Search Documents

By Thomas W. Wälde

BACKGROUND Foreign investment has been a major factor in bringing about the substantial mining industries of Chile, Peru, Bolivia, Venezuela, Brasil and Guyana. But economic nationalism and sentiment against foreiqn domination of vital national industries grew in the 1960s and most major mining projects were transferred into state owner ship. Among the state mining enterprises formed were CODELCO - Chile, MINERO-PERU/ CENTRCMIN - Peru, CCMIBOL - Bolivia (in 1952), Hierro-PERU, GUY-BAU/BIDCO - Guyana, etc. New investment during that time was discouraged because it was subject to the restrictive conditions of the investment regulations of the Andean-Pact, a grouping of Chile, Bolivia, Peru, Ecuador, Venezuela and Colombia. The philisophy was that mineral resources were to be developed exclusively by national enterprises. Essential foreign inputs had to be acquired "depackaged" as separate purchases of equipment and technical assistance services. As a result of the worldwide economic recession which hit the mining industries in 1980-1982, many projects that were viable in 1970 were not developed by the new state enterprises due to lack of capital, managerial and technical abilities and due to problems with marketing. As a consequence of the long-term decline of metal prices, governments experienced difficulty in getting investment organized through national or foreign enterprises and have had to face up to the trade-offs between national control and active mineral development. A change has since taken place in governmental policies. The 1981 Peruvian mining law, the 1982 mining law of Uruguay, the 1979/1980 mineral promotion laws of Argentina, all witness the gradual shifting of emphasis from restriction to promotion. The investment rules of the Andean Pact have been progressively softened through national regulation and today are more or less irrelevant. Nationalizations and forced renegotiations have not occurred in the last few years. Countries have gone to great lengths (without much success) to re-attract foreign investment on terms that accommodate the political sensitivities of the South American countries and the practical requirements of investors and financiers. For this analysis, three contracts have been selected which reflect this accommodation in three South American countries, where miner a1 production plays a major role in the national economy. These con tracts reflect both the attitudes and traditions of the individual countries, but also mark the shift in mineral investment policies that has taken place. EL INDIO AGREEMENT The 1977 investment agreement between Chile and St. Joe Minerals marked a dramatic relationship between Chile and foreign mining investor s. In Chile, mining of copper has played a major role in the country's history. Large scale copper mining was initiated and developed by Kennecott and Anaconda. The nationalization of these two companies under the Allende government in July 1971 started a wave of nationalizations of foreign-held mining and petroleum operations since then in many parts of the world. The military government supported the new Chilean state mining companies ((30DELCO and ENMI) , but it also attempted to accelerate mineral development by prom ting foreign private investment, thus reversing the nationalistic policies followed by the Allende and the preceding Frei government. The new policy by the military government is expressed in Decreto-Ley 600 (1974) which governs foreign investment in Chile. Decreto-Ley 600 is

Jan 1, 1985

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

A. G. Cockbain—The paper by Burlingame, Bitsianes and Joseph is of great interest in extending the work done on high grade sinters, particularly that of Hessle, and the development and application to them of the technique of McBriar, Johnson, Andrews and Davies on ironstone sinters. In this laboratory the work of McBriar et al. has also been continued and extended to cover high grade sinters, and a sectioning technique similar to that used by McBriar et al. was attempted on sinter cakes made in the laboratory sinter unit, using magnetite concentrates (containing 64 pct Fe). In these experiments no attempt was made to flush out the products of combustion with nitrogen before cooling. It was considered that free air penetration would occur on only a limited scale with the size of sinter cake made (14 in. sq x 12 in. deep). Chemical analyses of the zones showed generally similar features of those described by Burlingame et al. and especially the FeO rich region at and just behind the flame front, i.e. zones of ignition and combustion. This seems to indicate that the nitrogen atmosphere does not materially affect the states of oxidation in the sinter cake or at least that special care is not required unless the sinter cake is small. Burlingame et al. consider that FeO present has some significant part to play in the mechanism of sintering. This view does not find favor with the author. The reduction of iron oxides in the presence of red hot coke is a well known phenomenon, whether conducted in an atmosphere of nitrogen or in a crucible in air, and in view of the presence of some carbon in the hot sinter, especially just at the ignition zone, cessation of the progress of the flame front will in no way affect the reduction of iron oxides near hot coke. Even in a nitrogen atmosphere some CO and CO, will be generated by reduction and by continual oxidation and reduction of CO as the transfer agent, the oxidation state of the iron oxides can be lowered quite rupidly so long as free carbon exists with enough heat. Knowing the composition of the gas at the flame front (obtainable by probes), it would be possible to calculate the static oxidation state of Fe2O3/Fe3O2 in equilibrium with it and hence obtain a check on the chemical analyses to see if in fact direct reduction of the Fe2O3/Fe2O1 to FeO has taken place. Have the authors attempted this? It appears to this writer that what is required is some means of reducing rapidly the heat content of the ignition zone and immediately behind, and at the same time insuring no oxidation by the air. In ironstone sinters the difficulty of oxidation state of the iron did not arise on account of the very large slag bulk. However, in high grade sinters knowledge of this, and also the mechanism whereby high oxidation states can be obtained in the final sinter, is of great interest. R. D. Burlingame (author's reply)—The question has been raised as to whether the high FeO content found in high-fuel sinters is due to actual reduction at the advancing flame front or due to unavoidable direct reduction during the quenching period. For such direct reduction to have taken place in the freshly-formed sinter, a considerable amount of solid carbon would have had to escape combustion and be available throughout the hot sinter zone during the quenching period. A simple stoichiometric calculation with the limited data available indicates that a zone of freshly-formed sinter over 2 in. wide must have averaged roughly 2 pct C to accomplish the amount of reduction found. Furthermore, the presence of this amount of carbon would indicate that the fuel in the charge had not burned over a narrow front but over a zone at least 2 in. thick. In contrast to such a condition, the data of the present investigation indicate that the combustion of fuel is confined mainly to a narrow front in which high temperatures and reducing conditions favor. the formation of excess ferrous iron.

Jan 1, 1959

By E. T. Turkdogan, P. Grieveson

The self-diffusion coefficient of oxygen in a liquid silicate slag containing 40 pct SiO2, 40 pct CaO, and 20 pct Al2O3, was determined using the capillary eff;usion technique. Two stable isotopes of oxygen (O17 and O18) were used as tracers. After each diffision run, the slags were reduced with graphite, the evolved carbon monoxide collected and converted into CO,. The oxygen isotope concentrations were obtazned by measuring the (CO2)45/(CO2)44 and the (CO2)46/(CO2) ratios of the gas. It was found that for O17 Exchange of oxygen between neighboring silicate anions, possibly accompanied by the rotation of these complexes, is a probable diffusion mechanism. The exchange of oxygen atoms between holes in the silicate "lattice" may also be postulated. A full understanding of the properties of slags is unlikely unless the structural details are clearly established. Thus properties such as surface tension, viscosity, expansivity, electrical conductivity, ionic mobility, density, compressibility, and so forth, have been studied. Of importance also are the self-diffusion coefficients and the energies of activation for diffusion of the component ions. The self-diffusion coefficients of calcium, 1-3silicon,, sulfur,4 and aluminumS in a ternary silicate slag have been determined with the aid of radio-isotopes. The self-diffusion coefficient of oxygen in such a slag was investigated in the course of the work reported here.

Jan 1, 1962

By Jack R. Elenbaas, Donald L. Katz

A radial turbulent flow formula has been developed which permits the computation of the pressure drop for radial flow in gas wells whether the flow is laminar, turbulent, or partially laminar and partially turbulent. Using the formula a complete back-pressure curve has been calculated and analyzed by a comparison with existing back-pressure curves. A procedure is presented for computing the permeability of the porous media when the porosity, sphericity and average particle diameter are known. Introduction Recent studies on the flow of fluids through porous media have provided new methods for computing flow under turbulent conditions. The present study was initiated as an investigation of pressure -drop computations for flow through porous sands in gas wells and as an analysis of present-day back-pressure tests. Although laminar flow exists in the producing formation of gas wells under normal flow rates, turbulent flow does take place adjacent to the well bore. As the flow rate is increased, turbulent flow exists further and further into the producing formation and under open-flow conditions in relatively deep wells a considerable portion of the flow through the sand will be turbulent. In order to calculate a complete backpressure curve for relatively deep wells without resorting to extrapolation of curves drawn from data obtained in back-pressure tests or calculations made in the completely laminar region, it was necessary to have some means of calculating pressure drop for flow through porous sands under turbulent conditions.4.6 As a result, a radial turbulent flow formula was derived from the equations recently presented by Brownell and Katz.1 A rigorous solution of this equation involves a trial and error graphical integration. By making the assumptions of average viscosity, temperature and compressibility factor of the flowing gas, it was possible to graphically integrate the relation for the general case of radial flow of gases through the porous sand of gas wells. A chart has been prepared relating the value of the integral to the radius of the well bore and to the Reynolds number of the flowing gas. The chart actually performs the graphical integration and the solution of the formula is then reduced to a simple trial and error calculation. A typical back-pressure curve is calculated to show the transition from laminar to turbulent flow. This paper will briefly describe the pro-cedurcs for computing flow through porous media, including a method for predicting sand permeability from porosity and grain size and shape. Flow through Porous Media Brownell and Katzl recently reported a correlation for computing flow of fluids through porous media by the use of an enlarged Reynolds number and friction factor in which the porosity of the bed is included as an additional prime variable. The enlargcd Reynolds number com-

Jan 1, 1948

By Donald L. Katz, Jack R. Elenbaas

A radial turbulent flow formula has been developed which permits the computation of the pressure drop for radial flow in gas wells whether the flow is laminar, turbulent, or partially laminar and partially turbulent. Using the formula a complete back-pressure curve has been calculated and analyzed by a comparison with existing back-pressure curves. A procedure is presented for computing the permeability of the porous media when the porosity, sphericity and average particle diameter are known. Introduction Recent studies on the flow of fluids through porous media have provided new methods for computing flow under turbulent conditions. The present study was initiated as an investigation of pressure -drop computations for flow through porous sands in gas wells and as an analysis of present-day back-pressure tests. Although laminar flow exists in the producing formation of gas wells under normal flow rates, turbulent flow does take place adjacent to the well bore. As the flow rate is increased, turbulent flow exists further and further into the producing formation and under open-flow conditions in relatively deep wells a considerable portion of the flow through the sand will be turbulent. In order to calculate a complete backpressure curve for relatively deep wells without resorting to extrapolation of curves drawn from data obtained in back-pressure tests or calculations made in the completely laminar region, it was necessary to have some means of calculating pressure drop for flow through porous sands under turbulent conditions.4.6 As a result, a radial turbulent flow formula was derived from the equations recently presented by Brownell and Katz.1 A rigorous solution of this equation involves a trial and error graphical integration. By making the assumptions of average viscosity, temperature and compressibility factor of the flowing gas, it was possible to graphically integrate the relation for the general case of radial flow of gases through the porous sand of gas wells. A chart has been prepared relating the value of the integral to the radius of the well bore and to the Reynolds number of the flowing gas. The chart actually performs the graphical integration and the solution of the formula is then reduced to a simple trial and error calculation. A typical back-pressure curve is calculated to show the transition from laminar to turbulent flow. This paper will briefly describe the pro-cedurcs for computing flow through porous media, including a method for predicting sand permeability from porosity and grain size and shape. Flow through Porous Media Brownell and Katzl recently reported a correlation for computing flow of fluids through porous media by the use of an enlarged Reynolds number and friction factor in which the porosity of the bed is included as an additional prime variable. The enlargcd Reynolds number com-

Jan 1, 1948

By W. Spencer Reid

ALTHOUGH there have been some developments during the last five years which have had far- reaching and important bearing on lead smelting, it cannot be said that any basic principles of pyrometal-lurgy have been discovered. Eighteen or twenty years ago the Dwight & Lloyd sintering machine was intro-duced and literally turned the roasting end of lead smelting upside down. There has been nothing com-parable to the advent of the sintering machine during recent years. Actual blast-furnace practice today is slightly, if any, better than it was five years ago ; although immeas-urably better than it was twenty to thirty years ago. Some tell us that as far as cleanness of slags is con-cerned, it is no better today than in the days of the old Romans. The metallurgist of a generation ago did very good work, considering the equipment he had available. It is true he was working with the cream of the ores, the clean oxides and carbonates and the low-zinc sul-fides. He was troubled very little with high zinc and selected his type of slag according to preference of -some authority such as Eilers, Iles, Raht, Hahn, etc. As these free-smelting ores were depleted the complex ores were encountered, and the metallurgist gradually discovered that he had to forget the old type slags and run a slag according to the percentage of zinc on the charge. I believe it is now universally agreed that SiO2 and CaO must be lowered and FeO raised in a slag as the ZnO increases. The ratio of these variations is practically uniform and can be relied upon over wide fluctuations of the determining element, zinc. These "bastard" slags, as they are sometimes inappropriately designated, are actually in daily use, and the metallurgist of today has been forced to adopt certain standards, as a guide to successful operation. These slags practically refute the old Eilers' theory that all good slags are chemical combinations of SiO2 with FeO and MnO, and CaO and MgO. Eilers' and the other type-slag theories were based upon the assumption that a good slag must con-form to a definite formula, such as 3 (FeO)2 SiO2 + 2 (CaO)2 SiO2 or 2 (FeO)2 SiO2 + 2 (CaO)2 SiO2 which respectively figure 31.3 and 36 per cent SiO2. The SiO2 was supposed to remain constant even with the entrance of impurities such as Zn and A1,0? into the slag. The increasing amount of impurities, espe-cially Zn, soon discredited the theory, for in actual practice the slag failed to run freely.

Jan 1, 1927

By N. Van Wingen

EFFective sand permeabilities can be ascertained from core analysis if the laboratory data are compensated to allow for the presence of connate or residual water. Such adjustments can be made by applying empirically derived correction factors. Effective sand permeabilities can be estimated also from analytical studies of field depth-pressure measurements. In one method the time rate of pressure build-up after a well is shut in from steady-state flow is required, and in the other the direct measurement of a steady-state rate of flow and the corresponding equilibrium pressure. The results of the investigation discussed in this paper demonstrate that these methods for determining mean effective sand permeabilities can be correlated. Introduction In recent years many investigators have demonstrated the practical value of an accurate knowledge of the physical and dynamical characteristics of reservoir sands containing oil and gas. Of these factors, which serve to completely define a porous medium as a container or carrier of fluids, the dynamical characteristics are of particular interest to the production engineer because they afford a direct measure of the rate at which the oil or gas content of a reservoir will become available. The constant that defines dynamically the porous medium as the carrier of a homogeneous fluid in viscous motion is the "permeability." Coke-analysis Method The generally accepted practice in com-piling permeability data has been to analyze in the laboratory core samples taken in the course of drilling through the productive horizon, and to obtain the mean measure of the productive ability or permeability for the interval open to production by graphical integration of the permeability profile. An average permeability ascertained in this manner, however, is useful to the production engineer only for comparisons of wells drilled in the same horizon, as permeabilities determined in the laboratory are measures of only the ability of a porous medium to transmit a single fluid. As a result of many investigations, it has been shown, however, that under actual reservoir conditions water is coexistent with the petroleum and that its presence greatly reduces the permeability of the sand to oil. Empirical relationships showing the effect of the presence of any immiscible fluid A (such as water) in a porous medium on the permeability of the medium to a fluid B (such as oil) have been established separately by Hassler,1 Dunlap,2 and the writer (Fig. I),3 so that the average specific or dry-core permeability as determined in the laboratory can be corrected to give the true measure of the ability of the horizon penetrated to transmit oil, provided the percentage of pore space occupied by connate water is known accurately.

Jan 1, 1942

By N. Van Wingen

EFFective sand permeabilities can be ascertained from core analysis if the laboratory data are compensated to allow for the presence of connate or residual water. Such adjustments can be made by applying empirically derived correction factors. Effective sand permeabilities can be estimated also from analytical studies of field depth-pressure measurements. In one method the time rate of pressure build-up after a well is shut in from steady-state flow is required, and in the other the direct measurement of a steady-state rate of flow and the corresponding equilibrium pressure. The results of the investigation discussed in this paper demonstrate that these methods for determining mean effective sand permeabilities can be correlated. Introduction In recent years many investigators have demonstrated the practical value of an accurate knowledge of the physical and dynamical characteristics of reservoir sands containing oil and gas. Of these factors, which serve to completely define a porous medium as a container or carrier of fluids, the dynamical characteristics are of particular interest to the production engineer because they afford a direct measure of the rate at which the oil or gas content of a reservoir will become available. The constant that defines dynamically the porous medium as the carrier of a homogeneous fluid in viscous motion is the "permeability." Coke-analysis Method The generally accepted practice in com-piling permeability data has been to analyze in the laboratory core samples taken in the course of drilling through the productive horizon, and to obtain the mean measure of the productive ability or permeability for the interval open to production by graphical integration of the permeability profile. An average permeability ascertained in this manner, however, is useful to the production engineer only for comparisons of wells drilled in the same horizon, as permeabilities determined in the laboratory are measures of only the ability of a porous medium to transmit a single fluid. As a result of many investigations, it has been shown, however, that under actual reservoir conditions water is coexistent with the petroleum and that its presence greatly reduces the permeability of the sand to oil. Empirical relationships showing the effect of the presence of any immiscible fluid A (such as water) in a porous medium on the permeability of the medium to a fluid B (such as oil) have been established separately by Hassler,1 Dunlap,2 and the writer (Fig. I),3 so that the average specific or dry-core permeability as determined in the laboratory can be corrected to give the true measure of the ability of the horizon penetrated to transmit oil, provided the percentage of pore space occupied by connate water is known accurately.

Jan 1, 1942

By JOHN BIRKNBINE

MR. NEILSON was born Aug. 12, 1842, at Philadelphia, Pa., where he died Dec. 30, 1906. His business career began with his graduation, in the class of 1862, from the Polytechnic College of the State of Pennsylvania. For a short time after graduation he was instructor in mathematics at the college, and then became associated with Messrs. Booth & Garrett, chemists, of his native city: In 1867 he was sent to the Adirondack mountains to care for mining interests of the late Jay Cooke, and spent about three years there, operating the forges at Elizabethtown, Essex county, N. Y. He also prepared an interesting monograph on Catalan forges and their operations. In 1868 he published a chart showing the material progress of the United States, and the cost of certain staple products during a series of years, which is believed to be the first of its kind issued in this country. In 1870 he made a trip to the Pacific Coast, prior to entering the service of the Pennsylvania Steel Company. In 1871, when the Logan Iron & Steel Co., of Burnham, Pa., failed, Mr. Neilson was appointed receiver, re-organized the company, became' its General Manager, and spent more than four years in this work. In the meantime, he became interested in the Freedom forge of the same place, and, with Mr. Wm. Burnham and Mr. Milton Brosius, laid the foundations for what is now the Standard Steel Works. From Jan. 1, 1877, to April 1, 1890, he was General Manager of these works, and closely associated with the Baldwin Locomotive Works. In 1878 he was in charge of the first consignment of Baldwin locomotives to Europe, which, with a picked crew of men from Baldwin's, he took to Eydtkennen, Russia, and placed in service. In 1890 he resigned from the Standard Steel Works and ac-

Jul 1, 1907

By L. E. Tanner

A study was made of the transformation kinetics of the commercial titanium-base alloys, Ti-2.5Al-16V and Ti-4A1-3Mo-1V, using two different heat treatment cycles: 1) step-quenching to aging temperatures from a ß solution anneal and 2) water-quenching from an a+ß solution anneal followed by reheating to aging temperatures. Metallographic examination and hardness testing provided the major portion of the data, while electrical resistivity, dynamic elastic modulus, and X-ray diffraction techniques were also used to obtain critical or confirnzatory data. TTT diagrams were constructed from these results. The sheet alloys, Ti-2.5Al-16V and Ti-4Al-3Mo-lV, are of current interest to the Department of Defense. As an aid to the planning of their respective heat treatments, a program was carried out to determine the transformation kinetics of these alloys using ß and a + ß reference states. This paper presents the TTT diagrams constructed from data obtained by metallographic examination and hardness testing, as well as by X-ray diffraction, electrical resistivity, and dynamic elastic modulus determinations. EXPERIMENTAL PROCEDURE Materials—Sheets of the alloys were obtained from the producers in the "mill anneal'' condition and were tested prior to shipment to assure their meeting mill specifications. Chemical analyses were also supplied and are presented in Table I. Heat Treatment—The majority of the data presented in this study were obtained from hardness testing and metallographic examination. Sample coupons were cut from the alloy sheets and heat treated on a mass scale. The annealing cycles were operated in the following manner: 1) The ß solution anneals were carried out in a horizontal tube furnace with the bare samples protected by a dynamic helium atmosphere. Following this treatment, the samples were quickly transferred to lead, solder, or oil-bath furnaces for aging. After prescribed times at the various reaction temperatures they were water-quenched. 2) The second cycle simulated commercial practice, which requires the alloys be quenched to room temperature following the a + ß sotution anneal. This anneal was carried out in a muffle furnace with a dynamic helium atmosphere. The specimens were then reheated from room temperature to the reaction temperatures in lead, solder, or oil-bath furnaces, followed by water-quenching after prescribed times at these temperatures. Information concerning the critical temperatures of the alloys was obtained from the literature and solution treatments were based on these values. A summary of the solution annealing treatments is found in Tables II and 111. The aging temperatures for the (a - ß alloys ranged in 50°C intervals from 200°C (392oF) to approximately 50°C below the ß/a + ß transus in the first cycle and approximately 50°C below the a + ß solution temperature in the second. The transformations in these alloys were known to be rather rapid, and thus aging times started at 0.5 min and went to a maximum of 7000 min. Hardness Testing and Metallographic Preparation— Heat-treated samples were sheared and mounted in Bakelite with their cut edges exposed. After a flat surface was ground, the hardness was determined in Vpn on an Armstrong-Vickers machine utilizing a 20-kg load. Three to four impressions were made on each specimen. After this procedure, the hardness impressions were removed and the edge surfaces of the specimens were prepared for metallographic examination in the usual manner. The etchant was 20 pct HF and 20 pct HNO3 in glycerine. Electrical Resistivity—It has been shown that the isothermal reactions in titanium-base alloys can be followed by measuring the changes in e1etrical resistivity attending these transformations. As mentioned earlier, the reaction kinetics of a-ß alloys are rather rapid; thus, it would be expected that resistivity data obtained from these alloys would be more significant if measurements were made continuously at the respective aging temperatures. To accomplish this end a special apparatus, based on the current-potential principle, was assembled. Its design was derived from earlier devices constructed by Colner and zmeska1 4 and Levinson.5 The set-up provided for the heat treatment zof machined specimens (approximately 2 x l0-4in. in cross section by 3 in. in length) and the determination of their relative

Jan 1, 1962

By Walter R. Hibbard, Harold Margolin

DURING preliminary tests on the aging of a Cu-plus 5 pct Ag alloy,' a specimen which had been overaged 24 hr at 550°C was annealed in a nitrogen-hydrogen atmosphere first for 2 hr and then for an additional 28 hr at 600°C. After each anneal the specimen was cooled to room temperature in about ½ hr and X-ray photograms were made. The first film, Fig. la, revealed two sets of copper-base lines, one intense and corresponding to the parameter at 550°C, the other fainter and shifted away from the beam, corresponding to the larger parameter at 600°C (see arrows). The 30-hr film, Fig. lb, revealed the same two sets of copper-base lines with a reversal of intensity. In neither case do the copper lines form a broad band which would be indicative of a range of compositions. This phenomenon is thus a "discontinuous" type of solution. A similar phenomenon was observed in a Ag-rich Cu-Ag alloy.' Finlay and Hibbard9 have suggested that directional rather than random solution of precipitate occurs in some alloys. Conceivably, for Cu-Ag alloys, the matrix-transition-precipitate precipitation sequence is reversible for the re-solution of the precipitate caused by rapidly raising the annealing temperature of an overaged specimen. A copper-base transition structure supersaturated with solute might be formed around the precipitate as it dissolves, thus obviating the necessity for a gradually changing solute composition of the matrix. The solute atoms then might be transferred rapidly and locally from the transition to the matrix phase in the proper amount and at the proper location to obtain directly the new ex- panded solid solution. The theory implies a minimum of diEusion of solute in the matrix (i.e., no significant range of matrix composition) and possibly suggests that the composition of the transition structure will vary with the conditions of re-solution. A transition copper phase found in aged Cu-Ag alloys1 might fulfill this function. Evidence regarding this suggestion could be obtained in Cu-Ag alloys by overaging a specimen until no trace of the expanded copper lattice is present and then subjecting the specimen to a retrogression treatment. Re-appearance of the transition copper phase would confirm the theory. Additional details could be secured by varying both aging and retrogression temperatures. References 'H. Margolin and W. R. Hibbard, Jr.: Effect of Ternary Additions on the Age Hardening of a Copper-Silver Alloy. Trans. AIME (1951) 191, p. 174; Journal of Metals (Feb. 1951) TP 3002E. 2 W. Ageew, M. Hansen, and G. Sachs: Decomposition and Changes in Properties of Super-saturated Silver-Copper Alloys. Ztsch. Physik (1930) 66, p. 350. 3W. L. Finlay and W. R. Hibbard, Jr.: Some Effects of Applied Stresses on Precipitation Phenomena. Trans. AIME (1949) 180, p. 255; Metals Technology (Sept.

Jan 1, 1952

By P. D. I. Honeyman

CHANGING trends in concentration, involving regrinding with the subsequent production of a finely divided, high-grade flotation product, presents a real problem to the modern copper smelter. In the treatment of such a material, handling difficulties are numerous and potential possible losses may be very great. In many plants, of course, preliminary roasting of the furnace charge remains an economical necessity. Under such circumstances, the operator has no alternative except to follow orthodox roaster reverberatory practice, though taking all possible precautions to avoid excessive dust losses and bad working conditions. In other plants, roasting is not only unnecessary but would be highly undesirable, and at best the charge would be merely dried before entering the reverberatory furnace. In the latter case the possibilities of raw charging loom large. The Miami plant of the International Smelting Co. handles the entire output of concentrates of the several mining companies operating in the Globe-Miami district. All of these companies produce a flotation concentrate which, at the Miami Copper Co. particularly, is all reground and is high in grade. In addition, the Inspiration Copper Co. ships a substantial tonnage of high-grade cement copper to the smelter from its leaching plant. Following the flow sheet of the original plant, all such material received was bedded, dried in Wedge furnaces and smelted in reverberatory furnaces. At times during the history of the plant it has been necessary to carry the drying operation further, to a partial roast, before reverberatory smelting. Since the charge contained over 80 per cent flotation concentrates, the handling of which in a dried condition was at best a dusty job, unusual precautions were taken to cut down dust losses. The Wedge furnace plant was equipped with a Cottrell treater and all hoppers and calcine cars were carefully designed to cut down dust loss in transferring the so-called calcine from hoppers to car and from car to furnace. In the furnace itself the dusting problem was a severe one. Arch erosion was very rapid and flues and waste-heat boilers rapidly filled up with a partly smelted flue dust.

Jan 1, 1932

By M. T. Simnad, C. E. Birchenall, M. H. Davis

The transport mechanisms previously proposed in wustite and hematite have been confirmed by movement of inert markers during the growth of these phases. By similar measurements the mechanism for magnetite has been determined. The rates of growth of multilayer scales on iron, magnetite and hematite on wustite, and hematite on magnetite have been measured. All rates are found to be diffusion controlled under the conditions of the experiments. MANY studies have been made of the rate of oxidation of iron in both the low temperature, film-forming region and the high temperature scaling range. The interpretation of the results has been greatly complicated by the formation of multi-layered scales containing the various phases of iron oxides. In most cases no attempt has been made to determine the composition of the scale and its dependence on time of oxidation in a quantitative manner. However, several recent studies'" have taken this variable into account. It is generally agreed that the growth of thick scales on iron follows a parabolic rate law for the increase of total thickness. In the thin film region agreement has been claimed with parabolic equations of various forms and with logarithmic equations. The discussion here will be concerned only with the formation of scales of considerable thickness, greater than several microns, although some of the conclusions may be applicable to thin films. A brief survey will be given of the solid phases of the iron-oxygen system, the stability of wiistite in bulk and in thin films, the relative densities of iron in the metal and oxides, and the kinetics of forma- tion of oxide scales on iron. New experimental results will be introduced at several points during the discussion, and an attempt will be made to formulate a mechanistic picture consistent with these observations. The experimental techniques are described in an appendix. Iron-Oxygen System Fig. la shows the iron-oxygen phase diagram. Wüstite ("FeO"): The lowest of the oxides has a NaCl type cubic lattice formed by close-packing of the relatively large oxide ions with the smaller iron ions arranged in the interstices. The ionic radius for 0' is about 1.3 A, while Fe++ has a radius of about 0.8A and Fe"' about 0.7A. Its range of existence on the phase diagram is very wide for an ionic material of this type and does not seem to include the stoi-chiometric composition FeO. These deviations appear to be well established as vacancies on iron lattice sites by the comparison of lattice parameters and densities for a series of compositions by Jette and Foote.4 The limits of the field are disputed, but the work which seems most reliable" indicates vacancies in from 5 pct to more than 12 pct of the iron sites. In order for the crystal to be electrically neutral, there must be electron holes which correspond to the formation of trivalent iron ions equal to twice the number of vacancies. Magnetite ("Fe³O4"): Considerable disagreement also exists in the literature about the stable range of the Fe³O4 field. Some diagrams show the Fe³O4 composition to be lower in oxygen than the formula indicates, but Schenck6 gives a diagram from the

Jan 1, 1952

By R. Maddin, C. H. Mathewson, W. R. Hibbard

Recent publicationsl.2 establishing the presence of cross-slip in strained metallic single crystals oriented wholly within the area of single slip as predicted from the generalizations of Taylor and Elam3 described these markings as they appeared during the initial stages of the deformation process. At that time, the plane having a common glide direction with the primary slipping plane was reported as the cross-slip plane although the specific direction was not confirmed. Consequently, in continuation of the research, it seemed advisable to investigate the micro-graphic appearance of cross-slip together with the Laue back-reflection X ray analysis and stress-strain data during the later stages of the deformation process. Accordingly, a single crystal of brass (72.75 pct Cu, 0.01 pct Fe, 0.01 pct Pb, 27.23 pct Zn) was polished mechanically and repolished electrolytically after the manner described in the earlier paper.' Three pairs of flat surfaces, parallel to the specimen axis, and (1) perpendicular to the plane containing the pole of the primary glide plane and the specimen axis, (2) perpendicular to the plane containing the pole of the cross-slip plane and the specimen axis, and (3) perpendicular to the plane containing the slip direction and the specimen axis, were polished mechanically and repolished electrolytically, resulting in a final minimum gauge diameter of 0.4864 in. in a gauge length of 3.36 in. The specimen was elongated in tension and load-extension readings were taken following the method described in the initial investigation.' Observed reorientations were obtained from a series of Laue back-reflection photograms at the center and ends of the gauge length and at various positions around the circumference of the specimen. These were interpreted after the manner of A. B. Greninger.4 Cross-slip (Fig 1 and 2) was found with the first appearance of the primary slip clusters and usually joined members of these clusters. In addition, a third set of entirely different markings (Fig 3) could be noted. The displacement of this third set by the primary slip lines was measured as 8300 at. diam (3.04 microns). Since the specimen was carefully observed at high magnifications before any deformation and no markings of any type could be noted, it would appear that this third set was formed during the deformation process prior to the initiation of classical primary slip. Additional extensions produced no unusual change in the appearance of either cross-slip or the third set of markings. The number of lines increased with increasing elongation and appeared, generally, in areas where earlier markings were present. The continuity of the clusters of cross-slip lines in Fig 4, 5 and 6 illustrates that they are neither noticeably displaced by nor do they displace the primary lines at this stage. In Fig 7, cross-slip appears in a long narrow localized band approximately 45 degrees from the stress axis. This somewhat resembles a twin band except for the lack of a sharp boundary. After a shear of 0.257, suffcient additional glide occurred on the cross-slip plane to displace the primary slip lines (Fig 8). Generally, where a large number of cross-slip lines could be observed in an area on one flat surface, few cross-slip lines appeared on the diametrically opposite position on the parallel flat (Fig 9). These, of course, were not matched observations on the same glide ellipses. It was extremely difficult to make such comparisons. The third set of markings (Fig 10) was extensively displaced by glide on the primary slip planes. A plot of the width of primary slip clusters versus their displacement of the third set of lines is shown in Fig 11. The slope and the linearity of the plot suggest that each primary glide plane slips to a constant maximum value of shear before further slip is transferred to another plane. A shear value of 0.28 was determined in this case. Heidenreich5 has presented a similar schematic representation of glide for aluminum. After the specimen had attained an elongation of 51.8 pct, corresponding to a shear of 0.973, cross-slip appeared very prominently in certain areas as shown in Fig 12, yet at diametrically opposite positions very little cross-slip could be noted, Fig 13. Classical conjugate slip was found at this advanced stage in the deformation, Fig 14, which corresponds to the axial location shown at 12 in Fig 15. It should be noted that cross-slip occurs within the conjugate slip clusters and on the same plane as the cross-slip associated with the closely spaced primary lines which constitute a background in less distinct focus. The third set of markings noted at all stages in the deformation of the

Jan 1, 1950

By Richard Addison, Ronald O. Cranor

Tailings dam construction and operation of Rosario Dominicana's gold/silver mine in the Dominican Republic is described. Impoundment of 8.5 kt/d of cyanide-process tailings is required in an intensive agricultural area which is also an earthquake and high rainfall zone. The earthfill embankment dam, incorporating internal gravel drains, is described together with methods of construction used. Methods of tailings transport, solution reclaim, and runoff water diversion that have evolved are discussed.

Jan 1, 1982

By S. F. Ravitz

In his excellent book on the Principles of Flotation, Warkl makes the following significant statement concerning the theory of flotation: Two questions of first-rate importance must be considered . . . First, it must be decided whether the sulfide minerals require a collector in order that they may float, or whether as has been claimed, they possess an inherent float-ability and need no collector. Second, it must be decided whether the xanthate type of collector can react with or be adsorbed by the unchanged sulfide minerals themselves, or whether, as many claim, reaction with the collector is dependent upon initial oxidation of the mineral surface. In the theory of flotation there are no two questions of greater importance than these. Ravitz and Porter2 presented evidence that galena can be floated without a collector, and even without any reagent, provided oxidation products are thoroughly removed from its surface. They found also that thoroughly cleaned galena floated faster when xanthate was used than when a frother alone or no reagent was used, and that, without a collector, the recovery decreased gradually upon exposure of the mineral to air. Their work, however, has met with considerable criticism.l(127).3-6 This paper is presented to answer the objections that have been raised, and to present additional data that confirin their results. The apparatus used to provide oxygen-free conditions for flotation has been described in detail by Ravitz and Porter. An atmosphere of purified nitrogen was maintained within the apparatus; all water and solutions used were freed of dissolved air, and could be transferred where desired by the use of nitrogen Pressure; nitrogen was used as the gaseous medium for flotation. The flotation cell was essentially a glass cylinder 15 cm. long and 4.6 cm. in diameter. Near the bottom was sealed a fritted glass filter, which broke up the gas into small bubbles, and 6 cm. above this filter was a side arm through which the froth overflowed. The pulp was agitated by a glass impeller, which entered the cell through a mercury seal. For each test 17 grams of galena and 75 ml. of water were placed in the cell, after which the speed of the impeller and the rate of gas flow were adjusted. Water was added gradually during the test to keep the froth level at the proper height. The mineral was prepared and cleaned in the following manner. Exceptionally Pure galena was crushed by hand on a clean bucking board, screened to —I50+ 200 mesh, and deslimed on a 200-mesh sieve with a fine spray of water. It was then boiled on a hot plate for a number of hours with several changes of the desired cleaning solution, after which both the solution and the mineral were placed in the "mineral flask" of the apparatus. The cleaning solution was drained off, and the mineral was boiled with oxygen-free water

Jan 1, 1943

By S. F. Ravitz

In his excellent book on the Principles of Flotation, Warkl makes the following significant statement concerning the theory of flotation: Two questions of first-rate importance must be considered . . . First, it must be decided whether the sulfide minerals require a collector in order that they may float, or whether as has been claimed, they possess an inherent float-ability and need no collector. Second, it must be decided whether the xanthate type of collector can react with or be adsorbed by the unchanged sulfide minerals themselves, or whether, as many claim, reaction with the collector is dependent upon initial oxidation of the mineral surface. In the theory of flotation there are no two questions of greater importance than these. Ravitz and Porter2 presented evidence that galena can be floated without a collector, and even without any reagent, provided oxidation products are thoroughly removed from its surface. They found also that thoroughly cleaned galena floated faster when xanthate was used than when a frother alone or no reagent was used, and that, without a collector, the recovery decreased gradually upon exposure of the mineral to air. Their work, however, has met with considerable criticism.l(127).3-6 This paper is presented to answer the objections that have been raised, and to present additional data that confirin their results. The apparatus used to provide oxygen-free conditions for flotation has been described in detail by Ravitz and Porter. An atmosphere of purified nitrogen was maintained within the apparatus; all water and solutions used were freed of dissolved air, and could be transferred where desired by the use of nitrogen Pressure; nitrogen was used as the gaseous medium for flotation. The flotation cell was essentially a glass cylinder 15 cm. long and 4.6 cm. in diameter. Near the bottom was sealed a fritted glass filter, which broke up the gas into small bubbles, and 6 cm. above this filter was a side arm through which the froth overflowed. The pulp was agitated by a glass impeller, which entered the cell through a mercury seal. For each test 17 grams of galena and 75 ml. of water were placed in the cell, after which the speed of the impeller and the rate of gas flow were adjusted. Water was added gradually during the test to keep the froth level at the proper height. The mineral was prepared and cleaned in the following manner. Exceptionally Pure galena was crushed by hand on a clean bucking board, screened to —I50+ 200 mesh, and deslimed on a 200-mesh sieve with a fine spray of water. It was then boiled on a hot plate for a number of hours with several changes of the desired cleaning solution, after which both the solution and the mineral were placed in the "mineral flask" of the apparatus. The cleaning solution was drained off, and the mineral was boiled with oxygen-free water

Jan 1, 1943

By Robert Warner

WHEN a new mine is opened, and often when an operating mine must adapt itself to physical or economic changes, a mining system must be selected in complete detail. In the past the plan chosen was usually the product of the local staff alone, however limited the training and experi-ence of that staff might be, which often resulted in the introduction of methods that were familiar to the staff, but not so well suited to the con-ditions as others unknown to the local men. A new management, noting the difficulties with the existing layout, might make modifications or complete changes, so that many mines in their history have seen a whole series of mining systems, each somewhat laboriously grafted on to its predecessor. This should not be interpreted as a condemnation of the older staffs for sticking to the tried systems, such as open square-sets in the early days at the Homestake, because they knew it would work after a fashion, nor does the statement apply to the technically trained, and usually broadly experienced staffs of most present-day properties. The older miners did not have the variety of tools and methods, nor the present freedom of transfer of information as to what the other man is doing, and so did the best they could under the circumstances. Finally, the higher grade of the ores made the choice less vital. The ever-increasing need to mine low-grade orebodies, with a fixed or even lower price for the metal produced, has caused an increasing need for low-cost mining. In most new mines this has simplified the problem of selection by eliminating from consideration all of the high-cost systems, but it has also complicated the choice by the necessity for refinement in detail and a close adjustment of the plan selected to all the conditions at the property. In these low-cost problems any textbook division of mining systems as applied to "beds, veins or masses" avails little as a guide. It should be realized at the outset that to' be successful under modern competitive conditions a system of mining must be worked out with elaborate detail, with careful time scheduling and control of the various elemental operations, and that after it is introduced it must be run with a large amount of technical direction.

Jan 1, 1933