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By P. Somasundaran

Flotation of minerals has usually been discussed in terms of solid-liquid interfacial phenomena. This paper discusses the relative importance of phenomena such as collector adsorption at other interfaces formed between the bubble, liquid and solid. Adsorption of collector ions of various chain lengths at liquid-gas and solid-gas interfaces has been obtained. The data have been analyzed under conditions corresponding to those of flotation to show the significant role of collector adsorbed on the bubble surface in determining the bubble-mineral attachment required for flotation, and consequently to suggest consideration of this role in the development of better flotation conditions. Vacuum flotation of quartz with alkyl ammonium acetate reported in the foregoing paper1 showed that the collector chain length has an effect on flotation even at concentrations below those necessary for hemi-micelle association of the hydrocarbon chains at a solid-liquid interface. This chain length effect might be explained by the following arguments: Hydrocarbon chains find it energetically favorable to be in a medium of low dielectric constant. Considering the possibility of an iceberg structure at the solid-liquid interface, such a structure would produce a region of lower dielectric constant at the solid-liquid interface than in the liquid phase, because the dielectric constant of ice is 2 to 3,2 while that of water is 80. Depending on chain length, this difference will certainly cause even individual ions to adsorb in higher quantities at the solid-liquid interface. Another mechanism to consider is the possible formation of dimers, trimers, etc and chain length would influence this formation. But, above all, the chain length effect on flotation at concentrations of low adsorption at the solid-liquid interface could be due to the significant but often-neglected role of the collector adsorption at the bub- ble surface. Collector ions or molecules are adsorbed both at the solid-liquid interface and the liquid-gas interface. Below the concentration for hemi-micelle association at the Stern plane adjacent to the surface, the bulk of the collector ions adsorbed at the solid-liquid interface are in the diffuse part of the double layer. If such systems, where there is a gas bubble coming in contact with the solid surface, are to achieve some degree of electroneutrality, those collector ions would have to migrate from the diffuse part of the double layer to the region directly adjacent to the surface during the induction period when the bubble is making contact with the solid. The time necessary for this migration would contribute to the induction period required for creation of the solid-gas interface. It seems reasonable that the induction period could be reduced sufficiently for flotation to occur if these collector ions were carried to the surface by the bubble. In an attempt to ascertain whether or not the bubble could possibly have sufficient collector ions at its surface to meet the requirement mentioned above, the adsorption density of the collector ions at the liquid-air interface was determined. For this purpose, the surface tension of alkyl ammonium acetate solutions was determined as a function of concentration. Adsorption densities of the collector at the liquid-gas interface were calculated using the Gibbs adsorption equation: where y is the interfacial tension and ri and pi are the adsorption density and the chemical potential, respectively, of the chemical species, i. Using the convention that the adsorption density of water at the interface is zero, the following relationship is obtained for the liquid-gas interface where lg refers to liquid-gas interface and RA+ refers to the alkyl ammonium ions. For dilute solutions, rf^-wri^&rfwW [3] where C is the concentration of the collector ions in solution. l?:: can now be evaluated using Eq. 3 and surface tension measurements.

Jan 1, 1969

By C. G. Dunn, P. K. Koh

Microstructure, magnetic torque, and texture data before and after grain growth were obtained on two 3.25 pet Si-Fe specimens having initially the same cold-rolled textures and the same primary recrystallization textures. The latter textures consisted of four components, two only of which were strong; the strong components were near (120) [001] and (320) [001]. The textures of the two specimens obtained by grain growth were different. In one specimen the two weak components were converted into strong components by a secondary recrystallization process; in the other specimen the primary recrystallization texture was retained by a normal grain-growth process. The difference in behavior of the two specimens was interpreted in terms of a difference in the relative grain sizes between weak and strong components; i.e., in terms of a geometrical factor that would alter the early growth rates of grains belonging to the two weak components of the texture. Specifically the growth rate was considered as the product of two terms: a driving force and a boundary mobility. The texture changes observed are considered to favor the oriented-nucleation growth-selectivity theory more than the oriented-growth theory. WHEN primary recrystallization and grain-growth textures form as a result of annealing deformed metals or alloys, the fundamental processes involved are nucleation and growth. Knowledge, therefore, about nuclei and the factors influencing their growth is required not only for the understanding of texture development but also for its control. In the oriented-growth theory of texture formation1, 2, 3 the problem of nuclei is generally disposed of by the assumption that nuclei are available in all orientations; the theory then has to explain the final texture from the initial texture and the way boundary mobility depends on orientation. In the oriented nucleation theory of texture formation"' nuclei are considered to be present only in certain orientations but the importance of growth selectivity is still recognized. For example, the mobility of boundaries of approximately the same orientation and of the coherent type in twins is believed to be low while that of high-angle boundaries, in general, is high. Because of this the theory may be described as an oriented-nucleation growth-selectivity theory. The main feature of the oriented-nucleation theory, however, is the importance given to nuclei; i.e., how they form in specific orientations and how they grow. In the present investigation two cold-rolled single crystals were used to study the effects of growth after primary recrystallization. The cold-rolled textures and the primary recrystallization textures were determined from portions of these specimens and reported earlier.",' The two cold-rolled crystals were in the (111) [112] stable end orientation, the recrystallization textures were nearly identical and consisted of two strong components, designated M and M', which were near (120) [00l] and (320) [00l], respectively, and also some specific weak components near (111) [110] and (111) [110]. It is well recognized that a single strong component in the primary recrystallization texture may be needed for secondary recrystallization3, 5, 8 but unfortunately when this is the case the amount of material left in deviating orientation may be too small either for growth or for positive identification. The present samples proved to be almost ideal for the study of minor components and their influence on texture changes produced by growth after primary recrystallization. The results obtained are interpreted in terms of present knowledge of grain-growth processes. Experimental Procedure Two lots of silicon-iron alloy of essentially the same composition, namely, 3.25 pet Si, 0.004 C, 0.009 P, 0.010 S, 0.035 Mn, 0.070 Ni, 0.090 Cu, 0.009 Sn, with traces of A1 and Cr and the balance Fe, were converted into single crystals 0.025 in. thick and 1.25 in. wide. The orientations were predetermined by the method of reorienting a seed crystal as described elsewhere.3 pecimen 1 from one lot had the (335) [556] orientation while specimen 2 from the second lot had the (111) [112] orientation.* Both crystals were cold rolled to a reduction in thickness of 70 pet while widening approximately 20 pet. Samples of each were selected for determining 1) the cold-rolled texture, 2) the time required at

Jan 1, 1959

By J. R. Vilelia

IN accordance with the custom of this society, we are gathered here, as we have every year since 1924, to honor the memory of the eminent American metallurgist and teacher, Professor Henry Marion Howe. Unlike many of the distinguished metallurgists who have preceded me as a Howe lecturer, I cannot bring to you reminiscences of his personality, for it was not my privilege to be associated with Professor Howe, or to be directly one of his students. Yet, Professor Howe and Professor Albert Sauveur, through the medium of their books, were my first teachers of metallography, as they have been of almost all American metallurgists of my generation. As a teacher, and for many years the acknowledged leader of American metallurgists, he exercised a profound influence in the growth of our science and was held in honor by the men of science of his time. I can speak no words of technical appreciation that will add luster to his fame, for by his prophetic vision, his teachings, and his researches he stands among the immortals in the memory of all metallurgists. In 1926, the third Howe Memorial Lecture was presented by Professor William Campbell' of Columbia University, who entitled it "Twenty-Five Years of Metallography." He took as a starting date for his chronology the turn of the century, which coincided with his arrival from England to work in association with Howe at the Columbia School of Mines. In that informative lecture Professor Campbell enumerated the important advances in metallography achieved during the first quarter of the century, and, it now appears, may have established the custom of reviewing such progress every twenty-five years. The scope of Professor Campbell's lecture was as broad as his metallurgical knowledge, for it embraced a wide portion of the field of metallography, both ferrous and nonferrous. Twenty-five years later, the Howe Memorial Lecture Committee saw fit to assign to me the honor of writing a lecture that would commemorate the work of Henry Marion Howe and would at the same time constitute the 25th anniversary of the lecture by Professor Campbell. The Committee suggested that this lecture might properly be called "Twenty-Five More Years of Metallography," a suggestion that I have adopted. I must confess, however, that I have not followed the precedent established by Campbell and have narrowed the scope of this lecture to an appraisal of those achievements which in my opinion have contributed most to the progress of microscopical metallography during the past twenty-five years. Progress in Metallography The metallographic methods most widely used today, with the exception of the electron microscope, were firmly established more than twenty-five years ago. In general, our specimens were prepared for microscopic examination in those days in much the same manner as they are today. It is true that new details of technique have been introduced from time to time, and that superior equipment is available today, but on the whole, these improvements have been in the nature of refinements, often a matter of personal preference, and none can be considered essential to the attainment of the ultimate goal of the art and science of metallography, which is to reveal the structure of metallic specimens with unequivocal clarity so that they may be interpreted correctly. Mechanical metallographic polishing, which was the only method available in 1926, is still universally practiced and still consists of abrading the metallic specimen with a series of abrasives of increasing fineness until a specular surface is attained. We have now the alternative method of electropolishing, but it is not widely used because, except in a few special cases, its results are inferior to those of competent mechanical polishing. Likewise, most of the etching reagents preferred today were in common use more than twenty-five years ago and were applied in the same manner as they are today. Valuable improvements have been made in the optical and mechanical performance of metallurgical microscopes, but there was no dearth in those days of excellent instruments equipped with achromatic and apochromatic objectives capable of yielding micrographs comparable in quality with the best that we can make today. In fact, it would be a difficult task for any metallographer today to make optical micrographs at magnifications in excess of 3000 diameters that would surpass those made by Lucas more than twenty-five years ago. One of these is shown in Fig. 1. Yet, it is unquestionable that on the whole, the micrographs appearing in the metallurgical literature today are vastly superior to those

Jan 1, 1952

By L. W. Pommier, F. B. Brien, A. K. Bhasin

The diflerential movement of solid particles through solid-liquid suspensions is very important to many branches of engineering. The flow of suspensions around immersed bodies is mainly of a turbulent nature. Problems are encountered when attempts are made, as is the general practice, to extrapolate the velocity and resistance relationships of Newton, pertaining to Newtonian systems, into non-Newtonian solid-liquid suspensions. The conventional velocity and resistance relationships for turbulent flow in fluids when applied to suspensions, do not take into consideration the two very important variables: suspension particle size and solid volume fraction. A study of the effect of suspension particle size (dgb) on the velocity of falling balls leads to the concept of a critical particle size (dgc) at which the suspensions will be Newtonian. This leads to the classification of static suspensions into two types: suspensions consisting of particle of diameter dgh > dgt, and those with dgh, < dgr. Separate velocity and resistance equations for these two types of suspensions have been proposed, taking into account both the solid particle size and solid volume fraction. The agreement between the velocities predicted from the proposed equations and the measured velocities, confirms their validity. The resistance force offered by suspensions to the movement of immersed bodies has been calculated from the proposed equations, and the effects of suspension particle size and solid volume fraction on the resistance force and velocity have been examined. The movement of immersed bodies in solid-liquid suspensions is of great importance in many areas of engineering such as minerals processing, oil well drilling, suspension flow in pipelines, and hydrometallurgy. A number of mineral dressing processes deal essentially with the movement of solids in suspensions—in particular, classification, thickening, filtration, ore washing, and gravity concentration—thus a study of the fluid characteristics of suspensions is of theoretical and practical interest.&apos; A rigorous analysis of the mechanisms of momentum transport of a solid-liquid system is complex indeed. The rheological properties of the suspensions deviate from those of liquids, varying, for example, with density, solid volume fraction, size and shape of the solid phase of the suspension, and with the density and viscosity of the liquid phase. The flow of suspensions around immersed bodies is mainly of a turbulent nature and hence studies of the turbulent flow characteristics of suspensions are of par- ticular importance. Problems are encountered when attempts are made to extrapolate the velocity and resistance relationships of Newton, pertaining to Newtonian systems, into non-Newtonian solid-liquid suspensions. Due to the numerous variables present in a suspension, certain limitations and assumptions become necessary in order to produce quantitative relationships for predicting their effects. The solid particle size and the solid volume fraction are two of the more important variables. By comparing the measured and calculated Newtonian velocities of falling balls in simple static suspensions, the existing velocity and resistance relationships have been modified to take these variables into account. In order to keep the study less complex, all other variables such as the characteristics of suspending liquid and shape of the particle are maintained constant. Objective The objective of the present investigation is to modify the Newtonian velocity and resistance equations in order to take into account the suspension particle size and solid volume fraction. Theory Liquids are classified on the basis of viscosity, which may be defined as the relationship between applied shear stress and resulting rate of shear.&apos; pure single-phase fluids composed of small light molecules behave as Newtonian liquids, having a single viscosity pa-

Jan 1, 1971

By R. H. Richman, F. Borik

A 0.3 pct C-12 pct Cr-6 pct Ni steel was rolled to 93 pct reduclion in area as austenite at 510°C, and then partially transformed as desired to ~rlartensite by qnenching to - 196°C. Pole figures for the austenitic matrix and for the martensitic product were separately determined by an X-ray transmission method. The deforitration texture of&apos; the warm-worked austenite is characlerized by (110)(225) components, and is thus closely similar to those produced in a brasses. The pole jigure of the martensite in partially transformed material agrees well with that which can be constructed by transfortnation of the {110)(225) orientations according to either the Kuvdjuniov- Sacks or the Nishi-yatuu relatiotship. Howeuer, an important result of this construction is that me-third of the predicted orientations are missing. A graphical analysis can then be used to show that in deformed austenite certain crystallographic variants of martensite (related to the most probable austenite slip systems) are suppressed, resulting in this preferred transformation. The evidence for preferred transformation is corroborated by the measured elastic anisotropy of warm-rolled and fully transformed H-11 steel. EXTENSIVE plastic deformation of a polycrystal-line aggregate in a manner that causes flow predominantly in one direction results in a preferred orientation of the constituent crystallites. The particular orientations that are produced depend upon the crystal structure and composition of the material, as well as upon the temperature, mode, and degree of deformation; in any case, the preferred crystallo-graphic orientations, or textures, are reflected in directionality of mechanical properties. Although such anisotropy may be exploited in certain specialized applications, it is more commonly diminished or eliminated by heat treatment lest it interfere undesirably in subsequent forming operations or in structural design. In the recently developed thermomechanical treatments that significantly enhance the strength of some steels,1,2 considerable deformation of the metastable austenite prior to the martensite transformation is essential to the strengthening process. If the austenite is textured by the deformation, and if the transformation to martensite proceeds according to one of the relationships established for transformation in annealed austenite, then it must be expected that the martensite will also possess a preferred orientation even though the multiplicity of martensite orientations possible in a given austen- ite crystal will tend to restore some degree of randomness. The existence of a residual anisotropy, both mechanical 3-6 and crystallographic,&apos; has been substantiated. In the latter crystallographic investigation, preferred orientations were determined for the martensitic structure of an SAE 4340 steel rolled 72 pct as austenite at 833°C and then quenched. However, the choice of a composition that transformed almost completely to martensite during the quench to room temperature did not permit direct measurement of the prior austenitic texture. In fact, when the "ideal orientations&apos;&apos; associated with well-known fcc rolling textures were converted, alone or in combination, to martensite according to the Kur-djumov-Sachs (K-s)&apos; or Nishiyama8 relations, the agreement obtained with the observed martensite texture was only fair at best. Recently a pertinent aspect of the austenite to martensite transformation was reported by Bokros and parker,10 who found that certain habit-plane variants of martensite were suppressed by tensile deformation of Fe-31.7 Ni single crystals prior to the necessary subzero cooling. It might be anticipated that the consequences of such preferred transformation are sustained during the formation of martensite in warm-worked austenite that has a well-developed deformation texture. The present investigation was undertaken first to establish more firmly the relation between preferred orientations in plastically deformed austenite and in the resulting martensite, and second to examine the textures for evidence of deformation-induced preferred transformation. EXPERIMENTAL PROCEDURES An alloy containing 0.3 pct C, 12 pct Cr, 6 pct Ni, and the balance iron, was selected because the mar-tensite-start temperature (M,) of about -100°C allowed convenient experimental manipulation of either austenite or martensite at room temperature. Furthermore, this composition can be readily deformed as metastable austenite at moderately elevated temperatures without intervention of appreciable isothermal or athermal decomposition products. The alloy was austenitized at 1150°C, aircooled to 510°C, rolled unidirectionally at this temperature to 93 pct reduction of cross-sectional area, and finally oil-quenched to room temperature. Partial transformation to martensite was accomplished by quenching to -196°C as needed. The rolled stock was reduced in thickness from 0.067 to 0.010 in. by etching in a solution of 5 pct HC1, 45 pct HNO3, and 50 pct water, and further thinned by careful mechanical polishing to maintain the two sides of the sheet parallel within 0.0003 in. After mechanical polishing to 0.005 in., electropolishing in 1:9 perchloric-acetic acid solution produced a final thickness of 0.002 in. The preferred orientations were determined from

Jan 1, 1968

By J. H. Schulman, M. H. Buckenham

Although much interest has been taken in the use of mixed collectors in flotation, this investigation is probably the first in which oppositely charged collectors have been considered. The results obtained and the techniques used could well be applied in the behavior of other mixe the behavior of other mixed collector systems and could possibly explain the effective flotation results which have been reported when various collector combinations have been used. Collectors conventionally employed in flotation systems are soluble in water, but many of their homologs of longer hydrocarbon chain length are insoluble. The properties and behavior of these insoluble compounds may be conveniently studied when they are spread as monolayers at the air/water interface on the Langmuir-Adam trough. Although some extrapolation is involved in applying effects observed at this interface to the solid/liquid interface where the action of collectors is most important in flotation, the technique nevertheless is most useful for the study and interpretation of flotation phenomena. Of particular interest in this field are investigations on the insoluble monolayers of the fatty acids, alkyl sulfates and alkyl amines; the penetration of these insoluble monolayers by soluble surface active components and their interaction with metal ions from the underlying solution.&apos;-&apos; Unfortunately, the insoluble xanthates and related compounds do not exhibit stable monolayer properties due to rapid oxidation at the air/water interface and, therefore, cannot be studied directly in this way. These approaches have enabled Leja and Schulman8 to suggest mechanisms explaining dynamic attachment of mineral particles to air bubbles involving collector-frother interaction and the adsorption of collectors onto mineral surfaces. In this and other papers 9-12 considerable evidence is presented to support the concept of collector-frother and metal ion-monolayer interaction and to emphasize the value of monolayer techniques in elucidating the flotation system. Molecular interactions resulting from monolayer penetration are determined by the nature of and the association between both the polar and nonpolar groups of the two molecules concerned. Stable complexes are formed on penetration when interaction takes place between both the polar and nonpolar groups, and although the resultant complexes are not necessarily true chemical compounds, the properties of the molecularly associated complexes are very different from those of the individual components. Shortening of, or changes from, a straight hydrocarbon chain in one of the reacting molecules reduces considerably the stability of the associated complex as do changes in temperature, pH and substrate composition. The effect of hydrocarbon chain length becomes most important when observed effects are to be applied in flotation studies where soluble homo-logs and, therefore, much shorter hydrocarbon chain lengths are used. The present investigation is based on Langmuir trough work carried out by Bowcott,l3 who studied the penetration of insoluble amine monolayers by potassium lauryl xanthate. Bowcott observed that cetyl amine monolayers were readily penetrated by xanthate, but found that with time the high film pressures resulting from penetration and association fell off, indicating decomposition and ejection of xanthate from the film. This decomposition was pH dependent. Of particular interest in this work were studies on an equimolecular mixed monolayer of the fully N-substituted ammonium compound, for example, cetyl trimethyl ammonium iodide (CTAI) and potassium cetyl xanthate. Despite the fact that the CTAI is water soluble and the xanthate on its own is incapable of forming a monolayer, the mixed film was stable up to a surface pressure of 67 dynes per cm. In this condensed state the xanthate was stabilized against atmospheric oxidation, although iodine injected beneath the film caused an immediate collapse. The stabilizing of xanthate against oxidation by association with an alkyl trimethyl ammonium bromide (TAB) could be important in flotation, and a study of the performance and behavior of mixed collectors therefore was undertaken. A modified Hallimond tube operated under controlled conditions was used to evaluate flotation. Surface tension measurements were made to investigate the properties of the soluble

Jan 1, 1963

By Jr. Ensign C. O., J. W. Trammell

The two principal methods of room-and-pillar mining practiced at White Pine make it important to predict variations in the thickness and rock types of a stratum called the upper sandstone. In full column mining, the nearly barren upper sandstone occurs between two ore horizons (called upper shale and parting shale, respectively), and is mined as a part of the ore column. In general, full column mining is not practiced where excessive upper sandstone thickness causes full column ore grade to be substantially lower than parting shale ore. In parting shale mining, the upper sandstone forms the mine roof. Difficulty in predicting upper sandstone character arose because the extent and directions of its variations were not apparent in the property&apos;s diamond drilling, in which holes are spaced on 1000-ft centers. A study of sedimentary features, undertaken to improve the predictability of trends in the upper sandstone, led to an interpretation of the sedimentary environment in which the sandstone was deposited. Ripple marks, mud cracks, and cross-bedding, as well as other, less well known features, such as channel casts, flute casts, and current crescent casts, were mapped or recorded. These data, coupled with the knowledge of regional facies changes gained from studying drill core, show that the upper sandstone was deposited by a series of streams flowing northeastward over the underlying parting shale. Deposition of the lowermost bed of the upper sandstone, near the ancient shoreline, was locally preceded by erosion of the parting shale, and the greatest thicknesses of sandstone are found in channels scoured out of the parting shale. Awareness of the rather strong linear trends in the upper sandstone makes it possible to project continuous areas of thick upper sandstone through apparently isolated "highs" in the upper sandstone thickness contour map, which is based on drill-hole information. Since local exceptions to general stratigraphic trends exist, a method was also needed for esti- mating, in detail, the thickness and degree of shali-ness of upper sandstone forming the roof in active parting shale mining areas. Because locally the parting shale was thinned by erosion during the deposition of upper sandstone, parting shale thickness is inversely proportional to upper sandstone thickness. Utilizing information taken from short drill holes into the roof, curves were constructed for the correlation of parting shale thickness (measurable in the mine) with the upper sandstone total thickness, as well as the thickness of its basal member. The White Pine mine is situated in Ontonagon County, approximately 6 miles south of Lake Superior, in the Upper Peninsula of Michigan (Fig. 1). The orebody mined by White Pine Copper Co. occurs in the lowermost 20 to 25 ft of the Nonesuch formation, a series of middle- to upper-Keweenawan shales, siltstones, and sandstones. This paper discusses the solution of problems in ore grade control and mine planning arising from the presence of an essentially barren sandstone stratum within the orebody. THE OREBODY AND MINING TYPES A brief description of the orebody and mining methods is necessary to show how the upper sandstone affects mine planning and grade control. In the mine, the cupriferous zone of the Nonesuch shale is divided into three major portions, as shown in Fig. 2. Lying conformably on top of the Copper Harbor formation (or "lower sandstone") is the lower part of the orebody, the parting shale. The parting shale is overlain by the upper sandstone. On top of the upper sandstone, the basal portion (8 ft) of the upper shale is quite similar to the parting shale. Both the upper shale and parting shale are divided into a number of smaller stratigraphic units, each having a characteristic copper content, as shown by the histogram of Fig. 2. Other authors1&apos;3 have dealt in detail with the stratigraphy and mineralogy of the orebody. However, in this article, we are concerned with the major subdivisions only, and it will suffice to note the low copper content of the upper sandstone, shown in Fig. 2. At present, two types of room-and-pillar openings are created in the orebody. In one type, called parting

Jan 1, 1964

By Wieland D. R., Hurst R. E., A. R. Hendrickson

Analysis of acidizing techniques, in correlation with reservoir data and a backlog of past treatments, has resulted in the development of a valuable engineering guide for planning acidizing treatments. Such treatments fall into three categories: (I) acid injection into the pores of the matrix; (2) acid injection into natural formation fractures at less than parting pressure; and (3) combination acidizing-fracturing treatments in which acid solutions (without propping agents) are injected at treating pressures sufficient to open and extend fractures through which the acid flows. Because the spending tirnze of acid during a specific well treatment does not change appreciably, maximunl penetration is attained when the first increment of injected acid is completely spent. Additional acid injection cannot be expected to further extend the benefits of the treatment. Depth of penetration will depend upon the reaction rate of the acid under treatment conditions, the injection rate of the acid into the matrix or fractures and the area-volume relationship existing in the flow channels. Based on Darcy&apos;s flow formula, extremely low injection rates must be used in order to keep bottom-hole injection pressures below formation fracturing pressure. As a result, only limited penetration of unspent acid will occur. Treatment records indicate that, in most acidizing treatments, formation parting pressures are exceeded, greatly extending acid penetration. Under these conditions, stimulation benefits are limited to the fracture area produced during the spending time of the first increment of acid injected into the formation. This area may be calculated from laboratory and well data to estimate depth of penetration. This, in turn, may be correlated with productivity data to assist The art of gas and oil well acidizing has been characterized by many changes in treating materials and techniques since its inception. These developments have been designed to provide greater production increases. prolong production declines and shorten payout time. Such improvements have been based primarily on data derived from laboratory research and field experience. As more of the variables influencing these treatments have been recognized and evaluated, acidizing has become less of an art and more of a science. Recent studies of fracturing treatments,&apos; in light of individual well conditions and the results of thousands of fracturing treatments, made possible the formulation of an engineering guide that is now being used to select optimum treating techniques and to forecast probable results of such treatments. A similar analysis of the factors controlling acidizing treatments has been made and is the basis for this paper, The findings herein can be used as a guide in the selection of acidizing solutions and techniques, tailored to fit specific well conditions and to provide optimum stimulation per dollar cost. Acidizing treatments may be classified into three basic categories—(1) treatments in which the acid is injected uniformly into the pores and flow channels of the matrix, (2) treatments in which the acid enters natural fissures and fractures in the formation at less than fracturing pressures and (3) injection of acid into the formation at a pressure sufficient to open and extend fractures into the rock through which the acid penetrates (without the inclusion of a propping agent). TYPE 1 — MATRIX ACIDIZING This category consists of treatments in which acid solutions are injected into a homogeneous carbonate

By Walter Crooke

Regenerative hot-blast stoves are now in general use in all parts of the world, and are so well understood and appreciated, that I need not take up your time with an account of their history and introduction into the United States. My object in writing this paper is to give you a short description of a stove that is now being very favorably received and adopted here (see drawing). The stove was first introduced into this country in 1887 by M&apos;Clure & Shuler (now M&apos;Clure & Amsler), who have the management of the patent right in the United States. The English design had to be modified to suit the exigencies of American blast-furnace practice, which, in many respects, widely differs from our English experience. In the first place, the fire-bricks used in America expand to an extent unknown in England, and it became necessary to make special provision for this by increasing the number of cross-walls, and by leaving a space at the top of the stove through which the lining could expand. The expansion laterally was, however, more difficult to provide for, as the combustion-chamber in the center, being the hottest part of the stove, must necessarily expand more than the outer walls, and therefore tend to squeeze up the flue-openings. On first introducing these stoves to American ironmasters, a feel ing seemed to prevail that a " four-pass " stove did not utilize the whole of its surface. They also had an idea that the " two-pass " stove let the burning gas go before all the duty had been extracted from it; so that it was found neceseary to design a stove of a special character to suit their wishes. Hence the "three-pass" chimney top stove now before your notice, the advantage claimed for which is that each stove is independent, requiring no underground chimney flue or stack, and can be erected at a very light cost. The working of these stoves has proved to be very successful wherever they have been introduced.

Jan 1, 1891

By R. H. Maes, R. E. de Strycker, J. J. Jacobs

A simple method, based upow density measurements, has been perfected in order to determine the critical temperature of liquid miscibility gaps. Applied to the Pb-Cu system, it yielded a value of 980"C for the critical tempevature of the miscibility gap in this system. In the Pb-Cu-As system, the immiscibility between lead and coppev evolves towards a miscibility gap be-tween lead and copper arsenides; the liquation temperatures were determined joy different avsenic contents and values up to 1065°C were found. Combining these results with those given by the clzemical analysis of liquid samples taken at dqj.event temperatures, it has been possible to make a cowzplete determination of the liquid miscibility gap in this ternary system. In the Pb-Cu-Fe-As system, a ternary miscibility gap has been discovered; for some compositions, the molten and slowly cooled alloys separated into three layers: an Fe-As alloy, a Cu-As alloy, and a lead-rich layer. ThE Pb-Cu-Fe-As system is of interest for the study of the behavior of speiss or arsenical alloys in the lead blast furnace. The speisses produced in lead metallurgy generally have complex compositions, but they may be considered, in a simplified way, as a mixture of copper, iron, nickel, and cobalt arsenides; there is often an excess of metallic constituants, and lead is also present. Speisses liquate from lead at various temperatures according to their composition; according to industrial experience, iron speisses are already distinctly separated from lead bullion at temperatures of the order of 1100°C, whereas copper speisses only begin to liquate from lead at much lower temperatures, near their solidification points, which were never accurately determined until now. Besides these considerations of practical interest, the present study is of importance for the knowledge of liquid miscibility gaps. Particularly the data of the literature about critical temperatures of liquation are incomplete and present sometimes considerable disparities; a method has been perfected in the present work to determine these temperatures with accuracy. MISCIBILITY GAP OF THE LEAD-COPPER SYSTEM Review of Literature. The generally admitted outline of the Pb-Cu equilibrium diagram is shown by Fig. 1. This figure, with its numerical indications, is taken from the review of Hansen and ~nderko;&apos; compositions are given in weight percent, as will be the case in the remainder of this paper. Between 36 and 87 pct Pb, Pb-Cu alloys separate into two layers, in the liquid state. The critical temperature of liquation has been much disputed in earlier studies, where values up to 1500°C were claimed; but a reliable study of ~ohnen,&apos; based upon differential thermal analysis, gave a value of 990°C; this rather low value was verified by a recent study of Schiirmann and Kaune? based upon thermodynamical properties of the Pb-Cu alloys, which predicted a value of 1002°C. Liquid miscibility gaps were also studied by means of chemical analyses. Satisfactory results were generally obtained with the method consisting in taking samples of the two liquid layers in equilibrium and submitting them to chemical analysis; however, this method becomes delicate near the critical temperature. With this technique, Friedrich and waehlerts ob-

Jan 1, 1968

By H. Kazemi

An ideal theoretical model of a naturally fractured reservoir with a uniform fracture distribution, motivated by an earlier model by Warren and Root, has been developed. This model consists of a finite circular reservoir with a centrally located well and two distinct porous regions, referred to as matrix and fracture, respectively. The matrix has high storage, but low flow capacity; the fracture has low storage, but high flow capacity. The flow in the entire reservoir is unsteady state. The results of this study are compared with the results of the earlier models, and it has been concluded that major conclusions of Warren and Root are quite substantial. Furthermore, an attempt has been made to study critically other analytical methods reported in the literature. In general, it may be concluded that the analysis of a naturally fractured reservoir from pressure transient data relies considerably on the degree and the type of heterogeneity of the system; the testing procedure and test facilities are sometimes as important. Nevertheless, under favorable conditions, one should be able to calculate in-situ characteristics of the matrix-fracture system, such as pore-volume ratio, over-all capacity of the formation, total storage capacity of the porous matrix, and some measure of matrix permeability. INTRODUCTION The analysis of flow and buildup tests for obtaining in-situ characteristics of oil and gas reservoirs has received considerable attention in the past decade. Most of the available techniques result in reliable conclusions in macroscopically homogeneous reservoirs or in the homogeneous reservoirs with only certain types of induced and/or inherent heterogeneity (such as wellbore damage, etc.). In general, the greater the degree of heterogeneity, the less the reliability of the information deduced from the pressure transient data. A commonly encountered heterogeneous system is a naturally fractured reservoir where two types of distinct porosities occur in the same formation. The region containing finer pores may have high storage and low flow capacities. This is called the matrix. The remaining region may have high flow capacity with low storage. The latter region is generally the set of interconnecting fractures and fissures of the rock, and for this reason it is called the fracture. Ordinarily, we wish to obtain the permeability and porosity of each region and perhaps the frequency of the fracture distribution in a reservoir. Such information is necessary for reservoir engineering. Other information, such as wellbore damage, will be useful in evaluating possible remedial work for such fields. Few authors have suggested theories to aid in calculating the in-situ characteristics of a naturally fractured reservoir similar to what we have described above. Pollardl suggested that a naturally fractured reservoir contained three distinct regions: a damaged or an improved region surrounding the wellbore, and the two remaining regions the same as described earlier. He suggested that the flow was taking place from the tight matrix into the highly conductive fractures, then into the we wllbore region and finally into the well column. He concluded that the average pressure buildup in each of these distinct regions can be expressed approximately in terms of an exponential decay function of time. He also hypothesized that the decay coefficients for each of these functions were significantly different from each other; consequently, each of these functions became dominant in turn, in the process of pressure buildup. Thus, by a proper graphic plot of the logarithm of wellbore pressure differences vs buildup time, each of these functions could be determined (see Fig. 1). Pollard suggested methods of determining the wellbore damage and fracture volume. Later Pirson and Pirson2 extended

Jan 1, 1970

By I. M. Roberts

THE war emergency has affected every phase of industry. The gas and coke-oven companies have sought faithfully to discharge their responsibility in this critical period and have willingly modified their operations where possible to meet the ever increasing demands made upon them. Our company made commitments for blast-furnace coke for war purposes which necessitated a reduction in coking time in order to produce the amount required to. meet the new demands. At the same time there were certain customers of long standing, who had been supplied with foundry and egg-sized coke produced on fairly long coking periods, who also were engaged in war work and whose patronage we desired to retain. Coke produced on short coking rates from the coal mixture we were then using would not have been satisfactory for these customers. The average width of our ovens is 19 ¾ in., which is a little wider than the more modern ovens of the present day. They were originally designed to give somewhat cool tops in order to produce a rich gas. This necessitates carrying the heats a little on the warm side so that the tops will be fully carbonized. A reduction in coking time, as is generally known, is accompanied by a reduction in the average size of the coke produced. This is due to the greater shrinkage that takes place at the higher temperatures required to carbonize the charges in a shorter time. The net result is that the coke is more cross fractured and longitudinally fractured and breaks up into small sizes on handling. The cokes produced from the better coking coals seem to be more susceptible to fracture at high temperatures than those from poorer coking coals. A coal mixture that produces a beautiful foundry-sized coke at 30 to 36 hr. may yield a product at 18 hr. that would be so badly fractured as to be unsatisfactory for foundry practice. COKING CHARACTERISTICS OF COALS Our problem was to find some economical innovation and develop a method that would enable us to reduce the coking time and still produce a coke satisfactory to our foundry trade. However, before discussing the results of our present operations, it might be well to present a few observations on the coking characteristics of coals in general. Most coke-oven operators carbonize a blended mixture of coals. It may consist of a single high-volatile coal with a single low-volatile coal, or of a combination of several high-volatile and low-volatile coals. Medium-volatile coals of the Eagle seam are used for the production of high-grade foundry coke. Medium and high-volatile coals are often blended with one or more low-volatile coals. The possibilities are almost infinite, but the combinations are limited by such factors as cost and facilities for handling multicoal mixtures, and by other practical considerations. Every coal has characteristics that make it blend better with a particular coal or coals in preference to others. This property has

Jan 1, 1944

By V. L. Elliott, C. L. Meyette

The conditioning of semifinished steel products such as billets, blooms, and slabs to remove surface defects before further processing to finished products is a necessary accompaniment to steel mill rolling operations. A knowledge of the kinds of defects which occur and of the conditions in melting, teeming, and rolling that may lead to their occurrence is favorable to the production of quality products. Surface defects may be classed as either of mechanical origin such as those that occur in the heating and rolling operations and include breaks, tears, guide marks, mechanical laps and the like, or they may have been in the ingot before heating and rolling. Examples of the latter are ingot cracks, blow-holes, scabs, and inclusions which lead to the numerous known types of seams and surface flaws. Most of the common types of surface defects and methods for their identification by visual examination or by the aid of macro-etch tests are well known. The conditions which caused their formation are also appreciably understood and this knowledge has been instrumental in the establishment of methods for metallurgical control. There are, however, defects of doubtful origin. In any endeavor to trace the causes for their occurrence, the question of first concern is: I. Whether they were formed in the rolling procedure. 2. Whether they existed in the ingot prior to rolling. In the case of semifinished products which are rerolled to finished products there is also the question of whether they were formed in the primary or in the secondary rolling. In metallurgical laboratories where numerous or routine examinations of the quality of rolled products are made over the course of time, there will doubtless be many puzzling cases of defect origin. Microscopic examination of the defects may, however, reveal a characterizing condition that can be used to classify them broadly with respect to their origin. Such a condition has been observed and, after detailed investigation, is described here with the thought that it may offer a usable and relatively simple solution to a bothersome problem. Basis For Classifying In this discussion the term "mechanical type defects" will be used to designate those that have occurred as a result of the rolling operations such as in rolling from the ingot to billets, blooms, or slabs or in rerolling to finished products. The term "steel type defects" will be used to designate those that were present in the ingot prior to primary rolling or that were in the semifinished product prior to secondary rolling to finished product. The basis for distinguishing between the two types of defects lies in the relative degree of subscale formation surrounding them. Subscale is defined1 as a zone of

Jan 1, 1949

By V. L. Elliott, C. L. Meyette

The conditioning of semifinished steel products such as billets, blooms, and slabs to remove surface defects before further processing to finished products is a necessary accompaniment to steel mill rolling operations. A knowledge of the kinds of defects which occur and of the conditions in melting, teeming, and rolling that may lead to their occurrence is favorable to the production of quality products. Surface defects may be classed as either of mechanical origin such as those that occur in the heating and rolling operations and include breaks, tears, guide marks, mechanical laps and the like, or they may have been in the ingot before heating and rolling. Examples of the latter are ingot cracks, blow-holes, scabs, and inclusions which lead to the numerous known types of seams and surface flaws. Most of the common types of surface defects and methods for their identification by visual examination or by the aid of macro-etch tests are well known. The conditions which caused their formation are also appreciably understood and this knowledge has been instrumental in the establishment of methods for metallurgical control. There are, however, defects of doubtful origin. In any endeavor to trace the causes for their occurrence, the question of first concern is: I. Whether they were formed in the rolling procedure. 2. Whether they existed in the ingot prior to rolling. In the case of semifinished products which are rerolled to finished products there is also the question of whether they were formed in the primary or in the secondary rolling. In metallurgical laboratories where numerous or routine examinations of the quality of rolled products are made over the course of time, there will doubtless be many puzzling cases of defect origin. Microscopic examination of the defects may, however, reveal a characterizing condition that can be used to classify them broadly with respect to their origin. Such a condition has been observed and, after detailed investigation, is described here with the thought that it may offer a usable and relatively simple solution to a bothersome problem. Basis For Classifying In this discussion the term "mechanical type defects" will be used to designate those that have occurred as a result of the rolling operations such as in rolling from the ingot to billets, blooms, or slabs or in rerolling to finished products. The term "steel type defects" will be used to designate those that were present in the ingot prior to primary rolling or that were in the semifinished product prior to secondary rolling to finished product. The basis for distinguishing between the two types of defects lies in the relative degree of subscale formation surrounding them. Subscale is defined1 as a zone of

Jan 1, 1949

By L. A. Weitzenkamp, N. M. Bashara

A study of the electrical conductivity of gold films less than 200 in thickness indicates a negative temperature coefficient of resistance and a thermal actiuatlon energy of less than 0.25 ev. The films consist of discrete metal islands of linear dimensions from a few angstroms to 1000A. Films were able to withstand applied fields up to 60,000 v per cm before breakdown occurred. A model for the conduction mechanism is proposed which involtes a Potential barrier due to work junction, irriage forces , and an electrostatic potential arising from separating an electron from a neutral island leaving behind a positively charged metal island. Activation energies of less than 0.25 ev ave consistent with this model, which includes a tunneling andor Thermal mechanism for conduction between the separate metal islands. An apparent satuvation effect in conductivity at high fields is observed experimentally. The saturation effect may be explained by the influence of the electrostatic contribution to the potential barriers for the transition through several islands adjacent to the original island which was activated to give up an electron. The proposed model gives Poor quantitative agyeement for the intermal electrical field between islands. ThIS paper will relate the structure of discontinuous metal films to the electrical properties and will emphasize the following topics: 1) the relation of the conduction mechanism to particle size and a comparison of particle size from electrical measurements with electron-microscope studies; 2) the saturation of the conductivity at high electric fields; and finally, 3) a comparison between the external field applied and the apparent field between particles. che- latter comparison points to a need for a modification in the model for the conduction mechanism first proposed by orter&apos; and expanded by Neugebauer and webb2 which will be dealt with in the discussion. The paper is based on results on gold films on glass microscope slides. The clms were vacuum-evaporated and were about lOOA thick, thickness being measured by interferometry. It has been observed that metal films of this thickness do not exhibit bulk metallic conduction. Films thinner than some critical thiclmess, depending upon substrate temperature and other factors, have conductivities which increase with increasing temperature with thermal activation energies of less than 0.25 ev. Electron-microscope studies3 have shown that these films consist of discrete metal islands having linear dimnsions from a few angstroms to approximately 1000A. When the metal is being vacuum-deposited on the substrate, islands on the order of a few angstroms appear first. As the deposition continues the islands may tend to agglomerate into larger particles and may eventually grow together into a continuous film,3&apos;&apos;&apos; In our tests the conductivity of the gold films was found to be about ten orders of magnitude less than the bulk conductivity of gold. When oxygen was introduced into the test chamber the conductivity decreased by a factor of about one-third. This can be related to an increase in work function for gold caused by adsorption of oxygen, as reported by Oullet and Rideal.s Exposure to an atmosphere of water vapor caused an increase in conductivity by a factor of 2 or 3 when a low field was applied. When the films were exposed to water vapor under a high field the conductivity increased by as much as two orders of magnitude. The activation energies measured were much less than the work function for gold, 0.25 ev or less, with the smaller activation energies observed for thicker films. It will be shown that the activation energy is a function of particle size and spacing. In general the model for the potential between metal islands would include the effective work function, the image force, the applied field, and an electrostatic term. The electrostatic contribution arises from the potential required to separate an electron from a conducting sphere. According to Neugebauer and webb2 the maximum potential due to the field and the electrostatic term only is

Jan 1, 1967

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen&apos; determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By D. R. Parrish, T. M. Geffen, R. A. Morse, G. W. Haynes

Flow tests on small core plugs have indicated that a large amount of gas is trapped and not recovered by water flooding a gas sand. Instead of I to 15 per cent pore space, as is usually assumed, the residual gas saturation is 15 to 50 per cent pore space, and is thus of the same magnitude as residual oil after water flooding oil sands. A thorough investigation was made to ascertain that large amounts of residual gas actually remain in reservoirs after a water flood and that this condition is not merely a laboratory phenomenon. In field experiments, the amount of gas left in a watered-out gas sand was measured by use of a pressure core barrel and the residual gas saturation of two watered-out gas sands was determined by electric log evaluation. In the laboratory, an investigation was made of factors that could possibly cause the value of residual gas saturation as measured on small core plugs to differ from that in the reservoir, and the effect of these factors on the amount of residual gas saturation was studied. The factors studied include flooding rate, static pressure, temperature, sample size and saturation conditions before flooding All evidence established that a relatively high gas saturation is trapped in water flooded gas sands and that this residual gas saturation can be measured in the laboratory by tests on small core plugs. INTRODUCTION There. has been general agreement among engineers that very high recovery of gas could be obtained from natural reservoirs By water displacement. Gas recoveries of 80 to 95 per cent of the original gas in place have become the normal expectation in water drive fields. The assumption of high recovery has been based on: 1. low density and viscosity of gas compared with water; 2. the erroneous assumption that the flow relationship in a gas-liquid system where gas is the displaced phase will be the same as when it is the displacing phase. It has long been recognized that gas can flow at very low gas saturations (in the range of 1 to 15 per cent pore space) in systems where liquid is being displaced by gas. By assuming the reversibility of this process, the conclusion was reached that the residual gas saturation following water flooding of a gas reservoir would be the qame (1 to 15 per cent) as that at which gas first flowed continuously as a displacing phase. Recent laboratory relative permeability Studies have demonstrated that the flow characteristics are very different in gas-liquid systems, depending on whether gas is displacing or being displaced by, a liquid. Also, it has been shown that there is no difference between the flow characteristics of oil and water or gas and water in water wet porous rocks. The residual gas saturation that can be expected following water flooding of a gas reservoir then would be in the same range as the residual oil saturation normally expected after water flooding an oil reservoir! i.e., in the range of 15 to 50 per cent pore space, depending on the rock characteristics. Obviously, such a difference in residual gas saturation means very important differences in recoverable gas reserves from water drive reservoirs. For example, if the original gas saturation in a field were 70 per cent, and the residual gas following flooding were 35 per cent, only half of the gas in place could be recovered by complete water drive, compared to the previously expected 80 to 95 per cent. This is a situation in which complete pressure maintenance could result in very greatly reduced recovery, since straight pressure depletion recoveries from gas reservoirs can approach 80 to 90 per cent. Such a change in thinking must be based on more complete information than a series of small core tests. Hence the work reported herein was undertaken with the objective of determining whether or not residual gas saturations indicated from small core relative permeability tests at atmospheric pressure and room temperature are representative of the residual gas saturations which could be expected after water flood of natural reservoirs. A study was made both through laboratory and fields tests to determine any differences in residual saturation which might be occasioned by differences in pressure, temperature, rate of flooding, and original saturation conditions. Four separate types of laboratory experiments and two field mesurements were made in this investigation. The apparatus and testing methods of each will he discussed individually. LABORATORY EXPERIMENTS, APPARATUS AND PROCEDURE Relative Permeability Tests Steady state flow experiments Here conducted using the Penn State type apparatus. The equipment used has beer (described in a previous publication? "Irreducible" water satu-ration was established in the core&apos; by imposing ,a capillary pressure of 45 psi before simultaneous flow of air and water

Jan 1, 1952

By D. D. Pollock, D. I. Finch

PREVIOUS work&apos; on a four-component system (Cu-Mn-Ni-Fe) resulted in the development of consistent relationships between the chemical composition and the electrical properties of these manganin-type alloys. The present study was undertaken to develop alloys with temperature coefficients of resistivity and thermoelectric properties more desirable than those of the manganin type, and to determine whether the relationships which had been found for the Cu-Mn-Ni-Fe alloys could be extended to five-and six-component alloy systems. PREPARATION OF ALLOYS The five- and six-component alloys were made from OFHC copper rod, ARMCO iron, electrolytic nickel, manganese cathode chip, and special high-purity aluminum and indium. A Cu-Mg master was used for deoxidation. The compositions of these materials are given in Table I. The alloys were melted and cast as indicated previously,&apos; except that no cover was used and the melts were teemed. EXPERIMENTAL PROCEDURE The finished wire size of 0.0808 in. diam was again selected for the reason that the test specimens would be self-supporting, thus eliminating any extraneous effects which might have been introduced by winding smaller diameter wire on spools or forms. The following tests were performed on the finished wires: A) Chemical Analyses—All of the components of these alloys were determined by premium gravimetric methods. The principle residual impurity contained in these alloys is 0.008 pct Mg (by weight), maximum. Tables II and 111 present the mean analyses computed from at least four determinations of each constituent. B) Electrical Characteristics—The test procedures forthe determination of the thermal emf vs copper, resistivity, and the resistance-temperature relationship are given in detail in Ref. 1. It was also shown that the resistance-temperature relationship is of the form Pt = P,n + At -B/2, [1] where P, is the resistance at t C expressed in percent of a given standard resistance, P, is this per- 0 centage at 0°C, and A and B are constants for a given, properly treated, composition. The results of the electrical tests are also given in Tables II and 111. INTERPRETATION OF DATA The modified Linde2 formula, known to be valid for dilute binary solid solutions, was applied to the complex Cu-Mn-Ni-Fe type alloys. This relationship is of the form where Ap is the increase in resistivity. Zb the valence of the solute, Zn the valence of the solvent, and K and K are designations assigned by Robinson and Dorn3 to the constants for the periodic group to which solute element belongs. The units of K, are -cm per valence difference squared per at. pct; those of K2 are pa-cm per at. pct. For the sake of brevity, these units are not repeated in the following discussion. Calculations were made to determine if this formula was accurate for five-component systems. No experimental studies were made of the Cu-In and Cu-A1 binary systems. The effects of indium additions upon the resistivity of copper are given by Linde. These data, along with those of the effects of Mn and Fe, permitted the calculation of the effects of Al.

Jan 1, 1959

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of &apos;cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.&apos; Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33&apos;7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By J. B. NEALEY

MANY nonferrous smelting plants have recently adopted natural gas as fuel with resultant economies, both in cost and efficiency of utilization. Not only has this fuel been used for roasting, reduction, sintering, drossing, and smelting, but also for power. All of the three big smelters near Salt Lake City, Utah, have been changed over from coal and oil firing to gas. Among these is the plant of the International Smelting Co., Tooele, an Anaconda subsidiary, smelters of both copper and lead ores. In the roasting division at Tooele are 32 MacDougall six-hearth roasters, each 16 ft. in diameter and 19 ft. high. Two gas burners are installed on each furnace. These burners are of the single-valve, automatic gas-air proportioning type using high-pressure gas at 10 lb.

Jan 1, 1933