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By R. M. Hudson

A study has been made of the decarburization of low-carbon sheet steels at temperatures from 1100" to 1475°F in mixtures containing hydrogen, nitrogen, water vapor, and in some instances carbon monoxide. Decarburization occurs principally by the reaction C (in steel) + H20 = CO + H2 and follows a first-order rate law. The decarburization rate appreciably increases with an increase in temperature up to about 1325°F, but the increase in rate is small with fur- Use of a dry hydrogen atmosphere results in a relatively slow decarburization of steel and use of a wet hydrogen atmosphere results in relatively rapid decarburization. It is now generally recognized' that the reaction C (in steel) + H2O = H2 + CO [l] accounts for most of the decarburization that occurs in wet hydrogen-containing atmospheres. The present article is concerned with the decarburization of low-carbon sheet steel in H2-N2 atmospheres ther increase in temperature. The limiting rate of decarburization can be predicted from a knowledge of the solid solubility and diffusivity of carbon and this rate is approached as the water-vapor content of an atmosphere is increased. Hydrogen contents above about 8 pct are beneficial only in that they permit higher levels of water vapor to be used without oxidation of the steel. A buildup of CO in the atmosphere lowers the rate of decarburization. containing various amounts of water vapor and carbon monoxide. The effectiveness of these atmospheres and the influence of temperature on decarburization rate will be considered. EXPERIMENTAL WORK The chemical compositions of the three steels used in decarburization-rate studies are listed in Table I. Steel A was a commercially hot-rolled rimmed steel that was cold-reduced at the Laboratory to furnish specimens 0.025, 0.041, and 0.059 in. thick. Most of the experiments in which this steel was used were made on the 0.041-in.-thick material. Steel B and Steel C were cut from 0.010-in.-thick commercially cold-reduced coils that were

Jan 1, 1963

By B. Woyski

Many writers, in discussing defects caused by oxidation and gassing of bronzes and red brasses advocate substantially the same cure for both. But from its nature, oxidation cannot take place if there is an excess of fuel in the furnace, while the gases absorbed by some alloys are products of incomplete combustion of the fuel. Hence the metal can be either oxidized or gassed, but it is doubtful whether these actions can take place simultaneously. Oxidation can be easily overcome by the use of deosidizers or it may be avoided by protecting the molten metal with suitable fluxes. Absorption of gascs is more difficult to overcome: the regulation of the air and fuel, so as to produce complete combustion, and the protection of the bath by mineral fluxes arc the most important factors. Gas expulsion, resulting in gas holes, porosity, unsoundness, and swollen or cauliflower-headed risers, is said to have several causes. One writer1 lists the most common causes in the order of their importance, as follows: Superheated metal, dirty or slaggy furnace conditions, using metals low in quality or those previously subjected to bad melting practice, poor grade of fuel, use of newly lined or damp ladles, indiscriminate mixing of scrap or illogical combinations of metal. Superheating the metal usually occurs when the heat is ready to be poured but for some reason must be held in the furnace. In this case, a careful furnace tender tries to avoid overheating the metal by keeping a mild fire; that is, a reducing fire which, unfortunately, results in gassing the metal. A dirty, slaggy furnace may result in gassing the metal by retarding the heating and prolonging the time necessary to bring the metal to the proper temperature, thereby increasing the chances of gassing in uncertain furnace atmosphere. It is doubtful whether rnetals of low quality have anything to do with gassing molten metal, except, possibly in the case of metals containing

Jan 1, 1923

By B. Woyski

Many writers, in discussing defects caused by oxidation and gassing of bronzes and red brasses advocate substantially the same cure for both. But from its nature, oxidation cannot take place if there is an excess of fuel in the furnace, while the gases absorbed by some alloys are products of incomplete combustion of the fuel. Hence the metal can be either oxidized or gassed, but it is doubtful whether these actions can take place simultaneously. Oxidation can be easily overcome by the use of deosidizers or it may be avoided by protecting the molten metal with suitable fluxes. Absorption of gascs is more difficult to overcome: the regulation of the air and fuel, so as to produce complete combustion, and the protection of the bath by mineral fluxes arc the most important factors. Gas expulsion, resulting in gas holes, porosity, unsoundness, and swollen or cauliflower-headed risers, is said to have several causes. One writer1 lists the most common causes in the order of their importance, as follows: Superheated metal, dirty or slaggy furnace conditions, using metals low in quality or those previously subjected to bad melting practice, poor grade of fuel, use of newly lined or damp ladles, indiscriminate mixing of scrap or illogical combinations of metal. Superheating the metal usually occurs when the heat is ready to be poured but for some reason must be held in the furnace. In this case, a careful furnace tender tries to avoid overheating the metal by keeping a mild fire; that is, a reducing fire which, unfortunately, results in gassing the metal. A dirty, slaggy furnace may result in gassing the metal by retarding the heating and prolonging the time necessary to bring the metal to the proper temperature, thereby increasing the chances of gassing in uncertain furnace atmosphere. It is doubtful whether rnetals of low quality have anything to do with gassing molten metal, except, possibly in the case of metals containing

Jan 1, 1923

By Charles W. DeWitt

The ore treated at the reduction plant (called Yangdei) of the Chiksan Mining Co., Korea, is brought from four of the company mines, and from the small tribute mines. The largest shipments come from Sajunkohl mine, situated about a mile and a half from the mill (Fig. 1). The ore is quartz of medium hardness. The average assay value in gold is $6.95 per ton. At the mine the ore is put into bins, and is then trammed over an 8 per cent, grade to the tipple bins above the mill, where the ore is drawn through the mill holes as desired. The capacity of the tipple bins is about 3,500 tons. Ore from Moonsukohl, Chung Tarrie, Yang Chun, and the tribute mines is brought in by bulls and bull wagons. The bulls carry from 350 to 800 lb.; the average wagon load is about 1,200 1b. (Fig. 2). One shovelful of ore out of every ten is taken as a sample. Considerable ore is brought in from the outside mines, and this method of sampling is

Jan 1, 1916

By John W. Bell

In the introduction to an excellent pamphlet, John Gross' makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 0, i8, 19, 21, 22, 23. 24, 30. 34), concluded that a foundation for the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.1 One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur O. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 23 2,3 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. STADLER'S HYPOTHESIS WORTHLESS It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left-the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things, that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in fine crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1942

TO THE BOARD OF DIRECTORS AND MEMBERS OF THE AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS GENTLEMEN : Submitted herewith are the report of the Treasurer for the year 1944 and reports for the same year of the following standing committees: Membership, Ad- missions, Papers and Publications, MIN- ING AND METALLURGY (Magazine), and Library. To these reports you are referred for additional details.

Jan 1, 1946

By D. L. Wood

INTERNAL oxidation of alloys has been investigated by Rhinesl,2 and by Meijering and Druy-vesteyn. Rhines showed that dilute Cu-A1 alloys can be internally oxidized without forming an external scale by annealing in an oxygen partial pressure equal to the decomposition pressure of Cu2O. The oxygen is supplied at the outside surface at a rate sufficient to maintain saturation of the surface with respect to oxygen. Oxygen diffuses inward and, at the interface between the subscale and the alloy, oxygen meets the solute and reacts to precipitate its

Jan 1, 1957

By Ernest Stütz

(New York Meeting, October, 1918.) THE problem of increasing blast: furnace efficiency through diminution of flue-dust production while operating with burdens consisting largely of fine ores has of recent years attracted the attention of metallurgists, whether directly or indirectly interested in the economies of iron smelting, and the various methods evolved from theory or practice have been submitted to wide discussion. After the very thorough and, at that time, exhaustive view of the whole subject, which was afforded to the industry by the meeting of this Institute in February, 1912, the subject was again taken up at the meeting of the Verein deutscher Eisenhüttenleute at Diisseldorf in December, 1912. While American and German conditions are not entirely identical, it may be of interest to give here the words of the gentleman summing up the discussion at the Diisseldorf meeting: ' The chief advantage offered by the use of briquettes lies in the fact that disturbances in the furnace, caused mostly by the presence of fine ores in the burden, are avoided, and that blast pressure can be considerably reduced. The resulting economies cannot be overrated, as, with lower blast consumption per ton of product, the installation will be able to take care of increased production. In consequence of lower pressure and speed of blast, heat is more efficiently utilized, flue gas temperature is lowered, and coke particles are less liable to be carried along with the flue dust, of which considerably less is produced. Finally, by increased regularity of operation and higher . temperature in the lower parts of the furnace, the quality of the product is improved. The question of briquetting iron ores has grown to be one of the most important in the iron industry, and, it is not any more a question of what is the cost of briquetting ton of ore, but what, in using ore briquettes, is the cost of production of a ton of iron.'

Jan 7, 1913

By Robert M. Jimeson

At the recent SME Fall Meeting in Salt Lake City, Robert M. Jimeson, Physical Science Administrator of the U.S. Bureau of Mines, cited the research programs underway in the Bureau's Division of Coal Research, and outlined their current status. These research programs have been selected by the Division because of their relative value and high probability of success in contributing to the conservation of the Nation's coal and to the expanded use of coal in current or new markets. Since about 50% of coal consumption in the United States is in the production of electric power, 20% in production of metallurgical coke, and over 20 % by industry in producing process steam and power, the Bureau has placed much emphasis on research that will maintain coal's leadership in these established areas. This emphasis is reflected in the projects discussed on these pages. Bear in mind that this survey is not all-inclusive. Other projects underway include studies on furnace performance factors, improved burner design, and other critical boiler work which can be used immediately by industry to improve efficiency of current practices in power generation; other investigations are aimed at reducing fireside deposits and corrosion of boiler and super- heater tubes, fly ash utilization, and control of SO, from flue gases (a major step in preventing air pollution). These plus many other projects during the past years have served to focus attention on the fact that the U. S. Bureau of Mines is presently making the largest single contribution to this Nation's coal research effort.

Jan 11, 1963

Jan 1, 1891

By Robert Hunt

(New York Meeting, February, 1913.) I HAVE frequently stated that while the chemical composition of steel is important, yet even greater importance is connected with the mechanical and heat treatment of the metal. During the past year I encountered such a positive example of that fact that I deem it worth putting upon record. A prominent railway system divided an order for open-hearth steel rails between two steel works, both of which are under the control of the one corporation; giving to one about 18,000 tons, and to the other 7,500 tons of the same section and to be made under the same specifications. The rolling results obtained in the two mills varied so widely that a study of the figures is intensely interesting and serves to illustrate the advantages obtained by careful ingot casting, and, quite as pertinently, the possible benefits of careful subsequent heating and rolling with moderate reductions in the rolling process. The smaller order was rolled complete in four installments during the same months that the larger order was being made in six separate installments; but, to permit of exact comparisons, the totals of the four installments (completing the order with the mill which I will call A) are given with the totals of the first four installments of the larger order, made by the mill designated as B. These rolling results are:

Jan 5, 1913

By E. C. Pechin

The attention of the members of the Institute of Mining Engineers is asked to a description of the minerals of Southwestern Pennsylvania, as representing the minerals of an enormous area, stretching continuotisly, with local variations, along the western slopes, and at the base of the Alleghany Mountains, through Western Pennsylvania, West Virginia, and Kentucky, and destined to play no mean part in the future of the iron trade of the country. The particular locality is at and near Donbar, in Fayette County, where the most careful examinations and extensive developments have been made. The deep gorges cut by the Youghiogheny and Monongahela Rivers, in their passage through the mountains and lower lands, give admirable facilities for observing the measures lying between the sandstones of No. 11 and the upper coal measures. Apart from its varied mineral and agricultural resources this section of country has great historic interest attaching to it. It was down the Monongahela that Braddock led his ill-fated army to its defeat under the wails of Port Duquesne, and it was up the Youghiogheny River and Dunbar Creek that the shattered remnants hastily fled to gain the camp of Colonel Dunbar, the second in command, who was entrenched upon a high knob, at the head of the creek which bears his name, and which is still known and visited as Dunbar's Camp. Numerous streams, runs, and localities preserve the names of the guides and pioneers who accompanied, in early colonial times, young George Washington, who was pushing his surveys into the trackless and hostile wilderness, and many of them taking up large tracts of

By John C. Branner

Within a couple of years I have received many inquiries in regard to the manganese-mines of Brazil. These inquiries were doubtless directed to mc because I had lived and traveled in Brazil for more than eight years, and was therefore supposed to be pretty well acquainted with its geology and mineral resources. Somewhat to my chagrin, I not only knew nothing of manganese-mines in that country, but I had never before heard of the mineral having been found here in quantity, and I did not even know in what State the mines were located. The present summer found me in Brazil again, trying to finish up some of my early geological investigations along the northeast coast, and I have used the occasion to find out something about the manganese-deposits. Very little is known of these mines, even in Brazil. While at Pernambuco I was told that they were in the distant interior of the State of Bahia. In August I reached Bahia, and there I found out, concerning the mines and their geology, enough to be worth telling for the benefit of those interested in the mining or using of this mineral. Thus far, all the manganese-ore shipped from this State has come from two mines, the principal one of which is known as the Pedras Pretas mine. This was the first mine opened, is the best developed, and was the original discovery; the second one is on an adjoining tract, and the general geology and natural conditions are about the same in both. The Pedras Pretas mine is on the Nazareth-Amargosa railway, twenty-six kilometers west of the town of Nazareth, which is on tide-water, at the head of navigation, and is reached from the city of Bahia by a small side-wheel steamer that runs across the bay of Bahia and up the Rio Jaguaripe

Jan 1, 1900

By R. J. Weege, A. W. Schillinger

Conventional underground mapping methods and diamond drilling are being applied in a study to determine the nature of the copper ore occurrences near the footwall of the Osceola lava flow top, commonly referred to as the Osceola Amygdaloid. The work to date suggests that structures formed by relatively impermeable barriers, created by flowage and injection of still-molten lava from the interior of the flow into the solidified, brecciated crust, acted as the ore receptacles. Ascending hydrothermal fluids traveling near the footwall contact were trapped and confined in these barriers which retarded the direct upward movement of the ore fluids and caused deposition of copper. Oreshoots located near the footwall appear to have been formed spatially independently from the hanging-wall oreshoots by fluids traveling simultaneously, but along different channelways. The barrier concept, as advanced by earlier writers to explain the concentration of the ore-bearing fluids into broad shoots constituting entire ore bodies, is found to be equally as applicable for the localization of smaller oreshoots within the Osceola ore body. Recently, the Calumet Division of Calumet and Hecla, Inc. completed the unwatering of the old mine workings on the Osceola amygdaloid. Two shafts were subsequently reactivated and mining commenced on the Osceola lode after an idle period of over 20 years. Early in 1961, the Calumet and Hecla Geological Dept. was assigned the task of locating additional reserves. Accordingly, an intensive mapping and underground diamond drilling program was initiated. Except for a very few years following the first mining on the amygdaloid, the Osceola lode had never been a high grade producer. It was, therefore, recognized from the onset that a concentrated effort would have to be made by the mining, milling, and geological departments to insure success of the project. Company reports contained many references to ore that had been located near the footwall of the Osceola amygdaloid. Information concerning the grade of this ore was meager, but it was known that at least some was very rich. In contrast to ore that occurred near the hanging-wall, however, the footwall copper did not appear to have a systematic distribution and a large amount of poor rock had to be removed in developing this ore. This, of course, resulted in high development costs and discouraged any extensive mining of footwall ore. The possibility of more continuity than had previously been suspected was recognized by other workers, in particular Dr. T. M. Broderick, formerly Chief Geologist of Calumet and Hecla, who suggested attempts be made on a trial basis to follow the footwall contact with the main development drift. As most mining was done on the Osceola lode before a geological department had been established by the company, and almost all of these openings are now caved, very little information concerning the geology of footwall ore was available. It was, therefore, decided that the first step in the exploration program would be to become familiar with footwall ore occurrences by mapping the geology as the openings were driven. It was possible that a mapping program would reveal the features that controlled the localization of the ore. Furthermore, if it could be shown that footwall ore was more continuous, or if its distribution was more systematic than generally believed, it would be possible to produce a high grade ore that could be blended with the lower grade hanging-wall ore. In connection with the geological program, the Michigan College of Mining and Technology Geophysical Dept. under the direction of Professor Lloyal Bacon, is making a geophysical study of the problems of locating footwall ore by electrical methods. GENERAL GEOLOGY OF MICHIGAN NATIVE COPPER DEPOSITS The native copper deposits of Michigan are located in Keweenaw, Houghton, and Ontonagon Counties. The host rocks are Keweenawan in age and are comprised of interbedded sediments and lava flows which form a belt two to four miles wide and over one hundred miles long. These rocks form part of the south limb

Jan 1, 1962

By P. K. Currie, J. V. Walters

Solution mining of magnesium salts (Carnallite and Bischofite) is taking place near Veendam, in the northeast Netherlands. The magnesium salts are used for the production of magnesia sinter, used as a base material for the manufacture of refractory bricks for furnaces. This paper gives, first, an introduction to the operational procedure followed in Veendam, with the emphasis on some of the unique aspects, and then discusses rock-mechanical aspects of the cavity behaviour. The creep behaviour of magnesium salts is described, and Finite Element calculations on cavity stability and potential surface subsidence are discussed.

Jan 1, 1985

By N. J. Grant, C. C. Wang

The Ti-Cr-O ternary system has been studied in detail near the titanium-rich corner within the limits of 10 wt pct 0, and 20 wt pct Cr. Studies were extended, but not in detail, to the region beyond 25 wt pct 0, (50 atomic pct) and 62 wt pct Cr (60 atomic pct). Four isothermal sections at 1400°, 1200°, 1000°, and 800°C are presented as well as two vertical sections at 1 and 2 wt pct 02. DURING the last decade much interest has been shown in the development of high strength titanium alloys for high temperature and corrosion resistant applications. Extensive research is being carried out at present, as the current literature indicates, in order to study the properties of titanium and to develop improved alloys. Two of the important alloying elements in commercial titanium alloys are chromium and oxygen and it would be desirable to know their combined influence upon titanium. For this purpose the present work was carried out to investigate the titanium-rich corner of the ternary system TiICr-0. The binary systems Ti-Cr and Ti-0 have been published recently. The Ti-Cr system was studied by several investigators " and their results are in close agreement. The eutectoid decomposition of the B phase has been shown to be extremely sluggish. TiCr, was the only intermetallic compound found in this binary system and was formed at 1350°C by a transformation from the p phase. TiCr? was established as the cubic C 15 (MgCu,) type of structure with 24 atoms per unit cell and was designated as the y phase. This terminology will be adopted in the present work. There was disagreement about the actual composition of this compound among the several investigators, although it is evident from their data that the compound probably has a solubility range of about 2 to 3 pct and is in the vicinity of 65 pct Cr. It has been indicated recently that a high temperature modification of this y phase (TiCr,) existed at a temperature above 1300°C." ' This high temperature modification was identified as a hexagonal C 14 (MgZn,) type of structure with 12 atoms per unit cell. The exact transformation temperature from the high temperature phase to the low temperature phase has not been established. A considerable hysteresis was observed and, due to the sluggishness of this transformation, the high temperature phase often co-existed with the low temperature phase at temperatures below 1300°C. A preliminary study of several Ti-0 compounds and the Ti-0 system had been carried out by Ehr-1ich."-"' The most complete binary Ti-0 system was the one reported recently by Bumps, Kessler, and Hansen." The first intermediate phase found in the system was the 8 phase which formed by a peritec-toid reaction of the phases a and Ti0 at temperatures below 925 °C. This reaction is extremely sluggish. The structure of this 8 phase was tentatively identified by these authors as being tetragonal and the lattice constants were found as c,, - 6.645A, a,, = 5.333A and c/a = 1.246A. Experimental Procedure The raw materials used for this investigation were TiO,, electrolytic chromium, iodide titanium, and sponge titanium. The TiO, was in the form of powder of chemically pure grade (99.8 pct pure). The chemical analysis of the electrolytic chromium was: 0, 0.50 pct; Fe, 0.07; Cu, N, and C, 0.01; and Pb, 0.001. The oxygen in the chromium was calculated as part of the final oxygen content of the alloys. The alloys were prepared by the cold crucible method using a tungsten arc. The entire system was evacuated and flushed with purified helium three times and then filled with helium. Each alloy was melted, turned over, and remelted at least four times to insure homogeneity. The total melting time was generally from 6 to 10 min. A master alloy of 25 pct 0,-75 pct Ti was prepared to facilitate alloying by melting compacts of TiOl powder with either iodide or sponge titanium, yielding the compound TiO. It was found necessary to bake the TiO, powder compact at about 150°C to remove adsorbed moisture. This was done to prevent the disintegration and spattering of the compact when the arc was struck. TiO, powder dissolved quite readily into the melt and no other trouble was encountered.

Jan 1, 1955

[PRESIDENT GEORGE OTIS SMITH, District 4 WASHINGTON, D. C. PAST PRESIDENTS SAMUEL A. TAYLOR, District 3 PITTSBURGH, PA. E. DEGOLYER, District 0 NEW YORK, N. Y. FIRST VICE-PRESIDENT W. H. BASSETT, District 1 WATERBURY, CONN.]

Jan 1, 1928

By Donald F. Taylor

TANTALUM and columbium are newcomers in the world of metals. Many of the metals described in this volume had been known and used for centuries before either tantalum or columbium was known to exist. The scarcity of the ores and the comparative difficulty of extraction delayed their technology until specialized methods of processing could be developed. HISTORY Early in the nineteenth century, 1801, Hatchett discovered a new oxide, which he called columbium oxide, and a year later, Ekeberg announced that he had found a new element, which he named tantalum. The preparation of the metal tantalum in impure form was first announced by Berzelius in 1824, but the actual production of ductile metal did not occur until 1903, when von Bolton, of Siemens and Halske, developed a process for the production of tantalum pure enough to be drawn into electric-lamp filament wire. The use of tantalum as a filament wire began to decline when ductile tungsten was introduced in 1909. In 1921, C. W. sake, of Fansteel Metallurgical Corporation, produced the first ingot of tantalum metal in America. The first ingot of columbium was produced in 1927 in the laboratory of the same company. There are several good reasons why tantalum and columbium are often mentioned together. They occur together in their important minerals, are similar in many of their properties, and are

Jan 1, 1953

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,' carbides,' and halides3'4 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.' Some work on the kinetics of fused salt electrochemical processes has been reported.'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' 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

By William A. Hustrulid

INTRODUCTION Prior to the mid-1970's, the U.S. Radioactive Waste Disposal Program was focused on salt deposits as the geologic medium of choice, almost to the exclusion of other rock types. These efforts are illustrated by the Project Salt Vault experiment in a salt mine at Lyons, Kansas, in 1965-1967 followed by attempts to locate a repository site in central Kansas. Preliminary evaluation of other geologic media led, in 1978, to the GAIN (Geotechnical Assessment and Instrumentation Needs for Nuclear Waste Isolation in Crystalline and Argillaceous Rocks) Symposium held at the University of California (Berkeley), for the purpose of preparing a state-of-the-art document together with research needs for some of the other possible rock types. Because possible sites had not been selected, nor would they be for some time, the primary emphasis was for research and development focused on generic rocks and generic sites. A basic ground rule at that time was that the host rock formation should provide the primary containment for the waste. Also, the U.S. Nuclear Regulatory Commission (NRC) was just drafting the proposed rules regarding site suitability so that this input was not available. The collection of baseline data, conduction of some critical experiments both in the laboratory and field, and the performance of scoping studies were deemed needed. Such work was indeed undertaken; and to date, a great deal of information has been compiled and much has been learned regarding the characteristics of rock masses, rock behavior

Jan 1, 1984