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By Nicholas J. Grant, Irmgard Rump, Bill C. Giessen

The system W-Hf was determined by use of metal -lographic and X-ray methods. The only interrnetal-lie phase W2Hf melts peritectically at 2650° ± 50°C. A eutectic between W2Hf and ß-Hf solid solution exists at 78 at. pct Hf arul 1930º ± 10°C. The addition of tungsten loulers the hafnium transfornzation; there is a eutectoid at 93 at. pct Hf and 1560°C. The solubility limits of the terminal solid solutions were determined. At the beginning of this investigation, the system had not been elaborated; only crystallographic work had been done to determine the structure of the occurring intermetallic compound W2Hf, and a certain analogy to the system W-Zr was to be expected. Special emphasis was placed in this program on the Hf-rich part of the diagram. Following the completion of our experiments, a phase diagram was suggested by Braun and RUdY.1 EXPERIMENTAL METHODS The investigation utilized tungsten powder supplied by the General Electric Co. with a purity of about 99.9 pct and hafnium crystal bar of about 97.7 pct purity, 2.3 pct Zr, supplied by Foote Mineral Co. Typical analyses are given in Table I. The procedures followed were identical with the ones described for the Re-Nb diagram.' Tungsten powder was compacted at 16,000 psi and the necessary amount of hafnium was added in the form of small pieces cut from the crystal bar, with a reasonable excess of tungsten powder to make up for powder losses on melting. High hafnium or tungsten melts were prepared from premelted tungsten and hafnium or by employing master alloys. The melting was done in a Heraeus arc-furnace under argon. Melting and remelting up to 8 times resulted in fairly homogeneous alloys. No weight

Jan 1, 1962

By Clair Upthegrove, E. S. Rowland

The widespread interest in the alloys of beryllium with copper is due principally to the fact that certain compositions show very favorable precipitation-hardening characteristics and are, in fact, the stronges nonferrous alloys known at the present time. Investigations have been conducted by Masing and Dahl and others on the physical characteristics of ternary beryllium alloys, in an attempt to produce precipitation hardening effects with a smaller amount of beryllium than that required in the binary copper-beryllium alloys (2.0 to 2.5 per cent Be). The results of these investigations show that ternary alloys of beryllium with Cu-Sn, Cu-A1 and Cu-Zn, among others, exhibit promising improrcmc~nts in physical properties after precipitation-hardening treatment and, while the increases in properties obtained are not as high as those reahzed from the binary copper-beryllium alloys, excellent properties arc obtaincd with beryllium contents averagirlg about one-half the amount reqnired in the binary alloys. This paper presents the results of an investigation of the equilibriun relations of certain alloys containing copper, tin and beryllium. The alpha-phase boundary of the ternary system is given for alloys containing from 0 to 1 per cent beryllium. The equilibrium conditions beyond the alpha-phase boundary are presented for alloys containing up to 32 per cent tin and 1 per cent beryllium. The data were collected by means of quenching experiments, microscopic examination and thermal analysis The results of some powder-method X-ray determiniations on the alloys, conducted by Mr. William Mikulas and Prof. Lars Thomassen at the University of Michigan, are used as evidence in this paper. The con

Jan 1, 1935

By E. S. Rowland, Clair Upthegrove

The widespread interest in the alloys of beryllium with copper is due principally to the fact that certain compositions show very favorable precipitation-hardening characteristics and are, in fact, the stronges nonferrous alloys known at the present time. Investigations have been conducted by Masing and Dahl and others on the physical characteristics of ternary beryllium alloys, in an attempt to produce precipitation hardening effects with a smaller amount of beryllium than that required in the binary copper-beryllium alloys (2.0 to 2.5 per cent Be). The results of these investigations show that ternary alloys of beryllium with Cu-Sn, Cu-A1 and Cu-Zn, among others, exhibit promising improrcmc~nts in physical properties after precipitation-hardening treatment and, while the increases in properties obtained are not as high as those reahzed from the binary copper-beryllium alloys, excellent properties arc obtaincd with beryllium contents averagirlg about one-half the amount reqnired in the binary alloys. This paper presents the results of an investigation of the equilibriun relations of certain alloys containing copper, tin and beryllium. The alpha-phase boundary of the ternary system is given for alloys containing from 0 to 1 per cent beryllium. The equilibrium conditions beyond the alpha-phase boundary are presented for alloys containing up to 32 per cent tin and 1 per cent beryllium. The data were collected by means of quenching experiments, microscopic examination and thermal analysis The results of some powder-method X-ray determiniations on the alloys, conducted by Mr. William Mikulas and Prof. Lars Thomassen at the University of Michigan, are used as evidence in this paper. The con

Jan 1, 1935

By S. K. Tarby, W. O. Philbrook

Limited experimental data and a critical review of the literature are given to indicate that the true equilibrium distribution of manganese between carbon-saturated iron and blast-furnace type slags has not yet been satisfactorily established as a function of the composition, temperature, and pressure of the system. THE distribution of manganese between carbon-saturated iron and blast-furnace type slags has been studied by a number of investigators.1-7 Generalization of the results of these works indicates that the weight percent distribution ratio, (%Mno)/[%Mn], decreases with increasing temperature and slag basicity, in accord with thermodynamic data and practical observation. However, where comparisons among these studies can be made for similar slag compositions and temperatures, the reported values of the manganese distribution ratio are discordant. The variations are attributed to failure of the experimenters to bring their systems completely to equilibrium with graphite and CO at 1 atm, as judged by departures from silicon equilibrium. Even in the most recent work,5-7 this problem was recognized but the authors made the questionable assumption that equilibrium could prevail for manganese distribution even though other reactions were still in progress. Manganese equilibrium values for three particular slag compositions were required incidental to a kinetic study8 and were determined experimentally. Special pains were taken to approach concurrent equilibrium with respect to silicon. Although the results were not completely definitive, they indicate that the true manganese equilibrium distribution ratios are lower than have heretofore been reported. The data are presented together with a brief commentary on the literature to suggest the need for further work in this area. EXPERIMENTAL METHOD Equilibrium runs were carried out in a stationary, induction-heated graphite crucible closed by a graphite lid and flushed continuously by a slow flow of carbon monoxide at 1 atm pressure. Temperature was controlled manually within ±3 deg C with the aid of immersed thermocouples in mullite tubes protected against slag attack by graphite sleeves. The desired temperature was established by a calibrated Pt vs Pt-10 pct Rh thermocouple and control was then maintained using a more stable W-Mo couple. Runs were made at 1500º and 1575ºC for durations of 7.5 to 10.5 hr. The charges were calculated to yield 400 g of metal and 100 g of slag. The primary slag compositions and designation numbers were as follows:

Jan 1, 1963

By C. S. Sivil

To modern civilization the platinum metals are of inestimable value. Their distinctive properties, both physical and chemical, render them indispensable in an age in which the processes of the laboratory are becoming an essential part of the daily life of the world. Generally, their function, though vital to particular processes, is not spectacular, and so remains unknown to all except the operators. Early Methods of Manufacture The properties of platinum were recognized as of prime importance for scientific work at a very early date, probably between 1750 and 1760. The difficulty of making articles from it seemed almost insurmountable, because no means of attaining the temperature necessary to melt it were known at that time. It is true that solid platinum could be obtained by fusing the metal with a more volatile metal such as arsenic, which was subsequently driven off by baking, but such a method, at its best, would give only a very brittle product, which was totally unsuitable for the purposes for which it was intended. Little, if any, progress could be made until it was discovered that platinum sponge, heated to white heat and hammered in an iron or clay mold, would metallize and retain the shape of the mold. This was a process that could not be wholly satisfactory but from it developed the method of pressing the sponge in a mold and forging it at white heat into wire or sheet. At present a somewhat similar process must be used for fabricating articles of tungsten, molybdenum and other metals of high fusing point, as with these metals we face today the same problems that the scientists of the eighteenth century encountered with platinum, but possibly the next significant advance in the metallurgy of these metals will be the devising of means to melt and cast them. TO some extent this method of preparing platinum has survived, particularly in Europe. There are one or two objections to it, but they are not serious, as they can be surmounted with proper precautions. In the first place, the material is spongy and its millions of cavities contain entrapped air. Unless this is removed by thorough forging above 1000" C. the resultant sheet shows blisters. To give such a thorough forging,

Jan 1, 1931

By F. R. Archibald, C. F. Jackson

THE prospect of winning aluminum from clay was recorded almost a century ago at a time when the metal was no more than a curiosity.? As the industry developed, and it has probably developed faster than that of any other metal, the expanding need for raw materials was adequately met by the ample supplies of bauxite ore. As with the other metals older in industry, however, lower grade ores have gradually entered the raw-material field through improvements in ore dressing, insufficienoy of high-grade ore supplies, favorable geographic location, or national necessity for domestic supply. So with aluminum, or alumina, which has been established as the requisite intermediate, the time may have come when a satisfactory process, with favorable location and suitable raw materials, can hold a sound place both in metallurgy and economics. It is the purpose of this paper to describe the Ancor process and its proposed application in treatment of clay in a plant now under construction at Harleyville, South Carolina, by the Defense Plant Corporation. DEVELOPMENT OF THE ANCOR PROCESS The Ancor process has developed through successive stages of laboratory investigation, pilot-plant demonstration using nepheline syenite and pilot-plant demonstration using kaolin-type day from South Carolina, and is now in preparation for unit trial on an operating plant basis using the latter material. The laboratory studies were carried out over a number of years in the laboratory of the American Nepheline Corporation in Rochester, N. Y., and for the same company in the ore-dressing laboratory of Beattie Gold Mines, Que. Ltd. at Duparquet, Quebec. Both companies are associated with Ventures Ltd., Toronto, and its associated American companies. The work was originally undertaken with a view to recovery of alumina and alkalies from nepheline syenite as an adjunct to the American Nepheline Company's established business in the glass and ceramic trades, but as a process developed the possibility of application to clay and other aluminous raw materials become apparent and the laboratory studies were broadened to include these as well. Under the more pressing impetus of wartime needs and possibilities, pilot-plant operations were undertaken at the Canadian Bureau of Mines Ore Dressing Laboratories in Ottawa, and for purposes of demonstration under joint sponsorship of the Canadian Bureau of Mines, The American Nepheline Corporation, and The Aluminum Company of Canada Ltd.

Jan 1, 1944

By Lyall Zickrick

Numerous brands of virgin pig lead are used in the manufacture of lead and lead-alloy cable sheath for commercial cables. In changing from one brand of pig lead to another a readjustment of press operating conditions is nearly always necessary. This is due largely to different flow characteristics, and some brands extrude at a much lower pressure than others; for example, copper-bearing lead requires much more pressure than a low-bismuth lead under the same operating conditions. With the modern type of lead press the extrusion practice in general differs very little. Molten lead at a temperature of 375" to 400" C. (710" to 750" F.) is cast in a water-cooled cylinder and allowed to cool or solidify into a slug for six to nine minutes, This slug is forced into the die block and around the core tube through which the cable runs. The • die block is held at an optimum temperature by means of gas flames, usually 175" to 225" C. (350" to 435" F.). Measurements of the temperature of the cable sheath taken at the time of extrusion have covered a range of 190" to 225" C. (375" to 435" F.). According to Tammann, the rate of extrusion for a metal under constant pressure through a simple orifice is almost doubled for each 10" C. rise in temperature. Because of the irregularity of die-block construction, such a great increase is not obtained in lead-cable extrusion practice. To obtain more definite information about the effect of small percentages of metals usually present as impurities in virgin pig lead, a series of compression tests were made covering several different brands of lead and various alloys. Since the usual temperature of the sheath is approximately 200" C. as it emerges from the die block, these compression tests were all performed at 200" C. Five different brands of virgin pig lead were selected, as follows: Brand A: A desilverized western lead of very high purity. This lead contains neit,her copper nor bismuth. Brand B: A bismuth-free southeastern Missouri lead, usually containing 0.05 to 0.08 per cent copper. Brand C: A copper-free mid-western desilverized lead of very good grade, usually containing around 0.06 to 0.10 per cent bismuth.

Jan 1, 1932

By John T. Norton, R. E. Hiller

The tremendous increase in the use of metals that have been prcpared by the various cold-working processes during recent years has greatly stimulated the investigation of problems concerned with the fundamental nature of these processes. It has been observed in practice that different methods of bringing about the same dimension changes in a sample result in a rather wide range of properties. Cold working reduces the ductility of a metal, or what is perhaps more nearly correct, its "working capacity," and naturally the manufacturer wishes to produce an article that has as large a working capacity as possible, and to produce it with the smallest number of operations. It has also been known for some time that cold deformation produces a parallel alignment of the crystal grains of a metal, and that the type of this preferred orientation depends to some extent at least upon particular processes employed in the deformation. The present investigation has for its purpose the study of the relations between the various factors of a cold-working process and the preferred orientation of the metjal crystals resulting from this deformation. The work is chiefly confined to a study of cold-drawn seamless tubing. Preparation of Samples The tubing samples used in this investigation were made of steel having a carbon content of 0.10 to 0.20 per cent, and were drawn on a standard type of draw bench. In order to obtain the large reductions, the annealed stock was coated with lead, for purposes of lubrication. The reductions of area stated refer to reduction from the annealed condition without intermediate heat treatment. The cold work was done as nearly as possible at room temperature. The samples of wire and strip used for purposes of comparison were of steel of approximately the same carbon content and were prepared in the manner indicated. X-ray Method of Investigation The condition of preferred orientation in cold-worked samples is best investigated by the X-ray method that employs a small circular beam of * Assoriate Professor of Physics of Metals, Massachusetts Institute of Technology. t Graduate Student, Department of Metallurgy, Massarhusetts Institute of Technology.

Jan 1, 1932

By E. P. Burtchaell

A method is presented for evaluating the effect of gravity drive upon the reservoir performance of a high relief pool. Conventional forms of reservoir analysis do not consider the alterations in the basic material balance data caused by gravity segregation of reservoir fluids. A procedure is outlined for structurally weighting physical and chemical data for use in the material balance equation. It is demonstrated how actual pool performance data can be utilized to evaluate the future reservoir performance of a gravity drive pool. INTRODUCTION Conventional reservoir engineering. procedure is inadequate for the analysis of an oil pool which has considerable structural relief, steep dips, and good permeability development. In, pools of this type, gravity drainage has an important part in the movement of oil to the wells and the effects of gravity on the overall pool performance should be included in any analysis of reservoir behavior. Many engineers have the opinion that the force of gravity in the movement of oil is not important until the later life of a pool.' Probably the basis for this belief is that gravitational effects may not be readily discernible until a pool is nearing depletion. This would be especially true for pools not having a high degree of structural relief and permeability development. Actually the effects of gravitational forces are at a maximum when the pool pressure is high, for during this period the hydrostatic head of the oil column is at a maximum and the viscosity of the oil is at a minimum. Oil recoveries from pools having favorable gravity drive characteristics may equal or even exceed recoveries which might be expected from water displacement. Field evidence indicates that in some reservoirs gravity drive has resulted in recoveries greater than that which could have been expected from gas expansion or water drive.'.3 Unfortunately, the possible effects of gravity drive on pool performance have been underestimated and other reasons have been sought to explain the high recoveries obtained. There are unquestionably many reservoirs to which the principles of gravity drainage can be effectively applied. It is the purpose of this paper to illustrate one method whereby gravity drive is included in the reservoir analysis of an oil pool. A hypothetical pool, typical of many California reservoirs, is used as an example. As used in this paper, "gravity drive" is defined as the overall effect of gravitational influences on the recovery of petroleum from the reservoir; "gravitational segregation" as the gravity separation of oil and gas within the reservoir; and "gravity drainage" as the downward movement of oil as caused by the force of gravity. SAND VOLUME DATA Fig. 1 presents a structural contour map of the pool under study. Maximum closure is 1950 feet with dips on the south flank approaching 45". The original gas-oil interface was set at -5200 feet. Average thickness of the producing sand was 200 feet. For use in subsequent calculations ill this paper, the pool was subdivided into 100-foot vertical increments and the sand-volume content of each increment was obtained. If the gross sand thickness is small, under 100 feet, the sand-volume content can be obtained by superimposing an isopachous map upon a structural contour map and planimetering the average thickness of each 100-foot increment. For sand thicknesses over 100 feet, one approacli would be to construct a sufficient number of cross-sections of the pool from which the weighted sand-volume of each 100-foot increment could be obtained. Variations in the sand body with depth, as determined by core data, can also be included in the above process. Table I presents a summary of sand-volume calculations, core data, and the original distribution of reservoir hydrocarbons in the pool. Fig. 2 illustrates the structural distribution of the sand-volume content. A total of 171,398 acre-feet is contained within the productive limits of the pool. Assuming an average porosity of 25% and an interstitial water content of 20%, the original hydrocarbon content was computed to be 227,075,000 barrels. DEPTH-PRESSURE DATA The determination of the initial vertical pressure arrangement in the pool is necessary for PVT and material balance calculations. Whenever sufficient data are available, a plot of pressure versus subsea depth of measurement should be made. From this plot a representative fluid pressure gradient can be established. Lacking sufficient initial pressure data, an initial pressure gradient may he estimated or calculated from avail-

Jan 1, 1949

By E. P. Burtchaell

A method is presented for evaluating the effect of gravity drive upon the reservoir performance of a high relief pool. Conventional forms of reservoir analysis do not consider the alterations in the basic material balance data caused by gravity segregation of reservoir fluids. A procedure is outlined for structurally weighting physical and chemical data for use in the material balance equation. It is demonstrated how actual pool performance data can be utilized to evaluate the future reservoir performance of a gravity drive pool. INTRODUCTION Conventional reservoir engineering. procedure is inadequate for the analysis of an oil pool which has considerable structural relief, steep dips, and good permeability development. In, pools of this type, gravity drainage has an important part in the movement of oil to the wells and the effects of gravity on the overall pool performance should be included in any analysis of reservoir behavior. Many engineers have the opinion that the force of gravity in the movement of oil is not important until the later life of a pool.' Probably the basis for this belief is that gravitational effects may not be readily discernible until a pool is nearing depletion. This would be especially true for pools not having a high degree of structural relief and permeability development. Actually the effects of gravitational forces are at a maximum when the pool pressure is high, for during this period the hydrostatic head of the oil column is at a maximum and the viscosity of the oil is at a minimum. Oil recoveries from pools having favorable gravity drive characteristics may equal or even exceed recoveries which might be expected from water displacement. Field evidence indicates that in some reservoirs gravity drive has resulted in recoveries greater than that which could have been expected from gas expansion or water drive.'.3 Unfortunately, the possible effects of gravity drive on pool performance have been underestimated and other reasons have been sought to explain the high recoveries obtained. There are unquestionably many reservoirs to which the principles of gravity drainage can be effectively applied. It is the purpose of this paper to illustrate one method whereby gravity drive is included in the reservoir analysis of an oil pool. A hypothetical pool, typical of many California reservoirs, is used as an example. As used in this paper, "gravity drive" is defined as the overall effect of gravitational influences on the recovery of petroleum from the reservoir; "gravitational segregation" as the gravity separation of oil and gas within the reservoir; and "gravity drainage" as the downward movement of oil as caused by the force of gravity. SAND VOLUME DATA Fig. 1 presents a structural contour map of the pool under study. Maximum closure is 1950 feet with dips on the south flank approaching 45". The original gas-oil interface was set at -5200 feet. Average thickness of the producing sand was 200 feet. For use in subsequent calculations ill this paper, the pool was subdivided into 100-foot vertical increments and the sand-volume content of each increment was obtained. If the gross sand thickness is small, under 100 feet, the sand-volume content can be obtained by superimposing an isopachous map upon a structural contour map and planimetering the average thickness of each 100-foot increment. For sand thicknesses over 100 feet, one approacli would be to construct a sufficient number of cross-sections of the pool from which the weighted sand-volume of each 100-foot increment could be obtained. Variations in the sand body with depth, as determined by core data, can also be included in the above process. Table I presents a summary of sand-volume calculations, core data, and the original distribution of reservoir hydrocarbons in the pool. Fig. 2 illustrates the structural distribution of the sand-volume content. A total of 171,398 acre-feet is contained within the productive limits of the pool. Assuming an average porosity of 25% and an interstitial water content of 20%, the original hydrocarbon content was computed to be 227,075,000 barrels. DEPTH-PRESSURE DATA The determination of the initial vertical pressure arrangement in the pool is necessary for PVT and material balance calculations. Whenever sufficient data are available, a plot of pressure versus subsea depth of measurement should be made. From this plot a representative fluid pressure gradient can be established. Lacking sufficient initial pressure data, an initial pressure gradient may he estimated or calculated from avail-

Jan 1, 1949

By William A. Johnson

THE mathematical analysis of diffusion curves in solid metals is Carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. EXPERIMENTAL PROCEDURE If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By S. Stutz

COAL, like most other minerals, only exceptionally occurs in a sufficiently pure state to he directly available for general manufacturing purposes. And even where this is the case, the small coal or slack is usually more impure than the lump coal, as the slate, clay, etc., from the roof and bottom of the vein become mixed with it in the handling it undergoes. These impurities often exceed ten or more percent in addition to the impurities of the coal itself. The most common impurities of the coal are slate, or shale, clay, and sulphur. The latter occurs in different forms, but most frequently as bisulphide of iron, or iron pyrites, and as sulphate of lime, or gypsum. In both cases the impurities add greatly to the amount of ash, and where they are present in considerable quantities the raw coal, and still more the coke made from it, is unfit for the, manufacture of iron. Coke will contain on an average at least ;fifty per cent, more ash and sulphur than the raw coal from which it is, made. To the manufacturer of iron every additional per cent. of ash which his coal or .coke contains is a source of additional expense, seemingly small, and yet very important in the aggregate. In the blast-furnace, for instance, the ash must be heated up to the melting-point, and, since it is composed largely of refractory substances, the consumption of carbon in melting it will be equal to at least one-half of its weight ; that is, a certain part of the coke is consumed for the melting and fluxing of the ash and is lost. Besides this, it is well enough known to the-iron-master that coke containing less ash makes the slag or cinder more liquid and less inclined to stick to- the walls of the furnace. Fuel containing much sulphur produces generally a white iron, poor in carbon, while from the same ore and flux, with a pure fuel, a good foundry iron might be obtained. The work of separating slate, sulphur, etc:, from the coal 'has as yet only been succesafully accomplished by the washing process. This process depends for its success on the differences in the specific

Jan 1, 1881

By D. T. Peters, J. C. Bisseliches, J. W. Spretnak

The pain boundary relaxation phenomenon in high-purity copper, 0FHC copper, and a precipitation-hardenable alloy o-fCu-2 uit pct Co has been studied by internal ,friction and elastic aftereffect techniques. The data were analyzed by assuming the broad distribution of relaxation times observed obeys a lognormal distribution law which enables calculation of the relaxation strength. Grain size had no effect on relaxation strength, although the peak width increased with increasing grain size and decreasing temperature. A double grain boundary peak was produced in high-purity copper by annealing to produce secondary recrystallization. The activation energy measured for 99.999 pct Cu is 37.5 * 3 kcal per mol and 46.5 kcal per mole for OFHC copper. A small peak in the Cu-Co alloy at about 220°C at 1 cps was deduced to be the grain boundary peak. Its height increased and its activation energy decreased with increasing aging time. Except for erratic peak positions the observations were consistent with the theory of pain boundary sliding. BEFORE the mechanism of the grain boundary internal friction peak in metals can be satisfactorily explained, the detailed characteristics of the relaxation process must be documented. Of interest are the effect of grain size on relaxation strength, the high-temperature background, and peak width and position. The effect on the grain boundary peak of a precipitate at grain boundaries and of the change in distribution of the particles with aging time must also be explained by any existing or forthcoming theory. The model which has received the most attention was proposed by KG' and zener2 and proposes that the anelastic strain results from sliding of adjacent crystals at grain boundaries. The sliding is limited by the interlocking of grain corners. It follows, according to this model, that the relaxation strength is independent of and the relaxation time is proportional to the grain size. The proportionality between grain size, D, and relaxation time, t, has been confirmed by K&' and Bisseliches . In this case, the internal-friction peaks of various specimens can be superimposed by plotting Q-' as a function of the parameter vD exp H/RT where v is the frequency and H the activation energy. However, the data of Starr et 01.' and Leak6 fit better to a parameter containing D to an exponent near two. A meaningful relationship is not always deducible from the shift of peak temperature with grain size. KG7 demonstrated that a twofold variation in grain size obtained by varying the amount of cold work followed by identical recrystallization anneals will cause a peak shift that is too large to be accounted for even by an exponent of two. Since the decreased grain boundary area existing with a larger grain size is exactly compensated for by an increased sliding distance, the relaxation strength should not decrease with increasing grain size. The height of the internal-friction peak has generally been observed to be rather insensitive to grain size as long as the average grain diameter does not approach the specimen diameter. Exceptions have been reported by Koster, Bangert, and Lang8 for copper, and by Leak6 for iron. The observations for copper could well have been confused by the presence df 0.3 pct0. The possibility that the peaks may simply be increasing in width with increasing grain size and that the relaxation strength, which is proportional to the area under the peak, may remain constant was not examined. his point has been checked in this investigation using high-purity copper. Atomic mechanisms to account for damping by sliding at grain boundaries have been proposed by KG7 and Mott. KG predicts the activation energy to be identical to that for self-diffusion. Mott's "island" model suggests the activation energy is nL where n is the number of atoms in an island and L is the latent heat of fusion per atom. Other authors have felt that a value equal to the activa-

Jan 1, 1964

By W. R. Purcell, C. S. Brooks

The internal surfaces of rocks which are in contact with interstitial fluids are known to influence in some degree the recovery of hydrocarbons from pay zones. Despite the admitted importance of the influence of solid surfaces on hydrocarbon recovery, little information is available concerning the extent of surface of reservoir rocks. In this paper a description is given of the apparatus and procedure employed in the determination of the surface areas of sedimentary rocks, and values are reported for a variety of sandstone and limestone cores. In addition, consideration is given to the Kozeny equation, which relates surface area to porosity and permeability. A colliparison is made between the surface areas as calculated from this equation and the geometrical areas of a series of packs of spherical glass beads. Also, for a group of sandstone cores. Kozeny areas are compared with surface areas as determined by the gas adsorption method employed in this investigation. INTRODUCTION It has long been recognized that many processes which are of importance to hydrocarbon production are controlled in some degree by the extent of the surface of the reservoir rock through which the hydrocarbons move. For example, the recovery efficiency that is obtained in a given reservoir is certainly determined in part by the action of interfacial forces between the reservoir fluids and rock, and this action is influenced in turn by the extent of solid surface. Despite the admitted importance of surface effects to problems of petroleum recovery, little information is available concerning the extent of surface of reservoir rocks." It is the purpose of this paper to describe an apparatus which has been employed for the measurement of the surface areas of rock samples and to present the values which have been obtained for a variety of sandstone and limestone cores. In addition, the relationship of surface area to permeability and porosity, as given by the Kozeny equation, will be discussed. METHOD OF MEASURING SURFACE AREA The method of determining surface areas as employed in this work has previously found wide use in studies of porous solids such as catalysts. The method involves the measurement of the amount of physical adsorption of an inert gas, such as nitrogen or argon, on the bare surface of the solid at reduced pressure and constant temperature near the normal liquefaction temperature of the gas. With the aid of the theory of isothermal adsorption as developed by Brunauer, Emmett, and Teller,' it is possible to ascertain the amount of gas (and hence the number of molecules) which is required to cover the solid surface with a single layer of molecules. From a knowledge of the covering area per molecule the total surface ares of the solid can be computed. Since the Brunauer. Emmett, Teller (BET) theory has been adequately discussed elsewhere: it will suffice here merely to present their final equation as ordinarily employed for surface-area calculations. This equation relates the volume of gas, V, which is adsorbed at pressure, P, to the liquefaction pressure, Po, of the gas, and to the volume of gas, V.,, that is required to form a monomolecular layer: In this equation C is a quantity which is related to the heats of adsorption and liquefaction of the gas; for a particular solid-gas system at Constant temperature, C is considered to have a constant value. The basic adsorption data can be presented in the form of Equation (1) by plotting the quantity P/V(Po- P) as a func-

Jan 1, 1952

By O&apos, R. G. Meara, M. M. Fine

One of the principal activities of the Bureau of Mines connected with the recent war was to help to increase the supply of strategic and critical minerals. Fluorite was one of the most critical of the nonmetallic minerals because of the increased demand for it as a flux in basic open-hearth and electric steel furnaces and as a raw material for the production of artificial cryolite used in the aluminum industry. Wartime developments in the technology of hydrofluoric acid, such as the use of the anhydrous acid as a catalyst in production of high-octane gasoline and the use of organic fluorides as carriers for insecticides, also increased the demand for acid-grade fluorite. † In 1943 the consumption of acid-grade fluorite was advancing at a more rapid rate than production, and was only slightly less than production during the latter half of the year.' The outlook for the postwar market for fluorite is encouraging Steel production is expected to remain high until the domestic demand for commodities not manufactured during the war is satisfied. The uses for hydrofluoric acid are expected to increase under the impetus of war-initiated research. In consideration of these and other factors some authorities predict a postwar demand for fluorite equal to about 60 to 75 per cent of the wartime production.1,2 Others believe that the postwar fluorite industry will be permanently expanded over its prewar status3 Acknowledgment This paper is one of many reporting on various aspects of the Bureau of Mines program directed toward the more effective utilization of our mineral resources. The program has been under the general supervision of R. S. Dean, Assistant Director, since July 1942. The scope of the paper falls in the province of the Metallurgical Branch, whose activities embrace the separation of difficultly beneficiated ores, the production of pure metals from domestic deposits, the exploitation of marginal ore reserves, the recovery of secondary metals, and the improvement of present industrial metallurgical practice. The investigation was initiated at the request of Mr. J. H. Steinmesch, vice-president and general manager, Minerva Oil Co., Eldorado, Ill. His hearty cooperation and helpful suggestions, and those of Mr. 0. E. Anderson, mill superintendent,

Jan 1, 1947

By M. M. Fine, R. G. Meara, O&apos

One of the principal activities of the Bureau of Mines connected with the recent war was to help to increase the supply of strategic and critical minerals. Fluorite was one of the most critical of the nonmetallic minerals because of the increased demand for it as a flux in basic open-hearth and electric steel furnaces and as a raw material for the production of artificial cryolite used in the aluminum industry. Wartime developments in the technology of hydrofluoric acid, such as the use of the anhydrous acid as a catalyst in production of high-octane gasoline and the use of organic fluorides as carriers for insecticides, also increased the demand for acid-grade fluorite. † In 1943 the consumption of acid-grade fluorite was advancing at a more rapid rate than production, and was only slightly less than production during the latter half of the year.' The outlook for the postwar market for fluorite is encouraging Steel production is expected to remain high until the domestic demand for commodities not manufactured during the war is satisfied. The uses for hydrofluoric acid are expected to increase under the impetus of war-initiated research. In consideration of these and other factors some authorities predict a postwar demand for fluorite equal to about 60 to 75 per cent of the wartime production.1,2 Others believe that the postwar fluorite industry will be permanently expanded over its prewar status3 Acknowledgment This paper is one of many reporting on various aspects of the Bureau of Mines program directed toward the more effective utilization of our mineral resources. The program has been under the general supervision of R. S. Dean, Assistant Director, since July 1942. The scope of the paper falls in the province of the Metallurgical Branch, whose activities embrace the separation of difficultly beneficiated ores, the production of pure metals from domestic deposits, the exploitation of marginal ore reserves, the recovery of secondary metals, and the improvement of present industrial metallurgical practice. The investigation was initiated at the request of Mr. J. H. Steinmesch, vice-president and general manager, Minerva Oil Co., Eldorado, Ill. His hearty cooperation and helpful suggestions, and those of Mr. 0. E. Anderson, mill superintendent,

Jan 1, 1947

By B. Ramaswami, U. F. Kocks, B. Chalmers

This paper describes the tempetrature, solute (gold), and orientalion dependence of the plastic rleforlirnlion of silver single crystals. The virgin flow stress, To, and its temperatutre dependence incrense with increase in solute concentration. el decreases with decrease in temperature below room teiirperature and with increase in solute coucentralion. The dependence of 011 on temperature arid solute sontenl is due to the dependence of Ts on the two variables. An increase in ts, due to either the temperature or the solute conlent, results in a decrease of e11 in crystals of single-slip orientation and an increase of 011 in crystals of' (100) find (111) orientation. is orientation-dependent and at all the temperatures and in all the materials studied. The Leveling off of the engineering stress-strain curve in crystals of (100) 07-ientotion at a stress tl, is associated with extensive cross slib. The temperature and strain -rate dependence of tl are similar to those of indicating that a rate process is the cause 01 this phenomenon. The plastic deformation of silrer crystals of (110) orientation is multiple to that of crystals of single-slip orientation. THE work hardening of fcc crystals has been the subject of intensive investigations in the past 15 years. The effect of orientation, deformation temperature, solutes, second phase or precipitates, strain rate, etc., has been studied in a number of fcc metals.'-5 In spite of the considerable amount of work reported on the dependence of work hardening on the orientation, temperature, and solute concentration, certain aspects of the plastic deformation of fcc crystals have not been clarified. For instance, with the exception of a few investigations,6-8 where crystals of multiple-slip orientations have been studied, almost all the studies have been on crystals of single-slip orientations. Hence, a major portion of this study has been devoted to the dependence of plastic deformation on the multiplicity of slip systems and the enhanced possibility of dislocation interactions resulting from such multiplicity. Further, the abnormally low rate of work hardening observed at large strains at certain temperatures in crystals of the (100) orienta-tion 6-8has not been explained satisfactorily. It is the aim of this study to clarify this aspect of the orientation and temperature dependence of the plastic deformation of fcc single crystals. The work-hardening characteristics of single crystals of aluminum of ( 110) orientation have been studied at room temperatur "'12 and above." They have not been studied at temperatures where the virgin flow stress is dependent on temperature or where, in Seeger's terminology is important. The work hardening of single crystals of (110) orientation is of interest for another reason. As shown in Table I, the dislocation reactions that are possible in the (110) orientation are similar in certain respects to those that are possible in the (100) orientation. Hence, the deformation of single crystals of silver of (110) orientation was studied in the temperature range 100° to 900°K at intervals of 200°K. The effect of solute concentration on the plastic deformation of fcc single crystals of single-slip orientation has been studied by several investiaators.> In all of these investigations—with the exception of Ref. 20—single crystals of identical orientation have not been used, with the result that the orientation dependence of plastic deformation is superimposed on the effect of the solute. In addition, the effect of the solute on the work-hardening characteristics of single crystals of multiple-slip orientations has not been studied by the previous

Jan 1, 1965

By C. C. Henning

IN any line of human activity logical handling requires an amount of attention to each phase that is in keeping with the importance of that phase. In the complex and rapidly changing field of modern ferrous metallurgy it is difficult to allot the proper degree of attention to the various subjects, and it is not surprising that one or more subjects of major importance should for a time be neglected. Bessemer steel is a good example of a neglected subject. It is largely taken for granted, inferior physical quality is assumed for it, and there is a lack of interest in its technical development and commercial application. Availability of supply is limited. In spite of this technical indifference, limited source and lack of commercial exploitation, bessemer steel con-stitutes a large volume of tonnage in daily use. There is a fairly prev-alent idea even among technical people that bessemer steel survives mostly because of low cost and by reason of a dwindling residue of applica-tions sufficiently common to permit of its use. The difference in cost between bessemer and open-hearth steel is governed largely by the relative cost of manufacture of pig iron and the market price of steel scrap. During the past four years there have been long periods of time during which the price of steel scrap was low enough so that open-hearth steel was considerably lower in manufacturing cost than bessemer. As to application, it may be pointed out that thousands of tons of this material in the form of bessemer screw steel are applied for moving parts in automotive and other equipment. Some forging work and considerable heat treating, particularly carburizing, is performed on this grade.

Jan 1, 1935

By S. Stutz

Coal, like most other minerals, only exceptionally occurs in a sufficiently pare state to he directly available for general manufacturing purposes. And even where this is the case, the small coal or slack is usually more impure than the lump coal, as the slate, clay, etc., from the roof and bottom of the vein become mixed with it in the handling it undergoes. These impurities often exceed ten or more per cent. in addition to the impurities of the coal itself. The most common impurities of the coal are slate, or shale, clay, and sulphur. The latter occurs in different forms, but moat frequently as bisulphide of iron, or iron pyrites, and as sulphate of lime, or gypum. In both cases the impnrities add greatly to the amount of ash, and where they are present in considerable quantities the raw coal, and still more the coke made from it, is unfit for the manufacture of iron. Coke will coutain on an average at least fifty per cent. more ash and sulphur than the ram coal from which it is made. To the manufacturer of iron every additional per cent. of ash which his coal or coke contains is a source of additional expense, seemingly small, and yet very important in the aggregate. In the blast-furnace, for instance, the ash must be heated up to the melting-point, and, since it is composed largely of refractory substances, the consumption of carbon in melting it will be equal to at least one-half of its weight; that is, a certain part of tile coke is consumed for the melting and fluxing of the ash and is lost. Besides this, it is well enough known to the iron-master that coke containing lees ash makes the &lag or cinder more liquid and less incliner1 to stick to the walls of the furnace. Fuel containing much sulphur produces generally a white iron, poor in carbon, while from the same ore arrd flux, with a pure fuel, a good foundry iron might be obtained. The work of separating slate, sulphur, etd, from the coal has as yet only been successfully accomplished by the washing process. This process depends for its success on the differences in the specific

Jan 1, 1881

By W. M. McCardell, W. O. Winsauer, M. Williams

The mechanism by which an electrical potential difference is developed between two salt solutions separated by shale is shown to be a consequence of the electrical double layer of the shale surfaces. A mathematical derivation is presented to show -the dependence of the potential on the shale characteristic.? and on the concentration of the salt solutions. The equations developed describe adequately the potential-concentration behavior of a long shale core. The equations also describe the variation of potential of sand-shale mixtures with variation of clay content. Ion adsorption i* an important factor in he developments of the surface charge on the shale. and electrical resistivity and ion transference number data are emlployed to estimate the increase of surface charge with concentration. Since the potential is shown to be dependent on the characteristics of the particular .system. water salinities estimated from the potential log by previously proposed methods may be low in some rase;. INTRODUCTION That the electric well log exists today may he attributed to the ingenuity of the Schlumberger brothers who adapted to the logging of wells techniques which were originally developed as surface prospecting methods for the location of ore bodies Empirically it was found that the potential curve of the electric log usually gave values for clean sands which were negative with respect to the values for shales. It was suggested that the potential was responsive to porosity. It was postulated in explanation? that the potential was the sum of a streaming potential, which differed for sands and shales, and of an "electro-chemical" potential of undetermined origin. Mounce and Rust in 1943 showed that the streaming potential is small in most cases and that the potential is generated by a process in which shale and a salinity difference play-essential party. Dickey.:' in the same year, concluded that the potential is dependent upon adsorptive properties of reservoir rock. Wyllie in 1949. and Wyllie and Patnode, in 1950, measured the potential-: between two salt solutions separated by barriers of either naturally-compacted or artificially-compacted shales and concluded that the potential can be expressed by where E is the potential R is the gas content F is Faraday's constant T is the absolute temperature are the activities of the two uni-univalent solutions These authors postulated that shale. in the ideal case is impermeable to the migration of negative ions. Any potential less than the "ideal" shale potential was considered to be due to imperfections in the shale barrier. Although the studies by Wyllie and Patnode of the development of the shale potential are fairly recent. investigators in fields other than well logging have discussed the mechanisms responsible for analogous potentials over a period of several decades. Although it is evident that much thought has been devoted to the question of the origin of the potential observed in wells, it is also apparent that all of the explanations presented to

Jan 1, 1953