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By I. R. Kramer, L. J. Demer

Aluminum single crystals were pulled in an electrolytic cell allowing surface removal during the deformation. The extent of Stages I and 11 of the stress-st-aitz curve was increased and the slope decreased as the rate of metal removed from the surface was increased. An increase of the strain rate caused a decrease in the effectiveness of the metal removal. The data indicate that the work-hardening coefficient in Stage I is determined primarily by the conditions which exist on the surface of the crystal. In Stages 11 and 111, both surface effects and internal barriers are important. ALTHOUGH numerous investigations have been conducted on the plastic flow characteristics of metals in an attempt to explain the mechanism of work-hardening, relatively few studies have taken into account the influence of the surface. In all current theories of work-hardening it is assumed that the impediments to the movement of dislocations are within the crystal. The barriers due to the surface and the existence of solid and liquid films have been neglected even though it has been demonstrated that the surface exerts a large effect. A number of investigators1-l8 have shown that solid films on the surface of single crystals markedly affect their mechanical behavior. In general, the presence of a solid film tends to increase the yield stress and increase the work-hardening rate. Often, on single crystals, Stage I and, at times, Stage II regions are completely suppressed. Various mechanisms have been offered for the effects of oxide and metal films as well as the influence of electrolytes. Of these, concepts concerned with the locking of surface dislocation sources and the blocking of dislocations at the surface resulting in pileups appear to be actively considered at present. Barrett,11 Takamura,6 Gilman,19 Lipsett and King,20 Shapiro and Read,10 and Weiner and Gensamer21 are among those who have interpreted their results in terms of piled-up dislocations at the surface, while Adams.22 and Chalmers and Davis23 have explained their experimental observations in terms of locking of surface dislocation sources. In general, the change in plastic flow properties due to electrolytes has been explained in terms of the unblocking or unlocking of dislocations by the removal of the oxide films. In considering the two proposed mechanisms, it appears that the locking of sources of surface dislocations by a solid film should exert a primary influence only on the critical resolved shear stress for flow and not on the slopes of Stages I and 11. However, the blocking at the surface of dislocations from internal sources may also affect the critical resolved stress and furthermore exert an influence throughout the whole plastic range. In certain cases it does not seem feasible to explain the results of experimental observations in terms of locking of surface dislocation sources. The abnormal aftereffects found by Barrettll,12 by removing the oxide by an acid treatment are excellent evidence of the blocking of dislocations at the surface. Additional evidence in favor of a blocking due to a pileup of dislocations at the surface may be found from the observations that the critical resolved shear strength continues to increase with the thickness of the oxide layer until very heavy oxide layers are formed. If the locking of surface dislocations sources were the dominant factor, the critical resolved shear stress would not be expected to increase after all of the surface sources were locked by the formation of the oxide. This may be expected to happen after a few atomic layers of the oxide are formed. In spite of the above evidence on the strong influence of the surface on the plastic flow characteristic, this has been ignored in current theories of work-hardening. Seeger24,25 suggested that most of the dislocations may slip out of the crystal only when the specimen axis is within certain areas of the orientation triangle. In other areas the resolved shear stress in other glide systems is large enough to generate dislocations which can form Lomer-Cottrell locks, thereby decreasing the average slip distance in some directions and causing a larger hardening rate. Friede126 assumed that at the beginning of Stage 11, a large number of Lomer-Cottrell dislocations are formed by a catastrophic process which used up all the Frank-Read sources on the secondary slip-planes. In this manner a fixed number of Lomer-Cottrell locks is formed which act as barriers against which the dislocations can pile up. In Stage 111, Seeger24 and Diehl, Mader, and Seeger25 proposed that Lomer-Cottrell barriers are circumvented by the cross slip of extended screw dislocations. Cottrell and Stokes,27 Friedel,26 Cottrell,26 and stroh29 suggest that the Lomer-Cottrell dislocations collapse under the stress field of the dislocation pileup. It is the purpose of this paper to report the changes in Stages I, II,and III of the deformation process in

Jan 1, 1962

By Norman Orr, J. W. Gregg, Jack Wahl

The Pembina Cardium pool is a low permeability, stratified, solution-gas drive reservoir. Water-flooding has proven to be an effective means of pressure maintenance for all areas of the pool in which an economic rate of water injection can be maintained. The majority of water injection wells in the pool are converted oil well~ with capacities greater than 100 millidarcy-feet. If the average injection rate per unit of capacity can be in-creased the lower capacity areas of the pool can be economically flooded. Theory, laboratory work, and two . early miscible-flooding projects with-in the pool suggested that average water injection rates for converted wells could be increased two to three-fold by the initial injection of natural gas liquids and natural gas. How-ever, these two early projects received volumes of natural gas liquid!:' and high-pressure natural gas which would be economically prohibitive for routine stimulation. Area D, one of the Five-

Jan 1, 1962

By K. E. Tame

The Bureau of Mines is studying possible modifications in conventional uranium ore-processing steps to confine and permit controlled disposal of radioactive wastes. A potential method of minimizing pollution from radio-active nuclides, principally radium 226, in uranium mill waste streams is to reuse the waste solutions within the mill. Such reuse of waste solution in the Kerr-McGee Shiprock-type process was investigated in the laboratory. The Shiprock mill employs a two-stage acid-leaching process for dissolution of the uranium, countercurrent decantation for liquid-solid separation and washing, and organophosphorus solvent extraction for recovery of the uranium and vanadium from solution. The simulated use of barren raffinate instead of fresh water in the mill circuit was carried through a laboratory campaign of 28 interlocked leaching, washing, and solvent extraction cycles. About 99 percent of the uranium and 91 percent of the vanadium were dissolved from the are, Washing efficiency in the thickener circuit averaged about 99.5 percent when the pulp was washed with enough barren raffinate and makeup water to recover 2.5 tons of pregnant solution per ton of ore. The only solution discarded was that contained in the washed and thickened leach residue. A buildup of salts due to recycling of solutions did not adversely affect operation of the washing circuit.

Jan 1, 1962

By Joachim J. Hauser

William F. Hosford, Jr. (Massachusetts Institute of Technology)—Dr. Hauser has used a very interesting method to study the interaction of dislocations on different slip systems, but it should be pointed out that the analysis of the experiments is subject to a serious criticism. He states that "the effect of the compression can be adequately described by one slip system." The effect of frictional constraint during the compression makes this quite unlikely. When a block of metal is compressed its lateral expansion requires a sliding of the metal over the compression platens. The role of friction in the interface between the deforming metal and the platens is to increase the normal force required for the compression. Analyses1213 have shown that, in general, the additional force, p, required for the compression is a function of l/h where is the coefficient of friction, I is the length of the speci- men in contact with the platens. For a constant COefficient of friction, isho' shows that P should increase exponentially with pl/h for both plane strain and axially symmetric compression. For a compression specimen, Fig. 7, whose cross section perpendicular to the compression axis is a rectangle whith one dimension L, much larger than the other W, a much larger force would be required for appreciable flow parallel to L than for flow parallel to U7. Therefore lateral strain in the W direction, EW, should be much greater than the lateral strain in the L direction EL. Since L/H = 14.5 for Dr. Hauser's crystals, and since no lubrication was used, it seems questionable that appreciable lengthening of the crystals could occur. Because the theories of frictional constraint have been derived for isotropic polycrystalline materials, it was decided to make experimental measurements on a single crystal. A section 3.590 in. long was sawed from an aluminum single crystal with a square section of 0.249 in., so that L/W= 14.4. This crystal was tested in compression between dry ground steel platens. Fig. 8 shows the orientation of the crystal and the axis of compression. The face for compression was chosen so that the operation of the single-slip system which would be predicted in the absence of friction would lead to a larger strain in the length direction than in the width direction. The dimensional changes of the width and length as well as the height were measured frequently during the compression with micrometers. Width strains were calculated from the average of readings near each end and at the center. A plot of the length strain, EL, against the width strain E w is given in Fig. 9. The slope indicates that the EL amounted to only 2.5 pct of cw. Other compression tests on similar crystals with shorter lengths also showed severely limited elongation. Even for a crystal with L/W = A.0, EL was only about 26 pct of cw. Because of the frequent interruptions of the tests for dimensional measurements should have decreased the frictional constraint by allowing a reseating of the platens, even smaller elongations under continuous testing seem probable. These tests on long narrow crystals show that essentially plane strain conditions prevailed. We may assume that Dr. Hauser's crystals deformed similarly. That the compression can be described by the

Jan 1, 1962

By E. Teghtsoonian, K. G. Davis

THE preparation of cobalt crystals offers problems: on cooling through 400°C a phase transformation takes place whereby the structure changes from face-centered cubic to the low temperature close-packed hexagonal form. There are a few references in the literature which describe the preparation of cobalt crystals for magnetic work1,&apos; where melt-solidification methods were used. Reasons will be given why such methods were found unsuitable for our purposes. The following techniques were tried: 1) Solid state methods. Any mechanical shaping of tensile specimens would lead to uncertainty with regard to residual strains. With this in mind, following Kaa, strain-anneal and grain growth techniques were extensively investigated. In no Case were useful single crystals obtained. The transformation boundaries, which are crystallographically similar to twin boundaries, are probably extremely stable and inhibit the grain growth. 2) Growth from the melt. Normal melt-solidification methods were tried, using recrystallised alumina crucibles, and also a osoft moldo technique in which cobalt rod was packed in alumina powder. Trouble was encountered with gas evolution on solidification of the melt, giving porosity. Some adhesion of cobalt to the alumina also took place. Only a small proportion of the runs gave single crystals. 3) Zone-refining. Much the best results have been obtained using an electron-beam floating zone refiner. The refiner, based on a design by Calverly et Al .5 had a single-turn tungsten filament. It was operated at 600 v with an emission current around 45 ma. Commercial cobalt rod 1/8 in. in diam was given one pass at a rate of zone travel normally 25 cm per hr, under a vacuum approximately 10-5mm of Hg. Over 50 pct of the runs gave long sections of single crystal. Crystals up to 2o Cm long with good uniformity of cross section and straightness have been grown in this way. Increase in the length of the molten zone resulted in higher single-crystal yields, but control of zone stability was reduced. Sub-boundaries in the zoned crystals were few, and Laue X-ray spots were sharp. The success of the method is believed to lie in two factors, namely i) the absence of crucible restraints during the transformation, and ii) extreme axiality of heat flow during cooling. The axes of the zoned crystals were clustered around the [ 1010] pole, the pole of the basal plane being at least 60 deg from the specimen axis. Crystals grown at lower rates of zone travel showed the same orientation range, Fig. 1. This orientation is similar to that for other hexagonal metals grown from the melt, which is a little surprising when the mode of formation of the hexagonal phase is considered. The preferred orientation is probably caused by anisotropy of heat conduction, i.e., that crystal which can most effectively conduct heat away from the transformation interface will be favored. Fig. 2 shows the area on a standard cubic stereo-gram in which there are no poles more than 60 deg from one of the four < 111> directions. This area

Jan 1, 1962

By James Westfield

Following is a brief history of Bureau of Mines Division of Coal-Mine Inspection activities that have favorably effected health and safety and reduced Injuries at coal mines: The Federal cline Safety Code for Bituminous Coal and Lignite Mines of the United States was issued originally by the Director of the Bureau of Mines on July 24, 1946, after consulting with management and labor representatives of the coal-mining industry. The code has been used by Federal coal-mine inspectors while inspecting bituminous-coal and lignite mines for the existence of unhealthful and unsafe conditions and practices in these mines. A revised code was issued by the Secretary of the Interior on October 8, 1953, after further consulting with representatives of management and mine workers, and was incorporated in the 1952 and subsequent bituminous-coal wage agreements. The agreement of May 29, 1946, betweeen the Secretary of the Interior, acting as Coal Mines Administrator under authority of Executive Order 9728, and the United Mine Workers of America, covering bituminous-coal and lignite mines in Government possession, charged Federal coal-mine inspectors with the responsibility of making periodic investigations of the mines and reporting to the Coal Mines Administrator any violations of the Federal Mine Safety Code. Federal coal-mine inspectors also had temporary authority to close mines considered imminently dangerous, but authority under Executive Order 9728 was removed on June 30, 1947, when Government control of the mines was terminated.

Jan 1, 1962

By Edward L. Vickers

When I was originally asked to give this talk, I had certain preconceived ideas of the mining industry&apos;s reaction to Operations Research. It seemed at the time to be a rather simple task to collect these ideas for presentation here today. Jotting down these notions, I became concerned that overexposure to this activity called OR perhaps had clouded my outlook on what was actually being done on a nation-wide scale. I felt, to have a better cross section, a questionnaire of current industrial activity was in order. I solicited the response of some 75 mining companies varying in sizes and operating characteristics, and I am pleased to report that the response was good. I received answers from 51. The questionnaire was intended to measure the degree to which their concerns were actually engaged in OR efforts. With all due respect to the people who were so gracious as to answer the questionnaire, I feel that there is a tremendous misconception as to the designed purpose of OR. This is not to imply that there are no active OR groups in the mining industry. But by in large, the majority of the companies sampled appear to be somewhat confused as to what OR really is.

Jan 1, 1962

By H. Marquis

The present paper consists of a survey of the literature on the problems of abrasion and wear of metals and materials by suspended matter. This problem is a very general one in industry, and is especially notice-able in the operation of cyclones and other types of dust collectors. The problem of abrasive dust in corrosive gas environments, such as commonly encountered in metallurgical industries, is particularly severe. Very little work has been done in the study of this type of abrasive wear, especially at high temperatures. However, a general review is presented here of all the work published on related subjects, such as that involving sand erosion in turbines and water wheels and the effect of temperature on friction wear. Topics in this paper include: blasting wear by sand, quartz, limestone, silicon carbide and other refractory particles; methods of investigation; effects of velocity, temperature and *Canadian Armament Research and Development Establishment, Valcarter, P.Q. angle of attack; correlation between indentation hardness, scratch hard-ness and resistance to abrasion; the effect of protective coatings; resistance of various metals; etc.

Jan 1, 1962

By F. L. Jackson

The large scale transportation and storage of sulphur in the liquid state is a relatively new development, but is really only a logical extension of old mining and processing techniques, It is not known who the first person was to win a relatively pure sulphur from ore by melting, but this method was commercially used at least two hundred years ago in Sicily and is still in use today. The Frasch process of mining was invented over sixty years ago, and the development and improvement of-liquid sulphur pumping and handling techniques has paralleled the growth in the Frasch mining industry. During the last fifty years, improvements in the technology of using sulphur have included the premelting of sulphur prior to its being burned for acid production or conversion into CS2 and other compounds. Yet, until fairly recent times, sulphur produced as liquid has been solidified into large blocks at the producing point, broken down by blasting or with mechanical equipment, and shipped in bulk form as a solid.

Jan 1, 1962

By Engineering Staff

In 1958, the Iron Ore Company of Canada decided to proceed with the Carol Project. The ore deposits in the area are part of the highly metamorphosed southern zone of the Labrador Trough. They lie along the shore of W a bush lake, in the western part of Newfoundland-Labrador, 190 miles north of Sept-Iles. The project is designed to mine, by open-pit methods, 17,200,000 long tons of crude ore, grading 37 per cent iron, per year. This ore will be beneficiated to produce 7,000,000 long tons of concentrate, grading 66 per cent iron, of which 5,500,000 long tons will be pelletized. Production is scheduled to commence this summer. Initially, ore will be taken from 45-foot benches in the Smallwood mine, using jet-piercing production drills and large-scale blasting with "slurry" explosives. Four 13-yard electric shovels will muck the broken ore into 100-ton trailer trucks. The trailers will be hauled to two 2,000-ton loading pockets, which feed the ore into 100-ton railcars. Four ore trains, each comprised

Jan 1, 1962

By H. Rozovsky

This paper deals with the large iron ore concentrating plant owned by the Iron Ore Company of Canada. The plant is part of the Carol Project, which is being developed in the Wabush area of western Labrador. The mining and milling operations were officially opened in July of this year. The handling of fine material has always been considered a serious operational problem. The crushing, grinding and sizing of 50,000 tons of iron ore per day, in a dry state, could present sizeable problems in maintenance and orderliness. The operation, as a whole, embraces many recent developments in the iron ore industry. Mining operations include the latest techniques of jet piercing and blasting. Primary crushing involves a single crusher, which handles the complete production. Grinding of the ore includes the latest concepts of dry autogenous grinding in air-swept mills. The actual concentration of the ore is per-formed, in the wet state, by the use of spiral concentrators, with provision for possible flotation or magnetic separation, if required. The upgraded concentrates are either stored or pelletized, prior to shipment by rail to Seven Islands.

Jan 1, 1962

By R. V. Higgins

Many contributions to methods of forecasting the performance of waterfloods of a five-spot pattern have been made by investigators. In most of these forecasting methods, a previously selected sweep efficiency is used, and other simplifying assumptions are employed to obtain the objective. In this paper the calculated oil recoveries from several five-spot single- and multiple-layer stratified reservoirs were made with a minimum of assumptions, and because of the techniques used, no previously selected sweep efficiency was required. As a result, the accuracy of the forecast is increased. Permeability curves and continuously changing saturation gradients are used in every section of the pattern. By means of a potentiometric model, the flood pattern is divided into channels, the centers of which are the streamlines. The channels are divided into cells. As flood water enters, the permeability and saturation of each cell change with time. In this study the production from multiple-sand layers of different absolute permeability but with the same relative permeability-saturation relations are combined. The results are shown for a single- and 10-layer reservoir with a permeability variation of 0.60. The oil rate, water-oil ratio, and recovery are shown as functions of time for a 2- and 20-centipoise oil starting in primary phase and after fill-up.

Jan 1, 1962

By Philip E. Niebuhr

A procedure, which can be performed in the field by nonanalytical personnel, is given for sensitive spot tests for detecting tellurium or selenium. The expressed need of a field test for detecting small amounts of tellurium, which may be accompanied by relatively large amounts of selenium, has led to the development of this method. Tellurium search has been impeded by the lack of a satisfactory test from the standpoint of sensitivity and specificity. A quantitative laboratory method exists, but it is expensive and relatively laborious. Several other qualitative tests are known, but they require unstable solutions, which must be freshly prepared for use, and a greater variety of laboratory equipment. The particular advantages of the test described are its simplicity and the stability of the reagents required, there-fore is is well adapted for field use. Also, this test was found to be of practical use in the analytical laboratory when screening samples, thereby reducing analytical costs. The roughly quantitative interpretation of the results can save time by indicating the approximate size of the sample taken for a quantitative determination.

Jan 1, 1962

By Webber. G. R.

Variation in content of some of the major and minor elements in the Lake Dufault granodiorite near Noranda, Quebec has been studied. The element variation and specific gravity data show a pattern consistent with the concept of a concentrically zoned intrusive on the western side of Lake Dufault with a potassium-rich core and a calcium-rich inner zone. The part of the intrusive on the eastern side of Lake Dufault is of more problematical origin, but the suggestion is made that it has resulted from assimilation of volcanic rock by the intrusive. THE purpose of this investigation was to test the application of x-ray fluorescence analysis to the study of variation in chemical com-position of the Lake Dufault granodiorite. The Lake Dufault granodiorite is an intrusive body approximately six miles long by three miles wide located four miles north of Noranda, Quebec. This intrusive is of particular interest because of its -

Jan 1, 1962

By Wesley Holmes

Concentrating, nodulizing, and smelting studies were conducted at the Albany Metallurgy Research Center of the Bureau of Mines to determine whether (1) western iron ores of the type found in the Carter Greek deposit near Dillon, Mont., could be utilized; (2) concentrates of acceptable grade with good iron recovery could be attained by wet-magnetic beneficiation; (3) nodulized concentrates could be smelted with reductants readily available in Montana; (4) iron concentrates could be smelted without prior agglomeration; and (5) high-purity iron could be produced directly from high-grade concentrates, Three small samples and two tonnage samples from the Carter Creek deposit were uniform in chemical composition, and their iron content averaged about 31 percent. They were found to be banded gneisses, and magnetite was the principal iron-bearing mineral.

Jan 1, 1962

The public relations problems of users of explosives have greatly increased within the past few years. One reason is that explosives and blasting agents are being consumed in increasing quantities. The principal reason, however, is that more people have become physically affected by blasting. Mines, quarries, and construction sites that were formerly in relatively remote locations now find themselves near congested areas. New express traffic ways being constructed to connect the suburbs with downtown areas are being built through the middle of long-established business and residential neighborhoods. The public becomes aware of blasting by two physical sensations-vibration and noise. Vibrations are usually so slight as to be negligible, and in most cases the only sensation noted is noise. The reduction of vibrations to this low level has been primarily achieved by the use of blasting practices and explosive products recommended by vibration engineers based on seismograph recordings. Unfortunately, very little scientific attention was given to the accompanying physical sensation-noise.

Jan 1, 1962

By MacDonald W. L. F. C. A.

IN accordance with the usual approach to a participation in a panel discussion, this paper is, in some respects, intentionally controversial. I would suggest, how-ever that there is more than a grain of truth in many of the comments made. Before dealing with a particular problem. It is appropriate to set out a few of the more significant objective of an: accounting system: (1) The provision of historical data <•concerning past events, for the information of shareholders, tax authorities, etc. This data can also be used as a tool to predict the future. (2) The provision of a record to safeguard the company's assets and to form the basis of any claim for insurance or other damages. (3) The provision of an accounting framework in making an economic study of a proposed course of future action such as the development of an orebody or the outlay of a substantial sum for new equipment. ( 4) The

Jan 1, 1962

By H. Marquis

This paper is concerned with an analysis of a number of failures of large-size, hypervelocity light gas gun chambers and barrels. A brief description of the light gas gun principle and of the various types of guns is first given. The failures and the investigations carried out are then described in detail, with the failures divided into two groups. The first group comprises those failures caused by certain conditions to which the guns may be submitted, and includes, for example, severe local heating of the bore surface causing hardening and cracking of the steel. These conditions were accidental and steps were taken to prevent them. The remaining failures were due to faults in the material or in the heat-treatment, manufacturing or assembling procedures. Specific problems, such as hydrogen embrittlement, and the use of high strength gun barrels above their ductile-brittle transition temperature by preheating prior to firing, are briefly considered. Some interesting observations are also presented on the use of surface markings, and angles of fracture of large fragments, as an

Jan 1, 1962

By Robert L. Dean, Michael Hoch, Samuel M. Wolosin, Chung K. Hwu

The general shape of the 1450°C isotherm of the Ti-TiO-ZrO2-Zr region was evaluated from the surrounding binary phase diagrams and from thermo-dynamic data on the metal-oxygen binaries. The phase boundaries were accurately determined using X-ray and metallographic techniques. At 1450°C the system shows a large bcc ß field, which extends from the two metal-oxygen binary systems as a Gaussian error function, and is stable up to 30 at. pct 0 when Ti and Zr are present in equal amounts. At higher O Concentrations, the ß field is in equilibrium with t-ZrO . The following four regions, with three solid phases, are present: two a ß t-ZrO,, a TW t-ZrO,, and TiO t-ZrO2 c-ZrO2. On cooling the ß phase transforms into the a phase, going through the w transition phase. The isotherm at 1500°C for the region TiO-TiO,-ZrO, was obtained by using X-ray diffraction. At 1500°C a large c-ZrOz region is present as well as a large two-phase field, Ti0 c-ZrO,. The following regions, with three solid phases in equilibrium, were found These regions are relatively small. The solidus and liquidus relationships were determined by observing samples suspended in a tungsten crucible by means of a fine tungsten wire and heated in vacuum. Eleven univariant points were found. C-ZrO, decomposes through a peritectic reaction into liquid t-ZrO2. The activities of Ti and TiO in the TiO t-ZrOz and in the two a ß t-ZrO regions were measured using the Knudsen effusion method. In the a TiO t-ZrO, region the activities of Ti and Ti are the same, as in the a — Ti TiO binary. In the two a t-ZrO, regions, the Ti activity is high and the Ti0 activity very low, although all phases present contain at least 30 at. pct 0. This indicates a short-range order in the solid phases, Zr atoms being preferentially surrounded by 0. 1 HE system Ti-Zr-0 is of interest because of the wide ranges of solid solubility exhibited by the boundary systems; as titanium and zirconium both belong to the same group of the periodic table, large single-phase regions should occur within the system, with a great variation of properties (as the composition changes within the single-phase region). Furthermore, the possibility of modifying ZrO, to make it a more usable refractory by the addition of other metals makes this system also of interest. Because of the high affinity of titanium and zirconium for oxygen, the oxygen partial pressure is very low at all compositions; thus, there exists a ternary metal-metal-oxygen system in which the oxygen pressure is not an important variable, so long as it is low enough. When a sample is heated in vacuum to a temperature high enough for vaporization to occur, the vapor phase will consist of metal and metal-oxide gas, the oxygen concentration being very low. The phase relationships in the surrounding binary systems have already been reported in the literature; therefore, the study of the ternary diagram

Jan 1, 1962

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,&apos; carbides,&apos; and halides3&apos;4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.&apos; Some work on the kinetics of fused salt electrochemical processes has been reported.&apos;09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml&apos; have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962