartz sand. On the American continents, the alumina is mainly present as gibbsite, Al2O3 . 3H2O, and the same may be said of the best known deposits of the Dutch East Indies and some of the deposits in India. In France and other countries in Europe as well as in Africa, the alumina is present mainly as boeh-mite, A12O3 . H2O, but in some of these deposits it is mixed with minor amounts of gibbsite. Some other deposits, such as those in the islands of Haiti and Jamaica, evidently contain two or more hydrates or hydrous oxides of alumina in varying proportions. Perhaps the main portion of the alumina may be present as gibbsite and boehmite with the proportion between the two varying rather widely. In the silicate minerals, including clay, the alumina is chemically combined with silica and has not been separated satisfactorily by mechanical or physical ore-dressing methods. Low grade bauxites are mixtures of hydrates, usually gibbsite or boehmite, with clay, iron oxides, etc. In some low grade bauxites, it is possible to separate a portion of the gibbsite or boehmite, which may be present as relatively hard and coarse particles, from soft or finely divided clay minerals by log washing or similar methods. This has been applied to the product of some mines or parts of them, but on other ores it is not applicable. In some cases the gibbsite or boehmite is almost as fine and soft and of nearly the same specific gravity as the clay minerals so that washing and gravity separations are not successful. The iron oxide, the clay minerals, and a part of the titanium minerals are often so finely dispersed in the ore that any of the physical mineral separation methods, including separations by gravity, particle size, flotation, and electrostatic or magnetic separation, have not been commercially SUCCESSFUL except on relatively small lots of ore. For these reasons, the only available methods of separation on the general run of ores have been methods which would be classed as chemical rather than physical or mechanical separations. Aluminum oxide can be reduced by carbon at temperatures above 1800°C to form metallic aluminum and aluminum carbide or nitride. The temperature for rapid reduction of aluminum oxide to metallic aluminum is about the boiling point of aluminum and above the temperatures necessary to reduce iron, silicon, and titanium so that the direct reduction of an aluminum ore with carbon will produce an alloy of aluminum, iron, titanium, silicon, etc., which may be mixed with carbides and nitrides. Also a large amount of the reduced aluminum may be lost as a vapor except in the presence of some alloying agent such as copper or other metals. While it is possible to refine such alloys or mixtures so as to produce commercially pure aluminum, the methods which have been found are too expensive for the present market. One direct reduction method which found limited commercial use in Germany during World War II was the direct reduction of a mixture of clay containing very little

Jan 1, 1951

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.' Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"' are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".'" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.'" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966