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By John Chipman, Carl F. Floe

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By Arthur L. Christenson, Clarence E. Jackson

In the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition* may be corrected to the grain size observed in an actual weld? or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.8 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2Ioo°F. has been used. In studies of the end-quench hardenability specimen quenched from 2Ioo°F. instead of from a lower temperature of I7OO°F., it is impor-TaiiT to ascertain The relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6'7 French has considered this effect from both theoretical and experimental aspects. In French's studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been propped: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1944

By James A. Crookston, William D. Fitzpatrick

Committee C-8 of the American Society for Testing and Materials defines "Refractories" as "Material, usually nonmetallic, used to withstand high temperature," and it defines the term "Refractoriness" thus, "In refractories the capability of maintaining the desired degree of chemical and physical identity at high temperatures and in the environment and conditions of use." The ability to withstand high temperatures is critical to classifying a material as a "refractory." However, as the foregoing definition of "refractoriness" implies, the refractory material may be subjected to and is expected to resist not only high temperatures but a variety of other destructive forces incident to its use. These include abrasion, impact, thermal shock, chemical attack, and high level loads at high temperatures. The various industrial applications of refractories represent an infinite variety of combinations and degrees of severity of these destructive forces, including high temperatures. Naturally, such a variety of application conditions leads to a need for a wide variety of refractory products to satisfy those conditions. The number of refractory products available is great enough that some form of classification is necessary to a discussion of refractories. Refractories may be classified in several ways, but the most suitable one is based on their general compositions and to lesser degrees on their physical condition and distinctive properties. The primary types of brick include aluminosilicate brick (fire clay and alumina), basic brick (magnesia and chrome ore, alone and in various combinations), silica brick, insulating brick, and special refractories (carbon, Sic, ZrO,, zircon, borides, and nitrides). Brick are, of course, preformed and are usually heat treated at high temperatures before use, but are in some instances unburned and/or chemically bonded, including the relatively new class of tar-bonded magnesia and/or dolomite brick. In addition to preformed refractories, another broad category includes the so-called specialty refractories, which are usually made in the same types as itemized for brick-bonding mortars and high temperature cements, hydraulic setting castables or refractory concrete, plastic firebrick, and ramming mixes. Refractory grains, such as fire clay and high alumina calcines, dead-burned magnesite and periclase, and dead-burned dolomite are also considered refractory products. Brick are also classified on the basis of physical dimensions, as standard sizes and special shapes. The standard sizes are those which are of definite shape and design and are designated as 9 x 4 ½ x 2 ½ in. and 9 x 4 ½ x 3 in. straights and series. All other brick of non- standard sizes are referred to as special shapes. These come about as a result of a particular need for a given furnace or for a particular application.

Jan 1, 1975

By H. Bloom, H. E. Hawkes

STREAMS and rivers are the principal channels into which the weathering products of rocks and their contained ores are funneled. The inorganic load of a stream system is a crude sample of all the earth materials in the drainage basin of the stream, and the heavy mineral assemblage of sediments is one of the oldest and most successful guides to certain kinds of bedrock ore in unexplored terrain. Early application of this method was made possible by the ease of separation and identification of heavy minerals in the field with the simplest equipment. Water analysis for traces of base metals became a practical possibility about eight years ago with the development of rapid chemical tests that could be carried out at the field site.' , Since that time the water method has been widely used in mineral reconnaissance, and a substantial number of discoveries have been reported. Here again, the techniques developed for this work were relatively simple and could be performed easily at the field site. Sediment analysis by chemical methods, as distinguished from mineralogical, has received less at- tention. Some experimental work was done by Lovering and others," but to the authors' knowledge, chemical analysis of sediment samples has not been used in routine exploration programs until very recently. In spite of the obvious promise of this method, it was not pursued vigorously because of the lack of a simple and portable chemical test that could be used conveniently at the field site or in a field camp. Procedures that had been developed for trace analysis of soils all called for a rigorous chemical attack with hot acids—tests more conveniently applied in processing large volumes of routine soil samples at an established field headquarters. Recently an extremely rapid and simple test was developed by Bloom.4,5 The extractant used in this procedure is a cold solution of ammonium citrate. Elements measured are the heavy metals, principally zinc, lead, and copper. This method differs from the established procedures for soil analysis in that it measures only a small fraction, about 5 pct, of the total metal content of the sample. It has been found, however, that the significant pattern of metals in the sediments of streams below a base-metal deposit can be brought out as well and sometimes better by this simple cold-extraction procedure than by the more tedious methods requiring hot acids. To understand fully the significance of the relation between the readily extractable and the total

Jan 1, 1957

By C. G. Dunn

Nuclei that are formed during the recrystallization of a grain following plastic deformation generally have orientations that differ from the original. This aspect of recrystallization may be described in terms of orientation changes. It was shown previously, in an investigation on recrystallization in silicon ferrite,&apos; that the observed orientation changes were highly improbable on a chance basis, and that some mechanism must be involved. Analysis showed that the data could be satisfactorily classified into the smaller of two subclasses† of the 36 third-order twin transformations. No attempt was made at that time to classify the data within the special class of 12 third-order twin transformations, although results did indicate a greater probability for some of them to occur. A classification of this type would be more valuable, of course, with more data on orientation changes per old deformed grain. The present work fulfills this condition to some degree and also extends the scope of the investigation to include the effects of original orientation and the amount of plastic deformation. The effect of original orientation is of considerable interest because of the known effects of orientation on plastic deformation, particularly with regard to degree of fragmentation and the formation of deformation bands, and because the orientations produced by deformation should influence the orientations obtained through recrystallization. Barrett and Levenson2 reported that single crystals of iron deformed in the range 82 to 97 per cent could be put into three general classes; namely, crystals in class I maintained a reasonably sharp single orientation, those in class 2 transformed into two distinct orientations, and those in class 3 changed into a large number of major and minor orientations. Something similar would be expected for silicon ferrite crystals, and verification of this for a few cases of types class I and class 2 deformation has been reported elsewhere3 for single crystals of silicon ferrite cold-rolled in the range 10 to 20 per cent. As an example of class 2 deformation, it was shown that a crystal of silicon ferrite cold-rolled in a (110) plane in a <100> direction developed two layers, or deformation bands differing in orientation. When this happens it is possible to etch away one band and leave a single structure for use in studying the orientation changes that occur during recrystallization. when preferred crystal orientations are obtained in recrystallization, it is not particularly necessary to evaluate groups of common orientation, as was done previously (ref. I, Table 6); but an

Jan 1, 1947

By J. Russ, C. L. Clark

For many years attempts have been made to develop a laboratory test that would serve to indicate the proper temperatures to be used in the various hot-working applications to which metals may be subjected as they are being processed from the cast ingot to the desired finished products. That these attempts have not been very successful is indicated by the fact that most of the temperatures in use today in these operations have been developed over a period of years by trial and error. In other words, the selection of the proper temperatures for the hot-working of metals is generally an art rather than a science. Our knowledge with respect to the behavior of metals at elevated temperatures has been greatly extended during the past several years. While most of the work in this field has been done at proposed operating temperatures of equipment, rather than at processing or fabricating temperatures, one outstanding fact has been developed, which is applicable to the entire high-temperature range; that is, that the rate of deformation to which the metal is subjected is of the same order of importance as the temperature. The failure to properly recognize this fact has greatly retarded the development of a suitable laboratory test for determining hot-working temperatures. Influence of Rate of Deformation on High-temperature Properties It is not the intent of this paper to survey all the work that has been done On the effect of deformation rate On the properties of metals. The importance of this factor, however, was shown by Zay Jeffries&apos; as early as 1919, when he called attention to the existence of the so-called equicohesive temperature and to the effect of certain factors on the location of this temperature&apos; Fig. I is a diagrammatic sketch showing the effect of temperature On the relative strength of the crystals and grain boundaries and the type of fracture that will res depnding On the location of the test, or Or temperature with respect to the equicOhesive temperature. Since the type fracture varies, it also follows that at temperatures below the equicohesive temperature the major deformation occurs in the grains: while at temperatures above, the deformation results either from the movement of the grains with respect to each other or recrystallization of the strained material occurs almost instantaneously, producing new crystals at the fracture. As previously indicated, it is an established fact that the position of this equicohesive temperature for any given metal is dependent On the deformation rate&apos; For example, in 0.15 per cent plain carbon steel the location of this temperature under

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 C. G. Dunn

Nuclei that are formed during the recrystallization of a grain following plastic deformation generally have orientations that differ from the original. This aspect of recrystallization may be described in terms of orientation changes. It was shown previously, in an investigation on recrystallization in silicon ferrite,&apos; that the observed orientation changes were highly improbable on a chance basis, and that some mechanism must be involved. Analysis showed that the data could be satisfactorily classified into the smaller of two subclasses† of the 36 third-order twin transformations. No attempt was made at that time to classify the data within the special class of 12 third-order twin transformations, although results did indicate a greater probability for some of them to occur. A classification of this type would be more valuable, of course, with more data on orientation changes per old deformed grain. The present work fulfills this condition to some degree and also extends the scope of the investigation to include the effects of original orientation and the amount of plastic deformation. The effect of original orientation is of considerable interest because of the known effects of orientation on plastic deformation, particularly with regard to degree of fragmentation and the formation of deformation bands, and because the orientations produced by deformation should influence the orientations obtained through recrystallization. Barrett and Levenson2 reported that single crystals of iron deformed in the range 82 to 97 per cent could be put into three general classes; namely, crystals in class I maintained a reasonably sharp single orientation, those in class 2 transformed into two distinct orientations, and those in class 3 changed into a large number of major and minor orientations. Something similar would be expected for silicon ferrite crystals, and verification of this for a few cases of types class I and class 2 deformation has been reported elsewhere3 for single crystals of silicon ferrite cold-rolled in the range 10 to 20 per cent. As an example of class 2 deformation, it was shown that a crystal of silicon ferrite cold-rolled in a (110) plane in a <100> direction developed two layers, or deformation bands differing in orientation. When this happens it is possible to etch away one band and leave a single structure for use in studying the orientation changes that occur during recrystallization. when preferred crystal orientations are obtained in recrystallization, it is not particularly necessary to evaluate groups of common orientation, as was done previously (ref. I, Table 6); but an

Jan 1, 1947

By Harold W. Scott

Geological Engineering is now a recognized curriculum in most of the mining schools in United States. Graduates of these schools are scattered over the face of the earth, participating in exploration and mining enterprises of diverse character. They are engaged in the mapping of new mineral deposits, in the extension of old deposits, the estimation of reserves, microscopic analysis, and in the direction of exploitation and conservation of man&apos;s natural resources. The training of men qualified to carry out these technical phases of modern industry has fallen essentially to the mining schools. For the most part they have met the demand for technically trained men in the mineral industries. Schools Offering Geological Engineering Degree The mining schools have passed through the early stages of their development and at the present offer varied curricula covering the fields of geological engineering, mining engineering, and metallurgical engineering. Usually a B.S. degree is offered in any of these three fields. However, .there has been some tendency of recent date on the part of the Engineers Council for Professional Development to question the validity of a B.S. degree in Geological Engineering. The of this paper is to examine the curricula as offered in the mining schools, to evaluate their engineering content, and to propose minimum requirements for the degree of Geological Engineering in the mining industry. The curricula of eight institutions that offer the degree of B.S. in Geological Engineering or Mining Geology have been studied (Table 1). All except one of these schools are in or near mining districts and occur west of the Mississippi River. They are all state-supported institutions that have come into existence because of the state&apos;s need for technically trained men. A graduate from .a mining school is called upon to perform many duties of a technical nature. His initial task may be to make a geological map of a mine or the surface above, but before the map is finished he may be asked to take over the responsibility of getting the ore "on top." And finally, he might find it essential to know how to mill the ore. Certainly this requires technically trained men and the mining schools are essentially the organizations to do the job. The departments of geology in these schools are training geological engineers. Field Of Geology If we were to accept the opinions of some writers, we would be forced to conclude that all geology departments offer only a "dilettante" variety of subjects.

Jan 1, 1944

By C. L. Clark, J. Russ

For many years attempts have been made to develop a laboratory test that would serve to indicate the proper temperatures to be used in the various hot-working applications to which metals may be subjected as they are being processed from the cast ingot to the desired finished products. That these attempts have not been very successful is indicated by the fact that most of the temperatures in use today in these operations have been developed over a period of years by trial and error. In other words, the selection of the proper temperatures for the hot-working of metals is generally an art rather than a science. Our knowledge with respect to the behavior of metals at elevated temperatures has been greatly extended during the past several years. While most of the work in this field has been done at proposed operating temperatures of equipment, rather than at processing or fabricating temperatures, one outstanding fact has been developed, which is applicable to the entire high-temperature range; that is, that the rate of deformation to which the metal is subjected is of the same order of importance as the temperature. The failure to properly recognize this fact has greatly retarded the development of a suitable laboratory test for determining hot-working temperatures. Influence of Rate of Deformation on High-temperature Properties It is not the intent of this paper to survey all the work that has been done On the effect of deformation rate On the properties of metals. The importance of this factor, however, was shown by Zay Jeffries&apos; as early as 1919, when he called attention to the existence of the so-called equicohesive temperature and to the effect of certain factors on the location of this temperature&apos; Fig. I is a diagrammatic sketch showing the effect of temperature On the relative strength of the crystals and grain boundaries and the type of fracture that will res depnding On the location of the test, or Or temperature with respect to the equicOhesive temperature. Since the type fracture varies, it also follows that at temperatures below the equicohesive temperature the major deformation occurs in the grains: while at temperatures above, the deformation results either from the movement of the grains with respect to each other or recrystallization of the strained material occurs almost instantaneously, producing new crystals at the fracture. As previously indicated, it is an established fact that the position of this equicohesive temperature for any given metal is dependent On the deformation rate&apos; For example, in 0.15 per cent plain carbon steel the location of this temperature under

Jan 1, 1947

By Norris Johnston, Carrol M. Beeson

For many years the permeability of reservoir sands has been measured by flowing air through a cleaned and dried core sample. This differs from the true reservoir permeability in one important respect: the rock particles in the reservoir are surrounded by interstitial water, not air, and their physical shape and condition of hydration are greatly dependent thereon. Permeability as defined must be measured with a single-phase fluid. Since no means exist for removing the oil and gas from a core sample by simply flowing water through it, the sample must be cleaned and then resatu-rated with water before testing. The present discussion attempts to show that after the cleaning process a considerably different permeability is determined with salt or fresh water than is obtained with air. The postulate is made that the salt-water permeability is probably closer to the true reservoir permeability than is the measurement with air. This is discussed in relation to both physically possible and economically feasible measuremerits. Data On more than 1200 core samples are given to show the nature of the effects observed, and a plea is made for others to consider water permeability measurements as a routine necessity, eventually replacing air permeability in regions where the differences are great. Introduction Permeability is defined1 as a "a measure of the capacity of a porous medium to transmit fluids, when there is no interaction between the solids and the fluid." Darcy&apos;s law of liquid flow in porous media states: kA?P QµL/A?L [I] where Q represents milliliters of liquid of viscosity p centipoises passed per second through a porous medium of permeability k darcys and cross-sectional area A sq. cm. under a pressure gradient ?P/L atmospheres per centimeter, the flow being understood to be laminar or viscous, not turbulent. This equation defines the darcy. For the case of radial flow in a uniform sand, such as usually exists in the neighborhood of a well in an oil or gas sand, Darcy&apos;s law becomes:2 Here h is the net sand thickness in feet, Pe and Pw are pressures at the drainage radius4 and well radius, and re and rw are these radii, respectively. The productivity index3 is defined as the barrels of liquid produced per day per pound per square inch mean pressure differential between ferences and well bore, and is thus: By further definition, the specific productivity index is: or in terms of practical units, and allowing for shrinkage:

Jan 1, 1945

By J. Rogers, H. F. A. Hergt, K. L. Sutherland

IN 1938 Ralston4 reviewed the many attempts to find a satisfactory collector for the separation of cassiterite from its ores and in 1944 Dean and Ambrose2 summarized some further attempts. Generally, soaps and amines are effective but nonselective collectors. We have discovered that reagents containing either the polar group -SO4- or _S03- are excellent collectors for cassiterite and promise to be selective.1 The response to these reagents of cassiterite and of minerals commonly associated with it was studied, using the captive-bubble technique. Using these fundamental data, the practicability of separation and concentration of tin was investigated by flotation tests in a 2000gram Denver cell. EXPERIMENTAL METHODS Reagents All inorganic reagents were of Analar grade. The preparation and purification of sodium cetyl sulphate, cetyl trimethyl-ammonium bromide, laurylamine and cetylamine have been previously described.5 The other collectors were commercial surface-active agents, which were used without purification. Tests Captive-bubble Tests and Cylinder Flotation Tests have been previously described.5-10 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible, by a cross, and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, and the experimental results are indicated by a square. The curves show the limits of composition of solutions in which flotation in a cell would be possible but many factors other than those considered in these tests determine recovery and grade of a given mineral in practice. Flotation Tests in 500 and 2000-gram Denver Submachines.--Melbourne tap water, containing 12 parts calcium, 6 parts

Jan 1, 1947

By Carl F. Floe, John Chipman

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry&apos;s law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts&apos; law. It may be recognized as a special case of Henry&apos;s law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By J. E. Hilliard

A procedure is described for determining, from measurements on a section, the moments of any degree n (i.e., the mean value of Dn, where D is a linear dimension) of the size distribution of particles (or grains) in an opaque sarnple. The analysis is applicable to particles of alnzost any shape and to any mixture of shapes. However, if absolute values of the wloments are required, it is necessary to know what shapes are present and the relative frequency of their occurrence. In addition, certain shape-dependent parameters have to be evaluated before the formulas can be used. The measurement required is the distribution of intercept lengths. This can be determined either visually or with an automatic scanning instrument. Corrections me derived for the bias due to instrumental end effects. The proposed analysis has the following advantages over existing ones: 1) Confidence limits are easily estimated for the measured properties or, conversely, the number of counts required to achieve a given accuracy can be determined. 2) The analysis is not restricted to particles of a special shape. 3) The error resulting from any known degree of departure of the actual from the assumed particle shape can be estimated. 4) The computations are simple and, apart from a change in constants, are independent of particle shape. 5) The number of particles per unit volume can be determined by a simple counting procedure. MANY procedures have been described for determining the size distribution of particles from measurements on a section (or plane of polish). They differ from one another in the property measured on the section (radius, intercept length, profile area) and in the method used for the numerical solution of the integral equation relating the property to the particle size distribution. However, all existing analyses share at least two of the following disadvantages. 1) They are limited to a particular shape of particle (usually spherical). 2) It is very difficult to determine how the statistical sampling error is propagated into the computed size distribution. The investigator thus has no means of knowing the reliability of his result and, what is of equal concern, he is unable to estimate how many measurements are required to obtain a result of the required accuracy. 3) It is also difficult to assess the error resulting from any deviation between the actual and assumed particle shape. The foregoing limitations stem from the complex relationship between the particle size distribution and the distribution of the property measured on the section. As will be shown, they can be avoided by defining the size distribution in terms of discrete parameters

Jan 1, 1969

By Arthur L. Christenson, Clarence E. Jackson

In the establishment of the relationship between weldability and hardenability, two methods have been employed in correcting for the grain growth produced in the heat-affected zone: first, the hardenability calculated from chemical composition* may be corrected to the grain size observed in an actual weld? or, second, a hardenability test may be made on the steel quenched from a temperature high enough to produce a grain size comparable to that found in the heat-affected zone.8 In order to obtain grain sizes in the end-quench hardenability bar comparable to those resulting in the base metal from the welding cycle, a quenching temperature of 2Ioo°F. has been used. In studies of the end-quench hardenability specimen quenched from 2Ioo°F. instead of from a lower temperature of I7OO°F., it is impor-TaiiT to ascertain The relative cooling rates for various distances along the bar. It is a question as to whether the cooling occurs at the same rate or whether there is any significant difference from the standard cooling-rate curve published by Jominy and confirmed by others.4,5 This paper reports experimental evidence concerning the effect of quenching temperature on the cooling rates in the end-quench hardenability test. The effect of quenching temperatures on cooling rates has been studied by a number of investigators.6&apos;7 French has considered this effect from both theoretical and experimental aspects. In French&apos;s studies on complete quenching of spheres and rounds, an increase in the quenching temperature caused an increase in the cooling rate at 720°C. at the center of the specimen. The center cooling velocity also has been shown to be dependent upon the surface per unit volume for the type of specimens studied; the velocity of cooling increases with an increase in the surface per unit volume. Three methods of indicating the rapidity of cooling of a body of metal during a quenching operation have been propped: I. The time it takes for the metal to cool from the quenching temperature to a temperature halfway between the quenching temperature and the temperature of the quenching medium (half-temperature time): Grossmann, Asimow and Urban7 justify the use of this criterion by the fact that the half-temperature time includes the temperature and time of incubation as well as the zone of formation of pearlite and, further, the data so derived accord very closely with experimental values. 2. The time interval the metal remains in a given temperature range; for example,

Jan 1, 1944

By Brison Robertson, W. P. Fishel

THE carbide-forming tendencies of the various steel-alloying elements, or their affinities for carbon, is a subject that has received considerable attention, but little more than a probable arrangement of the elements as to their carbide-forming tendencies has been proposed. The physical properties of alloy steels depend upon the relative proportions of the elements present and their combinations. One important phase of this subject is the distribution of carbon between the various elements present. The distribution of carbon between iron and other elements evidently will depend upon: (I) the affinity of each for carbon; (2) the relative atomic masses of the elements present; and (3) the possible formation of compounds between the alloying elements and iron and between the elements themselves. In ternary steels the case is simplified, especially in systems in which the element and iron form no compounds. In such systems iron and the alloying element are competing for the carbon present. In this work the distribution of carbon between titanium and iron has been studied by measuring the relative amounts of iron carbide and titanium carbide present in a series of annealed steels in which the ratio of titanium to carbon extended from 0.527 to 4.61. EXPERIMENTAL PROCEDURE Ten Fe-Ti-C alloys, weighing about 250 grams each, were prepared by melting under a vacuum, in an induction furnace, Armco iron, carbon-free ferrotitanium (25 per cent Ti), and pure carbon. Vacuum melting prevented the formation of titanium oxides and nitrides, which would complicate the problem. The melts were made in graphite crucibles lined with sintered magnesium oxide. The ingots were cooled in the furnace under a vacuum and were then completely annealed at 950°C. The determination of the amount of titanium carbide present was based upon the established insolubility of titanium carbide in boiling dilute (I :4) sulphuric acid, and the complete solubility of free titanium and titanium-iron compounds in this acid. High-carbon ferrotitanium, which had been treated to remove free Ti and Fe, was found to be completely insoluble in the acid; and the carbon-free ferrotitanium used in making the alloys was found to be completely soluble. Others 1,2 have reported the insolubility of titanium carbide in sulphuric and hydrochloric acids. Turnings from the ingots were digested with boiling sulphuric acid (1:4) until all action had ceased. The carbide residue was filtered off and analyzed for titanium, and in some cases for carbon. This represents the titanium that was united with carbon. The filtrate from the carbide residue contains the portion of the titanium that wasin solid solution in the ferrite. Titanium

Jan 1, 1944

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 L. Wahl, M. Allard, B. Trentini

REMOVAL of sulfur in steelmaking is presently a problem of utmost importance as requirements on final sulfur contents in finished steels become increasingly strict. This is in spite of often increased sulfur contents in the fuels used during the different stages of steel processing. According to local conditions or current economic factors, sulfur can be removed during one or more of the processing operations; for instance, in a blast furnace operated under high temperatures and with a high slag basicity ratio and also by means of high inputs of manganese into the burden. These methods of proceeding are, however, expensive and in contradiction with the acid practice which is gradually being developed owing to the fact that it allows coke and lime savings and usually permits an increase of productivity. In the melting-shop, desulfurization can proceed in the open-hearth or electric furnace with one or several very basic slags, or with special prefused slags (Perrin process) mixed with steels poured from the open-hearth, electric furnace, or converter. Liquid pig iron has also been treated separately before being used in the melting shop, in order to reduce high sulfur contents. This external desul-furization has been developed in Europe for the basic Bessemer Thomas process, which is again in favor owing to the great flexibility of such installations and to the fact that the steel produced is not polluted by impurities coming from the scrap. Since the basic Bessemer process, as usually practiced, has a low desulfurizing power, external desulfurization is generally carried out in ladles by means of alkalies such as soda ash. This method, which has the advantage of being simple and costing little, has only a medium desulfurizing power, which implies the necessity for repeating the operation several times when a substantial amount of sulfur has to be removed or when very low sulfur contents are desired. Thermal losses are high and there is a considerable decrease in output. Moreover, the resulting fluid and corrosive slag, which is extremely difficult to eliminate, attacks the refractory linings of the mixers and steel furnaces. Therefore, it seems necessary to devise a simple method for external desulfurization which would not only remove substantial quantities of sulfur from the hot metal coming from an acid blast furnace, but which would also bring the sulfur contents down to the low level required in the making of high quality steel and iron. Principle of the Process In this paper a new method will be described for desulfurizing hot metal. It has been perfected by

Jan 1, 1958

By Brison Robertson, W. P. Fishel

The carbide-forming tendencies of the various steel-alloying elements, or their affinities for carbon, is a subject that has received considerable attention, but little more than a probable arrangement of the elements as to their carbide-forming tendencies has been proposed. The physical properties of alloy steels depend upon the relative proportions of the elements present and their combinations. one important phase of this subject is the distribution of carbon between the various elements present. The distribution of car. bon between iron and other elements evidently sill depend upon: (I) the affinity of each for carbon; (2) the relative atomic masses of the elements present; and (3) the possible formation of compounds between the alloying and iron and between the elements themselves, In ternary steels the case is simplified, especially in systems in which the element and iron form no compounds, In such systems iron and the alloying element are competing for the carbon present. In this work the distribution of carbon between titanium and iron has been studied by measuring the relative amounts of iron carbide and titanium carbide present ill a series of annealed steels in which the ratio of titanium to carbon extended from 0.527 to 4.61. Ten Fe-Ti-C alloys, weighing about 250 grams each, were prepared by melting under a Vacuum, in an Induction furnace, Armco iron, carbon-free ferrotitanium (25 per cent Ti), and pure carbon. Vacuum melting prevented the formation of titanium oxides and nitrides, which would the the problem. The melts were made in graphite crucibles lined with sintered magnesium oxide. The ingots were the in the furnace under a vacuum and "&apos;ere then completely annealed at 950°C. The determination of the amount of titanium carbide present was based upon the established insolubility of titanium carbide in boiling dilute (1:4) sulphuric acid, and the complete solubility Of free titanium and titanium-iron compounds in this acid. High-carbon ferrotitanium, which had been treated to remove free Ti and Fe. was found to be completely insoluble in the acid; and the carbon-free ferrotitanium used in making the alloys was found to be completely soluble. Others have reported the insolubility of titanium carbide in sulphuric and hydrochloric acids. Turnings from the ingots were digested with boiling sulphuric acid (1:4) until all action had ceased. The carbide residue was filtered off and analyzed for titanium, and in some cases for carbon. This represerifs the titanium that was united with carbon The filtrate from the carbide residue contains the portion Of the titanium that was in solid solution in the ferrite. Titanium

Jan 1, 1945

By A. C. Bulnes

This paper applies the methods of statistical analysis to the interpretation of core analysis data of dolomitic limestone from the San Andres formation at Wasson and the Clearfork formation at Fullerton. Probability relationships are shown to connect the porosity and the permeability and the porosity and the fluid saturation. For example, the porosity-permeability relationship expresses the probability that a sample of porosity,f, will or will not be permeable. The over-all porosity frequency distribution of the reservoir together with the frequency curves of permeability (one for each class interval of porosity) provide a precise basis for computing the weighted average productive porosity of the reservoir for any assigned value of the minimum productive permeability. The probability that the permeability of a core specimen from Fullerton will exceed a given value appears to be dependent on the percentage porosity of the specimen, its void structure type (i.e., porosity in the qualitative sense), and the given value of the permeability. If continuous profiles of void structure type and porosity are available together with the appropriate porosity-probability of permability plots, the nes pay thickness may be estimated. The Invasion Index of a well is defined in terms of the porosity and permeability data. This index is suggested as a basis for comparing wells as regards their suitability as fluid-injection wells. Three problems of importance in the exploitation of limestone reservoirs may be stated as follows: 1. The determination of the productive porosity of the reservoir. The productive porosity is defined as f = fPVP/V [II in which Vp, is the volume of the reservoir that is sufficiently permeable to oil to give up an appreciable fraction of its original oil in place during the economic life of the reservoir; fp, is the arithmetic mean porosity of the permeable volume v*, and V is the total volume of the reservoir. 2. The determination of the number of feet of oil-bearing porous rock that will produce at a commercial rate into the well bore; i.e., the net pay thickness. 3. The choice of fluid-injection wells in a secondary recovery program. The ultimate recovery of the reservoir is proportiona1 to the productive porosity. The productive capacity of the well is proportional to the net pay thickness. The principal purpose of this paper is to show that the methods of statistical analysis when applied to core analysis data of dolomitic limestones offer a useful approach to the solution of these three problems, as well as others of importance in reservoir engineering. The use of these methods was suggested by the work of Jan Law.1

Jan 1, 1946