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By B. C. Raynes

IN the early part of 1952, under the auspices of the U. S. Atomic Energy Commission, Horizons Inc. undertook an investigation dealing with the preparation of high purity thorium metal in order to develop an economically competitive production process for this metal based on a recovery of the metal by a fused salt electrolysis, since a survey of the literature of thorium chemistry indicated that electrolytic methods had not received much attention, despite the consideration that electrochemical production methods often offer attractive commercial potentialities. Thorium metal has been prepared by methods which fall into four general categories: 1) reduction of halides or double halides; 2) reduction of the oxide; 3) thermal decomposition of halides; and 4) electrolytic methods. Some of the important results obtained by various investigators since about 1900 in recorded attempts to prepare pure thorium metal are summarized in Table I. A bibliography of pertinent literature is included in this paper. Thorium is strongly electropositive and possesses a great affinity for oxygen and nitrogen. As a result the prospects for the production of high purity thorium from aqueous media or oxygen bearing compounds are remote. The most promising and profitable area of investigation for production of thorium metal lies in fused salt electrolysis. Thorium has been produced previously by this technique from halide salts in fused alkali chloride eutectic mixtures. Until recently, however, the lack of known large uses for thorium has inhibited the investigation of these methods. The basic problem in an investigation into fused salt production methods for thorium is to develop a suitable fused salt system for the economic preparation of thorium. The first portion of the work in these laboratories was a small scale investigation of the electrolysis of potassium thorium fluoride, KThF5, under a variety of conditions. High purity thorium was prepared in this manner, but the process did not appear to offer the simplest and most attractive continuous commercial operation. The work reported here relates to an all-chloride system employing thorium chloride as the cell feed. ThCL4 was produced as an anhydrous material stabilized in molten sodium chloride. This product, further diluted in NaCl, was subjected to electrolysis. The electrolytic process has been studied in cells capable of holding up to 50 lb total salt charge. Ductile, pure thorium metal has been reproducibly obtained in this operation. Considerable experimentation was carried out in the preparation of ThCL as a cell feed free from moisture, oxides, and other impurities. Thorium was cathodically deposited as a coarsely crystalline powder interspersed with residual bath salts. Aqueous procedures for separating and recovering the metal were developed. The thorium metal powder obtained has been evaluated with respect to its hardness, chemical purity, and certain other physical properties. Preparation of ThC1,—Thorium chloride, and the chlorides of some other metals (aluminum, beryllium, tantalum, zirconium, etc.) cannot be obtained from aqueous solution by direct heating and evaporation. Evaporation and heating of a solution of thorium chloride yields a hydrated salt or partially hydrated salt, and finally Tho,. Anhydrous thorium chloride is obtained by forming a hydrated ammonium chloride complex salt in acidified water solution, dehydrating this compound, and finally decomposing the double salt and subliming the ammonium chloride component. Various methods for the preparation of anhydrous thorium chloride, in accordance with this concept, were investigated as indicated in Table I1 from hydrated thorium chloride (ThCl, . 3H2O), and from thorium oxycarbonate (ThOCO,). In the method found most satisfactory for this work, thorium oxycarbonate was dissolved in an excess of concentrated HC1 to give a clear yellow solution. At least 2 mol NH,Cl were added to the solution per mol of contained thorium. Ammonium thorium chloride hydrate was crystallized from solution by cooling and saturation with HC1. The resultant complex, (NH,Cl),ThCl;xH,O, was dehydrated by evaporation at 130° to 150°C and thoroughly dried at about 250°C. The dried ammanium thorium chloride was then mixed with sodium chloride in proportions to form NaThCL or to produce a ThCL4-NaCl mixture with a given thorium content. The ammonium chloride was sublimed off at temperatures above 500°C in an inert atmosphere furnace to give an anhydrous chloride source electrolyte, essentially free of Tho, and of NKC1.

Jan 1, 1958

By V. Balasubarmanian, Rajendra Kumar

ISOTHERMAL formation of martensite in a copper-aluminum-nickel alloy was previously reported by Hull and Garwood.' In the present work an attempt has been made to investigate some of the character- istics of the formation of isothermal martensite in binary copper-aluminum alloys containing 14.00 and 14.50 pct Al, respectively. Chill-cast alloys were prepared from OFHC copper and aluminum of greater than 99.5 pct purity. They were homogenized for 24 hr at 950° C. Polished samples were soaked at 1000°C and quenched in water to retain the p phase untransformed; martensite did not form during the quench. The surface was then repolished for isothermal microscopic studies at room temperature. The salient features of the martensitic transformation in copper-aluminum alloys observed in this investigation are: a) The transformation progresses (i) by nuclea-tion at new sites and (ii) by simultaneous slow isothermal growth of existing martensite plates. Slow isothermal growth of martensite has previously been observed by Holden2 in an uranium-chromium alloy and by Hull and Garwood in copper-aluminum-nickel alloy. b) Martensite plates nucleate preferentially at the pin holes formed during the casting of the specimen, Fig. 1. c) Some of the martensite plates pass right through other plates lying in their path, Fig. 1. d) Martensite plates cross grain boundaries without any change in the direction of growth. e) An irregular network of markings, Fig. 2, appears simultaneously with the formation of martensite. It was less prominent in the case of 14.5 pct alloy. The markings may arise due to spontaneous deformation under the lattice strains of the martensitic transformation. Crossing of martensite plates was first observed by Kulin and cohen3 when a high-nickel steel was cooled to 77°K. They suggested that the rapidly advancing plates atquire considerable kinetic energy and strike the obstructing plate with a momentum so as to nucleate the process on the other side of the plate. This, however, fails to explain the present observation where the slow isothermally growing martensite plates cross each other. Such plates would not possess large momentum to bodily displace the obstructing plate. Fig. 1 shows the martensite plates crossing each other without body displacements. This should be contrasted with Fig. 3 of Kulin and Cohen's paper where crossing of plates is accompanied by shearing or body displacements of the plates. The present observations can, how-

Jan 1, 1961

By V. G. Leak, R. A. Swalin

The dilhsion of silver and trace concentrations of tin in liquid silver has been rrzeasured in the temperature range from about 975° to 1350°C. The difBsion dala. fil lhe following equations: fov self-diffusion of silver The ratio of DSn to DAg is found to be about 1.34. The higher diffusivity of tin is interpreted in terms of the coullombic repulsion which results from the fact that tin dissolved in silver has a valence of +3 relative to silver. THE phenomenon of diffusion has been well-described theoretically for hard-sphere gases and solids and found to be in good agreement with experimental data for certain gases and solids. Liquid-diffusion phenomena have not been well described theoretically and there is generally a lack of good experimental data. In this investigation self-diffusion and solute diffusion in liquid silver were studied. Silver was chosen as a solvent for two main reasons. First, silver is a noble metal and the atoms are considered to have a spherically symmetric charge field; hence the liquid may be considered to be a random array of approximate hard spheres. Mercury, gallium, and other lower-melting metals were eliminated from consideration since it appears possible that in their liquid states there is some residual long-range order and directional bonding. Second, silver behaves as a monovalent solvent and, while cadmium, indium, tin, and antimony all have nearly the same atomic size, they have chemical valences relative to that of silver of +1, +2, + 3, and +4, respectively. Slifkin, Lazarus, and coworkers1-5 investigated the diffusion of these solutes in solid silver and found that their diffusion rates increased with an increase of the excess valence of the solute. In the solid state the diffusion-rate increase was calculated to be due to a change in local modulus of the solvent caused by the excess valence of the solute.1"3 For the present investigation it was planned to determine the effect of valence upon solute diffusion in liquid silver. It was deduced that a coulombic repulsion between solute and solvent might be responsible for larger volume fluctuations in the vicinity of the solute thereby enhancing the diffusion of the solute atoms. Tin was the first solute investigated and was chosen for experimental convenience. If an excess-valence diffusion effect exists in the liquid state, the solute tin with its excess valence of + 3 might show a large enough effect to distinguish it from the self-diffusion of silver in silver. The silver self-diffusion data were obviously required as a base line for comparison. In addition silver self-diffusion was investigated with a view toward examining the data in connection with the Sutherland- Einstein: Coheen-Turnbull,7 and swalin8 theories of diffusion in liquids. I) EXPERIMENTAL TECHNIQUES The diffusion coefficients for tin and silver in liquid silver were determined in separate experiments using the capillary-reservoir method of Anderson and saddingtono but following closely the experimental techniques outlined by Ma and Swa1in. The radioactive alloy bath was prepared by plating either tin-113 or silver-110 m isotope* onto 99.999 *Isotopes obtained from Oak Ridge National Laboratory. pct Ag rods.* The silver and isotope were melted *Silver obtained from Cominco Co. and mixed in a graphite crucible under a purified argon atmosphere, then outgassed for capillary filling. Some of the fused-silica capillaries were filled individually as reported by Ma and Swalin, but most were filled in a different manner. A long piece of capillary tubing was sealed off on one end and held in the system so that the open end was just above the surface of the molten alloy. The system was evacuated, the open end submerged into the alloy, and argon was admitted into the system up to atmospheric pressure. The molten alloy was forced up the capillary several inches where it solidified and was subsequently cut into segments of the proper length for diffusion annealing. The apparatus for diffusion annealing was the same as that used for capillary filling except that a Pt—Pt, 10 pct Rh therinocouple was placed in the solvent bath in order to accurately measure the temperature during the run. A diagram of the dif-

Jan 1, 1964

By L. E. Tanner

A study was made of the transformation kinetics of the commercial titanium-base alloys, Ti-2.5Al-16V and Ti-4A1-3Mo-1V, using two different heat treatment cycles: 1) step-quenching to aging temperatures from a ß solution anneal and 2) water-quenching from an a+ß solution anneal followed by reheating to aging temperatures. Metallographic examination and hardness testing provided the major portion of the data, while electrical resistivity, dynamic elastic modulus, and X-ray diffraction techniques were also used to obtain critical or confirnzatory data. TTT diagrams were constructed from these results. The sheet alloys, Ti-2.5Al-16V and Ti-4Al-3Mo-lV, are of current interest to the Department of Defense. As an aid to the planning of their respective heat treatments, a program was carried out to determine the transformation kinetics of these alloys using ß and a + ß reference states. This paper presents the TTT diagrams constructed from data obtained by metallographic examination and hardness testing, as well as by X-ray diffraction, electrical resistivity, and dynamic elastic modulus determinations. EXPERIMENTAL PROCEDURE Materials—Sheets of the alloys were obtained from the producers in the "mill anneal'' condition and were tested prior to shipment to assure their meeting mill specifications. Chemical analyses were also supplied and are presented in Table I. Heat Treatment—The majority of the data presented in this study were obtained from hardness testing and metallographic examination. Sample coupons were cut from the alloy sheets and heat treated on a mass scale. The annealing cycles were operated in the following manner: 1) The ß solution anneals were carried out in a horizontal tube furnace with the bare samples protected by a dynamic helium atmosphere. Following this treatment, the samples were quickly transferred to lead, solder, or oil-bath furnaces for aging. After prescribed times at the various reaction temperatures they were water-quenched. 2) The second cycle simulated commercial practice, which requires the alloys be quenched to room temperature following the a + ß sotution anneal. This anneal was carried out in a muffle furnace with a dynamic helium atmosphere. The specimens were then reheated from room temperature to the reaction temperatures in lead, solder, or oil-bath furnaces, followed by water-quenching after prescribed times at these temperatures. Information concerning the critical temperatures of the alloys was obtained from the literature and solution treatments were based on these values. A summary of the solution annealing treatments is found in Tables II and 111. The aging temperatures for the (a - ß alloys ranged in 50°C intervals from 200°C (392oF) to approximately 50°C below the ß/a + ß transus in the first cycle and approximately 50°C below the a + ß solution temperature in the second. The transformations in these alloys were known to be rather rapid, and thus aging times started at 0.5 min and went to a maximum of 7000 min. Hardness Testing and Metallographic Preparation— Heat-treated samples were sheared and mounted in Bakelite with their cut edges exposed. After a flat surface was ground, the hardness was determined in Vpn on an Armstrong-Vickers machine utilizing a 20-kg load. Three to four impressions were made on each specimen. After this procedure, the hardness impressions were removed and the edge surfaces of the specimens were prepared for metallographic examination in the usual manner. The etchant was 20 pct HF and 20 pct HNO3 in glycerine. Electrical Resistivity—It has been shown that the isothermal reactions in titanium-base alloys can be followed by measuring the changes in e1etrical resistivity attending these transformations. As mentioned earlier, the reaction kinetics of a-ß alloys are rather rapid; thus, it would be expected that resistivity data obtained from these alloys would be more significant if measurements were made continuously at the respective aging temperatures. To accomplish this end a special apparatus, based on the current-potential principle, was assembled. Its design was derived from earlier devices constructed by Colner and zmeska1 4 and Levinson.5 The set-up provided for the heat treatment zof machined specimens (approximately 2 x l0-4in. in cross section by 3 in. in length) and the determination of their relative

Jan 1, 1962

By K. G. Davis, P. Fryzuk

The diffusivity of silver in liquid tin has been determined, using the capillavy-reservoir technique, over the temperature range 250° to 500°C. The new value, D = 2.5 x 10'* exp(-2480/ RT) sq cm per sec, differs from that obtained by other workers in an earlier investigation. The analysis of data from the capillary-reservoir technique is discussed. In a recent investigation of the solidification of dilute alloys, values for the diffusion constant of silver in liquid tin were required in the analysis of the formation of impurity substructures. AS a result, measurements were made of the diffusion constants in the temperature range 250° to 500°C (melting point of tin 232°C), for the alloy concentrations used in the solidification experiments and at higher concentrations, to verify previous determinations.I)2 The capillary-reservoir method was adopted, using experimental procedures similar to those followed by Ma and Swalin,1 with the main exception that radioactive silver was used in the present investigation to facilitate solute-concentration measurements. EXPERIMENTAL PROCEDURE a) 100 ppm Samples. Glass capillary tubes of 2 mm inside diameter and approximately 5 cm- long were sealed at one end, evacuated, and filled with tin of 99.999 pct purity. The region of shrinkage near the mouth was cut off, and the tubes were then placed in a graphite holder and immersed, with the open end up, in an unstirred bath of alloy containing 100 ppm Ag 110, where they remained for periods of up to 30 hr. On removal from the bath they were cooled by an air blower. The bath was kept under a small positive pressure of argon, and the temperature controlled to within +1°C. A 10-hr diffusion period was used in the majority of the tests, scatter on runs of less than 5 hr being rather large. The procedure outlined above was chosen in preference to putting alloy in the capillary and pure tin in the bath, in order to avoid segregation when the tubes filled with alloy were first solidified. To minimize segregation when the diffusion period was complete and the capillaries again solidified, the earlier samples were held in thin-walled silica tubes which could be cooled very rapidly. Later tests were made in precision-bore Pyrex tubes, to eliminate effects caused by variations in the capillary diameter. No consistent differences in diffusivity as measured in the two types of tube were detected. After removal from the glass tubing, the samples were sectioned into 2.5 mm lengths and counted for y activity, using a scintillation counter with fixed geometry. Samples were also drawn directly from the bath and counted, so that values for C/C,, the ratio of the weight of Ag 110 in the sample to that in the bath, could be obtained. b) 5000 ppm Alloy. To check for possible effects of concentration, the silver content of the bath was increased to 5000 ppm. Complete mixing was found to have taken place in the capillary after a 10-hr period at 300°C. It appears that the greater density of the alloy was sufficient for buoyancy forces to cause instability in the alloy-tin interface, leading to rapid convective mixing. For the 5000 ppm alloy, therefore, the bath was of pure tin and the capillary tube was filled with alloy. With this arrangement, values of D consistent with those for the 100 ppm alloy were obtained, Fig. 1. CALCULATIONS OF DIFFUSIVITY The terminology used applies to a capillary of pure tin immersed in a bath of alloy. 1) Error-Function Method. under the present experimental conditions, the rod of liquid tin into which silver is penetrating may be considered semi-infinite. Assuming the concentration at the mouth of the tube to remain constant at Co, the concentration C at distance x from the mouth of the tube at time / is given by3 Plots of the inverse error function of (1 -C/Co) vs .v gave straight lines passing through the origin with slope 1/2-, x being corrected for shrinkage both on solidification and while cooling to the melting point (total correction about 6 pct at 500°C). Values for log D obtained in this manner are shown in Fig. 1. A least-squares fit to the relation D = Do exp(-Q/RT)

Jan 1, 1965

By Frank R. Van Horn

It is customary to ascribe two general modes of occurrence to natural gas, namely, shale gas which, as the name indicates, is found in shale, and reservoir gas, which occurs in sandstone, conglomerate and dolomitic limestone. Both of these types are found in the Cleveland district. The shale gas has been produced on a small scale for a long period of years, probably dating back as far as 1883. Shale gas is a low-pressure gas, small in volume with variable pressure, and is limited to no definite horizon. It is generally independent of oil, may last for a long time, and is not dependent to any great extent on the structure of the rocks. There are many such wells in the district which range from 400 to 1,840 ft. in depth, although most have been completed at about 800 ft. This indicates that the wells pass through the Cleveland and Chagrin shales into the Huron or Portage shale of the Upper Devonian. During the last 2 years great interest has developed in a deeper-seated reservoir gas. What is commonly called reservoir gas is generally a high-pressure gas occurring in large volume at a definite horizon. Oil may, or may not, be associated with the gas, and in most regions in which reservoir gas is found, the geological structure is of great importance. This type of gas occurs in all large fields such as those of West Virginia which have been supplying Cleveland until the recent discovery of local gas at great depths in commercial amounts. Historical Outline The oldest well producing reservoir gas in the district was drilled in 1886 in Newburg for what was then known as the Cleveland Rolling Mill Co. This well was 3,000 ft. deep, and was thought to have reached the "Clinton" formation. Two "sands" showing small amounts of oil were recorded in the Niagara limestone at depths of 2,658 and 2,686 ft. This is about the horizon of the so-called Newburg sand which has proved to be of some importance as a source of gas and oil by recent drilling operations. The rock pressure was reported to be 400 to 500 lb. per square inch, but since the volume was only 14,000 to 16,000 cu. ft. daily, the well was not only considered unsuccessful but was thought to prove the absence of high-pressure gas in commercial quantities in the Cleveland district.

Jan 1, 1917

By J. H. Henderson, L. A. Wilson, R. L. Gergins, R. J. Wygal, D. W. Reed

This paper presents a method of predicting the production history of an underground combustion recovery process. A rigorous solution of the thermodynamics and hydrodynamics involved is beyond the scope of this report. However, a practical scheme to appraise combustion recovery performance has been Worked out. By prudent assumptions, regarding the attainment of steady-state conditions, a trial-and-error solution, which satisfies both material balance and three-phase relative permeability requirements has been evolved and tested. As a combustion zone moves through a formation the interstitial water, the water of combustion and a portion of the oil wil1 be vaporized. These vapors will move downstream to a cooler region of the formation where they will condense. Part of the remaining oil will be displaced by the imposed gas drive and what remains behind will be consumed as fuel. The fluids will distribute themselves downstrean? in a manner which will satisfy the three-phase relative permeability characteristics of the formation. Three distinct zones will exist ahead of the combustion zone: (I) a zone termed a water bank which contains three mobile phases, oil, water and gas; (2) a region containing two mobile phases, oil and gas, called the oil bank; and (3) a zone having the fluid saturution distribution which existed prior to combustion. The mobile water will impose a water flood on the oil in the region containing three flowing phases. The process can be visualized as a simultaneous water .flood and combustion-supported gas drive. It is possible to estimate the saturation distributions in the water bank and oil bank as well as the production history for any combustion temperuture if the porosity, three-phase relative permeability characteristics, oil viscosity and initial saturations are known. This has been done for injection pressures ranging from I to 100 atm, oil viscosities of 10 to 1,000 cp and porosities from 20 to 40 per cent. Several of these calculations have been checked in the laboratory, with the result indicating rather good agreement between the predicted and observed production histories. The analytical and experimental techniques are described and the comparison of predicted and observed performance presented. INTRODUCTION Considerable research by the oil industry during the past 10 years has been directed toward the thermal recovery of crude oil. Of all schemes considered, the one receiving the most attention is in situ combustion. This is a process in which part of the oil is actually burned within the reservoir rock. The uniqueness of the process lies in its potential. Theoretically, this potential generates from the following: (1) it may open the door to vast reserves previously not economically producible, (2) it may induce increased production rates where low rates are now realized and (3) it may give high over-all recovery efficiency. The general idea of the process has received considerable attention in the literature '-' and the following brief description is intended for orientation only. In situ combustion can be visualized by considering a linear system, one end of which represents the injection well and the other the producing well. The formation at the inlet end is raised to ignition temperature by placing a gas or electric heater at the face of the formation or by the ignition of thermite, charcoal or similar material. While heating, the water and part of the oil in the heated region is vaporized and moved out into the reservoir by the injection of gas containing oxygen. In addition, part of the oil is displaced as liquid by the imposed gas drive. The oil not displaced is modified to an immobile, coke-like material (hereafter referred to as coke) by the high temperatures existing immediately ahead of the combustion zone. This coke is used as fuel, and the combustion front advances through the formation at a temperature which is probably in excess of 800°F. As the combustion front advancek it will drive ahead all interstitial oil not rendered immobile and all interstitial water plus the water formed by the combustion of hydrogen. As a result the sand behind the combustion zone is freed of all oil and water. Although the general description of the process has been outlined in the literature, there has been no consideration of the behavior of the fluids moving downstream from the combustion front. It is the purpose of this paper to present a technique

By C. A. Heiland

WITH seventeen papers submitted. and thirteen presented in three sessions, the geophysicists had a most successful meeting at New York in February. The first paper on Monday morning dealt with the location of a diabase dike near Chapel Hill, N. C., by magnetic and resistivity methods. The magnetic indications were pronounced directly over the dike. whereas the anomalies of apparent resistivity were less distinct and displaced away from the dike. In the second paper, Professor Keys reported on the results obtained with four different methods of depth calculation on known portions of the Falconbridge

Jan 1, 1937

The experience of the Committee in connection with securing papers for the Butte meeting in August has shown that authors should begin early on papers contemplated for the New York meeting next February. So many papers come in at the last moment that it becomes exceedingly difficult to have them all read, indorsed, and delivered to the printer in time. Authors should remember that those serving on this Committee are doing so without pecuniary compensation, and it is hardly fair to expect them to devote so much of their time at the last moment from their private affairs. So many papers have to be sent back for corrections of one kind or another, that it is desirable that they be sent to the Committee at least three months previous to the date of the meeting. The Committee desires to be kept informed of contemplated papers on metallurgical subjects particularly. It is hoped that the Institute Transactions can be made an up-to-date record of metallurgical advance of all kinds. For the present, at least, the activities of the Committee include the refining and preparation of the non-metallic products such as phosphate rock, precious stones, cement, lime, gypsum, building stones, etc. Papers covering any of these subjects are desired. General papers covering geological, mining and metallurgical phases of an ore deposit can be sent either to this Committee or to one of the other Committees on Mining Geology or Mining Methods. C. W. GOODALE,Chairman. DARSIE C. BARD, Secretary.

Jan 8, 1913

By Will Mitchell, T. G. Kirkland, C. L. Sollenberger

R. S. Handy (Santa Rosa, Calif.)—It would be interesting to learn the comparative results of treating the Korean scheelite ore described in this paper according to the following procedure: I—Follow the procedure described in the paper to the recovery of the sulphides by flotation. 2—Dilute the residue from the sulphide flotation strongly with water and disperse the contained colloids by adding a mixture of 75 pct sodium silicate and 25 pct quebracho to dispersion point. 3— Settle the dispersed pulp and decant the supernatant colloids. 4—-Dilute, settle, and decant the pulp until the settled residue is crystalline. Not over 10 pct of the tungsten minerals should follow the colloids. 5—Treat the settled residue by flotation, having established the proper pH. Oleic acid homogenized with cresylic acid or kerosene is more selective for scheelite than is oleic acid alone. (The recovery of the contained tungsten minerals should be practically complete in this operation.) 6—Deflocculate the tungsten concentrate from step 5 with the same dispersion agents as in step 2 and treat the deflocculated pulp by gravity. The minerals that tend to float with scheelite are generally of low specific gravity and the separation is efficient. The heavier contaminants, such as pyrrhotite and magnetite can be removed magnetically, leaving a practically pure scheelite. E. J. Pryor (Imperial College of Science and Technology, London)—It occurred to me that instead of using temperature as a differentiating control, more precision might be obtained with a reagent of a type we developed here for the flotation of high grade fluorspar in cold pulps. This reagent, which is manufactured on a modest scale in England, is based on oleic acid, which has been modified by our patented process to ensure complete stable dispersion at any desired concentration in water. It thus becomes possible to utilise unimolecular layers with good selectivity. In the fluorspar flotation for which we developed it, it is possible to hold a tight control on depressing quebracho for the calcite without substantial loss of flu-orite, and recovery exceeding 99 pct is not uncommon in the mill where it is in use, even under wintry conditions. No attempt has been made yet to extend the use of the reagent, as we have not completely overcome

Jan 1, 1952

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

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Jan 1, 1938

By Basil B. Zavoico

The developments in the Russian oil industry during 1935 marked a very definite turning point from the time when the industry was being educated to the modern methods of oil-field finding and development, refining, transportation and marketing, to the time when the industry has thoroughly assimilated the modern technique and is now firmly standing on its own feet, as is shown by the remarkable qualitative, if not quantitative, progress in 1935. The oil industry promises that 1936 will be a record year in every respect with both quantity and quality approaching the desired high levels and standards. More particularly the Soviet Government is beginning to be successful in the development of new fields and such new production in geographically strategical points of the country will be in the coming years a factor of great importance in the industrial life of the country. The most notable achievements of the last year have been: the very successful development of the Ishimbaevo oil field in the Lower Oural-Permian Basin; the discovery and development of several promising oil fields in the Puta district of Azerbaijan, while large flush production of Baku area was extended 50 miles due southwest into the Saliani-Aliat district, where a 3000-bbl. well was completed early in 1936 at Pirsagat. Also, an apparently important discovery was made at Zikh, on the Apsheron Peninsula proper. These discoveries, as well as several important strikes in the deeper producing sands in the older fields of the Apsheron Peninsula, have greatly augmented the proven reserves of Russia and made them available either at the points where transportation facilities were already present or at points not too far distant from major industrial centers of the country. Of course, not all objectives were achieved during the past year, and several major difficulties remain to be solved in the coming years, the more important of which are: (1) supply of equipment and of parts; (2) the unavailability of competent technical men in sufficient numbers, which more particularly affects the distant fields; and (3) the problem of distribution of oil products throughout the country, especially the question of handling the needs of small consuming areas, which, while individually unimportant, in the aggregate require huge distribution.

Jan 1, 1936

By Basil B. Zavoico

The developments in the Russian oil industry during 1935 marked a very definite turning point from the time when the industry was being educated to the modern methods of oil-field finding and development, refining, transportation and marketing, to the time when the industry has thoroughly assimilated the modern technique and is now firmly standing on its own feet, as is shown by the remarkable qualitative, if not quantitative, progress in 1935. The oil industry promises that 1936 will be a record year in every respect with both quantity and quality approaching the desired high levels and standards. More particularly the Soviet Government is beginning to be successful in the development of new fields and such new production in geographically strategical points of the country will be in the coming years a factor of great importance in the industrial life of the country. The most notable achievements of the last year have been: the very successful development of the Ishimbaevo oil field in the Lower Oural-Permian Basin; the discovery and development of several promising oil fields in the Puta district of Azerbaijan, while large flush production of Baku area was extended 50 miles due southwest into the Saliani-Aliat district, where a 3000-bbl. well was completed early in 1936 at Pirsagat. Also, an apparently important discovery was made at Zikh, on the Apsheron Peninsula proper. These discoveries, as well as several important strikes in the deeper producing sands in the older fields of the Apsheron Peninsula, have greatly augmented the proven reserves of Russia and made them available either at the points where transportation facilities were already present or at points not too far distant from major industrial centers of the country. Of course, not all objectives were achieved during the past year, and several major difficulties remain to be solved in the coming years, the more important of which are: (1) supply of equipment and of parts; (2) the unavailability of competent technical men in sufficient numbers, which more particularly affects the distant fields; and (3) the problem of distribution of oil products throughout the country, especially the question of handling the needs of small consuming areas, which, while individually unimportant, in the aggregate require huge distribution.

Jan 1, 1936

By Alan M. Bateman

POSSIBLE postwar trends of the more important world minerals will be determined in part by their present world position and by the acts and forces that have operated during the war period, so it is desirable first to review briefly what has been happening in the foreign field of metals and minerals. When we first entered this war we of the mineral profession were all acutely conscious of our lack of strategic minerals and other materials, which had to be imported in great quantities-minerals such as manganese, chrome, tin, mercury, nickel, and antimony. But we realized also that we had to acquire vast quantities of those minerals of which we had thought we were bountifully supplied. Our assumed domestic abundances turned out to be woefully deficient, and demands also arose for new minerals never before produced in large quantities. Some threescore minerals entered the strategic list of our imports. Ores from new sources had to be sought, developed, and transported. Tonnages in the millions of such bulk materials as zinc, lead, copper, chrome, and manganese flowed to feed our war efforts. Sparsely distributed minerals such as tin, mercury, antimony, tungsten, cobalt, mica, and corundum had to be lured from their rock lairs in greatly increased quantities to feed the hungry maw of war industry, and the rare minerals such as tantalite, columbite, beryl, and quartz crystals had to be developed and procured in quantities never before dreamed of. New uses such as radio and radar created demands for many minerals formerly thought of only as adornments of museum collections and not as pressing industrial minerals. Such minerals were never before mined in quantity.

Jan 1, 1945

By William H. Baer, George M. Carlton, Blake M. Loring

IT is a well known fact that age-hardening alloys remain in a supersaturated, or partially supersaturated, condition only for limited periods of time at temperatures below the solvus. In order to develop optimum properties by subjecting the quenched alloy to precipitation or age-hardening treatment at a specified temperature, it is necessary that the cooling rate be sufficiently high to maintain the required degree of supersaturation of the solid solution. In practical applications the size and shape of the specimens obviously have considerable influence on the rate of cooling and there is need for more information on the effects of various rates of cooling. Cooling rates of quenched aluminum alloys generally have been established by the type of quenching medium, the temperature of the medium and the dimensions of the specimen.1,2,3 Except for the work of Roth3 little quantitative information is available on the measurement of cooling rates of aluminum alloys and the significance of the influence of various cooling rates upon the mechanical properties. The purpose of the present investigation was to study the use of the Jominy test for aluminum alloys (Table I). EXPERIMENTAL PROCEDURE The material for this investigation consisted of extruded rods 1 ¼ to 1 ½ in. in diam. The chemical compositions were as follows: [ ] The modified L-type Jominy specimen with dimensions shown in Fig I was selected as the most convenient means for obtaining a wide range of cooling rates. The standard Jominy specimen was not satisfactory because its cooling rate was not sufficiently high. The four flat surfaces machined at right angles along the length of the L-type specimen to a depth of 0-015 in. facilitated the hardness measurements. The specimens were machined from the extruded stock with no intermediate forging. New specimens were used for each aging experiment. The specimens were given solution treatments of 2 hr duration at recommended temperatures in a Hoskins furnace (Table 2). The temperature of the furnace was maintained constant to ±3°C. No protective atmosphere was necessary because the thin film of oxide that formed on the surface of the specimens had no effect on the hardness measurements.

Jan 1, 1948

By Edna A. Dancy, Ronald L. Pastorek, Gerhard J. Derge

In an earlier study1 in this laboratory, it was found that there is a minimum in the specific conductance of Ni-S melts in the region of the stoichiometric composition, Ni3S2. This and similar observations on other sulfide1 and telluride2 systems suggest that short-range order exists in the molten phase for several hundred degrees above the melting point, and a qualitative energy-band model has been proposed, with intrinsic semiconduction at the stoichiometric composition and degenerate electron and hole conduction at metal- and tellurium-rich compositions. This suggestion has been substantiated for the telluride systems by Seebeck coefficient measurements which showed a change in sign from negative on the metal-rich side to positive on the tellurium-rich side. In the present investigation, in order to substantiate still further the proposed model, Seebeck coefficient determinations have been extended to the Ni-S system over a composition range in the vicinity of Ni3S2. The experimental method was essentially the same as that used for the telluride systems, with minor modifications on cells for high sulfur melts to permit the use of tungsten wires and W— W-Re th~rmocouples instead of the chrome1 or alumel wires and chromel-alumel thermocouples originally used. Chrome1 and alumel both deteriorate very rapidly in atmospheres containing sulfur. The Ni-S alloys were prepared as described in the conductivity paper. Initially, a portion of the solidified melt was analyzed at the end of a run, but after this was found to be inaccurate because of segregation during cooling, the whole sample was analyzed. The nickel content, only, was determined, the sulfur content being obtained by difference. The results are summarized graphically in Fig. 1, and clearly show a change in the sign of the Seebeck coefficient in the region of the stoichiometric composition. This change of sign near Ni3S2, coupled with the minimum in the conductivity, is suggestive of an intrinsic semiconductor at the stoichiometric composition, with degenerate electron and hole conduction on either side of this composition, in keeping with the proposed model. The negative temperature coefficient of conductivity, normally indicative of metallic conduction, is not inconsistent with this model. In the completely degenerate region it would be expected, while in the vicinity of Ni3S2 the suggestion originally made by Argyriades, Derge, and pound3 for the Fe-S system can probably be applied. They proposed that the forbidden gap between the valence band and the conduction band is small, and that the increase in the number of the conducting species with increase in temperature is not large enough to compensate for the loss of mobility through thermal scattering. The research was sponsored by the Office of Naval Research under Contract NONR-760(22) Project NR 039-081. 'E. A. Dancy and G. J. Derge: Trans. Met. Soc. Aime, 1963, vol. 227, pp. 1034-38. 'E. A. Dancy: Trans. Vet. soc. AIME. 1964, vol. 233, pp. 270-77. 'D. Argyriades, G. Derge, and G. M. Pound: Trans. Met. Soc. . 1959, vol. 215, pp. 909-12.

Jan 1, 1965

By R. A. L. Black

13.8-1. Introduction. Table 13.8-1 shows that production from the African continent is an important part of total world mineral production. In three of the major particular resources listed, diamonds, gold, and cobalt, African production accounts for considerably more than half the world output. Overall, South Africa including South West Africa plays a dominant role in the mineral economy of Africa, other than in petroleum production. Table 13.81 also shows that much of the production is won by surface mining methods. In addition to the minerals listed in Table 13.8-1, Africa is a main world source for the following minerals: [Beryl 33% of total world production Columbium-tantalum 50%" " 1' Platinum group metals 20% l' " 11 Corundum 55%" " " 11 Vermiculite 30% (' " (6 Uranium oxide 15 0/, of free world production] South Africa and Rhodesia together account for nearly all of this production, except for columbium (niobium) of which Nigeria is the main producer. Thus the importance of southern Africa as a major mineral province can readily be appreciated. The consequences of serious political or military conflict between white-dominated southern Africa and the rest of the continent would be grave indeed, particularly for the West whose financial and economic interest in Africa as a whole is very large. The development of mineral resources in Africa involves the same basic elements as are involved anywhere else in the world: exploration, drilling and sampling, metallurgical assessment, and economic evaluation before, if it is justified, a prospect is brought to the productive stage. The same range of factors controls the economic viability of a project in Africa as elsewhere, of which the most important are:

Jan 1, 1968

FRank FirmstoNe, Easton, Pa.: The effect of lead on brass seems to have been recognized by Berthier, and the facts published by him as early as 1818 (Ann. des Mines, 1st ser., iii., 1818, p. 347 et seq.). He there says expressly that copper containing lead makes " dry " (see) brass, and that, for the same reason, blast-furnace

Jan 1, 1898

By Robert S. Shoemaker

Receiving the Richards Award is undoubtedly the most memorable event in my entire life. There should, however, be more names engraved on it. These are the names of men who were my teachers (but not all of the academic variety) and my friends, each of whom had a part in my ever continuing education and thus have a part of this award. There was Bill Caldwell who made me into a chemist, and Will Shorey who added a lot of ore dressing. There was Rush Spedden who put me to work in his minerals research lab, Joe Brennan who made me turn my research into plant practice, and Tom Meek who sent me all over the world on metallurgical jobs. Bob Cheatham and Abe Dor taught me to try to give the client what he needs rather than what he wants, while Ed Malouf and Casey Davis always gave their particular brand of advice at exactly the right time. And, lastly, there was Leo Abell and Frank McQuiston, both fine metallurgists and the best friends a man could have. In addition to those I have mentioned, there are literally scores of others I would like to acknowledge with my sincere appreciation.

Jan 6, 1974