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By F. Julius Fohs

CENTRALLY located with relation to the largest iron- and steel-producing districts of the United States, the fluorspar-deposits of Kentucky possess increasing interest and importance. As typical of the numerous fluorspar-mines of Kentucky and Illinois, I have selected for description the Memphis., because it and others of its immediate group exhibit the conditions characteristic of all. I. THE MEMPHIS MINE. This mine lies 5 miles NW. of Marion, in Crittenden county, Kentucky, a station on the Chicago and Nashville division of the Illinois Central R. R. For the first mile and a half out of Marion we see only Birdsville or Middle Chester sandstones of Mississippian age. Then we cross a fault of some 350 ft. displacement, and the Ste. Genevieve oolite sets in. Beyond the fault, oolite is the predominant rock, except that the bills to the north have a capping of Cypress or lowest Chester sandstone, 80 ft. below which is an outcrop of from 6 to 10 ft. of Ste. Genevieve (Rosiclare) sandstone. Occasional sink-holes are noticed, and as the mines are approached evidence of faulting is again seen.. A line of crude head-frames and open-cut dumps, extending for more than a quarter of a mile, marks the Klondike vein. The open-cuts are from 15 to 20 ft. deep, and in most of them, from the surface down, was found the reddish gravel which is really fluorspar-some of it white or purple and crystal-clear (if the red clay is washed off), and some carrying iron and silica, and stained by waters from the decaying limestone walls. In one of these cuts, at a depth of 20 ft., white and purplish honey-combed fluorspar was found, in which the larger cavities are due to limestone and calcite leaching, and the minute ones to the leaching of zinc-blende.

Apr 1, 1909

By B. D. Cullity, J. T. Norton, M. Telkes

M. Balicki—As one who some years ago spent much time searching for an alloy with high thermoelectric power that would be suitable for heat energy-electric energy converter based on the principle of a thermoelectric pile, I would like to make a few comments touching upon that aspect of this excellent paper. The specifications which one of the authors has formulated so aptly do not appear to me as complete, and I would like to add to them the following two demands: (1) Melting point not less than 500°C and (2) elongation on 2 in. at least 5 pct. Condition 1 would insure good thermodynamic efficiency of the pile by permitting a reasonably high temperature of the hot junction and at the same time making it suitable for such application as salvage of vast amounts of energy which is lost in the form of sensible heat of waste gas leaving industrial and other furnaces. Condition 2 is also a very important one; particularly, because of the fact that all elements and alloys which exhibit attractive thermoelectric properties seem to be as a rule very brittle. The design, erection, and maintenance of a pile incorporating a brittle material in one of the most crucial parts of the converter would be a very difficult and costly affair indeed. To illustrate this point I may mention great difficulties I encountered when trying to make thermocouples of silicon. Casting of 1/4-in. rods in iron or graphite mould yielded only broken pieces which had to be welded into a bar. Such a bar had to be handled very carefully during the determinations. Raising the molten silicon by vacuum into a silica tube and solidifying it there solved the problem of stability as well as that of electrical insulation of a bar. On tests this bar (98.5 pct Si) showed dE/dT = — 275.5 microvolts per degree C vs. copper. Thermocouples made of this grade of silicon and pure nickel developed 0.39 v when temperature of the hot junction was approximately 1000°C. The possibility Dr. Gonser has mentioned of trying to impart to metals good thermoelectric properties by alloying them with silicon, has been considered. The preliminary survey which I have made was, however, disappointing. Perhaps, it will be advisable to record the results obtained (table VI), as this might save repetition of search in fields already covered.

Jan 1, 1951

By C. Lupi

Zinc chloride electrowinning presents difficulties in obtaining smooth, compact and dendrite free deposits with a high current efficiency due to the presence of undesirable metal ions. However, it is hard to define a level of impurities tolerable in zinc deposition, and despite a lot of research in this field, the reaction mechanisms of the undesired metal ions are still not clearly understood. In this study, the influence of Fe, Cd, Co, Ni and Cu additions were investigated, as well as their synergic effect on the zinc electrodeposition process from chloride electrolytes and on the obtained deposit morphology. The tests were all performed in presence of TBACl which reduces the harmful effect of such impurities on the zinc reduction.

Jan 1, 2003

By Masashige Makifuchi, Hiroki Kumakura, Kota Nagai, Takahiro Kikuchi

"A large amount of platinum group metals (PGM) are used in automobile catalyst. It is important to recover the metals from wasted catalyst. Nomura and Kageyama (2013) suggested recovery process that PGM oxides were absorbed to perovskite-type oxide based on LaScO3. In their process, the PGM in wasted catalyst as absorbed to the perovskite-type oxide as PGM oxide. It has potential to each element in the process if the perovskite-type oxide is selected properly. In this study, the PGM oxide absorption properties of various perovskite-type oxides are investigated to develop a new recovery and separation process. The various perovskite-type oxide were synthesized with metallic platinum, palladium, rhodium at high temperature in air atmosphere. And the PGM contents in the perovskite-type oxide after the experiment are determined by chemical analysis. Some of them have the properties to absorb specific PGM oxide selectively. In addition, in order to increase the amount of absorption of PGM oxide and composition of the perovskite-type oxide experimental temperature was investigated. Then it is also found that doping another specific element to the perovskite-type oxide is effective to increase the amount of absorption of PGM oxide. Then a new recovery process of PGM from wasted automobile catalyst, in which PGM can be separate to each element, was designed.INTRODUCTIONA large amount of Platinum (Pt), Palladium (Pd), and Rhodium (Rh) are used in automobile catalysis (Figure 1) (Platinum, 2013). Natural supplies for these metals are limited and PGM mining can detrimental environmental impact. Therefore, the recycling of PGMs from wasted automobile catalysis is very important. The Rose process (Figure 2) was developed as a process to recover PGM from wasted automobile catalysis. In this process, the automobile catalysis is first crushed mechanically, and then extracting agent, copper (Cu), and flux are melted at high temperature. The mixture separates into a metal phase, (Cu alloy containing PGM) and slag. The PGM is enriched by oxidizing. Cu to Cu oxide. The PGM are then recovered and separated to each element in a wet process. However, it is hard to dissolve the PGM with acid because they are chemically stable and strong oxidation agent such as aqua regia is used. Moreover, to separate the PGM to each individual element, a solvent extraction process is required."

Jan 1, 2016

By F. F. Lines

IT is not the intention of the writer to enter into a discussion of the relative merits of the duplex process as compared with the straight scrap and pig iron process, working under the same conditions, but rather to present in a general way several modifications of the former process, and then describe the method adopted by the Maryland Steel Co., as best suited to local conditions, and also to meet the metallurgical problem presented in the removal from the iron of an unusual constituent-chromium. The principal factors to be considered in deciding whether or not duplexing should be employed are: (1) Chemical constituents of pig iron. (2) Variety and quantity of steel to be produced. (3) Relative cost of pig iron and scrap. (4) Regularity of operation. (5) Capital to be invested. (6) An existing Bessemer plant. Having decided to adopt the duplex process, several combinations may be used, viz.: (1) Acid-lined converter with basic open hearth. (2) Acid-lined converter with electric furnace. (3) Basic-lined converter with basic open hearth. (4) Basic-lined converter with electric furnace. (5) Basic open hearth with electric furnace. The combination of an acid-lined converter with a basic open-hearth furnace is the one most commonly employed, and as it is the one best adapted to the conditions encountered at the plant of the Maryland Steel Co., we will briefly outline the advantages and disadvantages of the different methods of working.

Jan 4, 1915

By G. R. Fitterer

NONMETALLIC inclusions in steel have received much attention by metallurgists during the past few years. Many investigators have been emphatic in stating their belief that these impurities are the chief causes of steel failures, while others think that their effects are negligible. One of the main reasons that definite information on the effects of these impurities is lacking is that no reliable method has been developed for the exact determination of the amounts of these different impurities in steel. Some valuable new information has been brought out by a reliable method for nonmetallic inclusions which has been developed at the Pittsburgh Experiment Station of the U. S. Bureau of Mines, in cooperation with the Carnegie Institute of Technology and the Metallurgical Advisory Board. This procedure satisfactorily extracts some of the more common inclusions from steels, thus enabling the investigator to correlate steel failures with inclusion content. Although the data given herein are the first to be published on the subject of the electrolytic extraction method, the interest in the subject is evidenced by the fact that it is already being used by some 20 to 30 steel companies for their various purposes. Some of the comments received from these laboratories indicate that the method is highly satisfactory: the unfavorable comments, when traced to their sources, have been found to be based on some small mistake made in either installation or operation. The chief discrepancy seems to have occurred in attempts to apply the method to the extraction of inclusions from alloy steels. The procedure can be used only for the plain carbon steels and for such low alloy steels as those containing the usual amount of copper (0.2 to 0.3 per cent). Steels containing the carbide-forming alloys such as chromium, tungsten, etc., present far too many difficulties for the accurate determination of inclusions. Luckily, the iron and manganese carbides do not offer any difficulties and no contamination of the oxide-sulfide residue results. It is highly probable that some modification of the following

Jan 1, 1931

RESEMBLING in some respects the enterprise at R Chuquicamata is that of the New Cornelia Copper Co. at Ajo, Arizona. Controlled from its inception by the Calumet & Arizona Mining Co., New Cornelia became a unit of the Phelps Dodge Corporation when the latter absorbed the Calumet & Arizona company in 1931. Both Ajo and Chuquicamata are situated in low mountains in extremely arid desert country. Both ore deposits consisted-the past tense is used advisedly because the oxidized ore has nearly all been mined at Ajo-of a horizon of leachable oxidized ores overlying sulphide or concentrating ore. The principal technical problem in each case was the development of a method for treating the oxidized ore. In both instances the capping of waste rock was comparatively thin and power-shovel mining in open cuts was the obvious method of exploitation. Nature had smiled on neither place in the matter of climate. Though Ajo does not have the persistent winds for which Chuquicamata is notorious, the comforts of living are largely artificial. And it is only fair to emphasize that at each place the mining companies have achieved remarkable success in providing these comforts. Of course, in point of size New Cornelia must be content with the inferior role. From May, 1917, when production was started, to the middle of June, 1930, the company leached 16,368,000 tons of oxidized ore, thereby virtually exhausting the ores of this class. Up to the same date, about 15,000,000 tons of sulphide ore had been mined, and a rough estimate gives 170,000,000 tons remaining in reserve. The total tonnage does not loom very large in comparison with Chuquicamata's billion tons; but it is exceeded by similar figures for only four of the Porphyry group.

Jan 1, 1933

By Pekka Taskinen, Hannu Johto

"Copper sulfide concentrates often contain impurities such as lead and iron. The phase stabilities of the sulfide impurity systems in metallurgical process conditions are in many cases unsatisfactorily known. Thermodynamic information of a system gives better understanding of its behavior of metal making processes, but also has effects on the economic and environmental factors of the production process. In this study, isothermal equilibrium and quenching experiments of the stable phases of the system Cu2S-FeS-PbS at 700 and 900 °C were carried out and based on the experimental results, Gibbs triangle of equilibrium phases of the system was outlined.IntroductionThe knowledge of stabilities of phases and the thermodynamic properties of many sulfide systems in the temperature range of 500-1200 °C are quite limited. Especially, the knowledge of liquidus surfaces of multicomponent sulfide systems is essential for making many metallurgical processes more environmental friendly and allowing the utilization of complex concentrates. In this work, the aim was to investigate the phase stabilities of the quasiternary system CU2SFeS- PbS using evacuated silica ampoules. Of greatest interest were the properties of the liquidus surface in the system, in order to be able to predict better the formation of a liquid phase in metallurgical processes."

Jan 1, 2012

By D. E. Nash

Environmental compliance programs for mining companies are not only important management tools, but can deflect serious civil and criminal penalties if violations of environmental laws do occur. The paper discusses the legal foundation for such programs and their basic structure.

Jan 1, 2001

By J. J. Kanter

The choice of a nonferrous metal or alloy for a given Application is frequently predicated upon a consideration of properties other than merely the capacity to withstand stress. When ability to withstand stress is the dominant engineering requisite of the material to be used, economic considerations seldom lead to the choice of nonferrous metals and alloys. In most instances where a nonferrous metal is used it is because of some special quality of either corrosion resistance, electrical properties, thermal properties, antifriction, or fabrication advantage that commends its application. The mechanical properties, as a rule, present an incidental engineering consideration entirely secondary to the special quality deciding its use. Indeed, great ingenuity has often been exhibited by engineers and metallurgists in overcoming the mechanical shortcomings of a nonferrous base material. in order to take advantage of some outstanding property. . With this thought in mind, we might better appreciate some of the problems in stress design. encountered with nonferrous metals and alloys pertinent to a symposium on their creep characteristics. Our considerations must necessarily be far from complete because of the broad range of materials in the nonferrous category for which creep properties assume a technical interest. Creep deformation of these metals can be subject for study at temperatures ranging from ambient to incandescent, depending upon which one is under consideration. Whereas the steel metallurgist thinks of creep as an essentially high-temperature engineering consideration, the same is not necessarily true in the field at hand. The diversity of the creep problems in the nonferrous field is perhaps accountable to some extent for its virginity as a symposium subject. Each research has necessarily been sponsored by some organization or group interested either in promoting the use of a certain nonferrous base or in obtaining data toward the solution of a mechanical difficulty encountered in applying a material indispensable for its special attributes. Perhaps as many techniques of creep testing have been used as there are base metals implied under "nonferrous." Some of the creep problems that have occasioned researches are associated with steam-pressure vessels such as tubes, drums, castings, and forgings of copper-base and nickel-base alloys, cable sheathings of lead and lead-base alloys, electrical transmission lines of copper and aluminum, engine parts die-cast from alloys based on zinc, aluminum, copper— soldered and brazed joints-—as well as numerous duties at extremely high temperatures met with alloys based on cobalt, nickel, tungsten, molybdenum, platinum, and other precious or semiprecious metals. Postwar technology will have the benefit of much creep research on nonferrous metals, which for reasons of security cannot be discussed on this occasion. Suitability OF Metals As already intimated, the bulk of the constructional metal that ordinarily is

Jan 1, 1945

By H. E. Lee, P. C. Feddersen, D. R. Gittinger, G. W. Dunn, J. B. Schuettenhelm

The new Bunker Hill slag-treatment plant, designed ior, a capacity of 300 to 400 tons of hot slag per day, was "blown in" April 5, 1943. In the ensuing I5-months period, 157,530 tons of slag was processed, with an average recovery of over go per cent of the zinc and practically all of the lead contained. In addition to this high metal recovery, utilization of the waste heat in the gas and fume venting, the process has enabled the generation of 231,376 tons of steam at 250-lb, gauge. Over the first six months opcration the volume of slag treated averaged somewhat under 300 tons per day. Reclaimed dump slag made up only about 1 5 per cent of the plant feed. In October 1943, preparations for the smelting of additional tonnages of dump slag were completed and the plant capacity was increased to an average of about 420 tons of slag per day. During the nine-months interval since that date, monthly averages of 450 toils per operating day have been maintained several times. The new plant (Fig. I) is constructed in close proximity to blast-furnace operations. The fuming furnace and other necessary equipment are housed in an eastward extension of the existing blast-furnace building. Beyond this housed extension the dust-laden gas is conveyed about the perimeter of a large rectangle formed by the flues, cooling towers and baghouses. The course of a 10-ft. balloon flue, which transports the fuming furnace gas, describes the west and south perimeters. This flue connects with a set of cooling towers located at the southeast comer. The flue and cooling-tower system serving the deleading kiln constitute the north side and the two baghouses, serving the kiln and furnace operations, -border the east side. From these baghouses the several discharge gas flows are come biped and conveyed in to the rectangle, being vented to atmosphere by means of a fan through a centrally located zoo-ft. brick stack. In general, the plant design and operation follow quite closely that dictated by experience gained in years of slag-fuming practice by the Anaconda Copper Mining Go., at East Helena, Mont., and the Consolidated Mining and Smelting Co. of Canada, Ltd., at Trail, B.C., and more recently by the International Smelting and Refining Co. at Toocle, Utah. : Fuming operations at the East Helena and the Tooele plants are more or less identical. Trail practice differs chiefly in the methods employed for the storage of the hot feed slag and in the methods utilized for the handling and cooling of the fuming furnace gas. The new Bunker Hill fuming plant closely follows Trail procedure in the treatment of the furnace discharge gas while East Hclcna methods have been adopted for the storage of feed slag.

Jan 1, 1944

By Dean W. Lynch

Arizona: The San Xavier Indian Reservation mine is located approximately 2 ½ miles northwest of Asarco's Mission Mine southwest of Tucson. The company plans to produce oxide and copper-bearing siliceous ore at this operation, construction of which is scheduled for completion in 12 months. Asarco also plans a copper leaching and iron precipitation plant at its mine. The plant will leach 4000 tpd of oxide ore using sulfuric acid produced at the company's acid plant now under construction at Hayden. Copper precipitates will go to the smelter at Hayden. A drilling program at the Sacaton copper prospect in Pinal County, has disclosed two porphyry copper deposits. One deposit, mineable by surface mining, has approximately 17 million tons of material averaging 0.80% Cu. A deeper deposit suitable for under- ground mining has approximately 12 million tons averaging 1.5% Cu. Although Asarco intends to place this property in production, no startup date has been determined.

Jan 1, 1970

By Donald A. Brobst

The minerals barite (BaSO4 barium sulfate) and witherite (BaCO3 barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1973 consumed at least 80% of the world's produc¬tion of 4.4 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The re¬maining 20% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity fill¬ing, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world's demand for barite is expected to increase, and geologic circumstances are favor¬able for the discovery of new deposits of com¬mercial value. Witherite is much less common and abun¬dant than barite, although it is more desirable in many ways as a raw material for the pro¬duction of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world's barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir condi¬tions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemi¬cally, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite ho¬mogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber in¬dustry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and li¬noleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other sub¬stances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weight down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1975

By Waldemar Lindgren

I. INTRODUCTION AT the time of the discovery of America the old world had a scant supply-of the precious metals. Both the northern and the southern part of the new continent proved wonderfully rich in gold and silver and its treasures were eagerly looted; though the looting has lasted four centuries, the nines of its mountain chains are far from being exhausted. Even the later discoveries in Australasia and eastern Siberia could not rob the Western Hemisphere of its position as the greatest gold and silver producing region of the world, though finally the developments in a narrow and circumscribed area in South Africa wrested from the Americas their supremacy in the production of gold. Nevertheless the history of the two parts of the great western continent has been strikingly different. At first the Spaniards extracted vast treasures of silver from Mexico, Peru, and Bolivia, while Colombia and some placer deposits in Peru yielded a smaller quantity of gold. A couple of centuries later, a stream of gold began to flow from Brazil, the silver production from the countries mentioned above continuing strong in the meanwhile. Later on, the yield of South America diminished, but to offset this there began a wonderful series of discoveries in North America. The gold fields of California astonished the world; and when the cream of these had been skimmed off there began a no less amazing development of the Central Cordilleran gold and silver districts, which soon wade the United States the greatest producer of the precious metals. Aided by ever improving technique, extensive exploration, and a system of railroads, the yield was maintained and increased. Still later followed the discoveries of the gold fields of the arctic region and silenced those who had maintained that the zenith in gold production had passed. Recently the province of Ontario in eastern Canada

Jan 4, 1916

"The pumping of the underground water of the Butte mines is largely done from two central plants of the Anaconda Copper Mining Co. The mines of one part of the mining district are served by a modern and mechanically efficient underground plant at the High Ore mine, and the remaining part by a similar one at the Leonard mine. Properties not affiliated with the A. C. M. Co. have separate pumping plants, although in several instances that company handles the water of outside companies, under which arrangement costly single plants are dispensed with. An extensive system of underground crosscuts and drifts connects these mines to both the main pumping plants, so that either may receive the water from all the mines in case there should be a failure in the other to perform its designed service.Quintuple) vertical electric pumps, 7 inches by 12 inches each, of a capacity of 600 gals. per minute under a head of 1,203 feet, are installed at both the plants. Each pump is direct connected to two 150 h-p. motors using 2,300 volts, the motors being on top of the pumps.At the High Ore plant the power cable of 400,000 c. m. is placed in a nearby shaft, the cable at present being hung from the surface to the 2,200 level. From this cable feeders of 300,000 c. m. are laid in connecting crosscuts to the pumping station at the High Ore shaft.The Leonard motors use 440 volts. The practice of building the pumps with the motors on top requires stations with high roofs, but permits the operation of the pumps if they should be submerged by an unusual flow of water."

Jan 1, 1913

3-D finite element modeling was performed to study the effect of bedding plane sliding and separation and tensioned bolt in layered root It was found that the major influence zones of a tensioned bolt are restricted to the neighborhood of the anchor points; that bedding plane sliding and separation releases the vertical stress in the roof above entry but greatly increases the horizontal stress within the first layer of the roof, and that there is a triangular zone between the two adjacent bolts at and near the roofline level that is beyond the influence zone of the bolts which is liable to fail if conditions exist. Based on the results, three possible modes of roof failure are proposed for the design of tensioned bolting.

Jan 1, 2001

By Gerald A. Zicg

The Sheep Creek project area lies between 15 and 20 miles north of White Sulphur Springs in west central Montana, on the southern flanks of the Little Belt Mountains. The Sheep Creek project is a joint venture in which Cominco American Resources, Inc., has a 50% operating interest and BHP-Utah International, Inc., has a 50% participatory interest. The property consists of over 40,000 acres of leased fee land and lode claims. Modern exploration of the Sheep Creek area began in 1973 and 1974, when Homestake Mining Co. examined the extensive Sheep Creek gossans with soil sampling, trenching, and drilling. Cominco American Inc. began exploration in the area in 1976. Between 1978 and 1985, Anaconda Copper Co., Exxon Minerals Co., and Freeport also conducted exploration programs in the area. In 1985, Cominco completed consolidation of the district, gained BHP-Utah International, Inc., as a joint venture partner, and the joint venture drilled the first significant copper mineralization on the property. Of six bodies of copper mineralization so far located, the best defined are an upper copper zone, which includes a probable resource of 4.5 million metric tonnes grading 2.5% Cu and 0.1 % Co, and a lower copper zone which includes a possible resource of 4.5 million metric tonnes grading 4% Cu. Exploration drilling of the property is in progress.

Jan 1, 1991

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By I. D. Shah

Thermal decomposition of copper (II) sulfate (CUS04) and copper (II) oxy-sulfate (CuO?CUS04) are important steps in the overall oxidative roasting of covellite (CuS) and chalcocite (Cu2S). Nonisothermal thermogravimetric techniques were used to investigate the decomposition reactions in flowing Na and air. Thermal decomposition of CUS04 and CuO?CUS04 followed "linear" kinetics with an apparent activation energy of 55±2 and 66±3 kcal per mole decomposed, respectively. These apparent activation energies comply with those previously reported when isothermal kinetic techniques were used. The addition of oxygen decreased the rate of decomposition, while small amounts of iron which were admixed with CuO?CUS04 did not have a significant effect. Neither oxygen nor iron had any appreciable effect on the apparent activation energy of the decomposition reaction.

Jan 1, 1972

Several of the current concepts of brittle fracture involve consideration of, the existence of defects or flaws. Griffith 1 observed that the tensile strength of brittle materials was several orders of magnitude less than might be expected from the calculated strength of the molecular bonds. He was able to show that the stress concentration at the tip of an elliptical crack is sufficient to raise the local stress level many fold. He therefore proposed that real materials do contain such stress risers in the form of minute cracks and that this accounts for the rather large difference between theoretical and actual strengths of brittle materials. The degree of stress magnification depends to a great extent upon the orientation of the crack with respect to the general stress system, and to the general geometry of the crack. It is but a small step to extend the theory to include flaws and defects of other sorts which, though they may be less tractable mathematically than cracks, may still function as stress risers in a real sense in real materials. Brace 2 proposed that the application of the Griffith theory to rock material could be tested in two ways: "(a) by finding the orientation of cracks from which macroscopic fractures have developed and (b) comparing failure strengths from tests at different conditions of loading." In 1963 the author and coworkers at the Bureau of Mines, Twin Cities Mining Research Center, working on a problem involving relationships between strength, sonic velocity, and microstructure "eveloped an experimental technique to examine several somewhat similar questions; namely. does the frequency of occurrence of actual or potential stress risers dictate the relative strength of the material as proposed by Weibull;4 can actual flaws or defects in the rock structure be identified and related to strength and perhaps other properties in accordance with Griffith's theory; and is the anisotropic strength and elastic behavior of certain rocks related to the preferred orientation of these actual or potential stress risers? The experimental approach developed to answer these questions appears equally applicable to the testing of Griffith's theory as proposed by Brace. Basically the approach consists of a series of point-load tensile tests followed by petrofabric examination of thin sections prepared from the specimens in order to identify and apply a quantitative measure to microstructural defects which may have contributed to the failure process. In the point-load test, tensile stresses are induced by a compressive load applied to the center of a disc-shaped specimen by means of two opposing hemispherical indentors. Failure generally occurs as a single fracture parallel to the axis of loading and bisecting the disc. Because of the geometrical symmetrical the induced tensile stresses are symmetrical about the loading axis

Jan 1, 1967