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Contents A-Metal Mining B-Minerals Beneficiation F-Coal

Jan 11, 1951

By A. H. Jones

The Belmont mill at Tonopah, Nev., was designed and constructed by the Belmont staff. Ground was broken in August, 1911, and milling operation started July 25, 1912. The metallurgical flow sheet, and the machinery adapted 60 carrying out operations in accordance with this plan, were decided upon from experience gained in the treatment of Belmorlt mine ores at the old Belmont mill at Millers, Nev. The detail drawings were madc by the engineering staff of the Tonopah-Belmont Development Co., under the supervision of Otto Wartenweiler, who also had direct charge of the construction, consulting with the General Superintendent of the company, Frederick Bradshaw, and the writer.

Jan 1, 1916

Joseph E. Thropp, Jr., Indiana Harbor, Ind.:—To what do you attribute the fact that in some localities the by-product coke sells at a premium over the ordinary bee-hive coke for foundry use ? If the cell-structure is preferably soft and rather thick in coke for foundry use, as I understand it, do you mean that by-product coke has soft and thick cell-walls ? William H. Blauvelt, Syracuse, N. Y.:—As I say in one of the paragraphs of my paper, the tendency seems to be towards the manufacture of foundry- and furnace-coke under somewhat different conditions. The development of the best cell-structure in coke, of course, has not reached perfection, but we are making progress, and we are inclined to believe that under ordinary conditions the best furnace-coke, that is, coke with the hard cell-wall and the well-developed cell, is produced at fast coking-time and high heats, whereas the best foundry-coke seems to be produced at somewhat lower heats. In one of our plants we are making furnace-coke in 16-hr. coking-time, and foundry-coke in 20-hr. time. Foundry-men want the strong, tough coke. I think the furnace-men present will agree that the best furnace-practice requires a hard coke, with a well-developed cell-structure. Replying to the question as to the reason for higher prices being realized for by-product foundry-coke than for bee-hive coke, of course, the immediate reason is that it suits the foundry-men better. Perhaps one cause may be that we are able, by the selection of coals, which is not usually practicable at bee-hive plants, to get a quality and analysis best suited to foundry-work, with high carbon-content, and with cell-structure and physical strength especially suited to the foundry-men's ideas.

Jan 1, 1913

By G. H. F. Gardner

The velocity and attenuation of elastic waves in sandstones were measured as a function of both pressure and fluid saturation. A large change occurs in these quantities if water is added and the rock is not compressed, but the change is small if the rock is subjected to a large overburden pressure. Measurements were made by vibrating cylindrical samples in both the extensional and torsional modes at frequencies up to 30,000 cycles/sec. Formulas were derived which enable the attenuation of dilatational waves in dry rocks to be deduced from the data. Similar experimental methods were used to investigate the properties of unconsolidated sands. Velocities were found to vary with the 1/4 power of the overburden pressure and attenuations to decrease with the 1/6 power. The effects of grain size, amplitude and fluid saturation were studied. Formulas by which the effects produced by a jacket around the sample may be calculated were derived. The practical application of these results to formation valuation is discussed. INTRODUCTION The attenuation of elastic waves in the earth has been of interest to the seismologist and geophysicist for many years, but only recently to the petroleum engineer. Engineering interest has been brought about by the success of velocity logging devices, for it is possible by modification of these instruments to measure the attenuation of sound waves in addition to their velocity and, hence, deduce the mobility of formation fluids as well as the porosities of the rocks which contain them. The main problem is to decide whether field measurements can be made with sufficient accuracy to be of practical use. This problem can only be solved after we know the magnitude of the attenuations which are typical of the earth at various depths. The logarithmic decrement of a fluid-saturated rock is the sum of a "sloshing" decrement and a "jostling" decrement, the former caused by the mobility of the fluid contained within the rock and the latter by the granular framework of the rock. Sloshing decrements can be calculated' using Biot's theory, but the jostling losses are less well understood. The present paper reports an experimental investigation of jostling losses in consolidated and uncon- solidated sands, particularly with respect to the effect of overburden pressure and fluid saturation. Born' showed that the decrement of a sandstone may increase dramatically when only a few per cent by weight of distilled water is added, and that the additional loss is proportional to the frequency of vibration. His measurements were made with no compressive stress on the framework of the rock. M. Gondouin3 investigated similar phenomena for fluid-saturated plasters but also did not compress the samples. In the present paper it is shown that compression of the framework reduces this effect, so that at depth the jostling decrement of a sandstone may be expected to be almost independent of fluid saturation and frequency. Decrements for many sedimentary rocks have been given by Volarovich,4 but all for the state of zero overburden pressure. Anomalously low velocities have been logged in shallow unconsolidated gas sands. Results of the present investigation confirm that these velocities are not caused by correspondingly high attenuations, because the jostling decrement in a packing of sand grains is small and much less than in a consolidated sandstone at the same depth. Velocities in sands have been measured by Tsareva5 and by Hardin6 as a function of pressure, but the corresponding decrements do not appear to have been measured previously. The widely used "resonant bar method" of measuring velocities and decrements was employed. Comments on variations of this technique have recently been published by McSkimmin.7 The main novelty of the present technique was the application of pressure to the samples. It was found possible to do this by placing the apparatus inside a pressure vessel, provided the conditions leading to large additional losses were avoided. These conditions are discussed below. EXPERIMENTAL TECHNIQUE Cylindrical samples were caused to vibrate in both the extensional and torsional mode of vibration and the amplitude of vibration was measured as a function of frequency in the neighborhood of a resonant frequency. The resonant frequency, fr, is related to the corresponding elastic modulus by the formulas where E and N are Young's modulus and the modulus of rigidity, p is the density of the sample, and A the wavelength of the vibration.

Jan 1, 1965

By H. H. Kellogg

A model of the slag-fuming process for recovery of zinc oxide fume from lead blast furnace slags, adapted to solution by a digital computer, is presented. The model incorporates the variaticm with time of the following: the fuming of zinc and lead, the change in the ferrous-ferric ratio in the slag, the transfer of sulfur to and from the slag, the temperature of the liquid slag, the temperature of the gases and fume which exit to the flue, the heat losses to the water jackets, and the amount of frozen slag on the water jackets. The assumptions which underlie the model-some of which are but crude approximations—are discussed. Despite some obvious shortcomings, the model simulates faithfully many of the important features of practical slag-fuming operations. The behavior of the model is compared with the operation of the American Smelting and Refining Co. fumzace at El Paso, Tex. The model is used to predict the effects on performance of changes in the coal rate, the temperature of the secondary air, and the composition of the coal. THE fuming of lead blast furnace slag for recovery of zinc oxide is standard practice today, and it has been the subject of several previous attempts at mathematical process analysis.'-' The mathematical process model described in this paper incorporates many of the features from the earlier studies, but it is a far more complete and realistic representation of the commercial process in that the following additional features have been included: the fuming of lead as well as zinc; the transfer of sulfur between slag and gas; the addition of slag feed in batches, over a period of time; tapping of the final slag over a period of time; the change of slag temperature with time. The additional features of the present model add greatly to the mathematical complexity, but this difficulty has been obviated by programming the model for solution by a digital computer. The IBM 7094 computer solves the model for one operating cycle of the fuming furnace in less than 1 min. It is doubtful if the same calculations could be completed with the aid of a desk calculator in less than a month. The computer program, written in the Fortran IV language, is too lengthy for presentation here.* Instead, this paper As shown in the sections which follow, it does simulate with remarkable faithfulness most of the known behavior of the industrial process. On the other hand, the model contains several gross simplifications of both the chemistry and heat balance, necessitated by the lack of more exact knowledge. In addition to these known weaknesses, it is not unlikely that those more intimately acquainted with industrial practice than the author will find other additions to or modifications of the model which will improve its utility and reliability. CHEMISTRY In brief outline, the present model treats the fuming furnace as two units, A and B, in series. In A the batch of slag reacts with the continuous stream of air (primary and secondary) and fuel injected at the tuyeres, to produce a stream of hot, reduced gases containing zinc vapor. The zinc content of both the slag and the product gas changes with time because of the batch nature of the process. Unit A is called the "lower furnace" in this paper; physically, it is considered to be that part of the fuming furnace which lies below the charge port. In B, the "upper furnace", the product gas from A is burned with the stream of "tertiary" air, to produce zinc oxide fume. The performance of B also depends on time because of the time dependence inherited from the product gas of A. The rate behavior in the lower furnace determines the important features of the process—the rate of elimination of zinc and lead from the slag, and the amount of fuel required for this purpose. Bell, Turner, and peters' published the first useful model of the lower furnace. They employed the assumption that, at any instant of time, the slag and reduced gas reach a state of equilibrium, according to the reactions: They cited only indirect evidence in support of their assumption of slag-gas equilibrium, yet several more recent laboratory studies of the activity of zinc oxide in slags4-8 have produced evidence which supports their view. On first acquaintance it seems unlikely that a high-output "rate" process like slag fuming would even approach an equilibrium state. The author, in an earlier study,' established, however, that the gas-slag interface in a fuming furnace was capable of such high mass-transfer rates that a close approach to equilibrium between gas and slag was quite probable. In devising the present model it was decided to assume a state of equilibrium between slag and gas at the outset, and then to modify this assumption as necessary in order to make the model agree with the be -havior of the actual process. Up to this time the assumption remains a part of the model, since no behavior

Jan 1, 1968

By E. J. Roberts

The theory is developed that the tons ground through a given mesh per day in a wet ball mill is proportional to the percent plus that mesh in contact with the balls and the net power applied to the balls at this point. A grindability test is described. DURING the course of a study of the fundamentals of classification in 1937, the need for a more basic understanding of the action of a ball mill became acute. Unless one knows how classification affects grinding, one cannot hope to effectively improve on classification. The methods of evaluating grinding efficiency that depend on surface developed were studied but soon discarded for two reasons: 1. There was no apparent method which could be generally used to give a reliable figure for the actual new surface developed as a result of grinding. Subsequent papers have not changed this conclusion. 2. The practical evaluation of grinding in the main ore dressing applications was in terms of the percentage retained on a screen which passes 90 to 99 pct of the material and not in terms of surface area. The Probability Theory With the background of our experience in the field of closed-circuit grinding, together with the papers of Lennox,1 Gow,2 Gaudin,8 Fahrenwald,4 Coghill, and others, the approach of the theoretical physicist was then tried. The thought was somewhat as follows: When one grinds in a ball mill, a given expenditure of power leads either to a certain number of point to point blows per hp-hr or to a certain distance of line contact per hp-hr, depending on whether the action of the balls is considered to be cascading or rolling. It is also assumed that the balls actually come together on each blow or during the roll. Then a volume of slurry will be covered per minute which is some function of the size of the particle being considered (see fig. 1). All particles coarser than this size will be reduced through this size. This volume of slurry contains a certain weight of ore, depending on the percent solids and the density of the solids. If we fix the percent solids and the density of the solids and let w be this certain weight of ore in the volume covered, then, in mathematical terms, what we have just postulated is, w —— 8 hp (a) dt If W is the total weight of ore present in the mill, then we can write. W w/8 hp (b) W dt and if C is the cumulative percent plus the size chosen at the start of the time interval dt, w w c/dt W 8 hp x c (c) wc But wc/100 is the weight plus the size chosen which at 100 wc the close of time dt is finer than that size, and W is the decrease in the percent plus of the whole mass of ore or —dC. Then, —W dC/dt 8 hp x C. (d) In other words, the mesh tons ground through a given size per unit of time is proportional to the hp and the percent plus the mesh. A crude analogy would be to picture a 1-ft-wide steam roller going down the road at 1 ft per sec. If we place one egg on the road per square foot, one egg will be smashed per second. If we place a dozen eggs per square foot, a dozen eggs will be crushed per second. Similarly, if all the particles in w are plus the mesh, i.e., C=100, we should have a maximum rate of reduction. If only 10 pct of them are plus the mesh (C=10), we would have only one tenth the maximum rate; if only 1 pct are plus the mesh, the balls have a hard time finding anything to work on. This is where the term "probability theory" comes from. The chances of the balls crushing a particle through a given mesh depends directly on the concentration of particles coarser than this mesh in the general pulp in the mill. Giving W the units of tons and dividing equation (d) through by W, we obtain -dC hp ----- = k---— C [1] dt ton where k is a constant for any one size of particle, density of solid and moisture content of pulp. Eq 1 is the rate equation for a first order reaction and says that the rate of decrease of the percent plus a given mesh with time is directly proportional to the hp per ton applied to the body of ore and to the percent plus the mesh in the ore mass as a whole. Since it is a differential equation, it only

Jan 1, 1951

By E. J. Roberts

The theory is developed that the tons ground through a given mesh per day in a wet ball mill is proportional to the percent plus that mesh in contact with the balls and the net power applied to the balls at this point. A grindability test is described. DURING the course of a study of the fundamentals of classification in 1937, the need for a more basic understanding of the action of a ball mill became acute. Unless one knows how classification affects grinding, one cannot hope to effectively improve on classification. The methods of evaluating grinding efficiency that depend on surface developed were studied but soon discarded for two reasons: 1. There was no apparent method which could be generally used to give a reliable figure for the actual new surface developed as a result of grinding. Subsequent papers have not changed this conclusion. 2. The practical evaluation of grinding in the main ore dressing applications was in terms of the percentage retained on a screen which passes 90 to 99 pct of the material and not in terms of surface area. The Probability Theory With the background of our experience in the field of closed-circuit grinding, together with the papers of Lennox,1 Gow,2 Gaudin,8 Fahrenwald,4 Coghill, and others, the approach of the theoretical physicist was then tried. The thought was somewhat as follows: When one grinds in a ball mill, a given expenditure of power leads either to a certain number of point to point blows per hp-hr or to a certain distance of line contact per hp-hr, depending on whether the action of the balls is considered to be cascading or rolling. It is also assumed that the balls actually come together on each blow or during the roll. Then a volume of slurry will be covered per minute which is some function of the size of the particle being considered (see fig. 1). All particles coarser than this size will be reduced through this size. This volume of slurry contains a certain weight of ore, depending on the percent solids and the density of the solids. If we fix the percent solids and the density of the solids and let w be this certain weight of ore in the volume covered, then, in mathematical terms, what we have just postulated is, w —— 8 hp (a) dt If W is the total weight of ore present in the mill, then we can write. W w/8 hp (b) W dt and if C is the cumulative percent plus the size chosen at the start of the time interval dt, w w c/dt W 8 hp x c (c) wc But wc/100 is the weight plus the size chosen which at 100 wc the close of time dt is finer than that size, and W is the decrease in the percent plus of the whole mass of ore or —dC. Then, —W dC/dt 8 hp x C. (d) In other words, the mesh tons ground through a given size per unit of time is proportional to the hp and the percent plus the mesh. A crude analogy would be to picture a 1-ft-wide steam roller going down the road at 1 ft per sec. If we place one egg on the road per square foot, one egg will be smashed per second. If we place a dozen eggs per square foot, a dozen eggs will be crushed per second. Similarly, if all the particles in w are plus the mesh, i.e., C=100, we should have a maximum rate of reduction. If only 10 pct of them are plus the mesh (C=10), we would have only one tenth the maximum rate; if only 1 pct are plus the mesh, the balls have a hard time finding anything to work on. This is where the term "probability theory" comes from. The chances of the balls crushing a particle through a given mesh depends directly on the concentration of particles coarser than this mesh in the general pulp in the mill. Giving W the units of tons and dividing equation (d) through by W, we obtain -dC hp ----- = k---— C [1] dt ton where k is a constant for any one size of particle, density of solid and moisture content of pulp. Eq 1 is the rate equation for a first order reaction and says that the rate of decrease of the percent plus a given mesh with time is directly proportional to the hp per ton applied to the body of ore and to the percent plus the mesh in the ore mass as a whole. Since it is a differential equation, it only

Jan 1, 1951

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By Ralph L. Erickson

The discovery of a Carlin-type gold deposit at Cortez, Nevada, in 1966 can be attributed directly to the use of geochemical exploration techniques. Most mineral deposits owe their discovery to geologic concepts, geologic analysis, and luck, but at Cortez, geochemistry as an exploration tool played the clearly dominant role in discovery. Of course, the economic significance of the discovery had to be determined by exploration and development drilling. The story of the discovery began in 1959 when field work was initiated on a new project, "Geochemical Halos Utah and Nevada," by R.L. Erickson and A. P. Marranzino for the US Geological Survey. The Cortez district was selected for geochemical work because it was an area with good geologic control where we could address the problem of how to prospect in barren outcrops for concealed ore deposits in potentially favorable structures (buried thrust zones) or favorable host rocks in the subsurface. Geologic mapping of the Cortez 15-min quadrangle, just being completed by Gilluly and Masursky (1965), showed that the quadrangle contained excellent exposures of both the upper and lower plates of the Roberts Mountains thrust fault, a major structural feature of north-central Nevada. Roberts (1960) had noted that a number of mining districts were associated with windows in the thrust. In 1959, Erickson and Marranzino did some reconnaissance rock sampling and spring-water sampling in the siliceous clastic rocks of the upper plate of the thrust. Results of this reconnaissance prompted a full-scale sampling program in 1960 in the upper plate rocks on the west flank of the Cortez window. Results of the investigation showed that anomalously high concentrations of metals occur in the upper plate rocks, and further, that the distribution of metals is fault controlled and shows a pronounced zoning pattern (central copper zone; intermediate zinc, copper, and lead zone; and outer arsenic zone). The anomalies were interpreted as primary leakage halos that originated from metal occurrences in the thrust zone or in carbonate rocks below the thrust and moved upward along normal faults that cut both upper and lower plate rocks. Erickson gave a talk about these anomalies in the summer of 1961 to the local AIME Section in Reno, Nevada; two short reports were published that year-" Geochemical Anomalies in the Upper Plate of the Roberts Thrust Near Cortez, Nevada" (Erickson et al., 1961) and "Hydrogeochemical Anomalies in Four Mile Canyon Near Cortez, Nevada" (Erickson and Marranzino, 1961). These releases prompted blanket staking in the area by several small companies. In 1963, geologic and geochemical mapping were started by the USGS in the lower plate carbonate rocks of the Cortez window west of the quartz monzonite stock at Mount Tenabo and north of the old townsite of Cortez. The results of the work showed anomalously high concentrations of arsenic, antimony, and tungsten in jasperoid, fracture filling, and shear zones in Silurian and Devonian carbonate rocks. The anomalous area was about 1.6 km (I mile) long and 300 m (1000 ft) wide. A brief report, "Geochemical Anomalies in the Lower Plate of the Roberts Thrust Near Cortez, Nevada" (Erickson et al., 1964a), was published in 1964. During this same time period, 1959-1964, several exploration or mining companies were active in the general area (chiefly mapping geology and acquiring property). In 1964, American Exploration and Mining Company (Amex) concluded that the entire Cortez district was worthy of an extensive exploration effort involving drilling as well as geologic, geophysical, and geochemical studies. To carry out the program, Amex formed a joint venture group with the Bunker Hill Company, Vernon Taylor, Jr., and Webb Resources. Their early efforts were directed to the upper plate rocks and to the lower levels of the old Cortez silver mine. The group also drilled some shallow rotary assessment holes adjacent to the area of the arsenic, antimony, tungsten anomaly in lower plate carbonate rocks described in Erickson et al. (1964a). Assay results from these holes offered little or no encouragement to the joint venture group. Splits of these drill samples were made available to the USGS. In order to enhance any metal content present in these rocks and to determine the mineral residence of any metals detected, heavy-mineral concentrates of each 3-m (10-ft) sam-

Jan 1, 1985

By O. D. Gonzalez, H. A. Wriedt

Alloys ranging from pure iron to pure nickel were saturated with nitrogen gas at 918°, 999°, and 1217°C and analyzed. The solubility of nitrogen at 1-atm pressure was obtained as a function of nickel content for the whole range of iron-nickel alloys and the temperature dependence of solubility is shown for the experimental alloy compositions. The heat of solution and the entropy of solution of nitrogen in the alloys as func-tiom of composition up to 41 pct Ni are given. 1 HE acquisition of more exact thermodynamic information for systems composed of iron with various alloying elements continues to interest ferrous metallurgists. The interstitial alloying elements, especially carbon, hydrogen, and nitrogen, comprise a field of particularly intense study. A recent investigation of carbon solubility in Fe-Ni alloys held at 1000°C in gases of fixed carbon activity showed an unpredicted minimum in the solubility near 72 pct Ni.1 The present investigation was undertaken to see if a similar anomaly in solubility existed for nitrogen in Fe-Ni alloys. The solubility of nitrogen in ? iron at known nitrogen activities has been measured several times.&apos;-&apos; Corresponding information for the solubility of nitrogen in solid Ni and Fe-Ni alloys is not available. Juza and sachsze9 reported that metallic nickel dissolved 0.07 pct N in equilibrium with Ni3N at 445°C. This result was regarded as dubious by Turkdogan and Ignatowicz10 who found less than 0.0004 pct N in nickel specimens equilibrated at 600°C with ammonia-hydrogen mixtures having fugacities of N2 gas up to 35,000 atm. Such fragmentary reports indicate only that nitrogen gas has a very much lower solubility in nickel than in iron. MATERIALS A purified iron from Battelle Memorial Institute was used for solubility measurements. This grade contained more than 99.95 pct Fe, the highest content of any measured individual impurity being 50 ppm for each of As, C, Cu, and Pb. The nickel and iron-nickel alloys, supplied by the International Nickel Co., contained 0.02 to 0.04 pct C, 0.17 to 0.19 pct Mn, 0.04 to 0.08 pct Si, < 0.01 pct P, <0.03 pct S, and <0.20 pct Co as principal impurities. The Fe-0.59 pct Mn alloy was of zone-melted quality, the highest concentration of any individual impurity being 15 ppm Al. The "prepurified" grade of nitrogen gas from Matheson Co. had a nominal nitrogen content of 99.996 pct. An "electrolytic" grade of hydrogen gas from National Cylinder Gas. CO. in which the principal impurity is water vapor was admixed with the nitrogen to prevent oxidation of these specimens. This grade was preferred to a purer grade because the presence of some oxygen helps in suppressing contamination of the specimens, for instance, by silicon from the porcelain furnace tube. EXPERIMENTAL PROCEDURE The specimens were equilibrated in vertical tube furnaces through which a 99 pct N2-1 pct H2 gas was passed at ambient pressure. For the 915", 918", and 999°C runs, a wound-resistance furnace was used, and for the 1217°C runs, a furnace with a tubular silicon carbide element was used. The temperature control system on both furnaces was similar: a Weston "Celectray" controller with a modulator, responding to the electromotive force of a thermocouple with its hot junction in the furnace, switched the furnace current between high and low settings. The temperature distributions in the working zones of the furnaces were determined with calibrated Pt/Pt-10 pct Rh thermocouples. The overall uncertainty in temperature was estimated to be ±3° at 915° to 999°C and ±5° at 1217°C . Consideration of the small temperature coefficients of the equilibria studied, together with the error limits in the method of analyzing for nitrogen, showed that further refinement in temperature uniformity would give no improvement in resultant accuracy. The reactive gas was generated by mixing together "prepurified" nitrogen and "electrolytic" hydrogen directly from cylinders commercially supplied. The flow rates of nitrogen and of hydrogen were fixed by setting with bleeders the pressure drops across the individual calibrated flow meters of constant resistance. For any given alloy, the solubility of nitrogen at 1-atm pressure (% N) was obtained from the analyzed nitrogen content of equilibrated specimens (% Na)according to Sieverts&apos; law, thus

Jan 1, 1962

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,&apos; but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By Mark J. Klein

An internal-friction profile induced by nitrogen in Cr-35 at. pet Re was studied as a function of nitrogen concentration and heat treatment. From these studies, the solubility of nitrogen in this alloy was deduced. The equilibrium solubility of nitrogen in chromium does not appear to be substantially changed by the addition of 35 at. pet Re to chromium. However the precipitation kinetics of nitrogen from solution are significantly decreased. IT has been found that rhenium has a beneficial effect on the low-temperature ductility of Group VI-A metals. As part of a study to investigate the mechanism of this increased ductility, it was of interest to compare the concentration of interstitials retained in solution in one of these ductile bee alloys with the concentration retained in solution in its base metal. In this regard, a study of the solubility of nitrogen in ductile Cr-35 at. pet Re was selected for this phase of the investigation because the solubility of nitrogen in the base metal, chromium, has been determined over a fairly large temperature span.1-3 In addition, nitrogen is known to have an embrittling effect on chromium,4 but does not appear to have a comparable embrittling effect on Cr-35 at. pet Re.5 The experimental method selected for this study was the measurement of internal friction. This technique allows interstitial-concentration measurements to be made in bee metals that are sensitive to small changes in the concentration of a particular interstitial, even when other interstitials are present. When subjected to a cyclic stress, interstitial atoms in solid solution give rise to an internal-friction peak whose origin is the stress-induced ordering of interstitials into preferred lat- tice sites. These internal-friction peaks signify a dissipation of elastic energy which is greatest when the period of oscillation is comparable with the relaxation time for the attainment of an equilibrium interstitial distribution. For dilute interstitial binary alloys, the height of the internal-friction peak is proportional to the concentration of interstitial atoms in solid solutions. snoek8 has shown that the internal friction, Q-1, may be expressed by the equation where A is the relaxation strength, ? is the angular frequency, and 7 is the relaxation time. The relaxation strength, A, is proportional to the concentration of interstitials taking part in the relaxation if no interaction occurs between solute atoms. Thus values of peak height, which can be determined as a function of temperature, give a measure of the relative concentration of interstitial atoms in solution at various temperatures. If equilibrium has been attained, the peak heights will be proportional to the interstitial solubilities. The constant that relates A to the interstitial concentration can be determined experimentally from peak-height measurements as a function of concentration for specimens of constant crystallographic orientation. When this has been done, Q-1 measurements can be used to determine solubilities according to the equation C - KQ-1 where C is the soluble interstitial concentration and K is a constant that can be experimentally determined. It is possible, however, that lattice imperfections may bind interstitials to certain lattice sites. Internal friction does not measure these interstitial~, but does measure interstitials which are free to move in the normal lattice sites when subjected to an applied oscillating stress. On alloying the pure metal with a substitutional

Jan 1, 1965

By Clarence E. Jackson, George G. Luther

The ever increasing array of information concerning the measurement of the effect of the welding process on the properties of a steel is an indication of the tremendous effort that is being expended in this field. The methods that have been considered may be divided into two groups: first, those that measure directly the effect of welding on the ductility of a steel, and, second, those that observe the change in some property, such as the hardness of the heat-affected zone, and assume a direct correlation between this change and the resultant ductility. The nick-bend test is a direct method designed for studying the effect of welding on the ductility of a steel. The test specimen (Fig. I) consists of a bar cut from a plate with a bead weld on the surface. The specimen is prepaxed with a saw-notch placed so as to restrict deformation to the heat-affected zone under the bead weld when tested as a static bend. Failure is caused by rupture of the low-ductility metal in the heat-affected zone. The angle at maximum load is used as an index of the effect of the welding process on the material. In the development of the nick-bend test considerable scatter was noted in some of the results, although the agreement of duplicate specimens welded at the same time and tested consecutively was excellent. Upon further investigation it was found that the change in ductility was dependent upon the interval of time between the welding operation and the testing of the specimen. For the six steels of Fig. 2, the angle at maximum load in lour cases was doubled and in one case was tripled. All steels that have been studied show an improvement in the angle of bend for longer intervals between welding and testing. This same behavior has been found in weldability tests using the Navy T-bend

Jan 1, 1945

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky&apos;s approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky&apos;s approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963

By C. R. Ince

THE term "differential flotation" is used to denote a flotation operation in which separation is effected between two or more minerals of the same class; e. g., lead sulfide from zinc sulfide, pyrite from blende, chalcopyrite from pyrite, chalcopyrite from blende. At present, so far as published work shows, there seem to be two theories as to the mechanics of differential flotation. The earlier and more generally accepted theory is that the so-called depressing agents alter the surface of one or more of the sulfides in the ore, either by chemical action or adsorption, so that it is no longer amenable to flotation, but that these depressed sulfides can be revived, after the unaffected sulfide has been floated, by reagents which react chemically with the altered surface and make it amenable to flotation. More recently, Professor Taggart1 has advanced the theory that slime adsorption is an important factor in differential flotation. He believes that, with the proper use of a class of agents, which he calls .dispersion agents and which include practically all the depressing agents, one can cause the slime to adsorb differentially on sulfide surfaces. A gangue-slime coated sulfide surface will act as a gangue particle and will not float. If, subsequently, an agent that will remove the gangue-slime coating is added, the sulfide again assumes its original surface and can be floated as an ordinary sulfide. This-is the basis of the slime theory of differential flotation. Timber Butte mill at Butte, Mont., is a typical lead-zinc flotation concentrator. Neihart ore, chosen for investigation in this work, is one of the custom ores treated at that mill. Practice at Timber Butte mill in February, 1928, was as follows: A combined lead-zinc concentrate was first made using 0.2 lb. per ton on the ore of potassium xanthate and 0.03 lb. per ton of Cleveland Cliffs oil after 1.5 lb. per ton of lime and 1 lb. per ton of calcium chloride has been added just before the ball mill. The concentrate was then thickened to 70 per cent. solids. Potassium cyanide to the amount of 0.3 lb. per ton and zinc sulfate in the quantity of 0.5 lb. per ton were added to the thickened pulp and the whole

Jan 1, 1929

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days &apos;steel&apos; was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days &apos;steel&apos; was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By M. Baeyertr

Since 1915 many papers and books have covered industrial applications of X-rays from various angles. Two of the more recent are a paper by Fink and Archer, which describes in detail the technique of radiography, and a paper by Clark2, which embraces the whole field of X-ray metallogmphy. This paper, therefore, is confined to work of the X-ray Laboratory of the Western Electric Co., which naturally divides into two categories: radiography and diffraction patterns of various types. Radiography Radiography is the field in which the application of X-rays has had most general appeal among the industries which produce or use metals and alloys. Equipment permitting the examination of heavy sections of metals less permeable than aluminum or other light alloys requires apparatus capable of generating hard X-rays over a considerable period of time. The equipment used in the work presented in this paper is practically identical with that described by Fink and Archer in their paper on radiography in industry and is easily capable of penetrating 1/8 in. of lead. Radiography is used in two major groups of problems: (1) in the development of cquipment and tools and (2) in studies of materials. So far there has been no instance in which the use of radiography for routine inspection is justified. This is partly due to the fact that the manufacture of telephone apparatus involves the production of many identical parts by standardized procedures and equipment that has had development and trial before being put on a regular production basis. It is during this stage of development of equipment and tools that radiography has been used to particular advantage.

Jan 1, 1931

By A. K. Mukherjee, John E. Dorn

The effects of strain rate and temperature on the critical resolved shear stress for (321)[111] slip were determined for the silver-rich CsCl type of intermetallic compound AgMg. The flow stress increased only slightly as the test temperature was first decreased below room temperature; a rapid increase in the flow stress was obtained with yet further decrease in temperature from about 250&apos; to 4OK. The effect of both the temperature and strain rate on the flow stress over the low-temperature range could be rationalized satisfactorily in terms of the Peiwls mechanism when the deformation was controlled by rate of nucleation of pairs of kinks. IN spite of the well-documented interest of metallurgists and engineers concerning the mechanical behavior of intermediate phases and intermetallic compounds, very little definitive information is available on this important subject. As recently summarized by westbrook,1 only limited and modest progress has been made thus far in elucidating the details of the mechanism of plastic deformation for the intermetallic compounds; the available information largely concerns phenom-enological descriptions of empirical observations and experimental facts, principally with reference to poly crystalline aggregates. The present report on the elucidation of the rate-controlling mechanism for slip in the bcc structure of AgMg is part of the comprehensive program of a systematic investigation on the mechanical behavior of intermetallic compounds. The intermetallic compound AgMg has a CsCl type of lattice structureZ and is completely ordered up to its melting point of 820c3 This material was selected for our present investigation because of its simple crystal structure, moderate and congruent melting point, ordered structure persisting up to the melting point, and some solubilities of the constituent elements, which could be expected to help in the growing of single-crystal specimens. Whereas previous investigations on the properties of AgMg include hardness,*"6 slip systems,7 tensile flow stress of polycrystalline specimens,&apos; and electrical resistivity,4 the current investigation will be directed principally at elucidating the rate-controlling dislocation mechanism responsible for slip in single crystals at low temperatures. It will be shown that the strain rate is consistent with a model involving the rate of nucleation of pairs of kinks by the Peierls mechanism for plastic deformation. EXPERIMENTAL TECHNIQUES Single-crystal specimens of the AgMg intermetallic compound were prepared and tested as follows: 1) A master alloy ingot of AgMg was produced by melting and chill casting the high-purity silver (99.995 wt pct) and high-purity magnesium (99.997 wt pct) in an induction furnace under a helium atmosphere. 2) Sections of the above-mentioned ingot were placed in a graphite mold containing a spherical cavity in which a single-crystal sphere of 1 in. diam was grown under helium by the Bridgman technique. 3) The operative slip systems were investigated at room temperature on a singlecrystal of AgMg, from measurements of the angles made by the slip traces on the two surfaces of the specimen, which were at 90 deg to each other. The investigation confirmed that the AgMg compound undergoes slip primarily in the (321) plane and in the [Ill] direction, but a small amount of secondary slip was also noticed in the (112) (111) system. No slip was observed in the (110) planes. 4) The single-crystal sphere, mentioned earlier, was oriented in a graphite mold containing a cylindrical cavity of 3/8 in. diam above the spherical receptable to give the angle xo = 45 deg between the axis of the cylindrical bar and the normal to the slip plane (321), and the angle AO = 45 deg between the slip direction [Ill] and the axis of the bar. Oriented single-crystal bar seeds were produced by melting, under a helium atmosphere, a polycrystalline bar in the cylindrical cavity above the oriented spherical seed and by growing an oriented single-crystal bar from the seed. 5) Finally, oriented single-crystal specimens were grown from these cylindrical seeds. 6) The cylindrical specimens were machined in a High-Tension Spark Cutting unit to give a 2-in. gage length. The spark-machined gage section was elec-tropolished in a bath containing 200 ml of H3PO4,

Jan 1, 1964

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,&apos; in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts&apos; method and a quenching method. In the first method, the Sieverts&apos; technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts&apos; Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,&apos; to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts&apos; apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier&apos;s analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964