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By H. A. Kendall, W. C. Goins

Several investigations in recent years have shown that drilling rates are increased significantly with increased hydraulic horsepower. But, there has been no over-all method of designing jet-bit programs that efficiently uses the surface power. A study of present practices indicates that frequently as little as 50 per cent of the possible effects at the bit are used. Some observers have indicated that the best utilization of hydraulic horsepower (maximum effect on drilling rate) occurs when the bit hydraulic horsepower is maximum; others have stated that jet impact force is more important, and others have believed that maximum jet velocity is required. Limited efforts to date have shown some optimum conditions for bit hydraulic horsepower and impact, but these conditions cannot exist during drilling of a large part of the hole and do not provide a basis for designing a complete jet-bit program. This paper shows the maximum obtainable bit horsepower, impact force and jet velocity at all depths, taking into account the limitations of the pump, piping, hole and minimum circulating rate for adequate cuttings removal. Ranges of operation are developed; and flow rates, surface pressure and bit pressures are specified for each range to provide a maximum of any one of the desired effects. It also is shown that, by proper selection of nozzle sizes and by following the rules presented, the maximum obtainable quantities can be effectively utilized from surface to total depth. Finally, a simple graphical method of selecting nozzle sizes and flow rates is presented which can be used with familiar bit-company hydraulic tables and calculators to design jet-bit programs for maximum bit hydraulic horsepower, impact or jet velocity, as desired. These programs make most effective use of the pumps. Heretofore, there was no method available for designing field tests which adequately separated the effects of bit horsepower, impact and jet velocity. The programs and procedures developed in the paper are dissimilar and, when used in future field testing, should demonstrate which program is the most important in obtaining the fastest drilling rate. INTRODUCTION During the past decade, rig hydraulics has come into increasing prominence. There has been a definite trend toward providing higher horsepower pumps, jet-type bits have had increased use, numerous investigators"" have reported increased drilling rates as a result of increased hydraulics, and bit manufacturers have provided tablesa-" and calculators that are now commonly used 10 design jet-bit programs. Opinion has varied as to the hydraulic quantity which has the great- est effect on drilling rate. Papers and data have been presented that show pump horsepower,'9 it hydraulic horsepower and jet impact force,' each to be the most significant factor affecting drilling rate. Examinatibn of jet-bit programs of the bit companies indicates emphasis on jet velocity. Only pump horsepower can be eliminated because it can be used to produce any one of the bit effects which, a priori, must be more relevant factors. This contradictory state of opinion and practice regarding the bit effects is unfortunate, but several published references have been concerned with making one or another of the factors maximum; and, because these in each case have given results applicable to only intervals of the hole drilled, there seems to be ample reason to complete the previous efforts. It also is believed that the differences in programs for each effect, where they exist, should be delineated so that future use may determine which hydraulic effect is the more relevant. It is the purpose of this paper to: (1) show the theoretical maximum bit hydraulic horsepower, jet impact force and jet velocity available at all depths, taking into consideration all necessary restrictions on operating conditions; (2) illustrate procedures by which the maximum available horsepower, impact force or veIocity may be obtained; and (3) present a graphical method for rapid selection of jet-nozzle sizes and flow rates to be used with conventional procedures to design jet-bit programs for maximum bit horsepower, impact force or velocity as desired.

By Orville R. Lyons

This paper presents a method whereby the amount of misplaced material and the difficulty of the separation can be used to compare coal cleaning equipment of all types, from effectiveness and capacity standpoints. The correlations presented do not include all types of equipment currently available, but the method can be used to evaluate any make or type of coal cleaning equipment, both old and new. THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,' but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."' Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."' It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913," by the United States Bureau of Mines in 1938,' by Hancock in 1947," and by the national French research agency Cerchar in recent years.' In 1950 Andersone proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or k0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1953

By H. A. Hoffman

Competition from an all-flotation plant, with demonstrated economies and efficiencies, plus a change in smelting contract and introduction of improved cyclones lead to conversion from gravity-flotation. Detailed descriptions are given of equipment installed and procedures used at St. Joseph Lead's Federal mill. Future plans include further quality control by instrumentation in all aspects of the mill operation. Also planned are improvements in materials handling systems. Competitive conditions will continue to dictate improvements and changes in the mill flowsheet. The advent of all-flotation mills in the Lead Belt was introduced by the Indian Creek mill in late 1953. This modern and efficient plant then became a pattern for the other mills in this area to re-evaluate their circuits in an effort to develop flowsheets that would improve operating conditions and metallurgy. The Indian Creek mill demonstrated that all-flotation would require considerably less operating and maintenance labor than the combination of tabling and flotation that was common in the Lead Belt at that time. Two significant changes occurred in recent years to allow all-flotation to be seriously considered in other Lead Belt mills. One was a change in the smelting contract which did not require gravity concentrate. Another was the development of cyclones which provided classification of the flotation feed in a very small space. Since the Federal mill was the largest concentrating plant in the Lead Belt it was felt that the greatest savings could be made by investigating the all-flotation possibilities at this mill. Interest was stimulated by the milling and ore dressing Depts. to determine if this mill would be converted without undue cost, provided the metallurgy could be improved. Accordingly, laboratory tests were initiated to learn what metallurgical benefit could be derived. Numerous tests were run which indicated that grinding to all-flotation would improve the tailing by as much as 0.02 pct Pb. This was quite significant when multiplied by the tonnage of ore treated. Projecting the added cost of power for extra grinding and flotation, and the additional flotation reagents required, plus additional new equipment that would have to be purchased, it would still add up to a considerable saving. The all-flotation mill would reduce man power by some 30 pct, and make a metallurgical improvement. Operating costs could be reduced bv 2$ per ton. The metallurgical improvement would amount to 4$ per ton, for a total of 6$ per ton of ore milled. An estimate of the cost of the conversion was set at $250,000. With the savings as estimated this could be paid off in about two years. On paper it therefore seemed attractive enough to justify a mill test. MILL TESTING One section of the Federal mill was made available for use as a separate test circuit. Cyclones and density controllers were borrowed from the Viburnum and Indian Creek mills. Denver flotation cells were obtained from the Desloge mill that was then shut down. Two 10-cell groups of Fagergren flotation machines, consisting of eight roughers and two cleaners in each bank, were segregated from the remainder of the plant. The 9x12-ft rod mill was continued as a primary grinding mill. The two 6%x12-ft mills on this section were converted from rods to balls, and the speed increased to 22.0 rpm. Cyclones were installed to close the circuit of these ball mills. The ground pulp from each of the ball mills was fed separately to its own bank of flotation cells so that two completely separated test circuits could be run in parallel. This test circuit operated on a three-shift basis from Dec. 22, 1959 to Mar. 21, 1960. The first few weeks were occupied in developing conditions for proper metallurgy and trouble-free operations. Results were rather erratic but as the ore dressing laboratory and the mill operators became more familiar with conditions they were able to obtain expected results, which could be duplicated day after day. The last five weeks of testing indicated the best results and are tabulated in Table I. During the first two weeks a Denver unit cell was used on No. 1 flotation circuit. Even though it recovered almost one half of

Jan 1, 1962

By Orville R. Lyons

This paper presents a method whereby the amount of misplaced material and the difficulty of the separation can be used to compare coal cleaning equipment of all types, from effectiveness and capacity standpoints. The correlations presented do not include all types of equipment currently available, but the method can be used to evaluate any make or type of coal cleaning equipment, both old and new. THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,' but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."' Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."' It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913," by the United States Bureau of Mines in 1938,' by Hancock in 1947," and by the national French research agency Cerchar in recent years.' In 1950 Andersone proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or k0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1953

By J. L. Huitt, S. R. Darin

The use of a partial monolayer of propping agent to obtain a high flow capacity for a hydraulically induced fracture is discussed. From the results of laboratory work it was shown that a modified form of the Kozeny-Carman relation could be used to describe the flow in the partial monolayer propped fracture. With equations presented in the paper, the density pattern of the propping agent (number of particles per unit of fracture surface) that results in the maximum flow capacity for the fracture can be determined. The maxitnum flow capacity obtained with a partial monolayer is often an order of magnitude greater than the flow capacity obtained in greater width fractures containing multilayers of the propping agent. INTRODUCTION One of the predominant factors controlling the success of a hydraulic fracturing operation is the propping of the fracture. The trend in hydraulic fracturing recently has been an increase in the ratio of propping agent-to-fluid. The primary purpose of this increased ratio is to sustain a propped fracture of greater width. It was shown in a recent study' that for some formations low concentrations of propping agent would result in "closing" or "healing" of the fracture. In some cases, in an effort to insure sufficient propping agent concentration, the fracturing operation is designed to obtain a pack of the propping agent in the fracture. The placing of a pack of propping agent in the fracture provides a fracture of maximum width; however, the width alone does not control the flow capacity of the fracture. The flow capacity is dependent on the permeability of the fracture, as well as the fracture width. Thus, increasing the permeability to obtain larger flow capacities is as important as obtaining a greater width fracture. By increasing the concentration and particle diameter of the propping agent, fractures of sufficient flow capacities are obtainable for effective well stimulation in a number of formations. However, in some of the recovery techniques, the fracture capacity obtained by commonly used practices in fracturing is inadequate. One such recovery technique is gravity drainage via a horizontal fracture placed near the base of the productive zone. For this recovery technique, the fracture capacity desired is usually one to two orders of magnitude greater than the fracture capacity normally obtained in fractures propped with the size of sand commonly used (20-40 mesh). By the use of particles of larger diameter, the permeability of a pack2 is increased; however, even a multilayer pack results in a fracture flow capacity lower than that desired for some formations. For example, a fracture of 1/4-in. width, packed with 8-12 mesh sand of about 2,000 darcies permeability, would result in a fracture flow capacity (permeability X fracture width) of only 40,000 md-ft. If the fracture flow capacity needed is an order of magnitude greater than that cited in the example, an approach different from the formation of a pack in the fracture is needed. One approach is a partial monolayer of large-diameter propping agent. In working with this type of fracture system, it was found that the flow problems were unique to the system; therefore, the study discussed in this paper was made. THEORY AND RELATED STUDIES Previous studies, although related to that described in this paper, have not pertained directly to the flow in a fracture propped with a partial monolayer of propping agent. However, studies such as flow between parallel plates,' flow in packed columns,' fracture flow capacity' and flow in simulated fractures reduce the scope of this flow problem considerably. A fracture propped with a partial monolayer of dropping agent may be considered to be between two extremes — between an open fracture and a bed of particles packed In a conduit of fracture geometry. Thus, it seems appropriate to review the extreme cases.

By K. C. Hong, R. B. Jensen

The problem of determining the optimum set of steam volumes and cycle lengths for a single well undergoing multicycle steam stimulation in order to maximize the cumulative discounted net income has been formulated mathematically and programmed for a digital computer. The mathematical fonnulation of the problem and the method for its solution are discussed in this paper. The oil production performance during each stimulation cycle was simulated by either a constant percentage or a harmonic decline. Using simple analytical expressions for production performance, the cumulative discounted net income and cumulative time of operation were related to the pertinent process and cost parameters and two principal process control variables (cycle length and steam injection volume). The discrete maximum principles was used to transform the equations for cumulative time of operation and cumulative discounted net income into a set of simultaneous equations. The simultaneous equations then were solved by trial and error on a digital computer to determine the set of cycle lengths and stem injection volumes that gives maximum cumulative discounted net income over the project life. INTRODUCTION Steam stimulation is a process for improving the oil recovery rate from wells producing high-viscosity crudes. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three phases: steam injection, soaking (steam condensation), and production. Significant increases in production rate following the stimulation operation result from heating the reservoir around the wellbore. As heat is removed with produced fluids and dissipated into nonproductive formations, the production rate declines, usually to near the prestimulation value. Typical production responses are given in case histories reported by Owens and Suter,l and are depicted in Fig. 1. Duration of the production phase is equal to the time for the oil production rate to decline to some specified value and is called the cycle length. (Cycle length is defined as the producing portion of the cycle and does not include the downtime required for steam injection and soaking operations.) Termination of the production phase coincides with the start of steaming for the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable. Models 2-4 have been developed to simulate behavior of a single well during one cycle of steam stimulation and have been used to investigate the effects of system and operating conditions on the production responses. However, these investigations have not shown how the models can be used to determine a most profitable set of operating conditions for a multicycle stimulation project. Perhaps these models are too complicated mathematically to be adapted readily to an optimization study. This paper presents a method for optimizing a multicycle steam stimulation project based on simple production performance models. First, the performance of a steam-stimulated well during each cycle was simulated by either a constant percentage or a harmonic decline model. Using these simple analytical expressions for production performance, the cumulative discounted net income (before tax) and cumulative time of operation for each cycle were related to the pertinent process and cost parameters and two process control variables—the cycle length and the steam injection volume. Finally, the profit function to be maximized was formed. The analogy between the above problem and problems of optimizing multistage decision processes that have been reported extensively in the chemical engineering literatures5-10 in recent years has led this investigation to the use of the discrete maximum principle.5-7 This principle was used to transform the equations for cumulative discounted net income and cumulative time of operation into a set of simultaneous equations characterizing the optimum operating conditions in terms of the two control variables. These equations

Jan 1, 1970

By J. N. Ong, J. P. Ratledge, J. H. Boyce

SINCE German operators opened the Tsumeb mine in the early 1900's, continuous operation has been interrupted only by enforced shutdowns during two world wars and the depression of the 1930's. Original metallurgical practice was blast furnace smelting. This was applicable only to low zinc ore, leaving large tonnages of high zinc ore to be stockpiled on the surface. A gravity concentrator using tables, buddles, and jigs operated for several years, but differential flotation of the ore did not get beyond the experimental stage. When the property was put up for sale by the South African Custodian of Enemy Property there was an estimated 434,000 tons of ore on surface dumps. The dump material, assaying 4.48 pct Cu, 15.8 pct Pb, and 10.9 pct Zn, had become highly oxidized during a stay of many years on the surface. But these dump ores had to be used in evaluating possible metallurgy because the shaft became flooded after the 1940 shutdown and underground ore was unavailable. Many companies examined Tsumeb but quickly lost enthusiasm because of the formidable metallurgical problems presented by the dump ore. However, on the basis of extensive test work, the present company decided that differential flotation would be successful and purchased the property after competitive bidding. Geology and Mineral Association is Complex The Tsumeb mine lies near the northern boundary of South West Africa at an altitude of 4200 ft. The village of Tsumeb is 335 air miles northeast of Wal-vis Bay, territorial port of entry. The orebody is a hydrothermal replacement deposit associated with an irregular intrusion of aplite cutting folded pre-Cambrian dolomite beds. In plan the deposit is a lens of 250x600 ft maximum dimensions. In section the orebody dips 55" south from the surface to 2000 ft, below which there is a reversal in dip to 75" north. Mineralization is localized in the aplite and in the adjoining brecciated dolomite. In the upper levels the ore is largely confined to a single lens, but below the 1890 level massive sulphide ore forms north and south lenses that partially enclose a pipelike body of medium to low grade disseminated ore, part of which is of too poor a grade to mine. Drilling below the 24th, or bottom level, has disclosed that a high percentage of the mineralization from the 3000 to 3300-ft horizons is comprised of copper and lead oxides. The deep oxidation may be local, since it appears due to circulating waters in a major fault cutting the orebody. Tsumeb ranks as one of the highest grade base metal deposits in the world. It is geologically and mineralogically famous for 41 copper, lead, zinc, vanadium, and germanium ore minerals, but its complex mineral assemblage is not attractive to metallurgists. In addition, there is a gradual change in oxidation intensity from the upper levels to the lowest level now operating, which is the 24th. This is well illustrated by the copper minerals. In the upper levels malachite and azurite are predominant, in the intermediate levels chalcocite, and in the lower levels tennantite. Throughout the mine there are sufficient heavy metal soluble salts to activate zinc, and large amounts of depressants are required even for so-called clean sulphide ores. When the same sulphide ore is exposed to prolonged oxidation aboveground, as was the case with the dump ores, reagent requirements become fantastic. Plant Construction First staff members arrived at Tsumeb in March 1947, and by May essential services had been restored and mine unwatering began. In 2 1/2 months company employees built a temporary jig and sorting plant for treating existing dumps to provide a saleable product during high metal prices. Meanwhile, concentrator design and construction was contracted to a South African firm, with subcon-

Jan 1, 1956

By R. R. Webster, H. T. Clark

The side-blown converter has been investigated as a possible commercial process for the production of low nitrogen steel. During this work, two converters of 3-ton and 22-ton capacity were operated on a pilot plant basis for a total of 214 heats. The steel made in these converters was low in nitrogen and possessed good cold working properties. Some problems of converter operation remain to be solved. IN plants operating with a high iron capacity, sev-eral different refining methods are used in the conversion of the molten pig iron to steel. These include various ore practices in stationary and tilting open-hearths, the duplex process employing the Bessemer converter and open-hearth, and the Bessemer process. At J&L, a considerable part of the iron produced is handled by the Bessemer process, either alone or in conjunction with duplexing, and therefore an appreciable portion of the steelmaking research effort has centered about the method. This paper covers research work on the development of the side-blow converter for the commercial production of low nitrogen ingots and includes descriptions of the operation of a 3-ton and a 22-ton experimental converter at the Aliquippa Works. The refining of iron to produce steel requires the removal of a large portion of the carbon and silicon and the control of manganese, phosphorus and sulphur which are present in the iron in varying amounts. The first large-scale means of refining iron was the acid Bessemer process which was brought into use almost 100 yr ago. This method, using compressed air as the refining medium, accomplishes substantially complete removal of carbon, manganese and silicon. Phosphorus and sulphur are not affected but, by choice of an iron composition sufficiently low in these elements, a commercial product can be produced. Since the process will handle large tonnages rapidly, operates without external fuel and with a minimum of additional equipment, it quickly became the major tool in the early expansion of the steel industry. Later, the basic open-hearth process, by affording control of phosphorus and sulphur and by consuming the large quantities of steel scrap that were becoming available, forced the acid Bessemer process into a secondary position in the industry. During the past two decades the demand for steel to be used in cold forming and drawing operations has gradually increased. Bessemer steel, because of its work hardening and aging characteristics, is not as suitable for these applications as basic open-hearth steel, consequently the decline of the process was accelerated. More recently, because of changing economic conditions, this long range trend appears to have been arrested or perhaps reversed. Ingot production data for recent years furnishes only an incomplete picture of the importance of the converter in the American steel industry; open-hearth furnaces utilize large tonnages of blown metal for which no published statistics are available. Metallurgical Aspects The fundamental difference between Bessemer and open-hearth steels apparently lies not in the method of manufacture but, rather, in the differences in chemical composition of the two steels. It is further believed that the principal features distinguishing Bessemer from open-hearth steel are the higher nitrogen and phosphorus contents of the former. Evidence supporting this position is supplied by tests on laboratory induction furnace heats that were made to contain varying amounts of phosphorus and nitrogen but were otherwise similar to normal low carbon silicon-killed steels. Fig. 1, 2 and 3, summarizing the test results, are taken from G. H. Enzian's paper titled, "Some Effects of Phosphorus and Nitrogen on the Properties of Low Carbon Steels."' Fig. l indicates that phosphorus has a marked effect on the cold work embrittlement of steel as shown by the work brittleness test of Graham and Work.' In the low nitrogen steels, which as a group have the better cold working properties, the effect of phosphorus variations is the more pronounced.

Jan 1, 1951

By H. Wilton Clark

VARYING in thickness and in number from place to place, coal seams in the Canadian Rockies also range in pitch from nearly horizontal to vertical, sometimes with overturns. Over the entire coal-bearing area there are considerable differences of rank in coals of the same geological age, and there are marked differences in ash content and wash-ability characteristics. Correlation of seams at mining operations within a few miles of each other has often proved impossible. These factors influence mining methods, and, of course, production results. The oldest coal formations of western Canada are of Lower Cretaceous age, as the carboniferous sediments are marine and contain no coal. Coal is also present in formations of Upper Cretaceous and Tertiary ages. The rank of coal varies from semi-anthracite in some operations in the Kootenay and Luscar formations of the Lower Cretaceous in the Rockies to lignite in the Tertiary fields of the Saskatchewan prairies. Fig. 1 shows the general extent of the formations. The pitching seams, chiefly Lower Cretaceous, occur in the western belt of the Rocky Mountain foothills and the eastern slopes of the Rockies themselves. (The road to Tent Mt. strip pit, elevation 7000 ft, is shown on p. 832.) Formations extend from the U. S.-Canadian boundary for several bundred miles in Alberta and continue for a similar distance in British Columbia. Present geological estimates show a probable reserve of the order of 25,000 million tons of coal ranging from high volatile bituminous to semi-anthracite, with a large percentage of coking coal, constituting one of the major world reserves of that type. It should be noted that although the quoted estimate probably errs on the conservative side, the question of access to the seams in a mountainous terrain will always be a problem; a wide divergence may exist between actual reserves and the quantities of coal economically recoverable. An excerpt from the Canadian government Report of the Royal Commission on Coal 1946 states that conditions favorable to coal formation were intermittent and these intervals relatively brief in comparison with periods in which no coal was formed. Conditions were favorable to the growth or accumulation of vegetation in one area, while fresh water sediments and marine shales were being deposited in other areas. During periods of emergence the coal deposits were subjected to erosion or were covered by coarse sands and gravels from the mountains, whereas during submergence they were covered by fine clays deposited in embayments of the sea. During some of the periods of coal formation, volcanic activity deposited beds of fine volcanic ash and dust with the coal-forming vegetation. Coal deposits reach their greatest development in the mountains and thin rapidly to the east into the plains area, where they are deeply buried beneath younger sediments. For example, in the Fernie area of southeastern British Columbia there are in places 22 seams having an aggregate thickness of 150 ft in a stratigraphic interval of 3500 ft, whereas at Cole-man in the Alberta Crowsnest area the measures are only 800 ft in thickness and contain a maximum of five seams aggregating about 47 ft of coal. At Belle-vue, 10 miles further east, the measures are reduced to 430 ft with only three seams aggregating about 37 ft of coal. Subsequently the tremendous forces involved in the upthrust of the Rocky Mountains produced great displacement of the coal-bearing formations and at the same time a change in geologically young coals from low to high rank. The floor or footwall of most seams consists of carbonaceous shales, which are almost as adaptable to bending as the coal seams themselves. The seams show very few cleats or cleavage planes and have been so weakened structurally that as mined 50 pct or more will pass through a ¼-in. screen, seldom

Jan 1, 1955

By L. L. Handy

The most common method of identifying hydrocarbon-bearing strata in a well that penetrates many different formations involves measurement and interpretation of the electrical properties of the formations as determined by electrical logs. Even though this method is used extensively, and even though in a great many instances it is capable of indicating presence of oil or gas, situations arise for which it is extremely difficult, if not impossible, to deduce the presence of hydrocarbons. These situations may involve the following. 1. A thin formation, bounded by highly resistive formations, in which it is impossible to obtain the actual resistivity of the uninvaded zone with existing logging devices. 2. A formation in which invasion has been so extensive that a value for the uninvaded zone resistivity cannot be obtained. 3. A very shaly formation in which the resistivity index, I, is lower than that usually associated with productive formations. 4. Laminated formations comprised of thin productive sands separated by thin shale streaks in which the individual sand and shale streaks are too thin to permit measurement of uninvaded-zone resistivity with existing logging devices. 5. Productive formations in which the water saturation is high. To extend the utility of electric log interpretation to identification of hydrocarbons in all types of formations, there is strong incentive to find a method not subject to these limitations. Some time ago, in connection with research on the wettability of reservoir rock, an investigation was conducted in which the resistivities of cores were measured shortly after they were removed from a core barrel, and again after they had been extracted and restored to their original oil and brine saturation.' The resistivities after extraction were generally lower. Other tests made on the cores indicated that they were more nearly water wet after they were extracted; thus, it was assumed that the observed changes in resistivities were due to a change in wettability of the cores. Other experiments'," have shown that resistivities of rock samples are sharply dependent on wettability. These experiments have shown that oil-wet samples are more resistive than water-wet samples. To obtain an understanding of how the wetting properties of the surfaces of core material affect electrical resistivity, a series of experiments was conducted. Two groups of core samples were prepared for testing. One group contained brine, but no residual oil. The other group was saturated with brine, flooded with oil to a low water saturation, then flooded with brine to a final residual oil saturation. Resistivity measurements were made on each group. Both groups were then flooded with the original brine to which a chemical had been added that renders sand and clay surfaces preferentially oil wet, a so-called reverse-wetting agent. very little change in resistivity was observed in cores containing only water. The group containing residual oil, however, showed resistivity increases of 100 to 200 per cent. These experiments showed that the resistivity of a core containing oil could be altered by changing wet-tability of the core. Moreover, the possibility was introduced that reverse-wetting agents might be employed as the basis for a logging method for identification of oil-bearing strata. Since behavior of a porous rock containing gas and water might be expected to be similar to that of a rock containing oil and water, such a method should also be applicable to identification of gas-bearing zones. In principle the wettability of the invaded zone could be reversed without altering conductivity of the interstitial water or the hydrocarbon saturation therein. Those strata showing significantly increased invaded-zone resistivities would, therefore, contain hydrocarbons; those with no significant change would be filled only with water. Addition of a reverse-wetting agent to a hydro carbon -bearing zone which is, by nature, already preferentially oil wet would not result in an enhancement of its resistivity. It is generally believed, however, that most hydrocarbon-bearing strata are preferentially water wet.

By G. K. Manning, W. E. Few

T has been known for some time that both'inter-granular carbide and intergranular oxide phases cause brittleness in molybdenum. Parke and Ham' indicated that 0.0025 pct 0 present in molybdenum after solidification from the melt was sufficient to induce intergranular brittleness during forging. However, material containing 0.06 pct C could still be forged. However, adding this amount of carbon to insure deoxidation causes the formation of carbides on freezing. These carbides are precipitated at grain boundaries, and Rengstorff and Fischer' have shown they have an unfavorable effect on the room-temperature ductility of molybdenum. Take? in 1928 proposed that the solubility of carbon was a constant value of 0.30 pct from room temperature up to 1800°C. In 1935, Sykes, Van Horn, and Tucker' obtained X-ray data suggesting that the solid solubility of carbon in molybdenum was between 0.07 and 0.09 pct at temperatures from 1500" to 2100°C. The a-solubility line for carbon was included in the Mo-C diagram given in the Metals Handbook as a tentative line based on the data of Sykes, Van Horn, and Tucker. In order to determine the partial phase diagrams for these systems, it was necessary to construct a high-temperature furnace suitable for heat treating molybdenum at temperatures up to 4000°F. A molybdenum resistance furnace was built for this purpose in which samples could be heat treated in a purified atmosphere and quenched from any desired temperature.' Experimental Work Solubility of Carbon: Arc-cast molybdenum supplied by the Climax Molybdenum Co. and 18-gage molybdenum wire samples produced by powder metallurgy at the Fansteel Metallurgical Co. were used in determining the a-solubility line for the MO-C system. The cast molybdenum contained 0.032 pct C initially. Two lots of 18-gage wire were used, one containing 0.011 pct C and the other 0.005 pct C initially. All material contained a carbide phase as received. Fig. 1 illustrates the carbides found in the untreated material. Heat treatment in a purified hydrogen atmosphere was found to reduce the carbon content in the as-cast molybdenum. Purified argonT also decarburized molybdenum samples at temperatures above 3500°F; however, the carbon content remained constant during heat treatment in purified argon at lower tem- peratures. The argon was purified by passing it over titanium at 750 °C and then through a magnesium perchlorate drying tower. The hydrogen was purified by passing it through a commercial hydrogen deoxidizer, followed by a drying tower. Specimens having different initial carbon contents were heat treated in argon at 3500°F for periods ranging from 5 min to 5 hr and were analyzed for carbon. Samples of the same final carbon content had the same microstructures regardless of time at temperature. Furthermore, a gradient between center and surface in the amount of undissolved carbide particles present was never observed. It was concluded that at these low carbon levels, and at the high temperatures involved, diffusion proceeds so rapidly that the specimen is always substantially homogeneous in carbon content, in spite of the gradual loss in carbon. Based on the above findings, the following procedure was used to determine the carbon-solubility limit at 3000°, 3500°, and 4000°F. At each of these temperatures, a number of samples were heat treated, as shown in Table I, and rapidly cooled to room temperature. Since the samples lost carbon in proportion to the length of time heated, a series of samples were obtained of varying carbon contents. By use of a rapid cooling rate, the phases present at the high temperature were retained at room temperature. All samples were examined microscopically. Those found to contain either no excess carbide phase or only a very small amount were then analyzed for carbon. The samples actually analyzed for carbon

Jan 1, 1953

By P. Shahinian, M. R. Achter

In a comparison of the creep -rupture properties of nickel in air arid in vacuum there is a reversal in relative strengths with variations in stress. At low stresses the properties are better in air while at high stresses they are better in vacuum. In the early stages of creep in a high stress test the specimen in air nzay have the lower creep rate but the one in vacuum is creeping at a lower rate in the later stages. A mechanism, involving two competing processes in terms of oxidation strengthening and weakening by surface-energy reduction, is proposed to explain these reversals. It had generally been assumed that, relative to their properties in air, the high-temperature strengths of metals would be increased in an inert atmosphere as a result of the elimination of the deteriorating effects of oxidation. However, several recent investigations have shown that the creep strength may be greater in air than in nonoxidizing gases. Pickus and Parker1 found that the creep rate of nickel was lower in air than in hydrogen or nitrogen. Internal oxidation was mentioned by Shepard and Schalliol as a possible cause for the longer creep life of Hastelloy C in air than in vacuum or helium. Sweetland and Parker, who observed lower creep rates for aluminum and copper in air than in helium, discuss the possible applicability of the dislocation-barrier mechanism to explain their results. Surface oxide layers may interfere with the escape of dislocations through the surface or with their generation there. In addition to showing the strengthening in air of low-alloy and stainless steel, and nickel and cobalt-base alloys, shahinian4 presented notch-effect data which indicate the role of stress concentrations; alloys of relatively low ductility were more sensitive to atmosphere strengthening when notched specimens were used. Although Bleakney's copper wires had a lower reduction of area in air than in vacuum, it is difficult to interpret his results in terms of strength changes since the stresses employed were not measured. In contrast to these data showing the strengthening in air, a number of investigations, most at relatively low temperatures, have demonstrated that the environment may cause a decrease in strength. These results are generally explained in terms of the effect of environment on surface energy. In a review of the subject, Benedicks and Harden use the concept of atomic bonding to explain how the adsorption of impurities would decrease the energy of a clean surface. A decrease in surface energy would facilitate the propagation of cracks or extension of the surface. Use of this mechanism is made by sato7 to explain the weakening of steel specimens bent in various liquids, by Potek and Shcheglakovs for the reduction of fracture strength of steel in molten metal, and by Benedicks and Harden for the reduction of strength of a variety of materials in a number of liquids. A similar explanation might be used for the results of Forestier and Clauss. The fracture stress of fine wires pulled in a variety of gases, including air, is lower than in vacuum. They attributed their results to the "tendency" for the gases to condense on the metal surface. That the strength of metals is affected by the type of gas in which the test is conducted has been demonstrated convincingly; the mechanism of the effect, however, is still uncertain. This investigation represents one in a series to explore the influence of variations in alloy composition and test conditions on the atmosphere effect in the expectation that the results would afford an insight into the processes taking place. To determine the effect of specimen composition, the present investigation was conducted

Jan 1, 1960

By C. B. Alcock, R. G. Hudson

Sulfur pressure measurements above FeS in equilibrium with iron have been carried out by the Knudsen orifice method. A comparison is made of the weight loss of the cell per unit time obtained in the above experiments, that calculated from Richardson and Alcock's measurements of the S2 pressure above FeS in equilibrium with iron, and the dissociation constant for diatomic sulfur from spectroscopic and thermal data. EXTENSIVE equilibrium measurements have been made to determine the sulfur potentials of a great many systems of metallurgical interest.' In order to confirm their reliability, to supply data which may be of use in further thermodynamic calculations, and to establish the reliability of the Knudsen orifice in obtaining accurate thermodynamic values at high temperatures, the present investigation on the pressure of the gaseous species above FeS in equilibrium with iron has been carried out. The Knudsen orifice method has been used for these pressure measurements. Experimental The apparatus and general technique for this investigation are the same as that reported for the determination of the vapor pressure of silver.' To reduce the residual gas pressure in the evacuated chamber, a titanium getter, maintained at run temperature, was introducbed. Several types of Knudsen cells were used—platinum, zircon, and fused silica. The orifice in the zircon cell was fashioned with a small diamond wheel. The same precautions were used in this investigation as were employed in the work on Mo2S2.3 The FeS-Fe mixture was prepared by heating a sample of pure FeS,, supplied by K. K. Kelley of the Bureau of Mines, with excess iron powder, cp grade, obtained from the Fisher Scientific Co. These two substances were heated in a closed Armco iron crucible at 960°C, held in a vacuum of less than 10" mm Hg for 24 hr. The mass was then removed from the cell and ground in an agate mortar. In this form it was charged to the various Knudsen cells. Heating the Knudsen cell for an additional two days was sufficient to obtain constant rates of weight loss of the cell. The data obtained in this investigation are recorded in Table I. To establish whether or not a sulfide of iron is volatile at these temperatures, 0.7646 g of the FeS-Fe mixture, described above and containing 69.2 pet Fe, was placed in the zircon Knudsen cell. Run Nos. 103 to 109 were performed on it. After the completion of these runs, the total amount of iron left in the cell was obtained by chemical analysis. It contained 0.537 g Fe, compared to 0.529 g in the original charge. Thus, there was an apparent gain in iron of 1.5 pet. This is attributed to unknown experimental error, and the conclusion is that no sulfide of iron is volatile. The vapor pressure of pure iron4 is about one thousandth that of the sulfur pressure' at these temperatures. The vapor pressure of iron inside the Knudsen cell will be almost exactly that of pure iron, since in the iron-rich phase the percentage of sulfur is of the order of 0.025 pet.At this low percentage of sulfur Henry's law is probably obeyed by the sulfur. Thus, the iron will obey Raoult's law. In any event, the vapor pressure of iron will be lower than that of pure iron and, since the vapor pressure of pure iron is negligible compared to the pressure of sulfur, the weight loss of the cell due to the vaporization of iron should be negligible. Since neither iron nor FeS is volatile to an appreciable extent, the total weight loss of the cell must be due to the vaporization of sulfur. Discussion and Calculations On the assumption that S, is the only gaseous species present in appreciable quantity, its pressure

Jan 1, 1957

By K. H. Ribe

Water often enters an oil reservoir during completion or workover operations on a well and forms a partial "water block" to oil production. A mathematical study of radial two-phase flow, neglecting capillary effects, has been employed to study the formation of such a water block and subsequent re-moval by production from the well. The effects of reduced oil permeability about the well on the well productivity were studied. The fluid saturation distributions about the well during formation and removal of the water block have also been computed. Several relative permeability relations and viscosity ratios were employed. If water has invaded the formation, its influence through relative permeability effects alone can cause the following. 1. Oil productivity will be depressed for extended periods after production is resumed and will build up only gradually as the water is removed. 2. Oil injected for treatment of water blocking will delay rather than promote restoration of full well productivity by enlarging the region invaded by water. Thus, unless the specific action of chemicals contained in the oil is needed, oil injection appears undesirable. INTRODUCTION During oilwell workover operations, water may enter the oil-bearing formation from the wellbore. When production is resumed, oil must flow through the region invaded by this water. The presence of this region can cause both well productivity and oil production rate to be low and oil to be produced with high water-oil ratio for some time after production is initiated. This situation is sometimes described as a water block. The introduction of water into the formation may result in other actions which also lead to reduction in well productivity and which are also usually included in the connotation of the broad term, water block. Often considered, for example, are the possibilities of clay swelling by contact with fresh water and the formation of emulsions with the formation oil. If it is suspected that such specific actions have taken place, remedial treatments are undertaken which usually involve the injection of chemicals in oil. Since the introduction of water, even in the absence of specific interactions with the formation or oil, will cause a temporary water block (which might be misinterpreted as evidence of a more severe situation), it is of importance to evaluate the magnitude and duration of this blocking which results purely from the reduction in relative permeability to oil in the vicinity of the wellbore. It is also of interest to evaluate the effect of oil injection on the productivity of a well blocked by water in this manner. Inasmuch as this unfavorable condition may persist for some time, it may lead to premature condemnation of a workover or premature abandonment of a potentially productive pay zone. A quantitative evaluation of the influence of water entry on the oil productivity through changes in relative permeability was made by solving a radial form of the Buckley-Leverett equation. The distribution of water saturation around the wellbore during the entry of water was calculated and was followed by a similar calculation of the saturation distribution during the period of resuming production. At any stage in the removal of the invading water, knowledge of the distribution of its saturation permitted calculating the attendant loss in oil productivity. The influence of the shape of the relative permeability relationships was also evaluated by carrying out the calculations for two hypothetical cases. Further, the effect of the oil-water viscosity ratio was examined by repeating the calculations, for several ratios of unity and greater, with the same relative permeabilities. Fi-nally, results are presented to show how the length of time a well must be swabbed to resume production depends on the length of time it has been subjected to invasion by water. STATEMENT OF THEORY Differential Equations Water is assumed to enter a producing formation which is initially at the connate-water saturation and contains no gas. The water and oil are treated as in-

By M. W. Cox, V. F. Hollister

EXPLORATION for metallic mineral deposits is carried on by those special adaptations of methods which the explorer believes will yield most economically or satisfactorily the particular answer sought. In this project the usual methods of geologic observation, recording, and interpretation, when combined with magnetic geophysical methods and geochemical soil sampling, led to disclosures of appreciable zinc mineralization where none was visible in surface exposure. Since 1945 considerable work has been done with geochemical prospecting methods, chiefly in determining the presence and distribution of various elements existing in minor amounts in rocks, soil, vegetation or waters of mineralized areas. Such work, in which the U. S. Geological Survey has taken the lead, finds a ready place in the field repertoire of the exploration geologist as a supplement, not a substitute, for other methods. The Chollet project was carried out in 1951 by the American Smelting & Refining Co. near its Van Stone mine in northern Stevens County, Wash., in the area shown in Fig. 1. The Van Stone mine is located in the Onion Creek drainage of the Selkirk Mountains, midway between the towns of Colville and Northport, Wash., and some twenty airline miles west of the Metaline mining district. Its zinc-lead orebodies, currently yielding about 1000 tpd of ore, occur as bedding replacement deposits in the middle Cambrian Metaline formation near an intrusive granodiorite contact. The target of exploration at the Chollet prospect was a similar geologic environment along the intrusive contact about 5 miles west of the mine. Geographic Setting The Chollet ground covers a north-facing slope at 3000 to 4000-ft elevation. Second-growth jack pine and tamarack with some hemlock and yellow pine make a thick forest cover. A heavy under-forest of alder, willow, and lesser shrubs occupies the draws, see Fig. 2. Grassy slopes appear at higher elevations. The lower slopes are underlain by a thick blanket of glacial till and alluvium so that outcrops are scarce; however, perhaps 50 pct rock exposure prevails at higher elevations. This part of northern Washington annually receives about 25 in. of precipitation, which largely falls as snow in the winter months. Summers are dry with occasional rainy periods. General Geology The Van Stone mine and the Chollet prospect lie along the southern margin of a westerly extending lobe of the Kaniksu batholith, one of the series of granodioritic masses that are intrusive into Cretaceous and older rocks in northern Washington and southern British Columbia. The margin is composed of complexly deformed Paleozoic sediments ranging in age from the lower Cambrian Maitlen phyllite on the east, through middle Cambrian Metaline formation (limestone and dolomite), to Ordovician Ledbetter slate on the west. In general the formations strike N10 to 50E and dip steeply northwestward, although dip reversals and minor folding occur. This general rock distribution is shown on Fig. 3. In this area the Metaline formation, which is the host rock for mineralization, appears to be of about 4000-ft thickness that can be conveniently divided into the same three units defined by Park and Cannon' for the Metaline area. The basal part consists of 1000 ft of interbedded white limestone, argillaceous limestone, and gray silty argillite. The middle part, approximately 1500 ft thick, consists of fine-grained black, gray, and white dolomite. This unit also contains minor interbedded limestone. The upper part is a gray massive limestone about 1500 ft thick that grades upward into slaty limestone and slate capped locally by a thin black jas-peroidal dolomite which is either the uppermost member of the Metaline formation or the basal member of the overlying Ledbetter (Ordovician)

Jan 1, 1956

By K. M. Rolls, F. W. Reuter, J. Wulff

The superconducting behavior and microstructural characteristics of a nominal Nb-40 wt pct Ti-0.239 wt pct O alloy were studied as a function of ther mo -mechanical processing treatment. Critical current density us applied transverse magnetic field was obtained for 0.010-in.-diam wires at 4.2°Kin steady fields 14 to 110 kG. Both optical metallogvaphy and transmission electron microscopy were used to delineate the micros tructures of the same wires. It wan found that a 1-hr 500°C precipitation heat treatment after cold drawing to final size led to the highest critical current density. Heat treatment at 600°C also led to a high critical current density, but the precipitate differs in kind and form from that at 500°C. The resistire critical field was also found to be sensitive to precipitation heat treatment since the effective composition of the superconducting phase changes. This is discussed in terms of the oxygen in interstitial solid solution. Two types of high-field superconducting wire are at present used in the construction of high-field superconducting solenoids. These types are solid-solution alloy wire such as Nb-Zr and Nb-Ti and composites of the brittle inter metallic compound Nb3Sn. The latter generally have a high super cur rent-carry ing capacity which is difficult to vary if properly made. The supercur rent- carry ing capacity of the former can be varied drastically and often predictably by suitable thermomechanical processing treatments. In general, the critical current density Jc of the solid-solution type of alloy is increased by cold work and by additions of interstitial elements along with aging heat treatments. The imperfections which result are be-iieved to be responsible for the observed increase in Jc. In 1962 Kneip and coworkers1 found that the critical faurrent density of Nb-Zr alloys could be increased by proper heat treatment preceded and followed by cold work. Betterton and coworkers2 using a Nb-25 at. pct Zr alloy found that small additions of oxygen or carbon enhanced the effect of this heat treatment. They suggested that the interstitials present aided precipitation in the alloy, leading to a filamentary structure with superior properties. If the precipitation heat treatment was omitted, interstitial additions had a negligible effect on Jc. wong3 showed that higher heat-treatment temperatures lowered Jc. Walker and co-workers,4 who studied microstructure (by transmission electron microscopy) as well as superconductivity, found that the Jc anisotropy introduced by cold rolling was itself affected by heat treatment. They were unable to clarify the relation between microstructure and critical current density, although evidence of precipitation was indicated. More recent investigation of Nb-Zr alloys,5,6 besides showing that structural defects and fiber ing due to cold work and precipitation serve to raise Jc, also elucidate important optically observable microstructural changes which occur upon precipitation. In these reports, coarsening of the microstructural features was found to decrease Jc. Vetrano and Boom,7 who studied Ti-20.7 at. pct Nb, found that Jc was increased to a maximum by a 415°C, 3-hr heat treatment following quenching from 800°C and cold working. Heat treatments can also affect the resistive critical field Hr. Final-size heat treatments of Nb-Zr wire can lower Hr drastically if gross phase decomposition occurs5'* or moderately if the effects of cold work are eliminated without changing significantly the composition of the phase of interest.3,5,6,8 The percentage of oxygen which can be added to Nb-Zr alloys to enhance Jc is limited by the difficulty of subsequent cold drawing. Since Nb-Ti and Ta-Ti alloys in contrast can tolerate appreciably higher percentages of oxygen, it was decided to investigate the superconducting behavior of various alloys in these systems. The present paper describes the results of adding oxygen to a nominal 40 wt pct Nb alloy as a function of thermomechanical treatment. I) EXPERIMENTAL PROCEDURE A small alloy ingot was prepared from high-purity niobium, iodide, crystal-bar titanium, and Nb2O5 powder by arc melting on a water-cooled copper hearth in a gettered argon atmosphere. The ingot was turned and remelted fourteen times to insure homogeneity. After final melting and rapid cooling, it was machined round to 0.415 in. diam, jacketed in stainless steel, and cold-swaged to 0.117 in. diam. The jacket was removed and swaging continued to 0.051 in. diam followed by wire drawing in carbide dies to 0.010 in. diam. Although it was intended that about 1500 ppm O (by weight) be added, inert gas fusion analysis indicated a 2390 ppm 0 content, apparently due to additional oxygen pickup in the arc furnace. Even so, the alloy was sufficiently ductile to be cold-worked to greater than 99.9 pct reduction

Jan 1, 1967

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,' metal purification,2'3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10'1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge' or where melting is achieved, "dripping" from the charge is encountered.'' At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By L. C. Michels, O. G. Ricketts

The disorientations between s?nall grains, whose growth has been arrested at an early stage of recrys-tallization, and the deformed matrix in cold-rolled aluminum single crystals were determined using transmission Kikuchi line and electron diffraction patterns. The orientations of the recrystallized grains were found to be random, and the disorientations of these grains with the matrix weve found to be intermediate to large. This leads to the conclusion that the observed vecrystallization began in small areas of large disorientation present in the cold-worked structure. heavily cold-worked thin sections of aluminunz single crystals and of polycrystalline aluminum and nickel were produced directly by a mechanical technique. The specinlens thus prepared were heated with the electron beam to bring about vecrystallization during observation in the electron microscope. Motion pictures taken du.ring heating and the electvon, microg.raphs taken both before and aftev heating allowed the recrystallization process to be traced to its ovigin. Re cvystallized grains originated in very s,mall regions of the cold-worked structure and developed through rapid migration of high-angle boundaries. The boundaries either were present as such in the matrix or were formed out of dense dislocation networks. SIGNIFICANT advances have been made in recent years in the study of nucleation of recrystallization using the technique of transmission electron microscopy of thin metal foils. Bollman1 in a study of heavily rolled polycrystalline nickel found support for the Cahn-Cottrell2,3 theory of nucleation. According to this theory nuclei form by the initially slow growth of subgrains formed through polygonization. During this initial period of slow growth (the incubation period) the migrating boundary of the subgrain increases its disorientation with the cold-worked matrix and thereby increases its mobility to become a rapidly migrating high-angle boundary. Bailey4,5 investigated the annealing behavior of several metals deformed both in tension and by rolling and concluded that recrystallization took place through the migration of high-angle boundaries. With low deformations these boundaries were present in the metal before deformation. With high deformation it was not possible to tell whether the boundaries were pieces of the original grain boundaries or were produced either during deformation or by polygonization during ameal- ing. Direct observation during heating of metal foils indicated that subgrains form by polygonization and grow at an uneven rate. The grain size obtained decreased with decreasing foil thickness indicating that the foil surface resists boundary motion. Votava,6 in heating stage experiments on rolled copper, observed nuclei to appear suddenly and grow in jumps of differing magnitude. However, he found no special dislocation configurations where the nuclei appeared. Fujita,7 as a result of a study of subgrain growth in heavily worked aluminum, concluded that the boundary of a recrystallized grain initially forms from the boundary of a group of subgrains. This occurred by a process of deposition of vacancies and dislocations in the group boundary as the boundaries within the group disappear. HU8,9 directly observed a similar process in heating stage experiments on 70 pct rolled Si-Fe single crystals. The growth of subgrains appeared to proceed by a coalescence mechanism. The observed fading away of the boundary between two subgrains was explained by the moving out of dislocations from the disappearing boundary into the connecting or intersecting boundaries around the subgrains. The subgrain size and degree of disorientation with the surrounding structure were thus increased. With the increase in disorientation occurred a corresponding increase in boundary mobility, which eventually allowed the boundary to migrate rapidly. This process was observed to occur within "microbands" consisting of parallel narrow segments disoriented by a few degrees present in the as-rolled structure. The conclusion of Rzepski and Montuelle10 that growth is preceded by the coalescence of blocks through disappearance of their common boundaries supports this view. In contrast to Hu's coalescence model for nucleation were the conclusions of Walter and ~och.""~ Working with the same material as Hu, of the same orientation and rolled to the same reduction, they concluded that nucleation occurred by the Cahn-Cottrell mechanism. They observed, in agreement with Hu, that recrystallization began in the "microband" regions which they referred to as "transition" bands. Bartuska13 studied subgrain growth in heavily rolled nickel using a beam heating method in the electron microscope. He concluded that nuclei for recrystallization form from the largest most perfect subgrains present in the cold-worked structure by rapid intermittent migration of parts of subboundaries. In rare instances he observed subgrain growth by coalescence. EXPERIMENTAL PROCEDURE The materials used in this study were 99.999 pct A1 supplied by A.I.A.G. Metals, Inc., and 99.999 pct Ni supplied by Johnson and Matthey and Co., Ltd. The Hitachi HU-11 electron microscope, with uniaxial

Jan 1, 1968

By James H. Courtright, Kenyon Richard

TOQUEPALA is a porphyry copper deposit in which mineralization is localized by a large breccia pipe formed in close genetic relation to intrusive rocks. The deposit is in southern Peru, 55 airline miles north of the small city of Tacna and the same distance inland from the port of 110. Quellaveco and Cuajone, geologically similar deposits, lie 12 and 19 miles north of Toquepala. Chuquicamata is 400 miles to the south. The deposit is high on the southwestern slope about 20 miles from the crest of the Cordillera Occidental of the Andes Chain. It lies in a mountainous desert where the steep southwesterly slope of the Andes is dissected by a succession of rapidly downcutting, deep canyons. Local topography is moderately rugged with a dendritic drainage pattern and an elevation of 8000 to 14,000 ft. Volcanic peaks along the crest of the Cordillera rise over 19,000 ft. Local precipitation, including a little snow, amounts to about 10 in. during January and February, but general runoff in the region is slight. Throughout southern Peru the springs and streams are widely separated. Crude canals irrigate small farms on terraced slopes along the streams and provide sparse subsistence to the semi-nomadic inhabitants. During the past decade, engineering and geological explorations of the region, as well as the mineral deposits themselves, have required construction of a network of several hundred miles of roads. Before this, roads extended only a few miles inland. Many areas still can be reached only by trail. Toquepala was briefly described in 19th century geographical literature as a copper deposit, and it received desultory attention from Chilean prospectors early in the present century. It was first recognized as a mineralized zone of possible real importance by geologist O.C. Schmedeman during an exploration trip for Cerro de Paso Copper Corp. in 1937. The discovery was late as compared to earlier recognition of Chuquicamata, Potrerillos, and Braden of Chile and Cerro Verde of southern Peru. This was due partly to the region's difficult accessibility but principally to the obscure character of the outcrop evidence of copper. From 1938 until 1942 Cerro de Pasco Copper Corp. partially explored the deposit by adits and diamond drillholes. This campaign was supplied by a 60-mule pack train continuously shuttling over a 30-mile trail. Northern Peru Mining & Smelting Co., a wholly owned subsidiary of American Smelting & Refining Co., undertook regional engineering stud- ies in 1945 and drill exploration in 1949. According to published data1 the deposit contains 400 million tons of open pit ore averaging a little over 1 pct Cu. It is currently undergoing large-scale development by Southern Peru Copper Corp., which is owned by American Smelting & Refining, Phelps Dodge, Cerro de Pasco, and Newmont Mining. Summary of Geology: The deposit is situated in a terrane composed of Mesozoic(?) and Tertiary volcanic rocks intruded by dioritic apophyses of the Andean Batholith. These formations are exposed in a northwesterly trending belt about 15 miles wide. Along the northeast they are unconformably overlain by Plio-Pleistocene pyroclastic rocks, which occupy much of the crest of the Andes, and along the southwest they are covered by the Moquegua formation of Pliocene(?) age. The mineralized area, oblong in shape and about 2 miles long, has been a locus of intense igneous activity. Several small intrusive bodies having irregular forms occur within and adjacent to a centrally located, large breccia pipe. The mushroom-shaped orebody consists of a flat-lying enriched zone of predominant chalcocite with a stem-like extension of hypogene chalcopyrite ore in depth within and around the pipe. This breccia pipe is relatively large and has been formed by repeated episodes of brecciation. Small satellitic pipes occur at random within a 2-mile radius of this central pipe. These too were individual sourceways of mineralization, although not always of ore grade. Within and around the zone of breccia pipes and mineralization there are a few faults and veins, but these are discontinuous random structures of minor significance. There are no regional or local systems of faults or other planar structures recognized which could account either for the mechanical development of the breccia pipes or for their localization as a group or as individuals. Hydrothermal alteration is pervasive in the zone of mineralization. Clay minerals appear to be abundant in places, but their percentages are undetermined. Quartz and sericite are the principal alteration products, and in many instances original rock textures are obliterated. The principal sulfides, hypogene pyrite and chalcopyrite and supergene chalcocite, occur mainly as vug fillings in the breccia and as small discrete grains scattered through all the altered rocks. Sulfide veinlets are relatively scarce. Sulfides are more abundant and alteration is more intense in certain rock units, such as the diorite and most of the breccias. Although the Toquepala mineral deposit is similar in most respects to the porphyry copper deposits of southwestern U. S., it most closely resembles the Braden deposit of Chile, as described by Lindgren

Jan 1, 1959

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.' It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957