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By John M. Dale

As much as half of the world's known reserves of elemental sulfur occur at or near the earth's surface in natural or native sulfur deposits of volcanic or sedimentary origin. Yet these reserves constitute only a small percentage of the world's supply. Looked on as marginal materials, they remain relatively untouched despite the current demand and improved prices for sulfur. There are two main reasons for this. The first is the nature and occurrence of the deposits. They are generally small and widely scattered in remote and often arid locations, and the gangue constituents of the ore are apt to vary considerably-not only between deposits but also within deposits. The second reason is the lack of workable and economically feasible processes for recovering sulfur from the ores in such deposits. Historically, the older thermal processes in which the sulfur is vaporized away from the gangue were probably the most successful, but they were inefficient and created pollution problems. A few of the historical processes remain in operation today. Recently, however, an improved thermal process to handle all sulfur-containing surface ores has been designed under sponsorship of the Pan American Sulfur Co. A schematic diagram of this process is shown in Fig. 1. The process equipment consists of a paddle trough conveyor retort which is operated as a closed unit to prevent any air or oxygen from entering the system. Ground surface sulfur ore and heated pebbles are fed to this unit simultaneously. The ore and heated pebbles are slowly conveyed and continuously mixed down the conveyor retort. Heat from the pebbles and heat supplied to the outside walls of the trough conveyor retort raise the ore temperature above the boiling point of sulfur. Sulfur vapors and steam originating from moisture in the ore are ducted to a condenser, and the sulfur is recovered as a liquid. The gangue and the pebbles are discharged from the trough conveyor and separated-the gangue being discarded, and the pebbles being conveyed to a direct-fired rotary pebble heater where they are reheated before they are again charged into the rotary trough conveyor retort. The hot gases which pass countercurrent to the pebbles are ducted to the outside of the rotary trough conveyor where they pass countercurrent to the flow of the ore in order to maximize heat recovery and utilization.

Jan 4, 1969

By R. G. Knickerbocker

The copper smelter and refinery of The Messina (Transvaal) Development Co. Ltd., at Messina, South Africa, was erected in 1920 and 1921, but initial operations were deferred until late in 1922 on account of the collapse of the copper market in the interim. Because the anticipated production was to be only 20 tons of copper per day from a high-grade matte containing 60 per cent copper, and because the ore did not contain gold or silver in quantities sufficient to pay for separation from the copper bullion, it was decided to design the plant along lines quite different from the modern smelteries treating large quantities of sulfide ores carrying appreciable amounts of gold and silver. The plant was built, therefore, for the production of copper by the Nicholls-James process. By this method two-thirds of the copper matte produced was roasted in a Merton calciner and charged into a bath of the remaining one-third portion of unroasted matte in a reaction furnace. The original design was not only novel in providing for the Nicholls-James process, but also in comparison with new plants built elsewhere, because of factors inherent in the locality. Sources of supply for machinery were very remote; it takes three months after the placing of an order to accomplish delivery of machinery into Messina from the United States. Native labor was available at 30 to 40¢ per 8-hr. shift. These factors permitted plant design which provided no overhead cranes, no matte ladles, no slag pots or other usual mechanical means of transportation between departments. The design resulted in a compact simple plant with furnaces arranged close together and terraced so as to provide for gravity transfer of molten material from one furnace to another and for manual disposal of products. Fig. 1 shows the relative location of furnaces. The three furnaces are parallel on successively decreasing elevations. A superimposed feed floor was provided above the furnaces. All three furnaces were provided with coal-dust burners served from a Bonnot system of coal-dust transportation, and the waste gases were discharged into waste-heat boilers. A short trial of the Nicholls-James process developed several facts which brought about a decision to abandon the process. Owing to the

Jan 1, 1934

By D. C. Seidel, E. F. Fitzhugh

The Colorado School of Mines Research Foundation has developed a hydrometallurgical process for recovering nickel from oxidized ores, including both the iron-rich laterites and magnesium-rich, soft silicates. Known as the HSO-HTCP (Hydrothermal Sulfidization Oxidation-High Temperature Cementation in Pulp) Process, the system consists of feed preparation, sulfidization, oxidation, precipitation (cementation), and calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Nickel sulfide ores lend themselves readily to concentration before smelting or pressure leaching, but neither of the major oxidized ore types — the iron-rich laterites and magnesium-rich, soft silicates-has been directly concentrated. Upgrading of crude ore in current practice is limited to cobbing lumps of the harder, lower grade rock (protore) from the softer, enriched silicate ore, because only a small percentage of the nickel in these ores occurs in discrete, contrasting mineral particles. There is no apparent mineralogical contrast in the superficial, iron-rich lateritic ores and, in fact, there is no firm assurance that the nickel atoms are within the lattices of the limonite minerals, or else irregularly adsorbed on the limonite. Within underlying, "rotten rock" silicates, occasional veinlets of gamierite and related nickeliferous silicates are found.' The gamierite veinlets, however, are only incidental, and the majority of the nickel atoms occur as erratic replacements of magnesium atoms in the micaceous chlorites of the ore mass. Pyrometallurgical processes account for nearly all the nickel currently being recovered from oxidized ores. Plants in New Caledonia, Oregon, Japan, Brazil and Greece smelt the ores to make ferronickels or a sulfide matte,2 and the ammoniacal leaching3 at Nicaro, Cuba, is preceded by a reducing roasL4 The only fully hydrometallurgical installation has been the politically ill-fated Freeport Nickel Co. enterprise, and this process was limited to lateritic ores.5p6 A hydrometallurgical technique which might handle both laterite and the typically richer silicate ores has been an enticing goal. The technique described here was developed at the Colorado School of Mines Research Foundation, Inc. on behalf of the Republic Steel Corp. It uses sulfur, heat, air and metallic iron to recover nickel from these ores. Inasmuch as the ores are treated as aqueous slurries, the cost of drying a plant feed that normally carried 30% or more moisture is eliminated, and there are no dust problems. Patent applications have been filed by Republic Steel Corp. on the procedures used for getting the metal into solution and on the subsequent recovery without liquids-so l ids separation of the slurry. It is referred to as the HSO-HTCP Process (Hydrothermal Sulfidization Oxidation — High Temperature Cementation in Pulp). THE PROCESS FLOWSHEET The results of various experimental studies have been combined to form the continuous flowsheet illustrated in Fig. 1. This flowsheet serves as a general pattern showing the sequence of the operations which include: (1) feed preparation; (2) sulfidization; (3) oxidation; (4) precipitation (cementation); and (5) calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Feed preparation: In general, the silicate ores can be considered as earthy rather than hard, and preparation might be carried out before the addition of water in a trommel, or with water in a scrubber or log washer. This breaks up the earthy particles, allowing the hard lumps to be separated by screening. The oversize material from most ores is relatively barren and may be discarded. If there is occasion to control the iron-magnesium ratio in the plant feed, laterite, which normally breaks up readily into fine sized particles, and silicates are mixed in suitable proportions. The fine product slurry from the initial steps is mixed with elemental sulfur and fed to a conventional ball mill, although the amount of actual grinding that takes place is relatively small. The object of milling is to complete the disintegration to natural particle size and to produce an intimate mixture of the ore and elemental sulfur. This pulp, which is almost entirely -200 mesh, has a pH of about 7.0 and normally can

Jan 1, 1969

By R. H. Schnitzel

Internal-friction peaks have been observed in tungsten single crystals at about 300° and 400°C. The characteristics of these peaks are similar to interstitial peaks observed in other bee metals; therefore, the origin of these peaks appears to he the Snoek mechanism. The interstitial responsible for the peak at about 300°C has not been identified. Carburizing increases the magnitude of the peak at about 400°C; consequently, it appears reasonable to suppose that the specific interstitial associated with this peak is carbon. The activation energies associated with the 300° and 400°Cpeaks are about 35,000 and 45,000 cal per mole, respectively. INTERNAL - friction peaks resulting from the stress-induced diffusion of interstitials (Snoek relaxation peaks) have been frequently observed in bee metals.1-5 Attempts to detect Snoek relaxation peaks in tungsten have, however, not been fruitful.' Failure to find Snoek peaks in sintered tungsten can perhaps be attributed to one or more of the following difficulties: a) the relatively low purity of the sintered tungsten; b) the lack of extensive metallurgical knowledge about tungsten-interstitial alloys, such as suitable interstitial dosing and quenching procedures; and c) the inconsistency of some of the interstitial analyses of tungsten, which reflects itself in one's inability to be sure of the nature of the specimens. This present investigation did not overcome all of these difficulties for successful tungsten internal-friction measurements. Some of these difficulties still persist and new difficulties were encountered during the course of this investigation. Nevertheless, the use of electron-beam tungsten single crystals having somewhat greater purity levels than sintered tungsten combined with appropriate carburizing and quenching procedures permitted a reasonable attempt to be made. As a consequence, internal-friction peaks were observed in these tungsten single crystals at about 300° and 400°C. These peaks were found to be unstable, since they annealed rapidly away during a sequence of internal-friction measurements. Hence, it was necessary to construct an apparatus having a faster heating rate to study some of the details of these peaks. From the behavior of these peaks as well as our knowledge of similar peaks in other bee metals, one can reasonably conclude that these peaks are caused by residual interstitial impurities within these crystals. Further investigation of these peaks after the application of various metallurgical treatments lent credence to this supposition. EXPERIMENTAL TECHNIQUE The internal friction of tungsten single crystals was measured using two different pieces of apparatus both of which are of essentially the same conventional design, namely the KE type of torsion pendulum. The important difference between these two types of apparatus was in the attainable heating rate and method of protection of the specimen from atmospheric contamination. The apparatus designated "number 1" was enclosed in a vacuum chamber which was heated by an externally mounted furnace. It had a slow rate of heating which was estimated to be about 4°C per min from room temperature to about 350°C and then about 1°C per min to 600°C. The internal friction of tantalum was measured with this apparatus and the established Snoek peaks were found.' These tantalum peaks in the temperature range from room temperature to 400° C served as a check for the apparatus. The apparatus designated "number 2" having a faster heating rate than number 1 was not elaborate. It consisted of a mounted nickel tube to which split heating elements were attached. Argon was used as the protective atmosphere. The measured heating rate was about 12° to 15°C per min whereas the cooling rate was somewhat slower at about 10° C per min because of the increased difficulty encountered in stabilizing the temperature. No surface oxidation of the specimen was noted after any test. This apparatus was also checked with the known peaks of tantalum.1 The preparation of the single-crystal specimens for internal-friction measurements consisted of centerless grinding the crystals from an approximate 0.200 in. diameter to 0.030 to 0.040 in. in diameter, and then electropolishing them to about 0.020 in. in diameter. Single crystals processed in this manner are designated as being in the virgin condition. Since the length of crystal varied from 3 to 9 in., the test frequency varied from about 1 to 2 cps. The frequencies of measurement, axial orientations, and chemical analyses for the various crystals are listed in Table I. The controlled addition of carbon into tungsten is a difficult problem. Attempts to find the critical conditions necessary for an equilibrium treatment were not fruitful. Therefore, a simple nonequi-librium method was used. The addition of carbon to these crystals consisted of appropriately combining three treatments—carburizing to achieve a case, annealing to partially dissolve the carbon into the

Jan 1, 1965

By J. W. Richards

There are two essentially different 'types of case-hardening processes; that using a dry mixture in which the object to be case-hardened is packed and kept for the necessary time at the necessary temperature, and the "liquid" proccss, employing a bath of fused salts into which the object is immersed and which by immediate contact case-hardens the surface of the article. The Shimer process belongs to the second class, and was a war emergency invention. Of the liquid melts used as baths, the most effective and most frequently used are melted potassium cyanide and melted sodium cyanide. These may be used either pure or mixed with salts that reduce the melting point and the percentage of .cyanide present. The use of these baths since 1914 has met many commercial difficulties because of the high price and frequent commercial scarcity of the cyanide salts; at present sodium cyanide has practically entirely displaced potassium cyanide. Another trouble is the danger to the workmen handling the cyanide salts, which are extremely poisonous, and the annoying and poisonous vapors or gases given off in the workshop, unless an effective system of hoods and ventilation is provided, so as to prevent the gases from the baths mixing with the air of the room. Porter W. Shimer, of Easton, Pa., has invented a substitute1 for the bath of melted cyanides which case-hardens with equal or greater facility and effectiveness, gives off no poisonous vapors, and costs for chemicals materially less than the cyanide costs in the previously used baths. The process has been in use over a year in a large American works and the following statement embodies the results of practical experience in the use and operation of the process. The Shimer liquid or melted bath consists of a mixture of easily fusible salts that do not possess case-hardening properties, into which is immersed fresh calcium eyanamid, which imparts to the bath case-hardening properties. The composition of the non-case-hardening salts appears rather immaterial. Good results have been obtained by using a mixture of sodium chloride, calcium chloride, and barium chloride in equal proportions by weight; also a mixture of one part sodium chloride

Jan 1, 1920

By AIME AIME

THE initial meeting on Mining Methods* opened at 10 o'clock Monday morning with Scott Turner as chairman and W. Spencer Hutchinson as vice- chairman; about 60 attending. After preliminary announcements Theodore Marvin was called on for his paper,, entitled "Rock Tunnel Methods," which has been appearing serially in The Explosives Engineer. Marvin read the introduction and called attention to the account of one or' two particularly' interesting projects, such as the. Brooklyn water supply tunnel. E. D. 'Gardner, Char1e.s S. Hurter, L. D. Lamont and Spencer P. Howell took part in the discussion, Howell commenting on the fact that, in one case cited, misfires had occurred through detonator wires 'coming in contact with the case of an unapproved flashlight, .,: and that all flashlights should be approved.

Jan 1, 1931

By Henry A. Wentworth

Electrostatic separation of ores in its present form is generally known as the Huff process, from the name of Charles H. Huff, of Boston, Mass., through whose constant and persistent labors (with the invention of Clinton E. Dolbear as a basis) the successful commercial process embracing separative machinery and the various electrifying devices has been developed step by step, and the finances for the long period of development provided, and the method finally established and recognized throughout the world as an important and successful addition to the ore-dressing department of metallurgy. The permanent field-success of electrostatic separation began in 1908 with a 20-ton Huff experimental mill built specially for the purpose by the American Zinc, Lead & Smelting Go., in Platterille, Wis., a plant which was a success from the start and was gradually increased in capacity as the market-conditions warranted to 100 tons of concentrates per day. Much credit is due to the above-mentioned company for its initial

Jan 1, 1913

By G. W. Maynard

In this paper I desire to embody the results of some personal observations of the working of the Siemens direct process as I witnessed it for a part of three days at the works of the Siemens-Anderson Company, in Pittsburgh. This preliminary investigation was to have been followed up by one extending over a considerable period of time, and would have embraced analytical and physical tests. Circumstances over which I had no control, resulting in the temporay suspension of work, have postponed the presentation of a complete paper. If the opportunity is afforded me, I purpose doing this at a future meeting of the Institute. To those interested in the development of the process, reference is made to the papers of Dr. Siemens in the Journal of the Iron and Steel Institute for the years 1873 and 1877, and to the paper of our late lamented brother, Holley, in the 8th volume of the Transactions of our owu Institute. Dr. Siemens, in the introduction to his paper "On the Manufacture of Iron and Steel by Direct Process," read before the Iron and Steel Institute in september, 1877, says: " In mixing comparatively rich iron ore in powder with about 25 per cent. of its weight of pounded coal, and in exposing this mixture for some hours to the heat of a common stove or of a smith's fire, metallic iron is formed, which, on being heated to the welding-point on the same smith's hearth, may be forged into a horseshoe of excellent quality. The admixture with the ore of some fluxiug materials, such as lime or clay, will, in most cases, be of advantage to rid the iron of adherent slog." This is the keynote of the Siemens direct process. Dr. Siemens says further: " If we regard the production of wrought iron from an abstract point of view, we perceive that we have to accomplish two things, viz., the deoxidation of the ore, arid the fusion of the earthy matter mixed with it; and if we calculate the amount of carbon necessary to accomplish this end, weshall rind that in using, say, hematite ore, consisting of peroxide of iron with from 10 to 15 per cent. of silica, we shall require barely 40 per cent. of carbonsceous matter per ton of iron contained in the ore to effect its reduction, and also the fusion of the slag."

Jan 1, 1882

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate 0.f solution of nitrogen in y iron in the temperature range 1000° to 1200°C. It is shown that, when purified reacting gas is used, the rate-controlling process is the diffusion of nitrogen into the iron. The difhsiuity of nitrogen in y iron is calculated from the results and the equation logD = —(8800/T) — 0.04 is recommended to represent the temperature dependence of the diffusivity. In some experiments using unpurified nitrogen, solution rates are found to be slower than those attributable to a solely solid-state diffusion process. Indications are that in the presence of impurities in the gas, e.g., H,O, chemisorption of nitrogen at the surface is hindered and becomes a rate-controlling process for the transfer of nitrogen across the gas -metal interface. ALTHOUGH the solubility of nitrogen in y iron at known nitrogen activities has been well-established,'-a the kinetics of the solution of nitrogen in iron are not known. The work of Darken, Smith, and Filer' indicates that at temperatures below about 1300°C the rate of solution of nitrogen in y iron is controlled by a chemical reaction at the metal surface, while at temperatures above about 1300°C the rate-controlling process is the diffusion of nitrogen in the metal. Fast and verrijps studied the denitro-genization of y iron using wet hydrogen at 950°C and their results clearly indicate that the rate of nitrogen removal is controlled by diffusion of nitrogen in the metal. In Part I of this series of papers, the kinetics of the solution of nitrogen in y iron are discussed in the light of the present experimental work. EXPERIMENTAL Apparatus. The reaction chamber consisted of a platinum wire-wound resistance furnace with a re-crystallized alumina reaction tube. The temoerature of the furnace, which was automatically controlled to approximately 1°C, was measured with a Pt/Pt-13 pct Rh thermocouple and a potentiometer. The temperature distribution in the working zone of the furnace was determined using a calibrated Pt/Pt-13 pct Rh thermocouple and the hot zone was found to be approximately 3 in. long with a temperature variation of * 3°C. A series of experiments was also carried out at 1000°C and pressures above atmospheric using a pressure vessel which was similar in construction to that described elsewhere.1° Materials. Ferrovac E grade iron used in all ex-

Jan 1, 1964

By J. J. Bodmer

In 1855, Franz Uchatius patented, in England, his process of manufacturing cast steel. The first experiments, on a practical scale, were made at the Ebbw Vale Iron Works, Monmouthshire. The charge consisted of a mixture of cast iron with about 20 per cent. of a pure iron ore, and with or without other ingredients. In order to obtain the cast iron in a subdivided condition, Uchatius granulated molten pig-metal by running it into water, which during the operation was kept well agitated, and found that "the finer the iron is granulated, the softer will be the resulting steel." The writer is not aware that granulated iron has been used practically, otherwise than in the above-named process; and until 1866 no other process of subdividing iron than by granulation was known. In April, 1866, an English patent was obtained by the writer for subdividing blast-furnace and other slags and metals in a molten condition, by passing the same through one or more pairs of rolls. In reference to iron the idea was, in following up the direction pointed out by the Uchatius process, to obtain better results in the puddling process by means of a thorough amalgamation (not simply a mixture) of the iron with the oxides and other ingredients in the charge itself. Experiments were made. A quantity of iron direct from the blastfurnace was subdivided (or laminated) by passing it through a pair of plain rolls. The rolls were hollow, and water was made to pass through them to keep them sufficiently cool. Without giving differential speed to the rolls, sheets were obtained about one-sixteenth inches thick, and from about one hundred square inches surface, downwards. With differential speed, the iron falls from the rolls in

By R. W. Hertzberg, R. W. Kraft

A study of the fracture behavior of unidirectwn-ally solidified Cu-Cr eutectic alloy was performed. Fractured whiskers, grain boundaries, and the interface between proeutectic Cr dendrites and the Cu matrix were the predominant failure initiation sites where grain size was larger. Strain induced void formation was restricted at lower solidification rates. This was attributed to a lack of adequate plastic constraint and a probable preferred orientation. A modification of the Crussard et al. model is presented to explain the appearance of "elongated dimples" on the shear fracture surface. A Cu-Cr alloy containing about 1.8 at. pct Cr solidifies by a eutectic reaction forming filamentary crystals of chromium within a continuous copper solid solution matrix.' Webb and Forgeng2 have shown by bend tests that the extracted chromium filaments, which are ordinarily curved and branched (due to random solidification), have the high strengths associated with whiskers. If an ingot of the eutectic alloy is unidirectionally solidified and appropriate control exercised over the thermal gradient, growth rate, and impurity level, the chromium fibers can be forced to solidify as fibers which are substantially parallel to the growth direction, Fig. 1. Uniaxial tensile tests on these straight chromium fibers extracted from controlled ingots3 have confirmed the earlier bend test results on curved fibers. Combining the facts that the strength and modulus of the chromium filaments are higher than the more ductile copper matrix and assuming that a "good bond" exists between the two phases, the Cu-Cr controlled eutectic system fulfills the requirements for effective fiber reinforcement of ductile matrices as established by studies on fiber glass reinforced plastics and other two-phase systems.4 Therefore, it was decided to study the fracture characteristics of morphologically simple specimens of chromium fiber reinforced copper (i.e., specimens of the controlled eutectic with substantially parallel reinforcing fibers) with the objective of establishing the dominant aspects of fracture. PREVIOUS WORK Comparatively little work has been done to understand the manner in which ductile alloys fail be- cause of the limited demand for this kind of information. Ordinarily ductility is specified for safety or similar reasons and when a part deforms plastically its useful life is terminated. In recent years, however, a number of investigators have begun to

Jan 1, 1963

By C. E. Abbott

THE Birmingham district, Alabama, is distinctive in the proximity to one another of its deposits of iron ore, coal and flux. These three basic requisites for the making of iron and steel are found within a radius of 10 miles. Both dolomite and limestone are produced, the former for blast-furnace flux and the latter for basic open-hearth operations. The Tennessee Coal, Iron and Railroad Co., a subsidiary of the United States Steel Corporation, operates a limestone mine at Muscoda, near Bessemer, 12 miles southwest of Birmingham, served by its own railroad transportation system. The mine has a capacity of 130 tons per hour. Average analyses of a recent month's production are as follows: Fe2O3 Si02 A12O3 CAC03 MGCO Lump, per cent 0.51 0.22 98.63 0.14 Crushed and washed, percent 0.70 0.26 98.36 0.18 Lump stone, 2 1/2 to 7 1/2 in., is used in open-hearth operations at Fairfield Steel Works. Fine crushed and washed stone, 1 ¼ to 0.063 in., is calcined at the, lime-burning plant and used for lime charges at the Ensley open hearths.

Jan 1, 1936

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

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

John Birkinbine, Philadelphia, Pa.: We have in the Institute two Dudleys—Dr. Charles B. Dudley, who has so thoroughly studied the chemical composition and physical behavior of rail-steel, and Dr. P. H. Dudley, whose investigations and

Jan 1, 1900

By D. K. Deardorff, Haruo Kato

D. K. Deardorff and Haruo Kato (U. S. Bureau of Mines)—We wish to refute the 1875" 20°C value that Giessen, et al., report as the transformation temperature of hafnium. Although these authors state that their work along this line will be reported later, we can't leave their value undiscussed, for we believe it to be 125°C too high. Our value of 1750° 20°C, which the authors mention, has been substantiated in our laboratories by the use of three other methods. The first method of substantiation was by heating and cooling curves using a hafnium/tungsten thermocouple, the couple having first been calibrated against a t/Pt-10 pct Rh couple. The second method was by quenching and metallography of dilute Hf-Ta alloys. The third cussion, it may be pointed out that the observations of Rogers referred to large unidirectional strains where the internal cracks or voids appeared only after a strain of 32 pct or more. On the contrary the internal fissures observed, as a result of fatigue cycling, occurred for a total extension of some 5 pct and furthermore followed the directions of the slip zones. Finally, it is not our contention, as implied in Dr. Alden's last paragraph, that the tensile stress is an important factor in crack propagation. Indeed, in connection with the reference to the companion report, special note is made of the fact that "Deformation was apparently concentrated in grains which have a slip plane nearly perpendicular to the specimen axis and thus near the plane of maximum applied shear." This dependence of the growth of fissures on the orientation of the slip planes with respect to the direction of maximum applied shear is clearly shown in work on the torsional cycling of single crystals which has been submitted for publication. method was by heating and cooling curves with W/W-26 pct Re thermocouple. Counting the original resistometric method, four different methods have yielded 1750" 20°C as the transformation temperature of hafnium. All our work on determination of the hafnium transformation temperature has shown that the specimen under test must be quickly heated to and through the transformation temperature if the lowest possible transformation value is to be determined; otherwise a higher value not representative of pure hafnium will result. Speed was emphasized in all methods. In our resistometric work the corresponding voltage, amperage, and temperature readings were taken quickly and the transformation temperature was usually reached within 5 min total heating time. In the thermal analysis work involving Hf/W or W/W-26 pct Re thermocouples the transformation temperature was attained within three minutes total heating time, this time being less because the two variables were

Jan 1, 1963

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By Alan D. Randolph

INTRODUCTION The production of fines is an unwanted side-effect in most crystallization processes. The definition of “fines" is relative to the size of the desired product and varies from <30 mesh for coarse KC1 fertilizers to subsieve organic material produced by salting-out pro- cesses. Sometimes a well-developed fines distribution is necessary in the production of large crystals, e.g. the fines removal stream from a potash crystallizer. The production of fines is usually not desired in a crystallization separation step. However, product purity can either improve or degenerate with a decrease in crystal size depending on the relative importance of product washing vs mother liquor occlusions in determining over-all purity. Typically, both washing efficiency and mother liquor occlusions decrease with decreasing particle size. Fine crystal distributions have historically been difficult to measure and categorize; however this situation is changing rapidly with the use of electronic particle counters of the electrical zone- sensing or light scattering type. In fact, fine-crystal measurement is perhaps the key to better understanding and control of coarse- crystal crystallization processes. The fine-crystal distribution carries much useful information from which nucleation and growth rates can be inferred. The purpose of this paper is to briefly discuss a few crystallization processes in which production and/or measurement of fines is important and to categorize the process conditions which yield a fine- crystal product.

Jan 1, 1980

By M. S. Azun

M.S. Azun I have many objections to the content of the author&apos;s paper. Before discussing it, however, I would like to repeat the property of semivariogram function. Second order stationary properties of regionalized variables (ReV&apos;s) such as semivariogram function ?(h) are perfectly known in geostatistics. Also, the kriging equations in the language of mathematical statistics using second order stationary properties are well understood. However, the way to use the sample (estimated) semivariogram function in any one of the kriging procedures is vague. The sample semivariogram function is given as follows: [1 N-hy*(h) = 2(N h) i21 {Xi-Xi+h}Z, h=0, 1, N-1] where N is the total number of samples, Xi is the sample value at the i - th location, X i+h is the sample value at the i +h - th location, and h is the distance among the samples. An estimation variance of sample semivariogram function of first lag is smaller than that of higher order lag. The theoretical semivariogram function reaches the variance of samples asymptotically. But this is not easily observable because of the larger variation involved in the estimate of semivariogram function. In general, an estimation procedure is done for h = 0, 1, 2,…., up to the greatest integer less than N/2, even though sample semivariogram function can be computable through N-1. After estimating semivariogram function, the critical question of how to model sample semivariogram function arises. As seen in the above equation, sample semivariogram function is discrete and can be smoothed by the model being selected. Therefore, modeling of sample semivariogram function is the most important step in geostatistics. It not only smoothes a discrete function but also affects the results of the kriging procedure. When the only aim is to model the semivariogram function, which is the basic point of the author&apos;s paper, one can employ any fitting techniques, such as curve fitting, or any ar¬bitrary functions, which are called submodels in the paper. The term "arbitrary function" is used rather than "submodel" because there is no basic understanding of developing them. The author suggests that the sum of those submodels can also be used for the modeling of sample semivariogram function. The combination of any arbitrary functions brings many problems instead of giving an insight of the domain structure considered. The author used two arbitrary functions and the nugget effect in response to sample semivariogram function (Fig. 10). For the same example, he stated that the parameters involved in the mixed arbitrary function model can be accepted when the discrepancy between sample semivariogram function and the model is small visually. For verifying the fitting behavior of any selected model, one should not be contented with the visual satisfactory. Some statistical measure such as goodness of fit has to be used. The author&apos;s practice is no more than an exercise in curve fitting without any fundamental understanding or conceptualization of the underlying physical mechanism. Furthermore, the selection of any model is not an easy task if the purpose is the search for the "best" response to the observed second order properties of ReV&apos;s. I suggest that the Markovian model (Azun, 1983), on the basis of a theoretical understanding of underlying mechanism, which gives more information about the occurrence of regionalized variables, is used to respond all properties of ReV&apos;s. There are a lot of problems for modeling of onedimensional sample semivariogram function. Thus, it is not appropriate to go to higher order dimensional sample semivariogram function modeling. In the meantime, I would recommend that one can connect the values of standardized sample semivariogram function rather than simple values of semivariogram function in the two-dimensional estimation. The standardized values can be computed in dividing the semivariogram function value by the number of sample pairs involved in each lag regardless of the directions. In conclusion, geostatistics is an interdisciplinary area in mining that uses the principles of mathematical statistics. Thus, it should not violate any probabilistic and statistical rules. When Matheron was developing the theory of geostatistical study in the early years of geostatistics, many mining people had a reservation accepting the geostatistical tools. However, this does not mean that we, the geostatisticians, might try to convince those people using some "strange" tools or rules as some authors implied (Baafi and Kim, 1984). Instead, we have to develop and explain the geostatistical tools staying only in the framework of statistical concepts and properties. ? References Azun, M.S., 1983, "Stochastic Process Modeling of Spatially Distributed Geostatistical Data," Columbia University, Ph.D. Thesis. Baafi, E.Y., and Kim, Y.C., 1984, "Discussion - Comparison of Different Ore Reserve Estimation Methods Using Conditional Simulation," Mining Engineering, Vol. 36, No. 3, p. 280. Reply by J.M. Rendu The interactive method proposed by Rendu allows practitioners to develop semivariogram models that take into account not only the numerical information obtained by sampling, but also highly significant additional information that often cannot be quantified. The geology of the deposit - including hypotheses concerning its genesis, sampling methods, assaying methods, and mathematical methods used to calculate the semivariograms - all have an influence on the numerical results obtained and on how these results should be interpreted. If all the information concerning the spatial distribution of values in a mineral deposit was contained in the sample values, it could be argued that statistical techniques alone would produce optimum models. However, this is rarely, if ever, the case. Methods that allow the user to take into account his experience and his geologic understanding of the deposit should not be rejected for the sake of theoretical statistical purity. ?

Jan 1, 1986

By W. M. Myers

Certain minerals possess inherent color and other properties that make them suitable for the pigmentation of paints, mortar, plaster, concrete, face brick, and other materials. Their production is one of the most ancient of mineral industries and their use by primitive man is well known. These natural pigments have some economic factors in their favor, particularly wide geographic distribution, low cost of production, ease of preparation, chemical stability, and permanence in use so that they continue to form the basis of a small but useful industry. When used in paints such pigments act as a filler and supply body and opacity in addition to color. Natural mineral pigments are prepared for the market by the comparatively simple operations of washing, grinding, blending, and calcining. Any one, or all of these processes may be applied to a single pigment. The development of synthetic pigments and the use of byproduct materials have introduced competition with the products of nature and are having a growing influence on the economic position of the mined minerals. Development of the Industry The industry developed to commercial stature in Pennsylvania largely because of the presence of beds of ocher extending from Easton in a southwesterly direction toward Reading, and a variety of small iron mines in the region. The mining of paint ores in the Lehigh Valley was active as early as 1850 and shortly after the Civil War the establishment of mills expanded production and led to the development of new products and eventually the manufacture of synthetic pigments. Pennsylvania continues to maintain it.s leadership as a producer of mineral colors. Production is recorded also in New Jersey, Illinois, Virginia, Ohio, and Georgia. Iron as a Pigment Iron in various compounds is the most important pigment in nature. The iron pigments are characterized by stability, light fastness, good covering power, high index of refraction, and economy in production. Ferrous compounds display a typical green coloration. This has not been employed as a commercial pigment to any great extent except incidentally in such greenstones as have been used in construction, or crushed and sized for application as a granule to roofing. Ferric oxides are characteristically red and form an important group of industrial pignents. Hydrated ferric oxides exhibit various shades of yellow and are present in such familiar pigments as ocher and sienna. The addition of small amounts of manganese oxide or carbon as organic matter to the yellows produces the brown umbers. Magnetite is one of the few black minerals that grinds to a black powder. The mineral pigments vary from earth colors of low intensity and great dilution of iron content to almost pure iron compounds with high tinting strength and correspondingly greater value. There has been some relationship between the mining of iron ores and the production of mineral pigments; although the production of colors is not carried on appreciably as a byproduct of iron mining. A number of mineral pigment producers, particularly in the eastern states, have operated mines which in the past were small producers of hematite, bog ore, or carbonate ore. The knowledge of the location of the deposit and its possibilities as a producer of pigment are due to its past history as a producer of metallic ore. Many iron compounds may be changed in color by calcination, the end product being Fe2O3, a stable red oxide. The yellow hydrated oxides may be changed to red. The gray carbonate, found in Carbon County, Pa., calcines to a fine red product. Ferrous sulphate (copperas) often available in tonnage as a byproduct of the steel industry, breaks down under heat or chemical action leaving a residual red oxide. Pigments produced by calcination or dissassociation of compounds possess the advantage of fine particle size and ease of grinding. Mineral Pigments MINERAL BLACKS Many black minerals grind to a light colored powder. This characteristic is familiar to the mineralogist as the white streak produced by a black

Jan 1, 1950

By D. R. Cook, W. M. Shepard, H. T. Morris

The East Tintic district in central Utah has produced ores of gold, silver, copper, lead, and zinc valued at more than $120,000,000. All of this ore has been produced from blind ore bodies in Paleozoic sedimentary rocks that are concealed beneath hydrothermally altered volcanic rocks and cut by intrusive bodies of Eocene age. The Paleozoic rocks, which range in age from Early Cambrian to Mississippian form the core and limbs of a large, northtrending asymmetric anticline that is cut by low-angle thrust faults, high-angle transcurrent faults, mineralized fissures and faults, and normal faults that are both older and younger than the mineralized fissures. The ore bodies generally may be grouped into two classes: ( 1) massive replacement bodies that are rich in silver, lead, zinc and manganese and (2) fissure veins that are valuable primarily for their content of gold, copper, and silver. The replacement ore bodies are localized chiefly in the Middle Limestone Member of the Ophir Formation of Middle Cambrian age where it has been thrust-faulted against older or younger rocks and cut by northeast-trending mineralized fissure zones. The fissure veins primarily are productive only in the Lower Cambrian Tintic Quartzite. Extensive lowgrade deposits of lead-zinc-silver ore recently have been discovered in Devonian carbonate rocks in the Lower plate of the East Tintic thrust fault but as yet are unevaluated. The principal guides to ore include: ( 1) intersections of northeast-trending fissures and crossbreaking faults that brecciate the carbonate rocks; (2) zones of late-stage pyritic, calcitic, and sericitic alteration in the lavas; ( 3) primary geochemical anomalies in the altered rocks; and ( 4) mineral zoning patterns of the known ore bodies. The present development of the Burgin mine would seem to assure the continued productivity of the district for at least a decade.

Jan 1, 1968