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By William F. Cerini, Willis R. Battles, P. H. Jones

A test for determining the plugging characteristics of an oil-well injection water has been developed. It consists in measuring changes of the filter rate of a water at constant pressure with cumulative throughput when passing the water through a medium grade sintered glass disk. Application of the test method was made to the water used in the Union Oil Company's experimental water flood of the Chapman zone in the Richfield field, Orange County, Callfornia. This water developed increasing plugging tendencies upon aging, even though the finished water from the plant filter exhibited few such characteristics. The plugging material was found to consist of calcium carbonate, ferric hydroxide, and organic substances that were presumed to be bacterial. Various method of stabilizing this water to prevent the formation of plugging material were attempted. Lowering the pH to approximately 6.4 by injecting carbon dioxide provided a moderately satisfactory means for stabilization but a better method of stabilizing this water was found to be first aging and then filtering. Introduction An experimental water-flood project was started on the Chapman zone of the Richfield field in March 1944 and has been described in a previous paper.' It consists of a single injection well drilled between old producing wells. A water-treating plant using primary alum flocculation, sedimentation and chlorination followed by secondary flocculation, sedimentation and fltration is employed to process the water before in@ion. In all of the water-treating operations, the system is open to the air, and no attempt is made to prevent the loss of carbon dioxide or absorption of oxygen by the water. The clear water is stored in a covered concrete basin and pumped through a Transite line to the suction of a high-pressure pump at the injection well' The high-pressure tubing in the well to the injection zone is cement lined. The untreated injection water is a mixture produced with the oil from the Chapman and Kraemer zones and is supplied from the disposal system. Because the injection well was relatively deep (injection zone about 3400 ft.) and would be expensive to replace, it was believed imperative to supply a nonplug-ging injection water and to develop laboratory procedures for evaluating the treated injection water with respect to its formation plugging properties. This report describes the development and application of the test procedure based on the assumption that the plugging properties could be determined by measuring the progressive decrease in flow rate of the water through a porous medium. If the quality of the injection water was good enough so that the plugging action on the porous medium was of small magnitude, it was reasoned that the tendency to impair flow in the formation would not be serious.

Jan 1, 1946

By A. H. Daane, B. J. Beaudry

The Sc-Ti system was studied by thermal, metal-lographic, and X-ray methods. Scandium was found to transform at 1334 °C from a (hexagonal) to ß which was concluded to be bee since a continuous series of solid solutions is formed between ß scandium and ß titanium at elevated temperatures. There is a minimum in the solidus at 51 wt pet Ti and 1300°C, a monotectoid at 1050°C and 49 wt pet Ti, and a eutectoid at 875°C and 91.5 wt pet Ti. The maximum solubility of titanium in a scandium is 13.5 wt pet at the monotectoid temperature, while the maximum solubility of scandium in a titanium is 6.5 wt pet at 875°C. SCANDIUM, a member of Group 111 A of the periodic table, and now called a rare-earth metal,' has become of interest recently due to its low density (2.99 g per cc) and relatively high melting point (1539°C).Spedding,' et al. have described a method of preparation of pure scandium metal and have made a study of its basic properties. Since scandium is approximately 10 to 12 pet smaller in at. diam than the other rare earths while its electronegativity and valence are the same, a knowledge of its alloying behavior in contrast to these elements should be very helpful to fundamental alloy theory. Since scandium is quite scarce and difficult to prepare in pure form, its use as a structural material by itself seems quite unlikely. However, its use in special cases as an alloying addi- tive to other low-density materials is a possible application; the Sc-Ti system was chosen for this reason and for others of fundamental interest. Scandium was suspected of having a high temperature bee form as do some of the other rare-earth metals.3'4 Since titanium has a high-temperature bee form, a continuous series of solid solutions at elevated temperatures between ß scandium and ß titanium would prove the existence and structure of the high-temperature form of scandium. The existence of a continuous series of hexagonal solid solutions at room temperature was predicted by Burkhanov and Savitskiy,5 but Hias shown to be incorrect in early X-ray studies. EXPERIMENTAL METHODS Materials. The metals employed in this investigation were crystal bar titanium and distilled scandium prepared by the method described by Spedding,2 et al. The major impurities are listed in Table I in PPm. Alloy Preparation. All the alloys examined were initially formed in a nonconsumable electrode are-melting furnace under an atmosphere of purified helium or argon. A curve based on the observed weight loss of 0.6 pet* when titanium was melted

Jan 1, 1962

By Henry Eyring, Jay W. Fredrickson

MANY theories have been advanced to explain the phenomena of elastic and plastic deformation. The object of this report is to present a mechanism for deformation, not radically differing from existing theories, but embodying certain principles and concepts of these theories. This proposed theory cannot be the complete answer to the age-old problem of deformation but it is believed that it will be a step further in the proper direction. The plastic properties of solids have recently been reviewed by Seitz and Read.1 Zener2 has reviewed and correlated the existing work on the anelasticity of metals. With these and othersa3,4,5 present theories of deformation are well-known. Of the many theories now extant, those receiving most attention have been proffered by Griffith,6 Becker,7 Smekal,8 Polanyi,9 Orowan10 and Taylor.11Although differing quite widely in details, these theories are based more or less on a common principle of flaws or dislocations that exist in the crystal lattice. The effect of stress concentrations surrounding a flaw or crack has been treated most recently by Fisher and Hollomon.12 The various authors differ as to the exact nature of the flaws or dislocations, the causes of their appearance, or the manner in which they initiate slip. All of the theories agree that the number of dislocations increases with progressing deformation. It is universally agreed that the shearing process is not a simple gliding of ideally perfect atomic lattice planes. It is also agreed that the "macroscopic process of gliding, or slip, is brought about by the spreading of a large number of locally initiated "glide steps" through the whole crystal. The occurrence of these "glide steps" is closely related to the presence of some kind of deviations from the "ideal" lattice structure, even in the undeformed crystal. These deviations are overcome "one at a time," in a manner of speaking, due to some stress-concentrating effect." PROPOSED THEORY Many solids show a continuously increasing deformation if subjected to a constant load of suitable magnitude in an extended range of temperature for a sufficient time. This deformation, or flow, may be said to be due, in general, to the tendency of the atoms or molecules in an elastically stressed body to readjust themselves in such a way that if the deformation were kept constant, a release of stress would take place. If rupture does not occur, this process of relaxation causes the rate of flow to obtain a final constant value, as shown in the curve (Fig I) obtained by Taylor and Quinney.14 In. this state the release of stress by relaxation exactly counterbalances the increase due to the elastic strain on the test pieces. .

Jan 1, 1948

By Arthur C. Simmons

Production of oil within the state of Pennsylvania in 1940 was slightly more than the 1939 total, and this increase was due entirely to the new flush Music Mountain field south and west of the main Bradford pool. The influence and magnitude of Music Mountain production will be separately described, inasmuch as it is an important producing unit within the state. Production Bradford Field The production listed herein for Bradford field includes only the part of the field that is within the state of Pennsylvania. Approximately 4000 bbl. per day, or 10 per cent of the total Production of Bradford field comes from Cattaraugus County, New York, and should properly be attributed to production obtained within the New York state area, although locally and economically the Bradford field, situated both in New York State and Pennsylvania, is included as a single statistical unit. The 1940 average production in the Bradford field was 34,831 bbl. per day, as compared with a daily average in 1939 of 35,340 bbl., or a decrease from 1939 of 509 bbl. per day. The decrease in production from the Pennsylvania portion of the Bradford field would have been more pronounced if a portion of the crude from the Music Mountain field were not included with the statistics for Bradford field. The decline can be attributed largely to the fact that more properties of lower average recovery were being drilled in 1939 and 1940 than in previous years, and apparently a subnormal amount of drilling occurred in 1938 and 1939, when about 2100 wells were drilled each year. The full effect of the 1940 drilling is not felt immediately and undoubtedly will affect the producing period of 1941. It appears probable that the water-flood area in the Bradford field has reached a definite peak unless some unusual economic condition should cause abnormal prices and an excessive rate of development such as occurred in 1936 and 1937. Virtually all of the production in the Bradford field was obtained by water-flooding methods, as natural or stripper wells are uneconomical and air and gas repressuring have not proved so efficient as water-flooding as a secondary recovery method. Central and Southern Pennsylvania Central and southern Pennsylvania produced a total of 4,604,763 bbl. of oil during the calendar year of 1940; that is, an increase over the 1939 total of 166,728 bbl. The daily average production was 12,581 bbl., or an increase over 1939 of 422 bbl. per day. Table I includes the total oil production for the state of Pennsylvania for the years 1937 to 1940, inclusive, and the daily average for each of these years. It is impractical to make a complete subdivision by districts, consequently the only segregation is the production from the Bradford field (within the state of Penn-

Jan 1, 1941

By Arthur C. Simmons

Production of oil within the state of Pennsylvania in 1940 was slightly more than the 1939 total, and this increase was due entirely to the new flush Music Mountain field south and west of the main Bradford pool. The influence and magnitude of Music Mountain production will be separately described, inasmuch as it is an important producing unit within the state. Production Bradford Field The production listed herein for Bradford field includes only the part of the field that is within the state of Pennsylvania. Approximately 4000 bbl. per day, or 10 per cent of the total Production of Bradford field comes from Cattaraugus County, New York, and should properly be attributed to production obtained within the New York state area, although locally and economically the Bradford field, situated both in New York State and Pennsylvania, is included as a single statistical unit. The 1940 average production in the Bradford field was 34,831 bbl. per day, as compared with a daily average in 1939 of 35,340 bbl., or a decrease from 1939 of 509 bbl. per day. The decrease in production from the Pennsylvania portion of the Bradford field would have been more pronounced if a portion of the crude from the Music Mountain field were not included with the statistics for Bradford field. The decline can be attributed largely to the fact that more properties of lower average recovery were being drilled in 1939 and 1940 than in previous years, and apparently a subnormal amount of drilling occurred in 1938 and 1939, when about 2100 wells were drilled each year. The full effect of the 1940 drilling is not felt immediately and undoubtedly will affect the producing period of 1941. It appears probable that the water-flood area in the Bradford field has reached a definite peak unless some unusual economic condition should cause abnormal prices and an excessive rate of development such as occurred in 1936 and 1937. Virtually all of the production in the Bradford field was obtained by water-flooding methods, as natural or stripper wells are uneconomical and air and gas repressuring have not proved so efficient as water-flooding as a secondary recovery method. Central and Southern Pennsylvania Central and southern Pennsylvania produced a total of 4,604,763 bbl. of oil during the calendar year of 1940; that is, an increase over the 1939 total of 166,728 bbl. The daily average production was 12,581 bbl., or an increase over 1939 of 422 bbl. per day. Table I includes the total oil production for the state of Pennsylvania for the years 1937 to 1940, inclusive, and the daily average for each of these years. It is impractical to make a complete subdivision by districts, consequently the only segregation is the production from the Bradford field (within the state of Penn-

Jan 1, 1941

By Sylvan Z. Beer

The factors that determine the yield and crystal size in the two-temperature synthesis of A lp were examined. Low yields and small crystals were associated with low temperatures and pressure. Attempts to grow large crystals in the critical and supercritical region of phosphorus were unsuccessful. Crystal size increases markedly at elevated temperatures. Crystals grown at temperatures as high as 1450° C fluo-resced, under uv excitation, at energies close to the estimated band gap of about 2.4 ev, while crystals grown at lower temperatures tended to fluoresce in the red region of the spectrum. Those grown in the supercritical region showed no ALP fluorescence. Heating the high-temperature-grown ALP under vacuum greatly increased its fluorescence efficiency and moved the emission peak to higher energies. I HE III-V compounds, with few exceptions, have been prepared by the two-temperature method. In its classic form this technique is applicable to closed systems where at least one of the components, in this case the column V element, is a liquid or a solid with a high vapor pressure. One advantage of this method over flow systems is in its simplicity. In addition, because it is a closed system, it can, under the circumstances to be described later, be run at higher pressures of the volatile species than in flow systems. In instances where the III-V compound is soluble in the parent III metal to about 1 mol pct or higher, solution growth can be made to take place by slow cooling. This, for instance, is one way in which single-crystal GaP1 and Inp2 have been grown. Initial attempts to synthesize and grow A1P by this technique were not too successful; the yield was low and the crystals obtained were exceedingly small. The conditions required for improving the yield and growth by this technique were, therefore, sought. Two obvious conditions which could be controlling were examined. These were the temperature of the aluminum and the pressure of the phosphorus. The range of temperatures studied extended from about the melting point of aluminum, 660° to about 1450°C. The latter is dictated by the vapor pressure of aluminum which reaches about 1 Torr at that temperature and the limitations of the materials of construction as described in the next section. The pressure range of interest covers from below 1 atm to above the critical pressure of phosphorus, 82.2 atm. EXPERIMENTAL The Temperature of Aluminum as a Variable. A series of experiments were run in the conventional two-temperature manner. All refractories and quartz were dried by heating at 800° to 900° for a minimum of 24 hr, and usually much longer, before use. The aluminum

Jan 1, 1969

By F. M. Stewart

A paper by Hurst and van Ever-dingen in 1949 led to the practical solution of many nonsteady-state flow problems.' Subsequently, applications of this material have been discussed by several authors. The purpose of this note is to outline a simplified direct procedure for water-influx pressure predictions for pressures above the bubble point. The prcposed procedure is unique in that after the "time-conversion factor" and the "influx constant" are obtained, predictions are made without trial and error. The elimination of trial and error is made possible by expressing certain PVT characteristics as explicit functions of pressure. The procedure is applicable to fields producing at pressures above the bubble point and under radial water drive from an infinite aquifer. In the usual applications it is required to predict (1) withdrawals given future pressure history or (2) reservoir pressure, given future withdrawals or production. The theory, assumptions and conditions under which the nonsteady-state solutions hold are covered in the references and are not repeated. The simplified direct procedure outlined here has been developed from published solutions for the so-called "pressure case". A similar direct procedure for the same special conditions has been developed for the "rate case"; however, in this instance the procedure is lengthy and offers no advantage over the trial-and-error solution. Consequently, this paper covers only the procedure based on the pressure case. DISCUSSION Under the pressure case prediction of withdrawals from a water-drive field, given the future pressure history, involves the use of a nonsteady-state water-influx term together with the material balance equation. The solution of a particular problem requires the following steps: (1) division of past pressure and production data into equal time intervals; (2) computation of cumulative water influx vs pressure drop for each time interval of past history using the material balance equation; (3) determination of the best values for the "time-conversion factor" and the "influx constant" by equating the nonsteady-state influx term with the influx computed in Step 2 (this requires a trial-and-error procedure); (4) prediction of influx for a given pressure drop using the influx term and the computed factors from Step 3; and (5) calculation of fluids produced using the predicted influx in the material balance equation. A forecast of the water-oil ratio or water production rate is required to complete the calculation. It is assumed that a reliable estimate of original oil in place is available, as well as the production and pressure history, and data on reservoir fluid characteristics. If the original oil in place is unknown, it may be computed simultaneously with the tinie-conversion influx factors2,3. However, the oil in place so computed may be considerably in error3; consequently, it is usually preferable to use oil in place estimated from pore-volume data unless there is considerable doubt as to its accuracy. The Material Balance Equation Above the Bubble Point Above the bubble point the simpli-

By E. H. Burdick

THE difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated mineral-spyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying 1 per cent is considered good grade; 0.7 to o.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of 1.0 per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent WO3 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 6o to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1942

By E. H. Burdick

THE difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals-pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of 1.0 per cent W03 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent WO3, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1942

By E. H. Burdick

The difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals— pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of I .o per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1943

By E. H. Burdick

The difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals— pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of I .o per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1943

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

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951

By G. Sachs, E. J. Ripling, S. I. Liu, J. J. Lynch

INTRODUCTION IT is a generally recognized fact that by repeated straining the fracture stress of any metal is reduced to a fraction of its value for static loading. The value of this fatigue strength depends upon numerous factors, such as the states of strain and stress, the limits of straining, and the number of repeated loadings or cycles.1.2,3 The large volume of previous investigations on fatigue is concerned entirely with large numbers of cycles, say exceeding 10,000 and up to 500,000,000. However, the changes in fracture stress and fracture strain occurring after a small number of repeated loadings have attracted little attention. Apparently the only investigations of this type are those byLudwik4,5 who subjected steel, copper, and aluminum wire to repeated torsion. In each test the torque was varied between identical values in the two directions of twisting. Depending upon the magnitude of the moment, fracturing occurred after a number of cycles, up to 10,000. The results of Ludwik's tests will be discussed later. Such torsion does not readily yield actual stress and strain values. Therefore a preliminary study was made of the effects of repeated direct stresses, i.e., tension and compression stresses. Because such tests are considerably more tedious than torsion tests, only high stresses were used in the preliminary work, yielding definite changes in metal properties after a few cycles. It was found in these tests that strains could be controlled more readily than stresses in the investigated range of high stresses. This paper, consequently, deals with the effects of strains of equal magnitude but different signs. The metal was first prestrained in static tension by a certain amount then subjected to compression to yield the same amount of strain after unloading. This loading cycle was repeated up to a maximum of seven times. After various cycles, the stress-strain curves in tension were determined, up to fracturing. As material for these tests, the aluminum alloy 24ST was selected because it exhibits a comparatively small amount of necking in the tension test. This alloy permitted, therefore, rather accurate control at the high strains necessary to produce fatigue failures at less than seven cycles. The results of this investigation appear sufficiently interesting to extend the method of attack in various directions. It is intended to study (I) the effects of cycles up to a few thousands and (2) the effects of strains of different magnitude in tension and compression, respectively. The latter variable also includes as a special case the effects of compressive strains.

Jan 1, 1948

By G. A. Parks, C. Kovacs

The xanthate flotation of chrysocolla can be improved by preheating the ore to 500° to 600°C. Addition of water vapor reduces the preheating temperature required. The temperature range of flotation improvement correlates well with the range over which dehydroxylation occurs. This observation is consistent with changes in the structure and properties of the mineral as detected by measurement of solubility, D.T.A., T.G.A., X-ray diffraction, and infrared absorption and with recently proposed explanations of chrysocolla flotation. A brief experiment by one of the authors several years ago showed that exposure of chrysocolla to high temperature water vapor resulted in increased recovery by subsequent xanthate flotation. Recently renewed interest in flotation and thermal properties of chrysocolla1-5 prompted further study of this effect and more detailed reporting.6 This paper explores the response of pure chrysocolla recovery in Hallimond tube flotation tests to the time and temperature of exposure and to changes in the water vapor pressure. Brief attention is paid to the effects of such treatment on accessory minerals. A single experiment with flotation of chrysocolla from an ore is reported. MATERIALS Chysocolla from Inspiration, Gila County, Ariz. was crushed in a porcelain mortar, cleaned of visible and magnetic impurities, and screened to obtain -48 +65 mesh (Tyler) material for flotation test work. The clean material contained 28.5% Cu and was identified as chrysocolla by comparison of X-ray diffraction, D.T.A., and infrared absorption data with that reported for similar materials by others.4,5,7 Samples of malachite and chalcopyrite, prepared in a similar way, were also identified by X-ray diffraction. The sources of these materials are unknown. A sample of chysocolla-bearing oxidized copper ore from Pima, Ariz. was crushed and dry ground for thermal activation and subsequent flotation. PROCEDURES Activation: The apparatus used for exposure of materials to high temperature water vapor is illustrated in Fig. 1. The furnace temperature was controlled to ±5°C Water vapor pressure was controlled by pre-saturating a nitrogen carrier stream with water in an adjustable thermostatted saturator (multiple bubbler). A water manometer and capillary orifice flow meter were used to measure nitrogen flow rates for activation and for subsequent Hallimond tube tests. Gas flow rate and temperature were adjusted prior to introduction of samples. Exposure time was measured from the moment of introduction of the sample to the furnace, hence includes an initial drop below the control temperature. After heating, the samples were removed from the furnace and stored at room temperature in air. Representative samples of activated materials were examined by X-ray diffraction and infrared absorption.

Jan 1, 1967

By M. C. Udy, C. H. Lorig

THROUGH the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the general effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. LITERATURE Two general factors should he considered in a study of reduction of iron oxide: (1) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe3O4-FeO-H2-H2O, Fe304-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnas1 published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at one temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1942

By C.H. Lorig, M.C. Udy

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By M. C. Udy, C. H. Lorig

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By E. A. Smith, E. R. Parker

METALLURGISTS and engineers have always been interested in the mechanism of high-speed deformation because metals are rapidly deformed in various applications and manufacturing processes. The deformation of metals by impact loads has recently engaged the attention of a number of investigators. Many of their results have not been disclosed but some of the published investigations1-8 have shown that the tensile strength, yield strength and elongation generally increase with increasing strain rate. The investigation reported herein is an attempt to determine the reason for this increase in strength and elongation. Single-crystal copper specimens were broken in tension at impact velocities up to 100 ft. per sec. The distribution of slip bands in the fractured crystals was found to depend upon the strain rate. In the bars broken at high speeds, the slip bands appear to be more numerous. This might account for the higher strength as well as the greater elongation. EXPERIMENTAL PROCEDURE Single crystals of copper (approximately 99.98 per cent) were made in graphite molds by the conventional method of lowering the mold out of the hot zone of a hydrogen furnace at a rate of one inch per hour. Solidification progressed from the bottom upward, forming a single crystal. The crystals were about 0.30 in. in diameter and 4 in. long. They were made into test bars by sliding threaded steel bushings over each end of a crystal and then flowing silver solder between the crystal and the bushing. The inside diameter of the bushings was slightly greater than the diameter of the crystals, to allow space for the silver solder. The bushings were placed so that the gauge length of the crystals was one inch. The assembly is shown in Fig. I, with two views of a fractured crystal. Annealed polycrystalline copper bars of similar shape were machined from solid stock. X-ray measurements were made on all single crystals to determine their orienta¬tions. The results are shown in Fig. 2, where the location of the axis of each specimen is indicated on a standard projection. The bars were broken in a commercial variable-velocity tension im¬pact machine, which has been described in detail elsewhere.7,8 The stress and strain were recorded by means of wire strain gauges and a special commercial oscillo-raph, also described in detail elsewhere.9,10 The equipment and method can be briefly described as follows. The impact machine consists of a motor-driven flywheel containing a two-pronged hammer. This hammer is held retracted in the flywheel

Jan 1, 1944

By P. J. Soltis

Direct as well as indirect evidence of a-phase ordering was found in a "near-a" type titanium alloy, Ti-8Al-1Mo-1V. The annealed alloy showed an anomalous decrease in second-stage creep rate at 950°F (510°C) and 47,500 psi. Anomalous increases were noted in initial yield stress after 500 hr creep exposure and in tensile strength after 1100 hr creep exposure. Debye-Scherrer X-ray diffraction patterns obtained on fine-grained polycrystalline speci-ment showed much line broadening and development of superlattice lines after 500 hr at 510° C. Examination with the light and electron microscopes failed to reveal phase changes in thermally exposed material, but detailed metallography is presented illustrating the plastic and fracture characteristics of the alloy. Electron-metallographic evidence is presented, however, which shows the nature of the nucleation and growth of ordered regions from the disordered a in annealed material. In the original phase diagram of the binary Ti-Al system constructed by Ogden et al.1 aluminum was shown to be soluble in a titanium over a wide temperature range at concentrations up to about 30 pct. Subsequently, a number of papers2-7 have appeared which indicate the existence of either intermetallic compounds and/or ordered phases in the a field up to 25 pct Al. In the most recent of these, Goldak and Gordon paw7 have determined unequivocally the ordered hexagonal D019 structure for Ti3Al in a 25 pct Al alloy. No superlattice lines were observed above 1112°F (600°C). Previously, the embrittle-ment encountered by Crossley and Carew4 in low- temperature heat treatments of binary Ti-Al alloys low in aluminum had been attributed to the appearance of a new phase in light micrographs. In the present work, direct as well as indirect evidence is presented showing the existence of a-phase ordering in what is essentially the binary Ti-8A1 alloy containing small percentages of the ß stabilizers molybdenum and vanadium, i.e., the "near-a" Ti-8Al-1Mo-1V alloy. Although Bohanek and Kessler8 have shown that this alloy has good stability at temperatures up to 1100°F (593°C), the present work shows instability at 950°F (510°C) where long exposure times were used. Light and electron microscopy proved very useful in revealing the mechanical behavior of ordered a and led to the conviction that ordered "near-a" alloys may have remarkably good properties and useful engineering applications.

Jan 1, 1965

By F. W. Steadman, Charles S. Barrett

Deformation bands of surprising regularity are found in large-grained poly-crystalline copper after cold-rolling (Fig. I). Individual bands frequently are large enough to permit a determination of their orientation by means of etch pits and an optical goniometer. Measurements have been made on 21 areas in seven different grains, and these, combined with X-ray studies of nine single crystals that had been cold-rolled after mounting in a polycrystal-line block, have contributed to a better understanding of the preferred orientations in rolled copper just as similar studies have for rolled iron1 and brass.2,3 Particular attention was given to determining orientations that are stable during rolling and to the manner of fragmentation and rotation of unstable grains. The possible role of twinning was also carefully investigated. The texture of polycrystalline copper after cold-rolling is well established by the pole figures that have been plotted by Schmid and Staffelbach,4 Iweronowa and Schdanow,6 and Brick and Williamson,8 all of which are in substantial agreement. There has been some divergence in the list of individual "ideal" orientations that have been used to describe the texture by these observers and others," although the orientation (110) [II2]—that is, (110) parallel to the rolling plane and [TIP] parallel to the rolling direction—is generally recognized as the most prominent orientation and (112) [III] one of the lesser orientations. Other orientations have been given by some observers as (236) [535], (100) [00I], and (110) [00I]. The texture of copper has also been described as (I35) [533].6,7 The sum of these orientations provides a reasonable approximation to the complete pole figure, but it does not follow that these specific orientations are necessarily of fundamental significance, for the choice of indices is arbitrary, within limits. Furthermore, a detailed investigation of the ideal orientations in cold-rolled iron discloses continuous ranges of equally favored positions rather than definite positions of high stability,' and similarly Brick's observations in a single crystal of a brass2 suggest that all orientations in the range between (110) [II3] and (110) [II7] are about equally stable. Materials and Methods The material used was vacuum-cast electrolytic copper kindly supplied by L. L. Wyman, of the General Electric Co.* Slicec 1/2 in. thick and 21/2 in. square, cut from the ingot, were rolled with 50 per cent reduction per pass to final thicknesses between 0.02 and 0.04 in., and etched to develop cube-face etch pits suitable for goniometric work.8 The etch was light on some strips and deep in others.

Jan 1, 1942