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By J. B. Fisken

(Butte Meeting, August, 1913.) BEFORE touching upon the immediate subject of this paper a few facts of a historical nature as to the general application of electricity to mining might be of interest. As to what was actually the first application of electricity to mining, opinions will no doubt always differ. My experience does not go back far enough, nor are the records to which I have had access of any value as covering this point. Sydney F. Walker, a man whose pioneer experience in the application of electricity to mining purposes dates back as far as 1876, ,gave an interesting resume of the subject in an address before the South Wales branch of the Association of Mining Electrical Engineers at its 1.913 session, and, unless his statements are shown to be wrong, they should be accepted as facts. According to Mr. Walker, the ignition of charges of blasting powder was the first operation in mining to be accomplished with the aid of electricity. Very frequently this energy was furnished by a static machine and occasionally by a magneto generator. Later, this was followed by the application of electricity to bell signals, and we are told that this application was looked upon skeptically and regarded as an expensive experiment by the mining managers of those early days. At the Paris Exposition of 1878, there was exhibited an electric lamp, which suggested future possibilities to the mining engineers of those days. The first successful application of electric lighting to underground excavations that I have been able to find any record of is that of M. Blavier. In the year 1879' he installed two Serrin lamps and successfully illuminated one of the large underground chambers in the Angers slate quarries. Another early application of electricity to the lighting of mines is that in the large chambers in the salt mines of Maros-Ujvár, in Hungary; these have been regularly and successfully lighted elec-

Jan 6, 1913

By AIME AIME

SINCE the preparation of the Fall Meeting announcement the Montana Section has extended an invitation to the members traveling to Spokane to make at least a short stop at Butte, en route. Accordingly, the train schedule below has been worked out as an alternative to that announced in the general circular. This will permit a half day in which to visit either mines at Butte or the smelter at Anaconda and an opportunity for an evening meal with our Montana members. An interesting time is assured either way and the chance to renew acquaintance with Butte friends will be well worth will

Jan 1, 1929

By James F. Kemp

In submitting an additional contribution to the discussion on ore-deposits in the recent volumes of the Transactions, it is my desire to adhere closely to matters of material importance as affecting the actual processes. Judging from the discussion by Professor Van Hise, and from one or two reviews or other articles by associates of his in geological work, the impression seems to prevail that, in so far as my paper* referred to his masterly essay, I was guilty of misconceptions regarding both the part attributed by him in it to the igneous rocks and the ubiquitous presence of the ground-water. I should regret extremely to be wanting in these particulars or to have misunderstood one for whose great services in this and other branches of geology no one has a higher esteem than myself. I have, however, in the most careful way, and with these points in mind, read his essay again, and, taking it as a whole, I cannot gain any different impression of relative magnitudes than the one first received. The importance of the igneous phenomena and the restrictive influence of the processes described by " cementation " in their effect upon the ground-water, as set forth in Professor Van Hise's "Discussion" (Trans., xxxi., 292), impress me as being in very marked contrast with the same things in his first essay. If the point seems to anyone of sufficient importance, it can easily be decided by reading the originals. My paper was the result of some years of observation, reading and reflection, and was meant to be an independent contribution, controversial only in some subordinate particulars. In depicting the drama of the deposition of ores, I cannot but feel that Professor Van Hise assigned to the chorus and the scene-shifters some characters which, it seems to me, should

Jan 1, 1903

By Clarence A. Seyler

The object of all classification is to group together things which are alike, and separate those which are unlike. This object is essentially a practical one, enabling us to apply past experience to new conditions. Many costly large-scale experiments lose half their importance for want of proper description of the coal used, and the consequent impossibility of predicting that other coals will behave in the same way. I do not, therefore, make a fundamental distinction between "scientific'' and "use" classifications, except in so far as use depends on conditions, such as size or impurities which are not related to the nature of the coal substance itself. The characters chosen to define the classes of coal must be such as are accompanied by as many other properties as possible. It is not to be expected that any system of classification will enable us to predict every property of coal, since all specimens have an individuality of their own. But specimens can be grouped by a number of resemblances into species. Further, species which resemble each other can be grouped into genera. Elementary Composition as a Basis of Classification There can be little doubt that the ultimate or elementary composition of "pure coal" is the best basis of classification. It was soon after the perfection of the method of elementary analysis of organic substances by Liebig that Regnault, the distinguished chemist and physicist, laid down the principle that coals of the same kind vary only between narrow limits of elementary composition. This is still the widest generalization that can be made about coal. Upon it the metallurgist Gruner based his classification. In some quarters the value of the ultimate composition was denied, Stein going so far as to say that it teaches us nothing of importance about coal. One still hears statements that it is like crushing a work of art in a mortar and analyzing the powder, or like counting the number of times a given letter occurs in a sentence. Such comparisons are misleading, and the criticism might be applied to organic chemistry as a whole. Nor is the existence of isomerism, or of entirely different substances which

Jan 1, 1928

By Arthur Knapp

The ordinary well log is subjected to a great deal of criticism, much of which is well founded. Sometimes, though, the difficulty in interpreting the log is due to the fact that the geologist or engineer using the logs does not know the limitations of the drilling method used. The rotary drill, especially, has inherent limitations that make it difficult to secure definite information at all times. The identification of well-defined key beds is about all that can be expected from the rotary log. The formation in a drilled hole, as reported by the driller, has a direct relation to the speed with which the drill makes the hole or to the reaction of the various strata on the bit, called the "feel of the bit." When this is not thoroughly understood by the geologist or engineer endeavoring to interpret the log, the result is an erroneous correlation with other wells or a discarding of the log as worthless. General Terms Hard and Soft.—Hard and soft are relative terms. In the case of well logs, they are very misleading as they are used in connection with both resistance to abrasion and resistance to percussion. In technical rock classification, hardness is relative resistance to abrasion. The term brittleness is used in connection with resistance to blows. These terms are misleading to the geologist or engineer who is not familiar with both the cable-tool, or standard tool, method of drilling and the rotary method. In the case of the standard tools, the driller's report of the hardness of the formation is in terms of its resistance to blows. For instance, a cable-tool driller might be able to make from 30 to 50 ft. a tour in a brittle limestone, which he would call soft and at the same time he might call a relatively soft (from a purely mineralogical standpoint) gypsum hard, because it is somewhat elastic and is not readily broken by blows. The rotary driller would reverse the terms. The limestone is hard in that it resists the abrasive action of the bit, while the gypsum might be soft in that it is readily cut by the rotary bit. It is rare that wells drilled by the standard tools are correlated with those drilled by the rotary, but the technologist who has worked with well logs from one system might be misled when working with the other.

Jan 1, 1921

By Van H. Manning

In substance, the international aspects of the petroleum industry, as these relate to the United States, are as follows: The domestic production is not keeping pace with the domestic demands; our best engineering talent warns us of the imminence of a decreased production by our oil wells, although more oil is needed; and the only practical source whence this increasing demand can be supplied for some time to come will be the foreign fields. Other nations have given thought to the future and, in recent years, have shown a tendency to adopt strong nationalistic policies regarding their petroleum resources, policies that hinder or prevent the exploitation of these resources by other nationals. In consequence, we find that, facing a probable shortage of the domestic supply, our nationals are excluded from foreign fields; and this in spite of the fact that foreign nationals have been permitted to enter into and exploit our own oil resources on an equality with American citizens and without hindrance or restrictions. This country has supplied the larger part of the petroleum consumed by the world and yet, with a failing supply imminent, it finds that those countries that, have been drawing upon our resources to supply their needs are showing a tendency to exclude us from their resources. In this way we shall be transferred from a position of dominence to one of dependence; and only by sufferance of those countries that are now seeking financial or political control of petroleum supplies, shall we be able to obtain the oil we will need. Impoetance of Petroleum Petroleum has become, during recent years, one of the essentials of our social and industrial life. All civilized countries recognize that the world is dependent on petroleum as on nothing else except textiles: foodstuffs, coal, and iron. Today, the tendency is toward an ever-increasing consumption of petroleum and its products as new and more efficient uses are found for them. The utilization of petroleum is extending more and more into the structure of our civilization. Consequently,

Jan 1, 1921

By Oliver Bowles

WHILE vast quantities of limestone and dolomite are used in metallurgy, the estimated production in 1926 being 23,860,000 tons, there are many problems connected with their use which have not received adequate study. The literature of metallurgy is notably lacking in comprehensive discussions of fluxing or furnace stone. Approximately 900 lb. of limestone is used for every long ton of pig iron produced in the blast furnace, but this important constituent of the charge receives little attention compared with the intensive study that has been applied to ores and fuels, the other important constituents of the charge. In an effort to elucidate some of the doubtful points, the writer has made a wide review of metallurgical literature, and has had the disappointing experience of finding not more than a paragraph or two on metallurgical stone for each two or three thousand pages of literature reviewed. Furthermore, the limited information supplied is in some instances contradictory and even absurd. For example, a correspondent in a reputable metallurgical magazine classifies magnesia and silica together as impurities in flux "that must be melted and run off as slag." From the furnace operator's viewpoint it is desirable that as complete knowledge as possible be obtained concerning the effects of chemical composition and physical character of the stone on its action in the furnace and on the quality of the metal produced. A better knowledge of these features is advantageous also to the quarry operator in that it enables him to work more intelligently in producing stone that will best satisfy the metallurgists' requirements. The following pages comprise a brief compilation of data now available. Much of the information is well established and probably acceptable to most metallurgists. On some points there is room for debate, and the chief purpose in presenting a paper at this time is to arouse discussion which will throw more light on controversial points and thus assist the author in preparing a more comprehensive and accurate dis¬cussion of metallurgical limestone problems.

Jan 1, 1928

By John R. Freeman

THIS paper relates entirely to the casting of brass under fluid pressure in steel dies Die castings of metals and alloys of low melting point have been available for many years but the development of brass die castings has been relatively recent, occurring within the past five years The successful development of brass die castings has resulted from the availability of alloy steels that would give satisfactory life as dies and the development of suitable die-casting machines The melting point of copper is 1084° C (1983° F ) and of a high brass about 900° C (1652° F ), as compared to 327 5° C (6215 °F) for lead, 419 4° C (786 7° F) for zinc and 658 7° C (1217 7° F) for aluminum, temperatures that ale indicative of the casting temperatures required for the various types of alloys, of which the melting points are somewhat lower than those of the pure metals TYPE OF DIE-CASTING MACHINE In the well-known plunger and gooseneck types of die-casting machines used for casting the alloys of relatively lower melting point, much of the working mechanism is immersed in the molten alloy For alloys having the relatively high melting point of brass, this obviously is impossible Machines with a separate melting chamber are essential Two rather distinct types are in extensive use at the present time, the Pack and Polak machines, the former designed by Charles Pack and developed at the American Brass Co , the latter developed by Zoseph Polak, of Prague, Czechoslovakia The principles of operation of these machines have been described in articles by Pack1,2,3 and by Sieg 4

Jan 1, 1935

By A. L. Mular

The flotability of crushed zinc oxide pellets which were doped to produce more n-type or less n-type (more p-type) properties was studied with a Halli-mond tube. Flotation data are presented to show that the pH at which 50% recovery occurs and the collector concentration for 50% recovery depends upon the concentration of doping agent added substitu-tionally for zinc in zinc oxide. The time of sintering of pellets has a slight effect on flotation behavior. A speculative model is proposed to explain the observed behavior in light of the fact that zinc oxide is a semiconductor and has a space charge region at the surface. Experimental verification is necessary before the proposed model can be established as correct. In recent years, the attachment of flotation reagents to minerals has been shown to depend upon the behavior of an electrical double layer which exists in the liquid near the mineral-liquid interface.' Thus, a mineral placed in water will undergo a surface re-arrangement, most likely be preferential dissociation of lattice atoms or by surface adsorp-tion-desorption reactions, to form a dissociation electrical double layer with the solution. Among the many factors which influence adsorption processes, the past history of the mineral itself is one of the most important. Because of trace impurities, minerals from different localities may exhibit marked differences in flotation behavior. This is not unexpected, since investigators who have studied the detailed structure of the double layer's3 have known for some time that the impurity content of many minerals may exert strong influence on double layer variables. For this reason, their studies were usually made with minerals of high purity. The precise relationship between impurities in a mineral and double layer parameters such as capacity and electrostatic potential has been obscure. However, impurities in a semiconductor type mineral which is in contact with a solution have been recently shown to produce changes in the properties of a space charge layer which extends into the bulk of the semiconductor to a distance of one micron or more.4 The double layer is influenced by the space charge layer, whose origin is best discussed in terms of the band theory of solids. A qualitative description of the behavior of impurities in the bulk of a semiconductor, from a chemical point of view, is useful at this point. Briefly, impurities or defects (lattice vacancies, interstitials, etc.) in semiconductors such as PbS, ZnS, FeS2, Cu2S, NiS, NiO, Fe2O3, ZnO, CdS, MnO2 and many others, behave somewhat like acids or bases in water. For example, water dissociates into hydrogen and hydroxyl ions according to

Jan 1, 1965

By J. E. Sherborne, P. H. Jones, E. C. Babson

A study of the Chapman zone in the Richfield field, Orange County, California, indicates that the quantity of oil recovered by present methods will be only a small portion of the oil originally in place. Since the volume of residual oil is believed to be of large magnitude, an experimental water-flooding operation has been initiated in order to determine whether water-flooding offers promise as an economical method of recovering some of this residual oil. A single injection well was drilled between old producing wells, and a water-treating plant using alum flocculation and chlorination was designed and built. Water has been injected into the input well for six months at rates in excess of 100 bbl. per day. Production from one of the neighboring wells has increased materially, the oil production having risen from 7 to 30 bbl. and the water From I to 40 bbl. per day. While definite conclusions regarding the economic success of water-flooding in the Chapman zone are not justified at this time, it has been demonstrated that water can be injected into the zone on a sustained basis and that this water will displace appreciable quantities of oil from the sand. Introduction As a result of an investigation of subsurface conditions in the Chapman zone of the Richfield field, it was concluded that ultimate oil recovery from this zone would probably be low and that natural water encroachment was so localized as to be of little importance from a recovery stand- point. Furthermore, it was found that in many portions of the zone the wells were approaching an unprofitable level of production. When these data were presented to the management of the Union Oil Co.; their reaction was that an attempt should be made to develop methods of recovering at least a portion of the large quantity of oil remaining in this zone. After some investigation, it was decided that wafer-flooding offered the most likely means of accomplishing this end, but reservoir conditions in the Chapman zone differ so widely from those encountered in any of the flooding projects described in the literature that it was difficult to evaluate the probability of success. Despite encouraging results from laboratory tests, it was not even certain that water would displace an appreciable volume of oil from the Chapman sand under reservoir conditions. Therefore, it was decided to initiate a small-scale project, for two purposes: first, to determine whether water would displace oil from the Chapmall sand and, second, to obtain information and experience for future operations if water-flooding appeared to be a promising method of secondary recovery. Reservoir Data The Chapman zone is the upper of the two producing zones in the Richfield field, being found at depths from 3000 to 3700 fi.. The productive portion of the zolle consists of a large irregularly shaped sand body, which is more than 400 ft. thick at the top of the structure. As the margin of the field is approached, the sand is replaced

Jan 1, 1945

By H. R. Thresh, A. F. Crawley

THIS paper reports the results of viscosity measurements on cadmium and indium undertaken as part of a continuing program of liquid metals research at the Mines Branch, Department of Energy, Mines and Resources, Ottawa, Canada. For several years this work has continued with support from the Canadian Zinc and Lead Research Committee and the International Lead and Zinc Research Organization. In the literature, existing viscosity data for cadmium are conflicting and for indium are scarce. To achieve reliable viscosity values, further work was deemed desirable. Viscosities were measured using an absolute technique applied to an oscillating closed right cylinder of liquid metal. The apparatus, constructed in this laboratory, and the techniques involved in its use have been described in an earlier paper.' In calculating viscosity coefficients from the experimental data. Roscoe's2 mathematical analysis was used. Because accurate viscosity determinations are dependent on accurate density data, and since the available data in the literature are conflicting, the densities of liquid cadmium and indium were also determined in this laboratory by a pycnometric technique. This increased the control exercised over all the variables contributing to the accuracy of viscosity measurements. For both density and viscosity determinations, cadmium and indium of 99.999 pct purity were used. These materials were obtained from Cominco Ltd. In order to suppress excessive evaporation losses and help prevent oxidation, a technique developed in measuring the viscosity of zinc' was used for cadmium. This involved maintaining an atmosphere of purified hydrogen in the viscosimeter during the rela- tively long periods while the experimental temperature was changed and stabilized between individual determinations of the logarithmic decrement. Then, immediately prior to a decrement measurement. the viscosimeter was rapidly evacuated to a pressure of about 2 X 10-6 torr. On the other hand. with indium. no difficulties arise from vaporization or oxidation. In this case. therefore. the apparatus was held under a constant vacuum of about 2 x 10-6 torr. When all sources of random and systematic error have been evaluated, the technique is considered to yield data accurate within 10.5 pct. The viscosity of cadmium was measured to a maximum temperature of 451.8°C and that of indium to 346.5°C. These temperatures are. respectively. 130° and 190°C above the melting points. Two separate runs were made on indium. The results are given in Table I and, when plotted. yield the smooth curves evident in Figs. 1 and 2. Values of A and C to fit the well-known Andrade1 equation were determined by a regression analysis. The equation is: where n = coefficient of viscosity. i = specific volume. T = temperature in °K Despite its empirical nature. Andrade's equation has been shown by many workers to describe accurately the temperature dependence of viscosity. During the current research program, this equation has been found to fit the data precisely for all the metals and alloys that have been studied.5,6 The A and C' values for cadmium and indium are given in Table 11. Comparing the magnitude of the present data with those of previous workers,7-10 as has been done in Fig. 1, it is evident that the results of Fisher and Phillips10 deviate markedly from the rest. With the exception of one point from Gering and Sauerwald,7 all other data agree within ±2.5 pct. However, the agreement between the present results and the work of Menz and sauerwald9 is especially good over the entire experimental temperature range. Such agreement may be expected since Menz and Sauerwald's

Jan 1, 1970

By F. E. Jaumot, A. Sawatzky

IT as long been recognized that there is a need for accurate systematic data on diffusion in solids. Originally, such data were needed to check existing theories but, more recently, it would appear that it could be used most advantageously as a guide to, or a check for, much needed extensions of the theory of diffusion. The awareness of the conditions which are important to experimental accuracy, the availability of the materials for accurate experiments, and the techniques have improved to the extent that it would now seem to an experimentalist that, unless extensions of the theory are made which take into account the fundamental parameters of the atoms, the electrons, and the lattice in some detail, the field of diffusion will rapidly become an empirical or semi-empirical field. The present series of experiments was designed to provide accurate data on the diffusion of the elements of the IB and IIB subgroups in silver; that is, to provide data on the diffusion in silver of three face-centered-cubic elements with roughly similar chemical properties, but with different atomic or ionic sizes and, similarly, for three noncubic elements. The elements of these two subgroups have different valences, so that the data will not give any significant information on differences due to the crystal structure of the solute. The present paper reports data on the diffusion of copper and mercury in single crystals of silver; the data for the other elements of the IB and IIB subgroups were reported previously by the authors1'2 and by Tomizuka and Slifkin.8 Experiment The general technique used was identical to that previously described1,2 and will not be repeated here. In all cases, the sectioning technique and high specific activity isotopes" were used. The short half-life of Cu64 made decay corrections more important than for the other isotopes, and necessitated around the clock shifts while data were being taken. Each section was counted at least twice (as was true for all longer half-life isotopes) and a monitor was counted along with each sample. Data for the diffusion of mercury in silver are presented at a greater number of temperatures than for the other solutes. This is a result of two circumstances. First, six (of 30) samples had to be discarded because of pitting or recrystallization which occurred during the diffusion runs, even though the samples had sustained high temperature prediffusion anneals. Either of these was a very rare phenomenon in the other experiments, and their occurrence in this case is considered in more detail below. Second, the curves of the logarithm of the activity of the sections vs the square of the penetration deptht were, in general, quite good, but frequently seemed to show one point to have high activity and the next point to have slightly low activity in terms of the best straight line. When this occurred, there was remarkable regularity of the high-low sequence. In any event, the results, as far as diffusion coefficients are concerned, were not affected by this amalgam effect. In fact, the mercury data had the highest internal consistency of any of the data. Results Diffusion of Copper in Silver—-Diffusion runs were made at eight temperatures In the temperature range from 700° to 950°C, for times ranging from 5 to 45 hr. A linear curve of the logarithm or the activity vs the square of the penetration depth was obtained for all samples. Table I summarizes the results for individual samples and Fig. 1 gives a plot 02 the logarithm of the diffusion coefficients as

Jan 1, 1958

By Strathmore R. B. Cooke, Eugene L. Talbot

THE perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds.1, 2 Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydrocarbons."' * The large contact angles probably result from the terminal —CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride.5 From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others. Since the fluorinated analogues of the conventional hydrocarbon flotation collectors possess enhanced surface properties, a few were selected for testing. Because a survey of all possible minerals and reagent combinations would be out of the question, hematite was chosen to represent a nonsulphide system and pyrite to represent a sulphide system. The fluorinated reagents used in these experiments were prepared in the research laboratories of Minnesota Mining & Mfg. Co. Some were synthesized especially for this research. They are not available cokmercially. Separation of Nonsulphide Ores: The separation of oxides from silica has always been a challenge to the flotation industry because differences in surface properties of the minerals are normally insufficient to produce clean concentrates. Oleic acid," rosin acids,' and amine salts% ave been used to considerable extent to effect separation of metal oxides and silica. The system hematite-silica was chosen to represent the nonsulphides both because of its difficulty of separation and because large tonnages of easily obtainable material are available, such as gravity concentration tailings and nonmagnetic taconites on the Mesabi Range. The wash-ore tailings used here contained approximately 35 pct iron after desliming. Samples of the material used in this work were part of the same lot used by Chang, Cooke, and Huch9 and were prepared in an identical manner. Reagents for Nonsulphide Ores: Since one of the purposes of this investigation was to compare hydrocarbons with fluorocarbons, reagents of known behavior such as oleic acid, and the alkali metal salts of certain resin acids (Dresinates), were established as standards. Hydrocarbons and fluorocarbons of comparable chain length and other experimental fluorocarbons were tried as collectors for hematite. A list of the materials used and the concentrations of their stock solutions are given in Table I. Since silica can be selectively floated from hematite by conventional reagents," a few fluorocarbon reagents were also tried for this purpose. Their composition and concentrations are given in Table 11. Most of these reagents served the dual function of collector and frother. In the case of F-11 flotation did not occur but it served as a frother when F-6 was employed as a collector. Reagent grade sulphuric acid and sodium hydroxide were used to regulate the pH. Deionized water containing less than 0.1 ppm of salts expressed as NaCl was used for all solutions and flotation tests. The pneumatic flotation cell consisted of a 350-ml fritted glass Buechner funnel with a source of filtered air which could be controlled by a needle valve." A 50-g sample of ore and 250 ml of deionized water were added to the flotation cell and stirred slowly. The reagents were added and the pulp was conditioned before air was admitted to the cell. Approximately 15 ml of the pulp were removed for pH determination before flotation was started and were then returned to the system. The pH was again measured after flotation. Air was admitted to the cell until no further flotation occurred or until the character of the float changed markedly. Both the float and the nonfloat products were filtered, dried, weighed. and assayed for iron. The cell was washed in hot water and rinsed with deionized water after each test. Occasionally the cell was cleaned with concentrated hydrochloric acid to remove iron oxide particles from the glass frit. Experimental Results: Above a pH of 8, sodium oleate was an effective collector for hematite. The emulsification of equal parts of heavy fuel oil (20"

Jan 1, 1956

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.'.' It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.' Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By AIME AIME

IT is unlikely that any oil field has ever threatened the future course of the oil industry as does Kettleman today. It seems that nature has striven to outdo herself in combining in this field every possible factor conducive to a tremendous production of the petroleum product in greatest demand-gasoline. This field already has 13,700 acres of proved land and an oil zone of known thickness of 1400 ft. It has wells yielding several thousand barrels of oil of virtually motor fuel grade, together with millions of cubic feet of gas at almost unheard of pressures. The field would have been the. answer to an oil man's prayer in times of under-supply, but now it is the oil man's nightmare, for drilled in -the manner of most other fields and without regard to available markets for oil and gas, the greatest physical and economic losses in the his¬tory of the oil industry will result.

Jan 1, 1930

By H. H. Kaveler, Z. Z. Hunter

Variation of the horizontal permeability (parallel to the bedding plane) in the vertical section of reservoir rocks has long been observed as a characteristic of a normally heterogeneous system which reservoir rock represent. The use of a recently developed water injection profile device offered opportunity to measure with a high degree of reliability the rate of inflow of water into Burbank sandstone in wells previously cored. Water injection profiles were not correlative with core permeability profiles in such wells. Apparently the vertical permeability substantially influences the flow between strata in a formation in a manner as to void the usual conclusions that have been drawn from consideration of the horizontal permeability measurements alone. The results obtained in comparing water injection profiles with horizontal permeability profiles suggest that many of the usual production operations based upon "selective" behavior or treatment of rock exposed in well bores need to he re-valuated and re-examined. INTRODUCTION Petroleum reservoir rock are heterogeneous systems. Heterogeneity exists in respect to lithologic character insofar as such rock are composed of distinguishable solid phases. Heterogeneity also exists in respect to certain properties, such as porosity and permeability, that vary due to variation of the physi-cal structure of the rock. Except in exceptional cases, both the horizontal permeability (measured parallel to the bedding planes) and the vertical permeability (measured perpendirularly to the bedding planes) exhibit significant variation in any common source of supply. The variation in horizontal permeability. as reflected by con. analyses. has drawn the greatest attention of petroleum technologists probably out of the general notion that the mass movement of fluids in a reservoir is predimonantly in the horizontal direction. Furthermore, in the usual case, the rock permeability measured in the horizontal direction is greater than that in the vertical. The variation of horizontal permeability of reservoir rock has been the basis for developing a number of operating practices and procedures intended to improve the petroleum production operation. Many such procedures are referred to as "selective" in the sense that the practice is intended to control the flow to a more. or less. permeable interval within the common source of Supply. It is often said that such practices are "tailored" to the permeability profile. The practices referred to involve, among others, the following: selective perforation of casing; selective shooting, acidizing and plugging: plugging back to intervals of low permeability; and, regulation of flow to prevent coning of water or gas, or irregular encroachment of water or gas. Certain expressed notions involving a concept of "by-passing," or "trappingl" that are held to be particularly harmful in causing the avoidable loss of recoverable petroleum have grown from observed variations in the horizontal permeability. Oftentimes estimates of the reserve of a common source of supply are tempered by conclusions relating variation in horizontal permeability to recover-ability of the oil-in-place. Certain conclusions attributed to the significance of the variation of the horizontal Permeabilitv often extend to the design and operation of pressure-maintenance projects involving both water flooding and gas-injection. Many advocate increasing the number of injection wells, advocate maintaining uniform and equidistant input-output well patterns, or advocate so-called "dispersed" gas-drive techniques rather than gas-cap injection because the permeability profile of cored wells is supposed to indicate that "by-passing" or "trapping" would otherwise exist. It is important, therefore, to have an opportunity to test whether the variation in the horizontal permeability found through core analyses of a typical reservoir rock is sufficient to establish the paths of fluid flow in a reservoir. It is particularly important to have an opportunity to determine whether flow at the sand face of a well conforms to the permeability profile as established by core analyses. In that manner, the merit of certain 50-called "selective" operating procedures and other notions may be evaluated. The purpose of this paper is to compare horizontal permeability profiles of wells in the Bartlesville (Bur-bank) sandstone with water injection profiles, for the purpose of showing that there is no correlation between the horizontal permeability of a core and the water intake characteristics of a typical sandstone. GENERAL CHARACTERISTICS OF BARTLESVILLE (BURBANK) SANDSTONE The Bartlesville sandstones of Northeastern Oklahoma are off-shore bar deposits.' Although other reservoirs had different processes associated with their deposition or with the formation of their porous, permeable structure, the l!artlesville sandstones on which these field Fields were made are, in every respect. typical petroleum reservoir rock. The permeability of the Bartlesville sandstones shows a typical variation in both the horizontal and vertical direction. Furthermore, the permeability profile logs of wells in any pool are not correlative, even as between wells as close as 660 ft and 330 ft apart.'. The same condition exists in such sand-tones as the Jones Sand at Shuler' and is the ordinary and usual characteristic of reservoir rock. THE FIELD DATA The data reported herein are those obtained from coring of nine wells on the center of ten-acre locations for the purpose of providing water-injection wells in the Bartlesville (Burbank)

Jan 1, 1952

By E. A. Gulbransen, J. W. Hickman

Recent work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution type over the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions~i In order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where cu+ is o.,,6-,4 and ~i++ is o.,oh;, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with elec-trans. This in in the copper- nickel alloys corresponds to 40 at. pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is flied at 60 at. Pet Or or 4O at. pct nickel. Matt and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel has the configuration: 3ds 4s2 and copper: 3 dl0 4s) then at 60 at. pct copper or 40 at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. Survey OF Literature The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1949

By L. A. Panek

During the past three years, USBM has developed an apparatus and technique for direct measurement of existing pressure and change of pressure in mine rock. This relatively simple and inexpensive monitor is reliable for months after being installed. It is used to determine shift of ground pressure created by different sequences of mining, to ascertain the cause of rock failures, and to evaluate the need for artificial support. The technique has been employed to measure pressures in limestone, greywacke, concrete, diabase, and soft iron ore. When rock is subjected to a load it is deformed. Ordinarily this is observed in a mine as the displacement of one point with respect to another—the deflection of the roof, which may be observed as a convergence between roof and floor; or the extrusion of material from the rib, which may be observed as a decrease of the distance between the rib and the post of a timber set. The effect of excessive pressure may be a rockburst if the rock is strong, or it may be squeezing ground if the rock is soft. Some desirable effects of high stress (high in relation to strength) are the caving of roof in a longwall mining operation, the caving of ore in block caving, and the decrease in mechanical energy required to break down the mineral seam in a retreating pillar-robbing operation. In any case, whether the observable effect of rock load is desirable or undesirable, it is a displacement, and depends on the following four factors: 1) The structure—the size and shape of openings, pillars, and linings, the geologic bedding and jointing. 2) The mechanical properties of the rock—prin-cipally the strength, modulus of elasticity, and flow characteristics. 3) The load or applied stress—primary sources are the weight of superincumbent rock, which increases with depth, and unrelieved tectonic stresses; secondary sources are redistributed pressures caused by other nearby openings, especially large mined out zones (rock pressure depends partly on the rock structure created by mining). 4) Duration of load, related to the length of time the opening is exposed. CONTROL OF ROCK DISPLACEMENT Rock displacement can be controlled by control of these four factors. Consider now the means of exercising such control over these factors. Control of the structural features is obviously possible to a great extent, as such control is exercised largely by choosing the method of mining and the methods of natural and artificial support. Rock properties vary, even within a particular mine, but they are controllable only in the limited sense that control may be exercised by choosing the beds or zones to be mined so that rocks with undesirable properties will not occupy critical positions within the rock structure created by mining. Rock pressure is the most complex of the four factors through which ground control can be achieved because it is invisible, difficult to measure, and poorly understood. Rock pressure is controllable only to the extent that control is exercised on the rock structure created by mining. Considering openings within a particular mine, time of exposure varies, and is readily controllable because it is easily measured and easily understood — the longer an opening stands, the greater the likelihood of failure or excessive convergence. Control is exercised by choice of an appropriate sequence of driving openings of different classes, such as haul-ageways and rooms, which are required to remain well supported for different lengths of time under different conditions. Again, control is exercised through the method of mining. All controllable factors can be controlled by proper design of the mining method. The orientation and relative positions of the mine workings and the sequence of their excavation are likely to be much more important to ground control than is the design of artificial support. This implies that the major decisions in regard to ground control are made, knowingly or not, at the time the mining method is chosen. WHY MEASURE ROCK PRESSURE In addition to restrictions on the several factors, control implies the measurement of these factors in some sense, whether only qualitatively by visual observation, or by actual quantitative determination with a measuring instrument. Rock pressure is the most difficult of these factors to measure, largely because of the interaction between the measuring device and the rock. Nevertheless, the quantitative

Jan 1, 1961

By John S. Brown

IN 1925 the writer undertook a detailed statistical study of all producing areas in the Joplin district as a basis for evaluating programs and measuring objectives. For this purpose, the published figures in the yearly volumes of Mineral Resources were used, supplemented for earlier years by publications of the Missouri Geological Survey and other local and less official sources. When all else failed, the available data were projected backward to hazard a reasonable guess as to the unrecorded early output of important areas. Fortunately, the proportion of such prehistory production is not a large factor in any of the totals. These results were used during the next few years to measure the relative importance of various producing areas and to predict the peak period of development of the all-important Picher field. For the purpose of this review, the charts have been completed to the end of 1950. During World War 11, the U. S. Bureau of Mines became interested in a similar study and issued comprehensive statistical tabulations of data up to 1945 ( Info. Circular 7383), which have been checked against the figures used herein. This tabulation, however, does not include all the earlier data used by the writer nor does it offer any estimates of the wholly unrecorded era in the beginnings of the earlier camps. The area covered in this study is shown in Fig. 1 on which are indicated the relative location and approximate outlines of the principal producing camps. This also shows the approximate yield to date of each major camp in terms of combined lead and zinc concentrates. The output of zinc concentrates is roughly seven times that of lead. Hence, the economy of the district has depended primarily on the price of zinc, with lead as an important byproduct. Over much of the productive period, lead concentrates averaged about twice the value of zinc concentrates per ton, and in certain mines or areas the proportion of lead to zinc was substantially above average. The Joplin district is largely flat prairie but is partly moderately dissected, partially wooded land with a relief generally less than 100 ft. The rocks are almost flat-lying, nearly parallel to the surface, and the chief ore formation is the Mississippian Boone limestone, including its cherty phases. This formation either outcrops in the producing areas or is covered by a thin veneer of Pennsylvanian shales. Virtually all the ore occurs within 400 ft of the surface, and a large part at less than 300 ft in depth. Most of the land was divided into small farms or town lots before mineral development; tracts seldom exceeded 160 acres, and averaged considerably less. Mineral rights followed the surface ownership, segregation was rare, and a system of leasing for mineral development became well established early in the region's history, many landowners deriving small to sizable fortunes from royalties. Because of the shal-lowness of the ore and other factors, prospecting and mining was cheaper than in almost any comparable mining district in the United States. This situation, coupled with the widely divided land ownership, offered a fertile field for promoters and speculators and led to the rise of many small mining concerns. Only in its later history, under stern economic compulsion, has control tended to centralize in a few companies. Under these conditions, any important new discovery or successful development had much the effect of a gold rush or an oil boom. Every property in the area was leased quickly, promptly drilled, and, if ore was found, it was soon on the market. Many companies and individuals participated, and the average producing lease-hold probably was about 40 acres in extent. Any important field thus was attacked by anywhere from 10 to 100 or more producers. Production zoomed, eventually steadied or wavered, and ultimately subsided, leaving a desolation of tailings mountains, cave-ins, empty housing, and wreckage. The object of this paper is to depict the pattern of this process, so far as metal production is concerned, and to note the way in which it reacted to economic and political pressures. Production Charts In Fig. 2 is charted the production record, in tons of lead and zinc concentrates combined, of eight of the principal camps, which together account for approximately 99 pct of the total district production, over the years from 1870 to 1950. This period covers all but the very minor beginning of mining history. Two important camps are divided by state lines; hence, it has been necessary to combine production records for the two portions, based on estimates that may be slightly in error. Certain camps are sub-dividable into important units for which separate figures are available in whole or in part and have been charted as fractions of the major unit. The corresponding price of zinc is shown above all the charts. Three camps, Aurora, Neck City, and Galena, show a remarkably symmetrical graphic pattern, which is interpreted as the norm. The curves rise steeply to a peak, level off for an irregular interval, and then drop sharply to zero on a slope corresponding roughly to that covered by the initial rise. The three portions of these charts seem appropriately characterized by the designations of youth, maturity, and decline. On the whole, with some irregularities, the production in each of the three periods seems to be almost equal. A fourth camp, Granby, fails to conform to the normal pattern. It exhibits a very long period of reasonably uniform, stabilized production corresponding to maturity, followed by a rather precipitate decline. Its youth is hidden in the era of prehistory. This habit of steady, long-continued production at an even keel is attributable to the fact that this camp, more than any other, was controlled largely by a single principal owner at any given period over most of its history and this permitted the imposition

Jan 1, 1952

By T. W. Healy, P. Somasundaran, D. W. Fuerstenau

The flotation behavior of quartz in the presence of alkyl ammonium acetates as a function of alkyl chain length has been interpreted in terms of hemi-micelle formation at the solid-liquid interface. The van der Waals cohesive free energy that is responsible for hemi-micelle formation has been found from these results to be 1.0 kT per CH2 group. This is in excellent agreement with literature values obtained from research on the properties of micelles in bulk systems. Collectors of the type CH3(CH2)n-2CH2-P, where P is a polar group and n is the number of carbon atoms in the straight alkyl chain, will induce flotation of an appropriate mineral at lower concentrations as n increases. This reduction in collector concentration with increasing n has been reported for such systems as xanthates on sulfides1,2 and amines on quartz.' The effect of chain length of alkyl surfactants on such solution properties as conductivity,' surface tension,' and solubility6 and such interfacial properties of solids as contact angle7 and electrokinetic potential8 have received considerable attention, but only limited quantitative descriptions of the effects have been given. The electrokinetic studies of alkyl amine salts on quartz indicated that the solution concentration of collector at which the marked change in electrokinetic potential of quartz occurs decreases systematically as the length of the alkyl chain increases. The aim of the present work was to obtain a quantitative description in terms of current theories of flotation of the effect of the hydrocarbon chain of alkyl ammonium acetates on the flotation behavior of quartz. BASIC PRINCIPLES The marked changes in electrokinetic potentials of quartz in dodecylammonium acetate (DAA) solutions were postulated to result from the association of adsorbed collector ions into two-dimensional aggregates, called hemi-micelles.9 Subsequently, the rapid increase in flotation rate of quartz was shown to coincide with hemi-micelle formation." We would like to discuss briefly the concept of hemi-micelles in terms of recent interpretations of micelles in bulk solution. Micelle hypothesis: In dilute solutions, alkyl ammonium and related salts behave as ordinary strong electrolytes, but at a certain concentration there is a marked change in physical properties of the solutions, e.g., in equivalent conductance, transport number, freezing point lowering and viscosity. To account for these phenomena, McBainl1 introduced the concept of micelles, which are aggregates of long-chain ions. It is believed that the ionic heads of the constituent ions of the micelle are in contact with water, whereas the nonpolar groups turn away from it and are in contact with each other. Work must be done to bring these charged polar groups together, but energy is gained (i.e., so called van der Waals cohesive energy) when hydrocarbon chains are expelled from the water and allowed to associate. For a given polar group, the tendency to form micelles will therefore strongly depend on the hydrocarbon chain length. Theoretical treatments of micelle formation by Shinoda12 and Phillips13 and others lead to the following expression for the concentration at which micelles form (the critical micelle concentration or cmc) in aqueous solutions of long- chain electrolytes

Jan 1, 1964