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By J. F. Fidiam, T. F. Ford, A. G. Loomis

It is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analvsisl of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acidsl for example, sodium tannate or gallate—and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shutdowns. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells. It is safe to assume that the application of colloid chemical principles can also help in solving other outstanding problems of drilling fluids, such as the development of cheaper and more efficient viscosity reducers ; the development of chemicals that do not lose their effectiveness in a short time during drilling operations; the finding of chemicals to preserve the plastering properties of muds when concentrated brines are encountered or in drilling through salt beds; improvement in the plastering properties of poor muds by further defloc-culation, and, conversely, the prevention of excessive deflocculation of certain marine shales sometimes encountered; the preparation of muds suitable for the successful drilling of heaving shale formations; the finding 0f chemicals to treat the mud to prevent or to diminish lost circulation; the development 0f muds that will not impair 6

Jan 1, 1941

By Ervin E. Underwood

IT has been recognized for many years that dis-persed particles have great value in raising the creep resistance of metallic alloys. In fact, some of the most successful high-temperature alloys owe their superiority to this factor above all others. A recent observation by Glen1," indicates that even better high-temperature resistance to deformation results in alloys capable of two successive precipitation reactions. The ramifications of this finding are of great interest. Unfortunately, our understanding of the reasons for such notable improvements has not kept pace with technical developments. In an effort to uncover some of the basic facts governing strengthening by particles, a program was initiated at the Battelle Memorial Institute with the primary goal of comparing creep strengths in single-phase and two-phase (precipitating) alloys. The effects of precipitation from solid solution on the creep properties of alloys are generally such that the resistance to creep is increased. However, if alloys are heat treated to different degrees of hardness before creep testing, it is often found that those possessing the maximum hardness initially do not necessarily have the maximum creep resistance. Depending on the stresses and temperatures involved other structures may prove more desirable. Considerations of the above nature indicate the importance of defining the initial state of the alloy. Here, it was decided to start with quenched single- phase alloys in which precipitation and creep deformation proceed concurrently. Equipment and Experimental Procedures Preparation of the Specimens—Four 25 lb ingots were prepared from 99.999 pct Cu and 99.996 pct Al to compositions of 1, 2, 3, and 4 wt pct Cu. Spec-trographic and chemical analyses are listed in Table I. After heat treatments and intermediate reductions, the alloys were cold rolled to 1/8 in. thick sheet. The final cold reductions amounted to 50, 40, 20, and 10 pct for the 1, 2, 3, and 4 pct Cu alloys, respectively. The specimens for creep testing were machined into tensile flats 7 in. long, 3/4 in. wide (at the shoulders), and 1/8 in. thick. The reduced sections were 1/4 in. wide and 21/2 in. long. After heat treatments at 540°C to an ASTM grain size of 1 1, the specimens were quenched into water at room temperature, then electropolished in a glacial acetic acid and perchloric acid solution. The gage marks were Knoop impressions placed 2 in. apart on the reduced sections. Blanks of 1 x 1 in, were cut from the same sheets for the age hardening runs and were given the same grain size heat treatments. The specimens and blanks were stored in a refrigerator at —40°C until needed for testing. Creep Measurements—Creep tests were conducted in a constant temperature room which was maintained at 26° ±1°C. A split-type, hinged, vertical-tube furnace was mounted on a horizontal track so that the specimen could be enclosed suddenly. Thus, it took about 15 min for the specimen to come within 5°C of the test temperature. The temperature variation along the specimen was controlled to about

Jan 1, 1958

By T. F. Ford, J. F. Fidiam, A. G. Loomis

It is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analvsisl of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acidsl for example, sodium tannate or gallate—and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shutdowns. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells. It is safe to assume that the application of colloid chemical principles can also help in solving other outstanding problems of drilling fluids, such as the development of cheaper and more efficient viscosity reducers ; the development of chemicals that do not lose their effectiveness in a short time during drilling operations; the finding of chemicals to preserve the plastering properties of muds when concentrated brines are encountered or in drilling through salt beds; improvement in the plastering properties of poor muds by further defloc-culation, and, conversely, the prevention of excessive deflocculation of certain marine shales sometimes encountered; the preparation of muds suitable for the successful drilling of heaving shale formations; the finding 0f chemicals to treat the mud to prevent or to diminish lost circulation; the development 0f muds that will not impair 6

Jan 1, 1941

By B. L. Landrum, P. B. Crawford

Theoretical and potentiometric model studies have been made of the effect of non-uniform lateral permeabilities on pattern sweep efficiency and production capacity in waterflood and gas-cycling programs. It is shown that a diflerence in directional permeability by a factor of three may result in a sweep efficiency of only 43 per cent for a five-spot pattern or a sweep of either 79 or 38 per cent for a direct line-drive square pattern, depending on the direction of the line-drive flood. Changes in the pattern conductivity varied from about 0.8 to 1.34 over this same permeability variation, depending on the pattern used. It is suggested that measurements be made to determine the possible magnitude and extent of the directional permeability phenomenon early in the field developinent and certainly prior to the initiation of any fluid-injection progmm. INTRODUCTION Irregularities in reservoir sand properties long have been a major difficulty to anyone attempting to explicitly describe the field characteristics of oil production. In particular, it is well known that vertical and lateral permeabilities often differ appreciably; however, the existence of large regions with lateral permeabflity variation is not widely recognized. A number of years ago, extensive studies were conducted by the Secondary Recovery Research Labcratory of the Pennsylvania Grade Crude Oil Association, primarily on the Bradford field. Johnson and Hughes' reported a permeability trend in the northeast-southwest direction. They indicated that flow in the preferred direction may be 25 to 30 per cent greater in that direction than in the northwest-southeast direction. They also reported that similar effects may be found in other nearby fields. The origin of the permeability variation has been discussed by Griffith Hutchinson' described the results of labora- tory tests on limestone cores, pointing out that per-ferential directional permeabilities were significant in one-half of 10 formations studied and that the average permeability ratio was 16:1. Barfield, Jordan and Moore analyzed the fluid-injection displacement performance in the Spraberry and reported that the effective ratio of permeability parallel to the major axis to the permeability perpendicular to this axis was 144:l and that it inclined along an angle of about 30". To prevent the reduction of sweep efficiency which would normally result from flooding or cycling in such reservoirs, well spacing could be varied from the customary square to a diamond-shaped pattern. Johnson and Hughes' presented a method for determining the desired shape. Another method will be discussed in detail in the next section. It is the purpose of this paper to investigate quantitatively the effect of directional permeability upon the sweep efficiency and production capacity of the five-spot and line-drive well patterns. Information currently in the literature will be applied to this particular problem and augmented by a potentiometric model study. It is stressed that the effects herein discussed may or may not be of great importance because field data on this phenomenon are far too scant to form such an opinion. It is suggested that, if conditions similar to those found by Johnson and Hughes frequently exist (as may well be the case), more consideration cdrtainly should be given to this problem.

By F. M. Lewis, J. E. Goodman

A larger, slow-speed, under-loaded ball mill and hydraulic classifier have almost doubled grinding efficiency at the lsabella mill. TENNESSEE Copper Co. operates two ore con-A centrators, the London and Isabella mills near Copperhill, Tenn. In 1948 and 1949 the small ball mills and rake classifiers in the London concentrator were replaced by one large ball mill and one hydraulic classifier. This new ball mill was designed oversize so that it could be operated at slower than normal speed. The proper operating conditions were established and the results published.' Later it was found that this mill operated more efficiently with a small ball charge." While this London grinding practice was being developed, the Isabella grinding circuit was not changed in any way. It remained a conventional two-stage rod mill—ball mill combination, the rod mill in open circuit and the ball mill in closed circuit with a rake classifier. Study of the data indicated that grinding cost could be lowered by converting to the London practice, but not enough would have been saved to warrant the expense of converting. No plan for improving this grinding operation could be developed. In 1953 this study was reopened when plans were made to increase the Isabella mill output from 1150 to 1500 tpd. At this time the grinding circuit consisted of a 6x12 rod mill followed by a 6x12 ball mill in closed circuit with a 6-ft rake classifier. Another 6x12 ball mill and 6-ft rake classifier would have been sufficient equipment and would have been the simplest and cheapest installation. However, this would have offered no improvement in grinding efficiency or operating cost. If, on the other hand, the grinding operation could be converted to the London practice, by installation of one large 101/2x9x9 tricone mill and a 10-ft hydroscillator,2 lower operating costs would justify the additional investment. Economics: Table I presents estimates for the two schemes for enlarging the Isabella mill. In the first scheme, column 1, one 6x12 ball mill and one 6-ft rake classifier were to be added. In the second scheme, column 2, the existing small ball mill and rake classifier were to be retired and one large mill and hydroscillator were to be installed. Estimated savings from the difference in operating costs made an attractive return on the additional investment for the large mill and hydroscillator. Actual costs of carrying out this plan are tabulated in column 3b. It will be seen that these costs follow the estimates in column 3a very Closely. The return on the additional investment is calculated from the difference in the operating cost in column 1 and the actual operating cost in column 3b. This too come very close to the estimate. Power and Steel: Power requirements and steel consumption for the rod mills and ball mills, both actual and estimated, are presented in Table 11.

Jan 1, 1958

By E. C. Harder, E. W. Greig

Bauxite is known mainly as the ore from which aluminum is smelted but it has large use also in the manufacture of artificial abrasives and in the production of a number of useful chemicals as well as of aluminous cement "ciment fondu." An important and growing use is in the manufacture of refractory products. Composition Dana and earlier mineralogists gave the mineral formula of bauxite as A1203.21120 and the composition as A1202, 73.9 pct; H2O, 26.1 pct. A specific mineral of this composition has, however, never been identified by either microscopic, chemical or X ray examination, and therefore it is concluded that bauxite is a rock consisting of one or more aluminum minerals together with impurities. The term is now used synonymously with aluminum ore and it embraces gibbsite (hydrargillite or alpha trihydrate), A1203. 3H20 (A1203, 65.4 pct; H2O, 34.6 pct); boehmite (alpha monohydrate), A1203•H20 (A1202, 85 pct; H2O, 15 pct) ; diaspore (beta monohydrate), A1203•H20 (A1203, 85 pct; H2O, 15 pct), and mixtures in various proportions of any two of them. Bauxite of the Mediterranean region in Europe is predominantly boehmite, as in France and Istria, subordinately a mixture of gibbsite and boehmite, as in Dalmatia, or of boehmite (or gibbsite) and diaspore, as in Greece. The bauxite of North and South America, tropical Africa, Asia, and Australasia consists largely of gibbsite, but boehmite in appreciable amount occurs in many places. Corundum (A1202) is not included un¬der bauxite, although gradations from bauxite to emery or corundum exist. All bauxite, irrespective of the aluminum minerals composing it, contains certain impurities in variable amount, including silica in the form of clay minerals (kaolinite, halloy site, and others) or quartz, iron oxide (as hematite or goethite), titania (as leucoxene or rutile), iron sulfide (as pyrite or marcasite), iron carbonate (siderite), and calcium carbonate (as calcite); the last three mentioned in minor amount and of local occurrence only. Bauxite belongs to a group of partly consolidated materials called laterites, formed by surface weathering. This group includes also impure siliceous, ferruginous, and phosphatic bauxite and siliceous and aluminous iron ores and manganese ores and nickel and chrome laterites. Phosphorus and manganese minerals locally form important impurities in bauxite deposits. Properties Gibbsite is white or light shades of gray, cream or pink. Its hardness is 2.5 to 3.5; specific gravity, 2.3 to 2.4; crystal system, monoclinic, crystals tabular parallel to 001, often fibrous, concretionary, stalactitic; luster, vitreous to pearly; generally translucent; cleavage, parallel to 001; disassociation temperature, approximately 300°C. Boehmite, a relatively new and important mineral described by J. Boehm15 in 1925, confirmed and named by J. de Lapparen64 in 1930, has some properties not yet definitely determined. It occurs in grayish, brownish, and reddish shades. Its hardness is between that of gibbsite and diaspore; specific gravity, 3.01 to

Jan 1, 1960

By P. A. Beck

ACCORDING to the traditional definition,1 re-x crystallization is a process taking place upon annealing of cold worked metals, characterized by the appearance of new strain-free grains, growing at the expense of the cold worked grains until ultimately the new crystals completely replace the cold worked structure. In metals like brass this process was observed long ago to take place simultaneously with the return of the mechanical properties to those characteristic of well annealed material. The above definition implicitly assumes that the matrix in which the new grains are growing is essentially still in the cold worked condition at the time it is absorbed by the new grains, i.e., that the energy stored in the metal during cold working is not greatly decreased by recovery, prior to recrystallization. Accordingly, the bulk of this energy is assumed to serve as the driving force for the process of recrystallization. Recently, a great deal of evidence accumulated, indicating that the traditional concept may be considerably in error. Suzuki' found that by far the largest portion of the stored energy of cold work in compressed polycrystalline copper is released in the early stages of annealing, well in advance of recrystallization. Thus, the new recrystallized grains are undoubtedly growing in a matrix which is, at least energetically, no longer in the cold worked condition, but has nearly returned to the annealed state. It is true that in Suzuki's experiments the major hardness changes due to annealing were observed to take place concurrently with the formation and growth of the new grains, but this process apparently involved the release of only a minor residual fraction of the stored energy of cold work. Confirming in this respect the views of Wood," several recent investigations by various techniques lead to the conclusion that the grains of many, if not all, metals in the cold worked condition consist of small, slightly disoriented "crystallites" or "sub-grains".* (After appreciable deformation at room temperature, the subgrain size in copper appears to be about 7.104 cm and in high purity aluminum about 2.10-4 cm.) Recent investigations which demonstrated this phenomenon most convincingly are those of Heidenreich8 with hammered high purity aluminum, of P. B. Hirsch and collaborators7,8 with cold worked polycrystalline aluminum, copper, nickel, iron, gold, etc., and of Warren and Averbach9 with a rolled copper plus 2 pct Si single crystal. In addition to the existence of slightly disoriented sub-grains, the cumulative evidence from these investigations also shows that in the cold worked condition the subgrains themselves are severely strained. With regard to the early stages of annealing, Heiden-reich's results indicate that within the subarains of hammered high purity aluminum the strain gradually disappears, without discernible migration of the subboundaries. This recovery process presumably accounts for the major portion of the energy release

Jan 1, 1953

By B. H. Sage, W. N. Lacey

The results of an extensive experimental program relating to the effectiveness of gravel screens have been correlated. The factors considered in some detail include gravel size and condition of packing, sand size and size distribution, fluid velocity, fluid viscosity, and thickness and arrangement of grave! screens. Good agreement between calculated values based upon probability considerations and experimental results relating to the influence of the thickness of the gravel screen was obtained. All of these factors are treated in the correlation in order that their influence may be taken into account in ascertaining the characteristics of an effective gravel screen for a particular set of conditions. The details of the experimental program are not given in the present paper but a description of generalized behavior and typical experimental results are recorded in graphic form. Introduction Gravel screens have been placed in water and oil wells for a number of yearsl,2,3 with the dual objective of increasing the productivity and decreasing the entrance of sand into the well bore. An understanding of the factors controlling the effectiveness of gravel screens in this connection is of industrial interest because it will lead to the proper selection of gravel. Some of the fundamental considerations involved in the migration of sand through a coarser body of porous materials were investigated by Coberly and Wagner4 and further experimental work has been carried out by Gumpertz.5 Apparently the pertinent phenomena are somewhat complex and are influenced by many variables. The present paper deals with the prediction of the behavior of gravel screens under the conditions encountered in practice but does not attempt to discuss the experimental methods or results that were obtained as a background and upon which the prediction is based. Influence OF Gravel Screens upon Productivity The use of a gravel screen may increase the productivity of a well by increasing its effective diameter, and this constitutes one of the objectives of its use. The permeability of most gravels and coarse sands that are employed in practice is so large compared to that of the sand in place that relatively little loss in production rate will arise from the use of material fine enough to cause the desired resistance to sand migration. For example, in Fig. I is depicted the approximate variation in the permeability of closely sized spherical gravels under the conditions of packing likely to be encountered in screens. The dotted lines indicate the variation that might be found because of differences in packing. It should be realized that the permeability is not a single-valued function of the average grain diameter but is related to a large number of factors, including the size, the size distribution and the shapes of the particles. However, Fig. I does permit a rough estimation of the permeability of closely sized spherical gravels and shows that the permeability with even the smaller particles is very large compared to that of most petroleum production horizons.

Jan 1, 1942

By W. N. Lacey, B. H. Sage

The results of an extensive experimental program relating to the effectiveness of gravel screens have been correlated. The factors considered in some detail include gravel size and condition of packing, sand size and size distribution, fluid velocity, fluid viscosity, and thickness and arrangement of grave! screens. Good agreement between calculated values based upon probability considerations and experimental results relating to the influence of the thickness of the gravel screen was obtained. All of these factors are treated in the correlation in order that their influence may be taken into account in ascertaining the characteristics of an effective gravel screen for a particular set of conditions. The details of the experimental program are not given in the present paper but a description of generalized behavior and typical experimental results are recorded in graphic form. Introduction Gravel screens have been placed in water and oil wells for a number of yearsl,2,3 with the dual objective of increasing the productivity and decreasing the entrance of sand into the well bore. An understanding of the factors controlling the effectiveness of gravel screens in this connection is of industrial interest because it will lead to the proper selection of gravel. Some of the fundamental considerations involved in the migration of sand through a coarser body of porous materials were investigated by Coberly and Wagner4 and further experimental work has been carried out by Gumpertz.5 Apparently the pertinent phenomena are somewhat complex and are influenced by many variables. The present paper deals with the prediction of the behavior of gravel screens under the conditions encountered in practice but does not attempt to discuss the experimental methods or results that were obtained as a background and upon which the prediction is based. Influence OF Gravel Screens upon Productivity The use of a gravel screen may increase the productivity of a well by increasing its effective diameter, and this constitutes one of the objectives of its use. The permeability of most gravels and coarse sands that are employed in practice is so large compared to that of the sand in place that relatively little loss in production rate will arise from the use of material fine enough to cause the desired resistance to sand migration. For example, in Fig. I is depicted the approximate variation in the permeability of closely sized spherical gravels under the conditions of packing likely to be encountered in screens. The dotted lines indicate the variation that might be found because of differences in packing. It should be realized that the permeability is not a single-valued function of the average grain diameter but is related to a large number of factors, including the size, the size distribution and the shapes of the particles. However, Fig. I does permit a rough estimation of the permeability of closely sized spherical gravels and shows that the permeability with even the smaller particles is very large compared to that of most petroleum production horizons.

Jan 1, 1942

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

The subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small. percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for Io Years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. 1). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, non-metallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, Probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to Ioo mg. per sq. cm. per day, the corrosion rate of high.purity magnesium is 0.15 ± 0.05 mg, per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in inin in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable, In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0,001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. while the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1942

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

The subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small. percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for Io Years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. 1). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, non-metallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, Probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to Ioo mg. per sq. cm. per day, the corrosion rate of high.purity magnesium is 0.15 ± 0.05 mg, per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in inin in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable, In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0,001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. while the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1942

By B. H. Cody

The Morenci concentrator of the Phelps Dodge Corporation is a part of the project that was completed after five years had been spent in development of the open-pit mine, equipment and process testing in the former No. 6 concentrator, and construction of the reduction works. The reduction works, of which the concentrator is a part, is about a mile and a quarter southeast of Morenci, on the highway that leads up Morenci Canyon. The concentrator has a nominal capacity for the treatment of 45,000 tons of ore daily. The original plant, which has a rated capacity of 25,000 tons of ore daily and is now in its fifth year of operation, began production on Jan. 30, 1942. The addition, to increase the capacity 80 pct, began operation on Dec. I, 1943. The equipment of the original plant has been described in Mining and Metallurgy (May 1942). NO changes in equipment were recommended for installation in the concentrator extension and only one major change, forced by a shortage of maintenance labor, has since been made. Metallurgical treatment has been altered in some ways as experiments progressed and as labor and economic conditions dictated. No complete description of the operation of the concentrator has been published, so this paper will record such operating and equipment changes as have been necessary, the operating methods that have been developed and the metallurgical results that have been obtained. Descriptions are given in the order of the processes with a flowsheet and an equipment list of each process for convenient reference. The questions asked by engineer visitors have guided the detail in which operation and maintenance are described. During the period Jan. 30, 1942 to Sept. I, 1946, ore milled has totaled 43,595,253 dry tons, from which 1,643,885 tons of concentrate have been made, containing an indicated production of 783,164,-809 lb of copper. The principal results obtained in operation of the concentrator during the years 1942 to 1945, inclusive, and to Sept. I, 1946 are shown in Table I. A graphic general flowsheet of the plant is given in Fig I. Ore The Morenci ore that is now being treated is a medium-hard monzonite porphyry in which the principal sulphide minerals are chalcocite and pyrite. A minor amount of covellite is present. Chalcopyrite and bornite have been observed under the microscope. The chalcocite occurs mainly as a coating on pyrite. Some of the coatings are so thick that the pyrite presents the appearance of being an inclusion in chalcocite. Some are less than one micron thick and are barely visible at 500 diameters magnification of a polished cross section. Some chalcocite is present as a in in the gangue. Various oxidized copper minerals are present as a result of oxidation in place but they represent a minor proportion of the copper minerals of the ore body. Oxidation

Jan 1, 1949

By J. A. Berger, R. J. Towner

A method for determining the disorientation between sub-grains that .share a common tilt or twist boundary from measurements on X-ray micrographs is described. The method may be applied to subgrains of almost any orientation having boundary angles in the range from about 1 min to 1 deg of arc. An adaption of the Berg-Barretl method has been made to allow calculation of small angles of about 1 min to 1 deg of arc: between adjacent subgrains from the relative displacement of their images on X-ray micrographs. schulz4 gave equations for determining subgrain disorientation where the axis of subgrain rotation and the reflecting crystal planes were parallel to the specimen surface. In our method, however, they need not be parallel and, indeed, may have va:rious orientations. His camera setup, involving a fine-focus X-ray tube for obtaining high resolution with continuous radiation, was different from the one used in the present investigation (a 1.2 x 1.2 mm effective source and characteristic radiation). The X-rays produced a slight magnification in the subgrain images in the Schulz method, but not in the present method. The commonly available type of X-ray tube used permitted relatively short exposure times with a fine-grained photographic plate, which could be magnified optically many times for the examination of small subgrains. The method is illustrated by results obtained on {110} tilt boundaries in a polygonized aluminum single crystal of 99.994 pct purity. The flat crystal was stretched 6 pct in tension and then heated at 500°C for a cumulative time of 5 hr. Earlier, cahn5 studied subgrains formed by polygonization in stretched and heated aluminum crystals. He observed kink bands to have well defined boundaries lying in (110) planes, at least in the early stages of deformation. Cahn found that the (110) tilt boundaries formed by polygonization were directly related to the lattice bending about the <211> axis which lay in the (111) slip plane perpendicular to the <110> slip direction. DESCRIPTION OF THE CAMERA Our camera was similar in detail to Honey-combe&apos;s.6 Unfiltered copper radiation was used at 35 kv, and 20 ma. With the particular specimen used here to illustrate the method, a 1.2 by 1.2 mm effective source and a distance of 780 mm from target to specimen were employed, giving a convergence of 5 min of arc in the primary beam. The distance was 9.5 mm from the specimen to film. The upper 1/2- by 1-in. portion of the front surface of the specimen was irradiated with the film in parallel position. Since the specimen had been inhomogeneously deformed, many regions were in a position to reflect characteristic radiation at the Bragg Angle. Five minute exposures were satisfactory with Kodak Single Coated X-ray Film, 1 1/2 hr

Jan 1, 1961

By O. Katz, A. Spilners, M. Simnad

THE oxidation of titanium has been studied in recent years by a number of investigators.&apos;-W ne of the most important aspects of the reaction of titanium with oxygen, which has been observed by several of the investigators, is the extremely high solubility of oxygen in the metal. A detailed study of the Ti-0 systeml% as shown that the solubility limit of oxygen in a-titanium is approximately 14.5 wt pct 0 from 800" to 1700°C. The unusual oxidation behavior of titanium may be ascribed to this phenomenon, since part of the oxygen uptake enters into solid solution in the metal and only a part is available for scale formation. A more complete study of the kinetics of oxidation of titanium would require information on the influence of oxygen in solution in the metal upon the oxidation rate. Such information would also be of interest in regard to the theory of oxidation of metals. The authors have measured the oxidation rates of oxygen-saturated and oxygen-free titanium between 800" and 1200°C and have found appreciable differences in their rates of oxygen uptake and in the activation energies. The experimental set-up was similar to that described in a previous paper.u The course of oxida-dation was followed continously by attaching the specimen to a sensitive spring balance and observing the extension of the spring with time of oxidation. High purity electrolytic oxygen was used and precautions were taken to purify the gases employed. The specimens were prepared from iodide titanium and were ground on metallographic polishing papers to a fineness of 4/0. The furnace was first evacuated and filled with argon; the specimen was lowered into the furnace, which was then evacuated and filled with oxygen, after the specimen had reached the oxidation temperature in argon. The samples were presaturated with oxygen by means of the following procedure: Each specimen was first heated in oxygen at 1200°C until its increase in weight indicated 13.8 pct by weight uptake of oxygen. The furnace was then immediately evacuated and filled with purified argon five times. The specimen was heated in the argon atmosphere for a period of 72 hr at 1200°C in order to saturate the metal with oxygen by complete absorption of the scale. The temperature was lowered to the oxidation temperature, the furnace was evacuated and filled with oxygen, and the oxidation rate was followed by noting the extension of the spring balance. No oxide film was visible on these specimens at the start of the oxidation experiments. Titanium samples in the oxygen-free as-received condition were also oxidized and their oxidation rates measured. The results are shown in Figs. 1, 2, and 3, which indicate that the initial rates of uptake of oxygen by both the oxygen-saturated and oxygen-free specimens are parabolic at these temperatures. The rate of uptake of oxygen is, however, appreciably lower

Jan 1, 1956

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

The rate of oxidation of titanium in the temperature range 650° to 950°C has been measured. &apos;The linear rate law obtained is explained by interface reaction control of the process. Tracer experiments indicate the oxygen diffuses in at least one phase of the scale. THE kinetics of oxidation of titanium, principally at low temperatures and under varying oxygen pressures, have been reported.¹,² In the present investigation the rates of oxidation of titanium have been determined by the gravimetric method in the temperature range 650" to 1000°C under 1 atm of oxygen. Some of the scales formed were powdered and an endeavor was made to identify the phases present by X-ray diffraction. Alexander and Pigeon1 ascribe a logarithmic rate law to the growth of thick films formed at temperatures up to 565"C, and Gulbransen and Andrew&apos; suggest that the parabolic rate law holds up to 600°C. In both cases large initial deviations from those relationships are apparent and no explanation is offered. In the present experiments it is shown that a linear rate law holds in the temperature range 650" to 1000°C, and it is suggested that the initial deviations observed are due in part to a spurious surface area effect and also to the high solubility of oxygen in titanium metal. Positive information on the mechanism of oxidation is not available, but oxygen ion diffusion through the lattice is inferred from the re- sults of trace experiments. X-ray analysis of the scale confirms Gulbransen and Hickman&apos;s&apos; observation on the presence of rutile TiO². Experimental Details The titanium used in these experiments was prepared by the reduction of titanium tetrachloride with magnesium and was used in the form of rolled sheet. Samples approximately 0.040x0.5x0.75 in. were cut and polished to a fineness of 4/0 on metal-lographic polishing papers. Individual samples, suspended on a platinum wire, were lowered into the hot zone of a furnace, in vacuo, by means of a winch, and oxygen was admitted after the desired temperature was attained. The increase of weight of single samples oxidized for fixed times at certain temperatures was determined by weighing the sample before and after oxidation on a chemical balance. In these instances the sample was used for only one time at one temperature. In some cases the course of oxidation was followed by attaching the sample to a sensitive spring balance and noting periodically the extension of the spring with time of oxidation. Kirkendall type experiments were carried out by marking the surface of the titanium prior to oxidation with a solution containing radioactive silver. After drying, the specimen was heated in vacuo to decompose the silver nitrate used, leaving a small amount of metallic radioactive silver on the surface. Following oxidation, these samples were mounted, ground, and then placed in intimate contact with

Jan 1, 1952

By J. C. M. Li

A dislocation model is constructed for a cylindrical tilt boundary of which the axis of tilt is parallel to the axis of the cylinder. The strain energy per unit area calculated from this model agrees with thut of an infinite vertical wall of edge dislocations. Based on this model, a dislocation mechanism for the shrinking of such a cylindrical boundary is proposed. The power relation between the grain boundary velocity and the driving force is accounted fm by the stress dependence of dislocation velocity. The activation area for grain boundary motion is found to correlate with that .for Creep in aluminum. In the preceding paper&apos; the velocity of a curved grain boundary is found to be a power function of the driving force, [1] where M is the velocity at unit driving force, y is the grain boundary energy, and p is the radius of curvature. This finding adds another nonlinear rate equation to metallurgical phenomena. While a macroscopic theory for the steady state as just presented2 can be used to understand the shape of the moving boundary, such theory usually does not provide any information about the atomistics of the process. It is attempted in this paper to discuss the nonlinear rate equation in terms of a dislocation mechanism. A DISLOCATION MODEL FOR A CYLINDRICAL TILT BOUNDARY Before a dislocation mechanism can be proposed for the motion of a cylindrical tilt boundary, it is necessary to construct a dislocation model for the boundary. For simplicity, a tilt boundary in a simple cubic lattice will be examined. Although this does not represent the situation in aluminum, it is expected that the general features will be similar. The details of the model in the fcc lattice can be constructed when a refinement of the simple model is called for. A cylindrical low angle tilt boundary in a simple cubic lattice is shown in Fig. 1. Two sets of edge dislocations are needed as shown. A schematic representation is shown in Fig. 2(a). In terms of a continuous distribution of dislocations, the density of dislocations n, of Burgers vector b, in the small segment ds of the grain boundary is Similarly the density of dislocations n, of Burgers vector bz in the same segment ds is where is the tilt angle of the grain boundary. Based on this continuous distribution of dislocations in the grain boundary, it can be shown that the interaction between a small segment of the boundary and the rest of it is zero. Furthermore, the stress produced at any point inside or outside the cylinder is also zero. This shows that the model is acceptable in the sense that the boundary has no long-range stresses. Since the model of continuous distribution of dislocations in the grain boundary does not reveal the interactions among individual dislocations, a discrete dislocation model has to be used for such purpose. For simplicity, an equivalent model is shown in Fig. 3. This arises because the total Burgers vector is, from

Jan 1, 1970

Discussion of the paper of G. P. Hulst, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin No. 92, August, 1914, pp. 1865 to 1871. L. S. AUSTIN, Salt Lake City, Utah.-One question that I would like to ask is in regard to the sampling kettle which stands beside the softening furnace. How is the sample taken or melted? G. P. HULST.-The sampling kettles in question are of 45 tons capacity and are fired with coal. The lead bullion comes in on a high line in car-load lots of 30 to 40 tons. The entire lot is trucked from car, weighed over scales and thrown into the sampling kettle, which has been previously cleaned. The kettle is fired and the bullion melted, then heated up until no frozen bullion&apos; remains in the .bottom or adheres to the sides of the kettle. The kettle is scraped clean, sides and bottom, and the wet dross is skimmed Doff clean into molds. The kettle is stirred thoroughly during the period in which 24 to 30 samples of approximately ½ assay ton are taken. These samples are taken in a long-hand loci iron mold, providing for taking six to eight "gumdrops." The mold is inserted and heated to the same temperature as the molten metal, and gumdrops are clipped out and cooled in the mold by dipping &apos;the bottom of. the mold into Water. The samples should be free from fins. The gumdrops represent the contents of the kettle, and in assaying, they should not be clipped, but weighed up and the result computed. The dross bars are weighed and sawed according to old hammer and punch sample template. The sawdust represents a sample of the dross. In eases of high gold in the bullion there is a slight correction in the assay. This method of sampling was developed at the Omaha plant of the American Smelting & Refining Co., W. T.. Page, Manager, in 1903 or 1904, for adjusting differences in checking smelter sampling. L. S. AUSTIN.-The base bullion which you treat is very clean. It has been remelted, and skimmed before shipment. How rapidly can you get it through the softening furnace, and how does it compare with ordinary base bullion? G. P. HULST.-Twenty-four hours is the softening limit on these charges. In other words, it is charged into the furnace, heated up, and the first and second skimmings are taken off, and it goes into the kettle the next day; that is, 24 hr. elapse from the time the bullion is charged to the time it is in the kettle. L. S. AUSTIN.-It seems to be a long time to hold such a pure bullion. I suppose, though, it comes around conveniently so that you have a time for all the other operations of refining. Isn&apos;t that the case? MR. HULST.-Every refinery is based on those principles.

Jan 11, 1914

By Charles C. Rodd

Prior to 1938, proration procedure in Kansas required the physical testing of wells in order to set up a basis for allocating production. Subsequently the use of liquid-level data and bottom-hole pressure data was authorized on certain types of wells as a basis for calculating well capacities, thereby permitting wells to be tested at low rates and with small volumes of production. This paper gives some attention to the equipment used for obtaining liquid-level data but in general it is devoted to the theoretical and physical factors involved in well testing by drawdown methods. These tests are divided into two classifications: (I) liquid-level data used directly to calculate capacities, and (2) liquid-level data and liquid-level measuring equipment used in connection with other data to determine bottom-hole pressure. Equations and calculations for both types are shown. Well capacities calculated from fill-up data have not been used generally but offer a simple means of testing some wells. Theoretical factors and calculations for such tests are shown. In the state of Kansas, proration laws required that the "ability of a well to produce" be given consideration in state allocation orders and for many years this was the only factor used in prorating the allowed oil. The "ability of a well to produce", was the quantity of oil that could be obtained from a well in a prescribed period, usually 24 hr. Early in the history of State-regulated proration, Kansas operators realized that, unless some restriction were placed upon equip- ment, the competition between producers to obtain large well "potentials" might result in a race to install the largest pumping equipment. Consequently, restrictions were placed upon the size of tubing and length of pump stroke that could be used in pumping wells during potential tests. Later, restrictions were placed also upon the size of tubing and chokes that could be used in flowing walls. Despite the restriction setup, better pumping equipment was designed and installed, pumps were improved, and various devices were invoked to obtain high rates of production for short periods of time. By 1937 pumping cycles of forty to forty-five 54-in. strokes per minute were not uncommon, and numerous wells had produced at the rate of 3500 bbl. per day for short periods. Such production was far beyond any rate that could be long sustained. Equipment necessary to take "potentials" was several times larger than that needed for normal producing purposes, and repairs and replacements required by the high pumping speeds were excessive. Also, many operators suspected that the high rates of production main tained during &apos;"potential" tests were conducivc to early water encroachment. By 1938 large-scale physical testing of wells in Kansas ended, the use of the bottom-hole pressure gauge had become common, engineers and operators were becoming familiar with the term &apos;&apos;productivity index," and bottom-hole pressure was being used as a factor in allocation in many areas. There were many drawbacks, however, to large-scale use of

Jan 1, 1943

By B. L. Averbach, E. E. Underwood

The vapor pressure of zinc in equilibrium with solid ß AgZn alloys has been measured by the dew-point method. The thermodynamic activities of silver, and the molar heats of formation have been calculated. Similar measurements have been made for the ternary alloys formed by adding gold to AgZn. An apparent particle size effect has been observed for AgZn filings. The vapor pressure of zinc over filings is 15 to 20 pct higher than over the solid alloys. STATISTICAL methods have been used to inter pret the thermodynamic activities of the components of a solid solution in terms of average equilibrium atomic configurations. In some cases, the atomic arrangements can be measured by X-ray methods, and the results are usually expressed in terms of short range order parameters. Only in the cases of Cu³Au and AgAu have there been sufficient X-ray and thermodynamic data to verify the assumed correlation between the X-ray and the thermodynamic measurements. In Cu³Au the agreement is good; negative deviations from Raoult&apos;s law are observed and the number of Cu-Au nearest neighbor pairs predicted on the basis of the thermodynamic treatments agrees quite well with the number of such pairs observed by the X-ray methods. The ß brass alloys present a different set of conditions. The ordering is so rapid in these alloys that the disordered state cannot be retained on quenching. In contrast, the disordered state in CuAu is easily retained on quenching. On heating, the ordered ß brass loses its long range order continuously as the critical temperature is approached; in Cuau the order decreases slightly on heating and then drops discontinuously to zero at the critical temperature. These differences indicate that the short range order configurations in ß brass systems may be of a different character than in Cudu systems. However, X-ray measurements of local order cannot be made in the Cu-Zn alloys because of the similarity in scattering factors. The alloy AgZn is isomorphous with CuZn, however, and recent experiments have indicated that there is a good possibility of observing short range order in this system. Another complication arises in the case of ß AgZn. The disordered body-centered cubic structure exists above 280°C. On quenching from above this temperature an ordered structure of the cesium-chloride type is formed. On slow cooling, however, a complex hexagonal structure, the 3 phase, is produced; and if an ordered quenched alloy is reheated the phase begins to form above 80°C. It is thus difficult to study local order by X-ray methods in single crystals of AgZn since the C phase formed on heating does not necessarily return to a single crystal of the original orientation. This problem has been met, however, by adding a few percent of gold to the AgZn. The gold suppresses the formation of the c

Jan 1, 1952

By Marshall B. Standing, Donald L. Katz

DENSITY data are reported on 16 saturated hydrocarbon vapors at pressures ranging from 1000 to 8220 lb. per sq. in. and at temperatures ranging from 35° to 250°F. These data have been used to extend the compressibility-factor chart for natural gases up to 10,000 lb. per sq. in. The relatively large quantity of high-boiling constituents present in high-pressure vapors in equilibrium with crude oils makes it necessary to include in the analysis of the gas the molecular weight, density, and possibly boiling range of the heptanes and heavier fraction. Relationships have been presented by which the density of gases may be obtained directly from the temperature, pressure, and gas gravity provided the gases have a common source or are similar in composition. INTRODUCTION The densities of natural gases are necessary in many engineering computations in petroleum production and utilization. Gas reserves, changes in reservoir pressure, gradients in gas wells, metering of gases, pipeline flow, and compression of gases are typical problems requiring the density of the gas. A decade ago, engineering computations used ideal gas laws with deviations up to 500 lb. per sq. in.4 Recent discoveries of pools having pressures up to 7500 lb. per sq. in., and installation of pressure-maintenance and recycling plants, have increased the need for data on gas density at high pressures. METHODS OF COMPUTATION The accepted method of computing the density or specific volume of natural gases is the use of the ideal gas law corrected by a compressibility factor. The method proposed by Kay7 of correlating compressibility factors for gaseous mixtures on pseudocritical properties5 appears to be satisfactory for natural gases.2 The methane-compressibility factor has been shown to deviate systematically from the behavior of natural gases2 and a chart giving these corrected factors is available. A method of computing specific volume of gaseous mixtures from partial molal volumes has been reported by Sage and Lacey.8 Complete data for the computation are not yet available for all hydrocarbon gases. Most of the reported data on gas densities have been in the single-phase region removed from the dew point or saturation condition. Since most gases in the reservoir or while on contact with liquid during flow are saturated, the determination of densities under conditions of saturation is particularly important. Although there is no reason to believe that the saturated gases differ in behavior from those considerably removed from their dew points, the usual experimental determinations find difficulty on approaching the dew-point conditions. This paper reports the density of 16 saturated gases in equilibrium with crude oils. The relationships developed to compute the density of gases to high pressure&apos; have been modified and enlarged. A simplified method of obtaining gas density is presented in the form of charts, which apply for specific groups of gases.

Jan 1, 1941