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By R. Woodward Moore

A graphical method of analyzing the data obtained from shallow earth-resistivity depth tests is presented. The method is based upon empirical results and has no theoretical basis. The usual apparent resistivity-electrode spacing curve is used together with a cumulative resistivity-electrode spacing curve plotted on the same sheet. The greatly reduced scale required for plotting the cumulative values of resistivity together with the effect of the summation of the individual resistivity values serves to minimize the effect of purely local surface anomalies and inadvertent errors of measurement. The point of intersection of tangents or straight lines drawn to intersect at zones of maximum curvature in the cumulative curve indicates the depth to the underlying material. Numerous figures are presented in which data from published reports and from recent field studies are analyzed and the results compared with actual depths established by borings or with depth values obtained by the use of theoretical methods of analysis. Smoothly rounded curves of apparent resistivity such as are often obtained in the field, and which have been a serious drawback to attempts to analyze the data empirically heretofore, appear to be susceptible to rather accurate analysis by the method described. The method is best suited to analyses involving shallow two-layer formations. It has been applied successfully, however, in analyzing the data obtained from tests made over shallow three-layer formations. As with most empirical methods, its chief advantage is its simplicity and ease of application. There have been published many papers that discuss the interpretation of data obtained from earth-resistivity tests when using the four-terminal method of electrode spacing developed by Wenner.' The majority of these have dealt with theoretical analyses for two-layer and three-layer formations. Some sets of "master curves" have been presented for use in analyzing field data to determine the depth to the first and possibly the second horizon below the earth's surface. Although practically all of these theoretical methods of analysis have appeared to have particular merit and some have been used successfully in practice, they have been found to be of little value where the local conditions surrounding the test failed to conform to those assumed in the theory. In certain fields, particularly in civil engineering, relatively shallow explorations are often involved and geophysical methods of test must compete with the direct methods of exploration ordinarily used. Only when it can be demonstrated that geophysical methods of test can materially reduce the time and cost of a given exploration project will the civil engineer abandon direct methods in favor of the interpretations of geophysical exploration data. Empirical methods of analyzing earth-resistivity data have been used in many instances in the past. Such methods have been employed for a number of years by the Public Roads Administration in research work relative to the application of

Jan 1, 1946

By B. Habermann

Artificially consolidated sand models, representing one-quarter of a five-spot, have been developed and used to study factors aflecting misciblt. displacrmenr. Sweep efficiency at breakthrough, size of the mixing zone between two miscible liquids and per cent area contacted by drive after breakthrough were determined tor the high mobility ratios encountered in actual resvrvoirs. Quantitative relationships between the degree of viscous fingering and mobility ratio were obtained by measuring the length of the fluid interface. Scaled miscible-slug experiments, supported by field evidence reported in the literature, have shown that when the slug is followed by dry gas the process is less efficient than expected. In addition to low areal sweep efficiencies encountered for high mobility ratio displacements, the effectiveness of a miscible slug is greatly reduced. This is caused by an accelerated growth of the mixing zone between the driving and the displacing fluids. INTRODUCTION Considerable interest in miscible displacement as a secondary recovery process has been shown by the oil industry in recent years. In addition to extensive laboratory investigations, numerous field operations have been initiated so that 39 miscible displacement projects had been reported' in the United States by early 1959. By far the most popular approach in these projects is the use of an LPG slug followed by dry gas. Laboratory tests have indicated that with a small miscible slug, amounting to several per cent of the hydrocarbon pore volume, practically 100 per cent recovery of the oil in place can be achieved and that all of the slug material can be recovered by a subsequellt gas drive. However, these experiments were conducted on small-diameter long cores that can be considered as essentially uni-dimensional reservoirs that do not represent actual field conditions. It soon became apparent that the inherently adverse mobility ratios existing in the reservoir cannot be ignored in any miscible displacement field project. When a less viscous fiuid such as an LPG slug drives a more viscous reservoir oil, fingers develop that reduce the areal sweep efficiency. The slze of the miscible slug to be used is a subject of some controversy. It has been proposed that the size of siug needed be calculated by setting lengths of the mixing zone proportional to the square root of the distance traveled. This proposal is based on experimental evidence' and theoretical considerations"' in which fingering was not a factor. A prerequisite for successful application of the miscible displacement process to field operations is a better understanding of the following factors. L What is the effect of mobility ratio on the rate of deterioration of a miscible slug? 2. How large a slug should be used for given reservoir conditions? 3. What is the sweep efficiency? The purpose of this investigation was to provide some additional laboratory data that should help to answer these questions. More specifically, it was intended to study more quantitatively the effect of viscous fiinger-ing, mobility ratio and slug size on the efficiency of this relatively new secondary recovery process by means of experiments on thin, horizontal, porous medium models.

By David W. Brunton

From the old-fashioned " grab-sample " to the modern timing-device, which takes a machine-sample with mathematical precision, there is a wide gap, which was only crossed by many years of toil and unremitting endeavor. Even to-day, notwithstanding the advancement in the art, " grab-sampling " is still practiced—sometimes to afford the unscrupulous mine-promoter a basis for fairy-tales with which to entrap the too-gullible investor, and often by milling and smelting companies to determine the amount of moisture in custom-ores. The latter practice is almost as reprehensible as the former, and it causes more trouble and ill-feeling between seller and buyer than all other factors put together. -NO reputable concern to-day would think of attempting to determine by grab-sampling the amount of gold, silver, lead, or copper contained in an ore, and yet many buyers expect the miner to accept the results of grab-sampling in the determination of the amount of water contained in the ore, forgetting that accurate results are just as necessary here as in the determination of the metals, because the result determines the percentage of weight of the ore which shall be excluded and considered to have no value whatever. Samples for the determination of moisture should be taken with as great care as samples for the determination of metallic content, and in order to avoid the extra expense of a separate operation moisture-samples should be taken from the sample-safe. As the sample reaches the sample-bin in a smaller stream and by a more circuitous route than the " reject" travels in its path to the outgoing car, it loses more moisture en route, and a constant should be added to compensate for this difference. Carefullg ,con ducted experiments have shown that the differ.elice in loss of moisture between the two routes does not exceed 10 per cent. in summer and 7 per cent. in winter. For instance,

Jan 1, 1910

By H. Y. Hunsicker

A graphic method has been devised for three-di-mensional analysis of hot deformation and for correlating the amount and directionality of the deformation with resulting directional properties. Deformation is evaluated in terms of dimensional change ratios referred to three orthogonal axes. Since all combinations of the three ratios can be represented in a triangular coordinate field with logarithmic scales, a two-dimensional chart of extent of deformation and degree of asymetry is possible. The entire gamut of shape changes from upsetting through flat-rolling to rod-rolling is accommodated. The resulting coordinate system is a base upon which can be represented the properties of the wrought products measured in the directions of the axes employed fir evaluating the deformation. When property data are available for many types and amounts of deformation, a three-dimensional figure can be constructed, and the projection of this figure is referred to as a ''3d'' chart. Experience in using such charts to plan fabricating operations for a variety of thick-section forged and rolled products of heat-treated aluminum alloys has verified its practical value for optimizing directionality relationships. MechANICAL anisotropy of thick section products of heat-treatable aluminum alloys is recognized by producers and users of these products, and the extent of the directional differences is apparent in property tabulations included in handbooks, standards, and specifications.' Attention has also been directed to the existence of important directional differences in the resistance of these products to stress-corrosion cracking. Metallurgical structure factors responsible for these directional differences include, among other possibilities, shape and alignment of grains, voids and nonmetallic inclusions (when present), volume fraction and spatial distribution of secondary phase particles and solid-state precipitates, crystal-lographic textures, and Bauschinger effect. The contributions of the individual factors vary with alloy composition, heat-treated temper, type of working process (forging, rolling, extrusion), and the amount and directional nature of the deformation. In general, the cast ingot used as the starting material for producing these wrought products exhibits only a modest degree of directionality. A monotonic and continuous transition from this nearly isotropic state with progressive hot deformation would appear probable, assuming that the working temperature is sufficiently high to cause continuous dynamic recovery. Several years ago a project was undertaken to evaluate the effects of hot deformation and metallurgical structures on the directionality of thick wrought aluminum alloy products, and the method to be described was developed as an analytical tool in this investigation. DIRECTION NOMENCLATURE The nomenclature system adopted by industry for the three mutually perpendicular directions employed in testing aluminum alloy products includes four terms: "longitudinal", "transverse", "long transverse", and "short transverse". These terms are conventionally related to the external geometry of the product but also by implication to the deformation and resulting metallurgical structure. Occasions arise in which through use of unusual fabricating methods, intentional or otherwise, the structure does not have the usual relationship to external geometry or may be very complex because of inhomogeneity of deformation throughout the piece. The longitudinal direction is generally parallel to the primary rolling direction or to the direction of extrusion. In the case of forging, it is parallel to the direction of maximum extension (not maximum "working" or "flow", as frequently stated). The term transverse is applied to any direction perpendicular to the longitudinal direction in a product having symmetry about the longitudinal axis, and generally, although not always, the deformation to produce these forms is nearly symmetrical in the transverse plane. This term then may be applied to a round, square, hexagon, or other polygonal, symmetrical shape produced by extrusion or rolling or by forging, if produced by a simple, symmetrical drawing procedure. The type of microstructure generally associated

Jan 1, 1970

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By S. E. Bronisz, Dana L. Douglass

a Uranium was deformed by cold rolling, and the effects of this plustic deformation on the microstruc-ture of the metal were observed by the technique of transmission elecbon microscopy. The recrystalli-zation of selected cold-wmked samples was also studied by this method. The samples were prepared for examination by electrolytic thinning in a standard metallographic electrolyte which has not been previously reported as being used in producing thin foils of uranium. The microstructural changes observed in the a uranium were generally similar to those seen by optical microscopy. The changes in the microstructure of a uranium following cold work and recrystallization treatments have been the subjects of several studies employing optical and X-ray techniques.12-19 These studies indicated that twinning was the redominant mode of deformation at room temperature20 and that the regions of high energy associated with the deformation twins were preferred sites for the initiation of recrystallization.15,18, Recently several workers have prepared thin foils of uranium suitable for examination by transmission electron microscopy.'-lo The foils thus prepared have been used to study fission fragment damage; a particular dislocation reaction,' and gas precipitation." At this laboratory the microstructural changes occurring during the cold working and recrystallizing of a uranium samples have been studied by using transmission electron-microscopy techniques. The foils used in this work were electrolytically thinned in a polishing bath not reported previously in the literature as being used for this purpose. EXPERIMENTAL PROCEDURE The uranium used in this investigation was depleted a uranium sheet 4 mils thick. The results of a spectrochemical analysis of this material are shown in Table I. The as-received uranium was cut into strips, 1 in. wide by 5 in. long, and annealed in vacuo at 600°C for 2-1/2 hr. The resulting microstructure consisted of relatively uniform, equiaxed grains having diameters of 10 to 50 p. Cold Working. The cold-worked samples were prepared by rolling several of the annealed uranium strips to various thicknesses. The strips were reduced 3.5 ± 0.5, 6.0 ± 0.6, 10.0 ± 0.5, 19.5 ± 1.0, and 28.5 ± 2.0 pct in thickness. It was not possible to achieve these reductions with a single pass through the rolling mill, so the strips were turned end for end during the rolling procedure. The cold-rolled strips were stored in dry ice until samples from them could be thinned and examined (within 24 hr after rolling). Annealing. The samples used in studying the re-crystallization behavior of a uranium were obtained by annealing sections of the strips which had been reduced 10.0 and 28.5 pct. These samples were sealed in evacuated Pyrex capsules and were annealed in a tube furnace at temperatures from 200" to 600°C and for times from 1/2 to 2 hr, see Table l. Thinning: The samples from the rolling and heat treatments were prepared for examination in the electron microscope by electropolishing in a bath composed of 25 g chromic acid, 133 ml glacial acetic acid, and 25 ml water. This electrolyte has been used and recommended for preparing specimens for optical metallography It was necessary to mask the edges of the sample with a stop-off paint in order to prevent preferential attack in these areas. The paint used was made by dissolving polystyrene in benzene. The electrolytic cell consisted of a cylindrical stainless-steel cathode placed in a beaker containing the electrolyte, with the sample as the anode positioned at the cell axis. The temperature of the electrolyte was held below 15°C by cooling with liquid

Jan 1, 1963

By W. J. Taylor, H. J. Mutz, A. F. Brock

THE International Kickel Co. of Canada Ltd. operates five underground mines and an open pit. Four of the mines, the Frood-Stobie, Creighton, Murray, and Garson, are on the south range of the Sudbury Basin, map above, within a radius of 10 miles of the city of Sudbury, Ontario. The fifth mine, the Levack, is on the north range of the Sudbury Basin, 30 miles to the northwest of the city. The open pit is operating on surface ores of the Frood-Stobie orebody. Two pits were opened at the Frood-Stobie mine; the Frood section was started in 1938 and the Stobie section in 1942. To meet the heavy demand for nickel during World War 11, open-pit production was accelerated until it constituted over 40 pct of Inco's total tonnage. As a consequence open-pit ore was depleted considerably alhead of schedule; the Stobie pit was completed in the summer of 1951, and it is expected that mining at the Frood pit will be completed in 1953. The major program launched 10 years ago to develop additional underground production as a replacement of open-pit tonnage thus had to be greatly speeded up. This conversion to all-underground mining will be completed within the next two years, and the underground mines will then have an annual hoisting capacity of 13,000,000 tons. One of the new mines in the underground expansion program, the Murray, was brought into production in 1950. Ore production from the new Stobie section of the Frood-Stobie mine was commenced on a limited scale in 1951 and will be increased as the program progresses. Delivery of ore to the new Creighton mill was started in the summer of 1951 from the caving project launched at Creighton mine. When mining was started in the Sudbury district 65 years ago the ore deposits were opened on a small scale and mining methods conformed to a general pattern of small open cast pits, followed by open stopes as mining was extended below the pits. The open stoping methods used were heading-and-bench and shrinkage. In certain cases a type of cut-and-fill mining was used with drywall tramways and dry-wall chutes in the fill. As the mines were deepened,

Jan 1, 1954

By E. R. Parker, D. L. Martin

In a previous paper one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a. strengthening, so that a longer life at a given stress and .temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver.2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. Experimental Procedure Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1944

By D. L. Martin, E. R. Parker

In a previous paper one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a. strengthening, so that a longer life at a given stress and .temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver.2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. Experimental Procedure Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1944

By H. Ries

Introduction BODIES of pyritic ore in schistose rocks have long been known in different parts of the world. The several occurrences resemble each other in being usually of more or less lenticular shape, inclosed in walls of schist or gneiss, and carrying pyrite, chalcopyrite, and pyrrhotite in varying proportions, as the chief ore minerals. The deposits differ, however, in that sometimes one, sometimes another, of the three sulphides mentioned may predominate. The orebodies in general are more or less closely conformable with the schistosity of the wall rocks, although in cases this may not hold true. The boundaries may or may not be sharp, but in general are fairly distinct. The lenses vary in size, may occur singly, or in groups; in the latter case they may be in line, overlapping, or occasionally parallel. Pinching and swelling of individual lenses is not uncommon. The genesis of these pyritic bodies has provoked much discussion, and they have been variously classed as sedimentary, igneous intrusions, hydrothermal replacements or impregnations, etc. Indeed, in some cases different geologists have most positively assigned widely diverse origins to the same deposit, as in the case of Rio Tinto 1 and Rammelsberg.2 It is true that in the light of modern criteria, we have been able in a few cases to decipher clearly the process of origin and so there seems no doubt now regarding the genesis of the deposits at Rio Tinto, Spain;3 Rammelsberg, Germany ;4 Ducktown, Tenn.;5 southwestern Virginia;6

Jan 8, 1917

By Alan Arias

On grinding in pure water, zirconium, tantalum, iron, and stainless-steel powders were extensively comminuted and simultaneously oxidized with hydrogen release, whereas nickel, copper, and silver powders did not react with water and their particle sizes increased. On grinding nickel, copper, and silver in water pressurized with oxygen, nickel and copper became extensively comminuted and were oxidized, whereas silver did not react with oxygen and its particle size increased. From these results and other considerations , it is hypothesized that for extensive comminution of ductile metals and alloys to occur on grinding they must react with the grinding media. UlTRAFINE metal and alloy powders are finding an ever-growing number of applications in metallurgy and in other fields.' Of particular interest are ultrafine metal and alloy powders suitable for dispersion strengthening.2'9 Various research programs on dispersion strengthening are being carried out and in some of these programs the ball-milling method is being used to produce dispersion-strengthened materials. This method usually involves the simultaneous grinding of metal or alloy and a dispersoid followed by consolidation of the resulting powder mixture. To obtain the ultrafine powders required for dispersion strengthening,' grinding is carried out in many liquids, including aqueous and nonaqueous media, with or without grinding aids.4'5 Nonaqueous liquids usually contain water as an impurity and some grinding aids may contain water of hydration.5 The water present may affect the grinding process. The writer has shown5 that. on ball milling chromium in water, the chromium is oxidized and hydrogen is released. It was surmised that the same reaction may occur on ball milling other metals and alloys in waterbearing liquids. Therefore, the investigation of ball milling in water was extended to metals and alloys other than chromium. In the course of the investigation, however, it became apparent that the data-to-gether with the results from a few additional experi-ments—could be used to postulate a comminution mechanism for ductile metals and alloys. A well-known comminution theory is that of smekal.7 According to this theory, comminution is possible because of the weakening effects of surface cracks and other imperfections in materials. This theory imposes a lower limit of about 1 µm for the ground particles. The beneficial effects of liquids and additives on the rate of grinding are well known.8 Mechanisms by which liquids and additives may aid in grinding were reviewed by Rose and Sullivan.' One aspect of these effects is based on Rehbinder's theory of crack propagation in materials under stress.9 According to Reh-binder's theory, liquids or additives may promote the spread of cracks in stressed materials by lowering the surface tension at the crack tip. Rose and Sullivan surmise that the same mechanism may be operative during grinding, thereby facilitating comminution of the particles. In addition, Rose and Sullivan reviewed how additives may act as dispersants as a result of their being adsorbed on the surface of the particles being ground. This concept has been suggested by Quatinetz, Schafer, and smea15 to explain from their experiments the major role of additives that enabled them to grind metal down to 0.1 µm. Discussions of other comminution theories and additional sources of material on the subject will be found in Ref. 10. None of these previous suggestions and theories, however, can account for all phenomena encountered during ball milling of metals to submicron size in this and in a previous investigation by the author.6 The objectives of this investigation were to determine the behavior of metal powders during ball milling either in pure water or in oxygenated water and to gain an insight into the grinding mechanism. Zirconium, tantalum, iron, nickel, copper, and silver powders were ball-milled in pure water. These metals were selected because their oxides cover a wide range of free energies of formation. For comparison purposes, an alloy-type 430 stainless steel-was also ball-milled in pure water. The pressure of the hydrogen released during ball milling was monitored in order to determine the oxygen that combined with the metal or alloy. In order to obtain more information on the nature of the grinding process, nickel, copper, and silver powders were also ball-milled in oxygenated water (water pressurized with oxygen). The oxygen that reacted with the powders was determined from the pressure decrease in the mills. The powders resulting from ball milling in pure water and in oxygenated water were subjected to surface area, optical microscopy, and X-ray diffraction analyses. With these data, the oxygen calculated to be combined with the metals during ball milling, and comparison of the free energies of formation of the oxides of the milled powders with that of water, a comminution mechanism was postulated. MATERIALS, EQUIPMENT, AND PROCEDURES The materials used in this investigation were powdered metals, deaerated distilled water, high-purity helium, and commercial grade (99.5 pct purity) oxygen. The powdered metals used were zirconium, tantalum, iron, nickel, copper, and silver. A 16 pct Cr, ferritic stainless steel, type 430, was also used. The purities (or nominal compositions) and the surface areas of these metals and the alloy are given in Table I.

Jan 1, 1970

By W. C. Phalen

SALT-MAKING PROCESSES THE production of salt in the United States divides itself at the outset into two distinct classes: (1) The mining of rock salt and its purification and separation into marketable sizes, and (2) the production of salt by evaporation from brines, bitterns, and other solutions. The processes employed at the present time in the manufacture of salt by evaporation may be outlined as follows: 1. Solar evaporation. 2. Direct-heat evaporation (a) in open kettles; (b) in open pans. 3. Steam evaporation, (a) in jacketed kettles, (b) in grainers. 4. Vacuum-pan evaporation. In this paper only the solar-evaporation processes practised in different parts of the United States will be described. SOLAR EVAPORATION Localities In the Eastern States the solar-evaporation process is not generally employed for climatic reasons. In the Western States, particularly in California and Utah, the great bulk of the salt produced originates in the solar-evaporation process. Of the Eastern States producing salt, this process, so far as the writer is aware, is employed in New York State only.

Jan 9, 1914

By Robert F. Mehl, Gerhard Derge

The gamma-alpha transformation in iron and iron-rich alloys is of such practical and theoretical importance that many papers have been published upon the subject relating to critical temperatures, transformation rates and accompanying property changes. Although crystallo-graphic studies are of less immediate practical usefulness, the opportunities which these offer to furnish data on the basic atomic movements which characterize the transformation are not to be neglected1. The early work on the crystallography of this transformation has been reviewed in the fourth paper of this series2; since then several important papers have appeared. Our present knowledge may be briefly summarized as follows. Kurdjumow and Sachs, working with a 1.4 per cent carbon steel3, established the orientation relationships subsisting between the face-centered gamma and the metastable tetragonal lattices in freshly quenched martensite, and between the face-centered gamma and the body-centered alpha lattices in tempered martensite. The orientation relationship observed in the latter case may be stated in terms of planes and directions observed to lie parallel in the two lattices: {111} ?//{110}a [110] ?// [111]a (This notation is used throughout as the most descriptive means of expressing the fact that any (111) plane of the gamma phase may be parallel to any (110) plane of the alpha phase, and that a [110] direction in a particular (111)? plane is parallel to a [Ill] direction in the corresponding (110)a plane.) From these relationships the atomic movements that transform the gamma lattice into the alpha may be inferred. In the present experiment these may be considered as consisting primarily in a shear of the atoms parallel to the {111} planes in [110]? Directions

Jan 1, 1937

By A. A. Bauer, M. S. Farkas, F. A. Rough

An investigation of the d-phase relationships between the uranium-zirconium and uranium-molybdenum systems was conducted. A ternary cut joining U-31.5 at. pct Mo to U-74 at. pct Zr is presented on the basis of differential thermal analysis, metallographic and X-ray diffraction data. HyDothetical isothermal ternary sections, inferred from the determined d-phase relationships, are presented for the uraniztm-zirconium-molybdenum system. A ternary eutectoid, at 454ºC, was found in zirconium-rich alloys. Its composition, based on metallography and electron-beam micro-analysis, is estimated as U-61.7 at. pct Zr-7.1 at. pct Mo. URANIUM binary systems have been studied extensively in the past to supply basic information needed in reactor-fuel development. Alloys of uranium with zirconium, molybdenum, and titanium are of particular interest because, in these binaries, extensive or complete solid solubility between the body-centered-cubic forms of these elements and y uranium exists. In addition, an intermediate phase of limited solid solubility forms in each of these systems by transformation of the high-temperature ?-uranium phase. Previous investigation of the phase relationships existing between the intermediate 6 phases in the uranium-zirconium-titanium and the uranium-molyb- denum-titanium ternaries have already been reported.1,2 The results of an investigation of the phase relationships existing between the 6 phases in the uranium-zirconium-molybdenum system is reported here. The phase equilibria that occur in the solid-state portions of the pertinent binary systems are shown in Fig. 1. Phase nomenclature appearing throughout the report is as shown in these diagrams. The crystal structure of the phases in this system are given in Table I. EXPERIMENTAL PROCEDURES Alloys were cast and fabricated to 1/4-in.-diam rod. Specimens were heat treated and examined by metallographic and X-ray techniques. Thermal-analysis data were obtained.

Jan 1, 1960

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By F. Peter

I. GENERAL INTRODUCTION. TECHNICAL progress takes place in two directions: the improvement of methods, affecting the quality of the product; and increase in the economy of operations, affecting its cost. In the iron-industry, practice is pretty well settled, and. revolutionary changes of method are, for the present, not to be expected. Hence, in this industry, the principal endeavor is to reduce costs by the use of labor-saving inventions, such as the machines brought into use during the last decade. But it is not alone necessary to reduce the labor-cost; complete economy requires also a saving in raw material. Under this head we may rank the coal employed as metallurgical fuel; and it follows that progress includes the economic use of fuel, so managed as not to injure quality of product. In the present paper it will be shown how, by suitable utilization of the heat from the furnace, a large portion of it may be made available for other purposes. Such utilization of waste-gases is important in all industries which employ furnaces (especially heating- and smelting-furnaces); and in the first rank of these stand the iron-, glass-, and porcelain-manufactures. The following pages are devoted chiefly to the waste-gases of smelting-works, and especially to those reverberatory-furnace gases which are not combustible.'

Jan 12, 1913

By D. B. Kibler

Pill Florida hard-rock field extends from Suwanee and Columbia Counties in northwest Florida to south of Croom, Florida, in Hernando County this area is approximately 100 miles long and varies from 2 to 30 miles 1n width Florida hard-rock phosphate was discovered at Hale Springs, about one mile northwest of the town of Dunnellon Marion County, in the year 1888, by Albertus Voight who lived within a few hundred yards of the spring Soon after this discovery there was a great influx of land speculators and wildcat operators into the vicinity of Dunnellon A few years later phosphate was found in Alachua, Levy, Citrus and Hernando Counties, and a great number of small crude plants were built from Newberry, Alachua County, all the way to Croom, Hernando County Phosphate was found in many places as "outcrops " Looking for outcrops was the first method used by the early prospectors in searching for deposits Several years passed before any systematic method of prospecting was used EARLY MINING The early method of mining hard-rock phosphate was with picks and shovels, wheelbarrows, mules and wagons The pick-and-shovel method was used altogether until about 1900, when some of the larger operators began to use railroad-type steam shovels of from 1/2 to 1-yd capacity Picks and shovels, with negro labor loading the phosphate ore (called "matrix") into wooden side-dump skip-cars, was continued until about 1907 From the discovery of hard-rock phosphate until approximately 1905, overburden was removed with mules and scrapers At some places, the overburden was loaded into side-du nip skip-cars by negro laborers and the cars were then pulled up an incline with a steam hoisting engine The maximum depth of overburden that could be economically removed by hand labor mules and scrapers was approximately 15 feet About 1905 one of the companies erected a producer-gas powerhouse near Dunnellon and generated its own electricity and about the same time the larger companies began using hydraulic methods for the removal of overburden From the year 1888 through the year 1939, approximately 75 companies were operating at one time or another in the hard-rock territory, on approximately 500 locations The hard-rock deposits are more irregular and have higher mining costs than the pebble-rock deposits, therefore they have not been competitive in the domestic market, but because of the higher grade of the hard rock it is in demand for the export trade Discovery of phosphate outside of the United States has made it increasingly difficult in recent years for the hard-rock companies to survive, so today only three companies are operating These

Jan 1, 1941

By L. S. Darken, H. A. Wriedt

THE constitution diagram of the iron-copper system derived by Daniloff' exhibits, at the iron-rich end, phase fields similar to those of the iron-carbon diagram. At 1484° 1094°, and 850°C there are, respectively, a 6-y-L peritectic, a y-E-Lperitectic, and a a-y-E eutectoid. The phase designated E is copper-rich, containing 4 pct Fe or less according to the temperature. The composition of copper-saturated ferrite (a-solid solution) has been determined previously only twice as a function of temperature. By electrical conductivity measurements, Buchholtz and Köster2 found 3.4 pct Cu in ferrite at a eutectoid temperature of 810°C. They represented the composition of saturated ferrite by the equation, log (%Cu) = 4.32-4125 (1/T) Gregg and Daniloff3 reported that Köster later modified his opinion, raising the indicated eutectoid temperature to 833 °C and the copper content of eutectoid ferrite to 3.7 pct. The literature contains several indications4-7 that the work of Köster and his co-workers is not reliable. Norton,8 using an X-ray method, found that 1.4 pct Cu dissolved in ferrite at the approximate eutectoid temperature of 850°C and that the solubility decreased to about 0.3 pct at 700°C. Below 700°C his experimental data show almost no change in solubility. These findings, although inconsistent with the work of Ruer and Goerens4 and of Smith and Palmer,7 have been used generally since their publication. In investigations involving the observation of arrests in temperature during continuous heating or cooling the precise location of the eutectoid temperature has been obscured by a large hysteresis. The more reliable work 579 where the results are not effected by this hysteresis indicates a eutectoid temperature between 840° and 850°C. The foregoing discrepancies, along with a few observations in this Laboratory relating to the precipitation of copper from ferrite, prompted us to rein-vestigate the lower temperature portion of the Fe-Cu system. In this investigation the solubility of copper in ferrite was obtained by the chemical analysis of high-purity iron equilibrated with copper-silver alloys. This method eliminated the necessity for retaining by a quench the physical state of the specimen existing at the equilibration temperature. EXPERIMENTAL The reaction of the iron with the copper alloy was

Jan 1, 1961

By R. D. Carnahan, J. E. White

A study of dispersion strengthening in TD-Nickel (nickel plus 2 vol pct Tho2) was conducted employing microstrain techniques at ambient room temperature. It was found that optimum strength was due primarily to the incorporation of stored energy developed by a variety of thermal-mechanical treatments. The relatively low strength of the recrys-tallized condition implies that the dispersed particles themselves offer only token resistance to deformation. The development of resistance to large-scale recovery or recrystallization at temperatures near the melting point requires a more extensive sequence of strain-anneal cycles than does the development of optimum strength. A micro-Bauschinger effect was observed which appears to be related to the lattice resistance to the movement of free dislocations. The effect was nearly identical to that in pure nickel indicating that the presence of the dispersed phase and considerably increased dislocation density (stored energy) only alters the number or effectiveness of barriers. THE early stages of deformation of engineering materials can be conveniently studied by utilizing strain-gage techniques which permit resolution of strains less than 5 X 10-7 in. per in. for testing in four-point bending (Carnahan and white1). The present investigation, part of a continuing study on the very early stages of deformation, was designed to reveal the true role of a dispersed phase in promoting high strength in a commercially available dispersion-strengthened alloy. Although this technique has been used for some time to study microdeformation in pure metals and alloys, it has just recently received attention as a means of investigating dispersion strengthening. Studying the very early stages of deformation in alloys which depend upon a finely dispersed inert phase for strength may prove to be a very important method for a better understanding of these materials. It is essential to obtain considerable clarification of actual dislocation movement and the kinds of deformation barriers which exist before optimum properties can be designed into this type of material with any degree of confidence. Considerable research on a variety of dispersion-strengthened materials has resulted in two different schools of thought regarding the strengthening mechanism. One faction2-4 favors the idea that the particles themselves resist the motion of dislocations. The criterion for yielding is the fracture of the dispersed second-phase particles due to an array of piled-up dislocations. Other invesfigators5-a have shown that particles are effective primarily by allowing a greater buildup of stored energy or dislocation density through thermal-mechanical treatments in the composite than the pure matrix material. The particles themselves, then, are not exclusive obstacles, but the complex network of particles, dislocation tangles, subboundaries, and grain boundaries are strength determining. The development of such a complex dislocation network in SAP has been studied recently in some detail by Goodrich and Ansell. The ability of dispersion-strengthened alloys to resist softening or recrystallization is also of considerable importance; however, the criteria for maximum stability may not necessarily be those for maximum strength. In this study, in addition to the evaluation of the microstrain properties of TD-Nickel, it is felt that considerable clarification of the true dependence of strength and stability on the dispersed phase is shown. I) MATERIAL AND PROCEDURE TD-Nickel is a dispersion-strengthened alloy developed by the E. I. DuPont de Nemours Co., which contains 2 vol pct thoria (Tho2) in a pure-nickel matrix. The average ThO2 particle size is approximately 0.1 p and the interparticle spacing is less than 1 u. The material was supplied by DuPont in two conditions: hot-extruded bar stock, and stress-relieved cold-rolled sheet 0.025 in. in thickness. The bar was extruded at 2200°F from a cold-pressed and sintered billet. The sheet stock was prepared from the extruded material by a process involving ten or more 50-pct cold reductions by rolling with intermediate anneals at 1800° to 2000°F. Test specimens used in this study were prepared in the form of rectangular parallelepipeds measuring 0.375 by 1.375 in. in thicknesses ranging from 0.025 to 0.040 in. Samples prepared from sheet and extruded stock were mechanically polished before heat treatment and were handled with extreme

Jan 1, 1964