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By V. A. Zanadvoroff

The mine and concentrator of the Howe Sound Co., Chelan Division, are at Holden, in a remote section of the Cascade Mountains of northwestern Washington. Holden is at an elevation of 3200 ft., in the narrow valley of Railroad Creek. This creek drains into Lake Chelan, at a point some 40 miles up the lake from the town of Chelan. The concentrator treats 2000 to 2500 tons of low-grade copper-gold-zinc ore per day. Concentration is achieved by the differential flotation process, with recovery of 94 per cent copper and 82 per cent gold in the copper concentrate, followed by the recovery of 65 to 70 per cent zinc in the zinc flotation circuit. The final flotation tailing is deslimed, and coarse . sands, representing 60 to 70 percent of the total, are cyanided. The tonnage of tailing material amounts to 1900 to 2370 tons per day. General Considerations The property is within the Chelan National Forest. Railroad Creek is a fishing stream, being stocked regularly with trout from State hatcheries. Consequently, in planning a milling operation, the Howe Sound Co. was obliged to avoid any pollution of the stream by tailing material, and also destruction of valuable stands of timber. Moreover, the selected tailing- disposal sites should not mar the natural beauty of the valley. In addition to these requirements, the problem of tailing disposal at Holden was complicated by topography and climatic conditions. The valley is long and narrow, averaging 1200 to 1500 ft. in width. Its walls are flaring at a steep angle. There are no extensive flat areas suitable for deposition of tailing. All valleys tributary to Railroad Creek, also the well-marked paths of snowslides, must be avoided. Finally, the direction of prevailing winds and possible dust hazard arising therefrom dictated the necessity of selecting the tailing-disposal sites downstream from the mill building and two campsites. Heavy snowfall during the winter months of November to March, inclusive, impedes building of the retaining dike, making it necessary to prepare the needed storage space during the summer months. It is inadvisable, also, to do any dike building during the freezing weather, because the dike becomes unstable with the spring thaws, producing inevitable "sloughing" of the built-up borders. Tailing-disposal Sues The existing tailing-disposal areas are near the south wall of the valley. They were developed, and put to use in the following sequence: No. I. Area.—Covers approximately 10 acres. Built up to the height of 60 ft. and abandoned. Total length of dike border is 1900 feet.

Jan 1, 1947

By W. O. Philbrook, K. M. Goldman, G. Derge

EQUILIBRIUM conditions for steelmaking reactions have been studied extensively over the past two decades by a .number of investigators, with gratifying results. Equilibrium data are essential to the understanding of any process, and such knowledge has the practical utility of placing a limit beyond which control measures cannot succeed. When, however, the driving rate of an industrial process is so fast that there is not time for reactions to reach equilibrium, it then becomes necessary that the factors which control the rates of reaction be known in order to establish full control of the process. The desulphurization of molten pig iron by slags within the iron blast furnace is one such process in which the actual degree of sulphur absorption by the slag does not approach the equilibrium distribution obtained for similar slag-metal systems in the laboratory.' A study of the rate-controlling factors governing the desulphurization of iron by slags is becoming increasingly important as the sulphur content of raw materials increases with depletion of higher grade ores and coal. Following up an initial study on kinetics,' this paper reports some results of a continuing laboratory investigation on the mechanism of sulphur transfer between molten iron saturated with carbon and slags of the CaO-SiO,-A12O3 system. Laboratory experiments cannot reproduce in detail the conditions which prevail in the hearth of a blast furnace, but they will contribute to an understanding of the smelting reactions and perhaps will explain some apparent inconsistencies in the factors controlling the equilibrium distribution of sulphur between iron and slags under reducing compared with oxidizing conditions. The mechanism of a reaction—that is, the individual steps and the sequence in which they occur to produce the overall reaction which is ordinarily observed—must be elucidated to learn which steps are the slow ones, or "bottlenecks," that fix the pace of the process as a whole. In the desulphurization reaction, for example, the overall rate might, in principle, depend upon the rate of diffusion of sulphur in the metal or in the slag, upon the speed of some homogeneous reaction taking place entirely within one of the phases, or upon some heterogeneous reaction taking place across the slag-metal interface. Even some side reaction or the back reaction might have some influence. Evidence on all of these points will be presented in this paper. The rate of diffusion of sulphur in both iron and slag is so slow that it seems necessary to assume that convection provides the mechanism of carrying

Jan 1, 1951

By C. E. Agnew

The Eastern district, composed of New Jersey and eastern Pennsylvania, with its native ores, was the cradle of the iron industry of the United States. The district attained and held the leadership in production of pig iron for over 100 years, from pre-Revolutionary days to approximately 1875. The first shipment of Lake hematite ore was made in 1853. It was a small shipment, transported by a sailing vessel and a canal barge, but it was the beginning of the end of the supremacy of the Eastern district, although at that time the ore was supposed to be too rich to be successfully smelted with the block coal then in use at western furnaces. The iron made from the first shipment of Lake ore was worked into nails by the Sharon Iron Co., at Sharon, Pa. The writer's great-grandfather, David Agnew, and his brother, John P. Agnew, owners and operators of the Sharpsville furnace, Sharpsville, Pa., worked the shipment through a furnace. Because of this, the writer feels some satisfaction in having been one of a group that solved the problem of making profitable an operation using Eastern district ores exclusively. With the development of Lake mines, and the production and use of coke, the Middle West district gradually assumed the position of leadership in production; because, even though the ores were transported 1000 miles by water and rail, its cost figure on pig iron was better than that of the eastern producer whose furnace was next to his mine. Such a cost figure was possible because the ore was naturally rich in iron and reduced easily. It was possible to carry a heavy burden on the furnace, which resulted in large tonnage and low coke per ton of iron. This paper is in no sense a technical one. The purpose is to show that with the proper physical preparation of the Eastern magnetites they will reduce as easily as the Lake hematites, and because of the high iron concentration give the Eastern producer just as much advantage as formerly he was at a disadvantage in comparison with the Middle West producer.

Jan 1, 1938

By C. E. Agnew

The Eastern district, composed of New Jersey and eastern Pennsylvania, with its native ores, was the cradle of the iron industry of the United States. The district attained and held the leadership in production of pig iron for over 100 years, from pre-Revolutionary days to approximately 1875. The first shipment of Lake hematite ore was made in 1853. It was a small shipment, transported by a sailing vessel and a canal barge, but it was the beginning of the end of the supremacy of the Eastern district, although at that time the ore was supposed to be too rich to be successfully smelted with the block coal then in use at western furnaces. The iron made from the first shipment of Lake ore was worked into nails by the Sharon Iron Co., at Sharon, Pa. The writer's great-grandfather, David Agnew, and his brother, John P. Agnew, owners and operators of the Sharpsville furnace, Sharpsville, Pa., worked the shipment through a furnace. Because of this, the writer feels some satisfaction in having been one of a group that solved the problem of making profitable an operation using Eastern district ores exclusively. With the development of Lake mines, and the production and use of coke, the Middle West district gradually assumed the position of leadership in production; because, even though the ores were transported 1000 miles by water and rail, its cost figure on pig iron was better than that of the eastern producer whose furnace was next to his mine. Such a cost figure was possible because the ore was naturally rich in iron and reduced easily. It was possible to carry a heavy burden on the furnace, which resulted in large tonnage and low coke per ton of iron. This paper is in no sense a technical one. The purpose is to show that with the proper physical preparation of the Eastern magnetites they will reduce as easily as the Lake hematites, and because of the high iron concentration give the Eastern producer just as much advantage as formerly he was at a disadvantage in comparison with the Middle West producer.

Jan 1, 1938

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By F. Keller, J. D. Edwards

The anodic treatment of aluminum presents problems of scientific as well as of commercial interest.l-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non-adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By F. Keller, J. D. Edwards

The anodic treatment of aluminum presents problems of scientific as well as of commercial interest.l-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non-adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By Frederic A. Delano

In adding one more to the list of papers that have been presented on the subject of steel rails, I wish to explain at the beginning that in enumerating the steps in the manufacture which, I think, have an all-important effect on the wearing-qualities of the rail produced, I do so with no little hesitation. As a student in the field, I am anxious for the opinions of others, and have finally decided to ask for it in this way. I have not stated everything which I think affects, in one way or another, the life of rails, but have confined myself to those steps in the manufacture which I felt most sure did do so. Recognizing the danger of being carried away by enthusiasm, I have endeavored to make my assertions with caution, and to understate my case rather than to overstate it; but if I have succeeded in throwing a ray of light on this vexed question and placed it in the eyes of some railroad men in an aspect which they have not fully considered, my boldness will be more than justified. I. Uniformity in the quality of the material charged into the converter assists the attainment of uniformity in the steel produced.— This is the argument which is used by the champions of the cupolamelting or indirect process, and has considerable weight. It takes vastly more skill to make good steel if there is a great irregularity in the iron charged into the vessel than if there is not this irregularity ; but on the other hand, there are certain advantages in the direct method, such as a lower sulphur-percentage from the same furnace-iron, while it is possible to get as great uniformity in the iron charged by having the furnace-capacity enough in excess of the demands from the converting department, to allow for occasional " slips " in the furnaces, and permit the mixing of the iron from two furnaces which are respectively too " hot" and too "cold." 11. Care in pouring ingots at the proper temperature into warm moulds, and the treatment of ingots before rolling, have important effects on the rails made from them. In other words, many of the failures in rails and the uneven wear of rails are often traceable to

Jan 1, 1888

By W. H. Echols

An oil-emulsion mud, consisting of a mixture of oil-base mud and bentonitic water-base mud, has been used experimentally in drilling 8 of the 35 wells in the Sivells Bend field, Cooke County, Texas. Experience indicates the oil-emulsion mud can be controlled in much the same manner as a water-base mud, and the "drilling" functions of the two types of mud are comparable. The average water-loss for the oil-emulsion mud was 3.8 cu cm per well. When using oil-emulsion mud to drill the last 2000 ft of 7000 ft wells, the mud costs were approximately 2½ times that of water-base mud. There is nothing to indicate well productivities have been affected through the use of oil-emulsion mud. However, drilling time and bit footages were increased and the holes were maintained more closely to bit guage. The apparent advantages gained through the use of oil-emulsion mud in the Sivells Bend field do not appear to justify the increase in mud costs. Introduction until a comparatively few years ago most of the development of drilling mud was directed toward improving the functions of the mud as related to actual drilling operations. The industry has long recognized that one disadvantage of rotary drilling over cable-tool drilling is the possibility of injury to producing zones through the blocking effect resulting from the infiltration of water or mud into the sands. Recognizing this disadvantage, considerable attention has been diverted toward the development of muds that will improve the quality of well com-pletions through the reduction or elimination of water into the sands, but without sacrificing too many of their "drilling" functions and at a cost commensurate with the benefits derived from their use. This phase of mud research has already found practical application, for example, in the development of the Rangely field, Colorado, it appears the use of oil-base mud during drilling-in operations will contribute appreciably toward making this exploitation more profitable. Much of the discussion to follow will be better understood if a brief sketch of the Sivells Bend field is given. The Sivells Bend field, discovered by The Texas Co. in 1944 and still in the process of development, is in a large bend on the Texas side of the Red River about 85 miles north of Dallas. Geologically, the structure is an unsymmetrical anticline, with faulting having contributed to its development. The productive sands are of the Strawn series of Pennsylvanian age, the sands being lenticular in character and varying considerably in development from well to well. At Present there are 35 producing wells in the field, producing from seven different sand lenses. The productive sand lenses vary from 15 to 50 ft in thickness and the individual sands have average permeabilities of from 75 to 375 md. The presently productive sands are encountered at depths of from 6300 to 7300 ft, but testing has indicated that commercial production might be obtained from other sands as high as 5200 ft. Histories of older Strawn

Jan 1, 1948

By W. H. Echols

An oil-emulsion mud, consisting of a mixture of oil-base mud and bentonitic water-base mud, has been used experimentally in drilling 8 of the 35 wells in the Sivells Bend field, Cooke County, Texas. Experience indicates the oil-emulsion mud can be controlled in much the same manner as a water-base mud, and the "drilling" functions of the two types of mud are comparable. The average water-loss for the oil-emulsion mud was 3.8 cu cm per well. When using oil-emulsion mud to drill the last 2000 ft of 7000 ft wells, the mud costs were approximately 2½ times that of water-base mud. There is nothing to indicate well productivities have been affected through the use of oil-emulsion mud. However, drilling time and bit footages were increased and the holes were maintained more closely to bit guage. The apparent advantages gained through the use of oil-emulsion mud in the Sivells Bend field do not appear to justify the increase in mud costs. Introduction until a comparatively few years ago most of the development of drilling mud was directed toward improving the functions of the mud as related to actual drilling operations. The industry has long recognized that one disadvantage of rotary drilling over cable-tool drilling is the possibility of injury to producing zones through the blocking effect resulting from the infiltration of water or mud into the sands. Recognizing this disadvantage, considerable attention has been diverted toward the development of muds that will improve the quality of well com-pletions through the reduction or elimination of water into the sands, but without sacrificing too many of their "drilling" functions and at a cost commensurate with the benefits derived from their use. This phase of mud research has already found practical application, for example, in the development of the Rangely field, Colorado, it appears the use of oil-base mud during drilling-in operations will contribute appreciably toward making this exploitation more profitable. Much of the discussion to follow will be better understood if a brief sketch of the Sivells Bend field is given. The Sivells Bend field, discovered by The Texas Co. in 1944 and still in the process of development, is in a large bend on the Texas side of the Red River about 85 miles north of Dallas. Geologically, the structure is an unsymmetrical anticline, with faulting having contributed to its development. The productive sands are of the Strawn series of Pennsylvanian age, the sands being lenticular in character and varying considerably in development from well to well. At Present there are 35 producing wells in the field, producing from seven different sand lenses. The productive sand lenses vary from 15 to 50 ft in thickness and the individual sands have average permeabilities of from 75 to 375 md. The presently productive sands are encountered at depths of from 6300 to 7300 ft, but testing has indicated that commercial production might be obtained from other sands as high as 5200 ft. Histories of older Strawn

Jan 1, 1948

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.' In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.' Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol'kenshtein's effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS' attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By A. G. Guy

Zinc vapor from a reservoir of liquid zinc maintained at lower temperatures was diffused into sets of copper-zinc alloys at 759° and 870° C and into sets of silver-zinc alloys at 650° and 700° C. Each set of ,four copper-zinc alloys consisted of pure copper and 90/10, 80/20, and 70/30 brass. Similarly the set of silver-base alloys consisted of specimens containing 0, 7, 15, and 20 pct Zn. Natural markers at the initial surfaces of the specimens ware "trapped" under a thin electroplate and their depth of burying was measured after diffusion. The ratio of diffusivities of the two components determined from these data and the chemical diffusion coefficient calculated by the Matano method agreed with previously reported results. The line of markers was irregular and was often discontinuous when a grain boundary was crossed. TECHNIQUES involving the vapor phase have been widely employed in studying diffusion phenomena in metals. Many investigators have evaporated the more volatile component from an alloy, but it is generally believed that the porosity created under these conditions interferes with adequate interpretation of the experimental results. The extensive work of Gertsriken6 has been criticized on this score. Accary1 found that the diffusion coefficient for de-zincification of brass is larger by a factor of five than that for zincification, although he attributed the difference to a higher vacancy concentration under conditions of dezincification. Balluffi and siegle2 thoroughly investigated the technique of adding a more volatile component to a less volatile base metal as a means for studying diffusion. They verified that no porosity forms in a brass under these conditions and that the diffusivities of the two components can be determined from observations of the motion of markers originally placed on the surface of the specimen. The mathematical analysis that they developed for treating the experimental data was modified in a later note, but essentially it involved using the graphical Boltzmann-Matano method that is customarily applied to solid-solid diffusion couples. The experimental method used in the present research was similar to that employed by Balluffi and Siegle except for two modifications. Balluffi and Siegle used alloy chips as the source of metal vapor. This procedure has the disadvantage that the concentration of solute at the surface of the specimen changes during the diffusion experiment as the alloy content of the chips is gradually decreased. This disadvantage was overcome by employing liquid zinc as the source of zinc vapor in a manner similar to that described by Herasymenko.9 There was then no limitation on the amount of solute usefully available, and several relatively large specimens could be diffused in a given experiment. The second modification was the use of natural markers on the surface of the specimen rather than larger, artificial markers, such as the alumina powder employed by Balluffi and Siegle. It was expected that the fine, natural markers would permit more precise measurement of the buried interface as in the case of ordinary sandwich specimens.10 EXPERIMENTAL The experiments were designed so that zinc from the vapor phase would maintain a constant zinc content at the surface of pure copper (or silver) and

Jan 1, 1960

By H. H. Evinger, M. Muskat

A methoD of calculating productivity factors for oil, gas, and water systems in the steady state is presented as an illustration of the quantitative application of the fundamental data on the flow properties of heterogeneous fluid systems. While the numerical results of the calculations cannot be applied directly to field conditions, because they are based on permea-bility data for unconsolidated sands and involve specific assumptions regarding the nature of the reservoir fluids, the methods of analysis and interpretation should havc significance in considering certain specific field situations when the necessary field and laboratory data become available. Moreover, it is felt that even under the idealized conditions to which the numerical calculations refer they should serve to give at least the orders of magnitude of the effects of gas-oil ratio and connate water on observed productivity factors. Within the indicated limitations, the computations imply that the foregoing factors can explain only a part of the apparent discrepancy between the homogeneous fluid productivity factors and those obtained recently in field measurements on the West Coast. IntroductioN Sufficient laboratory research has been carried out in the last several years on the fundamental features of the flow of heterogeneous fluids through porous media to call for consideration of what can be done with this type of information. It has, of course, already led to a, much clearer general understanding of the mechanics of oil production. However, examples of the quantitative application of the results of such laboratory studies are few in the literature. part of the explanation for this fact lies undoubtedly in the lack of sufficient laboratory data relating to practical fluids and sand systems such as would occur ill actual oil reservoirs. However, unless it can be shown that if such data were obtained quantitative applications could be made, serious doubt may be cast upon the desirability of carrying on further extensive experimental research work on fluid flow. The purpose of this paper is to present one approach to the problem of quantitative application of laboratory data to practical field problems. Because the published results on the basic experiments with three-phase fluid systems in porous media are limited entirely to uncon-solidated sands, the numerical applications made here will not pertain directly to any actual field situation. However, they should serve to illustrate what could be done with fundamental laboratory data if they were extended to cover the field of consolidated sands. From this point of view, it is hoped it will serve to encourage further laboratory research on this problem. The particular application to be treated here relates to the calculation of the productivity factors for oil-gas-water systems in the steady state. This specific problem seems especially appropriate for discussion in view of the recent publication by Johnston1 of the results of produc-

Jan 1, 1942

By D. H. Thompson, A. W. Tracy

E. A. ANDERSON*—At the outset, I note that you are using a humid atmosphere containing ammonia but that you make no reference to the variable of carbon dioxide content. Edmunds in his work in this laboratory found very marked effects on the rate of failure due to variations in carbon dioxide in the environment. This point is, of course, strongly related to the overall corrosion rate problem since the role of the carbon dioxide seems to be to permit the formation of hygrogroscopic salts which give a controlled moisture film on the specimen surface, which in turn seems to support the intergranular penetration more consistently than would otherwise occur. (2) Your results with various copper binary systems are very striking. It is curious, however, that the time-to-failure minima all occur at percentages of the alloying element which are considerably below the solubility limits as given in the conventional equilibrium diagrams. If your theory regarding the presence of these impurities in some concentration in the grain boundaries is correct, then either the existing diagrams are not accurate in the room temperature region, or there is a difference in solubility in the grain boundaries as compared -with the grains. A study along these lines might be very revealing. (3) The undesirable effect of silicon in copper calls to mind our own observations on the influence of silicon on the stress corrosion cracking resistance of alpha brass. In this case, silicon was found to have a very marked beneficial effect, particularly when a heat treatment capable of producing a grain boundary constituent was used. I should appreciate it if in the discussion of your paper this point should arise, you would attempt to clarify the difference between the copper-silicon binaries and the copper-zinc-sili-con ternary alloys. D. H. THOMPSON and A. W. TRACY (authors' reply)—(1) We have no data on the constancy of the carbon dioxide content of the air used for the test atmosphere but have believed that the normal carbon dioxide content of the air was as constant as could be obtained by using Edmunds' method of removing carbon dioxide from the air and then adding a measured quantity. In any event, the test atmosphere was the same for all specimens in a test run. We agree with Mr. Anderson that the carbon dioxide content is important in the formation of a hygroscopic film on specimens. (2) We can imagine that there could be a concentration of solute atoms at the grain boundaries which would be so small that present methods would not detect it even if it exceeded the solubility limit of the alloy. There could be somewhat greater solubility at the grain boundaries for an interstitial solute. There is a possibility that phosphorus dissolves in this way but we believe that none of the other solutes studied does. In our present studies we hope to find out something about conditions at the grain boundaries of some of the systems mentioned in the paper. (3) Mr. Anderson points out that silicon brass, which has had a high temperature heat treatment followed by a quench. is highly resistant to stress-corrosion cracking. Although the test conditions used by Anderson* et al were different from our test conditions, it is noted that the silicon brasses which had not had the special heat treatment were less resistant to stress-corrosion cracking than copper containing approximately equal amounts of silicon. G. R. GOHN†—Nonferrous metallurgists and particularly, materials engineers, have been accustomed to thinking

Jan 1, 1950

By Alfred R. Powell

Late in 1944 a group of petroleum and coal technologists was organized in Washington under the sponsorship of the Petroleum Administration for War and the U. S. Bureau of Mines. This group, known as the Technical Oil Mission, was placed under the authority of the Technical Industrial Intelligence Committee of the Joint Chiefs of Staff, which was then promoting the organization of other missions to be sent to Germany to obtain technical information regarding various industries in that country. The objective of the Tehnical oil Mission was to obtain technical data on German production of synthetic oil from coal and all other commercial practices and research projects connected with the oil industry. The primary purpose was to obtain such data as were immediately essential to assist the war against Germany and Japan, with secondary emphasis on technical information that would assist American industry after the end of the war. since oil-production facilities in Germany and the occupied countries controlled by Germany were the top targets for strategic bombing, the Technical Oil Mission was the first group under the Technical Induslrial Intelligence Com,mittee to enter Germany. A few members of the group flew to London in February 1945 and the majority of the remainder followed in March. In London they were joined by an equal number of British investigators and the combined mission was then sent into Germany under the authority of the Combined Intelligence Objectives Subcommittee (CIOS). A summary of the more important information gained by this combined British and American mission is presented below. German Oil Production The oil available to Germany, both natural and synthetic, and including production from occupied countries, reached a peak in late 1943 and early 1944 Production at this time was at the rate of 1,200,000 metric tons Per month, equivalent to 100,000,000 bbl. per year, or about 7 per cent of the wartime production in the United States. Of this production, jo per cent was crude oil from Romania and Hungary, 12 Per cent was crude oil from Germany itself, including Austria, 9 per cent cumprised coal-carbonization products, that is, tar and light oil, and only the remaining 29 per cent was synthetic liquid fuel made from coal or tar. Synthetic liquid fuel made in Germany was equivalent therefore to less than 2 per cent of wartime production of crude oil in the United States. The success of the strategic bombing campaign against German oil-production facilities is demonstrated by the fact that by September 1944 the Ploesti fields of Romania and much of the syrlthetic oil production had been eliminated, so that the amount of oil available to the German war machine was only 25 per Cent of the peak qualltity mentioned above. By early 1945, when the combined British and American oil mission was entering

Jan 1, 1947

By Alfred R. Powell

Late in 1944 a group of petroleum and coal technologists was organized in Washington under the sponsorship of the Petroleum Administration for War and the U. S. Bureau of Mines. This group, known as the Technical Oil Mission, was placed under the authority of the Technical Industrial Intelligence Committee of the Joint Chiefs of Staff, which was then promoting the organization of other missions to be sent to Germany to obtain technical information regarding various industries in that country. The objective of the Tehnical oil Mission was to obtain technical data on German production of synthetic oil from coal and all other commercial practices and research projects connected with the oil industry. The primary purpose was to obtain such data as were immediately essential to assist the war against Germany and Japan, with secondary emphasis on technical information that would assist American industry after the end of the war. since oil-production facilities in Germany and the occupied countries controlled by Germany were the top targets for strategic bombing, the Technical Oil Mission was the first group under the Technical Induslrial Intelligence Com,mittee to enter Germany. A few members of the group flew to London in February 1945 and the majority of the remainder followed in March. In London they were joined by an equal number of British investigators and the combined mission was then sent into Germany under the authority of the Combined Intelligence Objectives Subcommittee (CIOS). A summary of the more important information gained by this combined British and American mission is presented below. German Oil Production The oil available to Germany, both natural and synthetic, and including production from occupied countries, reached a peak in late 1943 and early 1944 Production at this time was at the rate of 1,200,000 metric tons Per month, equivalent to 100,000,000 bbl. per year, or about 7 per cent of the wartime production in the United States. Of this production, jo per cent was crude oil from Romania and Hungary, 12 Per cent was crude oil from Germany itself, including Austria, 9 per cent cumprised coal-carbonization products, that is, tar and light oil, and only the remaining 29 per cent was synthetic liquid fuel made from coal or tar. Synthetic liquid fuel made in Germany was equivalent therefore to less than 2 per cent of wartime production of crude oil in the United States. The success of the strategic bombing campaign against German oil-production facilities is demonstrated by the fact that by September 1944 the Ploesti fields of Romania and much of the syrlthetic oil production had been eliminated, so that the amount of oil available to the German war machine was only 25 per Cent of the peak qualltity mentioned above. By early 1945, when the combined British and American oil mission was entering

Jan 1, 1947

By A. L. Holley

The first session was held in the rooms of the American Philosophical Society, on Tuesday evening, February 26th. The President, Dr. T. Sterry Hunt, called the meeting to order, and after a few introductory remarks concerning the importance of theoretical and speculative science, which often involves principles of the highest economic value, and, more than all that, serves to enlarge our conceptions of the universe, and ennoble us, by the cultivation which it affords to our most exalted faculties, proceeded to discuss some points in the chemistry of the atmosphere. It is known that there is in the crust of the earth a great amount of oxidized carbon, not only in the shape of coal, but also in the graphite or plunlbago of the crystalline rocks, in the various bituminous shales or pyroschists, which are found in all succeeding rock-formations, and also in the forms of bitumen and petroleum. All the analogies of nature lead us to conclude that these various carbonaceous substances have had an organic origin, and have been generated by the deoxidation of carbonic acid, a process effected by the growing plant, and attended with the liberation of oxygen. He showed that the carbon of a layer of coal covering the whole earth's surface to the thickness of one meter, would, in its production from carbonic dioxide, liberate an amount of oxygen equal to that now present in our atmosphere. But bituminous coal contains also a large amount of hydrogen, derived from the deoxidation of water, which implies the liberation of a farther portion of oxygen. The amount from this latter source would equal, for the various coals and asphalts, from one-eighth to one-fourth, and, for the petroleums, onehalf of that set free in the deoxidation of the carbon which these hydrocarbonaceous bodies contain. From what we know of the composition of the stratified rocks, it is probable that they include an amount of deoxidized carbon and hydrogen many times greater than that contained in a layer of coal one meter in thickness, and, consequently, that the disengaged oxygen in past ages must have far exceeded that now present in our atmosphere. To this must be added

Jan 1, 1879