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By S. Leber, R. F. Hehemann

This investigation describes the kinetics of alloying in a (Cb-15 wt pct W. 5 wt pct Mo, 1 wt pct Zr) powder-metallurgy alloy. The degree of homogeneity obtained in hydrostatic ally pressed and vacuum-sintered samples is described by composition distributions resulting from analysis of X-ray dvfraction line profiles. Sintering variables and degvee of powder dispersion were evaluated. The utility of single-value parameters obtained from composition distributions is disaissed. The spatial distribution of composition, as revealed by anodically tinted metallographic sarrzples, was used to provide diffision models based on a concentric-sphere geometry. Diffusion equations developed from these models were found to be in general agreement with experimental results. The powder-metallurgy method for the production of refractory metal alloys has the ability to produce an inherently fine-grained, fabricable structure. The more general use of this method is inhibited, in part, by the presumed difficulty in obtaining homogeneity on a microscale. The degree of homogeneity therefore is an important, but usually neglected, variable in specifying the quality of a powder-metallurgy alloy. Convenient techniques for measuring the degree of homogeneity are now available,' and have been used to develop a model describing the process of alloying in a simple binary mixture.' In this investigation, the process of alloy formation has been studied in a more complex system. PROCEDURE The columbium-based F-48 mixture was prepared from the constituent powders shown in Table I. The particle sizes tabulated were provided by the vendors of the individual powders. Standard laboratory techniques utilizing a jar mill were employed for blending. The blended powders were hydro-pressed into 1-in. diam rods which were then sliced into thin discs for vacuum sintering. All samples were given a preliminary treatment at 1700°C for 2 hr. Varying degrees of homogeneity were obtained using additional treatments at higher temperatures. The degree of homogeneity obtained by a specific sintering treatment was evaluated metallographi-cally using the anodic-tinting technique described by olff,' and quantitatively by the analysis of X-ray diffraction line profiles using the X-ray diffraction technique developed by udman.' The diffraction technique is strictly valid only for binary systems. However, the relatively small difference between the lattice parameters of tungsten and molvbdenum when compared with columbium permitted the treatment of the complex composition of F-48 as a (W, Mo)-Cb pseudobinary. Calculations were weighted in accord with the W-Mo ratio in the F-48 composition. The contribution of the 1 pct Zr was ignored since it could not even be detected in the blended powder. Two factors are required to convert an X-ray line profile into a composition distribution. The variation of these factors with composition is shown in Fig. 1. Curve A was used to convert angular posi-

Jan 1, 1964

By Marston G. Fleming

CRITICAL pH has been defined by Wark1 as that pH value below which a mineral will float and above which it will not float in solutions containing a given concentration of collector but free from other depressants or activators. - The relationship between mineral, collector concentration, and pH is expressed in the form of a critical pH curve determined by the captive bubble method and is generally regarded as being fundamental to the system involved. The mechanism of alkali depression is currently in dispute, two general theories having received authoritative support. The view expressed in Taggart's chemical theory of flotation2 is that in the presence of a critical concentration of hydroxyl ions, all the metal ions available at the surface of the mineral are present as anions of the form [M (OH)x]-y. The formation of the necessary metal xanthate is thus precluded and, furthermore, any metal xanthate coating previously formed, at a lower pH, will be dissolved. Gaudin3,4 and the Melbourne school under Ware hold that alkali depression is caused by the preferential adsorption of hydroxyl ions by the mineral surfaces. This paper describes an investigation of the mechanism of alkali depression in each of the three systems: cerussite-aqueous carbonate-xanthate, cerussite-xanthate, and galena-xanthate. Alkali Depression of Cerussite by Control of Carbonate Ion Concentration Wark and Cox6 have shown that in the presence of Na2CO3 a higher concentration of xanthate is required to effect bubble contact with a cerussite surface than in carbonate-free solutions. To examine this depression of cerussite by sodium carbonate, a series of captive bubble tests was carried out on cerussite specimens in solutions containing 100 mg per liter of potassium ethyl xanthate and varying concentrations of sodium carbonate. The pH was adjusted by the addition of dilute hydrochloric acid. For purposes of comparison a standard critical pH curve was determined for cerussite with potassium ethyl xanthate in solutions containing no added carbonate. In the latter case pH adjustment was made with sodium hydroxide. The experimental method employed in both series was broadly similar to that described by Wark and Cox;7-9 a number of refinements suggested by Sutherland10 were adopted, and the procedure was further developed and modified to suit the particular requirements of the investigation. The relationship between pH and the concentration of potassium ethyl xanthate necessary to induce bubble contact at cerussite surfaces is shown in Fig. 1. The relationship between pH and the concentra- [ ] tion of sodium carbonate necessary to prevent bubble contact at cerussite surfaces in the presence of 100 mg per liter of potassium ethyl xanthate is shown in Fig. 2. Comparison of the. two curves shows that at a collector concentration of 100 mg

Jan 1, 1952

By F. J. Dunkerlery, V. Damiano, J. Fulton, F. Pledger

Grain-growth and recrystallization characteristics of a commercially pure zirconium prepared by the iodide process are reported. Grain growth from 640° to 800°C was continuous once initiated and obeyed D = kt". Recrystallization of zirconium occurred at temperatures of 450° to 550°C after deformations of 20 and 50 pct. Hardening from partially soluble inclusions prevented determination of the absolute rates of recrystallization, but the relative rates of recrystallization obtained are useful as a guide in fabrication practice. BASIC information needed as a guide in the hot and cold working and annealing of metals includes recrystallization and grain-growth data. A search of the literature revealed no such information for pure zirconium. This is a report of practical grain-growth and recrystallization results obtained for a commercial grade of pure zirconium on a project sponsored by the Office of Naval Research. In this work, isothermal grain-growth curves were obtained at five temperatures from 640" to 800°C inclusively; while recrystallization curves have been determined at 450°, 500°, and 550°C for the metal at the deformation levels of 20 and 50 pct. In addition to the usual variables of temperature, time, and deformation, distribution of the second phase found in all commercial grades of iodide zirconium is also treated as an important factor in these grain-growth and recrystallization studies. In conducting this work, two properties of zirconium were particularly pertinent in dictating experimental conditions. First, since zirconium undergoes a transformation from the a close-packed hexagonal form to the ß body-centered cubic form at 862°C, no recrystallization or grain-growth studies were made above 800°C. Second, because dissolved gases (oxygen, nitrogen and/or hydrogen) increase the hardness and lower the ductility of the solid metal, all annealing treatments in this investigation were carried out in vacuum or in a helium atmosphere. Materials and Methods The zirconium used in this investigation was prepared by the Foote Mineral Co. by deposition from its iodide. A spectrochemical analysis of the metal showed the following composition in weight pct: Hf, 2.1; Mg, 0.012; Fe, 0.035; Si, 0.095; Ti, 0.023; Al, 0.037; Mo, trace; Ni, trace; Cr, trace; Ca, 0.006. Conventional metallographic procedures involving hand polishing on wet metallographic papers, followed by final polishing on fine, levigated alumina on gamal cloth and a medium speed wheel were used throughout this investigation. Grain boundaries were revealed with modified Tucker's etch containing 20 parts glycerine, 2 parts hydrofluoric acid, and one part nitric acid. Grain-Growth Procedure: Three lots of zirconium, designated here as series A, B, and C were prepared for the grain-growth studies as follows: Series A was prepared by cold swaging the % in. as-deposited rod to a 3/16 in. final diameter, followed

Jan 1, 1952

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By D. P. Morton

Since 1923, which closed the speculative era in the bituminous coal fields of the United States, there have been wide annual fluctuations in the national production of bituminous coal. These changes in annual output have been variously attributed to: (1) increased competition from petroleum products, natural gas and hydroelectric power; (2) lower unit consumption of coal; and (3) fluctuations in the general business level. The purpose of this paper is to measure, from a practical standpoint, the net effect upon the annual trend of bituminous coal production, and to give those who are interested a basis for estimating in advance the probable output of bituminous coal. It can readily be shown that changes in the level of general business affect the national production of bituminous coal more than does any other factor. Therefore it is necessary to use some standard measure of the relative business level for purposes of comparison. The Federal Reserve Board Index of Industrial Production offers the basis for such a measure.l This Index, a weighted composite of 81 different series, rests upon the averages of the years 1935 to 1939 as 100, and is presented graphically in Fig. I. Even a cursory examination of the chart will indicate a definite uptrend for industrial production over a period of years. This uptrend is due to at least two factors: (I) an actual increase in national population, and (2) a probable increase in the per capita consumption of goods. This means that there is no such thing as a fixed Normal, rather Normal is a variable, tending to increase from year to year. In order to measure the amount of annual increase in normal, the Index of Industrial Production must be studied in relation to its major components, Durable Goods and Nondurable Goods, Durable Goods are those made from the lasting materials such as iron, steel, other metals, lumber, stone, cement, clay, glass. Nondurable Goods are those for early consumption, such as foods, textiles, tobacco, chemicals, paper, gasoline, and goods made of leather and rubber. The purchase of Durable Goods may be postponed, but Nondurable Goods must be purchased currently unless the standard of living is lowered. The Federal Reserve Indexes of durable and nondurable goods are shown graphically, 1920 to 1939, on Fig. a (pp. 764-765 of ref. I). It is apparent that fluctuations in the production of nondurable goods are not nearly so wide as in the production of durable goods, and that the curve of Industrial Production (Fig. I) would fall between the two curves on Fig. 2. It would, however, seem logical that both curves should follow the same long-term trend, or that over a period of two to three decades the relative proportion of durable and nondurable goods, in periods of normal production, should be the same. It is neces-

Jan 1, 1942

By R. C. Buehl, J. P. Riott, E. P. Shoub

PILOT-PLANT tests have demonstrated that it is possible to produce low-sulphur sponge iron (0.03 to 0.05 per cent sulphur) as a continuous process in an internally fired rotary kiln from iron ore or mill scale; a solid carbonaceous reducing agent; and dolomite to control the sulphur content. The proportion of dolomite employed is small, so that it does not add materially to the cost of the sponge iron. The entire operation is carried out at temperatures well below the melting point of iron, so that the product is discharged in granular form. Compared with other methods for the production of sponge iron, the rotary-kiln method has the advantage of simplicity and low cost of equipment and; in addition, requires little labor for the operation of the process. The pilot-plant equipment used for this work was sufficiently large to demonstrate that the production of low-sulphur sponge iron in rotary kilns is feasible and that the costs are not excessive for applications in which sponge iron has distinct advantages over competing materials. This report constitutes a part of a program by the Bureau of Mines under a special Congressional appropriation for studying gaseous and solid fuel reduction of iron ores. Numerous articles on various phases of these investigations have appeared in Bureau of Mines publications or technical journals. Other articles are being prepared and will be published in the near future. The present program, which is under the supervision of Dr. R. S. Dean, Assistant Director of the Bureau of Mines, was initiated in .1942. However, a considerable portion of the work was a continuation of previous research performed by the Bureau. Previous investigators1-4 utilizing the rotary kiln for the production of sponge iron did not develop a suitable method for controlling the sulphur content. A review of the literature shows that the sulphur content in the product usually exceeded 0.2 -per cent unless reducing agents with very low sulphur contents were employed. This high sulphur value made the product generally undesirable for use as melting stock in electric or open-hearth furnaces. The production of sponge iron in an internally fired rotary kiln has been described in detail in Bureau of Mines Bulletin 2702; consequently, this article will be confined mostly to new features of the process-that is, means for controlling the sulphur content of the sponge iron. Suitable raw materials include iron ores or mill scale; coal or coke for reducing them, and sized dolomite (-20+100-mesh) as the sulphur-controlling agent. A mixture of the raw materials in granular form is fed into the elevated end of the kiln, which is fired axially from the lower or discharge end. In the reducing zone, which is approximately one third the length of the kiln measured from the dis-

Jan 1, 1946

By E. P. Shoub, J. P. Riott, R. C. Buehl

Pilot-plant tests have demonstrated that it is possible to produce low-sulphur sponge iron (0.03 to 0.0; per cent sulphur) as a continuous process in an internally fired rotary kiln from iron ore or mill scale; a solid carbonaceous reducing agent; and dolomite to control the sulphur content. The proportion of dolomite employed is small, so that it does not add materially to the cost of the sponge iron. The entire operation is carried out at temperatures well below the melting point of iron, so that the product is discharged in granular form. Compared with other methods for the production of sponge iron, the rotary-kiln method has the advantage of simplicity and low cost of equipment and, in addition, requires little labor for the operation of the process. The pilot-plant equipment used for this work was sufficiently large to demonstrate that the production of low-sulphur sponge iron in rotary kilns is feasible and that the costs are not excessive for applications in which sponge iron has distinct advantages over competing materials. This report constitutes a part of a program by the Bureau of Mines under a special Congressional appropriation for studying gaseous and solid fuel reduction of iron ores. Numerous articles on various phases of these investigations have appeared in Bureau of Mines publications or technical journals. Other articles are being prepared and will be published in the near future. The present program, which is under the supervision of Dr. R. S. Dean, Assistant Director of the Bureau of Mines, was initiated in 1942. However, a considerable portion of the work was a continuation of previous research performed by the Bureau. Previous investigators1-4 utilizing the rotary kiln for the production of sponge iron did not develop a suitable method for controlling the sulphur content. A review of the literature shows that the sulphur content in the product usually exceeded 0.1 per cent unless reducing agents with very low sulphur contents were employed. This high sulphur value made the product generally undesirable for use as melting stock in electric or open-hearth furnaces. The production of sponge iron in an internally fired rotary kiln has been described in detail in Bureau of Mines Bullelin 2702; consequently, this article will be confined mostly to new features of the process—that is, means for controlling the sulphur content of the sponge iron. Suitable raw materials include iron ores or mill scale; coal or coke for reducing them, and sized dolomite ( — poi-100-mesh) as the sulphur-controlling agent. A mixture of the raw materials in granular form is fed into the elevated end of the kiln, which is fired axially from the lower or discharge end. In the reducing zone, which is approximately one third the length of the kiln measured from the dis-

Jan 1, 1948

By D. P. Morton

Since 1923, which closed the speculative era in the bituminous coal fields of the United States, there have been wide annual fluctuations in the national production of bituminous coal. These changes in annual output have been variously attributed to: (1) increased competition from petroleum products, natural gas and hydroelectric power; (2) lower unit consumption of coal; and (3) fluctuations in the general business level. The purpose of this paper is to measure, from a practical standpoint, the net effect upon the annual trend of bituminous coal production, and to give those who are interested a basis for estimating in advance the probable output of bituminous coal. It can readily be shown that changes in the level of general business affect the national production of bituminous coal more than does any other factor. Therefore it is necessary to use some standard measure of the relative business level for purposes of comparison. The Federal Reserve Board Index of Industrial Production offers the basis for such a measure.l This Index, a weighted composite of 81 different series, rests upon the averages of the years 1935 to 1939 as 100, and is presented graphically in Fig. I. Even a cursory examination of the chart will indicate a definite uptrend for industrial production over a period of years. This uptrend is due to at least two factors: (I) an actual increase in national population, and (2) a probable increase in the per capita consumption of goods. This means that there is no such thing as a fixed Normal, rather Normal is a variable, tending to increase from year to year. In order to measure the amount of annual increase in normal, the Index of Industrial Production must be studied in relation to its major components, Durable Goods and Nondurable Goods, Durable Goods are those made from the lasting materials such as iron, steel, other metals, lumber, stone, cement, clay, glass. Nondurable Goods are those for early consumption, such as foods, textiles, tobacco, chemicals, paper, gasoline, and goods made of leather and rubber. The purchase of Durable Goods may be postponed, but Nondurable Goods must be purchased currently unless the standard of living is lowered. The Federal Reserve Indexes of durable and nondurable goods are shown graphically, 1920 to 1939, on Fig. a (pp. 764-765 of ref. I). It is apparent that fluctuations in the production of nondurable goods are not nearly so wide as in the production of durable goods, and that the curve of Industrial Production (Fig. I) would fall between the two curves on Fig. 2. It would, however, seem logical that both curves should follow the same long-term trend, or that over a period of two to three decades the relative proportion of durable and nondurable goods, in periods of normal production, should be the same. It is neces-

Jan 1, 1942

By R. C. Buehl, J. P. Riott, E. P. Shoub

Pilot-plant tests have demonstrated that it is possible to produce low-sulphur sponge iron (0.03 to 0.0; per cent sulphur) as a continuous process in an internally fired rotary kiln from iron ore or mill scale; a solid carbonaceous reducing agent; and dolomite to control the sulphur content. The proportion of dolomite employed is small, so that it does not add materially to the cost of the sponge iron. The entire operation is carried out at temperatures well below the melting point of iron, so that the product is discharged in granular form. Compared with other methods for the production of sponge iron, the rotary-kiln method has the advantage of simplicity and low cost of equipment and, in addition, requires little labor for the operation of the process. The pilot-plant equipment used for this work was sufficiently large to demonstrate that the production of low-sulphur sponge iron in rotary kilns is feasible and that the costs are not excessive for applications in which sponge iron has distinct advantages over competing materials. This report constitutes a part of a program by the Bureau of Mines under a special Congressional appropriation for studying gaseous and solid fuel reduction of iron ores. Numerous articles on various phases of these investigations have appeared in Bureau of Mines publications or technical journals. Other articles are being prepared and will be published in the near future. The present program, which is under the supervision of Dr. R. S. Dean, Assistant Director of the Bureau of Mines, was initiated in 1942. However, a considerable portion of the work was a continuation of previous research performed by the Bureau. Previous investigators1-4 utilizing the rotary kiln for the production of sponge iron did not develop a suitable method for controlling the sulphur content. A review of the literature shows that the sulphur content in the product usually exceeded 0.1 per cent unless reducing agents with very low sulphur contents were employed. This high sulphur value made the product generally undesirable for use as melting stock in electric or open-hearth furnaces. The production of sponge iron in an internally fired rotary kiln has been described in detail in Bureau of Mines Bullelin 2702; consequently, this article will be confined mostly to new features of the process—that is, means for controlling the sulphur content of the sponge iron. Suitable raw materials include iron ores or mill scale; coal or coke for reducing them, and sized dolomite ( — poi-100-mesh) as the sulphur-controlling agent. A mixture of the raw materials in granular form is fed into the elevated end of the kiln, which is fired axially from the lower or discharge end. In the reducing zone, which is approximately one third the length of the kiln measured from the dis-

Jan 1, 1948

By J. Szekely

A rrlethod is presented for the estitnation of oxygen pickup by teettzed molten steel streams. Of the mechanisrt~s considered for oxygen absorption, physical entrainment appeared to be the most significant. The estent of this physical entrainment may be calculated by the application of boundary layer theory. It was found that the values of oxygen pickup thus predicted were in wry good agreement with data reported in the literature, in the case of short, well-defined metal streams. This entrainment model does not provide an adequate description of oxygen pickup by long streams, exoosed to external winds and where breakup of the streatn is likely. WheN molten steel is teemed into a mold or tundish it will absorb oxygen contained in its environment. Recently interest has been expressed in the measurement and possible prediction of the extent of this oxygen absorption: this interest owes its existence to two principal factors: a) the desirability of providing a quantitative assessment of the role played by the absorbed oxygen in impairing the quality of (vacuum degassed. stainless, or continuously cast) steel; b) the need for providing guidelines for stream protection methods. The purpose of this communication is to suggest a simple method for the prediction of oxygen absorption by continuous metal streams and to compare the predicted values with the data available in the literature. It is hoped that this method may provide at least an initial framework for the interpretation of additional data that might become available. FORMULATION Consider a continuous metal stream falling into a molten metal pool as depicted in Fig. 1. This system may absorb oxygen due to the following two mechanisms: 1) physical entrainment of gases (including oxygen) into the molten pool where reactions. thus absorption, will occur; 2) mass transfer (convec:tive diffusion) of oxygen to the metal stream. 1) Physical Entrainment. The physical entrainment may be calculated by using the concept of the diaplace-ttzent tlzickness of the laminar boundary layer, which will be stated briefly in the following.&apos; When a fluid flows past a solid surface, a portion of the fluid close to the surface is retarded due to fric-tional forces. This region in which the velocity of the fluid differs from that in the main stream is called the boundary layer. An illustration of this is given in Fig. 2 where it is seen that the thickness of the boundary layer increases as we move along in the x direction. In the laminar region, when Re, < 10&apos; the thickness of the boundary layer is given by the following relationship: f =4.64 Re;1" [1] where 61 is the boundary layer thickness, x is the length along the leading edge, Us is the velocity of the free stream, (i is the viscosity of the fluid (gas in this instance).

Jan 1, 1970

By Daniel R. Hull

IN 1026 Genders&apos; reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Ivor Jenkins

Processes employing &apos;controlled at-mospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been asso-ciated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and dificult prob-lems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases. Controlled atmospheres such as disso-ciated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,&apos; but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1948

By Ivor Jenkins

Processes employing &apos;controlled at-mospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been asso-ciated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and dificult prob-lems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases. Controlled atmospheres such as disso-ciated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,&apos; but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1948

By Gordon I. Gould

The treatment of quicksilver ores to extract the metal, for centuries one of the fundamentally simpler metallurgical operations, has undergone few if any material changes during the past iew decades other than improvement and change of type of equipment used. Of almost universal application and as the seldom deviated from process, the roasting method is still considered superior to chemical metallurgy. Likewise, roasting of the crude ore without previous beneficiation continues to be standard practice, although some successful operations have employed concentration prior to roasting. The roasting process has been carried out in a variety of equipment, devised for different tonnage capacities, to treat "special" ores, and to satisfy an inventive notion of the particular builder, but during the past 25 years there has been one outstanding change in roasting equipment. This change, though neither originating in nor confined to the United States, has probably been developed and applied to a far greater extent in this country than in any other mercury-producing country of the world. The change from manually or gravity operated furnaces, mostly huge brickwork affairs justified largely by simplicity, lack of power and mechanical requirements, and occasionally by excellent metallurgical results, to mechanical furnaces, began actively during World War I under the stress of requirements for in- creased production, a shortage of labor, 2nd other factors to be brought out later. During the twenties the change to mechanical furnaces became nearly complete at American mines with the development of several types, the rotary furnace predominating. During the thirties, and the period of low prices in the early part of this period, few changes were made other than mechanical improvements and an almost complete acceptance of two types: the rotary furnace and the hearth or Wedge furnace. These two types have been developed to a high degree of metallurgical efficiency, have proved to be mechanically simple and have far greater flexibility and lower operating costs than pre-World War I furnaces. Of the two types the rotary is the more popular, about 30 rotaries having been in operation in the United States in 1943 as compared with about six hearth-type furnaces. The units of smaller capacity for roasting mercury ores have almost without exception been indirectly fired, such distinction being commonly accepted as the difference between retorts and furnaces, which are fired directly. The difference between indirect and direct firing obviously permits of quite different conditions surrounding the ore being roasted in relation to the chemical reaction to take place. In the indirect-fired unit the ore is contained within the body of the retort in a stagnant if not completely oxygen-impoverished atmosphere. In the direct-fired furnace the ore is in contact with the gases of combustion, which may easily (if not too easily) be supplied with an excess of

Jan 1, 1944

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By F. R. Archibald, C. M. Nicholson

The present paper may be considered complementary to an earlier contribution on the same subject by F. R. Archibald and C. F. Jackson.1 It is particularly concerned with engineering and technological aspects of the operations at the Harleyville Alumina Plant during its period of operation from January 1945 to July 1946. The plant was built for and operated by Ancor Corporation, at Harleyville, South Carolina, as part of the government sponsored wartime program related to alumina production from domestic raw materials. The main purpose of the program was to secure technical and engineering data, based on actual plant experience, that might serve as a foundation for large scale production of alumina from raw materials other than bauxite. The Harleyville plant was directed specifically to treatment of clays found in very extensive deposits in the Carolinas and Georgia using the lime-sinter process developed by Ancor Corporation. It is considered that the purpose stated above has been served and this paper is to record and discuss some of the more important findings. The main factor in location of the plant at Harleyville was the presence in that locality of a rather remarkable deposit of high calcium limestone. The clay mining operation was centered near Aiken, S. C., and although a rail haul of ninety miles was involved there were, at the time, factors favorable to the Harleyville location offsetting, in part, the cost of transportation of clay, There are, no doubt, locations in the general area where clay and limestone deposits may be found in closer proximity hut they had not been proven up when the project was undertaken. Availability of power from the Santee-Copper development whose high tension line skirted the Property; ready access to rail and highway transportation; the promise, realized in actuality, of ample supply of soft water; and availability of labor supply were other factors of importance. Moreover, the general area has the decided advantage, for this type of operation, of a mild climate. Construction was begun in August 1943, and although stopped for a time priding review of the general situation that fall, it was resumed, albeit with less urgency, and substantially completed by the end of 1944. The total capital cost was approximately $3,460,000 The first alumina was turned out in April 1945 and from then until the plant was closed down in July 1946, the operations followed a succession of periods of production alternating with periods in which minor alterations were made in conformity with experience. Steady improvement was made and at the time Operations were discontinued it was considered that experience and the necessary engineering were in shape for removal of the remaining bottlenecks and a somewhat major revision in one section of the plant. Unfortunately this could not be carried out and it was necessary to discontinue the

Jan 1, 1949

By F. R. Archibald, C. M. Nicholson

THE present paper may be considered complementary to an earlier contribution on the same subject by F. R. Archibald and C. F. Jackson.1 It is particularly concerned with engineering and technological aspects of the operations at the Harleyville Alumina Plant during its period of operation from January 1945 to July 1946. The plant was built for and operated by Ancor Corporation, at Harleyville, South Carolina, as part of the government sponsored wartime program related to alumina production from domestic raw materials. The main purpose of the program was to secure technical and engineering data, based on actual plant experience, that might serve as a foundation for large scale production of alumina from raw materials other than bauxite. The Harleyville plant was directed specifically to treatment of clays found in very extensive deposits in the Carolinas and Georgia using the lime-sinter process developed by Ancor Corporation. It is considered that the purpose stated above has been served and this paper is to record and discuss some of the more important findings. The main factor in location of the plant at Harleyville was the presence in that locality of a rather remarkable deposit of high calcium limestone. The clay mining operation was centered near Aiken, S. C., and although a rail haul of ninety miles was involved there were, at the time, factors favorable to the Harleyville location offsetting, in part, the cost of transportation of clay. There are, no doubt, locations in the general area where clay and limestone deposits may be found in closer proximity but they had not been proven up when the project was undertaken. Availability of power from the Santee-Copper development whose high tension line skirted the property; ready access to rail and highway transportation; the promise, realized in actuality, of ample supply of soft water; and availability of labor supply were other factors of importance. Moreover, the general area has the decided advantage, for this type of operation, of a mild climate. Construction was begun in August 1943, and although stopped for a time pending review of the general situation that fall, it was resumed, albeit with less urgency, and substantially completed by the end of 1944. The total capital cost was approximately $3460,000. The first alumina was turned out in April 1945 and from then until the plant was closed down in July 1946, the operations followed a succession of periods of production alternating with periods in which minor alterations were made in conformity with experience. Steady improvement was made and at the time operations were discontinued it was considered that experience and the necessary engineering were in shape for removal of the remaining bottlenecks and a somewhat major revision in one section of the plant. Unfortunately this could not be carried out and it was necessary to discontinue the

Jan 1, 1948

By Carl J. McHargue

Rods of 99.99 + pct Al which had initial orientatzons of <001>, <118>, <115>, <111>, and random were swaged at room temperature. Changes in orientation as a function of deformation were studied on axis distribution charts. The <001> orientation appeared to be relatively stable due to the inhomogeneity of the deformation process. near the <100> zone were quickly reoriented towards <001>. Orientations on the <110> zone between <118> and <115> appeared to be stable to reductions of about 50 pct, then were reoriented toward <001>. At very high reductzotzs. movement away from the <111> orientation was observed. the requirement that a circular cross section be maintained. In addition to these mechanical factors, there are grain-boundary effects in poly crystalline materials which are not yet understood. Hartmann and Macherauch conclude, for example, that multiple slip occurs for all orientations in fine-grained aluminum and copper and that the choice of operative slip systems has no simple relationship to orientation.? Many investigators have attempted to avoid problems of interpretation caused by an initial texture by treating the starting material to obtain as ran- IT has been generally accepted that the deformation texture obtained at high reductions, e.g. 90 pct, will not be noticeably affected by a prior texture; whereas, that obtained at reductions of 40 to 50 pct may be significantly influenced by the specimen history.&apos; Some recent studies, however, have been interpreted as showing that an initial texture strongly influenced the deformation textures in rods at reductions greater than 90 pct. Freda and Cullity suggested that the <001> texture in a heavily cold-worked copper rod was due to a <001> texture in the original casting. McHargue, Jetter? and Ogle concluded that the <001> component in an aluminum rod extruded at liquid nitrogen temperature was remanent from a <001> texture in the cast extrusion billet.3 Most of the published work on the effect of initial orientation on deformation textures has been for cold-rolled or compressed single crystals,4-6 The primary interest in these studies was to examine various orientations with regard to their stability under flow? thus determining the possibility of such orientations being stable end orientations. There appears to be no published studies on the effect of initial orientation on fiber textures in polycrystalline specimens. A recent study, however, is concerned with the reorientation of individual grains in polycrystalline specimens pulled in tension.? Although the reorientation of single crystals loaded in simple tension is well known, the movements in the forming of wires and rods would be expected to be different due to the circular array of radial-compressive stresses exerted by the die walls or the rolls, and to

Jan 1, 1962

By Henry Lewelling

An experimental investigation of the relative effectiveness of standard bullets and "shaped charges" in perforating dense, hard formations is reported. A method is described which simulates the conditions under which a shot is normally fired. Results are evaluated on the basis of depth of penetration, extent 01 Fracturing. extent and nature of formation damage, and other physical characteristics. INTRODUCTION A study was made of the relative merits of bullets and "shaped charges&apos;&apos; as applied to well completions in hard, dense formations such as those encountered in the Permian Basin. The planning of the laboratory program stipulated that core samples should be prepared and mounted in such a way that perforation shots of either kind"" could be fired into them, keeping the factors pertinent to good shooting practice similar to what they would be in a well. The shooting was done in a buried tank. with the sample and shooting equipment covered with water. The depth of water was calculated to he sufficient to simulate the inertial effects of well fluids for the duration of an explosion (a few micro-seconds). Flow measurements were attempted on the specimens after perforation. Due to the lack of uniformity of the limestone, shale breaks. etc., these measurements proved to be of little value to the study. The mounting materials were removed. so that the character of the penetration. fracturing, etc., could be observed. METHOD Laboratory samples were selected from the hard. dolomitic sand cores from Block 31 Field. Core pieces having a 3 3/4 in. diameter and a useful length of 10 to 12 in. were used. Selection was aimed at those pieces having a minimum of shale streaks and other irregularities. The ends were cut off square Manuscript received in the Petroleum Branch office June 28, 1951. Paper presented at the Petroleum Branch Fall Meeting in Oklahoma City, Okla., Oct. 3-5, 1951. with the diamond saw. Prior to lbeing mounted. the cores were soaked in water to prevent them from absorbing water out of the wet concrete, thus weakening it. A set of steel capsules was fabricated for holding the core Samples. Seven-in. casing was cut in two-ft lengths. of which one end was closed by "orange-peeling" and welding, and the other was threaded to accept a standard bull plug. The bull plugs were fitted with copper tube connections .so that pressure could be applied when the capsules were made up. The cores were mounted in the capsules by means of wire centralizers whose function was to hold the Core in proper position while concrete was poured and set. A special aggregate was prepared wing a graded sand and gravel mixture

Jan 1, 1952