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By Walter R. Hibbard, Walter L. Finlay

INTRODUCTION THE key feature of the lattice coherency theory of precipitation hardening1-6 is the forced coherence between matrix and precipitate which elastically strains both lattices and is believed to be the major source of strengthening in precipitation hardening. In systems exhibiting age hardening, the atom movements leading to precipitation are not at all extensive and are such as to require the minimum amount of energy to produce the interface; that is, the new lattice forms in such a way as to be as nearly as possible a continuation of the old with a matched, coherent plane at the interface at least during the initiation of the precipitation. The crystallographic sequence whereby regions of the matrix change to the precipitate lattice usually can be resolved into a set of shearing operations.5,6 Conversely, the perhaps novel speculation is made that solution of a second phase is accompanied by shearing movements which are possibly the reverse of the precipitation shearing movements. A basic premise of the investigation reported in this paper is that precipitation and solution shearing movements constitute structural weaknesses which might cooperate with applied stresses to facilitate plastic deformation. Another basic premise of the investigation is that the application of hydrostatic pressure to a precipitation hardening system will significantly alter the degree of disregistry across the matrix-precipitate interface and thereby significantly affect the course of age hardening. Two binary precipitation hardening systems were investigated: 12 pct zinc in aluminum which undergoes transformations, both precipitation and solution, by a simple crystallographic mechanism; and 4 pct copper in aluminum which undergoes a complex transformation in precipitating and dissolving a second phase. The effects of the application of uniaxial tensile creep stress during elevated temperature aging of both systems and of hydrostatic pressure during the elevated temperature aging of 12 pct aluminum-zinc were then investigated. Previous Investigations Van Wert in 1935,7 studied the effect of hydrostatic pressure on the room temperature age hardening of a few precipitation hardening systems. The latter were rather unfortunately selected since none is known to exhibit any marked volume change on aging and the majority were complex commercial alloys the precipitation mechanisms of which are not known. Jenkins, Bucknall and Jenkinson,8 in 1944, applied tensile creep stresses to a complex coppernickel-silicon alloy at various temperatures. The complexity of the alloy and the industrial objective of the work did not permit an appreciable addition to the theoretical understanding of either deformation or precipitation hardening.

Jan 1, 1948

AN intermetallic compound, Ni3A1, has an ordered fcc structure of type Ll2, and shows peculiar dependence of the yield stress upon temperature; i.e., the yield stress increases by a factor of six upon raising the temperature from 77" to 900K1, 2 This compound is technologically important, since many nickel-base superalloys owe their high-temperature strength to the peculiar yield stress behavior of Ni3Al. The only study of the elastic behavior of this compound was made by Davies and Stoloff,1 who determined Young's modulus of poly crystalline Ni3A1 between 300" and 730°K. The determination of single-crystal elastic constants of Ni3A1 is therefore of interest in connection with dislocation dynamics and is reported in this paper. A single-crystal specimen, 1 by 1 by 3 cm, was cut from an ingot generously supplied by Dr. B. H. Kear of Pratt & Whitney Aircraft. Following initial machining with a Servomet and a surface grinder, the specimen was etched and annealed at 1100°C for 5 hr in vacuum followed by furnace cooling. Two parallel faces were oriented normal to within ±l deg of a [I101 crystallographic axis by the back-reflection Laue technique. The parallel faces were hand-lapped, etched, and polished by the usual metallographic procedures. Final thickness along the [I101 axis was (0.9325 * 0.0005) cm. Chemical analysis gave an average composition of 87.35 pct Ni. Total impurity content is esimated to be no more than 0.1 pct. The elastic constants were calculated from measurements of ultrasonic waves which were propagated along the [110] axis. A longitudinal wave and two shear waves whose displacements are aligned along the [ 110], [li~], and [001] directions, respectively, are necessary in order to completely specify the three elastic constants. Two 3/6-in. quartz transducers were bonded to the parallel faces of the sample with ~ac-seal.3 Although this bond was sensitive to thermal shock, it performed satisfactorily over the entire temperature range for both longitudinal and shear wave propagation. A frequency of 5 mHz was employed in the method of Williams and Lamb4 in order to measure the absolute value of the ultrasonic velocity. The pulse-overlap technique of Mcskimin5 was also used at this frequency in order to determine the shift in the ultrasonic velocity

Jan 1, 1970

By Wm. A. Haven

As soon as the likelihood of American participation in the war was established, and in spite of the fact that we can produce almost as much as all other countries combined, the demand for prompt deliveries of iron and steel products from American factories began to exceed their utmost capacity, and, after fifteen months of practically full operation, has continued to do so. Therefore, it would seem worth while to review some of the aspects of the supply and demand for steel as well as the efforts that are being made to bring them into balance. It is still being debated as to whether the situation should be defined as a real shortage that will persist through the emergency period or as a temporary one than can be relieved by less drastic measures than a Government-sponsored program of expanding existing plants and building new ones.

Jan 1, 1942

By M. C. LYNN

RECENT completion of a $40,000 lubricating oil plant will make it possible for students in the School of Petroleum Engineering at the University of Oklahoma to carry out on a large scale the entire process of refining crude oil, from the time it is received in tank cars and pumped through the 1/4-mile University pipe line to storage tanks on the campus until the various products appear in finished form. This plant is part of a $100,000 expansion program which this school has been carrying out during the past year. Two years ago the Oklahoma State Legislature appropriated $50,000 for the School to use in improving its laboratory facilities. A few months later a $30,000 PWA grant was ob-

Jan 1, 1937

By Benj. E. Shackelford

THE present paper is concerned with typical temperature values experienced in lamp-filament measurements as made on regular factory and engineering products. It deals with the relations existing between temperature, efficiency, lamp size, and life of incandescent lamps, insofar as they affect the rating of the product and its use by the individual consumer. The temperatures measured lie in that range covered only by the general method of radiation pyrometry, as opposed to direct methods used under contact conditions. The range of temperatures ordinarily experienced extends from about 2125° K., for the now almost extinct carbon-filament lamp, to 3200° K. for the comparatively new tungsten-filament motion-picture lamp. Most of the more common sizes of tungsten lamps have temperatures ranging from 2500 to 3000° K. Because of the high temperatures involved and the relatively small area of the sources used, we are practically restricted to two methods of measurement, both of which depend on the light radiated front the filament. The first and more usual method is that of the Morse pyrometer, dependent on the variation in temperature of the amount of light of a given color range yielded by the filament. In this case, the measured temperature is that of a small part of the incandescent body, that is, the part which is focused on the comparison filament. The second method, known usually in this country as that of "color match" and in England as "color-identity" is based on the color of the total light yielded by the filament, the comparison being facilitated by the use of an ordinary photometer- head. A more definite idea of the temperatures involved in the case of filaments of various vacuum and gas-filled lamps, is given by Fig. 1. The size of the lamp, in watts, is plotted along the horizontal axis and the temperature of the filament is plotted along the vertical axis. The lamps concerned are regular product, rated for 1000 hr. life. The temperature values for the old 16-candlepower carbon lamp and the new motion-picture lamp are shown by the cross and circle respectively.

Jan 9, 1919

By William Glenn

In their account of chromium, Roscoe and Schorlemmer (Treatise on Chemistry, London, 1879) state that "In 1762 Lehmann, in a letter to Buffon, de nova minerœ plumbi specie crystalline rubra, described a new mineral from Siberia, now termed crocoisite." In 1786 Lehmann analyzed it (Nicholson's Jour., Dee., 1798) and found that it contained chiefly lead, and that the " mineralizers " were arsenic and sulphur. It was next examined in 1189 by Macquart and Vauquelin, who stated that it contained an intimate mixture of iron, alumina, and lead peroxide. The account of their work was published over the name of Macquart. Vauquelin (Louis-Nicolas) was a Norman peasant, who had studied in the village school, and at the age of fourteen was a laboratory-boy in a pharmacy at Rouen. Later, he found his way to Paris, and in 1789 was assistant to Fourcroy, a pharmacist and a teacher of note. It was here that he met Macquart, with whom he did the work on Siberian red lead, and at this time his friend Cheradame taught him his Latin.

Jan 1, 1896

By R. E. Phelan

WHILE 1931 was a most important year in the history of Canadian copper smelting and refining, nevertheless, due to the low price of copper and the in- ability of the International Nickel Co. to market its full capacity of nickel. the production of both copper and nickel was considerably less than the total installed capacity for the production of these metals. IIY the nor- mal course of events, 1931 should have seen a great increase in the production. of both copper and nickel in Canada, because the large extensions to both the copper smelting plants and the copper and nickel refinery capacity, which had largely been completed in the year 1930, should be showing their effect.

Jan 1, 1932

By H. W. Hardinge

DISREGARDING for the present the economic side of a new device, let us turn to that feature of the conical pebble-mill which is of interest from a scientific point of view, and consider the device as a puzzle in which the theories of the cylindrical type of mill have been increased. Many articles have been written on the theory of the tube-mill, and explanations have been made which do not explain.; but these have evolved suggestions of practice which have resulted in changes in the tube as to length, diameter, feed, discharge, speed of rotation, rotation on hollow trunnions, rotation on rings, and changes in the operation as to quantity and size of pebbles, charge of load above or below the axis, crushing by causing the larger pieces of the material of the charge to act as grinders, etc. The practical worker in crushing is first interested in the endeavor to reach an economic means of accomplishing a desired end; but the improvements in crushing-practice have been largely left to the manufacturer of machinery, who, as a rule, has little, if any, knowledge of the specific requirements-such as sizing for concentration without pulverizing the metals, instead of pulverizing the rock or gangue; the metals being the more friable, while the rock is tough and not so easily disintegrated. A reversal of this practice is the aim of sliming direct for cyanidation. In the ordinary cylindrical mill, having a diameter of 4 or 5 ft. and a length of from 15 to 27 ft., it has been found that the maximum size of the particles of the charge must not exceed 1 mm. (about 25 mesh), some of which, upon entering the mill, is immediately reduced to a slime. The work upon the individual particle having been finished, it should be passed out of the mill; but, instead of this, the finely comminuted material

Jan 7, 1908

By E. D. Meier

SINCE Dr. St. Albans, in 1840, began to build successful watertube boilers—some of which are still in use—the gravity-return water-tube boiler has been built in many forms, more or less familiar to all who have studied the subject. A single firm in this country published recently a pamphlet, showing some fourteen modifications of their boiler during about as many years. There were hence available to the thoughtful inventor of this latest form many data showing what forms were to be avoided, as well as the effects sure to follow certain erroneous methods of construction in the older types. Improvements in materials, tools, and workmanship made possible, forms formerly prohibited by excessive cost. The first Heine boiler was built by A. Borsig & Co., for the

Jan 1, 1886

By Webster, Wm. Reuben

THE greatly enlarged demand for small sizes of seamless copper tube which has recently occurred, due particularly to the rapid growth of the electric household-refrigerator industry, has emphasized the superiority of phosphorized to tough pitch copper for the purpose of producing this commodity. In the manufacture of this material exceedingly heavy reductions by cold drawing are employed, customary practice involving as much as 90 per cent. reduction of cross-sectional area in four runs without intermediate annealing. Although this superiority has long been recognized by tube makers, no quantitative expression of it has heretofore been published. It is believed that the data herewith presented mill serve this purpose. Recent investigators are not in agreement as to the relative mechanical properties of copper containing small amounts of oxygen as compared with copper containing sufficient oxygen to produce that condition known as tough pitch. Hanson, Marryat and Ford1 found that "oxygen has a relatively small effect on the properties of copper." Johnson, on the contrary, states "it cannot be denied that it (tough pitch copper) is inferior to deoxidized copper . . . where severe mechanical manipulation is concerned." These authorities in the reports of their investigations, as might be expected from their conclusions, do not present data of a character requisite to a conclusive determination of the question.

Jan 1, 1927

By F. A., King

THE problem of the proper size and capacity of the open-hearth furnace has been a predominant issue ever since its inception some sixty years ago. The original furnaces, built in 1868 at Landore, England, were only to 3 to 4 tons capacity, and from' this there has been a steadily increasing and almost uniform rate of expansion until furnaces producing 300 tons are in successful operation today. At the end of the first half of this 60-year period, or about the year 1900, 50-ton furnaces we're common. Up to this time the problems of expansion had been largely those relating to suficient capital and the engineering development of larger units. But as 75, 100-ton and larger furnaces were proposed apprehension grew and other questions assumed leading consideration.

Jan 1, 1928

By Persifor Frazer

IN his “Final Report," Vol. II, part second, p. 763, Prof. Rogers sums up the metalliferous veins of the mesozoic sandstone by remarking that these are not associated with dykes or trap-rock, but are independent metalliferous injections. But singularly enough, in enumerating the different kinds of ores, no mention is made of

Jan 1, 1877

By A. P., Svenningsen

ECONOMICAL handling of a minimum of 25,000 tons of minus 3/4-in. ore per day, grinding it to 2 per cent on 65 mesh, and effecting a high recovery of the copper at the lowest possible cost were the principal aims in the design of the new Morenci concentrating plant. Dealing with a tonnage of this magnitude, it is obvious that lost motion cannot be tolerated. When ore is carried on a conveyor an unnecessarily long distance or elevated to a greater height than necessary, or when pulp flows in a launder by a circuitous route thereby losing elevation and distance, we have lost motion which is always costly both from the standpoint of construction and operation. In addition to the 25,000 tons of ore which must be handled, 100,000 tons of water per day has to be carried through the plant in the treatment of the ore. Though water is not so difficult to handle as the ore, the combined tonnage represents a figure which could easily run into a considerable monetary loss per day if all phases of the design were not carefully followed with the idea of eliminating any unnessary handing of materials.

Jan 1, 1942

By Persifor Frazer

In his " Final Report," Vol. 11, part second, p. 763, Prof. Rogers sums up the metalliferous veins of the mesozoic sandstone by remarking that these are not associated with dykes or trap-rock, but are independent metalliferous injections. But singularly enough, in enumerating the different kinds of ores, no mention is made of

By A. G. H. Andersen, A. W. Kingsbury

SILICON bronzes containing iron are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith' and of A. G. H. Andersen .2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 determined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at 1100°C. Hanson and Ford," using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. Of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West7 have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,1,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. PREPARATION OF SAMPLES Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates h in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1942

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By Schneider, W. G.

IT is not my purpose to burden you with many statistics. The charts herewith should be considered merely as indicating the trend. I believe' that is what is really of interest to us. It is difficult, if not impossible to forecast with any assurance future developments, because of possible new mines, competitive materials, curtailment' or increase in the use of the metal in certain markets, and many other factors that have a vital bearing on any industry. Fig. 1 shows United States smeltet output of copper, starting with 1845. It is estimated that in 1928 the smelter output of copper will be about 1,010,000 tons. Between 1895 and 1905 it increased about 200,000 tons, and between 1905 and 1915 about 240,000 tons. Between 1915 and 1925 the increase was about 140,000 tons. This is an average increase over 30 years of about 190,00Q tons per ten-year period. At the present time the indications are that this demand for increased production will continue. As to whether or not we have the supplies or facilities to maintain this increase or a greater one, remains to be seen. Provided it is possible for United States smelters to increase their production, they should be producing at the rate of about 1,210,000 tons or more per year by 1935.

Jan 1, 1928

By A. E. Brugger

SOME 2,000 years ago Pliny is supposed to have said, "Out of Africa always something new." It may perhaps even now be news to a great many that the Belgian Congo has in recent years been producing approximately a quarter of a ton of diamonds annually. For that is what the 1 1/4 million carats, the recovery from 40-odd operating mines, and about 20 or 25 per cent of the world's normal consumption, amounts to. In 1915, first exploitation operations produced less than 50,000 carats from two mines. The rapid expansion of operations following the Euro¬pean war meant a most rapid development of a virgin land. The interior is now reached by air in one day from the mouth of the Congo River, where steamers unload mail and passengers from Antwerp. This trip formerly consumed 4 to 6 weeks by a narrow-gage, wood-burning, railroad around the rapids of the lower Congo and Livingston Falls; by river boat to the heads of navigation, Djoko Punda on the Kasai or Luebo on the Lulua; and thence by caravan of native porters over narrow-trails to head¬quarters on the Tshikapa. Hundreds of miles of automobile roads have been constructed over veldt and through forest, bridging streams and ferrying rivers. The railway from Capetown to the Katanga copper district to the East, once two months away by trail is now reached in 2 or 3 days over fair automobile highway. Native "boys" who a few short years ago wore little more than a smile and a string of beads and to whom a wheelbarrow was a complicated piece of machinery, are today driving Fords, tending boilers and engines and operating electrical equipment, or are capable mine workmen, machinists and artisans, and dressed in all manner of cast-off white man's clothing. Even as late as 1920, due to difficulties of securing and transporting machinery during and just after the war, the crudest hand operations were the rule for the excavation, sizing, and concentration of the diamondiferous gravel. All washing and concentration is now mechanized, using steam or electric power, and where operations are sufficiently large to permit competition with native labor costs, excavation and transportation are also accomplished by machinery.

Jan 1, 1932

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 B. M. Larsen, T. E. Brower

A perspective is presented of the steel plant sulphur distribution and elimination problem from coal to liquid steel ready for teeming, giving distributions of sulphur over a range of coke sulphur content, and some methods of sulphur control, in the blast furnace, external desulphuriza-tion between blast furnace and open hearth, distribution between fuel, slag, and metal, and methods and limitations of control of sulphur in the open hearth furnace. AS a part of the 1951 AIME symposium on sulphur in steelmaking, it was thought that a discussion of the distribution of sulphur throughout the whole series of operations, from coal and ore to finished steel ingots, might have some value in giving a perspective on the whole problem. The following discussion is an attempt to present such an overall picture. The order is that of the actual plant operations, beginning with a very brief consideration of the coking process. Sulphur in Coal and Coke Since by far the largest source of sulphur entering the steelmaking cycle is in the coal used to make coke for the blast furnace, it would seem reasonable to eliminate some of it, either from the coal, or the coke, or during the coking process. This has appeared impracticable up to the present, at least, for two main reasons: the low activity of the organic sulphur in either coal or coke, and because of price limitations involved in treating a low cost material such as coke. A variable portion, usually M or less, of the sulphur is present in coal in the form of pyrites or similar compounds, and a large part of this sulphur may be removed in the coal washery. Most of the sulphur, however, is normally present as "organic" sulphur, intimately associated with the coal structure. Its distribution prevents any separation by mechanical means. Its low activity makes improbable ' any rapid chemical removal, although hydrogen will remove sulphur from both coal and coke. Thus, prolonged recirculation of coke oven gas in the coking process would tend to leave a smaller percentage of the total sulphur in the coke residue. Table I shows a typical distribution of sulphur from coal into products in the coking process. As the sulphur in the coal increases, the sulphur in the coke tends to increase in about the same proportion. Sulphur in the Blast Furnace The best picture of the situation in the blast furnace is provided by a sulphur balance of raw materials entering, and of products leaving, the furnace. The difficulties in accurate weighing and sampling of the variable solid materials entering this process, and the number of hours required for the raw materials to descend through the furnace under variable operating conditions, make it difficult to obtain an accurate balance. However, balances made over periods of weeks or months tend to average out some of these uncertainties. Table I1 presents three typical sulphur balances similar to a number that the writers have calculated. In most of these the slag volume calculated from the sulphur balance is, in some instances more, and in other instances less, than the value corresponding to the best input and output balances of the other slag constituents (lime, silica, alumina, etc.). Probably the greatest source of error in these calculations is the sulphur content of the slag. Despite some possible inaccuracies the balances of Table II show rather definitely the following points: 1—That 87 to 95 pct of the total sulphur input is in the coke and 95 to 97 pct of the total sulphur output is in the slag. Also, that if any sulphur leaves the furnace with the gas it is relatively small, amounting to a possible 1 pct or less. 2—At the lower sulphur coke level of 0.86 pct the total amount of sulphur charged is 15 Ib of sulphur per ton iron increasing to 26 lb per ton at the higher sulphur, intimately associated with the coal struc-rare burdens containing sulphur-rich ores will the total sulphur burden fail to be nearly proportional to the content in the coke used. 3—The 7 to 9 pct of the total sulphur input from the limestone of furnaces B and C is due to the relatively high sulphur content of the stone, 0.226 and 0.265 pct, respectively. In the case of furnace A, the sulphur content of the limestone was only 0.06 pct which resulted in only 3 pct of the total sulphur input coming from this source. It is rather interesting to compare the sulphur balances of a typical ferromanganese furnace with

Jan 1, 1952