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By T. M. Morris

A SEARCH of the literature reveals that no measurements have been made of the forces acting between a small solid particle whose surface is hydrophobic, and an air bubble to which the solid adheres, both immersed in water. Analyses have been made of the forces acting to support a greased solid on the surface of water, and the forces acting to cause a solid, whose surface is hydrophobic, to adhere to an air bubble in water. The latter analysis T. M. MORRIS, Junior Member AIME, is in the Department of Metallurgical Engineering and Mineral Dressing, School of Mines and Metallurgy, Rolla, Mo. New York Meeting, February 1950. TP 2734 B. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 16, 1949. This paper is the result of work done for part of a doctor's thesis at the Missouri School of Mines and Metallurgy. is often incomplete, however, because the internal pressure of the bubble has been neglected. It will be demonstrated that the internal gas pressure is not a negligible factor when dealing with bubbles of the size encountered in flotation. A study of the forces acting between an air bubble attached to a large flat surface is informative. It must be borne in mind, however, that this is not the condition present in a flotation cell, where the particle is small compared to the size of the bubble. The bubble is allowed to spread to its maximum contact angle on a large flat surface in the first case, whereas in the second case, the spread of the bubble is limited to the surface of the small particle which is presented to the bubble. Kabanov and Frumkinl studied the forces acting to cause adhesion of bubbles of hydrogen to a large surface of mercury, which served as an electrode in a dilute sulphuric acid solution. The force acting to hold the bubble to the mercury surface was found to be the vertical component of the surface tension between hydrogen and the sulphuric acid solution. The forces tending to cause the bubble to separate from the mercury surface were found to be: (1) the force exerted due to the internal pressure of the bubble acting upon the area of contact between the bubble and the mercury surface, and (2) the buoyant force of the bubble minus the hydrostatic force acting at the base of the bubble. These investigators photographed bubbles that were just on the verge of separating from the mercury surface. From these photographs, they measured the contact angle between the mercury surface and the tangent to the hydrogen-solution interface at the point of contact between bubble and mercury surface. They calculated the volume of the bubble and the internal pressure of the bubble. The equivalence between the upward acting and downward acting forces was remarkable. Wark2 pursued an investigation similar to that of Kabanov and Frumkin, and at the same time. His deductions verified those of Kabanov and Frumkin. He also considered the conditions present in flotation and was aware of the effect of the internal pressure of the bubble. Further, he proposed several conditions under which a small solid particle would adhere to an air bubble in water. In 1922, Edser," an English physicist, made the following statement. "It must be remembered that no particle could float stably, but for the possibility of variation of the contact angle, for if this were a constant, a slight tilt would inevitably cause the particle to sink." Wark criticized this statement, maintaining that the contact angle does not vary. The experimental data to be presented indicates that Edser was correct. Experimental Procedure: Briefly, the experimental procedure was as follows. A bubble of air was generated in distilled water. A rod of known diameter, one end of which was water repellent, was attached to this bubble. The weight of the 'rod was measured. The internal pressure of the bubble was measured with a manometer. The hydrostatic head from the surface of the water to the bottom of the rod was measured. The angle between the horizontal projection of the end of the rod and the tangent to the bubble at the circle of contact be-

Jan 1, 1951

By T. M. Morris

A SEARCH of the literature reveals that no measurements have been made of the forces acting between a small solid particle whose surface is hydrophobic, and an air bubble to which the solid adheres, both immersed in water. Analyses have been made of the forces acting to support a greased solid on the surface of water, and the forces acting to cause a solid, whose surface is hydrophobic, to adhere to an air bubble in water. The latter analysis T. M. MORRIS, Junior Member AIME, is in the Department of Metallurgical Engineering and Mineral Dressing, School of Mines and Metallurgy, Rolla, Mo. New York Meeting, February 1950. TP 2734 B. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 16, 1949. This paper is the result of work done for part of a doctor's thesis at the Missouri School of Mines and Metallurgy. is often incomplete, however, because the internal pressure of the bubble has been neglected. It will be demonstrated that the internal gas pressure is not a negligible factor when dealing with bubbles of the size encountered in flotation. A study of the forces acting between an air bubble attached to a large flat surface is informative. It must be borne in mind, however, that this is not the condition present in a flotation cell, where the particle is small compared to the size of the bubble. The bubble is allowed to spread to its maximum contact angle on a large flat surface in the first case, whereas in the second case, the spread of the bubble is limited to the surface of the small particle which is presented to the bubble. Kabanov and Frumkinl studied the forces acting to cause adhesion of bubbles of hydrogen to a large surface of mercury, which served as an electrode in a dilute sulphuric acid solution. The force acting to hold the bubble to the mercury surface was found to be the vertical component of the surface tension between hydrogen and the sulphuric acid solution. The forces tending to cause the bubble to separate from the mercury surface were found to be: (1) the force exerted due to the internal pressure of the bubble acting upon the area of contact between the bubble and the mercury surface, and (2) the buoyant force of the bubble minus the hydrostatic force acting at the base of the bubble. These investigators photographed bubbles that were just on the verge of separating from the mercury surface. From these photographs, they measured the contact angle between the mercury surface and the tangent to the hydrogen-solution interface at the point of contact between bubble and mercury surface. They calculated the volume of the bubble and the internal pressure of the bubble. The equivalence between the upward acting and downward acting forces was remarkable. Wark2 pursued an investigation similar to that of Kabanov and Frumkin, and at the same time. His deductions verified those of Kabanov and Frumkin. He also considered the conditions present in flotation and was aware of the effect of the internal pressure of the bubble. Further, he proposed several conditions under which a small solid particle would adhere to an air bubble in water. In 1922, Edser," an English physicist, made the following statement. "It must be remembered that no particle could float stably, but for the possibility of variation of the contact angle, for if this were a constant, a slight tilt would inevitably cause the particle to sink." Wark criticized this statement, maintaining that the contact angle does not vary. The experimental data to be presented indicates that Edser was correct. Experimental Procedure: Briefly, the experimental procedure was as follows. A bubble of air was generated in distilled water. A rod of known diameter, one end of which was water repellent, was attached to this bubble. The weight of the 'rod was measured. The internal pressure of the bubble was measured with a manometer. The hydrostatic head from the surface of the water to the bottom of the rod was measured. The angle between the horizontal projection of the end of the rod and the tangent to the bubble at the circle of contact be-

Jan 1, 1951

Membership at the end of the year 1951 was 19,711 including 2228 Student Associates. The data in the third column include these Student Associates. 1. This includes all the cash dues income received from new and old members of all grades. 2. All cash initiation fees received. 3. Net income received from advertising in the three journals. The figure was $72,273, for MINING ENGINEERING; $39,844 for the JOURNAL OF METALS; and $31,564 for the JOURNAL OF PETROLEUM TECHNOLOGY. Income in 1950 was $54,572, $30,390, and $18,443 from these sources, respectively. 4. Receipts from individual sales, nonmember subscriptions, and multiple subscriptions of members. 5. Includes Transactions volumes and the Petroleum Statistics volume. 6. Sales of all other printed matter except special volumes sponsored by certain Funds. Includes a considerable sale of preprints and reprints of technical papers. 7. Does not include dividends and interest from certain Funds whose income reverts to those Funds. 8. Miscellaneous income not included in any of the above categories. 9. The total income compares with $493,197 -in 1950, an increase of $29000.

Jan 1, 1952

By H. W. Kropholler, L. A. Cramer, E. T. Woodburn, J. C. A. Greene

A generalized mathematical structure is proposed whereby internal species mass flows within a flotation network are defined uniquely by a matrix of enhancement factors. An element of the enhancement factor matrix is defined as the ratio of the mass flow of that species leaving a given cell in the concentrate to the species mass flow leaving the same cell in the tailings. To predict the enhancement factors, knowledge of flotation kinetics effects is required. Recently experimental data has become available relating to the performance of industrial flotation circuits which indicate that the discrete or discrete-distributed kinetic schemes are capable of reasonably effective simulations. These simulations show the importance of including froth effects. The prediction of performance of networks from small-scale batch tests on flotation streams shows that the model for the froth phase used in the simulations does not scale-up well and that aeration effects are also difficult to predict. The network analysis should be useful in differential flotation of complex ores and it is disappointing-in this context that little information on the kinetics of activation and depression is available.

Jan 1, 1976

By C. L. Sollenberger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature's to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent.

Jan 6, 1958

By N. A. Gokcen, E. S. Tankins, G. R. Belton

Equilibrium in the reaction H2(g) + O[in liquid iron, cobalt, or nickel] = H2O(g) has been investigated over wide temperature and composition ranges. Oxygen has been found to obey Henry's Law in each of the three metals at 1550°C. The standard free-energy changes for the above reaction are given by: (1550° to 1700°C) ?Foco = -45,360(±290) + 16.16(±0.16)T (1490° to 1700°C) ?Fo Ni = -48,170(±220) + 16.12(±0.12)T (1465° to 1700°C) where the standard state for dissolved oxygen is the I wt pet solution. ThE thermodynamic behavior of dilute solutions of oxygen in molten iron has been the subject of many investigations over the last thirty years,'-'4 the majority of the investigators having utilized the reaction:

Jan 1, 1964

By L. F. Porter, G. J. Dienes

The effect of netltron irracliation on mart ensite transformation in the iron-nickel system was studied by means of electrical resistance and magnetic induction measuremertts. Irradiation lowers the M8 temperature of the allay, causes changes in the electrical and magnetic properties of the high-temperature phase which indicate either an accelemtion of phase separation or a clustering of nickel, and enhances strain recovery on specimens partially transformed to martensite prior to irradiation. Possible mechanisms to account for the effects; are discussed. 1 HERE is a good deal of evidence to indicate that neutron irradiation is capable of affecting phase changes in metals and alloys. While the mechanism of the effect often is not well understood, such studies hold promise of improving our understanding not only of irradiation damage but also of the phase changes involved. To date systematic and detailed investigations have been made of the influence of nuclear radiation on order-disorder transformations in the copper-gold, nickel-manganese, and copper-zinc system, and on precipitation reactions in the copper-iron, nickel-beryllium, and copper-beryllium system.' These solid-state reactions are diffusion controlled and the results can be explained largely on the basis of enhanced diffusion due to the presence of irradiation produced vacancies. Reversion of low-temperature eutectoid phases to the high-temperature phase has been observed in the fissionable uranium-molybdenum and uranium-niobium systems.2 Here it is necessary and logical to postulate a displacement spike mechanism to account for the effect. The only case of irradiation induced diffusionless transformation in metals is the allo-tropic transformation of p to a tin reported by Flee-man and Dienes. 3 They found that neutron irradiation markedly decreases the incubation time for transformation, but the mechanisnl is not well understood. Another diffusionless transformation which one might expect to be influenced by neutron irradiation is the martensite transformation. This transformation is known to be sensitive to strain, structural hardening, and the presence of imperfections.6,7 Since the transformation is diffusionless, one also

Jan 1, 1960

By Herbert Hoover

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplish-ing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowl-edge the very great willingness of these out-standing scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is pos-sible to run a qualitative and quantitative analysis of an unknown mixture of hydro-carbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to com-plete an analysis. Furthermore, it is un-necessary to separate a mixture of gases into its various components in order to complete the analysis.

Jan 1, 1940

By G. Sachs, G. Espey

Simple methods can be used for the determination of the residual stresses in thin walled tubing if the stresses consist of high tensile stresses at the one surface and high compressive stresses at the other surface. Such a stress distribution is approximated in sunk tubing and in deep-drawn shells. It is possible to cut sections from such articles in such a manner that a major part of the residual stress is relieved by a bending of the Part that is separated from the adjacent metal. The circumferential stress is evaluated from the change in diameter D, occurring on splitting a length of tubing (Fig. Ib) or from deflection resulting from the cutting out of a circumferential tongue (Fig. Ia) .6 The bending moment M released by such a flexure is. M - EI (I-I) = EI R1-R0 I - u2(R0-R1) I -V2 R0XR1 where E = modulus of elasticity, v = Poisson's ratio, I = moment of inertia of the section, R0 =. mean radius before splitting, R1 = mean radius after splitting. The release of this bending moment corresponds to the release of stresses, which, in a thin section, vary linearly from one surface to the other, and have the following value in a particular fiber a certain distance (x) from the surface: S = c d I - V2 x c x d 2 2 RI - R0____E (d ) R1 - R0 X R0 X R1 ~ i - u2 (2 x) Ro X R1 where C is the section modulus and d is the thickness of the section, the ratio M:C being d: 2 for a rectallgular section.* The maximum stress values at the surfaces are. Smax = +E X d X R1-R0 I — u2- 2 R0 X R1 For most purposes the simpler equations: EXd AD1 = ± I - u2 x dm2 and will be satisfactory, where D,, is the aver. age of the mean diameters of the tubing

Jan 1, 1942

By G. Sachs, G. Espey

Simple methods can be used for the determination of the residual stresses in thin walled tubing if the stresses consist of high tensile stresses at the one surface and high compressive stresses at the other surface. Such a stress distribution is approximated in sunk tubing and in deep-drawn shells. It is possible to cut sections from such articles in such a manner that a major part of the residual stress is relieved by a bending of the Part that is separated from the adjacent metal. The circumferential stress is evaluated from the change in diameter D, occurring on splitting a length of tubing (Fig. Ib) or from deflection resulting from the cutting out of a circumferential tongue (Fig. Ia) .6 The bending moment M released by such a flexure is. M - EI (I-I) = EI R1-R0 I - u2(R0-R1) I -V2 R0XR1 where E = modulus of elasticity, v = Poisson's ratio, I = moment of inertia of the section, R0 =. mean radius before splitting, R1 = mean radius after splitting. The release of this bending moment corresponds to the release of stresses, which, in a thin section, vary linearly from one surface to the other, and have the following value in a particular fiber a certain distance (x) from the surface: S = c d I - V2 x c x d 2 2 RI - R0____E (d ) R1 - R0 X R0 X R1 ~ i - u2 (2 x) Ro X R1 where C is the section modulus and d is the thickness of the section, the ratio M:C being d: 2 for a rectallgular section.* The maximum stress values at the surfaces are. Smax = +E X d X R1-R0 I — u2- 2 R0 X R1 For most purposes the simpler equations: EXd AD1 = ± I - u2 x dm2 and will be satisfactory, where D,, is the aver. age of the mean diameters of the tubing

Jan 1, 1942

By Frank G. Miller

The lower cost of producing oil from naturally flowing wells compared with pro-luction costs accruing from artificial lifting methods has stimulated much research, rith the joint purpose of extending the natural flowing life of wells and of increas-ng the productivity of small wells. The iboratory investigation described herein was made to determine the effect of a lotted liner on the pressure gradient in the icinity of the wall of a flowing well. Flow estrictions caused by the liner induce nergy losses between the oil-bearing for-lation and the inside of the liner, which lay be reduced by improved liner design, nd thereby the flow capacity of wells may e increased. These losses have been evalu-ted for rectangular slots of different sizes, nd means are suggested for reducing them. The dearth of information concerning the ature of the flow of fluids from uncon-slidated sands through small openings in he walls of. pipes—as represented by the ow of oil from an oil sand into a slotted ner—is acknowledged. Although the bene-ts to be realized by operators through the se of optimum liners is just beginning to e recognized generally, Coberlyl in 1937 ointed out that the functioning of screen is is an important factor in the pro-uction of oil. From his study on the :lection of size of oil strings for wells in California, Parks2 concluded, in part, that the perforated section of the oil string deserves continued study, especially with respect to the selection of perforations. The growing use of gravel packing resulting from certain research findings lends even more significance to the problem of selecting optimum liners, as the application of these methods usually requires slotted liners or other kinds of perforated liners. The present study was made to obtain further information for the guidance of engineers and operators in selecting slotted liners and to develop a laboratory method that may be used in analyzing possible pressure conditions surrounding most types of perforated casings used in producing oil wells, so that the present inadequate fund of knowledge on this important subject may be expanded. Discussion of ProbleM At the beginning of the investigation the following assumptions were made regarding bottom-hole conditions of a producing oil well and the oil-sand reservoir it penetrates: (I) Conditions of steady-state flow exist, (') a a homogeneous liquid is being produced) (3) no contaminating material (such as drilling fluid) is present between the liner and the face of the oil-bearing sand, (4) the well is vertical and completely penetrates a horizontal sand stratum of uniform thickness occurring between two impermeable strata, and (5) the flow is wholly viscous. If the foregoing assumptions are made, with the added requirements that the sand

Jan 1, 1941

By Frank G. Miller

The lower cost of producing oil from naturally flowing wells compared with pro-luction costs accruing from artificial lifting methods has stimulated much research, rith the joint purpose of extending the natural flowing life of wells and of increas-ng the productivity of small wells. The iboratory investigation described herein was made to determine the effect of a lotted liner on the pressure gradient in the icinity of the wall of a flowing well. Flow estrictions caused by the liner induce nergy losses between the oil-bearing for-lation and the inside of the liner, which lay be reduced by improved liner design, nd thereby the flow capacity of wells may e increased. These losses have been evalu-ted for rectangular slots of different sizes, nd means are suggested for reducing them. The dearth of information concerning the ature of the flow of fluids from uncon-slidated sands through small openings in he walls of. pipes—as represented by the ow of oil from an oil sand into a slotted ner—is acknowledged. Although the bene-ts to be realized by operators through the se of optimum liners is just beginning to e recognized generally, Coberlyl in 1937 ointed out that the functioning of screen is is an important factor in the pro-uction of oil. From his study on the :lection of size of oil strings for wells in California, Parks2 concluded, in part, that the perforated section of the oil string deserves continued study, especially with respect to the selection of perforations. The growing use of gravel packing resulting from certain research findings lends even more significance to the problem of selecting optimum liners, as the application of these methods usually requires slotted liners or other kinds of perforated liners. The present study was made to obtain further information for the guidance of engineers and operators in selecting slotted liners and to develop a laboratory method that may be used in analyzing possible pressure conditions surrounding most types of perforated casings used in producing oil wells, so that the present inadequate fund of knowledge on this important subject may be expanded. Discussion of ProbleM At the beginning of the investigation the following assumptions were made regarding bottom-hole conditions of a producing oil well and the oil-sand reservoir it penetrates: (I) Conditions of steady-state flow exist, (') a a homogeneous liquid is being produced) (3) no contaminating material (such as drilling fluid) is present between the liner and the face of the oil-bearing sand, (4) the well is vertical and completely penetrates a horizontal sand stratum of uniform thickness occurring between two impermeable strata, and (5) the flow is wholly viscous. If the foregoing assumptions are made, with the added requirements that the sand

Jan 1, 1941

By Shueling Woo, Charles S. Barrett, Robert F. Mehl

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

By J. G. Morlet, A. R. Troiano, H. H. Johnson

Delayed failure in steel occurs by controlled initiation and growth of a crack. The incubation period for crack initiation was measured. Crack initiation and Propagation are controlled by interaction between hydrogen concentration and triaxial stress state. The incubation period results from stress-induced diffusion of hydrogen to the point of crack initiation. THIS paper describes the phenomenon of delayed failureland the kinetics of crack initiation and propagation in uniformly hydrogenated steel. The investigation was prompted by service failures of high-strength-steel components at applied stresses far below the conventional yield strength, after the part had successfully sustained equal or higher stresses for an extended time interval. This delayed failure phenomenon, often termed static fatigue, is associated1 with the presence of hydrogen. This is not surprising, since the voluminous literature on flaking and hydrogen embrit-tlement demonstrates that hydrogen may exert a potent embrittling influence. Flakes, or internal hairline cracks in alloy-steel forgings, are related to the presence of hydrogen retained from the steel-making process.2 On the other hand, embrit-tlement arises from hydrogen introduced during surface treatments such as acid pickling or electroplating. Laboratory delayed failures have been induced in notch specimens of 4340 steel by electrolytic charging of the specimen surface with hydrogen and subsequent static stressing.l,4,5 Static fatigue was observed over a wide range of applied stresses; however, failure did not occur below a critical applied stress, designated as the static fatigue limit. In this instance the extended time for failure resulted primarily from the macroscopic redistribution of hydrogen. A crack formed to the depth of the hydrogen enriched "case* upon loading; further crack growth naturally awaited diffusion of hydrogen into the material ahead of the crack. The crack-propagation rate was therefore controlled primarily by the macroscopic diffusion of hydrogen into the specimen interior during the test. Thus, in this instance static fatigue was associated with the movement of a gross concentration gradient. However, delayed failure in steel of uniform hydrogen concentration is of greater fundamental interest, as well as commercial significance. With a homogeneous hydrogen distribution a different mode of delayed failure might be expected. As the heterogeneous hydrogen distribution became more uniform,4,5 the initial crack-propagation rate decreased markedly and, in fact, what appeared to be an incubation period for crack initiation was observed. However, the macroscopic concentration gradient precluded an accurate evaluation of these observations. Although the existence of an incubation period, up to this time, has not been established definitely, it is not amiss to point out some implications of the concept. It is of interest in all hydrogen-induced embrittlement phenomena, such as flaking, delayed failure, and hydrogen embrittlement. Much discussion has centered around the possibility of an

Jan 1, 1959

By R. C. Buehl, M. B. Royer

A three ton per day blast furnace using blast temperatures up to 2200°F was operated to recover manganese from open-hearth slag and manganiferous iron ore. The spiegel product containing 12 to 24 pct Mn was blown in a basic converter to high manganese oxide slag as described in the paper which follows this one. HE steel industry, which uses over 900,000 short tons of contained manganese yearly, depends on the maintenance of supplies of manganese from foreign sources such as India, Gold Coast, and Union of South Africa. Domestic ores furnish less than 10 pct of the yearly requirements of metallurgical ores and, unfortunately, the United States has no large, or even moderate, grade deposits that could supply a major portion of the requirements for many years. It may be necessary to obtain manganese from low grade materials, even though the cost is appreciably higher than when imported ores are used. An American Iron and Steel Institute questionnaire prepared in 1949 revealed the startling fact that open-hearth slags contained about as much manganese as is imported annually. The quantity of slag produced each year by integrated steel plants (not including cold-melt shops) and the manganese contained in the slag follows: Flush slag, 4,500,000 net tons a year containing 408,000 net tons Mn; tap slag, 7,230,000 net tons a year containing 364,000 net tons Mn; for a total of 772,000 net tons Mn. Some of this slag is returned to blast furnaces but about 75 pct would be available for the recovery of manganese. In several decades, when many of the present sources of high manganese ores have been depleted, open-hearth slag and manganiferous iron ore may become the major source of the manganese required for steel production. In 1948, manganese-ore imports from the U.S.S.R. were 427,000 net tons or 34 pct of the foreign ore. Imports from this source were only 81,000 tons in 1949. It became evident that adequate stockpiles of manganese could not be accumulated for many years. The Bureau of Mines initiated an extensive research program on methods for increasing domestic production of manganese and entered into a cooperative agreement with the American Iron and Steel Institute for recovering manganese from open-hearth slags whereby the Institute provided additional research funds and trained operating personnel. Description of Process and Equipment Numerous pyrometallurgical and hydrometallur-gical processes and combinations of the two can be applied to the recovery of manganese from open-hearth slag and manganiferous iron ore. The process being developed at the Pittsburgh Station of the Bureau of Mines consists of: 1—Reduction of open-hearth slag in a blast furnace to recover the iron and manganese as spiegel-eisen with 12 to 24 pct Mn. 2—Selective oxidation of the manganese from the blast-furnace metal in a basic-lined converter to produce a high manganese slag with up to 60 pct Mn content, which is a synthetic ore for the production of ferromanganese. This process has the advantage over other processes in that the equipment which would be used, such as blast furnaces and converters, has been highly

Jan 1, 1953

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.'' The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-' "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By J. Chipman, N. J. Grant, B. M. Shields

The vacuum tin-fusion method of analysis for hydrogen, developed by Carney, Chipman, and Grant, has been modified to permit the analysis of the evolved gases for hydrogen by means of a thermal conductivity cell. A properly prepared sample can be analyzed in 10 min with a probable error of ±0.12 ppm. A study of various methods for storage of hydrogen samples shows that samples can be safely held in a dry ice-acetone bath as long as six days. Storage in liquid nitrogen is necessary for samples to be held one week or more. HE vacuum tin-fusion method, as developed by I- Carney, Chipman and Grant,' is the only analytical procedure which has shown promise of being fast enough for use in the control of hydrogen during steelmaking. It was felt that further simplification and faster speed of operation could be effected by the use of thermal conductivity measurements for analysis of the gases evolved in the tin-fusion method. The application of conductivity measurements to the tin-fusion method is possible because: 1—the evolved gas is essentially a mixture of hydrogen, nitrogen and carbon monoxide with a hydrogen content usually over 50 pct, 2—the evolved gas is collected at a relatively low pressure, and 3— the thermal conductivities of CO and N2 are practically identical while that of hydrogen is very much greater. The major part of this research program was devoted to the construction and calibration of a vacuum tin-fusion apparatus which analyzes the evolved gases for hydrogen by means of a thermal conductivity cell. The second phase of the problem was associated with the development of a procedure for storage of samples prior to analysis. With the rapid quenching method for hydrogen sampling,' which seems to be the most practical for steel mill use, it is necessary that the samples be stored safely during the interval between sampling and analysis if the hydrogen content of the molten metal is to be maintained in the supersaturated solid samples. The thermal conductivity bridge has been used for a number of years in the analysis of certain gas mixtures. An elementary discussion of the theory and practice of gas analysis by thermal conductivity measurements is given by Minter.3 A more comprehensive discussion of the theory and of the various measuring circuits is presented by Daynes.' A complete knowledge of the theory and properties of the thermal conductivity of gases and gaseous mixtures can be gained by a study of the standard textbooks on the kinetic theory of gases."' The existing data on the thermal conductivity of single gases are reviewed by Hawkins: that for a number of binary gas mixtures by Daynes' and Lindsay." The thermal conductivity method may be applied to the determination of the composition of a binary mixture if: 1—the thermal conductivity of the mixture varies monotonically with composition, and 2— the two gases have measurably different thermal conductivities. The greater the difference between the two gases, the greater the sensitivity of the method.10 he method is applicable to the analysis of multicomponent mixtures when all of the gases in the mixture except one have nearly the same thermal conductivity. Fortunately, the mixture of hydrogen, nitrogen, and carbon monoxide evolved by the tin-fusion analysis' falls in this latter classification. The thermal conductivities of nitrogen and carbon monoxide are practically equal; and the thermal conductivity of hydrogen is approximately seven times that of the other two. Therefore, the thermal conductivity of a gaseous mixture of hydrogen, nitrogen, and carbon monoxide at known temperature and pressure can be related directly to the percentage of hydrogen in the mixture by suitable calibration. Usually the thermal conductivity of a mixture of gases is measured at atmospheric pressure where the thermal conductivity is independent of pressure over a wide pressure range. At very low pressures (below 1 mm Hg), the thermal conductivity of gases varies with the pressure. This phenomenon has been utilized in the Pirani vacuum gage for the measurement of pressures in the range of 10" to 10-0 mm of mercury.= Very little has been published concerning the variation of thermal conductivity with pressure at intermediate pressures between 1 mm Hg and 1 atm. However, preliminary measurements indicated that the thermal conductivities did vary with pressure over the range of pressures (up to 10 mm Hg) at which gases are delivered from the vacuum pump. Therefore, the calibration of the thermal conductivity cell had to be planned to include the effects of both gas composition and pressure. Such a calibration chart is shown in Fig. 4. Most industrial applications of the thermal conductivity method of gas analysis have used a compensated Wheatstone bridge circuit containing two

Jan 1, 1954

By Per Kofstad, Hallstein Kjöllesdal

The oxidation behavior of niobium (columbium) has been studied in the temperature range 500° to 1200°C and at oxygen pressures of 760,100, 10, 1, and 0.1 mm of Hg. The work comprises kinetic studies of the oxidation as well as structural investigations of the oxidized specimens by means of X-ray diffraction, electron diffraclion, electron microscopy, and metal1ographic techniques. The oxidation reaction has a highly irregular temperature dependence and is unusually sensitive to changes in the oxygen pressure. The complex oxidation behavior is suggested to be due to formation of different Nb2O5 modifications in different temperature regions. During oxidation oxygen is also dissolved in the metal. Formation of oxide whiskers take place on the oxide surface at temperatures above approximately 800°C. VARIOUS aspects of the oxidation of niobium have been studied.l-12 The investigations show that niobium has a complex oxidation behavior, and the oxidation

Jan 1, 1962

By M. D. Hassialis, A. F. Taggart

ark' observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility-product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith' The experimental work comprised accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1947