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By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By R. B. Adamson

The fatigue behauior of irradiated copper single crystals is compared to that of unirradiated crystals. Proton or electron irradiation did not substantially change the fatigue-lzj.e, fatigue-hardening-, or slip-line characteristics, while neutron irradiation did appear to alter these parameters. Postfatigue transrrzission electron microscopy did not reveal any marked structural differazces between irradiated and unirradiated specimens. Possible dislocatio~a mechanisnzs to explain the observed behavior are discussed. A LTHOUGH considerable work has been done to ascertain the effects of radiation on the tensile properties of metals (e.g., Refs. 1 and 2), little work of a basic nature has been reported on the effect of radiation on fatigue properties. Since it is known that fatigue properties are sensitive to conditions at the surface of the metal, it was felt that charged particle irradiation, whose penetration into metals is very small, might influence the fatigue behavior. To investigate this surface effect, irradiations with 10 mev protons and 1.5 mev electrons were conducted. The range of 10 mev protons in copper is about 0.236 mm; which is very small compared with the thickness of the specimens used (1.53 mm). The range of 1.5 mev electrons is somewhat larger, on the order of 0.665 mm.4 On the other hand, irradiation with reactor neutrons produces damage throughout the entire specimen, so neutron irradiation can be used to study the effects of bulk damage. The damage introduced by proton and neutron irradiation is expected to con!ist of large interstitial dislocation loops,5 tiny (<25A) vacancy loops," and/or various vacancy-rich regions called depleted zones.&apos; In the case of electron irradiation at about -173°C the damage is expected to consist of isolated Frenkel pairs.&apos; The effect of radiation damage on the fatigue properties of some engineering materials has been reported,g,10 but the results are not clear-cut or consistent. SPECIMEN PREPARATION Zone-refined copper was used to grow single crystals by a modified Bridgeman technique in an inert helium atmosphere. Using a seeding method, single crystals were obtained as bars about 6 in. long with a cross section of 3 by $ in. Immediately upon removal from the split-mold graphite boat in which they were grown, the very soft bars were embedded in a room-temperature setting plastic. They could then be cut into specimen lengths without introducing any long-range damage. Generally, four or five specimens plus one seed were obtained from each bar. The plastic material was dissolved away in acetone and the orientation of each sample was checked by the standard Laue X-ray

Jan 1, 1968

By B. M. Larsen, W. E. Shenk

THIS paper describes a method of reversal control of the open-hearth furnace that obtains in practice those effects considered below as essential to a completely automatic control, without appreciable interference with the natural rise and fall in temperature of the regenerative portions of the furnace system. Growing out of some studies of radiation pyrometry in open-hearth regenerators, it was developed during 1934-1938, and has been successfully applied to a number of commercial furnaces. The goal of open-hearth furnace operation is the highest rate of production of steel of proper quality consistent with good refractory life and fuel economy. This requires rapid heat transfer from furnace to charge, which in turn is dependent upon heating the furnace refractories to the highest safe operating temperature. The greater the heat input to the melting chamber, the sooner this limiting temperature will be reached, so that control methods in general that are designed to protect against overheating of refractories should help to maintain maximum fuel input and production rate. For the typical open-hearth system, with fixed regenerator capacity and with rate of fuel input usually restricted in its range of variation, our basic assumption is the idea that the only other important variable that is, the time interval between successive reversals-should also be held constant or within a small range. The present reversal control was designed therefore so that, under normal operating conditions, no arbitrary limitation is imposed other than to keep the reversal interval within the optimum time range. However, since a near approach to completely automatic operation involves protection of refractories through the balancing of furnace end temperatures as well as emergency protection against temperature peaks above some upper limit, it was also felt essential to employ, as an integral part of the control unit, a temperature-measuring instrument to register the true temperature of the refractory surfaces at some critical region in the hot ends of the regenerative zones. As the basic elements of the control, we thus have one "maximum" and one "minimum" time relay and a potentiometer recorder-controller, combined with switches and relays to operate as follows: x. Reversal normally occurs within an optimum range limited by the maximum and minimum settings to about 4 to 6 min. variation, but the actual interval usually is less variable and closer to the minimum setting. 2. The margin between minimum and maximum time is utilized, together with a "floating temperature limit" in the potentiometric control instrument, to correct any

Jan 1, 1945

By George H. Found

DURING recent years considerable interest has been focused on the energy-absorption characteristics of metal when it is cyclically stressed in vibration. The most familiar manifestation of this phenomenon, which is called the "damping capacity" or "internal friction" of a material, is involved in the dissipation of mechanical energy of vibration, which otherwise would build up to stress levels where the problems of noise and fatigue are involved. In addition to its engineering importance in structures, the damping behavior of metals, particularly at low stress amplitudes, has also been used as a unique metallurgical research tool with which to provide sensitive means for indicating certain structural changes within metals. Important contributions toward understanding the energy-dissipating mechanisms that are responsible for internal friction in metals have been made in the last few years. The information is not yet sufficiently extensive, however, to provide a useful metallurgical concept describing exactly how the structure affects the internal friction, or to encourage more general use of this technique among metallurgists. Three fundamental mechanisms have been proposed, as a result of recent experimental investigations, to account for the internal friction in nonferrous metals in low-stress amplitude tests. These include damping due to internal thermal currents that are created and flow in metal because of differential vibratory stress effects,1 damping due to localized inelastic stress relaxation at inhomogeneities within the metal,2,3 and damping related to plastic flow of a localized type for which an explanation has been sought in terms of the dislocation theory.4 How each of these mechanisms functions as a result of structural changes in the metal is, in general, not well understood because of insufficient experimental data for which the controlling variables have been segregated and because of uncertainties in regard to the nature of the structural changes themselves. In several investigations the effects of cold-working on the internal friction of polycrystalline brass and aluminum have been described. As reported by Köster and Rosenthal,5 and by Förster and Breitfield,6 there is an initial large increase in the damping when the metal is worked. The initial high value is not stable, but declines rapidly, at first, in a hyperbolic manner. About 100 hr, after straining, a stable value is reached of magnitude proportional to the amount of strain.7 In Fig. I is shown the relationship found by Zener and his collaborators between the internal friction due to cold-working of alpha brass and the amount of cold-working.8 Several investigators have made internal-friction measurements on worked poly-

Jan 1, 1945

By M. R. Tek, F. H. Poettmann, M. L. Grove

The general problem of single-phase natural gas flow through porous media has been considered both by mathematical analysis and field experiments. Theoretical studies on the fluid dynamics of natural gas wells resulted in derivations of expressions which permit a ber-ter understanding of the flow mechanism for conditions under which Darcy&apos;s law is no longer valid. In applying these results to natural gas production and testing technology, special emphasis war placed on the study of low permeability, slowly stabilizing formations. These applications resulted in a method of predicting the performance coefficients of tight natural gas wells. The calculation of the performance coefficient requires the determination of the "test-index", pkh/µ, the drain- age radius, R, and the effective wellbore radius, rw. Methods for estimating these parameters from field data were also developed. Field data from 15 wells were collected and analyzed. The measured values of the performance coefficients were compared with the predicted values. This statistical evaluation gave a bias of 7.14 per cent and a standard deviation of 11.6 per cent. INTRODUCTION The performance of a natural gas well is determined by the physical properties of the reservoir rock, the extent and the geometry of the drainage area, the properties of the flowing fluid, and the conditions of pressure distribution within the drainage matrix. The relation between the quantity of gas delivered and the pressure drop within the reservoir is characteristic of the behavior of each well and is often referred to as the back-pressure behavior of the well. It is well established that for normal, single-phase gas wells the relationship between the gas delivery rates and the bottom-hole pressure take, in general, the form, Q = c(P3 8 -P2 1)n. ,.......(1) where C is the performance coefficient, and n is the exponent corresponding to the slope of the straight-line relationship between Q and (P2 s, — P2 l) plotted on logarithmic coordinates. The determination of a well&apos;s performance by the back-pressure behavior not only permits the production engineers to analyze many operating problems, but also provides necessary information useful and essential to predict the future development of the field.&apos; Important engineering and production problems such as calculation of gas deliverability into a pipeline at a predetermined line pressure, design and analysis of gas-gathering lines, determinations of spacing and number of wells to be drilled during field development to meet future market or contract obligations, etc., all depend, at least in part, on the availability and use of reliable back-pressure curves.&apos; In the past the behavior of gas wells was evaluated

Jan 1, 1958

By John Guillermo Bartram

The oil industry continued relatively quiet in Wyoming in 1935, although production increased about 8 per cent over the previous year; 55 oil wells were completed in 1935, compared to 34 in 1934, and at the end of the year 44 wells were drilling, 33 in proven fields and 11 in wildcat locations. The total drilling a year ago was only 30. In the year 1935 Wyoming produced a total of 13,451,000 bbl. of oil, a gain of 912,000 bbl. over the 1934 figure of 12,539,000 bbl. Approxi-mately two-thirds of the increase, or 630,000 bbl., was from black oil fields and one-third, or 285,000 bbl., from light oil pools. Salt Creek, with production of 6,357,000 bbl., is still many times the largest field in Wyoming but in 1935 it made less than 50 per cent of the state&apos;s total, after producing more than all other fields in the state for 24 years; however, its decline was only 3.8 per cent from the previous year. Oregon Basin, a black oil field, held second place again with production of 1,163,-000 bbl., a good increase over 1934. Grass Creek, with increases in both its light and black oil, jumped into third place; and Lance Creek, with its new Sundance light oil production, was in fourth place in the amount of production. Frannie, which was in third place in 1934, dropped far back on the list because of lack of market. Byron and Garland, two other black oil fields in the Big Horn Basin, increased considerably. Big Muddy, a prominent light-oil field, was down with a natural decline; and Elk Basin, also light oil, produced less because of market conditions. During 1934 only three gas wells were drilled in Wyoming and 29 dry holes, 13 in proven fields and 16 at wildcat locations. Of the latter, 5 were on wildcat structures of considerable interest. Of the 55 wells completed during the year, 53 were in proven fields and of these 17 were small ones in the shallow Osage field and 10 were light-oil wells good for 1500 to 3000 bbl. each in the Lance Creek field. Discoveries Two of the oil wells were discoveries at Medicine Bow and Sheep Creek. Medicine Bow is a very large anticline with more than 3500 ft. of closure and is located in Carbon County in the south-central part of the state. In 1923 it showed some oil in the Upper Cretaceous Frontier

Jan 1, 1936

By John Guillermo Bartram

The oil industry continued relatively quiet in Wyoming in 1935, although production increased about 8 per cent over the previous year; 55 oil wells were completed in 1935, compared to 34 in 1934, and at the end of the year 44 wells were drilling, 33 in proven fields and 11 in wildcat locations. The total drilling a year ago was only 30. In the year 1935 Wyoming produced a total of 13,451,000 bbl. of oil, a gain of 912,000 bbl. over the 1934 figure of 12,539,000 bbl. Approxi-mately two-thirds of the increase, or 630,000 bbl., was from black oil fields and one-third, or 285,000 bbl., from light oil pools. Salt Creek, with production of 6,357,000 bbl., is still many times the largest field in Wyoming but in 1935 it made less than 50 per cent of the state&apos;s total, after producing more than all other fields in the state for 24 years; however, its decline was only 3.8 per cent from the previous year. Oregon Basin, a black oil field, held second place again with production of 1,163,-000 bbl., a good increase over 1934. Grass Creek, with increases in both its light and black oil, jumped into third place; and Lance Creek, with its new Sundance light oil production, was in fourth place in the amount of production. Frannie, which was in third place in 1934, dropped far back on the list because of lack of market. Byron and Garland, two other black oil fields in the Big Horn Basin, increased considerably. Big Muddy, a prominent light-oil field, was down with a natural decline; and Elk Basin, also light oil, produced less because of market conditions. During 1934 only three gas wells were drilled in Wyoming and 29 dry holes, 13 in proven fields and 16 at wildcat locations. Of the latter, 5 were on wildcat structures of considerable interest. Of the 55 wells completed during the year, 53 were in proven fields and of these 17 were small ones in the shallow Osage field and 10 were light-oil wells good for 1500 to 3000 bbl. each in the Lance Creek field. Discoveries Two of the oil wells were discoveries at Medicine Bow and Sheep Creek. Medicine Bow is a very large anticline with more than 3500 ft. of closure and is located in Carbon County in the south-central part of the state. In 1923 it showed some oil in the Upper Cretaceous Frontier

Jan 1, 1936

By J. J. Taber, I. S. K. Kamath, R. L. Reed

Alcohol floods of consolidated sandstone cores have shown the process to be strongly dependent on the phase behavior of the particular alcobol-oil-water system used. This means that in many cases the mechanism does not conform to the idea of a piston-like displacement. Instead, it is found that by changing the alcohol it is possible to change the relative velocities of the oil and water and, in fact, the entire mechanism of the process. The effects of rate, viscosity, initial saturation, distance travelled and hysteresis of relative permeability on the alcohol flooding mechanism are discussed. INTRODUCTION Reasons for interest in the use of alcohol to miscibly displace oil and water from a porous medium appear in the existing literature.l-7 The mechanism of the displacement has been considered and the apparent implications formulated into a theory which presumably would enable one to predict the essential features of the process.6 Unfortunately, most of the reported experiments have been performed with unconsolidated or artificially consolidated sands. With these systems some of the noteworthy facets of the process are obscured and resulting data appear uncertain. It is the purpose of this paper to show how the use of consolidated sandstones has led to revision of the mechanism and, hence, the theory of alcohol flooding. The practical result is increased pessimism toward the possibilities of commercial application of the simplest form of the alcohol-slug process. However, elucidation of the mechanism has made it possible to define the essential characteristics of a system of slugs which will behave in a nearly piston-like fashion and, thus, yield the best possible result. EQUILIBRIUM PHASE BEHAVIOR Fig. 1 is a diagram of the ternary system isopropyl alcohol (IPA)-Soltrol-calcium chloride brine. Brine was used to prevent plugging of the core and calcium chloride was used because sodium-chloride brine exhibits a solid phase with Soltrol and IPA. If alcohol is added in increments to the immiscible mixture of water and oil represented by Point A, the path followed by the successively equilibrated samples will be on the Line ABC and pass from the immiscible region to the miscible region by crossing the binodal curve at B. Consider the intersection D of this path with the tie Line EF. The quantity of oleic phase is proportional to the Segment ED and the quantity of the aqueous phase is proportional to DF. Compositions of the two phases are specified by Points E and F. It is clear that in the case shown the oleic phase is diminishing and entirely disappears when miscibility is achieved. Such will

By W. A. Koehler, M. E. Hinkle

THE oxidation of pyrites and marcasite in coal-mine strata to produce discolored acid mine drainage has long been explained by chemical reactions occurring in three stages: 1. The iron sulphide minerals are oxidized by air in the presence of water to produce a nearly colorless solution of ferrous (iron) sulphate and some sulphuric acid. 2, The ferrous sulphate and part of the sulphuric acid combine with additional oxygen to form ferric (iron) sulphate. 3. The ferric sulphate hydrolyzes to form a reddish-brown precipitate and additional sulphuric acid. Nevertheless, chemical data alone are not sufficient to explain all observed facts. The first stage seems to proceed more slowly in the chemical laboratory than in nature. The second and third stages normally occur to a marked extent within a few days with raw mine water. However, the visible discoloration that characterizes these latter stages will not develop for months if the mine water is sterilized. By means of bacteriological techniques, two organisms have been isolated from acid coal-mine drainage. These are believed to have a part in promoting the chemical reactions summarized above. One organism is considered to be Thio-6aciZZus thiooxidans, which is known to be able to convert elementary sulphur or sodium thiosulphate to sulphuric acid. Its relation to the formation of acid mine drainage has not Yet been established. Apparently it does not Promote the oxidation of ferrous iron compounds in mine drainage to the ferric state. The second organism has not been identified by name but is described as " Gram negative, non-spore-forming rods approximately 0.4 micron wide by 0.8 to 1.0 micron long." A pure culture of this when added to sterile mine water will cause the latter to become amber and develop the typical rusty precipitate. However, it has not been found to convert sulphur compounds to sulphuric acid. Further research is planned to determine whether or not these microorganisms play a significant part in the first stage of oxidation whereby pyrites and marcasite minerals go into solution. Some of the conditions found in abandoned sections of coal mines, such as a reduced Percentage of Oxygen and increased percentage of carboll &apos;dioxide in the air, as well as the existing temperature and acidity ranges, will be tolerated by and may even be favorable to these organisms. Acid Coal Mine Drainage Acid coal mine drainage has been the concern of coal mine operators, industrialists, sportsmen and public officials for many years. The amount of acid flowing into our streams in the coal-producing areas varies considerably from mine to mine and from

Jan 1, 1949

By Howard Thompson, H. N. Hall, Frank Nuss

Removal of bit cuttings is an important function of drilling muds. In an effort to obtain better understanding of the factors influencing the removal of cuttings, an extensive series of laboratory tests were made in which slip velocities of various sizes and shapes of particles were measured in muds of different physical properties. Empirical equations were then derived from these experimental data. These equations show that slip velocity is dependent on cutting size and shape, mud flow constants, and flow state of the mud. Applicability of these equations for field use is demonstrated by comparing computed slip velocities with slip velocities obtained from field tests. Drilling muds have many functions, but perhaps the most important is the removal of bit cuttings from the well. In a 10,000-ft well, the weight of rock which is drilled and must be carried to the surface is over 150 tons. In addition to this, the mud must remove any sloughings from the well bore. Failure of the mud to promptly remove either bit cuttings or sloughs from the well bore causes re-drilling and excessive wear on bit teeth, slows down drilling rate thereby increasing well costs, and greatly increases possibilities for stuck drill pipe when circulation is stopped for any length of time. Drilling muds lift bit cuttings to the surface by means of the upward velocity of the drilling mud in the annulus. Because a density difference exists between the rock being drilled and the drilling mud, there is a difference between mud velocity and the rate of bit cutting travel, called the net rise velocity. To evaluate the ability of any type of drilling mud in respect to lifting cuttings, some method must be known for predicting the rate of fall of cuttings through mud traveling upwards in the annulus. Equations for the rate of fall of particles through a true fluid have been satisfactorily determined by several authors. 1-6 Since drilling muds are not true fluids, but obey the laws of Bing-ham,7 it should not be expected that equations for rate of fall of cuttings in a true fluid would be applicable to plastic fluids such as drilling muds. Several authors have attempted to compute cutting slip velocities in muds using a viscosity value obtained with a Stormer viscosimeter; however, unsatisfactory results were obtained. Pigott8 took cognizance of the phenomenon of variation of viscosity with velocity in laminar Row, and calculated laminar slip velocities using a variable viscosity with Stokes law, and turbulent slip velocities using Rittingers law. Drilling muds obey the laws of plastic flow which involve factors not affect-

Jan 1, 1950

By Gustav S. Preller, A. M. Gaudin

For the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2-4 and has now received confirmation as to accuracy by an entirely independent method.&apos; This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8?2 or 16.2?2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8?2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura&apos;s results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2?2., with extreme values at 13.7 and 16.9?2. The average of 21 determinations made in connection with this study7 gave a parking area of 14.3 ± 0.27?². In view of this result and of the Harkins and Jura

Jan 1, 1947

By Gustav S. Preller, A. M. Gaudin

For the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2-4 and has now received confirmation as to accuracy by an entirely independent method.&apos; This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8?2 or 16.2?2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8?2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura&apos;s results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2?2., with extreme values at 13.7 and 16.9?2. The average of 21 determinations made in connection with this study7 gave a parking area of 14.3 ± 0.27?². In view of this result and of the Harkins and Jura

Jan 1, 1947

By O. U. Bradley

The extent of losses, due to evaporation, sediment, and water, in crude oil stored in steel tanks, is a very interesting question, and particularly so at this time, when every reasonable measure should be employed to eliminate all possible losses of this important natural product. Available information on this subject is incomplete; e.g., during the development of the Cushing Field, considerable surplus oil was stored in steel tanks, but from time to time, owing to changes in weather, some losses by evaporation and short storage room on the leases, these tanks were topped out, thus rendering inaccurate any system designed to determine the average rate of evaporation or other losses of the oil over a given period. Furthermore, the losses, as shown by the records at the time, as a result of hasty gages, failed to take into account the temperature and gravity of the oil. Losses may be classified roughly as occurring from evaporation, presence of sediment and water, and leakage. The coefficient of expansion and contraction of crude oil, in relation to temperature conditions, is of material importance; also, the rate of evaporation is dependent upon the gravity of the oil, as the escape of the lighter hydrocarbons in fresh Cushing oil, of from 40 to 42 gravity, on a warm day is considerable, and from available records of temporary storage, it is safe to assume that a loss of 1 to 11/2 per cent. in volume will easily occur in light crude oil of Cushing grade over a period of 6 months, including the summer season. The presence of sediment, water, and other impurities, in the oil will also cause more or less deterioration in quality, particularly when the fresh production is run direct from the gage tanks, or from the wells on the lease to steel storage, as is often the case when an oil field is being rapidly developed. The bad oil will settle to the bottom of the tanks and may be determined by thiefing and running a centrifuge test on the sample. The amount of water in the oil depends entirely on the conditions under which it is produced. Sometimes in large producing wells, with heavy gas pressure, some water may come in with the oil, particularly if the well has been drilled to the top of a water sand. Under these conditions, cut oil is often produced, which, if not settled out, is carried over into the steel tanks. The losses by leakage in steel tanks are difficult to determine, for

Jan 1, 1920

By Joseph L. Jernegan

The Whale Lode occurs in the main range of the Rocky Mountains, Park County, Colorado Territory, at Hall Valley. It has been opened up and worked to some extent by the Whale Mine, situated some 11,300 feet above the level of the sea. The mine, with 700 feet of the lode on either side of the discovery shaft, is the property of the Hall Valley Silver-Lead Mining and Smelting Company. The adjacent country rock is a compact, fine-grained gneiss; its general strike is about north and south, dipping steeply to the west. In the immediate vicinity of the mine, the strata are very nearly vertical. The gneiss incloses numberless veins of a reddish granite, in which the feldspar largely predominates over the quartz and mica, the latter oftentimes being scarcely perceptible. As a general rule these granitic veins seem to more frequently follow the lines of stratification of the gneiss than otherwise. They are of varying width, some large, some small; the larger are from 5 to 6 feet wide. Gash veins of feldspar and quartz are also of very frequent occurrence. The general trend of the lode is about northeast. and southwest, intersecting the country rock at about an angle of 45 to its stratification. It dips to the northwest at an angle of 65. I am unable to state accurately how far this lode has been traced upon the surface, but it is at least well known to extend entirely through the mountain upon which the mine is situated, and is traceable over the ridge by a hollow extending for some distance along the surface, in which the lode crops out. This hollow in the surface rock has probably been formed through decomposition of the vein matter by atmospherical influences. The width of the crevice is variable, generally between 5 and 10 feet; the pay vein varies from an inch, or less, to 36 inches. The vein is generally accompanied both on foot and hanging walls by a whitish, semi-decomposed fock, composed of quartz and decomposed feldspar, and in some places—where the process of decomposition has not reached as advanced a stage—a lightgreenish or black mica. This rock, therefore, is in places composed of all the constituents of gneiss, and is undoubtedly nothing more or less than the same in a decomposed condition. It is often very strongly impregnated with iron pyrites, generally crystallized in minute cubes, and it is probably owing to the presence of this min-

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By W. L. Fink, M. S. Hunter, R. H. Brown

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.&apos; The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when

Jan 1, 1941

By M. S. Hunter, W. L. Fink, R. H. Brown

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.&apos; The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when

Jan 1, 1941

By Elmars Ence, Harold Margolin

The partial isothermal section of the Ti-Cu-Zr system at 750°C has been studied. The crystal structure of Ti2Cu has been detevnlined as tetragonal and when expressed as face-centered tetragonal, a = 4.164, c = 3.611 A, and c/a = 0.867. TITANIUM systems in which ß-titanium decomposes eutectoidally into a and a compound rather readily are known as active eutectoid systems. Recently in active eutectoid alloys based on the Ti-Cu system, and containing additionally A1 and Zr, it has been found that zirconium may produce both moderate weakening and marked strengthening at elevated temperatures.&apos; In order to obtain some insight into the behavior of zirconium, an attempt was made to determine whether compounds of the type Tix Zr and TixZryCu exist. Only results of the Ti-Zr-Cu studies are reported here since data on Ti-Zr alloys will be presented in a separate publication. EXPERIMENTAL PROCEDURE Alloys were nonconsumably arc melted in argon atmosphere as 15-g buttons, prepared from materials of the following purities: Bureau of Mines electrolytic Ti — Bhn 63 OFHC copper Reactor Grade Zirconium Bhn .C 150 Prior to alloy preparation the electrolytic titanium was premelted to avoid excessive spattering of the charges during melting. The weight losses during melting did not exceed 1 pct of the total weight of the charge. The alloys prepared are listed in Table I together with analyzed compositions. in cases where they were determined. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. About 1 to 2 sec are required to remove the capsule from the furnace, drop it into the iced brine and break it. Because of the insulation effect of the quartz, this delay in quenching should not produce a large drop in temperature. In many instances, no difference or little difference has been detected between the same specimen quartz capsule quenched or directly quenched in vacuum by an impinging stream of water.&apos; Ti-Cu-Zr alloys were homogenized for 48 hr at 825°C prior to annealing at 750°C. Annealing for 5 days at 750°C produced the same results as 11 days at temperature and it was therefore assumed that 5 days was sufficient to establish equilibrium. Titanium-copper alloys were homogenized for 40 hr at 900°C prior to heat treatment for 6 days at 750°C. Specimens for metallographic examination were electropolished and etched with the following solution:

Jan 1, 1962