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By M. A. Torcaso, P. Raimondi

To study mass transport in systems simulating oil recovery processes, different porous media were saturated with a mobile (carrier phase) and a stationary phase. Slugs of carrier phase containing a small amount of solute were displaced with pure carrier phase. By analogy to the chromato-graphic processes, the velocity of the solute can be predicted from a knowledge of the partition coefficient and the saturation provided that equilibrium between the two phases exists. Equilibrium was found to exist for different porous media, solutes and rates. The conditions were varied over the range normally encountered in the laboratory and in the field. The longitudinal dispersion of a solute undergoing interphase mass transfer was also investigated. INTRODUCTION The production of hydrocarbons by gas cycling, enriched gas drive and C02 or alcohol displacement involves, among other factors, relative motion between two phases and compounds, hereafter called solute, which are soluble in both phases. The solute is carried forward by the faster flowing phase at a lower velocity than the average velocity of that phase. Retardation of the solute is caused by chromatographic absorption and desorption in the slower flowing phase and by the degree of departure from equilibrium. At equilibrium the concentration of solute in the two phases can be related by the equation* CSw = K Cso ,............(1) where C, and C are the concentration of solute in the aqueous and oleic phases respectively and K is the equilibrium ratio, or partition coefficient. Displacement theories must contain an explicit assumption with regard to equilibrium, i.e., whether the compositions can be related by Eq. 1. The existance of equilibrium depends, in general, on the relative velocity between the phases. Unfortunately, other factors such as gravity segregation and viscous fingering, also depend on velocity. For this reason, whenever effects of rate on displacement were observed,2-4 it was practically impossible to discern what caused them — lack of equilibrium or the factors mentioned above. Equilibrium between phases has been the subject of extensive studies in fields such as extraction or chroma to graphy. It has received only small attention in flow through the type of porous media encountered in oil production.5 For this reason a method was developed which makes it possible to study the movement of a solute as it is affected by rate, type of porous media, partition coefficient and carrier phase, but in the absence of segregation or fingering. The information obtained enables one to determine when the assumption of equilibrium can be made. Briefly, the method consists of (1) saturating the core with a mobile and an immobile phase, (2) injecting a slug made up of the same fluid as the mobile phase and a small concentration of mutually soluble solute, (3) measuring the lag and the peak height of the slug at arrival and (4) correlating these variables with fluid properties such as partition coefficient and mixing constants of the medium. PROPOSED MECHANISM The principles of chromatography are combined with the equation of longitudinal mixing to predict the velocity of a solute slug compared to the bulk velocity and the peak height of a slug.6-9 The equation so obtained is valid under equilibrium conditions only. Therefore, a comparison between experimental and predicted results will give a measure of departure from equilibrium. This work was done with either the oleic or the aqueous phase being immobile. For simplicity, the following development is based on the case where the oleic phase is immobile. However, the treatment is the same in either case.

Jan 1, 1966

By H. C. Brown

SINCE 1934 the steel industry has been utilizing the spectrograph for supplementing wet chemical analysis in the production control of electric and open hearth furnaces. This means of control made great strides during the war years because of the general acceptance of the spectrograph and the increased emphasis that was placed on rapid control methods. However, in the post war era, with the demand still on increased production, it became apparent that a still more rapid and economical means of production control was needed. Since the spectrograph had been used mostly in the analysis of low alloying and residual elements, it also became apparent that equipment was needed to extend the spectrographic technique to the analysis of the high alloying elements in stainless steel. For these reasons, companies manufacturing spectrographic equipment were prompted to start development work on direct reading instruments. In June 1949, the Applied Research Laboratories of Glendale, Calif., announced that a direct method of spectrochemical analysis for stainless type steels had been developed. This paper will describe the use of the Applied Research Laboratories Production Control Quantometer in the quantitative control of stainless, silicon, and plain carbon steels being made at the Butler Pennsylvania Div. of the Armco Steel Corp. The Armco Butler Div. has one 70-ton electric furnace and six 150-ton open hearth furnaces. The electric furnace is employed in the making of all types of stainless steel and the open hearth furnaces are used for the production of silicon, wheel, and plain carbon steels. The ARL quantometer was purchased primarily for the purpose of controlling the steelmaking in the electric furnace, but its use has been extended for the analysis of final tests (ladle tests) on a number of different types of stainless, silicon, and plain carbon steels. Because of this additional work by the quantometer, substantial savings in manpower and time have been realized by the laboratory. In the analysis of a set of preliminary tests from the stainless steel furnace, approximately 40 min in laboratory time are saved due to quantometric analyses. Despite the fact that more specialty grades of stainless steel are being made in the electric furnace, the average tons per hour have been increased since the quantometer was put into operation. Specialty grades require more furnace time than regular commodity grades of stainless steel. The installation of the ARL production control quantometer was completed on March 13, 1952. By May 1, 1952, the instrument was calibrated for nickel, chromium, manganese, silicon, and molybdenum, which are the elements necessary for the production control of the stainless steel furnace. Within the following month, training of personnel on the quantometer was achieved and a study of the accuracy of the instrument showed that the results obtained were sufficiently accurate for control purposes. Therefore, on June 11, 1952, the quantometer was placed on production control for all types of stainless steels. Starting September 11, 1952, the instrument was gradually placed on ladle analysis (final tests) as the analytical curves were refined and additional curves were drawn. The quantometer has been relatively free of breakdowns since placing it on production control. The samples from only one stainless steel heat have had to be analyzed by wet chemistry because of instrument trouble. The previously existing heat-time record was also bettered by 15 min on a commodity grade of 18-8 stainless steel. Scope of Control In general, the quantometer determines all elements necessary for the production control of all types of stainless steel heats and for the ladle analysis of various types of stainless steel heats. It is also used in reporting final results for silicon, manganese, chromium, nickel, molybdenum, tin, copper, and aluminum on all silicon steel grades and manganese, chromium, nickel, molybdenum, tin, and copper on several plain carbon steel grades. Table I shows the elements and the concentration ranges of these elements in the various types of stainless, silicon, and plain carbon steel that are determined on the quantometer. A study of the results obtained on ladle test samples of stainless steel types 410, 430, 430 Ti, 446, 301, 302, 304, 304L, 305, and 17-7 PH will be discussed. Also included in the study are the results obtained on ladle test samples of a number of silicon steels. Apparatus In order to take full advantage of the potentials of the production control quantometer, the unit has been placed in an air-conditioned room with relative humidity control. The temperature is maintained at 73'22°F and the humidity at 45&5 pct. The air conditioning serves as a precaution to minimize the amount of adjustment and calibration needed during operation. It also reduces contaminating fumes and dust and thereby lessens the necessity for maintenance on the equipment. The quantometer is composed of three units: the high precision multisource unit, the 1.5 meter vertical spectrometer, and the console. The source unit supplies excitation conditions varying from spark-like discharges to arc-like discharges. The voltage to the source unit is supplied by a motor-generator

Jan 1, 1955

By K. Brack, G. H. Schwuttke

Annealing properties of subszerface amorphous lavers produced through high-energy ion implantation in silicon are studied. The buried layers are produced through the implantation of ions (nitrogen), ranging in energy from 1.5 to 2 mev. X-ray interference patterns, transmission electron microscopy, and resistivity profiling are used to study the annealing characteristics of the ion damage. The annealing experiments indicate a low temperature (below 700°C) and a high temperature (above 700°C) region. Significant changes occur in the amorphous layer during the high-temperature anneal. Such changes are corre-lated with the re crystallization of the amorphous silicon and the formation of subsurface (buried) silicon-nitride films. TODAY'S main problems in the field of ion implantation are related to the accurate determination and prediction of 1) the distribution profiles of implanted ions, 2) the lattice sites occupied by the implanted ions, 3) the lattice damage produced through ion implantation, and 4) the annealing characteristics of damage centers in the lattice. This paper reports investigations concerned with the problems listed under 3) and 4). EXPERIMENTAL Our investigations cover the energy range of incident ions from 100 to 300 mev and from 1 to 2.5 mev. The emphasis of this study is on the energy range from 1.5 to 2 mev. The experiments are conducted with single charged nitrogen ions. To implant the ions a van de Graaff generator is used as described by Roosild et al.1 Accordingly, a gas containing the desired ion specie is passed through a thermome-chanical leak into a radio frequency activated source. The positive ions are driven into the van de Graaff with the help of a variable voltage probe. Emerging from the accelerator the ions drift into a magnetic analyzing system and here the desired ion specie is bent 90 deg into the exit port. The ion beam leaving the analyzer is defocused and drifts down a 4-ft long tube to hit the silicon target. At this position the 20 pamp ion beam has a circular cross-section of 2.1 cm. N2 is used as a source gas for nitrogen ions. The implantation target is silicon with zero dislocation density, 2 ohm-cm resistivity, (111) orientation, mechanically-chemically polished, and 1 mm thick. The target is mounted on a water-cooled heat sink and kept at room temperature. A fluence of 1015 to 1016 ions per sq cm is used. RESULTS 1) Silicon Perfection after Bombardment. High-energy ion bombardment of silicon has some striking effects on lattice perfection. Some results were reported in detail previously at the Santa Fe conference2 and are here briefly summarized for the benefit of the experiments described in the following. 1.1) Identification of Surface Films on Silicon. After bombardment all samples are found to be coated with surface films. The films on the silicon surface vary in thickness and color; they can be transparent, slightly brown, or opaque. The films are thicker and darker in the high-intensity area of the beam and they delineate the bombarded surface area of the crystal. The films produce electron diffraction patterns characteristic of carbon and of SiO2. Carbon is predominant. The presence of carbon in these films was confirmed by use of the electron microprobe. Formation of the films occurs independently of the ions used and is attributed to a contaminated vacuum of the high-voltage machine. The carbon is most likely the product of the pump oil which is cracked and polymerized under ion impact. The films stick tenaciously to the silicon surface and burn off in a low-temperature Bunsen flame. 1.2) Mechanical Perfection of the Silicon Surface. The mechanical perfection of the bombarded silicon surface was investigated through optical microscopy, electron microscopy in which the replica technique is used, and optical interferometry. No mechanical damage of the surface was visible after bombardment. However, if a bombarded sample is soaked for several minutes in hydrofluoric acid (HF), gas bubbles may develop in certain spots of the silicon surface. It is also noted that in these areas the surface film starts to peel off. Relatively large patches of film come off if the sample is soaked in HF during ultrasonic agitation. After HF treatment, pits may be present on the silicon surface. The pit dimensions are estimated to be as large as 50 µ. The pits appear in the region of most intense irradiation. 1.3) Lattice Perfection After Bombardment. No lattice damage is found on the silicon surface. Electron transmission micrographs and selected area diffraction patterns of the surface show no difference before and after bombardment. Measured approximately 2 µm down from the surface, the silicon lattice throughout this depth is of good perfection. Well-defined Laue spots and Kikuchi lines are obtained from the surface as well as from the indicated area below the surface. However, some radiation damage is dispersed in this top layer. A sharp boundary line separates this surface layer from a highly damaged layer which extends further downward into the silicon. Typical of this

Jan 1, 1970

By Richard E. Ellwanger

Methods of utilizing flocculents as settling and filter aids for mineral processing slurries are reviewed. Broad chemical classifications and techniques for proper dilution, multiple addition, and combination treatments are discussed. A variety of custom built and commercially available systems for makeup and delivery of flocculents to the application points are in use throughout the mining industry. Those concepts which, in the author's opinion, are particularly important to the successful makeup and we of flocculants are presented in relationship to the available makeup and feed systems. Actual industrial applications are included in the presentation.

Jan 1, 1982

By Robert E. Reed-Hill, Edward R. Buchanan

A recent paper by Adams and vreeland30 describes dislocation density changes in zinc as a function of shear strain. The dislocation density was determined with the aid of an etching technique previously described by Brandt, Adams, and Vreeland.31 However, comparison of dislocation densities obtained by electron microscopy and this etching technique are not in good agreement, as will be shown below. Several zinc crystals of 99.999 pct purity were grown in air using a modified Bridgman technique.' These were annealed in air a 400°C for 1 hr and

Jan 1, 1969

By Donivan L. Gordon, Fred H. Dorheim

Often, as viewed by the public and many in the mining industry, abandoned limestone and gypsum quarries offer a simple, economic solution to the twofold problem of solid-waste disposal and land reclamation. In a state where about 75% of the existing quarries are in hydrologic connection with carbonate aquifiers the rationale for considering the storage of solid waste in them must be critically examined. Consistent with the requirements of water resources protection, criteria are suggested to evaluate the potentiality of using abandoned limestone and gypsum quarries as sanitary landfill sites.

Jan 1, 1975

By S. Weinig, E. S. Machlin

THE mechanism of the martensitic transformation has been the subject of a remarkable number of papers in recent years.' Because the task of evaluating all the available theories is a formidable one, the authors will confine themselves merely to the presentation of results of an experimental investigation of the habit orientation, lattice relations, magnitude and direction of average transformation shear strain, and orientation of subband markings for a single variant of the possible habit systems in an 11 pct Mo-Ti alloy. It is hoped that these data will assist in the establishment of a rigorous theory for the mechanism of the martensitic transformation. Experimental Procedure Specimen Preparation: A sample, approximately 1/2 x 1/4 x 1/4 in., was cut from a double arc-melted ingot composed of commercial-process A titanium and high purity molybdenum (nominally, 11 pct Mo). It was capsuled in evacuated Vycor at 10.-3 mm Hg subsequent to a double argon wash and homogenized for 48 hr at 1100°C. After a direct quench into H2O at room temperature, a large-grained specimen resulted, which, by X-ray diffraction and metallographic means, was subsequently shown to be in the body-centered-cubic phase, ß. Two adjacent, approximately perpendicular faces were polished and the ends of the specimen were ground parallel in a V-block. Fiducial lines were inscribed at 45" to the common edge of the polished surfaces in order that they would be perpendicular to the habit traces of the subsequently formed a plates.2 The specimen was then compressed between the ground ends in a Buehler press to stress induce the transformation ß to a'. Experimental Measurements: The habit-plane orientation, the orientation of subband markings, the orientation relation between the parent ß and the product a', and the transformation strain for the same plate were determined. To further establish the nature of the subbands, one surface was repol-ished and etched. The bands in the a' were still visible and were found to be optically anisotropic under polarized light. Back-reflection Laue patterns were obtained from the ß matrix and from a region comprising both a' plates and adjacent ß matrix (a Cu target was used). By superposition of the two X-ray diffraction patterns, it was possible to obtain a tentative orientation relationship between the two phases. This result was confirmed by a pattern taken after the specimen was rotated to make the basal-plane pole of the hexagonal a' phase strike the film. This necessitated cutting the specimen to expose the a' plate in the new position relative to the X-ray beam. Analysis of Experimental Measurements On the basis of the aforementioned X-ray patterns, the orientation between parent and product

Jan 1, 1955

By R. D. Fisher, A. G. Metcalfe, F. A. Crossley

AN investigation of the application of magnetic stirring to the consumable arc melting of aluminum and nickel demonstrated that grain refinement could be obtained when there was sufficient stirring force. Also, it was found that grain refinement could be obtained in aluminum by alternately reversing the polarity of the current through the magnetic stirring coil. The effect of the latter was to periodically reverse the direction of rotation of the molten metal.' Because of their promise, these findings were applied to conventionally cast aluminum. Shortly after this work was begun, Kondic2 reported experiments in which aluminum cast with 40° C (72° F) of superheat exhibited a grain size of 10 to 20 grains per cm2. When interrupted rotation was applied during solidification by mechanical means, a grain size of 800 to 1000 grains per cm2 was obtained. Magnetic Stirring Applied to Conventional Casting— The applicability of magnetic stirring to producing grain refinement in conventionally cast metal was evaluated in the following way. Three pounds of aluminum were cast into a clay-bonded graphite mold. The mold was surrounded by a magnetic stirring coil of 1000 turns. A direct current of 200 amp was passed through the casting by means of a graphite electrode which was immersed from the top. A current of 5 amp was passed through the stirring coil. The aluminum (1100 or 25) was superheated to 1600° F (871° C) and fluxed by passing chlorine gas through the melt for 2 min prior to casting. Two additional castings were made for comparison: 1) a conventional casting of metal superheated to 1600° F and 2) a similar casting through which 200-amp current was passed during solidification, but without current in the magnetic coil. Macrosections of these three ingots are shown in Fig. 1. Very remarkable grain refinement resulted in the magnetically stirred casting. It may be noted that the casting through which 200-amp current was passed has a coarser structure than the conventional casting. It would appear that this is due to the additional heat input generated by the current to the former casting. Mechanical Rotation Applied to Conventional Casting—A casting temperature of 1600° F was used throughout. Some 1 1/2 -lb castings rotated at 150 rpm were predominantly columnar with small areas of coarse, equiaxed grains close to the lower mold wall. Following these, a series of 3-lb castings was made. Macrosections of these ingots are shown in Fig. 2. The imposed rotational speed was 250 rpm. Turbulence or acceleration in the solidifying liquid was the significant factor. Fine grain size resulted in the material solidified during the period of acceleration of the liquid to the imposed rotational speed. When uniform rotational motion was achieved, the grain structure reverted to columnar. The final casting shown in the lower right-

Jan 1, 1962

By Robert U. King

The Climax Molybdenum Company's mine is situated on the Continental Divide at Fremont Pass in Lake County, Colorado. Elevations at the mine range from 11,000 it. to over 12,000 ft. The ore body is on the south flank of Bartlett Mountain, a prominent peak in the Ten Mile Range. A horizontal section of the mine, such as the Phillipson level (Fig. I), shows the outer ore zone as an annular ring varying in width from 300 to 800 ft., surrounding barren silicified rock. In vertical section the outer ore zone is dome shaped (Figs. 2 and 3), the apex of which is truncated at the surface by glaciation, exposing part of the ore body. The outer ore zone overlies the barren core and is itself overlain on the flanks of the dome with unmineralized rock. An ore zone of similar shape underlies the barren core of silicified rock, known as the Central Ore Zone (Figs. 2 and 3). Molybdenite is distributed uniformly through a zone of moderately silicified granite, schist and quartz monzonite (early) porphyry, around a highly silicified core. The molybdenite occurs in veinlets associated with fine granular quartz and pyrite, replacing altered and fractured granite, schist, and porphyry, and as coatings on numerous fractures cutting these rocks. Intense fracturing of all rocks is a characteristic feature of the Climax ore body. Most fractures are mineralized and no longer represent planes of weakness. Much fracturing is postmineral, however, and these fractures are generally filled with sericite or gouge, or remain as unmineralized joints separating otherwise massive rock into blocks of various size. Study and Mapping of Caving Characteristics Important differences in the behavior of caving of various blocks of ore at Climax have been recognized, involving arching of the rock over caved stopes, tendency of caved rocks to funnel, and size of caved rocks. Also, new problems have arisen associated with future mining on the Phillipson level, and may occur with proposed development of lower levels, such as excessive stress on mine pillars caused by large masses of overlying stable rock, and higher costs in maintenance of mine workings in soft, weak rock. To explain the differences and to provide solution for these problems, a study of geologic structure was undertaken early in 1944, to determine whether it would be possible to map cavability of rock from physical features exposed in mine workings and in diamond-drill cores. A comparison of known caved areas was made and rocks were classified structurally according to strength or degree of cavabil-ity. As nothing of this nature had been done before at Climax, the approach to the problem was rather indefinite. Several trials were made with negative results, but collectively indicated a suitable method. This was to examine all mine workings and diamond-drill cores, record-

Jan 1, 1946

By J. J. Kanter

The choice of a nonferrous metal or alloy for a given Application is frequently predicated upon a consideration of properties other than merely the capacity to withstand stress. When ability to withstand stress is the dominant engineering requisite of the material to be used, economic considerations seldom lead to the choice of nonferrous metals and alloys. In most instances where a nonferrous metal is used it is because of some special quality of either corrosion resistance, electrical properties, thermal properties, antifriction, or fabrication advantage that commends its application. The mechanical properties, as a rule, present an incidental engineering consideration entirely secondary to the special quality deciding its use. Indeed, great ingenuity has often been exhibited by engineers and metallurgists in overcoming the mechanical shortcomings of a nonferrous base material. in order to take advantage of some outstanding property. . With this thought in mind, we might better appreciate some of the problems in stress design. encountered with nonferrous metals and alloys pertinent to a symposium on their creep characteristics. Our considerations must necessarily be far from complete because of the broad range of materials in the nonferrous category for which creep properties assume a technical interest. Creep deformation of these metals can be subject for study at temperatures ranging from ambient to incandescent, depending upon which one is under consideration. Whereas the steel metallurgist thinks of creep as an essentially high-temperature engineering consideration, the same is not necessarily true in the field at hand. The diversity of the creep problems in the nonferrous field is perhaps accountable to some extent for its virginity as a symposium subject. Each research has necessarily been sponsored by some organization or group interested either in promoting the use of a certain nonferrous base or in obtaining data toward the solution of a mechanical difficulty encountered in applying a material indispensable for its special attributes. Perhaps as many techniques of creep testing have been used as there are base metals implied under "nonferrous." Some of the creep problems that have occasioned researches are associated with steam-pressure vessels such as tubes, drums, castings, and forgings of copper-base and nickel-base alloys, cable sheathings of lead and lead-base alloys, electrical transmission lines of copper and aluminum, engine parts die-cast from alloys based on zinc, aluminum, copper— soldered and brazed joints-—as well as numerous duties at extremely high temperatures met with alloys based on cobalt, nickel, tungsten, molybdenum, platinum, and other precious or semiprecious metals. Postwar technology will have the benefit of much creep research on nonferrous metals, which for reasons of security cannot be discussed on this occasion. Suitability OF Metals As already intimated, the bulk of the constructional metal that ordinarily is

Jan 1, 1945

By R. W. Heckel, R. E. Trabocco

The recovery process in 400 Monel filings was followed, principally, by using the Warren-Averbach technique of X-ray peak profile analysis. The deformation fault probability, a, was 0.006 in samples of unannealed filings. a , the twin fault Probability , was approximately 0.002 in samples of unannealed filings. Both a and 0 were found to "anneal out" at 600°F. The effective particle size and mzs strain increased and decreased in the (111) direction, respectively, with increasing annealing temperature. The actual particle size was found to be almost equivalent to the effective particle size. Tile small values of deformation and twin fault probabilities accounted for the similarity in values of the effective and actual particle sizes. Stored strain energy and dislocation density calculations based on rms strain decreased with increasing annealing temperature. The dislocation density decreased from 10" per sq cm in the unannealed filings to 10' per sq cm in the partially re-crystallized filings. The square root of the dislocation density based on strain to that based on particle size indicated a random dislocation distribution in the unannealed filings. The dislocation arrangement changed to one with dislocations in cell walls with increasing annealing temperature. THE recovery processes which occur in metals are generally thought to be a redistribution and/or annihilation of defects.' Investigators' have shown that recovery processes can be characterized by X-ray line-broadening analyses. Michell and Haig4 measured the stored energy of nickel powder by calori-metry and found the value to be greater by a factor of 2.5 than that from X-ray data obtained by the Warren-Averbach technique.= Minor increases in particle size occurred up to 752°F (recovery), while above 752°F the particle size increased greatly due to recrystalliza-tion. X-ray microstrain values decreased between room temperature and 392"F, remained constant from 392" to 752"F, and decreased from 752°F to a negligible value at 1112°F. Faulkner developed an equation for calculating stored strain energy based on X-ray line-broadening data which gave a closer correlation of measured and calculated stored strain energy based on the data of Michell and Haig. The stored strain energy released during recovery is predominately dependent on the decrease in dislocation density which was p-enerated from cold work.7 Stored energy has been measured8 in alkali halides during recovery and recrystallization and 80 pct of the stored energy was found to be released during recovery. Dislocation distributions have been studiedg in a number of fcc metals by thin-film electron microscopy. Howie and Swann" found the stacking fault energy of copper and nickel to be 40 and 150 ergs per sq cm, respectively. ~rown" has pointed out that these stacking fault energy values should be corrected to 92 and 345 ergs per sq cm, respectively. The dislocation distribution of a metal is directly dependent on the stacking fault energy of the system. Metals of high stacking fault energy such as aluminum cross-slip readily and do not form planar arrays of dislocations. Metals of lower stacking fault energy such as stainless steels" do not cross-slip readily. Cold-worked nickel has been found to form a cellular dislocation structure after annealing.13 The relatively high stacking fault energy of nickel and copperlo to a lesser extent favor cellular structures of dislocations rather than planar arrays after deformation. The present study of recovery was carried out on a Ni-Cu alloy (Monel 400) to compare with prior studies for pure nickel and pure copper. X-ray line-broadening techniques were used to measure the effect of recovery temperature on rms strain and particle size and the results were compared with previous studies on copper'4-'7 and nickel., Calculations were also made on stacking fault probabilities, dislocation density, dislocation distribution, and stored strain energy as affected by temperature. EXPERIMENTAL PROCEDURE The nominal analysis of the Monel 400 used in this investigation was: 66.0 pct Ni, 31.5 pct Cu, 0.12 pct C, 0.90 pct Mn, 1.35 pct Fe, 0.005 pct S, 0.15 pct Si. The annealed material was cold-reduced in two batches, one 50 pct and the other 80 pct. It was originally planned to conduct line-broadening studies of these bulk samples; however, rolling textures that developed produced low-intensity peaks which were not suitable for line-broadening analysis. Filings were prepared at room temperature from both the 50 and 80 pct cold-reduced specimens, series A and series B, respectively, and were not screened prior to heat treatment or X-ray studies. Heating to the annealing temperature, 200" to 120O°F, was accomplished in a matter of minutes in a hydrogen atmosphere. Following heat treatment, some of the filings were mounted and polished for microhardness measurements with a Bergsman microhardness tester, using a 10-g load. A G.E. XRD-5 diffractometer using nickel-filtered Cum radiation was used to obtain all diffraction patterns. Only (111)- (222) line-broadenin data were used in the present study since the {400f peaks were too weak to use. The Fourier analysis of the (111) and (222) peak

Jan 1, 1969

By F. W. Jessen, R. W. Durie

The development in the laboratory of mall salt cavities illustrated that the rate at which salt dissolved was affected by the rate at which fresh water was injected into the cavity. Experiments carried out with small salt cores indicated, however, that the rate of salt removal with forced convection was not significantly different from that with natural convection, provided the flow was in the laminar range. The rate of salt removal was apparently controlled by the water salinity, which was indirectly determined by the rate at which fresh water was injected. With turbulent flow at the salt surface, the rate of salt removal could be increased several-fold with the same salinity in the cavity. A quantitative evaluation of the rate of salt removal under natural convection was attempted by using techniques developed for the analogous heat convection system. The values of the rate of salt removal obtained experimentally were considerably greater than the calculated values due to surface irregularities. To determine the effect of these irregularities, the rate of salt removal was found for a smooth surface by experimentally determining the rate of salt removal as an irregular surface developed and then extrapolating this trend back to initial time. Excellent agreement between the experimental and calculated values then were obtained. INTRODUCTION Underground cavities leached from massive salt formations have been used extensively for many years for storing LPG products. The development techniques for storing methane gases in the liquid state at a low temperature leads to speculation that underground salt cavities of controlled geometry may be quite important in this field. In any case, the increasing number of salt cavities used for storage indicates an impending need for a better knowledge of the washing process to efficiently develop maximum storage volumes within specified regions. It is the purpose of this paper to discuss some aspects of -the mechanism of the dissolution of salt in the formation of cavities of controlled geometry. Although no attempt is made to resolve the problems that may be associated with the storage of methane in the liquid state in salt formations, the fact that salt cavities can be formed at reasonable cost would appear to justify investigation in this direction. Further, underground cavities have the advantage of allowing storage at higher pressures (and hence higher temperatures) than surface installations. Although the thermal conductivity of salt is somewhat higher than frozen earths, 0.017 cal/(sec) (cm)(c) for salt at 32F vs 0.005 cal/(sec) (cm) () for ice at this temperature, this disadvantage is offset by the higher storage temperature in underground cavities. For example, at atmospheric pressure, the temperature of liquid methane would be —258F. In a storage cavity at 2,000 ft, the pressure would be approximately 1,000 psia, which would allow a storage temperature of -9OF. The formation temperature would be roughly 110F at this depth, hence the total temperature differential would be 200F. Under surface storage conditions the corresponding temperature difference would be some 333 F (75 F + 258 F). The results of this difference can be compared more readily by substituting the appropriate values of thermal conductivity, temperature difference, heat capacity and density into the solution of the diffusion equation for the unsteady linear conduction of heat. For the underground salt storage, the heat flux is 15cal/(sec) (sq cm), where t is the time in seconds from the initiation of the cooling. For the surface system, and using the thermal properties of ice at the average temperature, the corresponding figure is 21cal/(sec) (sq cm). Hence, the heat losses through ice under surface conditions would be some 30 per cent higher than the underground salt storage. This ratio would vary, considerablv. Of course, for other conditions, but it indicates that an advantage over surface facilities may be obtained by storage in underground salt cavities.

Jan 1, 1965

By H. Herman, M. E. Fine

Kinetics of reversion and reformation of GP I were studied resistometrically in Al-1.7 at. pct Cu. The reversion process is over in roughly 1/2 minute at 205 "C irrespective of the amount of primary aging. After reversion the occurrence of an incubation time before reaging begins has been substantiated. The reaging kinetics is drastically accelerated by plastic deformation to the specimen. An incubation time is observed only if the specimen is aged before reversion. The incubation time and the effect of plastic deformation indicate that nucleation of GP I is heterogeneous. Simple clusters of copper atoms apparently do not act as nuclei for GP I. AFTER quenching aluminum-rich copper from the solid solution range, Guinier-Preston zones of the first kind, GP I, form very rapidly at room temperature. The rate, largely controlled by the concentration of vacancies, is initially most rapid1 (that is, at the time of the first measurement: 1/2 min) and decreases with time. The nucleation is thought to be athermal. If after aging for several days the GP I is dissolved by reversion at 205°C, according to measurement of Young's modulus an incubation period is observed before GP I begins to form on subsequent aging.2 Yet if the reversion is carried out immediately after quenching, both resistivity3 and modulus changes2 show no incubation effect. The zones which form after reversion have the same structure as those which form after the quench.4 Because of entropy considerations and also the short diffusion time, the solid solution after reversion, 2 min at 205°C, is probably more highly clustered than at the original solution treating temperature, 520" to 550°C. It appears most reasonable to associate with nucleation the incubation time observed on reaging after reversion. A simple cluster of copper atoms, many of which are presumed to be present after reversion, is then not a sufficient nucleus for GP I; a GP I nucleus must contain something in addition to a cluster of copper atoms. The purpose of the present note is to give some additional experimental information concerning the incubation time and rates of reaging after reversion. The existence of the incubation time has been verified by measurement of another property, the electrical resistivity. Acceleration of reaging after reversion by plastic deformation has also been investigated. In acl.dition, the kinetics of the reversion process itself was studied. EXPERIMENTAL Electrical resistance was measured by the poten-tiometric four probe method. The 1.7 at. pct Cu alloy was furnished by the Aluminum Co. of America in the form of 1/2 in. rod. The major impurities reported by Alcoa were Fe (0.002 wt pct), Si (0.003 wt pct), and Mg (0.001 wt pct). Specimens for measuremenl of resistance were prepared by rolling to 0.010 in., cutting 2 by 0.2 in. pieces, rolling the middle pclrtions of these to 0.005 in., and splitting the 0.010 in. sections up to the reduced central section to form current and potential leads. Aluminum extension wires insulated with ceramic tubes were spot welded to the leads. The specimen was supported by the lead wires. The whole specimen assembly was annealed at 500" C in an air furnace for more than 12 hr and then aged at room temperature. This was done to assure quick and complete resolution during subsequent solution treatments. These were carried out in Houghton's "430 Temper Salt" at 520'C for 1 hr. Unless otherwise specified, quenching was accomplished by quickly transferring the specimen from a salt pot to 25°C water. Aging was carried out in a 3 liter dewar of distilled water, rotated and stirred. The temperature was controlled to +0.01°C with a thermomercurial regulator in conjunction with a transistorized relay

Jan 1, 1962

By E. H. Rose

IN a year of sober reflection and stocktaking after the mineral-squandering spree of World War II, the role that beneficiation of low-grade must henceforth play in American mineral industry has become unmistakable. From the volume of research and development progress in mineral engineering during 1946, mineral dressers evidently have ample resoluteness to meet the challenge. Perhaps ,the most conspicuous trend of the year was the renascence of interest in gravity concentrating methods and more serious effort than ever before to make them effective in finer size ranges down to 200 mesh. This has been forced by the problem in iron ores where the low value of the product will not support a high flotation reagent cost, however good flotation pilot plant results may have been and however well the acute problem of variable feed may be met. The race is on between rabbit flotation and tortoise gravity methods and a surprising amount of betting money is being laid on the tortoise which already is showing previously unsuspected talent for speed. Mostly, however, a wait-and-see attitude prevails during the present preliminary heats. As evidence of the latter, two magnetic plants are now on the boards for magnetic taconites on the eastern Mesabi to establish a reprieve against the time when nonmagnetic taconites must be addressed. Incidentally, these operations will force the blast-furnace issue on preparation of fine material since a minus-100-mesh grind is contemplated.

Jan 1, 1947

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By J. S. Fulton

THOSE who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangement, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartment septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries) ; portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. PHASES Of the many papers published on various phases of the Bessemer process, nearly 170 according to one bibliography, over go per cent were concerned with the metallurgical phase and less than 10 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to one of the causes of the Bessemer process. Is it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By George A. Roberts

The development of an alloy system, high-speed steel, is used as an example of the progress of physical metallurgy. Tracing the history of men and their thoughts as they studied and invented and modified these materials, the story of high-speed steel since the 1890's is seen to be a long, slow, but steady progression of achievements. Today's multiplicity of high-speed steels are the result. Data are presented on quantitative metallography of carbides in high-speed steel with high vanadium content using the QTM instrument. Grindability as well as mechanical properties are related to the content of excess MC and M6C carbides in a series of high-speed steels and the newer matrix steels. These emphasize the present state of knowledge and show the current stages of thought that may affect the development in succeeding years. It is a great thrill for me, an ex-research metallurgist and ex-practicing metallurgical engineer, to speak to an audience currently engaged in both pursuits on the occasion of the 43rd Howe Memorial Lecture before the Iron and Steel Division of the AIME. I shall not review Henry Marion Howe's distinguished career, so adequately reviewed in Maxwell Gensamer's contribution in the 1965 AIME History of Metallurgy, except to point out that, while leading the life of an intellectual, he worked as a practicing research metallurgist and a practicing metallurgical engineer for significant periods of time and contributed greatly in both areas. For those of you who believe, as I do, that in the intellectual activity of metallurgy we are blessed with an intimate mixture of science and engineering (see Mehl's 1960 Howe Lecture), we might recall that Howe, while pursuing a life of writing and teaching in later years, served as the first Chairman of the Division of Engineering of the National Academy of Sciences. That metallurgists were called upon then to lead an engineering recognition movement is perhaps related to the strong part played by the AIME and its members in the recent establishment of a National Academy of Engineering and to the fact that a metallurgist is its head, 47 years after Howe served. I stress these engineering aspects for I wish to talk about a metallurgical engineering subject today. Alloy systems, physical metallurgy, and steel blended with an historical perspective and a report on new techniques to improve the old will, I trust, be of sufficient interest to bring these lectures back to the physical-metallurgy banner from which they have departed for 4 years. Those process metallurgists, open-hearth fiends, and physical chemists among you will just have to be patient. The development of an alloy system is the engineering application of scientific thought and fact. There are many interesting alloy systems, developed to a high degree of technology and sophistication over the past 40 to 70 years. These systems are bound together and related by a similar set of characteristics. For example, stainless steels are a system in which the members are related by a high chromium content which gives a corrosion-resistant characteristic. A subfamily in this system would be austenitic steels

Jan 1, 1967

By O. P. Arora, M. Metzger, G. R. Ramagopal

The rates of grain boundary and general corrosion were surveyed by an approximate method. Quantitative differences between their variations with the strength or cupric ion content of the acid yielded large variations in their ratio, highly selective intergranular attack being observed only under specific chemical conditions. The boundary corrosion rate increased with the copper content of the aluminum; this was attributed to an autocatalytic effect similar to the one shown for general corrosion. High- purity aluminum in hydrochloric acid exhibits striking intergranular corrosion and other structure-dependent corrosion phenomena of fundamental interest. The behavior is highly sensitive to the metallurgical and chemical conditions, the significance of many of which has not been established. The features of the intergranular-corrosion phenomenon, first described by Rohrman,l are summarized in the remainder of this paragraph. Strong attack normally occurs only at high-angle grain boundaries.' Usually 15 to 25 pctHCl is used to obtain a high rate, but this has also been obtained with weaker (7 to 15 pct) acid either by adding cupric or ferric ion to the acid3-5 or by passing an anodic current (-0.1 ma per sq cm).2,3,5,6 The two latter corrosion conditions produce strong attack of low-angle boundaries after certain heat treatments 2-4,5,7 The susceptibility of high-angle boundaries is influenced by the grain-boundary segregation of iron atoms; this increases the slow (µ per month) attack in 10 pct HCl8 but diminishes the rapid (mm per month) attack in 20 pct Hc14 (the present and most previous investigations deal with rapid attack). That segregation of elements other than iron affects intergranular corrosion has not been demonstrated, although analysis of data for iron alloys indicated that at least one other element must be considered.9 Intergranular attack occurs over a wide range of purity although it begins to become obscured above several hundred parts per million (ppm) total im- purities by the severe general corrosion which accompanies the higher iron contents and which is associated with the presence of a second phase or an inhomogeneous distribution of the dissolved iron.4,6,10 The variation of intergranular-corrosion rate with heat treatment1'3-6'"10 can be explained in some cases in terms of the distribution of the iron impurity but is not in general adequately understood. The present work dealt with two questions not previously considered in detail. The first proceeded from the view that the extent to which a special behavior is associated with the boundaries is indicated not by the intergranular corrosion rate alone but by the ratio of the intergranular to the general corrosion rate. A comparison of the two rates was therefore made for one lot of aluminum in acids of varying strength and metallic ion content. The second question was the effect of the copper content of the aluminum. For general corrosion, it has long been known that copper ions introduced into the acid by corrosion of the solid solution are reduced on the aluminum as patches of elemental copper which enhance the corrosion rate by providing cathodes of lower hydrogen overvoltage than were originally present.''-'3 Since the copper patches remain themselves unchanged, their action is "catalytic", and since they are products of corrosion, the effect is "autocatalytic." This phenomenon is significant at copper levels much lower than previously suspected, even at those typical of high-purity aluminum, as the authors have shown in a previous paper.l4 The present work shows that copper content affects intergranular corrosion. With polycrystalline specimens, truly quantitative rate measurernents are not readily made for intergranular corrosion or for general corrosion in the presence of rapid intergranular attack, and previous work in this field has tended to be qualitative. The present study made use of a simple procedure which provided fair approximations to the quantitative corrosion rates and fitted the purpose of surveying the behavior over % wide range of conditions and displaying certain large effects. The approximations involved in this work were usually outweighed by the experimental scatter, which tends to be substantial in a system as sensitive as this one. I) EXPERIMENTAL A. Material. The material procured, Table I, represented three low copper (1 to 3 ppm) lots, two of "normal" copper content (21 and 22 ppm), and two

Jan 1, 1962

By A. J. de Witte

It has been observed that upon invasion of a sand containing oil or gas and connate water by mud filtrate the hydrocarbons are more rapidly flushed by the filtrate than is the connate water.' In time, it appears that the following displacement pattern emerges: oil (or gas) is being swept ahead by connate water which, in turn, is pushed by invading fluid. Eventually the connate water may have "banked up" sufficiently to form a zone of appreciable thickness leading the invading front. In the extreme case, Fig. 1 shows how the situation will develop.' Immediately adjacent to the borehole (radius r) there is a zone, the invaded zone proper, where the connate water has been flushed out completely and which contains only residual oil or gas and mud filtrate. This zone (extending out to a radius ri) grades more or less abruptly into the next (thickness A), which contains only residual hydrocarbon and connate water. Beyond it, again more or less sharply bounded, extends the virgin formation with the original interstitial water saturation Sw. The various saturations are indicated in Fig. 1. The three zones generally will be marked by resistivity contrasts owing to their different fluid contents. As the connate water is usually more saline than the invading fluid, the second zone having a high connate water saturation forms a concentric cylindrical ring or annulus of low resistivity R, around the borehole.',' It will be referred to as the "low zone." Fig. 1 shows schematically the resistivity profile. It is clear that the phenomenon of a low zone could not occur in invaded water sands. The presence of a low zone, therefore, would be a qualitative indication of a hydrocarbon-bearing formation. Granted that the phenomenon is real, if it were pronounced enough to be detected, one might thereby have a means of locating oil or gas in the ground. This is the aim of the "displacement logging" method.' In any case, the presence of a low resistivity zone will affect the reading of electric logs. Using conventional log interpretation techniques, one must be aware of this and, if necessary, correct for it. Whether correction or detection should be the goal will depend primarily on the magnitude of the effect. The type of log which is likely to be affected most is the induction log. The current pattern of an induction log is concentric with the borehole. Any concentric ring of low resistivity, therefore, will tend to become crowded by current lines. This zone of maximum current density will obscure the relative contributions to the current conduction by other portions of a bed making, for instance, the contribution of the virgin formation less significant and thus detracting from the value or the induction log as an R, reading device. The present note is intended to ascertain the maximum possible effect of a low zone in the extreme case portrayed by Fig. 1 on three commercially available types of induction logs, sc., 5 FF 27, 5 FF 40 and 3 F 60. Type 5 FF 27 or 5 PF 40 is currently run in conjunction with a 16 in. normal and SP log. This combination is gradually replacing the regular electric survey (two normals and one lateral) as a standard log in many areas. On the basis of the scheme of Fig. 1 (sharp boundaries between successive zones), the thickness of the low zone may be computed for various amounts of infiltration measured by the ratio of invaded zone diameter to hole diameter D,/d. Referring to Fig. 1, we can set up a material balance for the water displaced from the invaded zone proper and the water present in the low zone. The volume of connate water displaced from invaded zone upon flushing by mud filtrate is: V1 = e p (r2 - r2) ? Sw . where c = bed thickness ? = porosity Su, = original connate water satu-ration. The volume of water finally accu-mulated in the low zone is: Vz = e p [(r1 -?)2 - r2 4] ? Sw . where SW1 = 1 — Sor = "water" saturation in the invaded and low zones both. The volume of water originally present in the low zone is:

Jan 1, 1958

By Ernest F. Burchard

The Pao deposits of iron ore are in the State of Bolivar, Venezuela, near Upata, about 30 miles south of the Orinoco River and 90 miles east of Ciudad Bolivar. They were discovered 4 or 5 years ago and have not yet been developed to the stage of mining. In March-April, 1929, the writer devoted a week to the examination of these deposits. The maps, drill records and chemical analyses presented herewith were derived from original sources, and the field photographs were made by the writer. The petrographic and metallographic data are from notes by C. S. Ross and M. N. Short, of the U. S. Geological Survey, who have kindly collaborated in these special phases of the study. The Iron Obebodies Topography and Accessibility The deposits are in a region of low mountains representing northern outliers of the Guayanan Highlands. These mountains reach altitudes of 1800 to more than 2000 ft. above sea level, as determined by aneroid barometer. The iron ore is found on mountain crests that reach altitudes of 1915 to 1930 ft., and may be followed down precipitous slopes for 200 • to 300 ft. or more. The greatest vertical range in outcrop is nearly 400 ft., and drilling has indicated that the ore extends to this depth below the surface in one place, at least. The superior hardness of the iron ore accounts for the preservation of the local mountain crests with the intermediate valleys eroded in softer granitic rock. The deposits of iron ore are reached by a private road for automobiles branching northeast from the Ciudad Bolivar-Upata road, a distance of about 12 miles. This road was used in 1928-29 by trucks for transportation of food and camp supplies, gasoline, drilling equipment, etc., but was not suitable for the transportation of iron ore. Between Ciudad Bolivar and the iron-ore area the western two-thirds of the automobile road passes through nearly level, open country known as the savanna, largely used for grazing cattle. About 96 km. (60 miles) east of Ciudad Bolivar at

Jan 1, 1931