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By Ralph Hultgren

IN solid solutions atoms of differing sizes occupy the same crystalline lattice, requiring that some of them be compressed and others expanded. The energy involved has been called misfit strain energy and is an important concept of crystal chemistry. If the atomic sizes and elastic constants of interatomic bonds are known, the misfit energy may be calculated,' provided certain simplifying assumptions are allowable. Usually, isotropic crystals are assumed and interatomic distances are taken to be the statistical average determined from X-ray diffraction. Such calculations yield values of the misfit energy of the order of 1 or 2 kcal per atom in alloys such as Au-Cu at compositions of 50 atomic pct. However, evidence has accumulated in recent times that atoms change their sizes with composition of alloys, implying electronic rearrangement of the bonds. The size changes have been found particularly by application of the X-ray method developed by Warren, Averbach, and Roberts.' Thus, Averbach, Flinn, and Cohen3 determined radii in Au-Cu alloys. Oriani4 showed that these new radii led to a calculated misfit energy in disordered AuCu, which was decreased from the values calculated by the usual theory more than twenty-fold, to only 80 cal per g atom. Thermodynamic calculations from the phase diagram5 also show misfit energy to be no more than a few hundred calories per g atom in this alloy. The question of what electronic rearrangements are possible therefore becomes compelling in estimating misfit energy. In the following pages the results of certain calculations on the AuCu tetragonal superlattice are submitted. Conclusions drawn from these should be applicable in large degree to disordered solid solutions. As in all ordered states, bonding distances in the superlattice are individually known, rather than being merely average distances as found from lattice constants of disordered states. Moreover, only the Au-Au and Cu-Cu distances are strained; the elastic constants of these are known in the elementary state. In the usual calculation it is necessary to assume elastic constants for Au-Cu bonds. Misfit energy has thus been calculable without the need of many simplifying assumptions usually made. It is still assumed that equilibrium bond lengths and elastic properties of the bonds are the same in the alloy as in the pure metals. As previously discussed, this is probably not correct. Also assumed is that the bonds are not affected by strain of neighboring bonds. A calculation of Young's modulus from compressibility data shows this to be far from true; extensive electronic rearrangements take place. It would seem that misfit energy cannot be calculated from elasticity data for the elements. The usual methods may, however, give an upper limit which is often much higher than the true value. The question of electronic rearrangement is, of course, a complex one. Pauling's theory gives a simple, approximate treatment of the relation between type of bond and bond distance. This has been applied with some success to the Au-Cu system, as will be shown in a later section. Misfit Energy in Au-Cu Alloys Hume-Rothery and Raynor6 discuss the Au-CU system as a type example of strain energy. The gold atom is 12.8 pct larger in diameter than the copper atom, near the size factor limit beyond which solid solubility is severely restricted. They therefore consider the misfit energy to be large, a conclusion for which they believe they find evidence in the phase diagram. Gold and copper are completely miscible in the solid state, but the alloy has a minimum melting point at an intermediate composition. From this Hume-Rothery and Raynor conclude that the strain energy is nearly large enough to prevent miscibility; the phase diagram tends toward a eutec-tic type. In Ag-Cu, which has almost identical size relationships, solid miscibility is quite limited; whereas in Au-Ag, where atomic sizes are nearly the same, there is complete miscibility without a minimum in the melting point. From their arguments the heat of formation of Au-Cu would be expected to be endothermic or only slightly exothermic, that of Ag-Cu to be endothermic, and that of Au-Ag to be exothermic. Deviations, from Ve-gard's law of additivity of atomic radii support these conclusions, since Au-Cu and Ag-Cu both have pronounced positive deviations, and Au-Ag has a negative deviation. Nevertheless, Au-Cu alloys form exothermically; indeed, considerably more exothermically than Au-Ag, Table I. Hence, strain energy must be much less important in this case than Hume-Rothery and Raynor have supposed.

Jan 1, 1958

By R. L. Bleifuss

Most pellets swell only slightly during reduction, but some swell so enormusly that their increase in size is termed catastrophic. Since catastrophic swelling produces irregularities in blast furnace operation, an understanding of the phenomenon is of practical as well as theoretical interest. Observations have shown that catastrophic swelling is characterized by the growth of a network of fine iron filaments. Evidence is presented to show that the growth of these filaments is promoted by the presence of calcium in the magnetite lattice of the original ore. During reduction, the limited mutual solubility of CaO and FeO produces an unstable condition that inhibits the uniform nucleation of metallic iron. Other elements in the magnetite lattice whose oxides are continuously soluble in FeO in the critical temperature range have no effect. Magmatic segregation or pyrometasomatic replacements are the most likely deposits to contain calciferous magnetite. Over the past few years there has been an increasing concern throughout the iron and steel industry over the tendency of pellets to swell during reduction. Although the tendency for swelling is only one of several attributes that determine the behavior of pellets in the blast furnace, swelling-reduction tests are now part of the normal evaluation procedure of many pellet consumers. During a swelling-reduction test, pellets display either the moderate increase in size known as normal swelling, or the enormous expansion known as catastrophic swelling. This paper is concerned with the origin and control of catastrophic swelling and how it is enhanced or inhibited by the presence of minor elements. Swelling Behavior The swelling behavior of pellets during reduction is indicated in Fig. 1. The lower curve represents normal swelling and the upper curve catastrophic swelling.' During the initial stages of reduction, that is, up to about 20-25% reduction, the two curves are considered to be equivalent. Beyond this point normal pellets undergo a gradual decrease in size with increased reduction. By contrast, pellets which exhibit catastrophic swelling show a second dramatic expansion between 25 and 70% reduction. The initial normal swelling develops as the hematite of the pellet is successively reduced to magnetite, and then to wustite. Work by Edstrom' and others has shown that the reduction of hematite to magnetite is accompanied by a 25% volume increase, whereas the magnetite to wustite stage shows a volume decrease. The volume increase overlaps the wustite field because magnetite is formed simultaneously with the wustite during topochemical reduction of the pellet. The catastrophic expansion is clearly related to the wustite, to

Jan 1, 1971

By A. Becker, J. A. Slankis

Equipment has been developed to utilize natural 8 Hz electromagnetic fields to measure rock resistivities. Telluric and magnetotelluric surveys have detected resistivity variations associated with geological contacts and metallic sulfide deposits. The fundamenfa1 premises of these methods are illustrated by the results of surveys across a Pleistocene-Precambrian contact in the Ottawa Valley and a near-surface sulfide deposit in Northern Quebec. Such interfaces are characterized not only by variations in apparent resistivity, but also, unexpectedly by the spatial anisotropy of the electric fields and the presence of a strong vertical magnetic field component in their vicinity. Standard geophysical electrical and electromagnetic methods (Heiland, 1940) for the determination of the electrical properties of the ground and the search of good electrical conductors necessitate the use of a transmitter and receiver which are coupled galvanically or inductively through the ground. The electrical properties of the ground are deduced from either the transfer function, or the impulse response, of the transmitter — ground — receiver system. Where deep penetration is desired these methods require powerful transmitters whose weight and size increase the cost and reduce the speed of operation. It is possible however, to resort to another class of electrical prospecting methods which employ ambient, natural electromagnetic fields in place of a transmitter.'-' In the audio and subaudio frequency ranges, these fields are generated by thunderstorm activity. At some distance from the seat of the disturbance, the e.m. fields propagate as plane waves with a horizontal magnetic field component. The incident wave, of course, induces currents in the ground. Where the ground is homogeneous the relation between the horizontal magnetic and horizontal electric fields vectors is particularly simple:' /E/ = \[SpT/H/ (1) where: /E/ = magnitude of horizontal electric field in millivolts/kilometer (RMS) /H/ = magnitude of the orthogonal inducing magnetic field in milligammas (RMS) p = rock resistivity in ohm-meters i = frequency of measurement in c/s In practice, the ground is seldom an homogeneous half space, lateral conductivity variations exist, (in the case of base metal prospecting these are the features actually sought) and the two field vectors are no longer simply related. The ratio of E to H is still useful, however, for the determination of an "apparent" ground resistivity. From a theoretical view point, the general problem of a two dimensional fault or dyke anomaly can be separated into two distinct cases. In the first case, where the e.m. energy propagates in a direction normal to the strike, the horizontal magnetic field remains constant and is oriented along the strike of the formation.3 As shown by d'Erceville and Kunetz," all the information about the anomaly is contained in measurements of the electric field component. In fact, away from the interface, the electric fields are proportional to the square roots of the resistivities:

Jan 1, 1970

By Leonard D. Jaffe, Donald C. Buffum

THE importance of temper brittleness in alloy steels has long been realized in Europe, In the United States recognition of its importance has developed within the last several years. Many brittle failures encountered in parts made of alloy steel are undoubtedly attributable, wholly or in part, to temper brittleness. These failures have occurred particularly at low temperatures, under shock loading, and in the presence of notches, restraints and combined stresses. It has been almost universally accepted that plain carbon steels are not susceptible to temper brittleness. As a result, considerable effort has been expended in attempts to discover the manner in which alloying elements introduce temper brittleness. It is desired to raise the possibility that plain carbon steels are not only susceptible to temper brittleness, but are much more susceptible than alloy steels, in the sense that they embrittle much more rapidly. It is suggested that previous views, (that plain carbon steels are not susceptible), are based upon an erroneous interpretation of the experimental results. INTERPRETATION OF PREVIOUS DATA For many years the standard criterion for susceptibility of a steel to temper brittleness consisted of comparison of the energy absorption, in a notched-bar impact test at room temperature, of specimens that had received two heat treatments.1 One specimen (or group of specimens) was quenched, tempered, and quenched from the temper. The other specimen (or group) differed only in having received an embrittlement treatment, which might consist of a slow cool from the tempering temperature, or of an isothermal hold in the range 450-550°C subsequent to quenching from the temper. If the energy absorption of the specimen receiving the embrittlement treatment was lower than that of the specimen not given this treatment, it was said that the steel was susceptible to temper brittleness, If the energy absorptions were the same, it was said that the steel was not susceptible. Several investigators2,3 found that plain carbon steels showed negligible difference in energy absorption in such tests (at least when their manganese content was below 0.60 pct), and concluded that plain carbon steels are not susceptible to temper brittleness. Recently the deficiencies of the criterion mentioned above have been pointed out.4-6 The criterion now generally used for susceptibility to temper brittleness retains the heat treatments used in the earlier scheme, but instead of the notched-bar impact tests being made only at room temperature, they are made over a range of temperatures, covering the transition from ductile to brittle fracture, If the transition temperature of the specimens receiving the embrittlement treatment is higher than those

Jan 1, 1948

By AIME AIME

FOR the use of workmen and employees, the company should establish a dispensary and a -hospital where workmen who suffer accidents or professional diseases may be taken care of; and at suitable places in the mine or metallurgical plant it should install first-aid stations. Workmen have a right to receive 75 per cent of their wages while they are unable to perform their work as result of a professional disease; but some companies pay full wages and in the case of natural disease, with the exception of venereal, alcoholism, injuries from fights, and chronic illnesses, 50 per cent of their wages up to a period of two months. The number of diseases the Law considers as professional is large and increases almost daily. Among the professional diseases, the one which has caused greatest harm to the miners and expense to the companies is silicosis. To avoid its propagation, companies should take every possible precaution that the working atmosphere is free from dust, abating this by frequent sprinkling of the workings using, wet drills and furnishing the workmen adequate protective apparatus such as respirators.

Jan 1, 1937

By Richard Pearce

In the treatment of auriferous copper containing bismuth, I have recently observed a small quantity of a grayish-white alloy, which on examination, proved to be Bi containing in solution, as it were, a crystalline alloy of Bi and Au. This compound makes its appearance on the surface of the auriferous Cu in small globules as the latter cools. These globules are rapidly attacked by nitric acid, and fine needleshaped crystals of Bi and Au separate out. They arc insoluble even in strong nitric acid. On examination, the crystals mere found to contain : Gold, 69.94 per cent.; silver, 0.63 per cent. ; bismuth, 29.43 per cent. (No. I).* The residue is very fusible, and at a temperature considerably below its melting-point it oxidizes rapidly, changing from its original gray color to a greenish-yellow (No. 2). On melting in a crucible under flux, a bronze-colored alloy is formed that has the specific gravity 15.47—somewhat higher than the calculated specific gravity of a simple mixture of the two metals in the proportions named. Alloys of Gold and Silver.—In following out my investigations by repeated examinations of this alloy formed at different times, I found that, in dissolving a miscellaneous lot of the alloy in nitric acid, some gold-yellow crystals were formed, which I succeeded in separating from the BiAu alloy by washing. These yellow crystals, under the microscope, showed distinct, regular, octahedral faces, and on examination they were found to be a crystalline alloy of Au and

Jan 1, 1885

By W. A. Ver Wiebe

The year 1939 in Kansas, with a production of 57,944,300 bbl. from 19,669 wells, shows a slight recession from the peak of oil production reached the previous year, when slightly over 59,000,000 bbl. of oil was marketed. The previous peak had been reached in 1917 with 45,451,000 bbl. marketed. Another still earlier peak had been reached in 1904, when slightly less than 5,000,000 bbl. was produced and sold. The production of gas probably reached a new peak during 1939 with a total of over 69 billion cubic feet. Between the peak of the year 1908, when over 80 billion cu. ft. was produced, and that of 1939 the production dropped to 16 billion cu. ft., in the year 1921. During the year 1458 wells were drilled. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or recompleted in a different geological horizon. Nearly 75 per cent (1029) of the total number of wells were completed as commercial oil wells (824 in western and 205 in eastern Kansas). The commercial gas wells completed number 71, of which 24 are in eastern Kansas and 47 in western Kansas. The remaining completions include 154 dry holes in eastern and 204 dry holes in western Kansas. Based on daily potential capacity the new discoveries of the year accounted for a cumulative initial production of 264,000 bbl. in eastern and 1,158,827 bbl. in western Kansas. It is interesting in this connection to note that the number of wells completed in the state rose gradually to a first peak in 1904, when 2782 were drilled. The number dropped off rapidly to 368 three years later, but rose to the second and highest peak in 1918, when 4671 wells were completed. In the period between 1904 and 1912 more gas wells than oil wells were completed. Between the high peak of 1918 and the somewhat lower peak of 1937, the low point was reached during 1931 with the completion of only 470 wells. In the matter of new pools discovered, Kansas again ranks high. The exact number depends somewhat upon the interpretation of a "new" area—whether it should be called a new pool or a long extension of an older pool. In some places this determination cannot be made until more wells are drilled within the area. Therefore, the figures given

Jan 1, 1940

By W. A. Ver Wiebe

The year 1939 in Kansas, with a production of 57,944,300 bbl. from 19,669 wells, shows a slight recession from the peak of oil production reached the previous year, when slightly over 59,000,000 bbl. of oil was marketed. The previous peak had been reached in 1917 with 45,451,000 bbl. marketed. Another still earlier peak had been reached in 1904, when slightly less than 5,000,000 bbl. was produced and sold. The production of gas probably reached a new peak during 1939 with a total of over 69 billion cubic feet. Between the peak of the year 1908, when over 80 billion cu. ft. was produced, and that of 1939 the production dropped to 16 billion cu. ft., in the year 1921. During the year 1458 wells were drilled. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or recompleted in a different geological horizon. Nearly 75 per cent (1029) of the total number of wells were completed as commercial oil wells (824 in western and 205 in eastern Kansas). The commercial gas wells completed number 71, of which 24 are in eastern Kansas and 47 in western Kansas. The remaining completions include 154 dry holes in eastern and 204 dry holes in western Kansas. Based on daily potential capacity the new discoveries of the year accounted for a cumulative initial production of 264,000 bbl. in eastern and 1,158,827 bbl. in western Kansas. It is interesting in this connection to note that the number of wells completed in the state rose gradually to a first peak in 1904, when 2782 were drilled. The number dropped off rapidly to 368 three years later, but rose to the second and highest peak in 1918, when 4671 wells were completed. In the period between 1904 and 1912 more gas wells than oil wells were completed. Between the high peak of 1918 and the somewhat lower peak of 1937, the low point was reached during 1931 with the completion of only 470 wells. In the matter of new pools discovered, Kansas again ranks high. The exact number depends somewhat upon the interpretation of a "new" area—whether it should be called a new pool or a long extension of an older pool. In some places this determination cannot be made until more wells are drilled within the area. Therefore, the figures given

Jan 1, 1940

By A. H. Geisler, F. Keller

Although the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron Microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the Precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstatten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged a1loys.l The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will sufficc to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. Preparation OF Specimens The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously,¹,² Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen, The specimen is polished accordillg to the usual procedure for microscopic examination.³ he specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended, Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens, The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet PoliShing operation are generally used, but frequently the as-rolled surface is Suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1947

By F. Keller, A. H. Geisler

Although the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron Microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the Precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstatten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged a1loys.l The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will sufficc to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. Preparation OF Specimens The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously,¹,² Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen, The specimen is polished accordillg to the usual procedure for microscopic examination.³ he specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended, Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens, The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet PoliShing operation are generally used, but frequently the as-rolled surface is Suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1947

By L. C. Armstrong

A. E. ROSS*—Mr. Armstrong in his paper stated that they had experienced considerable difficulty in drilling the quartz-feldspar intergrowths. The dia-mor~d loss was excessive and the diamond bits polished quite rapidly. Mr. Davidson, who presented the paper, stated that bortx stones in the range of 20 to 30 per carat had been used in the bits on this job. I would like to suggest the use of bits employing stones in the range of 60 to 100 per carat, an average of possibly 80 per carat. If these stones had been used the bits might have lasted longer and not polished so quickly. As a basis for this suggestion I would like to point out that in northern New York State we had at least two examples where bits employing stones in the range of 80 per carat had solved a difficult problem. Bits set with stones in the range of 20 to 30 per carat had been used previously and had failed. With the finer stones, the cost per foot of drilling decreased material1y. It should also be noted from a technical standpoint that the smaller stones require higher drilling speeds than the larger stones. Greater pressures are not normally necessary, and it is the higher speed which seems to be the major factor of importance. It should also be noted that the finer stones afford a greater number or cutting surfaces for the same carat weight in a bit. Then too, the smaller stones, by virtue of their size, serve as sharper cutting edges than larger stones. There is no doubt that the diamond bit employing smaller stones costs more to set than the bit using larger stones. However, with the technique developed at the shops of Sprague and Henwood, Inc., we feel that the relatively slight additional cost required to set these bits is more than paid for by the resultant lower drilling cost. We feel that the highest quality stone available is the most economical to use when hard fine grained rock is encountered. In summary, I would suggest that it might be possible to solve the problem presented in this paper by using a diamond bit employing stones at least as small as 80 per carat of the highest grade possible and by using the diamond bit at the highest speed available with modern drilling equipment. L. C. ARMSTRONG (author's reply) —It is generally agreed that the use of smaller, high-grade diamonds and of higher drilling speeds, as suggested by Mr. Ross, may be the best approach to the solution of the problem.

Jan 1, 1950

By T. Sterry Hunt

It is now five years since I called the attention of the Institute to the industrial importance of the coal and the iron ores of the Hocking Valley in Southeastern Ohio, and in a pamphlet on the region published soon after, in 1874, endeavored to resume the principal facts then known respecting it, including the observations of the geological survey of Ohio, made and published up to the time by Professors Andrews and Wormley, together with an estimate of the probable future of the region, and its relations to the coal and iron markets of the country. Since that time the labors of the Geological Survey have included a further study of the coal by Prof. Edward Orton, the results of which will be awaited with much interest. I may say from my knowledge of them, that while confirming the general conclusions of his predecessors, he has been enabled to add much to our knowledge as regards the correlation of the various members in different parts of the coal-field; and to show more clearly the positions and the importance of the ore-beds in the Hocking Valley region. The only ore mined in that vicinity previous to 1874, was below what is called the Great Vein or No. VI coal, and to the west of what is known as the Hocking Valley coal-field, and although experiments in a few furnaces in the State had shown that this coal could be used with advantage in iron-smelting there was not a single blast furnace within the field. My observations at that time, however, impressed me with the abundance of iron ore, not only below but above this important coal seam, and I then ventured to express the opinion that this region, from its cheap and easily mined smelting-coal, its native ores and limestones, and its geographical position and relations to the great markets of the West, and to the supply of rich iron-ores from Lake Superior, was destined at no distant time to become a great metallurgical centre, where iron could be made more cheaply than at any other equally accessible point in the country. The object of the present communication is to report progress, and to state how far my observations made in the region 1st month have justified the predictions of 1874. The five years which have elapsed have been, as all know, most unfavorable to the iron trade, and especially to new enterprises in untried regions, yet they have not passed without important industrial developments in the Hocking Valley, where not less than thirteen blast furnaces have been erected

Jan 1, 1879

By Carl F. Lutz, Robert F. Mehl

A layer of brass was formed on 0 brass using a vapor-solid reaction technique. The variation in composition with distance within the phase layer and across the a -ß interface was determined by an electron probe. The diffusivities were calculated as a function of concentration; the diffusion coefficient in brass was found to change by a factor of twenty-five over a compositional range of 8 at. pct. An explanation is proposed to account for the large change in the diffusivity, based on possible stresses in the diffusion zone; it is suggested that the concentration dependence of the thermodynamic factor might decrease the activation energy with increasing zinc content. ALTHOUGH the body of data on diffusion coefficients (D- values) in terminal solid solutions and in isomorphous systems is quite large, there is but little quantitative information for intermediate alloy phases. This paper recounts measurements of D-values for the ? phase in the Cu-Zn system. The experimental method employed consists in the forming of alloy layers and determining and analyzing the concentration-distance (c-x) curve. The experimental method employed could have been applied to several systems; the Cu-Zn system was chosen because the D-values in the a and ß phases are well known, and can thus be used for purposes of comparison. The rates of growth, of intermediate alloy layers are known for a number of systems. In nearly all cases the thickness varies parabolically with time, as to be expected if the rate of growth is controlled by the D-values. In a few cases, nonparabolic behavior has been noted.1 Nonparabolic growth may be the result of a) a variation of the composition at the phase interface with time, b) interface-controlled kinetics, c) short diffusion times coupled with long vacancy lifetimes (in vacancy diffusion),2 and d) crystal reorientation during diffusion in anisotropic systems.3 In the Al-Ni system4 and in the Al-u5 system parabolic growth kinetics are slowly approached after an initial transient period. In general those phases stable at a given temperature in a system A-B appear as separate phase layers when A and B are put in contact and given a diffusion he at-treatment. In most cases the compositions at the interface of adjacent phase layers are those read from the phase diagrams for the termini of the respective phases. This discontinuity in concentration is taken as independent of time, and the growth of one phase at the expense of another is assumed to be independent of interface kinetics, i.e., the rate of interface movement is controlled by volume diffusion in the phases concerned. wagner6 has given many solutions for multi-phase diffusion processes, assuming that the chemical diffusion coefficient, D, is independent of concentration, as have others. Jost7 has pointed out that the familiar Boltzmann-Matano solution is as valid for a (c-x) curve exhibiting concentration discontinuities at phase boundaries as for the usual single-phase case. Heumann and associates8,9 have applied this solution to the multi-phase case, but lacking concentration data within the several layers were forced to assume linear concentration gradients, thus calculating only average D-values. The purposes of the present study were: 1) to determine the dependence of D on concentration, 2) to calculate the intrinsic diffusion coefficients D?Cu and D?Zn, 3) to establish the time-law for the movement of the interface, 4) to determine the concentration limits at the ß-? interface, and, 5) to attempt to clarify the mechanism of diffusion. EXPERIMENTAL PROCEDURE The ? phase is exceedingly brittle; conventional solid couples and conventional sectioning methods were thus inapplicable. Vapor-solid couples were accordingly employed. Unfortunately the equilibrium vapor pressures of Zn for the ? phase are unknown; to escape this awkwardness, samples were enclosed in a capsule containing powder of an alloy of known composition, sufficiently large in quantity as to be effectively an infinite source, maintaining the concentration of Zn at the sample surface constant with time. The sources of Zn-vapor which can be employed in reaction with Cu, or a brass, or ß brass, to form a layer of ? brass satisfactorily wide in concentration range, are alloys of the phases ?, or ? + E or ? + d (depending on the temperature).

Jan 1, 1962

By J. W. Leomrd, B. A. Donahue

Results of research are presented examining the extent to which the analytical characteristics of the relatively distinct coal bands from a variety of coal seams can be related to each other. This paper dis-cusses an approach for developing a practical coal petrographic quality control program based on conventional analyses, most of which is part of the standard A.S.T.M. procedure. The work is a final follow-up to Part I of this series which was prepared by the authors as an approach to applying conventional coal petrography to single coal seams. Recent published work by the authors entitled Petrography for Coal Mining and Coal Prepration: Part I dealt with interrelating various chemical and physical properties of coal1 measured using conventional analyses made on distinct petrographic bands taken from single coal seams. Since most coal production facilities process coal from a single coal seam or from very closely related coal seams in the same area,2 emphasis on interrelating the properties within a single seam appeared appropriate. The distinct petrographic bands were analyzed on the assumption that such differentiated data would be more representative of a heterogeneous coal seam than the single analytical value commonly used to characterize each property of an entire seam.34 Effort was directed at demonstrating the extent to which the interrelated chemical and physical properties 5,6 could be developed into nomographs or petrographic standardization graphs. Thus, one analysis, determined on a series of petrographic fractions separated from a single sample, was used to estimate numerous other properties in each fraction by referring to the previously established petrographic standardization graphs. This conventional approach to coal petrography was undertaken as a suggested feasible means by which a few coal analyses could be employed to develope a more penetrating knowledge of the properties of coal from any given seam in order to monitor more extensively its performance at the point of utilization. Such procedures can support development of the type of in- formation commonly sought through automated testing and through the use of computers.7 The broad knowledge which can be developed through these procedures is intended for application in the generation of an analytical profile or broad characterization of coal. These estimates were not intended as replacements for individual coal analytical tests. In this expanded second part of the research program, distinct petrographic bands from nine coal seams in the Central Appalachian Region were physically and chemically analyzed to elucidate the extent to which this concept of conventional petrography could be broadened for application to numerous coal seams. In presenting this second phase of work, the relationships developed are presented individually and not in a connecting series of nomographs or petrographic standardization graphs as in the previous work, thus leaving open the combinations of possibilities to individual interpretation and application. MATERIAL AND EXPERIMENTAL WORK Nine coal seams, representing a wide range of rank, from the Central Appalachian coal fields were used in this study. The distinct petrographic bands from the Kittanning, Pond Creek, Jawbone, Tiller, Poca-hontas No. 3, No. 2 Gas, Eagle, Winifrede, and Pittsburgh coal seams were separated by carefully removing a portion of each band at the face of the seam. The following were determined: ash, sulfur, free swelling index, heating value, bulk specific gravity, volatile matter, Hardgrove Grindability Index, and Gieseler Plastometer measurements. Determinations, where procedures were available, were carried out using ASTM standard procedures.8 Bulk specific gravity was determined using a kerosene volume displacement procedure modified from a method applied by Headlee and McClelland of the West Virginia Geological survey,9 Those bands with a bulk specific gravity greater than 1.60, which is generally above the practical specific gravity cleaning range of bituminous coals, were excluded and no analyses were performed. Much of the initial organization of this second phase of work was developed through the extensive use of a computerized statistical monitoring program (see Ref. 4). However, in order to achieve the closest possible interpretation of results, the final organization of data proceeded mainly from exhaustive trial

Jan 1, 1968

By J. E. Warren, J. H. Hartsock

Because of the extensive utilization of hydraulic fracturing for the stimulation of low-productivity wells, the two related problems of fracture design and evaluation have become economically significant and, as a consequence, helve motivated this investigation. The producing characteristics of horizontally fractured wells were studied to determine the fracture configuration that should be employed as the basis for the design of the treatment and to develop a method that can be used to establish the degree to which the design objectives have been achieved. The equations which describe the steady-state flow of a single-phase fluid into, and through. a finite-capacity fracture were solved numerically for an idealized reservoir-fracture model. The numerical results were used to obtain an apparent skin effect for each combination of the parameters considered. Based on the computed results, subject to the limitcitions implied by the assumptions that were made, the following general conclusions were drawn. 1. For a radius of drainage at least four times us large as the radius of the fracture, an apparent skin effect that is independent of the radius of drainage can be calculated. 2. The productivity of the hydraulically fractured system, relative to that of the unfructured well, can be determined from the apparent skin effect and can be used to establish design objectives. 3. In the evaluation of a fracture job, it is not Possible to determine both the radius of the fracture and its flow capacity uniquely from the apparent skin effect; an independent determination of one of the quantities is necessary. lNTRODUCTION Although hydraulic fracturing has been employed as a method for stimulating the productivity of literally hundreds of thousands of wells during the past 10 years, it is only in the last few years that improvements in fracture design1-6 and fracturing technique' have combined to increase the probability of obtaining a successful treatment to such an extent that the mechanics of the method may be considered to be standardized. From an economic point of view, however, two related questions must be satisfactorily answered before hydraulic fracturing can be used in the most profitable manner. The two questions are the following. I. For a particular well in a given formation, what are the optimum design specifications for the fracture treatment? 2. Have the design objectives been achieved by the fracture treatment? The significance of these questions has been recoguized, and some attempts to obtain answers have been made. Howard, et al,8 endeavored to determine the optimum treatment, based on maximizing profits, for any given formation; unfortunately, this work was based on a crude method for approximating the productivity of a well. Carter and Tracy9 utilized the same approximation to study the effect of fracturing on the behavior of a well producing by virtue of a solution-gas drive. Electrolytic models were used by van Poollen10 to investigate the variation in productivity due to fracturing; however, only a limited number of results were presented. Later, from the same model results, van Poollen, et al,11 attempted to justify an approximate expression for determining the productivity of a fractured well. It is quite apparent that there is a definite lack of the practical information necessary for specifying the optimum fracture configuration to be considered for design purposes. The only detailed attempt to develop a procedure for evaluating the result of a given fracture treatment appears to be that of van Dam and Horner.12 These authors described a technique for analyzing pressure build-down data, obtained immediately after fracturing, to determine the final fracture volume, the final fracture porosity, the fracture area, the fracture thickness and the in situ fluid loss of the fracturing fluid. While this approach should be useful whenever acceptable pressure measurements are available, it does not yield a value for the flow capacity of the fracture. Since the problems of fracture design and evaluation are inversely related, it should be sufficient to study the effect of the fracture configuration on the performance of a well. The primary objective of this investigation is to evolve a technique for computing the desired solutions. The secondary objective is to analyze these computed results in order to prescribe a method for evaluating fracture treatments. Because this study is exploratory in nature, its scope

By L. Stone, H. Margolin

The Ti-C-N and Ti-C-O systems were investigated in the temperature range from 500° to 1400°C and in the composition range up to 2 pct C and 5 pct N or 0. Characteristic isothermal sections at 800°, 900°, 1000°, and 1300°C are presented. The Ti-N-0 system was studied in the temperature range from 900' to 1400°C with alloys containing up to 6 pct total alloying content. Characteristic isothermal sections at 1000° and 140O°C are presented. Melting-point data for all three systems are also included. THIS paper reports on one of a series of investi-gations which have been conducted on the phase diagrams resulting from interstitial alloying with iodide titanium. The other investigations involved delineation of the binary systems with carbon,' nitrogen and boron,h and oxygen. The Ti-0 binary system has also been investigated by Bumps et al.' In varying degrees, each of these interstitial elements has been shown to stabilize the low temperature a modification of titanium1-5 and each forms a face-centered cubic TiX compound (henceforth designated 6). In addition, the Ti-N and Ti-0 systems reveal a low temperature tetragonal phase (6) formed by a peritectoid reaction between a and TiX Experimental Procedure The development of experimental techniques for the study of titanium alloy systems has, to a large extent, become standardized. In this investigation, the equipment and procedures described in detail by Cadoff and Nielsenl have been used. Arc Melting: In general, binary alloys with carbon, nitrogen, and oxygen, prepared in the composition range of interest in this investigation, show negligible composition changes during arc melting. However, the possibility of the formation of some gaseous combination of alloying elements such as CO, CN, or NO during the preparation of these ternary alloys was considered. Calculations showed that the evolution of only 0.05 gram of such a gas would be detectable as a pressure change in the closed system used during preparation of these alloys. Such pressure changes were not observed. Consequently, nominal compositions have been used in plotting the data. The compositions of the materials used in the preparation of the alloys are shown in Table I. After melting for 3 to 5 min at 275 to 350 amp, the alloys were checked for homogeneity by microstruc-tural examination. Alloys containing up to 1 pct C were homogeneous in the presence of less than 3 pct N or 0. At higher alloying contents, some inhomo-geneities in the carbon distribution became evident. Alteration of the melting procedure toward longer times and higher currents did not improve the homogeneity of these alloys. Ti-N-0 alloys were homogeneous in the range to about 3 or 4 pct total alloying addition. Beyond this, almost all of the specimens showed as-cast microstructures consisting only of the phase. Consequently, inhomogene-ities could not be detected by examination of micro-structures. Ten alloys from each of the systems were analyzed for two of the elements present (oxygen being omitted in all cases and titanium being omitted in the Ti-C-N alloys). In all cases the analyses were found not to be sufficiently precise to serve as criteria for the total composition of these alloys. On the basis of phase distribution in heat-treated alloys, however, it appears that carbon is distributed throughout the alloys most uniformly, with oxygen and nitrogen following in that order. Heat Treatment: Specimens for heat treatment were wrapped in titanium sheet before sealing in the argon-filled quartz capsules. Heat-treatment times varied from 100 hr at 800°C to 0.5 hr at 1400 °C. After heat treatment the specimens were quenched by breaking the capsule in water. With the exception of alloys in the low composition region, heat treatment did not have an appreciable effect on the as-cast microstructures. Metallography: Following heat treatment, the specimens were prepared for metallographic examination by grinding on emery paper and electrolytic polishing. For the majority of the specimens a 10-sec etch with Remington "A" agent (25 pct HNO3, 25 pct Hf, and 50 pct glycerin) adequately

Jan 1, 1954

By C. L. Mantell

When considered from the viewpoint of world annual output, tin is one of the rarest metals. Its annual production is exceeded by that of iron, copper, lead, zinc. aluminum, magnesium; probably by that of the ferroalloys of manganese, chromium, and silicon, and possibly by the world production of sodium; while it exceeds only the output of such common metals as nickel, antimony, mercury, tungsten, molybdenum, silver, gold and the precious metals. Cassiterite, or tinstone, until the second World War was the only mineral that was an important source of tin. This mineral is frequently called "tin ore." The use of the term should be restricted to the ore containing the mineral, and not, in addition, to the concentrates of the mineral obtained from the ore or from stanniferous alluvial deposits. There is a general misuse of the term "tin ore" in the Malay Peninsula and adjacent localities, particularly where most of the mineral is obtained from secondary stanniferous deposits. The term "cassit-erite" is exclusively used in mineralogical, geological, and other scientific writings; it is unfortunate that it is not mole frequently used when referring to the occurrence of the mineral on an economic scale. Ores "Tinstone" js a very convenient old English term deserving a more frequent use. Tinstone is a dioxide of tin, or stannic oxide. When chemically Pure, as in the very rare transparent variety, it has a metallic content of 78.6 per cent tin. Frequently, however, the crystals and grains contain appreciable amounts of impurities, chiefly iron and tantalum. The impurities here referred to are those actually in the mineral itself. Tinstone usually has a deep brown or black color with an adamantine luster. Several other colored varieties are known, among them red ruby tin, yellow rosin tin, and yellow wax tin. the names jn each case being descriptive of the mineral's appearance. Ainalite is a variety of cassiterite con-taining almost g per cent of tantalum pentoxide. Sparable tin, tooth tin, and needle tin, as a result of their acute dite-tragonal pyramidal crystalline form, re-ceive their names from their crystallo-graphic appearance. Wood tin is a compact variety of cassiterite composed of radiating fibers resembling dry wood. Toad's-eye tin is a similar variety on a smaller scale in which the fibers appear to resemble the eye of a toad. Stream tin is water-worn tin-stone. Float tin is sometimes employed to describe the cassiterite occurring in soil derived from the weathered surface of a mineralized area. Stannite is an ore of tin of lesser impor-tance than cassiterite. It is a sulphide of tin, copper, and iron, sometimes known as tin pyrites or bell-metal ore. Its chemical com-position is sometimes expressed by the for-mula Cu,S.FeS.SnSz with zinc usually present in varying quantities. The tin con-tent varies from 22 to 27 per cent and there is about 29 per cent of copper, 13 per cent of iron, and 30 Per cent of sulphur.

Jan 1, 1944

By Olin M. Hart

Uranium ores occur in the Lower Cretaceous Inyan Kara group of heterogeneously stratified fluvial and fluvial-marine sandstones in the Black Hills of western South Dakota and northeastern Wyoming. There are three principal mining districts, each in the ancestral and present drainage area of a major river partially responsible for stripping the region to its present topographic form. Primary minerals in the deposits are coffinite and uraninite with minor amounts of paramontroseite and haggite. The ore minerals coat sand grains and fill interstices of complexly cross-stratified sandstone along solution fronts similar to "roll" type deposits of the other districts. Minerals of oxidized deposits are typically carnotite and tyuyamunite with different proportions of secondary vanadium accessory minerals. Ground water was the transporting medium and deposition of primary uranium and vanadium minerals occurred in reducing environments produced and controlled by physio-chemical characteristics of the sedimentary rocks.

Jan 1, 1968

By J.B. Pullen

The United Verde mine is in the north central part of Arizona, on the northeasterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruff-ner and associates in 1877. In 1888 the late Scnator William A. Clark secured control of the property and under his ownership it developed into one of the country's most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation's management. Except for shutdowns caused by general world-market conditions, production has been continuous from 1890 to date. Geology The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre--Cam-brian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-it. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. Aplan and vertical section of the mineralized zone showing the principal geological eatures is shown in Figs. I and 2. General Description and Physical Condition or Mine After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes —-mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became dificult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1943

By J. B. Pullen

The United Verde mine is in the north central part of Arizona, on the northeasterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruff-ner and associates in 1877. In 1888 the late Scnator William A. Clark secured control of the property and under his ownership it developed into one of the country's most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation's management. Except for shutdowns caused by general world-market conditions, production has been continuous from 1890 to date. Geology The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre--Cam-brian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-it. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. Aplan and vertical section of the mineralized zone showing the principal geological eatures is shown in Figs. I and 2. General Description and Physical Condition or Mine After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes —-mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became dificult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1943