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By W. A. Longacre

IN the geophysical exploration program of the Cleveland-Cliffs Iron Co. on the Marquette Range of Northern Michigan, the vertical intensity magnetometer has been used to obtain magnetic anomaly maps of large areas. A network of magnetic base stations has been established and the relative vertical intensity at each station measured carefully with respect to a prime base. In the search for the relatively nonmagnetic soft red hematite ore, the magnetic exploration is indirect, involving the study of dikes, faults, contacts, and other structural features. It was found that the magnetometer, adjusted to a scale value of approximately 40 ? per scale division, was satisfactory for this type of exploration, although many magnetic anomalies were encountered that required the use of auxiliary magnets.

Jan 1, 1952

By N. F. Fiore, M. C. Mangalick

DISLOCATION damping in single crystals is orientation dependent.&apos; If dislocations are distributed uniformly over all the slip systems in a crystal, and if each dislocation contributes identically to the damping process, then a damping loss or decrement 6 arises. In fact, however, for a crystal of axial direction (hkl), dislocations on certain slip systems are oriented to make a larger contribution to the damping loss than are dislocations on other slip systems. Thus the measuring damping, 6 (hkl) is proportional to an orientation factor (hkl), which weights the ability of each slip system in the crystal to contribute to the total damping. If it is assumed that dislocations are distributed uniformly on all slip systems, then for a given orientation of an fcc crystal this factor is determined2,3 by the three nonzero elastic constants Cll, C12, and C44 and the density p. In this communication measured values of elastic constants for two Fe-18Cr-Ni alloys are reported, and the dislocation damping results on two different orientations of each alloy are analyzed for orientation dependence. Elastic constants were determined by measuring the ultrasonic velocities of one longitudinal and two shear waves in (110) direction of the fcc crystals.4 Variation of velocities with the change in orientation is very small for (110) orientation,3 and so this direction is ideal for orientation factor and comparative damping measurements. Experimental Procedures. The nominal compositions of the alloys studied are given in Table I. These alloys were vacuum-melted and vacuum-cast from high-purity materials at U.S. Steel Applied Research Laboratories. The single crystals were grown by the modified Bridgeman technique. The specimens were homogenized at 1350°C for 20 hr, cut to shape and size with a spark cutter, and then annealed at 1100°C for 20 hr prior to use. In the KHz frequency range, the Marx composite piezoelectric oscillator was used to obtain the damping. The ultrasonic pulse technique was used to measure the ultrasonic velocities and the attenuation in the MHz frequency range. M.c.mANGALICK,-- StudentMemberAIME,formerly Research Assistant, University of Notre Dame, is now with Casting Laboratory, Chase Brass and Copper Co., Cleveland, Ohio. N. F. FIORE, Associate Member AIME, is Assistant Professor, Department of Metallurgical Engineering and Materials Science. University of Notre Dame, Notre Dame, Ind. This communication is part of a Ph.D. thesis presented by M. C. MANGALICK to the Graduate School of the University of Notre Dame. Manuscript submitted May 20. 1968. IMD Elastic Constants. Table I gives the values of the ultrasonic velocities. Values of C11, C12, and C44 calculated from these velocities are also given in Table I, and it is evident that there is very little variation in C11, C12, and C44 with nickel content. This slight variation may be attributed to inaccuracies in velocity measurements and practical differences in the orientations of the specimens. For example, in B the time interval for vl was 2.4 ± 0.05 sec giving an error in v1 of 0.235 x or 0.005 in. per sec. The elastic constants obtained by pulse technique were tested by calculating E<110>, Young&apos;s modulus for the (110) direction, from the equation: This value was compared with the value computed from the resonance bar measurements in which where fr is the resonance frequency and I, is the length of the specimen. In all cases, the values calculated from the ultrasonic velocity measurements

Jan 1, 1969

By A. L. Barnes

Residual oil in watered-out reservoirs is a tremendous reserve which has been unrecoverable by established production methods. A study of the new recovery methods indicated that the forward combustion urocess might- recover oil from such reservoirs; however, no thermal recovery operating experience in a watered-out system was available. The Delaware-Childers pilot thermal test was undertaken to test the feasibility of thermal recovery in this watered-out reservoir. The pilot test consisted of a 2.22-acre, inverted five-spot in the 600-ft deep Bartlesville sand. The reservoir in the pilot area had a porosity of 20.6 per cent, a permeability of 118 md and an average sand thickness of 45 ft. The reservoir contains a 33&apos; API, 6-cp oil. Combustion was started Nov. 22, 1960. The initial air injection capacity was 750 Mscf/D, but it was eventually increased to 2,000 Mscf/D. The test was surrounded by an active water flood; therefore, water production was initially high, but decreased as the heat wave moved toward the producing wells. Oil-bank arrival at an individual well was indicated by a drop in GOR and WOR, and an increase in oil production. Combustion-front arrival was evident at three of the pilot producers, and they were plugged. Cumulative oil production from pilot area wells war over 12,000 bbl. Operational difficulties were negligible and only conventional equipment was necessary. The combustion efficiency of this test averaged over 80 per cent. Results from coring showed that the leading edge of the combustion front tended to be wedge-shaped but a nearly complete sweep of the reservoir was eventually obtained. An isopach map based on evidence from 10 core holes and the existing wells showed that 126 acre-ft had been swept by the heat wave. Using this swept volume, an air requirement of 15.7 MMscf/acre-ft was calculated. It was calculated that 275 ,STB/acre-ft was consumed bv the heat wave. INTRODUCTION There is a large amount of oil remaining in reservoirs that have been water flooded. A study of ways to recover this oil showed that the forward combustion process might be applicable. Results from a number of forward combustion tests have been reported in the literature, but none of these tests were conducted in a watered-out system. The Delaware-Childers pilot thermal test was initiated in 1960 to define the operating characteristics of underground combustion in this watered-out Bartlesville sand reservoir, The purpose of this paper is to present the pilot test results in detail. FORWARD COMBUSTION PROCESS The forward combustion process consists of initiating combustion in the formation surrounding an injection well and driving this heat wave through the formation toward offset producing wells. As the combustion front progresses through the reservoir, oil and formation water are vaporized, driven forward in the gaseous phase, and recon-densed in the cooler part of the formation. These distilled liquids, water of combustion and gaseous combustion products, form a bank or three-phase region ahead of the burning front. This bank pushes mobile reservoir fluids toward the production wells. The rate of movement of the combustion front is controlled by the rate at which the nondistill able residue which serves as process fuel can be completely burned off the sand. The production performance from a heat wave conducted in a watered-out oil reservoir will differ from one conducted in a dissolved gas-depleted reservoir because of the difference in fluid saturations. The primary depleted reservoir contains connate water saturation, relatively high oil saturation and some gas saturation. The watered-out reservoir contains a highly mobile water saturation, residual oil saturation and little gas saturation. As the combustion front moves forward in either type of depleted reservoir, it drives the distillable oil, the water in place and the water of combustion ahead, and burns the nondistillable portion of the oil. The heat-wave process in a watered-out reservoir differs from the process in a

Jan 1, 1966

By K. P. Fournier

This report describes work on the problem of predicting oil recovery from a reservoir into which water is injected at a temperature higher than the reservoir temperature, taking into account effects of vis cosity-ratio reduction, heat loss and thermal expansion. It includes the derivation of the equations involved, the finite difference equations used to solve the partial differential equation which models the system, and the results obtained using the IBM 1620 and 7090-1401 computers. Figures and tables show present results of this study of recovery as a function of reservoir thickness and injection rate. For a possible reservoir hot water flood in which 1,000 BWPD at 250F are injected, an additional 5 per cent recovery of oil in place in a swept 1,000-ft-radius reservoir is predicted after injection of one pore volume of water. INTRODUCTION The problem of predicting oil recovery from the injection of hot water has been discussed by several researchers. l-6,19 In no case has the problem of predicting heat losses been rigorously incorporated into the recovery and displacement calculation problem. Willman et al. describe an approximate method of such treatment. 1 The calculation of heat losses in a reservoir and the corresponding temperature distribution while injecting a hot fluid has been attempted by several authors.7&apos;8 In this report a method is presented to numerically predict the oil displacement by hot water in a radial system, taking into account the heat losses to adjacent strata, changes in viscosity ratio with temperature and the thermal-expansion effect for both oil and water. DERIVATION OF BASIC EQUATIONS We start with the familiar Buckley-Leverettg equation for a radial system:* This is sometimes referred to as the Lagrangian form of the displacement equation. If the injection water is at some temperature Ti which is above reservoir temperature TR, then lw, the flowing fraction which is water, is a function of both water saturation and fluid temperature at any given time and position in the reservoir. The temperature dependence of lw results from the temperature dependence of the viscosity ratio µo/µm of which lw is a function. Thus:

Jan 1, 1966

By F. H. Kihlstedt

THE Larap iron deposits, 125 miles east of Manila, are the biggest high-grade iron deposits in the Philippines, and have in seven years produced nearly 4 million tons of 6o per cent ore. Magnetic surveying followed by churn and diamond drilling cheaply developed a score of million tons. The ore zone is a wedge of metamorphic rocks in fresh, Miocene sediments overlain by agglomerates, which seem to have filled a river valley eroded in the sediments. A mild overthrust of the competent agglomerates crumbled the shale in front. Solutions gradually turned it into more competent hornfels and deposited pyrite, then magnetite and pyrite in the pores. As the temperature rose large bodies of magnetite with some pyrite were deposited by replacement and in open cavities in tensional areas of overthrust shears. At still higher temperature magnetite and calcium-magnesium silicates formed other bodies in similar cavities, and finally the thrust zone was invaded by syenite porphyry, causing high-temperature alteration products. Possibly, as temperature abated, more high-grade ore was deposited. The complicated faulting indicates dynamic, chronological and spatial changes of mineralization rather than zoning in a static system. Noncommercial copper, molybdenum and some gold accompanied the iron mineralization. In the thirties the Philippines gained a justified reputation as a country of considerable mineral wealth. Traces of Chinese workings show that these earliest travelers and traders had in a small way exploited the latent gold resources in the Islands. The Spaniards continued this for centuries, but did not succeed in establishing any steady mining industry. Modern technology was required to get it started. The rapid development in the last decade before the war got its impetus from several financial factors, the return to sugar growers of previously collected taxes, the influx of Spanish capital during the civil war in [ ] Spain, the influx of Chinese capital when the Japanese started their "China incident," and others. Directly or indirectly much of this capital reached the mining industry; in particular, gold mining. Out of the turmoil of an exceptional mining boom emerged a sufficient number of good and well managed gold properties to send the production to a level above that of any single state in the United States at the time. Other ore deposits besides those of gold also received their share, and for a country without any heavy industries at

Jan 1, 1946

By T. S. Lundy, F. R. Winslow

DIFFUSION coefficients of Hf181 in the high-tem-perature bcc phase of reactor-grade hafnium were determined at temperatures of 1795° to 1995°C by standard lathe-sectioning techniques. The temperature dependence of the data may be described by an Arrhenius-type expression for this limited temperature interval. However, hafnium is classed with the "anomalous" bcc metals zirconium, titanium, and y uranium by the low values of Do and Q observed in this study. The hafnium metal was received as 1/2-in.-diameter crystal bar. Analyses by the Analytical Chemistry Division of Oak Ridge National Laboratory showed the major impurity to be zirconium— about 2.1 pct. The total interstitial content was about 225 ppm with 190 ppm of this oxygen. The Hf"&apos; was supplied as HfC12 in HC1 solution by the Isotopes Division of Oak Ridge National Laboratory. The hafnium bar was cut into disk-shaped specimens 3/8 in. long. One of the flat faces of each specimen was metallographically treated and then the isotope was deposited by vacuum evaporation from a tungsten filament. A 3 by 3 in. NaI (Tl) crystal with a single-channel analyzer was used for counting y rays with energies of 0.3 to 0.7 Mev. The as-deposited layers of isotope had counting rates of about 200 counts per sec. Specimens were annealed in argon in a tantalum resistance furnace. Temperatures were measured with a microoptical pyrometer calibrated for the particular furnace sighting conditions. All sectioning was done by standard lathe techniques. Section weights were determined on a semimicrobalance. A density of 12.5 g per cu cm was used in determinations of section thicknesses. Activities associated with the various sections were measured and the penetration data were treated using the computer code by winslow.&apos; In all cases, except for specimens annealed at temperatures below 1795°C, normal Gaussian penetration behavior resulted. At lower temperatures, plots of In A(x) vs x2 were nonlinear [~(x) = relative activity at a distance x from the

Jan 1, 1965

By F. H. Vitovec, D. W. Hoeppner

Pusk-pull fatigue tests were conducted on copper tricrystals of 99.988 pct purity to ascertain the role of grain boundaries in the initiation and propagation of fatigue cracks. Significant differences in behavior were found for specimens which possessed different transverse-boundary misorientation. In speciwens with low boundary angles cracks initiated within the transverse boundary, while higher angles led to transcrystalline fatigue failure. It is suggested that at low angular misorientation moving dislocations may interact with dislocations of the boundary or dislocations present in adjacent pains on favorably oriented glide planes, thus initiating a fatigue crack. MANY fatigue studies have been concerned with fatigue-crack initiation within grains and the mechanism causing initiation and propagation1-3 Although the initiation of fatigue cracks in or near grain boundaries of pure metals has been observed and reported in the literature, the mechanism of this phenomenon has received little attention.4"11 EXPERIMENTAL PROGRAM Testing Procedure. To investigate the role of grain boundaries regarding initiation and propagation of fatigue cracks, copper tricrystals were tested in push-pull. Axial-stress tests were used to avoid the stress gradients introduced by stressing of some other nature. Copper was selected as the most suitable test material since extensive work has been done on the formation of fatigue-induced slip in copper. Tricrystal specimens were used to provide a grain boundary geometry with one boundary transverse to the principal stress axis and one or more boundaries nearly coincident with the direction of maximum resolved shear stress. The boundary energy and the slip characteristics in the vicinity of the transverse boundary depend on the relative orientations of grains across the boundary. Testing was done at room temperature, at a frequency of 700 cpm, in an atmosphere of either air or argon. It is known that the incidence of grain boundary cracking increases with increasing temperature and decreasing frequency.4 The fatigue machine applied a uniaxial tension-compression load to the specimen by a flat spring which was actuated by an adjustable eccentric. Use was made of an adjustable head and a load cell which had strain gages mounted at 120-deg intervals around its periphery, thus providing a means for eliminating any detectable superimposed bending moment. A clip gage was mounted between the gripping heads to record the cyclic strain amplitude applied to the specimen. Each specimen&apos;s hysteresis characteristics were recorded by supplying the load and strain signals to an oscilloscope. Microstructural changes were observed and recorded with an optical microscope which was mounted on the fatigue machine. Immediately prior to insertion in the machine, each specimen was chemically polished. Extreme care was exercised while inserting the specimen in the test machine to avoid either bending the specimen or introducing a mean load. Each specimen was stressed in the tensile direction first and subsequently the load was reversed. Specimen Preparation. Tricrystal fatigue specimens of 99.988 pct Cu were grown from the melt using a modified Bridgman technique. Ingots about 1 in. high were grown to the configuration shown in Fig. 1. Upon sectioning the resultant ingot, several specimens were provided with an identical shape and grain boundary orientation. Except for plane sectioning and final polishing, this method eliminated machining the specimens. The apparatus used for growing the tricrystals is shown in Fig. 2. A spectrographically pure graphite mold, Fig. 3, was inserted in a vycor tube which was mounted on a vertical zone-refining table. Prior to insertion in the tube the mold was assembled as follows. The insert and graphite rods were fixed in position in the mold. The copper was then placed in the mold and the entire mold assembly was positioned in the vycor tube, Fig. 2. At this point the tube was sealed, evacuated, purged with helium gas, and finally placed under a slightly positive helium pressure. The heating coil was then adjusted to melt the copper charge, after which it was raised at a speed of 4 in. per hr. It is also possible to use

Jan 1, 1964

By C. Wagner

When an alloy solidifies and the composition of the solid differs from the composition of the liquid, atoms of the alloying elements rejected at the solid-liquid interface have to diffuse toward the bulk liquid. Diffusion may be supported by convection. Theoretical calculations have been made for a liquid without convection, for a liquid involving natural convection, and for solidification of a liquid alloy at the surface of a rotating disk as an example of forced convection. WHEN an alloy solidifies, the equilibrium composition of the originating solid phase differs in general from the composition of the liquid phase. Thus, segregation may take place, i.e., the composition of the solid phase formed at different times differs from the bulk composition. The degree of segregation depends on several factors such as the partition ratio of the alloying elements between the liquid and the solid phase, the rate of solidification, and convection. To clarify, a theoretical analysis has been worked out. The following presuppositions are made: 1—Calculations are confined to the solidification of binary alloys in which the concentration of component A (solvent) is much greater than that of component B (solute). 2—The equilibrium concentration of the alloying element B is assumed to be lower in the solid phase than in the coexisting liquid phase. 3—At the solid-liquid interface, partition equilibrium is assumed. 4—The dependence of the partition ratio of the solute between the liquid and the solid phase on concentration and temperature is disregarded since only small concentrations of the solute are considered. 5—The concentration of the alloying element B in the solid phase is supposed to be lower than the saturation concentration for the formation of a second solid phase. 6—diffusion in the solid phase is disregarded, since diffusion rates in the solid state are comparatively low. When the partition ratio of the solute between the liquid and the solid phase is greater than unity, a part of the solute is rejected at the solid-liquid inter- face and has to diffuse toward the bulk liquid. Thus there is necessarily a concentration difference in the liquid between the solid-liquid interface and the bulk liquid as has been pointed out by Hayes and Chipman,&apos; Rutter and Chalmers,&apos; Tiller, Jackson, Rutter, and Chalmers, and others (see Fig. 1). In view of the concentration gradient in the liquid phase, the ratio of the concentration of the solute in the solid phase to that in the bulk liquid differs from the equilibrium ratio, although at the solid-liquid interface, partition equilibrium is assumed. Under certain limiting conditions, the solid may even have virtually the composition of the bulk liquid as is shown below. General Equations Let u be the linear crystallization velocity in cm per sec, D the diffusion coefficient of component B in the liquid phase in cm2 sec-&apos;, c&apos;,, and c", the concentrations of component B in the liquid and the solid phase, respectively, in mol per cm", and s the distance from the solid-liquid interface toward the bulk liquid at a given time t. The partition ratio is assumed to be equal to a partition constant K. Thus. The difference in the specific volume between the liquid and the solid phase may be disregarded. In view of the discontinuity of the concentration of the solute at the interface according to Eq. 1, u(c&apos;, — c",), , , = tic&apos;, (S = 0)(1 — K) gram-atoms B per unit area per unit time are rejected at the interface and have to diffuse toward the bulk liquid. From Fick&apos;s first law it follows that uc&apos;,,(s = 0) (1 ~K) == - D(dc&apos;,,/?>s). _-„. [2] The concentration profile in the liquid near the interface depends on the interplay of diffusion and convection as is discussed in the following sections. A schematic concentration profile is shown in Fig. 1. The "effective thickness of the diffusion boundary

Jan 1, 1955

By B. C. Allen

Grain boundary grooving has been studied in chromium, molybdenum, and tungsten under a variety of conditions using high vacuum techniques and tantalum -gettered argon. The average surface free energy of solid chromium, and the chromium-liquid silver interface free energy were respectively found to be 2200 ± 250 and 500 i 130 ergs per sq cm from groove formation kinetics and estimates of pertinent volume difffusion coefficients. The results for chromium were unffected by variations in interstitial content ranging from 0.003 to 0.09 pct C, or 0.003 to 0.03 pct O. Surface diffusion is the primary mechanism of groove formation in chromium under 1 atm argon at 1200" to 140O°C, and is essentially unaffected by 0.003 to 0.09 pct C, 0.003 to 0.03 pct O , metastable nitrogen contents up to -0.01 pct, and up to 2 torr Ag vapor. At higher temperatures, the major mechanism is volume diffusion in argon or evaporation-condensation in stutic vacuum. Surface diffusion occurs in molybdenum at 0.5 to 0.96 and in tungsten at 0.5 to 0.9 of the absolute melting tempera -ture by a single mechanism, possibly by the migration of single adatoms or vacancies. Results were slightly affected by up to 23 tory Sn vapor, and in molybdenum were essentially unaffected by 0.5 Ti or carbon in the range 0.002 to 0.02 pct. Volume difffusion through the liquid is the mechanism of groove formation in chromium-liquid silver at 1200" to 1400°C and in molybdenum-, Mo-0.5Ti-, and tungsten-liquid tin at 1200" to 2000°C. The solid-liquid interface free energies involved were estimated from grooving kanetics. WHEN a grain boundary intersects a solid surface, a groove tends to form along the line of intersection at temperatures above about half the absolute melting point (0.5 TM). The groove progressively grows by preferential atomic migration either by diffusion or evaporation. Establishment of a groove angle occurs in accordance with the grain boundary and surface free energies involved. The motivation for groove formation is a reduction in the total surface free energy of the system. This study is a continuation of previous work on thermal grooving of chromium, molybdenum, and tungsten.&apos; The temperature ranges were extended, and the effect of metallic and interstitial impurities was evaluated. The results were such that certain interface free energies and surface self-diffusion coefficients were deduced from the grooving kinetics. EXPERIMENTAL WORK Materials and Preparation. As indicated in Table I, the 0.05-0.08-cm-thick chromium, molybdenum, and tungsten sheet used was nominally 99.99 pct after recrystallization. Two lots of molybdenum with about the same analysis, Mo-0.5Ti,* and tungsten were ob- *Alloy compsitions are expressed in weight percent . tained commercially. Extruded chromium rod,&apos; prepared from iodide process crystals, was warm rolled to sheet at 700°C. Sheet of three Cr-0 impurity alloys containing up to 0.03 pct 0 was prepared by warm rolling arc melted, extruded, and swaged rod. Two Cr-C impurity alloys containing up to 0.09 pct C were made by equilibrating unalloyed chromium with a known amount of CH4 for 24 hr at 1150°C in previously evacuated quartz capsules. Chromium containing nominally 0.015 and 0.06 pct N was similarly prepared by equilibration with NH3. The sheet was recrystallized to give a stable grain size about equal to the sheet thickness. Molybdenum and Mo-O.5Ti were recrystallized in a tantalum resistance furnace 1 hr at 1 x lo-5 torr at 2300" and 220O°C, respectively. Tungsten was similarly annealed for 1 hr at 2500°C. Chromium and its impurity alloys were outgassed at 1100°C and recrystallized 1 hr at 1700°C under 1 atm Ar. Except for nitrogen, the impurity content stayed roughly constant. Nitrogen in both alloys was reduced to <0.001 pct. In fact, over 80 pct of the added nitrogen was lost after outgassing at llOO°C and annealing sheet 1 hr at 1300°C in argon in the presence of tantalum. Such a rapid loss can be rationalized since -2 torr N are required for equilibrium with 0.04 pct N in solution,3 while the equilibrium pressure is ~10-5 torr over tantalum at 1300°C.4 The recrystallized sheet was cut into small coupons which were metallographically ground and polished on one side with a minimum of grain boundary relief. The surface roughness was on the order of 0.01 µ. The tin and silver used were nominally 99.999 spec-trographically pure. After being outgassed at 1100°C and equilibrated in a molybdenum crucible for 0.5 hr at 1800°C in argon, the tin contained 3 ppm 0, <0.3 ppm N, and 0.1 ppm H. Following outgassing at 900°C and equilibration in a chromium crucible 1 hr at 1400°C in argon, the gas content of the silver was 1 ppm O, <0.5 ppm N, and 0.3 ppm H. Grooving Under Argon or Vacuum. All specimens were placed in unsealed containers made from rod or sheet of the same alloy, thereby enabling the polished surface to achieve gas-solid equilibrium. The annealing fixtures are shown in Fig. 1. The specimen was placed in a resistance furnace with a tantalum or Ta-10W heating element plus tantalum fixtures or radiation shields. Chromium was outgassed at 1100°C, and molybdenum and tungsten were outgassed at 1900°C to 1 x l0-5 torr or at the grooving temperature, whichever was lower. In vacuum anneals, the specimen was then heated directly to the intended grooving temperature. In argon anneals, 99.996 Ar was admitted

Jan 1, 1970

By P. L. Raffo, T. E. Mitchell

Single crystals of Ta-Re alloys have been deformed in tension and compression as a function of solute concentration and temperature. The temperature dependence of the yield stress is decreased by alloying. At low temperatures there is a minimum in the yield stress (at about 2 at. pct) as a function of concentration. Three-stage hardening was not observed in the alloys. Linear hardening rates, where observed, were characteristic of stage II in pure tantalum. At low temperatures and high concentrations, work softening was often prominent at high strains. Electron microscopy revealed that dislocations are mostly of screw orientation, although heavily jogged and cusped, and often occurring in dipole pairs. The alloys become more prone to cleavage with increasing rhenium content, due mostly to an increasing yield stress rather than a change in cleavage strength. Alloying apparently decreases the Peierls stress of bcc metals at low temperatures by facilitating kink nucleation at solule atoms on screw dislocations. Higher solute concentrations further increase the yield stress. Quantitative calculations and comparisons with other bcc alloy systems are made to show that the predominant hardening mechanism is due to the interaction of dislocations with misfitting solute atoms close to their slip planes. The interaction is so localized that the core dilatation of dislocations could be important. CONSIDERABLE interest has arisen in recent years concerning the mechanical properties of unalloyed bcc metal single crystals.&apos;-7 These and similar studies on polycrystalline materials have resulted in a considerable understanding of the macroscopic yielding characteristics8, 9 and the process of work hardening.&apos;&apos; This latter advance is due in a large part to the increased use of transmission electron microscopy in P I RAFFO junior Membar AlMF is Metallyureist Iewis such studies and the general observance of three stages of work hardening in the shear stress-shear strain curves. The properties of substitutional alloy single crystals of bcc metals have not been determined in as much detail as in the pure metals. Insufficient systematic studies have been made on the effect of alloying on the magnitude and temperature dependence of the yield stress or the stress-strain curves. The alloy systems which have been studied to some extent have been Ta-W,11, 12 Ta-Mo," Ta-Nb,12&apos;14 Mo-Re,15 W-Re,16 and alloys of iron with nickel,17 platinum,17 vanadium,18 and aluminum.18 A large body of data exists on Fe-Si alloys, but these have mainly been a result of the experimental convenience of using this material in place of unalloyed iron, rather than a comprehensive study of the mechanical properties of the alloy system per se. The present authors have previously reported additional data on the properties of Ta-Re, Ta-W, and Ta-Mo alloy single crystals.1g Some of the data on Ta-Re alloys will be described later in this paper. Briefly, single crystals of Ta-Re (1.2 to 10.6 pct), Ta-W (6.2 and 10.2 pct), and Ta-Mo (2.9 and 9.0 pct) were grown by the floating zone method in vacuum. Compression tests were performed in the temperature range 77" to 623°K. Slip was found to occur in Ta-Re alloys at 77&apos; and 298°K on the (~ll)[lil] system and slip lines were coarser and straighter than in unalloyed tantalum. No three-stage hardening was observed in any of the alloy systems and the curves were nearly parabolic. At temperatures above 175°K the yield stress* increased monotonically with in- creasing composition while at 77" and 175°K the yield stress initially passed through a minimum after which it began to increase again for concentrations greater than about 2 pct Re. Similar minima were observed in Ta-Mo alloys and to a lesser extent in Ta-W alloys. The minimum was interpreted as being a result of a

Jan 1, 1969

A method has been developed to remove calcite from the leaching circuit in the uranium in situ leaching system. The process involves injecting the leachate and a pH control agent tangentially into an inverted cone reactor containing calcite seed catalyst. The leachate can be treated at high throughput to obtain clear effluent containing 5 ppm or lower Ca. Both lime and ammonia are effective pH control agents and consumed according to stoichiometry.

Jan 1, 1985

By Waldemar Lindgren

THE purpose of this paper is to present certain facts relating to Cordilleran differentiation and metallization. Theoretical discussions concerning the exact modus operandi of differentiation, the causes that led up to it, and the original distribution of the magmas have been omitted because the author feels that his knowledge is deficient. These subjects have been adequately treated in the admirable works of Iddings, Daly, Harker, Tyrrell, Shand, and Wolff. The facts here set forth seem to indicate that differentiation and metallization form one continuous process during the eastward movement of the magmas, culminating in the alkaline province of the eastern border of the Cordilleran Ranges.

Jan 1, 1933

By William P. Blake

Travelers in the desert regions of the southwestern portion of United States, especially along the valley of the Colorado of the West, can hardly fail to note that most of the rocky outcrope of the harder rocks have a uniform prevailing blackness of the surface, in strong contrast with the normal color of the interior of the rock when freshly broken. For example, the granitic or gneissic rocks of Pilot Knob, below Yuma, are blackened beyond easy recognition. So also rocks upon the lower Mojave in California are so thoroughly blackened, as if painted, that ordinary gneiss can scarcely be recognized without breaking it so as to show the interior color and structure. The discoloration is not confined to the rocky outcrops in place, but is found upon boulders and upon the loose rounded pebbles which strew the surface of the mesas along the Colorado river. These fragmentary rocks partake of the general blackening.

Jan 1, 1905

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman&apos; provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry&apos;s law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

By J. T. McGrath, G. B. Craig

Tensile tests on aluminum single crystals, grown from the melt, revealed that the yield stress of these crystals was raised as the amount of striation substructure was increased. The number of striation-type boundaries was varied by changing the rate of growth of the crystals. The results are interpreted in terns of a blockage of dislocation movement by striation boundaries. IMPERFECTIONS are known to have a large effect on the mechanical properties of metals. Teghtsoonian and Chalmers 1 studied a block or striation-type substructure in tin and found that the formation of the striations depended upon rate of crystal growth and orientation. They found that the angular misorienta-tion between neighboring striations varied between 15 min and 5 deg. Atwater and chalmers2 investigated striations in tin and lead, and found that purity was another factor which influenced their formation. There was a limiting purity above which the striations were straight and regular. There is little information in the literature concerning how substructures in melt-grown crystals affect strength. washburn3 introduced small-angle boundaries into zinc by a shear process and found a subsequent increase in yield stress which he attributed to the presence of these boundaries. Lauriente and pond4 found the critical resolved shear stress in aluminium crystals grown from the melt, to increase with etch pit density. The etch pits were used as an indication of growth imperfections. In Hibbard&apos;s5 work on lineage structure in copper crystals grown from the melt, he tested one crystal containing interlineage boundaries, and found a 50 pct increase in the critical resolved shear stress. Fleischer and Chalmers6, in a recent paper, mention briefly that, in the production of aluminium crystals from the melt when the growth rate was raised from 1.2 to 18 cm per hr, the yield stress increased 50 pct. They felt that the increase in yield stress with rate of growth might be attributed to a higher concentration of impurities in the gage length and also might be affected by the increased number of small-angle boundaries (striations). The present investigation was undertaken to determine the effect of the striation substructure on the strength of aluminum single crystals. EXPERIMENTAL PROCEDURE Aluminum single crystals of 99.9992 purity were grown from the melt using a technique described by Chalmers.7 The growth rate was varied from 0.6 to 20 mm per min, thus producing crystals with varying numbers of striation boundaries. To avoid prior deformation, the crystals were chemically cut to the desired length with a saturated solution of cupric chloride. They were then annealed at 580°C for 24 hr and allowed to cool slowly in the furnace. Finally, the specimens were electropolished using an electrolyte of 5 parts ethyl alcohol and 1 part perchloric acid. Each specimen was approximately 5 in. in length and 0.125 sq in. in cross section. The average orientations of the 5 series of crystals studied are shown on the stereographic projection of Fig. 1. The crystals were strained approximately 2 pct in a soft tensile machine. The strain sensitivity was 3.6 x 10-4 cm over a 5-cm gage length.

Jan 1, 1960

By R. T. McLamore

Lack of sufficient native permeability or skin damage caused while drilling wells for in situ leach mining projects may necessitate stimulating injection and production we1ls to increase the leaching rate to economic levels. Such stimulation processes could include acidization, hydraulic fracturing, or explosive fracturing. This paper describes an explosive fracturing process that is being developed primarily to stimulate the production of oil and gas wells, but may be useful in in situ leach mining projects as well. The process utilizes a liquid explosive that has unique safety features. The chemicals that form the explosive are subdivided into two pumpable, non- detonable components. Technology has been developed to pump these two components independently but simultaneously into the well and blend them together downhole to form the explosive. As such, surface facilities and personnel are not exposed to explosive hazards. The explosive formulations utilized in the process have been subjected to numerous safety and characterization tests and been qualified for use in deep wells with temperatures and pressures up to 250°F and 10,000 psi. The explosive composition can be varied to produce an explosive ranging, energetically, from a blasting agent to a high explosive that can be detonated after injection into a borehole, a porous media or into thin naturally occurring fractures within the roc

Jan 1, 1974

By C. H. Aldrich

For many years the City of Prescot, about 8 miles northeast of Liverpool, has been the home of British Insulated Cables, Ltd., one of the largest wire mills and manufacturers of electrical equipment in England. Since this location is close to the industrial center of the country and the seaboard, with good railroad transportation facilities, it was a logical site for the new refinery. Early in April, 1932, the writer was called upon to prepare a preliminary layout and estimate of cost of the proposed plant, and shortly afterward, following a discussion of these figures with officials of British Insulated Cables, in England, the decision was reached to proceed immediately with construction of the plant. The refinery was built by British Insulated Cables, Ltd. Designing of the plant was started early in May, 1932, orders for equipment being placed as rapidly as possible. On July 18 the first steel was erected and the first charge was cast on Jan. 5, 1933. No difficulties of any consequence were experienced in starting the plant and the grade of copper produced was quite satisfactory after the first charge. The initial capacity desired was 2500 tons of refined copper per month. Since only one furnace was to be built, it was necessary that it should have sufficient reserve capacity to catch up after unavoidable shutdowns. It was also necessary to lay out the plant so that it would operate efficiently at this tonnage and at the same time permit expansion in the future, if necessary, to several times its original capacity. In order to meet these conditions and also to take full advantage of the space available, the layout shown in Fig. 1 was adopted. The principal plant structures are a blister storage aisle, casting building, wire-bar storage building and a coal-pulverizing building. Additional smaller structures include a brick and charcoal shed, pumphouse, drill room, water-cooling tower, clay-preparation shed, substation and plant office. Incoming blister is received in either broad-gage railway cars or steam motor lorries in the blister storage aisle, unloaded by overhead electric crane to narrow-gage cars, weighed and sampled, then either sent directly to the furnace or placed in storage. After refining, the copper is cast on the wheel, passes through the cooling bosh and is

Jan 1, 1934

By T. Vasilos, J. T. Smith

THE mechanism of pressure sintering, or hot pressing, for ceramic materials, has been investigated by several researchers.1-8 Plastic flow has been suggested as the rate-determining mech-anism1,2 while grain boundary sliding3,4 and fragmentation processess have been found controlling in other studies. Vasilos and Spriggs5,6 have reported that pressure sintering occurs by a diffusion-controlled mechanism. For the pressure sintering of metals, investigations with lead7 and with tin6 have not identified the operative mechanism during consolidation of these powders. This note reports the results of a pressure sintering study initiated to determine the mechanism controlling the densification of spherical copper powder. Temperatures of 300°, 400°, 500°, and 600°C at 2500, 5000, 7500, and 10,000 psi pressures were investigated. The copper powder for this study was obtained from Metals Disintegrating Co., Elizabeth, N.J. The minimum purity was reported to be 99.9 pct. The powder size was -325 mesh and a lineal analysis showed the average size to be less than 1 p. An alumina die body and punches were employed. Graphite spacers were placed between the copper powder and the punches before pressing. It was expected that the graphite would form carbon monoxide with any entrapped air and form a reducing atmosphere within the die cavity. This condition was generally realized during pressing although a minor amount of oxidation occurred at 500" and 600°C. The oxide particles were located randomly in the pressed samples and were not considered to influence the densification process. Calibration tests showed the temperature of the copper pellet to be about 20°C less than the die wall temperature, probably resulting from heat losses through the punches. This difference was compensated during the experimental pressing operations. The hot pressing equipment employed for this work has been described by Spriggs et a1.9 and was calibrated with a Baldwin-Lima-Hamilton load cell. Travel of the punches was monitored with a dial indicator showing increments of travel to 0.0005 in. Relative density was calculated at selected time intervals for a known copper weight, punch travel, and die diameter. The accuracy of this calculation was *1 pct. Average grain size after hot pressing was obtained by lineal analysis. Typical densification curves are presented in Fig. 1 and Fig. 2 where relative density is plotted vs log time as a function of applied pressure for the 300" and 600°C pressure sintering temperatures, respectively. The curves for 400" and 500°C were similar to those at 300°C and consequently are not shown. The curves at 300°C as well as 400" and 500°C do not show an end-point or limiting density for a particular applied pressure. At 600°C, a density in excess of 95 pct of theoretical has been reached such that further densification is extremely slow for the 5000, 7500, and 10,000 psi pressures. It is suggested that further densification at these pressure levels may be retarded or prevented by discontinuous grain growth, by entrapped gases, and by other microstructural limitations as described by Cob1e.10 The curve for 2500 psi hot pressing pressure is a straight line over the time interval although a slight change in slope may be occurring at the last time intervals. The plastic flow models,1,2 derived for hot pressing, predict the existence of an end-point (or limiting) density dependent on the yield point of the material at the temperature of interest. The yield stress of copper at a 0.005 strain level has been

Jan 1, 1965

By H. Kenworthy, R. B. Fisher, R. G. Knicherbocker, M. M. Fine

The progress made to date in the mineral dressing of complex Arkansas titanium ores is reported in this paper. Concentrates of rutile, a dioxide of titanium, were produced by treating a submarginal ore from the Magnet Cove Rutile Co., Inc., Magnet, Ark. The rutile recovery at present is 45 to 50 pct of the total TiO2, with the possibility of increased recovery with additional research. The work reported herein is part of a general study which will later include results of investigation of other titanium ore bodies in the Magnet, Ark., area. The fragile character of the rutile minerals, the softness of the gangue, the occurrence of pyrite and leucoxene, and the considerable proportion of extremely small size rutile in the presence of montmorillonite- and illite-type clays in the Magnet Cove open-pit mine are the important factors in the mineral dressing of this submarginal rutile ore. History The occurrence of titanium minerals in the Magnet Cove area of Arkansas was recognized as early as 1890, but it was not until about 1912 that any appreciable prospecting for the minerals was undertaken. At that time drilling was begun, a shaft was sunk, and several drifts were driven, but beneficiation to recover the titanium minerals was not attempted. The only successful mining and milling operation of the Magnet Cove rutile deposit was begun in 1932 by the Titanium Corp. of America and continued until 1942. The ore was washed by means of a rotary scrubber and then deslimed in a drag classifier. The discharge was ground in a rod mill, classified, and tabled to recover a rougher rutile concentrate, which was screen-sized and retabled on cleaner tables. The cleaner concentrates were given a reducing roast, screen-sized, and magnetically separated to produce a finished rutile concentrate. Most of the rutile produced during this period was sold abroad. In 1942, the Titanium Alloy Corp. of Arkansas (a subsidiary of the Titanium Alloy Manufacturing Co. of New York) purchased the property and rebuilt the mill. Subsequently, the plant and property were acquired by the Magnet Cove Rutile Co., Inc., of Little Rock, Ark., the present owners. Very little titanium has been produced since 1942. Although the Titanium Corp. activities yielded enough returns to allow continued operation for approximately 10 years, certain factors must be recognized. These are: (1) production of rutile in that period was during a low in the economic cycle which permitted low-cost operation on a small scale, and (2) a considerable portion of the production was above the water level and no drainage problems existed. Prior to this paper there has been no published report of any mineral-dressing investigation of the lower levels of the ore body. Reference is made in another paper1 to an earlier investigation of Magnet Cove rutile by the Rolla laboratory, in which it is stated that recoveries of 12 to 17 pct of the rutile were obtained. The present investigation was undertaken to improve the known milling processes and to provide adequate metallurgical information about the ore treatment. Titanium Technology The titanium mineral of primary interest in the present investigation was the titanium dioxide, rutile. Rutile is one of the industrial minerals whose annual consumption is relatively small but strategically important. The domestic production of rutile was 7100 tons in 1948. The imports of rutile in the same year were approximately 8000 tons.2 A major use of rutile is in the production of welding-rod coatings, for which a product containing a minimum of 92 pct titanic oxide is desired. Other constituents, such as lime, silica, and sulphur, must be held to a minimum, but hard-and-fast specifications for these elements cannot be drawn. It is necessary to incorporate the rutile in a welding-rod coating, make a sufficient number of test welds, and then determine the tensile strength of the weld metal in the as-welded and stress-relieved conditions. Such a test gives

Jan 1, 1950

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack&apos; find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950