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By John Birkinbine

The iron industry of the United States, and, in fact, of the world, was established with charcoal as fuel. Long before the value of mineral coal was recognized, the carbonization of wood was carried on in connection with various metallurgical processes, but at the present time we look upon establishments using charcoal as the remnant of a former greatness, and are apt to sympathize with the operators because they have no other fuel to depend upon. In the iron

Jan 1, 1883

By E. Buehler, E. Berry

HE magnetic properties of dilute palladium alloys are of fundamental interest.''' Neutron diffraction studies3 have indicated that a better understanding of the behavior of these alloys could be realized with the availability of high-purity single crystals of palladium. Crucible melts of 99.999 pct pure palladium were found inadequate for such research. In a successful effort to fill this need, floating zone refining of palladium was undertaken. In this note the results of the initial experiments are reported. Zoning was accomplished in an argon atmosphere using 450 kc rf generator for an energy source. Samples 5 to 6 mm in diam were suspended in a gastight quartz envelope which could be moved vertically through the rf coil. A nominal upward traverse rate of 1.5 mm per min was maintained during a pass. Close coupling was found to be essential for stable retention of the liquid in the zone. Single crystals averaging 3.5 cm in length were obtained. Laue photography showed them to be continuous single crystals without gross imperfections. Several criteria were used for evaluation of the purity of the zoned material: magnetic behavior, low-temperature specific heat and residual resistivity ratios. Table I shows the residual resistance ratios obtained for two samples, one subjected to a single pass, the other zoned four times. It is appilrent that palladium can be zone refined with the electrically active impurities being transported toward the tail end. A decrease in susceptibility for zone-melted specimens over any previously measured material from 1.5" to 80'~ has been obserted by H. J. Williams and R. C. Sherwood4 substantiating the residual resistance data. The specific heat measurements are currently being made3 and will be published at some later date. Discussions with J. H. Wernick and S. C. Abrahams are acknowledged. We also wish to thank G. F. Brennert for the residual resistance measure ments.

Jan 1, 1962

By D. Kunstelj, M. Stubicar, A. Tonejc, A. Bonefacic

A. Bonefafcic, D. Kunsfeli, M. Stubicar, and A. Tonejc The present communication is concerned with the variation of the texture in aluminum wires with die angle and temperature, at constant speed of extrusion. Experiments were carried out concurrently on refined samples, with a stated purity of 99.997 pct pure A1 and commercial samples of 99.5 pct Al. Ingots of refined aluminum samples were machined to 30-mm-diam by 150-mm-long billets. These billets were transformed to 5-mm-diam wires by drawing. The final form, suitable for examination, was obtained by extrusion through conical-face dies with a 1-mm hole diam and extrusion ratio 5:l in diam. The initial form of the commercial aluminum samples was drawn wire 5 mm in diam. These samples showed a poorly defined texture with (111) as a major and (001) as a minor component. A similar defined texture appeared in the refined aluminum samples after drawing to 5 mm diam. Conical-face dies with different angles (defined by the axis and the generating line of the cone) were used in our experiments. The values of the angles were 27, 35, 45, 57, 63, and 90 deg. The extrusion container was fitted with a heating element and controller permitting temperatures up to 600°C to be maintained within i5"C. Extrusion was performed at 250°, 300°, 350°, 400°, and 500°C at constant speed (approximately 1 mm per sec) and constant die reduction. The extrusion product was a wire 1 mm in diam and approximately 20 cm long. In order to remove the surface layer with the "conical" texture and to reduce the absorption by the X-ray examination of the samples, the extruded wire was etched to 0.22 mm in diam. Experiments were performed in the middle sections of the 20-cm-long wires. In addition to the die of l-mm hole diam, dies with a 1.5-, 0.7-, 0.6-, 0.5-, and 0.4-mm hole diam and 63-deg die angle were constructed. In our experiments we did not find in these ranges any important difference concerning the texture of the extruded wires and we continued our work solely on the 1.0-mm die. The diffracted X-rays (Cu K radiation) were recorded photographically. Diffracted intensities were measured on the (111) reflection with a microphotometer. The relative amounts of texture components were determined from the areas under the diffracted maxima. We found the texture of extruded aluminum wires to be strongly influenced not only by the temperature of extrusion and the purity of the sample but also by the form of the die. It is generally admitted that cold-drawn aluminum wires have mainly a (111) texture with a small amount of (001) component, Table I of Ref. 1. In our experiments with wires extruded in conditions represented by Fig. 1, in some cases a single (001) texture was obtained. If these wires were drawn repeatedly at room temperature, X-ray measurements revealed a duplex (001)-(111) fiber texture. Further drawings increased the (111) and decreased the (001) texture component. In Fig. 1 the percentage of material oriented with (001) parallel to the extrusion direction is represented as a function of the temperature and the die angle (a), for commercial and refined aluminum samples, respectively. From these diagrams we may draw the following conclusions. The slope of the die (a) influenced more strongly the texture at the lower rather than the higher temperatures. Again, a stronger influence was found in the case of the commercial in comparison with refined aluminum samples. In the case of the commercial aluminum samples the amount of material with (001) texture increases with increasing wire temperature in an approximately linear manner. This effect is less pronounced in the pure aluminum samples, with the exception of the die with a = 45 deg. In this case the (001) texture decreases with increasing temperature, as shown in Fig. 1. Component (001) is more pronounced in higher-purity aluminum samples. Our experiments led to the conclusion that both (001) and (111) components are essentially stable in extruded aluminum wires. As we obtained a single (001) texture starting with a sample of drawn wire in which the (001) component was very weak, our experiments revealed that the (001) component is not a remnant of the initial texture; this is in disagreement with the findings of Vandermeer and McHargue.1 We gratefully acknowledge discussions with Professor M. Paic. 1 R. A. Vandermeer and C. J. McHargue: Trans. 7MS-AME, 1964, vol. 230, p. 667.

Jan 1, 1969

By E. R. Johnson

THE copper concentrator of the Braden Copper Co. is at Sewell, Chile, on the western flank of the main Cordillera of the Andes, at an air distance of approximately 50 miles southeast of Santiago, the capital of Chile. The region is mountainous and space is at a premium because of the rough terrain and the danger of snowslides. The ore, a porphyry copper, is mined by a block-caving method in the El Teniente mine. It is hauled to the crushing plant, a distance of 2.6 miles, through a tunnel because of the severe climatic conditions. The usual large, coarsely set, primary reduction machines found in many ore-treating plants are not required because of the mining method employed and the limiting 12-in. spacing of the grizzlies at the head of each ore pass in the mine. It is the purpose of this paper to describe the numerous improvements made in the crushing section of this large flotation concentrator during the past 15 years to increase the efficiency of the plant and to raise the daily output from around 20,000 to 30,000 tons. The reader should keep in mind that all changes were made within the existing building because of the limited space and the high cost of the heavy mill construction required to withstand the snow loads. The present plant, as well as the former, operates on a 24-hr, 7 days a week basis. FORMER PLANT The crushing plant commenced operations at its present site in 1921, the main equipment being No. 7 1/2 gyratories, followed by 48-in. horizontal Symons disk crushers. Fines were removed by 1-in. stationary grizzlies ahead of each unit. In 1924 a third stage of crushing was provided by the addition of 55 1/2-in. rolls in open circuit. During 1925, the Symons disks were replaced by 73 1/2-in. rolls. All the rolls were changed to closed circuit, with elevators and screens to give a final product of 9 pct plus 3-mesh. The flowsheet of a typical crushing section of this period is shown in Fig I. The ore was withdrawn from a common bin serving the five crushing sections in the plant by means of any number up to six 36-in. wide-apron feeders, which discharged onto a common conveyor belt. This conveyor was equipped with a magnetic head pulley and the crusher attendant was stationed near the discharge end to pick out pieces of mine timber that might be in the ore. The ore was discharged over a 1 3/4-in. spaced bar grizzly and the oversize of this grizzly was crushed by a No. 7 1/2 McCully gyratory crusher set at 1 3/4-in. opening on the closed side. The grizzly undersize joined the gyratory discharge and was conveyed to a set of 73 1/2 by 20-in. Garfield rolls set at I in. These rolls operated in closed circuit with a bucket elevator and two vibrating screens placed in parallel.

Jan 1, 1947

By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts' law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts' law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965

By O. N. Cole, R. E. Davis, T. D. Brotherton

Pvfoperties of rubidium and cesium are compared with those of other alkali metals. Methods for the preparation of rubidium and cesium metal are reviewed briefly, ad hazards and safety precautions required in handling rubidium and cesium metal are described. SimPle methods for handling laboratory quantities of elemental rubidium ad cesium under oil and under argon are illustrated. CESIUM and rubidium were both discovered by Bunsen and Kirchoff in the years 1860 and 1861. Cesium was discovered while Bunsen and Kirchoff were making a spectrographic study of spring water from Durkheim, Germany. It was the first element discovered by this technique. The element was given the Latin name "caesius" for sky blue because of the color it imparted to flames. Elemental cesium was first prepared by Setterberg in 1881 through electrolysis of a molten mixture of cesium and barium cyanides.' In 1861, Bunsen and Mirchoff discovered rubidium while making a spectrographic study of the alkali content of lepidolite ore from Saxony. Two prominent dark red lines appeared in the spectrum and so the element was named "rubidius" or dark red. In 1861 Bunsen and Kirchoff first prepared elemental rubidium through the electrolysis of molten rubidium chl~ride.~ The alkali metals are very similar in their chemical and physical properties. They are the most active metals, and all exhibit a single oxidation state of one. They are so reactive that they are never found in nature in the elemental state. The reactivity of he metals increases with atomic number. Rubidiurn and cesium ignite spontaneously in air and react explosively with water. This extreme reactivity makes necessary special equipment and techniques for the safe preparation and use of the metals. The cation: of Group IA can be separated from the metallic cations of other groups with relative ease, but the separation of the individual alkali cations is much more difficult because of their close chemical similarity. This close chemical and physical similarity of alkali metals can be inferred from the atomic radii, oxidation numbers, and ioni-zation potentials shown in Table I. A difficult but the most practical physical method of separating the elemental alkali metals from one another is by distillation. Only lithium has a boiling point sufficiently far-removed from the boiling points of the other alkali metals to make this method of separation feasible without elaborate and expensive equipment. This method is not used, however, for lithium because it possesses sufficient chemical dissimilarity from the other alkalies for it to be separated relatively easily as lithium hydroxide monohydrate or as lithium carbonate. Francium, the last member of the group, has no known stable isotopes. The naturally occurring

Jan 1, 1962

M. A. SCHEIL (presented in written form).-Messrs. Franks, Binder and Brown are to be congratulated for the splendid paper that they have presented. We have not made stress-corrosion tests with the cantilever type of specimen which they describe, but it is well known that a uniform stress across a certain portion of the gage length can be obtained with such a specimen. This type of specimen would appear quite expensive to make. The writer was interested in the authors' remarks concerning the erratic results obtained from specimens with cold sheared edges. It might be of general interest to record here some results we obtained with annealed sheet N4 in. thick of type 304 stainless steel. After specimen No. 4 had been exposed 65 days without any signs of cracking we applied a strain gage and measured the stress as 25,810 psi. This value is considerably higher than we find for some of the type 347 stainless alloys and suggests that 18-8 might have a different threshold value for stress-corrosion cracking than 18-8 columbium. The test data in Table I show that strain caused by cold work or polishing has a pronounced effect in lowering the time for failure. In my paper I showed values of 8 hr. and 17 hr. to stress crack cold-rolled type 301 stainless steel stressed beyond the yield point. This steel contained 8.31

Jan 1, 1945

By A. E. Outerbridge

It has been generally accepted as a fact that cast-iron, under the influence of repeated shocks, becomes brittle, and will finally break under a blow which otherwise it would have withstood. It will probably surprise metallurgists, therefore, to learn that experiment disproves the supposed fact, and establishes exactly its opposite. The result of about a thousand tests of bars of cast-iron of all grades, from the softest foundry-mixtures to the strongest car-wheel metal, enables me to assert with confidence that, within limits, cast-iron is materially strengthened by subjection to repeated shocks or blows. It is very well known that the usual process of annealing castings—such, for example, as car-wheels—increases their strength by relieving cooling-strains. But it is not well known (if known at all prior to this announcement) that the molecules of cast-iron are capable of movement—for they do not touch each other*—without the necessity of heating the casting, and that they can thus rearrange themselves in comfortable relation to their neighbors, and relieve the overcrowding near the surface of the casting. In more technical words, a molecular annealing may be accomplished at ordinary temperatures which will release the strains in the castings, precisely as does annealing by slow cooling in heated pits or ovens. A statement so surprising should not be made without sufficient data to establish its correctness beyond cavil, since it is contrary to former

Jan 1, 1897

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

D. N. Williams(BatteZle Memorial Institute)-The authors have presented an extensive collection of arguments pertaining to the role of stress in hydrogen embrittlement. The basic assumption of these arguments is that stress is essential as a driving force for diffusion of hydrogen. However, in view of the rapid diffusion rate of hydrogen in steel at low temperatures as evidenced by the ability to alloy with hydrogen by electrolytic charging, it seems unlikely to me that stress acts in this manner. Instead, I would like to suggest that stress may be essential for the nucleation of hydrogen in steel. I believe that such an assumption would equally well satisfy the experimental data presented by the authors. I should also like to comment on the interpretation of the data presented in Figs. 5 and 6. Fig. 5 shows the effect of hydrogen content on ductility in a rupture test. The curve as drawn by the authors indicates an abrupt transition from ductile to brittle behavior at about 0.001 amp per sq in. (5 ppm). The data points would equally well support a gradual transition from ductile to brittle behavior extending over the range from 0.0008 to 0.02 amp per sq in. (4 to 8 ppm). A gradual transition would be the ex-

Jan 1, 1962

By John V. Beall

When the mineral seekers came, they brought romance, excitement and, too often, transitory riches. It has been so for uncounted centuries. While the rich ore lasted, living was high and money flowed-mostly out of town. The whole creation was like a circus. The headframe went up like the center pole of the big top. The reduction works was an ingenious affair; an opportunity for self-expression by the mining engineer on the job. When the high grade gave out or the bottom dropped out of the market, the whole show folded. Machinery was scavenged for the next location. About all that was left were the raw footings, like giantsteps on the hillside; and the headframe above the silent diggings. Mostly, the people went away too. Arizona Territory was like that at the turn of the century. It can still happen. But, in copper, the age-old pattern has been disrupted. From Mineral Park in the northwest to Chino in the east and Cananea in the South, a growing number of companies have emerged-large, stable, productive. Southwest copper is truly a mighty industry, accounting for one fifth of world new copper production. In this period of scientific development, changes are fast, often dramatic. But even mining engineers, or possibly more so because they have an intimate knowledge of the industry, fail to appreciate the evolutionary changes that have shaped Southwest copper into what it is today.

Jan 10, 1965

US 4,192,852-Precipitation of iron values as a jarosite from a sulfate solution obtained as a byproduct in the hydrometallurgical processing of zinc sulfide ore The solution is cooled, partially neutralized, and clarified. The clarified solution is heated to a temperature of 80 to 100°C in the presence of sodium, potassium, or ammonium ions to precipitate substantially all of the ferric iron as jarosite The precipitate is thickened, filtered, and washed The residual solution may be processed for zinc or other nonferrous metal values R V. Pammenter and C J Haigh, assigned to Electrolytic Zinc Co of Australasia Ltd. Mar. 11, 1980. 16 pp. (423-42) Filed: 5-8-78 (903,524). Priority- Australia, 5-9-77 (PD0030) (Drawings below.)

Jan 1, 1982

By J. T. Price

The study was undertaken to investigate the effect in the charge to a blast furnace of zinc and alkali contents, which tend to form accretions and scaffolds in the upper sections of the furnace. Commercial iron oxide pellets were reduced in a CO:N2, 40:60 gas mixture in a 5-cm by 5-m counter-current reactor (Rist-type apparatus) designed to simulate blast-furnace conditions. Pellets from a commercial magnetite concentrate were prepared in the laboratory with zinc (1% ZnO) and alkali (1% KOH) additions to the concentrate. Reducibility, crushing strength and swelling tests were carried out and the results compared with test data from pellets prepared without additions. The results indicated normal behaviour for those pellets containing zinc, whereas those containing alkali swelled catastrophically under the same reducing conditions.

Jan 1, 1977

By G. L. Craig

In order to meet the unprecedented demand for copper it has proven necessary not only to develop every primary source, but also thoroughly to exploit the vast reservoir of metal in use that is not directly serving the war effort. To accomplish this, industry has been called upon to use its resourcefulness for developing methods of recovery that have not been previously utilized. It is in this connection that we have been asked to review the methods suggested for recovering the basic constituents of various types of the so-called clad or composite steels. As a background for a discussion of recovery processes, it seems appropriate to consider clad materials in general and their processes of manufacture. A composite steel has been defined as one consisting of two or more component parts of which the smallest shall comprise at least 3 per cent of the total mass. Clad materials or composites are produced commercially by several different methods of which the most important may be classified as: I. The Blacksmith or Forge Weld Method. This method is limited to carbon steels or low-alloy steels as the presence of even small amounts of common alloying metals prevent the formation of a satisfactory weld. The principle is the application of pressure to sections in contact at elevated temperatures. Because of the tendency of the iron to oxidize, borax is generally used as a flux to absorb the iron oxide. 2. Casting Process-In this method a composite ingot, billet or cake is produced by pouring one metal onto or about another. The bond may be accomplished by the action of the molten metal against a solid, in which case the bond may be referred to as mechanical; while in other instances alloying occurs at the interface producing an anchor by the formation of component parts of the two materials. 3. Cementation Process.-In this process any number of combinations of metallic and nonmetallic constituents which are mixed together may be used as a bonding agent. The combinations, whatever they may be, are placed between the materials to be joined and subjected to pressures at elevated temperatures to produce the desired bond. 4. Fusion Welding Processes.-Gas and electric joining for direct use or subsequent fabrication. 5. The, Assembly Process.-This method involves the joining together of prefabricated bars or plates followed by hot and/or cold working the assembly to the desired finished form. This method is advantageous in many cases because of its flexibility on small quantities as compared to the casting method. It is also possible to control the relative proportion of components more accurately. In this discussion we are concerned only with the scrap resulting from the manufacture of clad materials and our interest,

Jan 1, 1943

By R. P. Carreker, J. G. Leschen, J. H. Hollomon

THE external appearance of a crystal which has undergone plastic flow suggests that adjacent blocks of the crystal have glided bodily past one another along the slip planes. However, the great discrepancy between the shear stresses calculated to effect such a movement and those actually observed has for many years stimulated searches for more satisfactory interpretations of the slip process. Appreciable success in these efforts has been realized by assuming the presence in the crystal of various sorts of imperfections and by considering the consequences of the presence of these flaws when stress is externally applied, The theory that has received the most attention recently-that of dislocations-postulates the occurrence of small, mobile imperfections or dislocations which move through the crystal along the slip direction, each dislocation being attended by a local shear displacement of one interatomic distance. Thus only that portion of the crystal through which the dislocation has passed may be said to have slipped, Since each dislocation produces a displacement of only one interatomic distance, an avalanche or train of many dislocations would be necessary to account for the observed displacements of several hundred or thousand interatomic distances. The salient point of the theory of dislocations is the concept that a slip band does not suddenly appear in its entirety. On the contrary, it grows progressively across the slip plane as the individual dislocations successively appear and advance in a train through the crystal. However, the concept of growth is not intrinsic only to the theory of dislocations, since atomistic mechanisms other than that postulated by the dislocation theory can quite probably also describe the growth of a slip band. For instance, a slip band might resemble a disc-like interface that appeared and then grew continuously from a small size, producing a displacement that increased with the size of the disc, Whatever the precise mechanism, the concept of growth is in itself consistent both with -the observed low values of critical shear stress and with the experimental observation that slip bands. frequently do not traverse the entire crystal. The likelihood that slip bands grow implies that they must first be nucleated and that the initiation of slip can therefore be analyzed in terms of the general concepts of nucleation. Indeed, this suggestion was advanced1 several years ago, but the matter does not appear to have been further pursued. Recent advances in the theory of nucleations2,3,4 have encouraged such a treatment of the slip process. As will presently be demonstrated, this approach to the problem not only accounts successfully for the incubation periods that have been observed5,6 to precede slip but also predicts certain transient effects in the deformation process, The existence of these transients apparently has not hitherto

Jan 1, 1948

By E. H. Denny

IN the past few years many men, including technically trained engi-neers, have been asphyxiated in metal mines, coal mines, tunnels and surface wells where a few relatively simple precautions with regard to ventilation and air testing would have saved them. Death from mine gases is analogous in some respects to death from poison and from drowning. The respiratory passages of a victim who has breathed oxides of nitrogen from burning explosives are badly irritated and a few hours or even a day after exposure he may develop a quick and fatal pneumonia; if, however, he enters without respiratory protective apparatus an atmosphere deficient in oxygen (a condition that may occur in unventilated or poorly ventilated parts of all underground mines) he collapses and if not rescued dies more quickly and surely than a lone nonswimmer who falls suddenly into deep water. An example of an atmosphere virtually without oxygen was demonstrated by an air sample taken by a Bureau of Mines engineer wearing oxygen breathing apparatus in a Cripple Creek shaft some years ago, during the recovery of the bodies of two victims of asphyxiation; analysis of the sample by the Pittsburgh laboratory of the Bureau showed the presence of 18.40 per cent of carbon dioxide, 0.27 per cent of oxygen, and 81.33 per cent of nitrogen, although the atmosphere apparently was clear and normal. In a mine one can pass from good, breathable air to an atmosphere that will kill as quickly as one can dive from a board to deep water below.

Jan 1, 1938

By C. Richard Tinsley, Norman Miskelly, S. James Hodge

Construction of the Ranger uranium project, located 230 kms east of Darwin in the Northern Territory, Australia, commenced in January 1979. Energy Resources of Australia Ltd (ERA) was incorporated in February 1980 to acquire all the rights in the project. The total cost to ERA of these rights was A$407 million, made up of A$125 million in cash to the Federal Government and the issue of 125 million A$1.00 shares at par, plus a payment of A$16 million in cash to each of Peko-Wallsend Ltd. (Peko) and EZ Industries Ltd. (EZ). ERA's cash requirements to complete the project were estimated in October 1980 to be A$553 million. Project loans, secured by first ranking debenture stock, were arranged for a total of US$390 million, while second-ranking debenture loans totalling A$60 million were [ ] obtained from the vendors, Peko and EZ. Overseas participants (power utilities who had agreed to purchase uranium yellowcake under contract) arranged to take up 25% of the equity capital for A$102.5 million; Peko and EZ were allotted 30.5% each as satisfaction of vendors' consideration; and 14% representing A$57.5 million was issued to Australian residents in an underwritten public flotation in November, 1980. The loan and equity financing arrangements required the successful resolution of many complex and interlocking factors, including technical and economic feasibility, agreement with Aboriginal interests, compliance with Government policies, and securing of sales contracts.

Jan 1, 1985

H. W. MussEn, Collingwood, Ontario, Can. (communication to the Secretary*):—Doubtless all engineers who have paid more than a casual visit to Russia have come into contact with that formidable document, the " smieta," or estimate of the Russian manager. It is an institution which seems to be inseparable from Russian mining-methods. As Mr. Shockley points out, the year's costs a agree very closely" with the figures of the smieta made at the beginning of the year. In cases which have come under my notice, I have been satisfied that there had been a good deal of " rigging" of accounts to this end. The sum spent by the manager was carefully kept down to the total of the estimate, because it was well known that no more money would be forthcoming, and when this is done it is not a difficult matter to see that the right amounts come under the right heads in the final accounts. I do not say that this is always the case, but I have come across notable instances. Looking at it from the Russian owner's point of view, I think that the balance of the argument is usually in favor of the smieta as limiting " impulsive indiscretion" on the part of managers. The Russian Mining Code of to-day leaves much to be desired, but this is thoroughly appreciated by the official world there, and great changes are spoken of for the future. In many, if not in most, cases the laws are interpreted liberally, and a great deal is left to the discretion of the district mining engineer or inspector, with whom it is necessary to keep in close touch. As Mr. Shockley points out, the officials of a mine, who are always Russians, are held personally responsible for accidents resulting to employees, quite independently of any compensation which may be made to the sufferer. This seems startling enough, but I have always found that a penalty is imposed only

Jan 1, 1909

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.', ' Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,' are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952

By Lauren A. Wright, A. E. J. Engel

Under the designations "industrial talc" and "soapstone" are included earth materials of widely different chemical and mineral compositions. Talc, the mineral, is a hydrous magnesium silicate, with a suggested theoretical formula H2Mg3(SiO3)4 or H2O.3MgO.4SiO2, which postulates 63.5 pct SiO2, 31.7 pct MgO, and 4.8 pct H20.18 Single grains or leaves of talc, however, seem to have variations in water content that range from 3.5 pct to more than 7 pct, as well as slight differences in the proportions of MgO and Si02.20 Most of the industrial talcs produced in the United States do not approach the composition given above (see Table 1), but are essen- [ ]

Jan 1, 1960

By A. R. Calawa, T. C. Harman, M. Finn, P. Youtz

A study has been made of the growing, annealing, and diffusion parameters in PbSe, Pb1-ySnySe, and Pb1-xSnxTe. Single crystals of these materials have been grown using the Bridgman technique. For all of the above materials the as-grown crystals are p type with high carrier densities. To reduce the carrier concentration and increase the carrier mobility, the samples are annealed either isothermally or by a two-zone method. From isothermal anneals, the liquidus-solidus boundary on the metal-rich side of the stoichiometric composition has been obtained for some alloys of Pb1-xSnxTe and on both the metal- and seleniunz-rich sides for PbSe and alloys of Pbl-ySnySe. In Pbo.935 Sno.065 Se carrier concentrations as low as 5 x1016 Cm-3 and mobilities as high as 44,000 sq cm v-1 sec-1 at 77°K have been obtained. Inter diffusion parameters mere also studied. The ddiffusion experiments mere identical to the isothermal or two-zone annealing experiments except that the samples were removed prior to complete equilibration. The resulting p-n junction depths were determined by sectioning and thermal probing. Inter diffusion coefficients for various temperatures were calculated for both PbSe and Pb0.93Sn0.0,Se. RECENTLY, there has been considerable interest in the PbTe-SnTe and PbSe-SnSe alloys with the rock salt crystal structure. The unusual feature of these systems is the variation of energy gap EG with composition. Several investigations1-3 have shown that EG for the lead chalcogenides decreases as the tin content increases, goes through zero, and then increases again with further increase in tin content. The possibility of obtaining an arbitrary energy gap by selecting the composition is an especially attractive feature of these alloys for applications involving long-wavelength infrared detectors and lasers. In addition, some unusual magneto-optical, galvanomagnetic, and thermomag-netic effects should occur for alloys with low band gaps. If uncompensated low carrier density crystals can be obtained, then a small carrier effective mass, a large dielectric constant, and the resultant high carrier mobility should yield enormous effects at low temperature in a magnetic field. The relative variation of the energy gap with pressure should also be very large for these low gap materials. The primary purpose of this paper is to provide some information concerning the preparation of low carrier concentra- tion, high carrier mobility, and homogeneous single crystals with a predetermined alloy composition. I) DETERMINATION OF ALLOY COMPOSITIONS In all of the work described in this paper, the composition of lead and tin chalcogenides in the alloys was determined by electron microprobe analysis. Separate X-ray spectrometers are used to make simultaneous intensity measurements of the Pb La1 and Sn La1 lines emitted by the sample under excitation by a beam of 25 kev electrons focused to a spot about 2 µm in diam. These intensities are compared to the intensities of the same lines emitted by standards under the same conditions. The standards used are the terminal compounds of each pseudobinary system, i.e., PbTe and SnTe for Pbl-xSnxTe alloys, PbSe and SnSe for Pbl-ySnySe alloys. The composition of the sample is then obtained from theoretical calibration curves which relate the weight fractions of lead and tin in the alloy to the measured ratios of X-ray intensities for the sample and the standards. The lead and tin calibration curves for each alloy system were calculated by using corrections for backscattered electrons,4 ionization,5 and absorption,6 and assuming that the atom fraction of tellurium or selenium in the sample and standards is exactly +. Results obtained by using the microprobe are in good agreement with those obtained by wet chemical analysis. II) CRYSTAL GROWTH FROM THE VAPOR Early work on the vapor growth of PbSe was carried out by Prior.7 He used small chips of Bridgman-grown single crystals as the source material and frequently converted the whole charge of a few grams into one crystal. In the present work, vapor growth occurred using a metal-rich or chalcogenide-rich two-phased alloy powder as the source material. Small, nearly stoichiometric crystals are formed on the walls of the quartz tube. The procedure will now be described in detail. Initially, a 100-g charge containing (metal)o.51(chalco-genide)o 49 proportions or (metal)o.49(chalcogenide)o. 51 proportions of the as-received elements in chunk form are placed in a fused silica ampoule. After the ampoule is loaded, it is evacuated with a diffusion pump and sealed. The sealed ampoule is placed in the center of a vertical resistance furnace. The region containing the ampoule is heated to about 50°C above the liquidus temper-ature for the particular composition used. After about one-half hour at temperature, the elements are reacted and the molten material homogenized. The ampoule is quenched in water. The quenched ingot is crushed to a coarse powder for vapor growth experiments and to a fine powder for the isothermal annealing experiments which are discussed in a later section. Vapor growth experiments were carried out using the powdered, metal-rich or chalcogenide-rich alloys

Jan 1, 1969