Search Documents

By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.' Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.' For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969

By C. G. Dunn

It is well known that plastic deformation alters many of the properties of a metal and subsequent heat-treatment partially or completely restores these properties.l In the deformed or strained state, the metal is unstable and tends to change toward a condition called a "strain-free state." The transformation occurs through recovery, recrystallization, and grain growth—processes that may take place singly or in combination. The distortion of the lattice of an individual grain of a metal in a state of strain may be rather complex in nature, because plastic deformation produces: (I) dislocations within mosaic blocks; (2) elastic variations of the lattice spacings; and (3) gross alterations throughout the lattice, especially along slip planes, along composition planes between a grain and its mechanical twins, and along boundaries of deformation bands. These gross alterations are of the nature of bent planes or rotated regions of the crystal lattice and are revealed by a spread in the orientation of the grain. Although we cannot describe these strains and their formation accurately because of insuffcient knowledge, we can, nevertheless, use the information as well as possible to obtain a better understanding of recovery processes. In recovery, the lattice of a grain is not made anew as it is in recrystallization, but is improved or mended in such a way that the basic structure remains unaltered: Until recatly observations were .that recovery produced no marked changes in the shapes of spots in Laue diffraction patterns, whereas recrystallization did, but now it is known for silicon ferrite2 that Laue spots may become quite sharp entirely through recovery. Consequently, the shape of Laue spots alone would not be a suitable test to distinguish between recovery and recrystallization. There is considerable evidence that the micro-structure usually does not change visibly during recovery. Absence of a visible change in the microstructure, therefore, provides a sufficient test of recovery in many cases. However, including this observation in a definition of recovery as a necessary condition (this is usually done) is unfortunate, because recovery may, as will become evident later, produce new grain boundaries that are visible not only in the microstructure but also in the macrostructure. For the present, therefore, let us say that a necessary condition for a process to be one of recovery is that the principal orientation or orientations of a deformed grain be essentially unchanged throughout the transformation toward the strain-free state. Several transformations may occur that fulfill this condition, and the nature of the distortion in a grain indicates what these must be if the lattice is to be mended in part or fully. Consequently, it will be convenient as well as

Jan 1, 1947

By T. L. Joseph

IT is a distinct privilege to participate in this meeting convened to honor the memory of Henry Marion Howe, a distinguished scientist and metallurgist. Many have added to our rapidly growing fund of metallurgical knowledge but few have made the unique contribution of formulating basic concepts essential to an over-all comprehensive view of the subject of metallography. Of those previously selected to deliver this lecture, several have added a personal touch to their discourse because they were able to refer to their associations with Dr. Howe. It was not my good fortune to know him or to enjoy his inspiring influence. Like most of you, my contact has been with his published works, which are outstanding in that they provide lucid, detailed expositions of the nature and behavior of metals and alloys. His deep understanding and clarity of expression have greatly accelerated our progress in metallography and in the use of metals. The degree to which a man's thinking, experimentation and writing contribute toward an understanding of basic laws and phenomena determines whether his life's work is of transitory or permanent value. This occasion appropriately recognizes the fundamental importance of Dr. Howe's pioneer work in the field of metallurgy. On two former occasions, gray iron was selected as a subject for discussion. The fact that the production of pig iron has not been discussed before does not reflect any lack of interest on the part of Dr. Howe or former lecturers in the process that under- lies the production of steel. Although Dr. Howe's work in his later years centered around metallography, his earlier publications show a considerable interest in the production of iron and steel. He recognized that in the ascending spiral of metallurgical advancement we are not winding a single thread but are weaving a complex fabric. Specific evidence of his interest in the production of pig iron may be found in his book1 on The Metallography of Cast Iron and Steel. In explaining why blast furnaces have been in constant use for about 600 years, he says: "The process is economical because it utilizes with extraordinary completeness the calorific power of the coke due to the thorough transfer of heat from the gaseous products of combustion to the charge." This emphasis on heat transfer, overlooked in many more extended and more recent discussions of the blast-furnace process, illustrates Professor Howe's ability to see the essentials. Other distinct advantages of the blast furnace, such as the removal of much of the sulphur and practically all of the oxygen, were mentioned. It was also stated that although the blast- furnace process is complex in nature, its outward form is comparatively simple, thus permitting large-scale production at small labor costs. All who contemplate the production of metallic iron from its ores by any other process might well consider the

Jan 1, 1946

By Frank C. Kelton

A method is outlined for the analysis of large cores, developed primarily for the purpose of obtaining reliable data on fractured or vugular limestones. Porosity and fluid saturations are determined by a modified Dean-Stark extraction after initially bringing the samples to 100 per cent liquid saturation by a vacuum-pressure method. Horizontal permeabilities on the whole samples are determined in two directions, parallel and perpendicular to the di-rection of principal fracturing. Results are presented for various types of formations. A comparison is made between data obtained by this special method and the method of conventional analysis, and discussion is given of the relative advantages and limitations of each. In view of this comparison a modified method for the analysis of fractured and vugular formations is proposed, which method retains the advantages of the previously outlined techniques but gives promise of speeding up the analysis. INTRODUCTION For many years the greater part of the production in the Permian Basin was from formations of Permian and Pennsylvanian age. While production from these formations is still the predominant production. deeper prospecting has brought to light older formations with oil productive characteristics. Attempts to core these deeper horizons were at first usually characterized by poor recovery. The old rule of thumb, "good core recovery — poor well" was originated and remained in effect until recently. With the advent of diamond coring and the increased efficiency in drilling and coring operations. the old adage has lost its significance. Formations of Devonian. Silurian and Ordo-vician ages were successfully cored with varying degrees of recovery. The cores thus obtained were surprising and in some case; disappointing. Good recovery from these formations led to speculation as to the feasibility of analysis and the meaning of data obtained from conventional analysis. Commercial laboratories were engaged to analyze these cores. and their results indicated that data obtained by conventional methods would be of little value. From visual inspection it was apparent that in many cases the effective porosity for storage of hydrocarbons. and permeability. were contained largely in fractures and solution cavities rather than in the primary crystalline structure of the formation. In other cases the solution cavities augmented the effective porosity of the primary crystalline structure, or fractures enhanced the permeabiilty of the latter so that the formation might respond favorably to acidization and become commercially productive. Since the spacing of the cavities and fractures was often comparable to the core diameter, it was evident that the entire core should he analyzed instead of small fragments. On the basis of these observations, commercial laboratories were requested to devise a system of analysis which would yield data of practical value. Pro- cedures have accordingly been developed which seem to meet this requirement, and to date nearly 12,000 large core samples have been analyzed. It is the purpose of this paper to describe the methods used, to present typical results for several fractured formations and to compare the data obtained by this special analysis with that obtained by conventional analysis. Certain modifications and alternative procedures are finally suggested to speed up the analysis. CORE ANALYSIS PROCEDURE Fluid Saturations and Porosity The core sample, in segments up to 15 in. in length. is marked, weighed and examined under ultra-violet light to determine the presence of oil saturation. If present, the approximate quantity of oil and its location on intercrystalline, fracture or vugular surfaces is noted. This information is carefully recorded. The degree of fracturing and/or vugular development is also noted. The sample is then placed in a pressure cell and the air evacuated with a high speed vacuum pump. This evacuation is continued only long enough to reduce the pressure to approximately the vapor pressure of water in order not to remove excessive amounts of water. Water is admitted to the cell and allowed to penetrate the sample under atmospheric pressure, filling the pore space initially occupied by air and replacing the small amount of water removed by evacuation. Pressure up to 200 psi is applied to force water into the smaller capillaries, and the sample is left sub-

Jan 1, 1950

By E. H. Jr. Dix

THE consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathews1 and by Tammann.2 Campbell and Mathews described principally the beginning of solidification. They found the curve of beginning of solidification to rise gradually from the melting point of pure aluminum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AlSb. The curve then drops to the melting point of pure antimony. Tammann explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AlSb. The space lattice of the compound AlSb, according to Owen and Preston,3 is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony.

Jan 1, 1930

By M. F. Burr, F. V. Lenel, G. S. Ansell

The mechanism of materials transport was studied in a model experiment in which a silver sphere was sintered to a silver plate under an applied external stress near 800° C. For this purpose the rate of growth of the neck between the sphere and the plate which is proportional to the strain rate of the creep process involved in a neck growth was determined by measuring the change in electrical resistance of the away. This rate of neck growth will depend upon the magnitude of the applied external stress. By measuring the rate just before and just after a change in the external load and therefore the applied stress, the relationship between strain rate and stress can be derived. For material transport by slip in a pure metal it is expected that the strain rate should be proportional to the 4.5th power of the stress, while for transport by diffusional flow the strain rate should be proportional to the first power of the stress. It was found that for stresses above 5 X 10' dynes per sq cm (70 psi) the exponent in the stvain rate-stress relationship was near 4.5 while for a stress of 0.7 x 108 dynes per sq cm (10 psi) an exponent of 1.8 was determined indicating that under the conditions of the experiment the transport mechanism for creep in silver shifts from diffusional flow to slip in the region of 0.7 x 106 dynes per sq cm (10 psi). The importance of these findings for an understanding of the mechanism of material transport in conventional sintering (without an external load) is pointed out. In a paper by Early et al.,' the mechanism of material transport during sintering was treated as a creep process. It was pointed out that two possible types of creep processes could operate during sintering. In one of these material transport takes place by vacancy diffusion due to a gradient in chemical potential. The vacancy sinks in this diffusion process may be either grain boundaries, as in Herring-Nabarro microcreep, or regions beneath a surface of small radius of curvature. The diffusive transport may be by volume, grain boundary, or surface diffusion. In the other mechanism, creep takes place by slip, i.e., dislocation motion with its rate generally controlled by dislocation climb. One method of distinguishing between these two modes of materials transport is to investigate the creep rate, i.e., the rate of material transport as a function of stress. For material transport by vacancy diffusion, the creep rate is proportional to the stress.' For creep by slip, controlled by dislocation climb, the creep rate is proportional to a power of the stress. For pure metals this power is 4.5;374 for dispersion-strengthened material a fourth power relationship can be derived.5 This difference in the stress dependence of the strain rate is illustrated schematically in Fig. 1, in which the logarithm of strain rate is plotted vs the logarithm of the stress for material transport in a pure metal by vacancy flux and by dislocation climb. The stress range in which the two types of material transport overlap would be expected to be relatively small. In the experiments described by Early and coworkers compacts pressed from spherical copper powder were sintered isothermally under an applied axial external load in a dilatometer. During sintering the magnitude of the applied external load was changed and the rate of axial shrinkage of the compact before and after the load change determined. In order to find the stress dependence of the strain rate the magnitude of the stress acting on the neck area between the spherical particles before and after the load change had to be calculated. This stress is the resultant of the stresses due both to the externally applied load and to surface tension. The stress due to surface tension is a function of the geometry of the powder compacts. It can be determined, at least for simple geometrical arrays,'76 but it is difficult to obtain exact values of the stresses for actual powder compacts when only average values of particle diameters and of neck diameters between particles are available. The calculation of stress and the strain rate-stress relationship is therefore only very approximate.

Jan 1, 1968

By C. W. Clark, J. H. Schloen

Two papers have been written previously concerning operations at the Montreal East plant of Canadian Copper Refiners Limited. The first one,1 written in 1932, described silver-refinery operations at the time for producing silver and gold bullion from tankhouse anode slimes; the second,2 published in 1933, consisted of a description of the entire plant. Since publication of these papers the refinery has become the world's largest producer of refined selenium. The first selenium was produced in August 1934. Tellurium production on a commercial scale followed in October 1935. This paper will deal with selenium and tellurium production and also with present operations in the silver refinery. Blister cakes from Hudson Bay Mining and Smelting Co., Flin Flon, Manitoba, and commercial anodes from Noranda Mines Limited, Noranda, Quebec, are refined at Montreal East. Both these bullions have unusually high gold, selenium and tellurium content. The average assay of raw slimes produced from domestic and Noranda anodes is about 40 per cent Cu, 3600 oz. per ton Ag, 800 oz. per ton Au, 22 per cent Se and 3.7 per cent Te. EARLY SILVER-REFINERY OPERATIONS From the start of operations in 1931 until July 1934, the raw slimes were oxidize-roasted at 700° F. in a Nichols-Herreshoff furnace, acid¬leached with tankhouse discarded foul electrolyte (20 per cent H2SO4), filtered and charged directly to the doré furnace for refining to doré metal. This is the customary method for treating tankhouse anode slimes but was not suitable at the Montreal East plant because of the high selenium and tellurium content of our slimes. In the acid-leaching process about 50 per cent of the selenium and tellurium in the roasted slimes was dissolved in the electrolyte. These elements were recovered with the copper as a sludge in a small electrolytic

Jan 1, 1938

By C. A. Herbert, C. M. Young

WithIn the past few years, considerable development has been made in the coal-mining industry in Illinois and Indiana and it is the purpose of the authors to record its most important phases. Perhaps the two most striking features are the entry into the producing fields of certain large consumers of coal and the magnitude of some of the new operations. Mines are now being equipped by the Chicago & Northwestern R. R., the Chicago, Burlington & Quincy R. R., the Standard Oil Co., of Indiana, and the Union Electric Light & Power Co. of St. Louis. Besides, the U. S. Steel Corpn. has increased its coal-mining activities by commencing operations on its large holdings northeast of Benton, Franklin CO., Ill. Until recent years, the supply of coal has commonly been adequate and prices have generally been favorable, especially to large consumers, as the magnitude of their purchases enabled them to obtain satisfactory quotations from producers. In fact, most consumers of coal have believed that they could buy their fuel more satisfactorily in the open market than they could produce it themselves. The entry of the United States into the war was accompanied by various disarrangements of industrial conditions, and a demand for coal in excess of the supply seemed likely to be experienced for an indefinite period. Under these circumstances it seemed that the greatest assurance of a supply of fuel was its production by the operation of mines. In the case of the Chicago & Northwestern R. R. and the U. S. Steel Corpn. the production of coal has been carried on for many years with satisfactory results, but the C. B. & Q. R. R., the Union Electric Light & Power Co. and the Standard Oil Co. of Indiana had not been producers of coal, at least in this district. Apparently the most impressive feature of the newest mines is their capacity, for in some cases it is planned that production shall be in the neighborhood of 1000 tons per hr. There are mines now in this field having nearly that output, but these were not planned for such output; in fact, when the shafts were sunk and the machinery installed it was generally supposed that the daily outputs would be only in the neighborhood of 4000 to 5000 tons. Incidentally, there has risen

Jan 1, 1920

By Armando M. Lago

Secular and cyclical patterns of postwar sources and uses of funds of the mineral sector are analyzed. A simultaneous equation behavior model of sources and uses of funds is developed for both mining firms and integrated producers, and these models were put through the task of predicting the financial and expenditure be-havior of mineral corporations in response to mergers and changes in investment tax credits and depletion allowances. Finally, the quantitative analysis methodology is applied to the analysis of optimum capital structure of mining corporations. The postwar changes that have occurred in the expenditure and financial behavior of mineral corporations are reviewed, particularly the relative importance of factors that affect the industry's supply and demand for funds. This quantitative statistical investigation of factors affecting sources and uses of funds of mineral corporations is achieved through the formulation of a simultaneous equation model of sources and uses of funds. After a description of the study sample, the postwar cyclical and secular financial behavior of mineral corporations is analyzed in detail. An econometric model of mineral corporate financial behavior is formulated. This model is then estimated and reviewed. Policy issues regarding depletion allowances, investment tax credits, and industrial organization of the mineral sector are discussed. Finally, the optimum financial structure of mining firms is discussed and the effect of corporate financial structure on the mining corporations' average cost of capital is analyzed.

Jan 1, 1971

By C. G. Dunn

It is well known that plastic deformation alters many of the properties of a metal and subsequent heat-treatment partially or completely restores these properties.l In the deformed or strained state, the metal is unstable and tends to change toward a condition called a "strain-free state." The transformation occurs through recovery, recrystallization, and grain growth—processes that may take place singly or in combination. The distortion of the lattice of an individual grain of a metal in a state of strain may be rather complex in nature, because plastic deformation produces: (I) dislocations within mosaic blocks; (2) elastic variations of the lattice spacings; and (3) gross alterations throughout the lattice, especially along slip planes, along composition planes between a grain and its mechanical twins, and along boundaries of deformation bands. These gross alterations are of the nature of bent planes or rotated regions of the crystal lattice and are revealed by a spread in the orientation of the grain. Although we cannot describe these strains and their formation accurately because of insuffcient knowledge, we can, nevertheless, use the information as well as possible to obtain a better understanding of recovery processes. In recovery, the lattice of a grain is not made anew as it is in recrystallization, but is improved or mended in such a way that the basic structure remains unaltered: Until recatly observations were .that recovery produced no marked changes in the shapes of spots in Laue diffraction patterns, whereas recrystallization did, but now it is known for silicon ferrite2 that Laue spots may become quite sharp entirely through recovery. Consequently, the shape of Laue spots alone would not be a suitable test to distinguish between recovery and recrystallization. There is considerable evidence that the micro-structure usually does not change visibly during recovery. Absence of a visible change in the microstructure, therefore, provides a sufficient test of recovery in many cases. However, including this observation in a definition of recovery as a necessary condition (this is usually done) is unfortunate, because recovery may, as will become evident later, produce new grain boundaries that are visible not only in the microstructure but also in the macrostructure. For the present, therefore, let us say that a necessary condition for a process to be one of recovery is that the principal orientation or orientations of a deformed grain be essentially unchanged throughout the transformation toward the strain-free state. Several transformations may occur that fulfill this condition, and the nature of the distortion in a grain indicates what these must be if the lattice is to be mended in part or fully. Consequently, it will be convenient as well as

Jan 1, 1947

By F. O. Shuck, F. E. Butler

A diaphragm diffusion cell suitable for use with liquid metals was designed and tested by measuring the diffusion coefficients for a Hg-10 pct In alloy at 25°C. The binary diffusion coefficient and the coefficients for In and Hg tracers were measured at this composition. The measured coefficients for both tracers were less than the binary diffusion coefficient. When these coefficients were combined with the activity correction term of Darken, the predicted binary coefficient was somewhat higher than the experimental value. In recent years a number of investigators have been studying diffusion of liquid metals in order to gain a better understanding of the liquid state and to examine possible applications to liquid metal processing. The bulk of this work has involved either self-diffusion or diffusion of low concentrations of solute metals in an essentially pure solvent metal. The most common experimental technique employed has been the capillary-reservoir method of Anderson and saddington1 since it is well-suited to measurements involving low concentrations of solutes. As an expansion of previous studies, an investigation of the variation of diffusion coefficient over large composition ranges has been undertaken in this laboratory. Although it is possible to modify the capillary-reservoir method for such measurements, the technique loses its principal advantage of requiring only small quantities of solutes. Therefore, it was felt desirable to investigate other possible experimental techniques applicable to measurements over large composition ranges. A technique which has been used widely in measurements of other liquid systems and seemed potentially applicable to studies of liquid metals was the diaphragm cell. This method has been found to combine relative simplicity of operation with accurate and reproducible results. In use with normal liquids, the tyiical diaphragm cell utilizes a porous glass disk. However, because of the high surface tension, it is not possible to use a diaphragm of such fine pore structure with liquid metals. Furthermore. projected use at high temperatures makes the use of glass undesirable. Consequently, the first problem was the search for an appropriate cell design. EXPERLMENTAL Diaphragm Cell. A number of possible cell designs were examined. Prototypes of several were constructed and tested. The final design is shown in an exploded view in Fig. 1. The cell consists of two identical chambers, one on either side of a 0.20-in.-thick partition. The chambers are 0.15 in. deep and have a volume of 3.45 cu cm. Each chamber is provided with two small threaded holes for filling and emptying. The filling holes may be sealed with stainless-steel screws. Drilled lengthwise through the center partition is a 0.250-in.-diam hole. Inserted into this hole is a rod having seven 0.059-in.-diam holes drilled radially through it. The total "hole" volume is 0.078 cu cm. When the rod is properly aligned, the holes in it constitute the "diaphragm" through which diffusion occurs. The center section was of Teflon and the rod and face plates were of Plexiglas. Four such cells were constructed and used in this study. Subsequent to this investigation, a similar cell constructed entirely of iron was fabricated and tested at higher temperatures. Several considerations led to this final design. It is desirable to minimize the volume of the cell chambers to decrease the time required for a measurement. However, the total volume of metal in the diaphragm must be small in comparison with that in the chambers. To facilitate filling and emptying it is desirable to have a diaphragm which may be closed.

Jan 1, 1970

By J. L. Huitt, B. B. McGlothlin, D. K. Lowe

Published correlations for the principal aspects of hydraulic fracturing were combined into a digital computer program to facilitate the study of interrelated variables. The computer program includes individual relationships for fracture width during pumping, fracture area generated, propping agent embedment, flow capacities of propped fractures and transport of propping agents in horizontal fractures. The effects of more than 20 treatment and formation parameters on the predicted results of hydraulic fracturing treatments were studied. The effects of these parameters were determined for (I) fracture width during injection, (2) fracture width after the overburden comes to rest on the propping agents, assumed not to be crushed, (3) generated and propped fracture area, (4) location and concentration of propping agents in the fracture when injection ceases, (5) flow capacities of the various propped sections of the fracture and (6) expected increase in the well productivity. The effects of propping agent, formation and fracturing fluid parameters on well productivity are discussed. The parameters that were found to have the most pronounced effects on hydraulic fracturing treat~nents are injection rate, treatment volume, fracturing fluid coefficient, size and amount of propping agent, spearhead volume, well drainage radius and formation capacity. INTRODUCTION Many correlations have been published for predicting effects of various parameters that are considered in the design of hydraulic fracturing treatments. The Carter equation' can be used to predict generated fracture radius as a function of fracture width, fracturing fluid leakoff and other parameters. Fracture width can be determined by use of the Perkins and Kern correlation' in which the fracture width is related to the fracture radius, fluid injection rate and certain formation and fracturing fluid parameters. Wahl and Lowe et aL4 have reported methods of predicting the location of propping agents in fractures when pumping ceases. The former study is applicable to the case where the ratio of propping agent diameter to fracture width is less than 0.1. The latter is applicable when this ratio is greater than 0.1. These studies showed that the propping agent placement in horizontal-radial fractures depends principally on how the individual particles are transported in the fracture by the carrying fluid. Particle transport in fractures is determined by local fluid velocity in the fracture, fluid and particle properties, and the size of the particle relative to the fracture width. The distribution of propping agents, effective overburden pressure and formation rock strength control the propped fracture width6 by controlling the extent to which the propping agent particles embed into the fracture faces. From the distribution of propping agents and the propped fracture width, fracture flow capacities can be calculated or the various regions of the fracture. The flow capacities and the radial extent of these regions can be combined with reservoir information to predict the productivity increases for fractured wells. In all these studies, the effects of certain treatment and/ or reservoir parameters on one facet of fracturing can be predicted only if other facets which the parameters affect are fixed. For instance, fracture width and radius are interrelated; that is, to calculate the value of one, the value of the other must be known. Also, some parameters influence more than one aspect of fracturing. For example, prop-pant transport is a function of both fracture width and fluid viscosity. but fracture width is itself a function of fluid viscosity. Since these calculations are complex and the parameters interrelated, it is not possible to write an equation with which the over-all effects of treatment parameters can be solved explicitly. For these reasons, the correlations for determining the effects of the parameters which are most significant in hydraulic fracturing treatments have been incorporated into a digital computer program. COMPUTER PROGRAM The program, which was written for an IBM 7094 computer, can be used to predict results of most of the combinations and values for the treatment parameters that are ordinarily considered for fracturing treatments. A spearhead of fracturing fluid and a propping agent-carrying fluid with different fluid properties can be taken into account. Also, the total volumes and relative amounts of the spearhead and carrying fluids can be varied. Two different propping agents (as used in tail-in operations) and a wide range of formation properties and injection rates are considered. The computer program (Fig. 12) consists of several sets of calculations. First, the final flooded fracture radius and average fracture width at the cessation of pumping are calculated. This is done by simultaneous solution of the Perkins and Kern fracture width equation and the Carter equation for flooded fracture radius (equations used in the computer program appear in the Appendix). The next step is to determine local fluid velocity in the fracture as a function of time and radius. Since it is not possible to write this function in closed form expression, a table of velocity values is generated by the program and stored for subsequent use. The time span from the beginning of

By George B. Clark

THE " Munroe effect" of shaped explosive charges was discovered by Charles E. Munroe more than 50 years ago (in 1888), but it was not until World War II that it was put to any practical use. Both Allied and Axis armies used the principle effectively in bazooka projectiles, artillery projectiles and in fixed shaped charges. The first two were used primarily to combat tanks and other armor and the latter to assault pillboxes and other fixed concrete emplacements. Many engineers and others who saw the military application of the jet effect of shaped charges believed application would be possible in many industrial fields where blasting is used, such as mining and quarrying. Some work has already been done on the problem of making shaped charges applicable to mining operations. Experimentation conducted at the National Tunnel and Mines' was directed primarily along the lines of use of shaped charges for secondary blasting in connection with long-hole stoping methods. Experimentation initiated earlier and conducted by the author2 at the University of Utah on a more scientific basis was directed at revealing the basic principles of the functioning of shaped charges, as well as the feasibility of using them in mining operations after the principles of their operation had been clearly defined. It was found that: (I) a given design of charge required an optimum standoff to make it most effective, either in penetrating solid rock or steel (see Fig 3); (2) for a given design of charge there exists an optimum ratio of charge diameter to charge height above which the increase in effectiveness of the charge decreases rapidly (see Figs 4 and 5); (3) partial confinement has the effect of making charge performance much more consistent; (4) the higher power and higher velocity explosives tested are much more effective than relatively low-strength explosives; and (5) shaped charges may be adaptable to mining operations in secondary breakage and drilling blasting holes. Fig I is a diagrammatic sketch of the action of a shaped charge for two types of cavities, while Fig 2 shows the approximate manner in which the jets are believed to be formed when an explosive wave encounters the cavity, approaching it from the top. The experimentation already completed has laid the foundation for further research in the study of shaped charges. Standoff effects, effect of the strength of explosives and other features have been fairly well established. Such elements in the design of shaped charges as (I) geometry of cavity liners, (2) relative horizontal dimensions of explosive column, (3) effect of

Jan 1, 1947

By F. R. Brotzen, L. D. Whitmire

Single crystals of high-purity molybdenum were de-formed at temperatures from 195°to 473°K, and the effect of deformation on the electrical resistivily was deler-mined. To separale the resislivity components of point and line defecls some cryslals were annealed at 473°K. The vale of resislivily increase wilh strain was nearly linear and was strongly dependent upon the deformation temperature. Point dejects are annealed out without any effect on the flow stress. At low temperatures the flow stress is a linear function of the square root of the resistivity increase attributable to dislocations. ELECTRICAL-resistivity measurements have been used successfully to gain information on structural changes in metallic materials. During plastic deformation the electrical resistivity rises because of electron scattering from newly created lattice defects. Such measurements lend themselves, therefore, to corroborating results from direct observation of lattice defects and, to a certain extent, to correlating defect densities and distribution with mechanical properties. Published information on research with single crystals of the bcc metals of Group VI, particularly molybdenum, is still limited. Yet, molybdenum single crystals of relatively high purity can be readily prepared by electron-beam-melting techniques. Furthermore, some valuable information on the defect structure of deformed crystals by direct observation is available. Lawley and Gaigher,1 for example, have examined dislocation configurations in deformed molybdenum crystals by means of transmission electron microscopy. Their results revealed that the dislocation density and distribution were strongly dependent upon the deformation temperature. These findings differed from those by Keh and weissmann,2 who found that the average dislocation density in polycrystalline iron deformed between 138° and 298°K depended only on the degree of strain and not on the deformation temperature. Martin3 and peiffer4 showed that point defects introduced in polycrystalline molybdenum by cold work can be eliminated by annealing at a relatively low tempera-ture. In view of their work it became apparent that resistivity measurements of suitably annealed crystals could disclose changes in their dislocation structure and contribute to the understanding of the work hardening of molybdenum crystals. EXPERIMENTAL PROCEDURE Crystals were grown by electron-beam zone melting5,6 of 0.062-in.-diam molybdenum rods (99.99 pct) supplied by General Electric Lamp and Wire Division, Dover, Ohio. The crystals, about 4 in. long, were prepared by using five zone-refining passes at a speed of about 6 mm per min in a vacuum of about 5 X l0-6 Torr. The resistivity ratio of the crystal, p(4.Z°K)/p(273°K), was generally near 10-3. These crystals were used as tensile specimens of uniform diameter in the "as-grown" condition. They were oriented for maximum shear on the (011)[111] slip system (Schmid factor >0.49). The specimens were held in spherically seated Templin-type grips so as to minimize bending. Samples were deformed on an Instron machine at a strain rate of about 5 X 10-5 sec-1 in an isopentane bath with dry ice at 195°K, in ice water at 273°K, and in a vegetable-oil thermostat at 373° and 473°K. The temperature in the latter was maintained constant within +2°K. Resistance measurements were carried out with a Kelvin double bridge. The resistance of the potential leads was kept low by using large-diameter wires outside the low-temperature bath. Many of the resistance data were checked by measurements made with an ac bridge. Current and potential leads were spot-welded to the specimens. The distance between the potential leads, about 3 in., was also considered to be the gage length for the strain measurements. Diameter and gage length of the samples were measured optically with an error of less than 2 pct. These measurements were used also to insure that the deformation had been uniform over the gage length of the specimen. Resistivity changes were then determined from the resistance measurements at 4.2°K assuming constancy of volume. In the course of a test, the crystal diameter, gage length, and resistance at 4.2°K were determined first in the initial state and subsequently for various amounts of elongation.

Jan 1, 1968

By S. A. Braley

DRAINAGE water from coal mines is probably the most serious water pollution problem today, varying in importance according to location of the mines and geological structure. Drainage may be either acid or alkaline in character. Acid discharge, the most severely detrimental to a stream, is caused by natural oxidation of the sulfuritic material (FeS2) in the strata associated with the coal seam. Since the acid is the result of a natural reaction the acid water differs because it does not cease with abandonment of the mining operations. There is no known economical method of neutralizing acid mine water or any practical method to prevent oxidation of exposed pyrite. Since production of acid from a mine does not stop when mining stops, the total quantity produced depends entirely upon the excavated areas. The increasing volume of acid water in manv mines has greatly increased operating costs. Pumping is expensive and acid mine waters are destructive of all equipment, especially metals in pumps and piping, and necessitate the use of corrosion-resistant materials. Discharge of the acid mine drainage into streams neutralizes their normal alkalinity, causes them to become acid, and produces an environment unfavorable for aquatic life and unsuited for industrial or domestic use without costly treatment. Mine drainages vary in percentage composition over wide limits, although the usual dissolved substances are ferrous and ferric iron, aluminum, calcium and magnesium sulfates, and lesser amounts of sodium, potassium and manganese sulfates and chlorides. Some alkaline discharges may contain heavy concentrations of iron as iron bicarbonate. These waters may produce iron hydroxide deposits in the receiving stream but do not cause it to become acid. In the extensive literature on acid mine water there appears to be a great deal of confusion about the importance of various components and the methods for their determination. In many instances faulty conclusions have been drawn from use of unsuitable methods of analysis. It is desirable that the factors and terms used in evaluation of analyses of mine waters should be so clearly defined that any interested person could properly appraise any analytical report. Some analysts report complete chemical analyses of mine waters and neglect to record drainage volumes. Others report only a minimum of analytical data after taking no precautions to preserve the original composition of the water during the time elapsing between collection and analysis. Some use methods of analysis intended for so-called pure waters of the potable and boiler water classes. These methods are not applicable to highly buffered waters such as mine water. Probably the most common criteria for evaluation are pH, free acidity, or acidity or alkalinity to methyl orange or methyl red, total acidity or acidity to hot phenol-phthalein, and the sulfate content. If these determinations are made on carelessly collected samples after a few days to weeks standing in warm rooms, they do not in any way represent the character of the water flowing from the mines. It is hoped that a brief discussion of the fundamental value of some of these factors may lead to a bettqr understanding of the need for more careful evaluation of mine water discharges. The term pH is one used by chemists to express relative acidity or alkalinity in terms of concentration of effective hydrogen ion in a solution. It is defined as the negative logarithm of the hydrogen ion concentration or activity in equivalents per liter. pH = logarithm A neutral solution, which is one containing the same number of hydrogen and hydroxyl ions, has a pH of 7. As the hydrogen ions increase and the solution becomes more acid, the pH decreases toward zero; and as the hydroxyl ions increase and the solution becomes more alkaline, the pH approaches 14. When dissolved in water to a dilute solution acids like sulfuric and hydrochloric, commonly known as strong acids, ionize completely, and the pH or hydrogen ion concentration varies with molar concentration of the dissolved acid. However, in high concentrations of such acids, the pH or hydrogen ion concentration is less than the acid concentration because the acid does not completely ionize. In only very dilute solutions does the pH represent the total amount of acid that can be neutralized by an alkali. All ionization reactions are equilibrium reactions. If other chemicals are added to the solution of an acid and the added chemical produces an ion that is the same as one of the ions of the acid, the degree of ionization of the acid is altered and the pH changes to some value that represents the active hydrogen ion of the new solution. Thus if iron sulfate is added to a solution of sulfuric acid the pH increases, since the common sulfate ion suppresses the degree of ionization of the sulfuric acid and decreases the effective hydrogen ion. However, the total acidity of the solution is increased. There are two salts composed of iron and sulfate— ferrous and ferric sulfate. In these salts there is no hydrogen ion that can ionize to give an acid solution, but when they are dissolved in water, the pH is less than 7 and the solution becomes acid. This is caused by a reaction known as hydrolysis and is represented by the equations FeSO4 + 2H2O ? Fe(OH)2 + 2H + SO,: or Fe,(SO,)3 + 6H2O ? 2Fe(OH)3 + 6H+ + 3504 A solution with a total acidity of 5000 ppm according to the first equation will have a pH of 4.40 but one with an acidity of 75 ppm, according to the sec-

Jan 1, 1958

By Albert J. Phillips

IT is a privilege and a pleasure to deliver this, the Twenty-sixth Annual Institute of Metals Division Lecture. Eleven years ago C. A. Edwards addressed this audience on the subject "Gases in Metals." In spite of this relatively recent presentation, I propose to, present to you some quantitative considerations of industrial significance on the separation of gases from molten metals because recent observations and measurements, presented in the literature, have made it possible to evaluate mathematically the gases or gas-forming elements and to develop an understanding of the mechanism of gas separation that should permit, in many cases, the control of this baffling phenomenon. DEFINITIONS Before becoming involved in the subject it seems desirable, for the sake of clarity, to state certain definitions and axioms: I. We are dealing only with gases that separate from the molten metal either during cooling or in the transition from liquid to solid. Gases injected by the liquid stream and trapped in the solidified metal, or those forced into the solidifying metal from the mold due to either thermal or cher4ical effects are not considered. Neither are we concerned with the separation of gases within the metal after solidification is complete for the data on this subject are at least complete enough to permit the practicing metallurgist to satisfactorily control the phenomenon. 2. Only where there is a decrease in solubility or a change in equilibrium of either a gaseous element or an element that reacts to form a gaseous compound, can there be a separation of a gaseous phase from the liquid or solidifying metal. 3. The amount of gas separating from the liquid during solidification can be computed directly from the amount of the element contained in the liquid when freezing commences less the amount of the element found in the solid either as a separate solid phase or in solid solution. 4. There can be no separation of gas bubbles unless the told pressure of the gases in the liquid meld exceeds atmospheric pressure plus the hydrostatic pressure of ' the liquid metal head. (In addition, pres- sure resulting from surface tension in- creases the total pressure requirement for initial gas separation. Probably the remarkable differences in appearance caused by different gases in the same host metal are influenced greatly by the rate of diffusion of the gas in the liquid metal balancing the decrease in pressure as the gas bubble size increases and the surface tension effect decreases. Thus hydrogen with its high diffusion rate in liquid copper separates in the form of relatively coarse cavities for a given rate of heat extraction.) 5. Gas separation can take place at less than atmospheric pressure in the voids created by the shrinkage from liquid to solid, but since the voids are not caused by the gas the presence of gas in the voids is of importance only where it

Jan 1, 1947

"The reduction works of the Boston & Montana Reduction department, near the north end of this dam is one of the reduction plants belonging to the Anaconda Copper Mining Company, the other being at Anaconda. These works employ about 1,100 men and have a capacity of about 3,800 tons of crude ore per day. This plant is now being remodeled to embody results of experiments and investigations which have been made with a view to more economic.al treatment of ores. A brief description of the plant as it will be after the remodelling is as follows:Concentrator Department: Consists of six units or sections, each section treating from 550 to 600 tons of crude ore per day. This department is not being. remodelled at the present time. A concentrating process, however, has been developed and partially installed in the old mill, and an experimental section embodying this concentration process has also been installed at the concentrator at Anaconda."

Jan 1, 1913

By F. E. Bash

Constantan is an alloy of copper and nickel that is extensively used, under a number of trade names, as a resistance wire with a low temperature coefficient of resistance, and one of the elements of base-metal thermocouples, iron usually being the other thermoelement, although for low-temperature work copper is also used. Before the war, constantan was imported, in common with many other technical necessities. Since it required considerable time to receive the constantan after it was ordered, fairly large stocks were kept on hand; but after the beginning of the war no more was imported and the stocks of foreign material were exhausted about the same time that the steel and munition manufacturers began to need great quantities of it for thermocouples for the heat treatment of steel. To meet this demand, the International Nickel Co. began manufacturing constantan that met all the requirements of the users of resistance wire but did not give the same electromotive force against iron as the German material and consequently could not be used with instruments calibrated for a definite e.m.f.-temperature relation. It so happened that all the constantan made had an e.m.f. lower than that necessary to meet the specifications of the Leeds & Northrup Co. for whom this investigation was carried out. If some had been higher and some lower, good wire could have been obtained by a process of selection, but as it was no wire at all could be procured. To remedy this situation, a thorough investigation was started with the close cooperation of the International Nickel Co. and the Electrical Alloys Co. The specifications to which the constantan had to conform were that it should give an e.m.f. of 47.40 millivolts against pure iron at 1500" F. (816" C.) with the cold-junction temperature at 0" F., or a proportional e.m.f. at temperatures near 1500" F. The method of checking a wire was as follows: It was first welded to a piece of iron wire; Armco iron was found to be satisfactory but iron with greater than 0.1 per cent. carbon would give a lower e.m.f. against the same piece of constantan than pure iron. The couple was then insulated and the fire end was tied to the

Jan 1, 1921

By John A. Ames

Webster's dictionary nearly equates portland cement with its current primary definition of cement. While such equation may be a triumph of common usage, the confusion between the terms cement and concrete unfortunately is very widespread. Full definition of cement properly would extend to many substances, but for purposes of this chapter cement is restricted to "varieties" of portland cement including "portland-pozzolan" cement. Among the usually recited historical notes concerning cement is that it was developed by the Romans. Their use of cement in the great structures of Rome, and even in the far corners of their Empire, such as Hadrian's Wall in the north of England, testifies to the antiquity of a major cement industry. From English sources we know of John Smeaton's carefully proportioned hydraulic cement mixed in 1756 and of Joseph Aspdin's patented cement to which, in 1824, he gave the name portland cement. (He claimed that his cement mortar looked like the famous dimension limestone quarried from the Isle of Portland on England's south coast.) The year 1971 marked the centennial of portland cement manufacture in the United States. A fair historical account of the many real contributors to the cement industry between 1756 and 1972 unfortunately would be too extensive for this chapter. Development of rotary kiln practice and burning at higher temperatures clearly was the major move into today's technology. As part of the 4th edition of Industrial Minerals and Rocks, this chapter on utilization focuses on inferred interests of the anticipated readers. The main period for which statistics are cited generally is that since the 3rd edition (1960) of this same volume. Cement manufacture is the processing of selected and prepared mineral raw materials to produce the synthetic mineral mixture (clinker) that can be ground to a powder having the specified chemical composition and physical properties of cement. Cement making incorporates a number of distinct steps, but it is characterized by the key pyroprocessing (or "burning") step, which brings about the necessary changes in the raw materials. This pyro processing is a chemical process. Conversion of large volumes of mineral raw materials into specification-controlled cement at relatively low cost is the objective. Statistics on the cement industry are of uneven quality. The U.S. Bureau of Mines (USBM) is the principal collector of available data. These statistics can be only as good as the quality of information supplied by the reporting companies. The data perhaps most often questioned relate to productive capacity of the industry. The questions submitted by USBM are valid, nevertheless, and the information gained from them, as good as is available, is what is generally used. The Portland Cement Association also is a source of much quality information. The year 1972 witnessed a test of the adaptability of cement industry statistics. This was the year of conversion from barrels and sacks of cement as the units of measure to tons and hundredweights. The barrels and sacks related to volumetric measures in that a sack was judged to be 1 cu ft (weighing a "standard" 94 lb). A barrel was 4 sacks. Volumes of concrete are stated in cubic yards, and the number of cubic feet of cement in a cubic yard of concrete was a sensible approach to the mensuration involved. However, cements do not weigh the same amount from plant to plant or from type to type, and the buyer was more interested in getting an assured weight for his money than in "buying air." Thus, a sack, in accepted practice, became 94 lb instead of 1 cu ft, and a "barrel" became 376 lb, regard- less of whether it would fit into 4 cu ft of space. With the de facto dealing in weight rather than in volumes, the awkward numbers made little

Jan 1, 1975

By H. Hubert

The first attempts at direct utilization of blast-furnace gas in engines were made in 1895. For a considerable time the gas had been burnt in Cowper stoves for heating the blast for the furnace, and under the boilers which supplied steam to the blowing-engines, and others serving the furnaces. It was natural, therefore, that the idea of directly employing it in gas-engines should have occurred simultaneously to several engineers, notably to Lurmann and to Lencauchez, who had pointed out the blast-furnace as a powerful gas-producer. Nevertheless, nowhere had any attempt been made to apply it to this purpose up to the end of 1894, when Thwaite proposed it to Mr. James Riley, of the Glasgom Iron & Steel Company. About the same time investigations were being made in Belgium and in Germany, independently of Thwaite's experiments, which were not generally known on the Continent. The industrial world, which up to that time had hardly favored the idea, had thus been gradually prepared to receive it. The gas-engine, long restricted to small sizes and dependent upon the use of an expensive fuel obtainable only in large centers, now began to make headway. At the Paris Exhibition of 1889 two engines of 100 h.p. were shown and excited much interest among engineers. One had four cylinders, and was made at the celebrated works of the Deutz Company, and the other was a single-cylinder engine, exhibited by two French designers, Messrs. Delamare-Deboutteville and Malandin. In the meanwhile the design of gas-producers had made important progress, completely freeing the new engine from its

Jan 1, 1907