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By Frederic Benard

PRIOR to 1936, the Ontario Refining Co. received all incoming blister copper from The International Nickel Company's smelter in the usual form of 460-lb. cakes, or slabs. These were received in open cars in lots of 250 pieces. At the refinery the cakes were unloaded onto narrow-gauge cars, for convenient handling and pickup by charging cranes. In March 1936, an investigation was started on the feasibility of trans-ferring converter copper in the molten state from the smelter to the refinery anode furnaces, a distance of 114 miles. Although common in steel practice, the transportation of blister copper in this form had not previously been attempted and a preliminary study of the various factors involved was therefore necessary. For this purpose, a series of experiments was made in which molten copper, removed at different stages during the furnace cycle, was held in a small portable holding furnace. This vessel was essentially a refractory-lined steel cylinder provided with ports for filling and emptying, heated by an oil burner. Dimensions of the steel shell were 3 ft. 10 in. diameter by 7 ft. 3 in. long, and thickness of refractories depended oil the design and combination used for the particular experiment. The vessel was filled with approximately 2 ½ tons of copper at a predetermined temperature, the lining having been preheated to a definite point by means of an oil burner. All openings were well luted and temperature readings were made every 15 min. by means of an immersion-type thermocouple. In this manner the rate of heat loss resulting with different refractory design could be developed. The ratio of exterior surface to weight of metal was taken into consideration in comparing the experimental results with what might be expected for a full-sized unit, and observations were also made on type and degree of slag accretion. It was not possible to get as much information on this latter point as desirable, but all evidence showed that the problem would be control of slag build-up rather than attack oil refractories.

Jan 1, 1938

By LESTER W. STRAUSS

OUR early knowledge of history and geography attracted most of us to the mineral resources of South America. The romantic tales of the Spanish activities, which were curiously alluring, and Prescott's exceptional bi-Conquest histories-Mexico and Peru-no doubt fired our minds with the .then metallic wealth of the Spanish colonies. Later developments, intensified within the past eighty years, have, however, changed its fame which now rests on such metallics as copper and tin, and among the non-metallics on nitrate of soda and petroleum. South America proper, excluding Panama, is made up of thirteen countries, a coincident parity with our original thirteen States. Its area is given as 7,231,300 square miles, or slightly less than North America (8,037,000 square miles), is made up as follows:

Jan 1, 1930

By E. von Maltitz

IN his highly interesting paper on "Piping and Segregation in Steel Ingots,"1 Prof. Howe emphasizes the effect of successive phases of internal pressure in the ingot in the evolution of gas, and the consequent formation of blow-holes. From his statements in other places, it may be inferred that he does not here intend to ignore the other variable factor, temperature, but rather to discuss this one more particularly. At all events, it is my purpose not to engage in controversy with Prof. Howe, but rather to contribute, towards the complete elucidation of this important subject which we all desire, my own views and experience. If, in doing so, I specially emphasize other factors than pressure, I need not be understood as denying what I do not think it necessary to discuss fully. Nor, in presenting my own original conclusions, need I be understood as claiming to be the first who ever reached or announced them. Many things are asserted or suggested upon inconclusive evidence; and to confirm such tentative propositions may be as valuable a service as to overthrow them. In the following passage, Prof. Howe adduces analogies, based upon the behavior of charcoal and of water, respectively, which seem to me questionable "In general, the. solvent power falls as the pressure falls ; and in general it rises as the temperature falls. Thus, to heat a solid, for instance charcoal, may expel part of its dissolved gas ; and a tumbler of water drawn cold from the faucet gradually evolves gas, as it stands and warms up on the sideboard." (p. 238.) Charcoal is a solid body, which has the property not only of absorbing gases in large quantities, but also of expelling the thus absorbed gases upon heating. A comparison between charcoal and iron as to the absorption of gases is scientifically not possible ; the gas-content of charcoal is partly due to the

Sep 1, 1907

By Clyde Williams

IF you would allow me some liberties, I would restate the title of this talk as "Scientific Research, Our Greatest Resource," because that title would represent more clearly a present-day conception of the metals and minerals situation. It is a subject worthy of careful consideration. Canada and the United States are so similar and interdependent in their national economies that, in the following discussion, examples of conditions in the United States may be interpreted to apply to Canada as well. Moreover, it is a striking fact that the per capita value of mineral production in Canada and the United States in 1940 was almost the same. Therefore, in the consideration of this subject, I have made no attempt to differentiate between the two countries. Consumption of the world's mineral resources in the last few decades. and particularly during World War II, has been so enormous as to require some form of magic to ensure the continued progress of civilization in the face of a diminishing supply of these resources which are so critically essential. As C. K. Leith pointed out, in 1941, indus-

Jan 1, 1947

By L. S. Darken

IN the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be repre-sented satisfactorily by the simple equilibrium expression K - (p1)p1 (p2)p2 . (R1)r1(R2)r2 . where (P) denotes the concentration of a product and (R) the concentra-tion of a reactant in the reaction r1R1 + r2R2 + . . . Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a com-ponent is not proportional to its true mol fraction, But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple com-ponents and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satis-factorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature as ionization or the occurrence of polar and nonpolar molecules-are presumably less effective in metal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By James M. Henderson, John B. Pfeiffer

The recently completed liquid sulfur dioxide plant at American Smelting and Refining Co.'s Tacoma copper smelter in Washington last April is one step by the firm to meet ambient air quality standards in the vicinities of its three US copper smelters. At a capital cost of $18.5 million, the liquid SO2 plant will work together with an existing sulfuric acid plant to treat all gases generated by the copper converters. Designed to handle up to 45,000 cfm of converter gas utilizing the Dimethylaniline (DMA) process, this plant is expected to recover about 51% of the total smelter input.

Jan 11, 1974

By Robert T. Chapman

The revolution in equipment for blasthole drilling, ore loading, and ore hauling has been so rapid over the last ten years that it has generated an important new profit potential in the mining industry. With the new high-capacity machinery now available, it is possible for a mining enterprise to earn a profit from larger and lower grade orebodies than ever before despite the ever-increasing burden of rising costs. Just what such equipment can accomplish when coupled with improved mining practice has been demonstrated with startling success at the No. 1 mine of Minerva Oil Co. near Cave-in-Rock in Hardin County, Ill. The No. 1 is an underground operation which has been producing fluorspar and zinc ores and concentrates continuously since 1944. A few years ago, when the mine neared the familiar cross-roads where rising costs, increasing tonnages, and relatively static product prices converge, company officials decided to bolster the operation with new mobile equipment. They chose three machines which proved so effective that output at the No. 1 doubled between 1963 and 1965,while costs dropped by about 40% in the same period.

Jan 11, 1966

By P. A. Beck, M. V. Nevitt

All binary and a number of ternary u alloys formed by first long period transition elements were examined and found to be ferromagnetic at low temperatures. The Curie temperatures for these alloys were measured. It was found that the correlation of the Curie temperature with composition may be described qualitatively in terms of the contributions of the various component atomic moments to the saturation moment of the alloy. Ternary Fe-Cr-Mo u phase alloys were also found to be ferromagnetic, with a Curie temperature dependent on the iron content and largely independent of the unit cell dimensions. Similar relations were found for the Co-Fe-Cr and the Co-Cr-Mo a alloys, where the Co + Fe content appears to determine the Curie temperature. RECENTLY, it has become increasingly evident that the u phase is some kind of an "electron compound." Several papers1-' discussed the empirical correlation between the composition of the various u phases in alloys of the transition elements and the distribution of electrons in the partially filled d-levels of the component atoms. However, a picture of the latter can be formed only in a more or less intuitive manner, as in the Pauling theory," and the rigorous treatment of these problems is at present prevented by lack of adequate knowledge of the electronic structure of the transition elements in the metallic state. It appeared reasonable to expect that investigation of the magnetic properties, which are related to d-shell electrons, may help in clarifying the physical nature of the foregoing empirical correlation. Qualitative tests of samples of various compositions have shown that certain u alloys become ferromagnetic at liquid nitrogen temperature." The present investigation was undertaken to determine whether or not low temperature ferromagnetism is characteristic of a large variety of u alloys and to establish how the Curie temperatures of ferromagnetic u alloys are influenced by changes in composition and in lattice parameter. In the first portion of the in- vestigation, Curie temperatures were measured for a series of u alloys containing either vanadium or chromium with one or two of the elements manganese, iron, cobalt, or nickel. In the second phase of the work, data were obtained on the Curie temperature of ternary (Fe, Co, Cr)a, (Fe, Cr, Mo)a, and (Co, Cr, MO)U alloys, as a function of composition and of interatomic spacing. Experimental Procedures High frequency vacuum melting in high purity re-crystallized alumina crucibles was employed in the preparation of the u alloys, using metals whose lot analyses are given in Table I. Approximately two-thirds of the alloys were analyzed chemically, the analytical results being in acceptable agreement with the intended compositions, as seen in Tables I1 and 111. The specimens were annealed for homogen-ization in an atmosphere of purified 92 pct He and 8 pct H, mixture or in evacuated and sealed Vycor tubes at temperatures from 780" to 1300°C, depending on the temperature range of the u phase field for the particular composition. The annealing temwerature and time for kach alloy are given in Tables 11 and 111. Curie points were determined by an induction method; the change with temperature of mutual inductance between two coils was observed when the i-u specimen was inserted into the flux path between the coils. The transformer consisted of three coils each containing 1200 turns of 0.0050 in. diam enameled copper wire. The center coil, P in Fig. 1, served as the primary coil, and was linked magnetically with each of the two secondary coils, S, and S? which were connected in series opposition. The primary coil, P, was energized by an audio-oscillator, set at a frequency of 500 cycles per sec, while the signal from the transformer secondary circuit,

Jan 1, 1956

By J. F. KENP

THE White Knob copper-deposits are situated about three miles south of Mackay, on the Salmon River .branch of the Oregon Short Line Railroad, in Custer county, Idaho. An outline-map of this district is given in Fig. 1. The deposits have been known and spasmodically worked for many years, and a total of over 3.5 miles of tunnels, shafts and other workings has been driven with a view to their development. These extensive excavations have exposed the deposits sufficiently to permit a careful geological examination. The peculiar features which give special interest to this paper are the branching, free-like form of the ore-bodies; the absence of zones of secondary enrichment in the partly oxidized pyritic deposits, and the fact that while the deposits are associated in a general way with the contact of an eruptive rock with limestone, which it penetrates, the garnetization has taken place not in the limestone, as is the usual case, but in the igneous

Mar 1, 1907

By Northcutt Ely, Charles F. Wheatley

This chapter deals with the systems of laws by which governments regulate the exploration for and production of the minerals within their jurisdictions. It is a summary, restricted by necessary space limitations, of material assembled by the author for a forthcoming publication of the United States Bureau of Mines, "Summary of Mining and Petroleum Laws of the World." (Information Circular, 1959.) The present study is organized in three parts, dealing with (1) the historical background of these legal systems, (2) laws of the United States, and (3) laws of other countries of the world. The reader's attention is invited to the acknowledgments at the end of the chapter, which inadequately express the appreciation due those who have assisted in the collection of this material. Part I. Historical Development of Major Western Systems of Land Tenancy with Respect to the Ownership and Control of Minerals The use of metals in primitive societies was largely confined to the manufacture of weapons for self-preservation. The ruler's control over copper, then brass, then iron, was essential to maintenance of his own ascendancy at home and his group's position against neighbors who had access to similar metals. Ancient societies were thus characterized by the ruling group's ownership of minerals and metals. The Egyptian civilization, which emerged in the fourth millenium B.C. upon the agricultural subjugation of the lower valley of the Nile, was responsible for extensive development of the upper valley as a source of mineral wealth. The production of gold during the height of that civilization has been estimated at $30,000,000 per year, thus equaling the early placers of California and Australia. The mines of Egypt were the property of the Pharaohs and were controlled at their direction. Greek mining developed a different scheme of land tenancy which more closely resembled modem concepts. Development of mineral resources was

Jan 1, 1959

By JOHN R. SUMAN

OVERWHELMING proof of the importance of oil in a modern national economy is afforded by the present European War. Treat¬ies and national boundaries have been cynically violated to secure greater supplies of the precious fuel. Petroleum substitutes have been desperately, and far from successfully, sought. The whole German military theory of the drang nach Osten, the drive to the East, is directed at cutting the British supply of oil and securing a supply for Germany. This is a war of machines, and the machines of war feed hungrily on oil. In view of this fact, it is surely comforting to know that we are living today in a nation which has surpassed all the rest of the world not merely in unearthing the raw supplies of petroleum which lie beneath its surface but also in every phase of the industry in mining, refining, processing, production, and distribution.

Jan 1, 1941

By C. Kremer Bain

DURING the past several years of diamond drilling in Washington County, Mo., the St. Joseph Lead Co. has discovered a concentration of commercial lead-zinc ore at four different points within an area of 36 square miles. The largest and to date the most promising group of these orebodies is located in the Indian Creek area. It was considered to be of sufficient value to warrant development. The Indian Creek area is in the center of the northern half of Washington County, 11 miles northwest of Potosi, Mo., the county seat. The location is readily accessible from Potosi by car or truck over the all-weather Missouri State Highway No. 114. The topography is one of rolling relief, varying from an elevation of 700 ft above sea level on Mineral Fork and Indian Creek to a maximum of 1176 ft at High Point Tower. It is divided in equal halves between the drainage to Mineral Fork and to Indian Creek. The shaft site at 1060 elevation is on the divide between the two drainage areas. The Indian Creek side is rough and heavily wooded, with only a few cultivated clearings. The slopes to Mineral Fork are more gentle and rounded, with much of the area cleared for farm land. Most of the surface is covered with Potosi and Eminence formations, which show little evidence of any structure. Ore structure was worked out by extensive diamond core drilling, with holes varying in depth from about 700 to 1300 ft. As of Oct. 1, 1950, 218 prospect holes had been drilled within the 36-square mile area. The ore is disseminated galena with considerable accompanying sphalerite in the Bonne Terre forma-tion in the shape of irregular blanket-type deposits. The main controlling structural feature of the outlined mineral zone is a buried pre-Cambrian rhy-olite-porphyry ridge extending partly through the Bonne Terre formation, which laps against the por phyry and also covers it. The mineralized zone parallels and forms an irregular halo around the porphyry ridge and is concentrated in the Bonne Terre formation where the La Motte sandstone is cut out by the porphyry ridge. This is a very common mineral occurrence in the southeastern Missouri lead belt district. The La Motte sandstone, which normally underlies the Bonne Terre formation, is thus cut out entirely. In this area the Bonne Terre is usually about 275 to 320 ft thick, the La Motte varying in thickness from zero up to 400 ft. Commercial concentrations of ore are indicated at several places, the most notable being at the shaft site where an orebody at least 4000 ft long with widths of 500 to 600 ft has been outlined. The total thickness of mineralized rock reaches 150 ft in some holes, although total ore thickness runs from 8 ft to about 60 ft, often in more than one layer. Preliminary Planning Ore reserves as outlined lend themselves to open-stope mining with trackless haulage and mobile loading machines and drilling equipment. This type of equipment has proved to be very efficient during recent years in the company's lead belt operations. After a study of bids for shaft sinking and an estimation of comparative costs, it was decided that the shaft would be sunk by St. Joseph Lead Co. personnel using company equipment. Since the plant site is about 26 miles from the company's nearest lead belt operations, it was necessary to plan a complete surface plant, including mill, shops, office, change room, and warehousing facilities. Immediately following the filing of an application for a certificate of necessity, a headframe was selected for which detailed drawings were already available. The order was placed for fabrication so that it could be delivered and erected in time to serve for sinking the shaft. This eliminated the expense of a temporary headframe. Drilling was started on two churn drill holes near shaft location, and two 1000-gpm deep well pumps

Jan 1, 1954

By H. D. Wilde

DURING 1934 conditions in the production division of the petroleum industry were reasonably satisfactory but nevertheless a decided feeling of insecurity existed largely because of the uncertainty of controlling production to consumptive demand. Over-production, especially in the East Texas field, threatened a general collapse of crude prices but in spite of this, posted prices were high. Stimulated by the prevailing posted prices, wildcatting activities were wide-spread. Although a number of small discoveries were made, particularly in the Gulf Coast belt and Oklahoma, no fields of major importance, unless it was the Fitts pool in Southern Oklahoma, were brought in. Meanwhile, the Petroleum Division of the A.I.M.E. continued its activities. It sponsored the collection of production and geological data on both foreign and domestic fields. The data on all but a few producing districts in the world were published in the "Petroleum Development and Technology" volume of the "Transactions" and comprise one of the most complete tabula¬tions of this sort ever published. Work of this kind is being continued.

Jan 1, 1935

By W. G. Jewitt

YELLOWKNIFE, the most northerly Canadian gold mining district, is once more in the throes of a boom. Touched off by spectacular and well-publicized diamond-drilling results on the property of Giant Yellowknife Gold Mines, Ltd., mining companies and the general public are competing for mining claims and for the shares of companies owning mining claims in the area, with little regard for values. Such a stock-market boom has various unfortunate consequences but undoubtedly one beneficial result is that considerable amounts of money are made available for serious development. The Yellowknife mining area lies on the north shore of Great Slave Lake, in the Northwest Territories, at a latitude of approximately 62°30' north. The topography is a low-relief phase of that usual in the Canadian Laurentian shield. Roughly, one third of the surface is lake-covered, one third muskeg or overburden, and one third is bare

Jan 1, 1944

By T. Fraser, R. L. Sutherland

Under a cooperative agreement between United States Bureau of Mines and the Truax-Traer Coal Company, some operating-scale experiments have been made with the cyclone thickener in the preparation plant of the Shamrock No. 1 mine at Kayford, West Virginia. These tests were made with a 14-in. cyclone of the type developed by the Dutch State Mines in Limburg. It was applied experimentally to the thickening of solids in washery water to obtain performance data to show the range of sizes that may be recovered and other operating characteristics that would indicate the field of usefulness of this device in coal preparation practice. This is a progress report only. It covers results obtained in a series of 17 tests of the operation of what has been considered a unit of commercial size operating on suspensions of fine coal mixed with a relatively small amount of freeimpurities. The underflow material, after further dewatering in centrifuges, is a marketable grade of coal.

Jan 1, 1949

By G. L. Fisher, R. Maddin

The rate of self-diffusion in silver single crystals during torsional strain was measured over a wide range of tenperatures and strain rates. The torsional strain was applied in a cyclic manner by reversing the divection of twist aftev a certain fraction of the total strain was reached. Surface roughening was substantially reduced in cyclically strained specimens compared with those strained entirely in one direction. Diffusion coefficients were determined using a special sectioning technique whereby slices could be removed parallel to the surface of a strained torsion specimen. The accuracy of the technique was first determined using roughened specinzens statically diffused to various penetration depths. Simultaneous strain-diffusion experiments were then performed over the temperature range 550' to 800 using strain rates of lo-' to 2.2 x 10' sec-'. The increase in silver self-diffusivity during torsional plastic strain was small. In only one case was the enhancement greater than twice the static value of the diffusion coefficzent. The enhancements increased slightly with decreasing tenzperature and increased with increasing strain rate. A dislocation pipe mechanism of enhancement was found to explain the present results satisfactorily. The magnitude of the enhancements and the tenzperatures at which they were observed suggests that a steady-state dislocation density of 10' to 109 dislocations cm-2 existed during the high-tempevature deformation. The diffusion coefficient in an fcc metal can be increased by 1) an excess concentration of point defects and 2) the rapid movement of diffusing atoms along grain boundaries and dislocations. Plastic deformation may be responsible for enhancements by both of these mechanisms. The results of simultaneous strain-diffusion experiments have caused a controversy over the magnitude of the effect of strain upon diffusion. Experiments reporting large enhancements have been criticized for the manner in which the diffusion coefficient was measured. Several of these experiments have been contradicted by other results obtained in a similar manner. No enhancement was reported by two investigators''' who performed their experiments at high temperatures where strain is expected to have little effect upon diffusion. A recent theoretical analysis3 indicates that strain enhancement by a vacancy mechanism will be small and exist only at low temperatures and rapid strain rates. It is doubtful whether any experiment has yet proven that strain enhancements can occur by an excess vacancy mechanism. In the present research, experiments were performed at extremes of temperature and strain rate in an attempt to measure enhancement of diffusion by strain. Self-diffusion of silver during torsional deformation was chosen since two separate investigations4j5 indicate that at least a small enhancement exists under these conditions. An accurate method of determining the diffusion coefficient, mechanical sectioning, was employed after a technique was devised to apply it to the roughened surface of a strained torsion specimen. First, the accuracy of the technique was determined for different penetrations (2fi). Then diffusion experiments were performed at temperatures between 550" and 800°C at strain rates of 10"" to 10"" per sec. I) EXPERIMENTAL PROCEDURE Preparation of Specimens. The experimental procedure detailing the growth of crystals, their treatment, and the annealing techniques during straining are contained in earlier publications.496 The dimensions and orientations of the torsion specimens are shown in Figs. 1 and 2. licatiin of Torsional Strain. The torsion procedure was changed from that used previously. The specimens were strained in cycles to reduce the gross distortion and surface roughening inherent in twisting to high strains in one direction. For all strains above 0.30, the total surface strain was obtained as follows: the specimen was twisted to 0.10 strain in a clockwise direction; the direction was reversed; the backlash in the torsion apparatus was taken up; and the specimen was twisted in a counterclockwise direction through the initial starting point to 0.20 surface shear strain in the opposite direction. The strain reversal took no more than 1 min to accomplish. The total accumulated surface shear strain was arbitrarily taken as the sum of the 0.10 strain in the clockwise direction plus 0.20 in the counterclockwise direction. Although cyclic torsional strain was beneficial, surface roughening and specimen distortion were not entirely eliminated. The variation in the diameter at various points on the specimen was often much greater than the depth of the diffusion zone. Since serious errors might result if specimens were sectioned in the usual manner, a technique of lathe sectioning was devised to allow sections to be taken parallel to planes of equal concentration.

Jan 1, 1967

By SIDNEY ROLLE

ACURSORY glance through the literature on the subject reveals that the ablest minds in the land are devoting themselves to the great question of labor, of which employment is one of the fundamentals. Volumes have been written and the end is not in sight. Employment management is today about in the position that efficiency was 15 years ago. During the early days of the war, and perhaps for a year or so before, labor was plentiful. As the war progressed and Europe drew on us for munitions, employers began to compete with one another for', all, classes of labor. Labor was difficult to obtain, wages rose, the labor turnover increased, and employers began to install employment departments, welfare plans, and all sorts of schemes, but the labor efficiency dropped. As the war progressed, greater and greater production was demanded. New factors were introduced each day. The government, labor unions, industrial councils, all tended, it seemed, to make the situation almost intolerable. Wages rose to fantastic heights, the cost of living rose higher and higher, and the efficiency dropped still further.

Jan 1, 1921

By Galen H., Clevenger

THE first and most important thing that affects the majority of lead producers in the Rocky Mountains and the western mining regions is that zinc in an ever-increasing degree is inseparably associated with the lead. The Sullivan mine in British Columbia is not only a great lead mine, but also a great zinc producer. This mine could not reach its full measure of productiveness, nor was its great value established, until a reasonably good physical method was developed for separating the lead from the zinc prior to the recovery of each metal by an appropriate process. The western metallurgists and also metallurgists in other parts of the world have long faced the lead-zinc problem. This for many years stimulated a great deal of experimental work looking toward the development of a physical or chemical method of separating lead and zinc in concentrated form from complex ores. Space will not permit of going into this work in detail, but it is sufficient to say that with but few exceptions the western lead smelter continued smelting charges many times too high in zinc for the most efficient operation of lead furnaces. The zinc was not only lost, as the zinc content of many a western slag dump bears mute testimony, but the cost of lead smelting was increased by reason of the presence of the zinc. The owner of the ore under these circumstances could be paid nothing for the zinc and, indeed, he was penalized for it

Jan 1, 1926

By L. Thomassen, N. Spooner, J. M. Thomas

NI-CR and some Ni-Cr-Fc alloys, when used as electrical resistance heating elements in reducing atmospheres, at times suffer rapid breakdowns due to so-called "green rot." These reducing atmospheres are most frequently used in bright annealing and heat-treating furnaces which are kept for long periods of time at 1500' to 1800°F. The green rot is a preferential oxidation of the chromium in the alloy to such an extent that the remaining metal frequently becomes ferromagnetic. The Curie point (magnetic transition point) at room temperature for a pure Ni-Cr alloy is known to be at about 7 pct Cr.¹ This represents a severe loss in chromium for one popular grade of resistance alloy, which is nominally 80 pct Ni-20 pct Cr. The formation of oxides along the grain boundaries makes the ribbon brittle and gives the fracture a green, earthy appearance—hence the name. The authors have studied this phenomenon, simulating the industrial conditions by heating resistance ribbons in various reducing atmospheres, such as moist hydrogen or the atmosphere specified in the ASTM test.² This atmosphere contains 16 pct H2, 10 pct CO, 4 pct C02, 1 pct CH1, 1.5 to 2.5 pct H2O, balance N2. Little success was had in producing severe corrosion with the commercial 80 pct Ni-20 pct Cr alloys. It had been noticed, however, that 90 pct Ni-10 pct Cr alloy wires deteriorated very rapidly when placed in the bottom of narrow thermocouple protection tubes. The bottoms of the tubes with the wires were heated in air. This took place both in porcelain tubes and in Inconel* tubes either with the cold end open or loosely stoppered with asbestos. On examination the wires showed microstructures which would be classified as green-rot corrosion. Subsequent investigations with various alloy wires confirmed the observation that corrosion occurred in some wires, including 80 pct Ni-20 pct Cr alloys, much more rapidly in such tubes than had occurred previously in test atmospheres mentioned above. When 90 pct Ni-10 pct Cr alloys are oxidized with an abundant air supply, the oxide coat consists of both nickel and chromium oxides. In this case thermodynamic equilibrium between the oxides is not established. However, when oxidized 90 pct Ni-10 pct Cr alloy specimens were heated to 1500" to 1800°F inside small diameter tubes, the oxide coat transformed to a bright metallic outer layer of nickel or nickel-rich alloy, beneath which appeared a green oxide, followed by intergranularly attacked metal. The obvious explanation is that in the narrow tubes, thermodynamic equilibrium is being established according to the equation NiO + Cr (in alloy) ? Ni + Cr2O3 This reaction is favored due to the fact that the oxygen pressure over nickel oxide is more than 10"' times the oxygen pressure over the green chromium oxide. The initial oxygen in the tubes is depleted very rapidly by oxidation of the wire and of the tube, if it is metallic. A confirmation of the occurrence of the reaction, reduction of NiO by the chromium in the alloy, was obtained by putting oxidized nickel foil into an evacuated quartz tube along with a piece of bright 90 pct Ni-10 pct Cr alloy ribbon, and heating the tube at 1820°F for a number of hours. The nickel oxide on the foil was completely reduced to pure nickel, leaving a bright foil. The 90 pct Ni-10 pct Cr alloy became strongly magnetic and showed the typical green-rot structure. Weights of the samples before and after testing showed the weight loss of the foil to approximately equal the weight gain of the ribbon. Evidently the bottom of long, narrow protection tubes, stoppered or not, may under certain conditions act just as the sealed quartz tubes in respect to being a confined space in which oxygen is not freely replenished. This condition of oxygen depletion can be prevented by introducing a small amount of air into the bottom of the tube. Many conditions becloud the green-rot phenomenon, such as carburization, sulphidization, and the presence of other corrosive agents. However, these experiments have shown that the basic reaction is a case of internal oxidation which can occur simply by adjusting the oxygen pressure to a low enough level so that the atmosphere will leave the nickel intact and oxidize the chromium. The action of the other agents in commercial atmospheres can then be taken up as individual cases. From these and numerous other tests completed to date or still in progress, it is believed that a more critical evaluation of electrical resistance alloys for their resistance to green-rot corrosion can be made. A much better understanding of the mechanism for this type of corrosion should also result. A more complete report on these experiments will be published later. In the May 1953 issue: TP 35213 Discussion: Solubility of Carbon and Oxygen in Molybdenum by W. E. Few and G. K. Manning, discussion by N. A. Gokcen: p. 747, first column, the fifth, sixth, and seventh lines should be the first, second, and third lines, followed by the present first, second, third, fourth, eighth, ninth, and tenth lines.

Jan 1, 1954

"Located in Madison River Canyon, about 14 miles by road from Norris, Mont. Built in 1907 by Madison River Power Co.DAM: Rock filled wooden crib structure, 183 ft. long, 34 ft. high or 44 ft. to top of flashboards.SPILLWAY: 140 ft. long, equipped with flashboards 10 ft. high.PIPE: One 10-foot and one 12-foot wood-stave pipe, 7,515 feet long.PRESSURE: One pressure chamber, 32 ft. high, 30 ft. wide and 81 ft.CHAMBER: long, built of concrete.PENSTOCKS: 4 9-foot steel penstocks about 200 ft. long, one for each wheel.WATER WHEELS: 4 double horizontal, center discharge, Sampson special 44-inch turbines, 3,600 h-p., at 100 ft. head. Speed 300 r. p. m„ direct connected to generators.GENERATORS: 4 G. E., W. C., 2,250 k-w., 4,000 volts, 300 r. p. m., 3 phase, 60 cycles, alternators, with exciters mounted on same shaft.TRANSFORMERS: 12 G. E., W. C., 900 k-w., 60 cycles. High tension voltage 23,100, 34,650, 46,200; low tension voltage 4,000, 3,800, 3,600. Now operating at 46,200, delta connected. They can be connected Y for 40,000, 60,000 or 80,000.OPERATION: This is the principal plant of the whole system and carries most of the load."

Jan 1, 1913