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By AIME AIME

THE quarters provided for the session on Milling Methods, Monday afternoon, Feb. 17, were filled to capacity. Galen H. Clevenger presided and notables, such as A. W. Fahrenwald, A. O. Gates, F. A. Thomson, W. L. Zeigler and others who had not graced a milling meeting in New York in recent years, or per- haps even never before, were actually present and spoke "in person." The first paper, by A. W. Fahrellwald (T. P. 275), entitled "Classifier Efficiency ; An experimental Study," was summarized by the author, who clearly showed the inconsistency of determining the efficiency of a classifier by means of sizing tests, especially where the material classified consists of a mixture of minerals of different specific gravities. In place of sieve analysis the procedure recommended involves the use of a glass settling-tube which is considered to give ideal classification and thus serve as a standard against which mill classification will be compared and relative efficiency calculated. This procedure sounds logical. Perhaps the greatest difficulty may lie in securing an ideal classifier acceptable to every one.

Jan 1, 1930

By E. Gregory, C. G. Goetzel

The outstanding elevated temperature properties of materials made from sintered aluminum powder have been well established in recent years.1,2 and considerable investigation has been carried out on the structures which appear to be responsible for this type of strengthening.2,3 The maximum operating temperature of such materials is severely limited, however, by the low melting point of the aluminum matrix; and, therefore, considerable interest was aroused in methods of introducing the

Jan 1, 1959

By J. Holms Pollok

The determination of specific gravity dates from such antiquity, and the various published methods of determining it are so numerous, that one may well be skeptical as to the value of a new means of obtaining so well-known a quantity. I make no claim to any great novelty for the little device here described, the principles, though not the convenient details, of which are more or less embodied in the publications of Mr.

Jan 1, 1900

By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson' obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock' used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

By Fuad S. Maayeh, Robert J. Evans, Paul M. Yavorsky

A description and capabilities of the Mine Roof Simulator at the Pittsburgh Mining Technology Center is illustrated for testing longwall roof support equipment. This unique Mine Roof Simulator has the capacity to exert 3 million lbs. of compressive force vertically and 1.6 million lbs. of force horizontally to simulate loads on hydraulic supports typically found in longwall mining. The supports that undergo testing are instrumented with strain gauges and photoelastic coatings such that critically strained areas become readily apparent. These critically strained areas are redesigned or retrofitted with appropriate reinforcement and retested. A data base will be accumulated from several support designs that will lead to an optimized design that will have the potential to reduce downtime by malfunctions of supports and thus increase productivity. A typical test procedure and analysis is given for a two leg 350 ton shield along with a description for placement of strain gauges, displacement gauges, and hydraulic pressure monitors for critical sites.

Jan 1, 1982

R. W. Guard (General Electric Co., Schenectady)— The method of fractional replication discussed by the author has proven very valuable to us in applied research connected with alloy and process development where many of the same experimental difficulties exist. Several of our experiences may be of assistance to those who want to apply the method in these fields. Contrary to the author's observation that interactions are rarely significant, we have found in a number of cases that first order interactions exist which are significant and metallurgically important. Because of this difference there are two further precautions which should be taken in order to minimize the difficulties from this point. First, in evaluating the importance of

Jan 1, 1957

By M. E. Wadsworth

The chief value of a paper like this consists in its statistical tables, putting on record material useful to future inquirers. The data here given have been compiled from time to time as far back as 1874, and subsequently brought up to date. Much of the data could only be procured by personal inspection of the catalogues, as for example those relating to the Lawrence Scientific School, which were taken at that time from the catalogue of Harvard University, on file in the University Library, by the present writer, then an instructor in that institution. These tables of statistics were first prepared for publication by the present writer in 1888-1890 and published in his "Report to the Board of Control of the Michigan College of Mines " (Michigan Mining School) for 1886 to 1890. Later they were revised, enlarged and brought down to date in his reports to the same Board for 1890-92; and since that time they have been, at his request, revised, greatly enlarged and kept up to date by Mrs. Frances H. Scott, the efficient Librarian and Secretary of the Michigan College of Mines. Great credit is due to her for her devotion to this work and her untiring efforts to have the statistics complete as far as possible. The accompanying running commentary is given simply as a string to hold these statistics together, and in order to call attention to a few points. In compiling any tables like those accompanying this paper, one is confronted by serious difficulties, some of which render these results only approximate. In order to insure greater correctness and fullness in the statistics to be published the writer's reports for 1890-92 were sent to the president of every college, university, and technical school in the country, so far as known. Accompanying this was a personal letter which asked of each one his aid in correcting any errors, and in giving fuller statistics. But relatively few answers were obtained, and subsequently from one to many letters have been sent to each institution not formerly reply-

Jan 1, 1898

By D. S. Tomalin, D. F. Stein

The effect of reducing oxygen to low concentrations on the fracture of high-purity iron single crystals has been examined at 78° and 20°K. It is found that iron single crystals grown by the strain-anneal method usually contain a few occluded grain boundaries which may become embittled in the presence of oxygen, thereby nucleating cleavage fractures. High purity with respect to interstitial elements was found to inhibit twinning and evidence is presented for an orientation dependence of the resolved yield stress. Deformation occurred by slip rather than twinning at both temperatures of testing with elongations of as much as 9 pct at 20°K. THE fracture properties of iron single crystals have been observedl-3 to be a function of temperature, orientation, and purity. Allen, Hopkins, and McLennan1 demonstrated that at 78°K iron single crystals became increasingly brittle as the tensile axis approached the (001) pole of the stereographic unit triangle. Iron crystals with the tension axis near a (001) pole were completely brittle and orientations near the (011)-(111) boundary were very ductile, achieving a 100 pct reduction in area prior to fracture. Later work of Biggs and pratt2 and of Edmondson3 demonstrated that by reducing the carbon content of the single crystals the transition between brittle and ductile failure at 78°K could be shifted to orientations nearer the (001) pole. Ed-mondson went further and pointed out that any mechanism which tended to increase the yield strength of the iron (i.e., carbon addition, pre-strain) also increased the tendency for brittle behavior at 78°K. Thus by a reduction of carbon content Biggs and Pratt were able to obtain ductile behavior to within 20 deg of the (001) pole, and Ed-mondson was able to obtain ductile behavior to within 26 deg of the (001) pole. Edmondson's material had a total interstitial content (carbon, oxygen, and nitrogen) of approximately 60 ppm and, although Biggs and Pratt reported no analysis, indications were that their iron contained comparable impurities. Stein, Low, and seybolt4 purified iron single crystals to a total carbon, oxygen, and nitrogen content of approximately 20 ppm. They observed a lowering of the yield stress with this increased purity, and thus one might have expected an observation of increased ductility. Although they tested specimens of orientations which the previous workers had indicated should be ductile, the crystals failed at a 78°K in a brittle manner with little elongation. Stein noted,' however, that about 90 pet of the failures could be traced in origin to occluded grains. Allen et al.1 and Edmondson3 do not report examination of their cleavage surfaces, but Biggs and pratt2 reported that microscopic examination of the cleavage surfaces of many of their specimens revealed the presence of small occluded grains. Honda and cohen6 and Keh7 have also observed the initiation of fracture at occluded grains in iron single crystals. Therefore, the additional complication of occluded grains must be considered in studying the properties of iron single crystals and the origin of fractures determined if the ductility exhibited by the crystals is to be considered meaningful. Various investigators8-12 have studied the effects of impurities on grain boundaries in high-purity polycrystalline iron. Rees and Hopkins10 showed that the addition of oxygen to low-carbon (0.002 pet) iron weakened the grain boundaries, causing a shift from transcrystalline to intercrystalline fracture and a progressive decrease on the brittle-fracture stress with increasing oxygen content. In addition, it has been shown by Low and Feustel11 that the addition of carbon to polycrystalline iron containing oxygen eliminated grain boundary brittleness. Thus, oxygen can embrittle grain boundaries in high-purity polycrystalline iron, but the addition of an appropriate amount of carbon can eliminate the oxygen-induced brittleness. The oxygen content (19 ppm) of the iron "single crystals" employed by Stein el al. was large enough to suspect impurity effects at the occluded grain boundaries. Allen et al.1 Biggs and pratt,2 and Edmondson3 may have masked any occluded grain problem in their specimens considering the relatively high carbon levels they employed. stein13 demonstrated that the addition of as little as 0.9 ppm C to previously purified (less than 5 x 10-3 ppm C) "single crystals" would increase the elongation from a few percent to more than 20 pet at 78°K and the fracture was not associated with grade boundary initiation.

Jan 1, 1965

By Henry M. Howe

The natural effect of large ingot-size should be to increase segregation. I have previously pointed1 to the excessive segregation in many large ingots as tending to confirm this, but I have shown that in case of ingots less than 16 in. square this expected effect of ingot-size is liable to masked by that of Note.—The "maximum enrichment" of each ingot, i.e., the excess of the richest spot over the average of the whole ingot, is first calculated in percentage of that average. The average of the maximum enrichment of the several ingots of a given group is the abscissa in Fig. 1. The number beside each spot tells the number of cases which that spot represents. FIG. 1.—Influence of Ingot-Size on Maximum EnrichNent in Steel Ingots. other variables. Under these conditions we should expect that, if large ingot-size really does tend to increase segregation, this effect would be shown by taking the average of large numbers of cases, so that the effects of these other variables might off-set and cancel each other.

Jan 1, 1910

By Kenneth A. Gutschick, Robert S. Boynton

Lime has become a general and loosely used term to denote almost any kind of calcareous material or finely divided form of limestone or dolomite, as well as burned forms of lime. However, according to Webster, lime is only calcined limestone (known as quicklime, unslaked lime, or calcium oxide). It also embraces the secondary product of quicklime, i.e., hydrated lime or slaked lime (calcium hydroxide). There are two basic types of limestone used for lime manufacture-high calcium and high magnesium (dolomitic). The dolomitic quicklimes and hydrated limes correspond to their "high calcium" counterparts. The only difference is that the dolomitic types are a combination of the elements calcium and magnesium, in varying percents, whereas high calicum limes contain less than 5% MgO down to 1/2%. In either case a pure form of limestone of at least 97% combined carbonate content is needed to make salable lime, barring a few exceptions. The calcination of both types is diagrammed chemically as follows: [ ] In the foregoing reversible reactions the limestone is burned (calcined) in lime kilns, with the carbon dioxide content of the stone expelled as a gas. The weight loss during calcination of pure high calcium limestone is 44%; with equimolecular dolomitic limestone, the weight loss is 48%. Since lime has a strong affinity for CO_, particularly if moisture is present, it will readily revert to its original carbonate form. This occurs when quicklime "air-slakes" and adsorbs CO.. from the air. Thus, quicklime is perishable and should be stored in dry, water-tight areas. Depending upon the type of kiln used and the physical structure of the stone, the size of the quicklime may range from sandlike granules to 8 in. lumps. However, pebble sizes ranging from 1/4 in. to 2 in. are the most common. Screened quicklime fines are also com¬pressed (pelletized) into 1 in. pellets. For some purposes ground or pulverized forms of quicklime are used, ranging from No. 10 mesh to dust. Generally a pebble of quicklime is about the same size as the pebble of limestone before calcination (perhaps shrinking slightly). A more stable form of lime is hydrated lime. This is obtained by adding water to quicklime, slaking it into a dry, fine, subsieve size white powder. Because its affinity for moisture has been satisfied, it is not vulnerable to further moisture like quicklime. However, it has the same strong affinity for CO_. The following reversible chemical reactions illustrate how hydrated lime when heated (or dehydrated) can revert to the original oxide form:

Jan 1, 1975

By H. H. Taft

IT has long been known that the volcanic area south of Belmont, Nye county, Nevada, had mining possibilities. Some of the old-time prospectors knew that gold existed there. Its remoteness from any source of supplies, its long distances from water, the absence of game, and more, perhaps, the lack of grass for animals to subsist upon, has made this an unattractive region in which to search for mines. The decline of the Comstock mines, the exhaustion of sun-dry large and rich ore-bodies, the high cost of mining, marketing, and particularly the ruinously high freight-charges upon refractory ore that had to be shipped to distant smelters, have kept investors out of Nevada for the last few years; and mining people have hardly yet awakened to the importance of Tonopah, Goldfield and perhaps the newer and less developed districts. The discovery of Tonopah by J. L. Butler, who located the Mizpah Claim in May, 1900, and the fortunes soon realized there, attracted many people. As the boom declined, many went away, some scattering out into the surrounding country, and the population is now about 7,000. In the fall of 1902 a discovery of gold was made 23 miles south, in what is now known as the Sandstorm group, 4 miles NW. of Goldfield. In the winter of 1903-4 the Combination, January and Florence mines were discovered, and shipments of high-grade ore soon followed. In January, 1905, there were 10,000 people in Goldfield. In June, 1904, rich gold-ore was found 85 miles SE., at the foot of the south end of the Kawich mountains, but this discovery was kept quiet until a re-location could be made. On August 10, 1904, the Bullfrog claims, and a month later the Ladd mountain and neighboring claims, were located. The Shoshone group was located September 24. This district is

Nov 1, 1905

Edwin A. SpeRry, Denver, Colo. (communication to the Secretary*) :—Since writing my former paper on this subject I have had several discussions concerning some of the statements contained therein, with men who have had a large experience with the old form of buddle, both in this country and in Cornwall. The present paper gives a brief statement of some of the points debated, together with the arguments and proofs in their substantiation. The first point is the question of the capacity. In my origi-

Jan 1, 1904

By C. H. Herty

The reactions that occur in the basic open-hearth process are complicated and are subject to many different factors such as temperature, slag composition and rate of boiling of the bath. It is difficult, therefore, to present an extended theoretical discussion of open-hearth operations without confusing the theory of the process with the application of the theory. This paper attempts to present some of the theory of the open-hearth process without mentioning theory at any point, simply giving some of the practical applications of results founded both on theory and practice and on experimental work both in small and large furnaces. It is hoped that an answer to a number of questions commonly asked by the open-hearth operator may be found in this paper. Discussion of the subject matter is taken up more or less in the order in which a heat ie worked, beginning with the oxidation of the scrap charged, sulfur absorption by the scrap, calcination of the limestone, and extending into the pig iron for the charge, the slags formed during the process, and some of the phenomena occurring in deoxidation of the steel and in its action in the molds. Oxidation of Scbap When scrap is charged into a furnace it immediately begins to oxidize, Oxidation is carried out by.three reactions: Fe + H20 + FeO + Hz (absorbs heat) (1) Fe + C02 + FeO + CO (absorbs heat) (2: Fe+ ½O2 + FeO (gives off heat) (3: The product of oxidation contains some Fe3O4, but FeO usually predominates on account of the iron present in close contact with the scale formed For a given type of scrap the amount of oxidation is controlled by thc fuel and by the excess air being carried in the furnace, the temperature 01 the furnace, and the length of time that the scrap is in contact with the furnace gases. In general, less oxidation occurs when the furnace is rur hot so that the scrap melts rapidly. More important in operation thar the two variables atmosphere and temperature, is the type of scrap being

Jan 1, 1929

The Garfield plant of the American Smelting & Refining Company is situated about seventeen miles west of Salt Lake City, on the Los Angeles & Salt Lake Railroad, and has freight service by the Denver & Rio Grande Western. Western Pacific and Bingham & Garfield Railways. The site lies between the picturesque Great Salt Lake, with its mountain islands and the northern point of the Oquirrh Range, which forms the western boundary of the Salt Lake Valley.

Jan 1, 1925

By Benjamin C. Allen

The surface tensions of liquid chromium and manganese were determined by a modification of the dynamic drop-weight method and found to be, respectively, 1700 * 50 and 1100 * 50 dynes per cm at their melting points. Molten drops were formed LITTLE is known about the surface tension of liquid chromium and manganese, even though they are technologically important metals and widely used in steelmaking. In the past, direct determinations have been hampered by their high reactivity on the lower end of a vertically held rod inductively heated under argon. The technique essentially reproduced surface tensions reported for liquid nickel and zirconium using static drop-shape methods. and vapor pressure. In this work, surface tensions were measured by the drop-weight method, using induction heating under argon. EXPERIMENTAL WORK Chemical analyses of rods used are given in Table I. Chromium rods were prepared from iodide-process crystals which had been are-melted, hot-extruded, warm-swaged, and centerless-ground.'

Jan 1, 1964

By E. S. Hutchinson

The subject of the influence of coal-dust in mine-explosions has received considerable attention both in England and on the continent of Europe, but until the recent disaster at Pocahontas, Va., it seems not to have been of special interest to engineers in this country. The reason, perhaps, is that most of our bituminous mines are worked by short shafts, slopes and drifts; few have been specially dry; and the explosions that have occurred could readily be traced to fire-damp with 110 complicated circumstances. The object of the present paper is to bring together, for the convenience of members of the Institute, the principal English opinions upon this important subject. Messrs. Lyell and Faraday, in their report to the Home Secretary," in England, on the Haswell Colliery explosion in 1844, seem to have been the first to point out that dust fed the flame originating in a

Jan 1, 1885

By M. E. Tyrrell, Alan H. Goode

The application of a simple, two-dimensional computer technique for evaluating rock burst potential in cut-and-fill stopes was investigated. The principal purpose of the study was to compare the effectiveness of high-modulus fill and destressing as aids in the control of rock bursts. Two conclusions that are probably of general applicability are drawn. First, high-modulus fill is ineffective as a means of increasing the mine stiffness and acts to control rock bursts only if it supports enough load to reduce substantially the stresses on the unmined vein material. Second, destressing is most effective if it is performed when the vein material is near the point of failure.

Jan 1, 1975

Discussion of the paper of, RICHARD H. RICE, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 89, May, 1914, pp. 721 to 743. S. G. VALENTINE, Oxford, N. J.-In a paper read at the New York meeting of the Institute last February I presented some notes taken from our experience with the turbo blower operating on a blast furnace. In connection with Mr. Rice's very interesting paper there are a few items that might be of further practical interest. The question of the reliability of this type of blower will naturally be presented. In this connection we would say that our turbo blower has been in practically continuous use during the present blast, which was begun June 7, 1912, with only three interruptions for repairs of any consequence. Soon after blowing in there was developed a tendency of the blower to surge or pulsate. This occurred on operating at a point considerably below the normal capacity of the machine, and was checked with comparatively little trouble by throttling the intake slightly and taking up a small lost motion on the governor connections, a legacy of the previous blast that had not been attended to. All this required only a few hours' time. In. March, 1914, the furnace being banked on account of a blizzard that cut off our freight deliveries for five days, the opportunity was used to replace the carbon packing on the steam-turbine shaft and to repack the steam inlet valves. In June, 1914, the blower was off 8 hr. to replace an oil ring and scrape a bearing. With these exceptions we have made continuous use of the machine and find we can depend upon it with entire safety as a piece of machinery.

Jan 4, 1915

By Pablo Hadzeriga

Great Salt Lake brine was subjected, in laboratory scale, to conditions simulating solar evaporation. Solid phases and the variation in composition of the liquid phase throughout the potassium salts crystallization zone are presented. These experimental results are discussed and compare with stable equilibrium data of the quinary system Cl-, SO4, Na+, K+, Mg + + and H2O. The Great Salt Lake brine in Utah is a vast reserve of several potential chemicals which has attracted much attention in the recent past. From the standpoint of an ore reserve, it may be said that the lake contains a low grade ore which has to be concentrated by evaporation of water. Because of the fairly favorable weather conditions in the Great Salt Lake area, it seems reasonable to consider solar evaporation as an economical means of concentration. From the view of phase chemistry, the main constituents of Great Salt Lake brine make it belong to the five component system: C1-, SO4=, Na+, K+, Mg++ and H2O. Because of their low concentration, the presence of other elements may be regarded as having little effect on the equilibrium of the five main components. Equilibrium data for the quinary system of our interest has been available for many years. Using these data, it is possible to calculate how the brine of the lake will concentrate when subjected to solar evaporation. In practicing solar evaporation, the weather factor and supersaturation conditions cannot be ignored, but their introduction into calculations using equilibrium diagrams is almost an impossible task. With the experimental work presented in this paper, an attempt is made to compare the stable equilibrium data of the quinary system as applied to the case of the Great Salt Lake brine and the dynamic equilibrium when that brine is subjected to continuous solar evaporation. Sea water brine belongs to this quinary system when only the major constituents are considered. The study of this system has been carried on since the last decades of the nineteenth century. The reason for these intensive studies was to give a geological explanation to the underground potash deposits. AS a result, many theories were presented trying to relate the equilibrium data with the geological formation, paragenesis and metamorphism of these deposits. Two main approaches were followed for the equilibrium studies of this quinary system. One of them, and the best known to us, was the school started in Germany in the last century by J. H. Van't Hoff. The other one, which started about the same time, was the school of N. S. Kurnakov in Russia. Both approaches were different and as a consequence generated opposite theories about the geological formation of potash deposits. The Van't Hoff school studied the quinary system of sea water under careful laboratory control, resulting in stable phase diagrams. During these studies, Van't Hoff recognized the difficulties in crystallizing some double salts.' ". . . . we unexpectedly found that some compounds whose formation in the solutions under investigation was possible at 25°C, nevertheless totally failed to put in an appearance. These, not to mention the calcium salts, were leonite, MgSO4 . K2SO4 4 H2O; kainite, KC1-MgSO4 . 3 H2O; and kieserite, MgSO4 .H2O. Even exceedingly slow crystallization with the addition of the compounds themselves did not remove the condition of supersaturation in the case of these bodies." However, those salts (leonite, kainite, and kieserite) were included in the stable phase diagram at 25°C as shown in Fig. 1 using D'Ans data.3 The figure also shows the sequence of crystallization of the Great Salt Lake brine according to the stable diagram. In later studies by the Van't Hoff school, especially by D'Ans,3 Karsten,4 Autenrieth,5,6 attention

Jan 1, 1968

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951