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By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.' In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.' This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,' electrochemical potential,8 time lag,' and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda's result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.' MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By N. M. Levine

WHETHER the United States and its allies can W meet the challenge of a war brought by the Communists will depend largely on who wins the battle of steel production. At the present stage of the world situation, the United States and the other members of the Western family of nations have the lead on iron curtain countries. But we have no sure way of knowing what is happening at Magnetogorsk and other Russian iron and steel producing centers. We must also face the possibility that we may have to meet the challenge alone. The fortunes of war and world politics can strip us of friends and co-fighters quickly. The destruction of Hiroshima and Nagasaki are indicative of what the world can expect if war-madness ever grasps the earth again. Our domestic supply of high grade open-pit and underground iron ore is dwindling because of the drain of three wars and higher than ever civilian consumption. The production of iron ore and its eventual use in blast furnaces are the critical problems of an armed democracy today. The world crisis has led to efforts towards beneficiation for increasing ore supplies. The huge reserves represented by the magnetic taconites at the eastern end of the Mesabi, once in production, should provide us with a substantial portion of our native ore for many years. The estimated 10 to 20 million tons of concentrates annually can be increased in an emergency. If we had a certainty of peace for the next 50 to 100 years, the situation would be a stable, hopeful one, aided by importations of high grade ore from sources such as Canada and Venezuela. The hard truth is that we have little surety of peace tomorrow morning. Let us assume 'the U. S. could build sufficient processing plants for increasing production of magnetic taconites under the pressure of national emergency. We must also recognize the power of atomic warfare to contaminate an area as large as the Eastern Mesabi. Thus, it becomes imperative to seek some means of protecting our ability to produce the steel we may one day need to survive. The nonmagnetic taconites, completely dwarfing the magnetic taconites areawise as well as tonnage-wise, might provide us with this insurance. Present indications are that they will be considerably more expensive to treat, but in a desperate situation we might be very grateful for ores yielding 40 to 50 pct Fe recoveries at grades of 53 to 58 pct Fe carrying low phosphorus. The University of Wisconsin, because of the difficult iron ore situation in the state, has been working on the nonmagnetic taconite problem for the past three years in the hope of making a contribution toward its eventual solution. In Wisconsin, the Western Gogebic Range has been the state's most effective iron producing area. Today however, only two mines are in operation, both underground and approaching depths of more than 3000 ft. The range, however, does have a large supply of nonmagnetic taconites and presents a promising field for study. While the Gogebic offers one large source of nonmagnetic taconites, Michigan and Minnesota have even greater supplies of such material. Alabama, the northeastern states and the West all have low grade iron ore sources which might be utilized under extreme conditions. The Gogebic Range located in northeastern Wisconsin and northwestern Michigan has a total length of about 70 miles, about 45 of which are in Wisconsin. The iron formation averages 500 to 600 ft in width, dips 70' to the north and strikes at approximately N 63° E. The formation is sedimentary and consists of six distinct members characterized by alternating divisions of ferruginous chert and ferruginous slate. The footwall is generally quartzitic and the hanging wall of a sideritic slatey character. The iron minerals are mainly hematites with some magnetites, goethites, limonites and small amounts of siderite. In the area studied, very small amounts of iron silicates were observed. The magnetites occurred mostly in the Anvil-Pabst and Pence members, mixed with hematites and representing roughly about 10 to 20 pct of the total iron in the formation, thereby characterizing it as nonmagnetic. The gangue is of various forms of silica such as chert, opal and flint. Complete liberation of iron and gangue minerals is rare. There is always some iron present in the chert ranging from jasper-like solutions to fairly coarse iron oxide specks. Likewise, one always finds finely dispersed silica within the iron minerals. In late 1943 the Bureau of Mines carried out a trenching and sampling program in the two mile stretch between Iron Belt and Pence in Iron County, Wis. Preliminary work was based on samples from one of the four trenches cut by the Bureau of Mines. More detailed work following the preliminary analysis was then undertaken on samples composited from all the trenches, thereby giving a wider and more representative coverage of the area. A study of the

Jan 1, 1952

By G. W. Ostroot, S. Shryock

Cementing deep, high-temperature oil wells where static temperatures range from 350 to 400F has become routine in the part decade. In the United States there were 271 wells drilled deeper than 15,000 ft during 1963. Many of these wells had static temperatures higher than 400F. Bottom-hole static temperatures near 700F are now realities in the geother-mal (steam producing) wells of California's Salton Sea area. The detailed planning initiated prior to drilling the wells is discussed together with the methods, materials and equipment used in solving the cementing problems which are encountered. Data are also presented that lead to development of cementing compositions that provide adequate thickening time, do not retrogress in strength, and maintain low permeability under these extreme temperature conditions. Field data include the cementing programs used on eight relatively trouble-free geothermal steam wells in the Salton Sea area. INTRODUCTION Not too many years ago cementing oil wells with temperatures in the range of 300F caused considerable anxiety. In some areas of the United States it is now fairly common to cement wells having bottom-hole static temperatures in excess of 400F. We are now confronted with the problem of cementing wells with temperatures ranging from 500 to 700F. Temperatures in this order of magnitude are often found in geothermal steam wells. From where does this extreme heat emanate? There are many theories as to the source of this steam flow. The most widely held views are: (1) heat- ing of ground water fairly close to the surface by an intrusive mass of hot rock; (2) steam generation from a reservoir of metamorphic rock, normally found below 25,000 ft and not at the shallower depths of the Salton Sea reservoir; and (3) high-temperature gases (water vapor) escaping and migrating from molten or semi-molten rock (magma) at a considerable depth. Of these. No. 3 seems to be the most generally acceptable explanation. Heat from springs and fumaroles has been used for years as a means of heating and cooking; however, significant progress in harnessing the vast power of underground steam reservoirs has been relatively slow. The first large-scale attempt to use the heat generated by steam from wells was made in Italy around the beginning of the 20th century. In excess of 250,000 kw of electrical power is now being produced from holes around Larde-rello, Italy. Another very active drilling program was initiated in the volcanic area of New Zealand in 1949.' Natural steam for power projects in the United States began in the early 1920's. An early commercial steam field is located at the Geysers, approximately 75 miles north of San Francisco, an area discovered in 1847 and used for many years as a health resort. Steam originates from 15 wells that have been drilled since 1957. The present output from this project is 25,000 kw. Success of the Geysers operation has been responsible for several companies taking a careful look at the feasibility of producing steam for power generation in the Salton Sea area of Southern California's Imperial Valley. Geothermal steam activity in this latter area began in 1961 when O'Neill, Ashmun and Hilliard completed Sportsman No. 1, at that time the hottest wellbore in the world.' Since its References given at end of paver. completion seven additional wells have been successfully completed in this area. Many problems encountered in drilling steam wells had to be overcome to make the ventures successful. Formation temperatures encountered in the Salton Sea seemed to be a straight-line function (a gradient of 13F per 100 ft of depth).' This imposed severe conditions on all aspects of drilling and completion. This varied, to some extent, from gradients in the older geothermal areas. Not to be overlooked is the effect of these temperatures on casing creep or elongation by thermal expansion (Table I), because standard API flanged wellhead equipment makes no provision for this kind of performance. Floating equipment was redesigned, and changes in types of downhole equipment were made in an effort to eliminate anticipated problems. In the later completed wells, standard oil-well cementing equipment has been used. During the early development of geothermal steam wells there were some problems resulting from blowouts. However, these were eliminated in the deeper Salton Sea wells and no problems were encountered with the drilling mud. A sodium surfactant mud was used on the Sportsman No. 1 to drill from 2,690 to total depth. Nevertheless, it was necessary that a cooling system be added and the mud cooled before circulating it back into the well. The difficulty in evaluating the size of the steam area and its potential in terms of pounds of steam and years of productivity still has not been resolved. Economic complexities have also entered into the steam play in the Salton Sea. The wells at the Geysers were drilled at a cost of $15,000 to $20,-000, whereas the Salton Sea wells will cost more than $150,000. This cost differential has to some extent been accounted for because of the heavily

Jan 1, 1965

By George V. Smith, Daniel E. Sonon

Various mechanical properties of the Ni-Co-C alloy system were investigated to delineate the strengthening effect of carbon. Carbon concentration, cobalt concentration, vain size, temperature, and strain rate were varied so that thermal activation analysis and the Hall-Petch analysis could be used to evaluate the strengthening effect of carbon. Increasing carbon increased the strength of nickel and a Ni-60 pct Co alloy , with the effect becoming more pronounced at lower temperatures. Yield stress depended linearly on carbon concentration in nickel, but it depended on the square root of carbon concentration in the Ni-60 pct Co alloy. The Hall-Petch slope of nickel increased with carbon concentration; however, that of the Ni-60 pct Co alloy did not. The yielding behavior of these alloys was sensitive to composition, grain size, and temperature. Cobalt eliminated serrations in the flow curve of carbon-containing nickel at 300' and weakened them severely at higher temperatures. Pairs, or clusters, of carbon atoms appear to be responsible for the observed strengthening behavior. FLINN' conducted several experiments with carbon in nickel in an effort to provide information on the strengthening effect of interstitial impurities in solid solution in fcc metals and alloys. Strengthening which increased with decreasing temperature led him to conclude that carbon causes Cottrell locking in nickel. Fleischer2 analyzed Flinn's data and calculated that the strengthening effect of carbon in nickel was smaller by a factor of fifty than the strengthening effect of carbon in a! iron. Fleischer2 termed the magnitude of strengthening of carbon in nickel "gradual" and that of carbon in a! iron "rapid". He attributed "gradual" hardening to hydrostatic strains and localized changes in modulus of elasticity around solute atoms, whereas he attributed "rapid" hardening to tetragonal strains around solute atoms. Sukhovarov et a1.3-7 reported strain aging and serrated plastic flow in nickel, both of which they attributed to the presence of carbon. Serrated plastic flow has been rationalized by a process involving a series of dislocation pinning and multiplication steps.8, This process is more probable when screw dislocations are strongly pinned. Screw dislocations cannot be pinned by pure hydrostatic forces from the symmetrical strains of an interstitial impurity in an fcc lattice, except for small, second-order effects. However, they might be pinned by localized changes in modulus of elasticity around solute atoms,' by the pinning of the edge components of the partial dislocations of an extended screw dislo~ation,'~ or by clustered groups of solute atoms whose net elastic stress field is unsymmetric. The purpose of the present work was to investigate various mechanical properties of the Ni-Co-C a1loy system which are sensitive to pinning effects in order to delineate the specific pinning mechanism of carbon. Carbon concentration, grain size, temperature, and strain rate were varied so that thermal-activation analysis and the Hall-Petch analysis could be used to evaluate the pinning mechanism. Cobalt was added to lower stacking fault energy so that the number and extension of split, screw dislocations would be increased in order to test the possibility of pinning by carbon at extended screw dislocations. EXPERIMENTAL PROCEDURE Nickel and cobalt (both 99.98 pct-. pure) were melted with graphite in stabilized zirconia crucibles and cast at lo-' Torr to form Ni-C and Ni-60 pctCo-C alloys. Two ingots were heated to 1250°C and were forged to 1-in.-sq bars. These bars were machined to 4-in.-round bars, and then swaged cold to 0.144-in. -diam rods. Reductions in area of approximately 75pct were used with intermediate anneals at 900°C for 1 hr. The carbon content of batches of 0.144-in.-diam rods from each ingot was reduced to two levels by annealing 5-in. lengths in palladium-purified, dry hydrogen at 1100°C for 25 and 100 hr. The remaining material from each ingot was annealed at 10"5 Torr for 1 hr at 1100"~. These treatments gave a total of three carbon levels for both the nickel and the Ni-60 pct Co alloy. The 0.144-in.-diam rods were swaged to 70-mil wire, cut into test specimens, and then re crystallized at lom5 Torr in capsules for 1 hr at temperatures ranging from 760" to 1050" ~. The capsules were broken and the specimens were immediately quenched into water. Average grain size was measured using Hilliard's method of circular intercepts." Annealing twin boundary intercepts were counted in addition to grain boundary intercepts to establish an average grain size. Average grain sizes ranged from 5 to 140 p depending on the cobalt concentration and re-crystallization temperature. Tension tests were made in duplicate at various temperatures at a crosshead speed of 8.34 x 10"4 in. per sec with an Instron Universal Testing Machine. Specimens of 1-in. gage length with soldered ball ends were used at atmospheric and cryogenic temperatures. Pinch grips were used on specimens at elevated tem-

Jan 1, 1969

By F. B. Sherman, Keros Cartwright

Sanitary land filling has become one of the most widely used methods of disposing of solid refuse. A principal concern of regulatory agencies and the public itself is that landfill operations do not degrade the physical environment, including water resources, and the ground-water reservoir in particular. Knowledge of ground-water and engineering geology can guide landfill operations into suitable terranes or develop measures to compensate for natural limitations at a particular site. Experience and research in Illinois suggest four activities relating to landfill disposal that warrant attention by geologists and engineers: (1) regional delineation of favorable and unfavorable hydrogeologic conditions to facilitate planning and preliminary screening of potential landfill sites; (2) site evaluations, with considerations of geologic materials, topography, water levels, flow systems, and local occurrence and use of water resources; (3) research on aspects of the hydrogeologic environment that control effects of, or are modified by, landfills; and (4) formulation of practices in the siting, construction, and operation of landfills that prevent, mitigate, or isolate deleterious effects. The first two activities are basically in the domain of earth science, requiring the application of fundamental concepts of geology and hydrology and conventional site-exploration methods. The third activity, research, requires contributions from geology as well as other disciplines, including soil physics, sanitary engineering, and chemistry. The fourth calls for policy decisions by regulatory agencies and elected officials, using the contributions of scientists and engineers. Throughout history, man has disposed of unwanted materials by dumping. As urbanization has increased, haphazard dumping practices have given way to disposal under more controlled conditions because of increasing congestion of population and production of waste and greater concern for public health and environmental amenities. Many states and communities have already outlawed open dumping and open burning of refuse. The only practical methods of disposal of large volumes of refuse, therefore, are contained, high-temperature incineration, or burial in a sanitary landfill. In Illinois, regulation of solid waste disposal has been delegated to the Environmental Protection Agency. Each session of the legislature since 1965 has passed increasingly strict laws regulating waste diposal. As a result, the work of evaluating sanitary landfill sites has increased significantly for both the Department of Public Health, now the Environmental Protection Agency, and the Illinois State Geological Survey, which advises the Agency on matters of ground-water geology and pollution. In fact, our ground-water staff spends as much time on studies relating to waste disposal, primarily sanitary landfills, as on ground-water resource studies. Many other geological agencies are experiencing similar demands for increased assistance in solving waste-disposal problems. This paper summarizes some of the salient features of the sanitary landfill concept, describes activities of the Illinois Geological Survey in ground-water and engineering geology relating to landfills, and suggests policies that need consideration. A sanitary landfill is located and operated in such a way that vermin and pests, nuisances, and degradation of air and water are kept at acceptable levels. Some of the physical requirements of a sanitary landfill are all-weather roads for year-round access, fences to retain blowing paper, a daily cover of at least six inches of suitable earth material, and a final cover of at least 2 ft of earth material. Dumping into or adjacent to standing water generally is not allowed. Two common operating techniques are used. In the first, trenches are dug, the refuse is placed in them, and the earth removed from the trenches is used to cover the waste. In the second method, area fill, refuse is placed in low ground and covered with earth from adjacent high areas. The hydrology of the site is a prime consideration in locating sanitary landfills. Putrescible refuse, if saturated above field capacity, produces a leachate that usually has a high concentration of dissolved solids.2 As the leachate also acts as an agent for transporting bacterial pollutants, it constitutes a potential pollution hazard. To reduce the production of leachates, the topography of the landfill area should be such that surface water will not flow into or through the fill. Operations that will result in refuse disposal below or near the highest known water-table elevation may be required to take corrective or preventive measures to protect the ground water. In practice, under humid conditions such as prevail in Illinois, locations where disposal can take place above the water table are relatively few because surficial materials are commonly fine-grained, which permits slow gravity drainage and results in high degrees of saturation (100% moisture content) near the surface. At some sites, although disposal has taken place above the water table, ground-water mounds have developed, resulting in permanent saturation of the refuse. Permeability barriers usually are required to protect the ground-water reservoir from degradation by leachates. The convention in Illinois is to have a minimum of

Jan 1, 1972

By G. Borelius

ABOUT the turn of the century, Gibbs' thermo-dynamic theory of heterogeneous equilibrium, on the one hand, and the experimental methods of thermal and microscopic analysis, on the other, gave to the physical metallurgist his first scientific tool, the equilibrium diagram. The classical equilibrium diagram of a binary alloy system shows the boundaries between ranges of homogeneous and heterogeneous equilibrium in their dependence of concentration and temperature. A homogeneous solid sohtion which on cooling passes such a boundary is assumed to precipitate, forming a mixture of two phases with different concentrations. The equilibriunl diagram and the equilibrium theory, however, give no information about the time scheme of the process or the intermediate states passed during precipitation. For this reason it satisfies neither the practical need of the metallurgist nor the curiosity of the physicist. As a matter of fact, in the heat treatment of alloys for technical use the objective very seldom is the equilibrium state. Thus good mechanical properties of construction material are connected, for the most part, with some intermediate state. As these intermediate states are thermodynamically unstable, there is, from a theoretical point of view, always to be expected a decay of the good properties with time; and it is a matter also of practical interest to know whether this natural life time of a material is of the order of, say, ten or thousands of years. Thus, for many reasons, there is a current demand to complete our knowledge of equilibrium through knowledge of the kinetics of the precipitation phenomena. From the point of view of the physicist, the most interesting question in this case is whether there are any general laws governing the kinetics. According to a generally accepted view, precipitation is ruled by two more or less independent phenomena, the formation of nuclei of a new phase and the growth of these nuclei. It is also commonly accepted that there is a tendency for the velocity of growth to increase with increasing temperature because of the increasing mobility of the atoms. There is also a tendency for the velocity of growth to decrease in the neighborhood of the two-phase boundaries. So far, however, very little is known quantitatively about this fundamental phenomenon in the case of solid metallic systems. In our laboratory attention has been directed especially toward the nucleation phenomena, and a series of measurements have been carried out with the guidance of a work- ing hypothesis (based on experiences from previous work on order-disorder transformations in alloys) about the influence on the nucleation of thermo-dynamic potential barriers. However, before discussing the experiments, the theoretical ideas will be considered. In a binary solid solution the arrangement of atoms on the lattice points approaches with increasing temperature a state of full randomness, as illustrated by the ball model of Fig. 1, that might represent a [111] plane of a face-centered alloy with 30 pct "black" and 70 pct "white" atoms. In reality the atoms are changing places continually with their neighbors so that the picture should rightly have been a moving one. On account of this thermal motion the concentration of black atoms within a certain group of, say, a hundred or a thousand lattice points fluctuates with time around the bulk concentration of 30 pct in a manner governed by statistical laws. With decreasing temperature two independent changes in this state grow more and more important. First, the mobility of the atoms decreases, and second, the forces between the atoms will have an increased influence on the fluctuations. In alloys with a tendency for precipitation, which are the concern of this lecture, the distribution function of concentration fluctuations will broaden, so that the relative probability of great local variations from the bulk concentration increases. Fig. 2 gives an example of such a fluctuation. When the alloy is supercooled below the solubility limit into the range of two-phase equilibrium, the fluctuations will now and then at some point give rise to a state that resembles the equilibrium state and thus will form a stable nucleus that is capable of growing by diffusion processes. In discussions with colleagues and in the literature, I have often encountered the idea that three or four atoms of the dissolved metal could form a nucleus of the new phase. A look at the ball model might be enough to indicate that this cannot be true. If it were true, there should be nothing but nuclei, whereas we know from experiment that nucleation must be a rather rare occurrence. In fact we have, as will be mentioned later, certain reasons to believe that the nuclei are formed by fluctuations containing some hundreds of atoms, which should be the order of the number of black balls in the fluctuating group of the figure, if it were extended into three dimensions. As a working hypothesis we have assumed that the fluctuations producing nuclei, though large and rare, still are ruled by the distribution laws of fluctuations of the supercooled solid solution in its initial state. Thus the probability of nucleation will be connected to the thermodynamic properties of the solid

Jan 1, 1952

By S. E. Szasz, E. J. Moore, B. F. Whitney

An accurate value of formation water resistivity R, is essential in calculating formation porosity and fluid saturation from electrical well logs. In the cases where R, has not been measured directly, it must be obtained from other data, e.g., the SP curve. This paper deals with another approach: how to calculate R, from the chemical analysis of the formation water. INTRODUCTION It is known that the resistivity of aqueous solutions of pure salts depends on their concentration and on the temperature; the concentrations are given in MPL (mg of solute per liter of solution), or sometimes in ppm (mg of solute per kg of solution): MPL = ppm X specific gravity. Values for different pure salts are available in the literature, but not for solutions of mixtures which are of practical interest. The major component of the dissolved material in almost all formation waters being sodium chloride, it is customary to express the resistivity of formation waters in terms of equivalent sodium chloride concentration, i.e., the concentration of a solution of pure NaCl which has the same resistivity at a given temperature as that of the formation water under consideration. Thus, the problem of calculating R, from the chemical anaylsis can also be stated as how to convert the other constituents of the solute into equivalent NaCl concentration. Salts dissolved in water are at least partly dissociated into ions, and do not conserve their identity. If known amounts of several salts are dissolved in water, the solution does not necessarily contain the same salts in the original proportion, but perhaps some other combination of the ions, along with free ions in solution. This is why the chemical analysis of formation waters is often given in terms of ions, as if all dissolved salts were completely dissociated. Our problem then boils down to how to convert the concentrations of the various ions to equivalent concentrations of Na' and C1-. Dunlap and Hawthorne' have proposed to convert the concentration of all other ions to equivalent Na' and C1-concentrations by means of constant multipliers; e.g., 0.95 for Ca"; 2.0 for Mg"; 0.27 for HCO 3-; 0.5 for SO, -, etc. Their factors were based on measurements made at 68F on 26 formation water samples from the Texas Gulf Coast, ranging in concentration from 1,500 to 75,000 ppm. The Dunlap method is widely used in electric log interpretation, and is often extrapolated beyond its original concentration range. A comparison of R, values calculated by this method and values actually measured on formation water samples has shown large discrepancies, especially at higher concentrations. Therefore, two new methods were developed at Sinclair Oil Corp.'s Tulsa Research Center to calculate equivalent sodium chloride concentration from the chemical analysis of formation water samples. FUNDAMENTAL CONSIDERATIONS The resistivity of a solution, or its reciprocal the conductivity, at a given temperature is determined by the charge, concentration and mobility of the ions actually present. Monovalent ions such as Na' or C1- always carry the same charge. Compounds of polyvalent ions, however. may show incomplete dissociation, e.g., NaSO; + Na' instead of SO,-- + 2Na'. This happens especially in more concentrated solutions. Only very dilute solutions are completely dissociated, as assumed in the chemical analysis report. At higher concentration, the degree of dissociation depends not only on the nature and concentration of the particular salt under consideration but also on the nature and concentrations of the other solutes. Mobility of the ions depends on the viscosity of the solution. It also depends on the degree of hydration of the ions, which in turn is a function of the nature and the charge of the ions and also of the amount of free water available per ion, i.e., the total ionic concentration. The net effect is that the conductivity increases slower than proportional to the concentration, even if a solution contains only one salt such as NaC1, and is different for different salts (Fig. 1). Conductivity can even decline with a further increase in concentration, e.g., if additional salt is little dissociated but ties up some of the free water and/or causes an increase in viscosity. In solutions containing more than one salt, the contribution of one salt to the total conductivity depends not only on the fractional concentration of this same salt, but also on the concentration of all other solutes. A perfect method would give the conductivity or resistivity of a solution as a function of the concentrations of all solutes present. This is so complicated as to be impractical, and a simpler method must be found which is of acceptable accuracy. The Dunlap method, on the other hand. is too simple because it askmes that at any concentration the contrih-

Jan 1, 1967

By R. P. Abendroth

The hydrogen-water vapor ratio at which Fe-Cr alloy, chromium oxide, andiron chromite coexist in equilibrium was determined between 900" and 1200°C. A thermogravimetric method was used to determine equilibrium conditions. The results fit a straight-line relationship in the temperature region studied, and are given by Reduction experiments were also performed to confirm the results of the equilibrium investigation. ThE oxygen pressures at which Fe-Cr alloy, chromium oxide, and iron chromite coexist in equilibrium have been previously determined by Boericke and angert,' Morozov and Novokharski,' and Katsura and uan. Only one determination (at 1300°C) was made by Katsura and Muan, but it agrees with the results of orozov and Novokharski. The results of Boericke and Bangert, however, differ appreciably from the results of these investigators. Previous studies have assumed that the equilibrium metallic phase is pure iron, but Dahl and Van vlack have shown that the iron contains from about 1 wt pct Cr at 1000°C to over 2 wt pct above 1300°C. The chromium oxide also contains a small amount of iron in solid solution. In the present study, hydrogen-water vapor mixtures were equilibrated with the condensed phases, using a therrnogravimetric method to determine equilibrium conditions. The reaction can be written EXPERIMENTAL General Procedure. The starting material was a sintered pellet of Fe2O3-Cr2O3 solid solution with a hole in the center, and was placed on a fused silica hook. This assembly was raised into the preheated hot zone of the furnace in a helium atmosphere, hooked onto a fused silica hangdown suspended from one arm of an Ainsworth Model RV-AU-1 recording balance, and the starting weight determined. A flowing hydrogen-water vapor atmosphere was then exchanged for the helium by evacuation, and the sample reduced until the weight loss indicated the sample composition to be in the alloy-Cr2O3-chromite field. The tem- perature was adjusted incrementally until constant sample weight was achieved for several hours, to within 0.02 mg. A hydrogen-water vapor atmosphere of different composition was then admitted, and the same procedure carried out. At the end of a series of determinations, the sample was examined by X-ray diffraction to verify the presence of the desired phases. Microscopic examination of the silica hook showed no interaction with the sample, nor did it lose any weight. Several criteria were used to insure equilibrium besides constancy of weight. For a given hydrogen-water vapor composition, equilibrium was approached from both oxidizing and reducing sides by varying the furnace temperature slightly. The resulting slow weight loss or gain was observed for several hours. Constant weight could be re-established by returning to the original furnace temperature. The last criterion used was varying the relative amounts of the phases by further reduction or oxidation, and observing any changes in temperature required for constant weight for a given hydrogen-water vapor atmosphere. None were observed. This procedure was essentially the same as approaching the equilibrium from oxidizing and reducing sides, but larger weight excursions were carried out. Sample Preparation. Reagent-grade Fe2O3 and Cr83 powders were mixed in the desired proportions and heated in air at 1250°C for 2 hr. The mixture was re-ground and heated in air overnight at 1250°C. X-ray diffraction showed complete solid-solution formation as a result of this procedure. The solid solution was then pressed into l/2-in.-diam pellets using Carbowax 4000 as a binder. The hole was drilled in the center, and the pellets were sintered 24 hr at 1250°C in air on a bed of Fe2O3-Cr2O3 of the same composition, contained in an alundum boat. After cooling, the pellet surfaces were abraded with 310 paper to remove any surface compositional differences, such as loss of Cr2O3. Chemical analysis of the sintered pellets was 67.16 wt pct CrP3 and 33.02 wt pct Fe203. Atmosphere Generation and Control. The hydrogen-water vapor atmospheres were generated by passing Matheson ultrahigh-purity hydrogen, with no further purification, through two water bubblers contained in a constant-temperature water bath. Since the water-vapor dew points required in this study were below room temperature, the bath was insulated, and was cooled by thermoelectric-immersion devices. The bath temperature was controlled to 0.0l0C. Since rather high flow rates of about 900 ml per min were used through the furnace tube, an independent check of the dew point was made to insure saturation of the hydrogen by the water vapor. Although the dew point could only be determined to within 1/2"C, the determined dew points agreed with the water-bath temper-

Jan 1, 1967

By James C. M. Li

The Petch relation between the flow stress and the gain size is derived from a consideration of gain boundary sources of dislocations without the need of dislocation Pile-ups. Three mechanisms for inierpreting the yield stress: the gain boundary strength, the unpinning of Frank-Read source near a grain boundary, and the generation of dislocations from the grain boundary are compared and the condition of their equivalence is shown. The effect of the average angle of misfit of pain boundaries is found to be sma11 and so is that of the average angle of misfit of subboundaries having impurities. The effect of impurities on the ledge density in the grain boundary is treated thermodynamically and a relatwn is proposed for the variation of Petch slope with impurity activity. The effect of temperature on the Petch slope is interpreted as due to the change of ledge structure in the grain boundary. It is indicated that the effect of annealing temperature may be more important than that of the test temperature and therefore should be studied. The effect of plastic strain on the Petch analysis is deduced from a work-hardening equation in which the generation of dislocations has first-order kinetics and the annihilation of dislocations has second-order kinetics. It is concluded that the Petch slope will decrease with plustic strain if the rate of annihilation of dislocations is sufficiently large. Critical experiments which may shed light on the mechanism for the Petch relation are suggested. THE relation between the yield or flow stress, 0, and the grain size, l, was first proposed by all' and later studied more extensively by Petch and co-workers, who also proposed a similar relation for the fracture stress and deduced from these a grain-size effect of the ductile-brittle transition temperature. The microscopic mechanism used by all' and petch2 involves a pile-up of dislocations of like sign generated from a Frank-Read source. The yielding or flow takes place when the pile-up exerts sufficient stress at the grain boundary so that the plastic deformation can propagate from one grain to another. If the average strength of the grain boundary is ai and the average length of the pileup is lp, the Petch slope, k, is given by" where p is the shear modulus, b the Burgers vector, and v the Poisson ratio. This slope will be independent of the grain size if l/lp is a constant. This is possible, since, if the Frank-Reed source is situated near the grain boundary, lp = 1, and if it is situated in the middle of the grain, Ip = 1/2. cottrell,12 also using the pile-up mechanism, proposed that the stress concentration at the grain boundary will initiate Frank-Read sources near the grain boundary and in this manner a Lüders band can propagate from one grain to another. Assuming that the average distance between the Frank-Read sources and the grain boundary is 1, and the unpinning stress of the Frank-Read sources is op, Cottrell obtained the following Petch slope: This slope will be independent of the grain size if ls is independent of the same, which is not as obvious as the condition, Ip = I for Eq. [2]. In addition to this assumption, the direct relation between the Petch slope k and the unpinning stress, up, was recently questioned by Johnsonon grounds that it is inconsistent with the following observations: the independence of k with temperature and strain rate, and the small k in columbium, which, like iron, has a sharp yield point. As pointed out by ohnson," the most important objection both to the Hall-Petch mechanism, in which the strength of the grain boundary plays the role in yielding, and to the Cottrell mechanism, in which the unpinning of Frank-Read sources plays the role in yielding, is the lack of direct observation of the pile-ups. The dislocation structure in deformed iron has been examined recently in the electron microsope.'-' Dislocations appear to be generated from grain boundaries or other interfaces; they form clusters and tangles within the grain at very early stages of deformation, even in the Lüders band, if the deformation is slow or at normal and elevated temperatures. Although it is still too early to interpret bulk properties from thin-film observations, it does seem worthwhile to look for a mechanism for the Petch relation which does not require dislocation pileup. SUBBOUNDARY SOURCES In order to show that a consideration of grain boundary sources can lead to the same Petch relation as does the consideration of the strength of the grain boundary, we shall first discuss the case of a simple tilt boundary whose elastic properties have been studied in detail.17 The strength of a partially

Jan 1, 1963

By C. F. Jenkins, G. V. Smith

Serrated plastic flow in stable austenitic alloys based on Fe/Ni has been shown to be related to the presence of carbon and/or chromium in the systems. Strength peaks and plateaus in the serrated-flow temperature region for a commercial alloy correlate with an increased dislocation content, arising, presumably, from enhanced multiplication as a result of a strong interaction between dislocations and solute atoms. The data generally support a mechanism controlled by migration of vacancies, with the energy for vacancy motion being modified by the presence of chromium. Chromium atom -dislocation interaction is responsible for effects above 500°C, whereas the defect interacting with dislocations between 200" and 500°C is suggested to be a carbon-vacancy Pair. ThE phenomenon of jerky flow, serrated flow, or the Portevin-le Chatelier (P-C) effect in austenitic stainless steels is usually attributed to substitutional at1,2 mospheres1,2 or to precipitates&apos;-4 which form at dislocations during plastic deformation. On the other hand, evidence exists which supports a direct inter-stitial-dislocation interaction mechanism for serrated flow in fcc Ni-C,5,6 Ni-H7-9 and in nickel-austenites containing carbon." The present work consists in a study of serrated plastic flow in stable austenitic al-loys. The effects of carbon and of chromium were investigated separately, and a commercial stainless steel with different levels of interstitial impurity concentration was studied in an attempt to delineate the combined effects of the alloying elements. EXPERIMENTAL TECHNIQUES a) Materials and Fabrication. A commercial AISI 330 stainless steel and several specially prepared aus-tenitic alloys have been studied. The experimental alloys were prepared by arc melting the constituents under purified argon. Analyses of the materials are given in Table I. The commercial alloy was obtained as 5/8 in. bar stock and rolled to 0.092 in. sq, with several intermediate anneals. At this stage some of the material was annealed in Pd-purified hydrogen at 1100°C to establish different levels of interstitial content. All other heat treatments were in vacuum (10-5 torr). The "pure" alloy ingots were swaged to 0.120-in. rod and annealed in Pd-purified hydrogen at 1100°C. The analyses for these conditions are also contained in Table I. Following the above treatment, the final wire sizes Table I. Chemical Analyses of Test Materials Hrin Hydrogen at Cr, Ni, Alloy 1lOO°C wt pct wt pct C, ppm* N, ppm* Type 330 As-received 14.78 33.25 430 300 Type 330 64 14.78 33.25 40 50 Type 330 200 14.78 33.25 27 21 Fe/35 Ni 72 - 35.10 <10 62 Fe/35 Ni 200 35.10 <I0 44 Fe/35 Nil15 Cr 72 14.95 34.94 <I0 61 Fe/35 Ni/15Cr 200 14.95 34.94 <10 45 Fe/35 Ni/C $ 35.OM 380 *Sensitivity: N t 5 ppm Ct10ppm. f Nominal Ni content. % A master NiC alloy was used in preparation of this material; courtesy of D.E. Sonon. were obtained by either swaging or cold drawing. The test results did not vary with these techniques. b) Specimen Preparation. Two sizes of specimen and two gripping systems were used. i) 0.070-in. wire with a chemically milled gage section: 0.75 in. long, 0.060 in. in diam. These were fastened into grips containing tapped grooves. ii) 0.050 in. wire, gage length 1.5 in. Ball bearings were welded to the ends of the wires and the gage length was taken to include all material between the welds. Socket-type grips were used with these specimens. With specimens of type ii), joining was performed in a specially constructed brass jig, under argon, and automatic timing was utilized in the procedure. No adverse effects of welding were noted. Specimens were encapsulated and solution treated for 1 hr at temperatures selected to produce the same average grain size, -50 µ. Annealing twin boundaries as well as normal crystal boundaries were counted. The temperatures used are listed in Table 11. Table 11. Specimen Size. Temperature of Heat Treatment and Resulting Grain Diameters for Test Materials Recrystallization Resulting Material Condition Temperature Grain Sue AISI 330 Not H purified 0.070 120O°C 45 to 55µ in, wire AlSl 330 H , pure, 0.070 in. 1150°C 45to55µ wire Fc/35Nil15Cr Pure, 0.070 in. wire 1000°C 45tossp Fe/Ni Pure. 0.070 in. wire 775°C 45 to 55µ Fe/Ni/C Pure, 0.050 in. wire 850°C 10 to 20p AlSl 330 Not purified, 0.050 1150CC 45to55p in. wire AlSl 330 ti, pure, 0.050 in. 1150°C 45to55p wire

Jan 1, 1970

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of&apos; nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150&apos; C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-&apos;&apos; of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami&apos;s slution&apos; and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, &apos;Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By R. H. Jamison

A relatively new haulage system is described. Employed by the Delmant Fuel Co.. the "Full Dimension" system provides an uninterrupted flow of coal from a loader or continuous miner at the face to the main line transportation system. This system is said to provide a higher percentage of recovery as well as additional safety and production. Delmont Fuel Co. is employing a comparatively new system of transportation known as a Full Dimension system. Cne of these systems has been in operation for a year at the company&apos;s 10-B Mine as a part of a conventional section. A second was installed at the No. 10 mine in late 1960 to handle the production of a Colmol in a pillar section. SYSTEM COMPONENTS A Full Dimension system is a haulage system that provides an uninterrupted flow of coal from a loader or continuous miner at the face to the main line transportation system. The equipment required for this system consists of a series of interconnected chain conveyors that are mobile and articulated. They will retract or extend a sufficient distance for the development of a five-entry system; or, in the Colmol pillar section, it provides reach of 210 ft in all directions from the section belt. The components of this system are: l)One 160-ft chain line placed in tandem with the belt conveyor. It has a self-propelled drive, is 20 in. wide and 9 in. deep. Moving this conveyor requires the assistance of a loading machine or cutting machine. 2) One 40-ft piggyback that discharges along the entire length of the 160 ft chain conveyor. 3) A mobile bridge carrier, which is a self-propelled conveyor with four wheel steer and four wheel drive, twenty-eight feet long, it delivers coal to the receiving end of the piggyback. Axles steer individually making possible almost lateral movement. 4) Another 40-ft piggyback, duplicate of item 2 that delivers coal along the entire length of item 3 (mobile bridge carrier). 5) A second mobile bridge carrier, similar to the first, which deliver coal to the piggyback (item 4). 6) A third 40-ft piggyback, duplicate of items 2 and 4. This pig is attached to the loading machine and delivers its coal along the length of the second mobile bridge conveyor. Since the original preparation of this paper, the Delmot Fuel Co. has been able to eliminate the 160-ft chain conveyor. This was accomplished by connecting the outby piggyback directly to a loading machine with an extended boom. The loading machine loads directly onto the belt. This change has resulted in a substantial reduction in moving time and greatly increased flexability. A single trailing cable powers the entire string of equipment. It is attached to the side of the equipment in such a way as to keep it off the ground and afford maximum protection. The tramming rate of this equipment is 90 fpm. The conveyor capacity in a conventional section at Delmont&apos;s mines is 7.5 tpm and in the Colmol section is 5.5 tpm. This regulation is a simple function of conveyor speed. To visualize operation of this equipment, it would be well for me to touch briefly on local conditions in the Upper Freeport seam in which we mine. (Also, see the photographs of some of the equipment in use.) DELMONT&apos;S TOPOGRAPHY The Delmont Fuel Co. operates two mines in this seam in Westmoreland County, Pa. The No. 10 mine, which was opened in about 1912, is now almost worked out. Depending on economics in the industry, it has a life of two to four years on a declining production basis. A year ago a new drift mine was opened which is called No. 10-B. It is about two miles from the cleaning plant and is connected thereto by an overland belt conveyor. The new mine is being developed at a rate calculated to take up the slack as the old mine plays out. The Upper Freeport seam averages 4.2 ft in thickness in the area of the Delmont mines. It carries 4 in. of boney coal at the top of the seam and a middle man of from 2 to 4 in. We mine just above a 1-in. slate parting which has 4 to 6 in. of highly laminated coal beneath it. This material normally makes a very firm bottom. The roof varies from dark shale to sand rock and 36-in. bolts are placed on 4-ft centers for roof support. All working places are driven 20 ft wide on development and 25 ft wide on retreat. Selection of mobile chain conveyor equipment when it became available, was a very natural move for Delmont Fuel to make, because chain conveyors and piggybacks had been in use at the company&apos;s mines for about 12 years. Grades in the new mine

Jan 1, 1961

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,&apos; metal purification,2&apos;3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10&apos;1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge&apos; or where melting is achieved, "dripping" from the charge is encountered.&apos;&apos; At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By H. A. Jr. Koch, C. A. Hutchinson

Miscible phase displacement of oil from reservoirs has been emphasized in the past few years. The reason for this emphasis lies in the high oil recovery attainable by this process. Removal of capillary effects in the reservoir leads to recoveries approaching 100 per cent in the area contacted by the miscible phase. The miscible slug process is one means of obtaining a miscible displacement. Here a band or slug of I,PG is injected into the reservoir prior to gas injection. The idea is to maintain the band of LPG "wedged" between the gas and oil phases and thus achieve a miscible phase displacement. A second method lor achieving miscibility is through the injection of a gas which is not miscible with the reservoir fluid but which develops a zone of miscibility in [he reservoir through mass trans-ier with the reservoir oil.&apos; This mass transfer results in either an enrichment of the lean injected gas by intermediates from the oil or an enrichment of the oil by intermediates from a rich injection gas or one that has been enriched on the surface by LPG addition. We are interested here in discussing the process in which miscibility is developed at the displacement front by the evaporation of interrnediatcs from the oil phase into the gas phase. This process "builds up" its own slug of miscible material at the displacement front and therefore does not require the injection of LPG to obtain miscibil-ily. Each process has its own area of applicability. Generally, the high pressure gas process is applicable only with reservoir fluids which con-!ain a high concentration of inter- mediates. If the high pressure gas process is technically feasible at pressures less than 4,500 psi, it is probably more desirable economically than the slug process. The slug process has broad applicability in the shallower reservoirs and with reservoir fluids which contain a relatively low concentration of LPG and natural gasoline constituents. This paper deals with some new concepts of the high pressure gas injection process where it is proposed that flue gas can be substituted for hydrocarbon gas without sacrificing our goal of miscibility. MECHANISM Introduction Considerable effort has been devoted to study of the mechanics ot the high pressure gas injection proc-one generalization result-ing from some of these studies was that the composition of the injected gas is relatively unimportant in establishing the miscibility pressure* for a given reservoir fluid. This generalization is correct for the composition range of gases typically encountered in the field. Two such gases are a gasoline plant tail gas containing 85 per cent methane and 15 per cent ethane, and a field separator gas containing 70 per cent methane and 30 per cent heavier components. The most important factor which sets the miscibility pressure in the operation is the reservoir fluid composition, particularly the concentration of LPG-natural gasoline constituents. The injected gas is the agent by which the LPG-natural gasoline constituents are concentrated at the displacing front to create a miscible displacement. Based on these results, it appeared feasible that some inexpensive gas, such as flue gas, might be substituted for hydrocarbon gas for use in the high pressure gas process. A re-examination of the phase relations of the high pressure gas injection process should clarify the principle behind using flue gas (essentially nitrogen) as an injection gas. Three Component Diagram The phase relations of the high pressure gas injection process have been illustrated by the use of the three component diagrams.&apos;," In Fig. 1 we have arbitrarily represented the multi-component reservoir system by three components; methane, ethane through hexane, and heptanes plus. The solid curve ABC is the phase boundary curve. It represents the locus of compositions which have fixed saturation pressure at a fixed temperature; the lower branch AB shows bubble point compositions, the upper branch BC, the dew point compositions. Point B is the coniposition of the critical mixture at this temperature and pressure. The dashed lines (tie lines) connect vapor and liquid compositions which are in equilibrium. Let us consider Reservoir Fluid D which we wish to displace in 21 miscible manner by gas injection. Let us further restrict the discussion to the case where miscibility between an injection gas and the reservoir fluid at the displacement front is developed by gas enrichment in the reservoir. For this case, any gas whose composition lies between Points C and E on the right side of the three component diagram can be used to give a miscible displacement of Reservoir Fluid D. This is true because the more mobile injected gas moves faster than the displaced oil and is in continuous contact with virgin oil at the displacement front. This leads to a continuing enrichment 01&apos; the gas at the displacement front by evaporation of the C, - C,

By M. J. Pool

The partial molar heats of solution in liquid tin of cadmium, silver, tellurium, and zinc have been measured at 655°. 700°, and 750°K by liquid-metal solution calorimetry. Silver, cadmium, and zinc are endothermic at these temperatures while tellurium is exothermic. Only the heat of solution of silver depends on composition while all four elements show a temperature-de pendent heat of solution. The heat of solution of tellurium is constant up to 0.6 g-at. pct, becomes increasingly more exothermic, and reaches a limiting value at 1 g-at. pct Te. The limiting value has been used to calculate the heat of formation of SnTe at 750°K. The heat effects associated with the dissolution of the compounds Ag2 Te, CdTe, and ZnTe in liquid tin were measured at 750°K. These values are cotnOined with the measured hat effects at 750°Kfor silver, cadmium, tellurium, and zinc to detertrline the heats of formation of the telluride compounds. Cadmium lelluride exhibits a heat of dissolution which has a compositional dependence. THERE is a considerable amount of interest in the compounds of tellurium because of their electronic properties. Both cadmium and zinc tellurides are thermoelectric materials and considerable work has been done on their electronic properties but a limited amount of data is available on their ther-modynamic properties. This work was undertaken to elucidate the heat of formation data on cadmium and zinc telluride. Since both cadmium and zinc are in Group II it seemed to be of interest to compare the values obtained for them with the heat of formation of a Group I telluride. Silver telluride was selected for this comparison. In the course of the work it was also possible to determine the heat of formation of tin telluride and therefore to make a comparison of some of the Group I, 11, and lV tellurides with the metallic elements silver, cadmium, and tin being in the same period. There is also a great deal of interest in the energetic changes which occur upon addition of solute elements to a common solvent. This investigation provided an opportunity to study the partial molar heats of solution of silver, cadmium, tellurium, and zinc in liquid tin. The partial molar heats of solution are of theoretical interest because solute-solute interactions are a minimum in dilute solutions and application of solution models is simpli- fied. In order to complete the analysis of solute-solute and solute-solvent interactions the temperature dependence of the partial molar heats of solution was also measured. MATERIALS AND EXPERIMENTAL PROCEDURE All materials were of the highest purity available. The silver, zinc, cadmium, and tellurium were obtained from American Smelting and Refining Co. and were reported to be 99.999 pct pure. The silver telluride, zinc telluride, and cadmium telluride were obtained from Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp., and were electronic-grade material of 99.999 pct purity. Tin used for the solvent bath and for calibration was obtained from the Vulcan Manufacturing Co. and was reported as being 99.99 pct pure. The liquid-tin solution calorimeter used in this work is similar in principle to the differential twin-type calorimeter described by K1eppa.l Two of three identical calorimeter wells are used together during any set of experiments, one well being active and the other being passive. The wells are positioned 120 deg apart in an aluminum calorimeter block. Each well contains a multijunction thermopile and a Pyrex test tube to hold the liquid metal bath. Forty-eight of the thermopile junctions are distributed over the surface of each calorimeter well adjacent to the test tube and serve to integrate the heat effects occurring. The other forty-eight are next to the aluminum calorimeter block. The thermopiles for the three wells are connected differentially so that any change in temperature at the outer junctions (which will be the same for both wells because of the high conductivity of the aluminum block) will oppose for the two wells and result in no shift of the zero. The electrical output represents the true temperature difference between the two reaction vessels. A reaction occurring in the active well gives a comparison with another body of very similar thermal properties. In this way, any spurious heat effects due to slight temperature drifts within the entire calorimeter block are eliminated. The output of the differential thermopile goes to a dc amplifier with multiple ranges of from * 10 pv to 1 30 mv. The output of the amplifier is then fed into a Leeds and Northrup strip-chart recorder. The adiabatic temperature change is then calculated using the technique of Howlett, Leach, Ticknor, and ever.&apos; The aluminum calorimeter block is contained in a cylindrical furnace with main and control heaters

Jan 1, 1965

By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of silver and copper in dilute Ag-Cu-Sn alloys at 720°K have been determined using a liquid metal-solution calorieter. Values of the se2f-interaction coefficient n AgAghave been calculated at constant copper concentrations and n Cu Cuhas been determined at constant silver contents. The reliability of the experimental data is shown by the very good agreement between nCujAg and ij &$; these interaction coefficients have experimental values of -9100 and - 9590 cal per g-atom, respectively. Certain solution models are shown to be inadequate for prediction of solute interaction coefficients in dilute Ag-Cu-Sn alloys. In a previous publication&apos; the results of a thermody-namic study of dilute Ag-Au-Sn alloys were presented. The present work represents the continuation of a program to investigate dilute alloys of the noble metals with tin and in particular is concerned with solute interactions in the Ag-Cu-Sn system. By determination of the magnitude and sign of the various interaction coefficients in dilute alloys it is possible to gain some understanding of the different types of solute-solute and so lute-solvent bonding changes that occur as the solute concentrations are varied. Hence systematic studies of alloys with similar physical characteristics as regards size, structure, electronegativity, and so forth, of their components can contribute a great deal to present theoretical knowledge of solutions. The recent definition of an enthalpy interaction coefficient, 11, by Lupis and Elliott2 is of particular value in calorimetric studies such as the present one: where j and i are solutes and s is the solvent; Si is the relative partial molar enthalpy of component i and x represents the mole fraction of solute or solvent. Values of ?Hi can be obtained directly by solution calorimetry and data for n are thus easily determined, often with a high degree of accuracy. ?Hi is related to the relative partial molar enthalpy at infinite dilution, ?Hi and to the enthalpy interaction coefficients by the expression: ?Hi?Hi + X;nz+ ... [2] The aim of the present work was to determine the self-interaction coefficients n AgAgand 178: in alloys of different compositions and also to establish values for n Agcg| and ncuAg. Since it is a thermodynamic requirement (resulting from the Maxwell-type relationships which can be applied to partial molar properties) that nAgcu and ncuAg should be equal, a further aim of this study was to demonstrate the agreement between experiment and theory. EXPERIMENTAL A description of the liquid metal-solution calorimeter used in this research has already been published,3 and no further details of its construction and operation will therefore be given here. Copper supplied by the American Smelting and Refining Co. was indicated by them as being 99.999 pct pure, and the silver obtained from A. D. Mackay, Inc., was also quoted as being 99.999 pct pure. A solvent bath consisting of between 70 and 80 g of 99.99 pct pure Sn was used for each series of experimental drops. Its weight was accurately determined and the appropriate amounts of copper or silver were added to give alloys of the desired composition. Approximately 0.00125 g-atom additions were used for determinations of the heat of solution of silver in the bath, while, for copper, specimens consisting of approximately 0.0015 g-atom were used. The heat capacity of the bath was determined at regular intervals during a series of drops using tin or tungsten calibration samples. The heats of solution of silver and copper in pure tin were first determined as a function of their concentration in order to establish the self-interaction coefficients 7AgAg and ncucu Alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of copper were then used to study 17:: in alloys of different copper content, while alloys of the same mole fractions of silver were used to determine equivalent data for 178: at constant silver concentrations. The composition of the bath was held at the desired copper or silver concentration by making calculated additions of the appropriate solute throughout the experiment. From the limiting values of ?HAg in the constant copper content alloys it was possible to study ?HAg as a function of xCu and hence to determine 42:. A similar analysis of the re, values permitted calculation of nAgcu. Heat content and heat capacity data from Hultgren et al* were used to calculate heat of solution values from the measured heat effects at the experimental temperature of 720°K. RESULTS AND DISCUSSION Determinations of ?HAg. A preliminary investigation of the heat of solution of silver in pure tin at 720°K was first made in order to establish the value of nAgAg before additions of copper were made and also to compare the value of ?HOAg(l) with that obtained in the previous study of Ag-Au-Sn alloys.&apos; Then the heat of solution of silver in Cu-Sn alloys was investigated as a func-

Jan 1, 1970

By D. Cox, M. J. Duggin, L. Zwell

The carbides of approximate composition and Mn have been studied using X-ray diffraction techniques. Those carbides of the type (Fe,Aln)zC ave isostructural with cementite. The cell pararmeters a and c have minimum values at approximately 10 at. pd substitution of manganese for iron; no satisfactory explanation has yet been found for this phenomenon. The carbide fFeMn4)C has a monoclinic unit cell whose dimensions are close to those of ,11,15Cz A neu-troip-dij~ractiot~ study of (F&apos;eAlrz4)C~ reveals that, like MnsCZ, it is isostructural with Pd5Bz. The iron and manganese atoms occupy the palladium atom sites, while the carbon atoms were found to have the same atomic coordinates as the hovon atoms. A neutrorr-diffraction study of indicates that the carbon-atom positions are very close to those occupied in (Fez.,ll/lr~,.3)C. In both carbides studied, tlre iron and manganese atomzs were found to be essentially randomly distributed, although, in the case of (Fe,.811fn1.2)C, it is possible that there may be a slight preference of manganese atoms for- the general (d) positions and a corresponding slight preference of iron atoms for the special (c) positions. It has been found that a complete range of solid solution exists between Fe3C and Mn3C at 1050°C,I although Mn3C becomes unstable when the temperature is reduced to 95O0C,&apos; and can only be retained by rapid quenching. It is also known that a complete range of solid solution exists from Fe5Cz to M~SC~,~ although the stability range of carbides of the type (Fe,Mn)sCz as a function of the relative proportions of iron and manganese is not known. X-ray examinations of Oh-man&apos;s carbide3 and Spiegeleisenkristall,~ which have the approximate compositions (Fe3.67Mnl.33)C2 and (Fe3-,Mn,)C, where x lies between 0.4 and 1, respectively, have been made. The following carbides have also been studied: ] The lattice parameters determined during these investigations are listed in Table I. It is seen that carbides of the type (Fe,Mn)sCz have a monoclinic unit cell while carbides of the type (Fe,Mn)3C have an orthorhombic unit cell. It is evident that the variation of lattice parameters with manganese content is not linear for carbides of the type (Fe,Mn)3C. The coordinates of the atoms in (Fe2.7Mno.3)C have recently been determined by single-crystal analysis., The fractional atomic coordinates have been shown by Fasiska and jeffrey to be in good agreement withj those deduced from an earlier analysis of Fe3C by Lipson and etch.&apos; However, it was impossible to determine whether iron and manganese atoms occupied ordered positions because of the small difference between the atomic scattering factors of iron and manganese. The atomic positions in Mn5Cz (Refs. 8 and 9) and Fe5C2 (Refs. 7 and 8) have been obtained only by comparisons made with the isostructural compounds P~SB~.&apos; Since X-ray diffraction techniques were used in these investigations, accurate positioning of the carbon atoms, which have a low atomic scattering factor, was difficult. No attempt has been made to determine the atomic positions in the other carbides previously studied. It was felt that an investigation of the lattice parameters of a number of intermediate carbides of the types (Fe,Mn)sCZ and (Fe,Mn)& would be of interest. It seemed likely that a neutron-diffract ion study of such carbides would indicate whether ordering occurred between the iron and manganese atoms because of the large difference between the neutron-scattering cross sections of iron and manganese. It also seemed probable that such an investigation would provide a determination of the atomic coordinates of the carbon atoms. I) EXPERIMENTAL DETAILS Specimens, each weighing approximately 20 g, were carefully prepared according to the following proportions: The components were 500-mesh powders of 99.995 pct purity iron and spectroscopically pure carbon and a 200-mesh powder of 99.995 pct purity manganese. The component powders were intimately mixed by prolonged shaking, then each specimen was inserted into a spot-welded cylindrical container of tantalum foil, whose end was closed but not sealed. Each specimen in its envelope was then sintered at 1050° C for 24 hr in a thin-walled evacuated quartz capsule, such a time having been previously found sufficient for equilibrium to be attained.&apos; Each specimen was then quenched in order to attempt to retain the high-temperature phase, as the literature indicates that transformations may occur on cooling. Debye-Scherrer X-ray photographs were taken of each specimen using a 114.6-mm-diam camera, Fig. 1, patterns 2 to 6. The exposure time was 6 hr using filtered iron radiation at a tube voltage of 40 kv and a tube current of 12 ma.

Jan 1, 1967

By W. V. Green

Creep of tantalum was measured at temperatures from 0.6 to 0.89 of the absolute melting temperature. The creep curves include first, second, and third stages. Steady-state creep rate depends on the fourth power of stress. The activation energy for creep throughout this temperature range is approximately 114 kcal per mole, measured by the aT technique. Subgrain formation occurs as a result of creep strain, and pile-up dislocation arrays are observed in etch-pit patterns. BECAUSE of its high melting point-which is exceeded only by those of rhenium and tungsten—and its high room-temperature ductility compared to most of the other high-melting-point metals, tantalum will undoubtedly be utilized in an increasing number of high-temperature applications. Alloying studies directed toward increased high-temperature strength must use data on tantalum itself as a base line in order to evaluate the effectiveness of the alloying additions. However, to date, no systematic study of creep of tantalum at temperatures above one-half of its melting point has been reported in the literature. Conway, Salyards, McCullough, and Flagella1 have measured linear creep rate of tantalum sheet as a function of stress, but at only one temperature, 2600°C. This paper describes a relatively thorough study of the high-temperature creep of tantalum. METHOD Material Tested. The commercially supplied, l/2-innch-diameter tantalum rod used for this work was electron-beam-melted, cold-forged, rolled, swaged, cleaned chemically, and vacuum-annealed for 1 hr at 1000°C, all by its manufacturer. The vendor&apos;s analysis included 60 to 170 ppm C, 3.4 to 4.2 ppm H, 60 to 80 ppm 0, 15 ppm N, and a hardness ranging from 66 to 81 Bhn and averaging 76 Bhn. Creep eimens Used. Two creep-tested specimens are shown in Fig. 1. The 1/4 in.-diameter gage section was 3/4 to 1 in. long, and terminated either at shoulders 5 mils high or at 20-mil-diameter tantalum wires spot-welded to the circumference of the gage section. Both kinds of shoulders served equally well as fiducial marks for optical strain measurements. The spot welding did not alter the creep behavior in any detectable way; the 5-mil- high sharp shoulders did not result in any detectable localized effect on the strain. Before testing, each tensile bar was first mechanically polished -id then electrochemically polished according to the method referred to by Forgeng2 as the "Thompson Ramo Woolridge" method, which was suitable for tantalum after small adjustments of technique were made. Two tensile bars tested at low stresses had 1/8-in.-diameter gage sections and utilized only the weight of the bottom grip for the applied load. Although these diameters were smaller than were desired for other reasons, applied loads were known with high precision in the tests in which they were used. Testing Procedure. Two different constant-load creep-testing machines were employed, one of which has been described by Smith, Olson, and Brown.3 In both, the tensile bar is held vertically on the axis of a cylindrical tungsten tube or screen heater by threaded tungsten grips. The tensile bars and associated grips are heated by radiation from the incandescent heaters, which are heated by their own electrical resistance. Both testing machines use pins to hold the bottom grips in place. The load is applied to a tensile bar through hanging weights, a constant force-multiplication lever, a pull rod sealed to the chamber lid, and a top grip threaded to the pull rod at one end and to the tensile bar at the other. In one machine, the vacuum seal is a bellows with a low spring constant; in the other, the seal involves a rotating "0 ring". With the latter, rotation is converted to translation with a crank shaft, so that elongation of the tensile bar is accommodated with no change of tensile load. The incandescent tensile bar is viewed by an external optical system through slots in the radiation shields and heater, and an enlarged image is projected on a ground-glass screen. Gage-length measurements are made on this image with cathetometers on traveling microscopes. With regard to creep-test results, the two machines were identical. Thorium oxide coatings were applied to the threaded ends of the tensile bars, to prevent diffusion welding of the tensile bars to the grips during testing. Specimen temperatures were measured with an L. & N. optical pyrometer which had been calibrated against a standard carbon arc, and were corrected fir window absorption by calculation from the measured spectral transmittance of the quartz observation windows. Longitudinal temperature gradients in the tensile-bar gage length and temperature drifts during testing were detectable but small, and were estimated to be 10°C or less. Accuracy of temperature measurement was confirmed by comparing the temperature measured on the surface of a special

Jan 1, 1965

By M. E. Fine, A. A. Henderson

Investigation of the tensile properties of silver based aluminum alloy crystals was undertaken because it appeared attractive for studying strengthening effects due to Suzuki locking with minimum complication. Yield drops were observed in all alloy crystals (1, 2. 3. 4, and 6 at. pct Al) after strain aging at room temperature. No yield drops were found in similarly grown and tested silver crystals. The yield effects are attributed to Suzuki locking but the major portion of the solid solution strengthening to other mechanisms. INVESTIGATION of the tensile properties of single crystds of silver alloyed with aluminum was undertaken because it appeared to be a system in which segregation at stacking faults associated with partial dislocations1 would be the dominant factor in anchoring dislocations. First, silver and aluminum have closely similar atomic sizes and thus solute atom locking of a dislocation due to elastic interactions should be unimportant. Second, while both X-ray2 and thermodynamic3 investigations show short-range ordering in silver-based aluminum alloys, the degree of local order is quite small (X-ray measurements give v = EAB - 1/2(EAA + EBB) = - 0.025 ev and thermodynamic measurements give v r -0.007 ev) and should not be important in strengthening dilute alloys. Third, the stacking fault energy of silver is probably low (as indicated by the profusity of annealing twins) and is very likely diminished further and quite rapidly by aluminum additions since the A1-Ag phase diagram shows a stable hexagonal phase at only 25 at. pct Al. Also, a careful investigation in this laboratory4 has shown that the ratio of twin to normal grain boundaries in recrystallized alloys increases with aluminum content. Thus, with minimum complication from other factors, Ag-A1 alloys seem attractive for studying strengthening effects due to segregation at stacking faults of extended dislocations. EXPERIMENTAL METHOD Single crystals measuring 250 by 5 by 1.5 mm of pure Ag (99.99 pct) and Ag-A1 alloys (A1 of 99.999 pct purity) of nominal compositions* 1, 2, 3, 4, and 6 at. pct were grown in high-purity graphite molds from the melt under a dynamic vacuum (1 x l0-5 mm Hg). The technique consisted of moving a furnace having a hot zone (which melted about 0.5 cm of alloy) over a horizontal, evacuated quartz tube con- taining the mold and alloy at a rate of 3/8 in. per hr. Chemical analysis showed roughly the first inch of the crystal to be solute poor, the last inch solute rich; and the center section uniform in composition within the sensitivity of the analytical method (± 0.2 at. pct Al). The center section of the crystal was cut into five specimens. Gage lengths of reduced cross section, measuring from 1.5 to 2 cm in length, were mechanically introduced by means of jeweler&apos;s files and fine abrasive cloth with the crystal firmly held in polished steel guides. One-third of the cross section was then removed by etching and electro-polishing, the crystals were all subsequently annealed for several days at 850°C in a dynamic vacuum (<1 x 10-5 mm Hg) and furnace cooled to 200°C. The crystal orientations were determined using the usual back-reflection Laue technique. The Laue spots were sharp and of the same size as the incident beam. However, microscopic examination showed the crystals to contain substructures with subgrains of the order of a micron in diameter. The details of this substructure are presently under investigation. Tensile testing was done with a table model Instron using a cross-head speed of 0.002 in. per min. For testing at various temperatures the following media were used: 1) 415oK, hot ethylene glycol; 2) 296ºK, air, acetone, water; 3) 273ºK, ice water; 4) 258ºK, ethylene glycol "ice" in ethylene glycol; 5) 200°K, dry ice in acetone; 6) 77ºK, liquid nitrogen. EXPERIMENTAL RESULTS A) Yield Behavior—A portion of an interrupted stress-strain curve for a 6 at. pct A1 crystal of the indicated orientation tested at room temperature is shown in Fig. 1. Initially, at (a), there is a small, gradual yield drop of about 10 mg per sq mm2. However, on stopping the test, and aging for a few minutes at (b), a sharp yield drop is found. Aging for longer times at (c) and (dl results in larger yield drops (and larger AT&apos;S). At, defined in Fig. 1, is usually larger than the yield drop by about 20 pct; however, this increase in the lower yield is transient since extrapolations of the flow stress curves join as may be seen from Fig. 1. (Both Laue and low-angle scattering photographs revealed no evidence of precipitation in a strain-aged 6 at. pct A1 crystal.)

Jan 1, 1962

By Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968