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By A. U. Seybolt

A FEW copper-zinc-base alloys meet die-casting requirements reason- ably well, although improvements are desired. Aluminum bronzes, high-tinbronzes and some copper-nickel-zinc alloys can be die-cast, accordingto Herb,1 but seldom are because of such factors as higher melting ranges and greater cost than certain of the brasses. Fox2 has summarized the copper-base die-casting alloys that were in commercial use in 1937 and has given the effects of different alloying constituents. Table 1 gives some of the properties of these alloys as reported by Fox. TABLE 1. Commercial Die-casting Brasses a Constituent Yellow Brass Low-silicon High-siliconb Brass Brass Nickel Silver Composition, Per Cent Cu 57-59 63-65 80 -81.5 42.0 Zn 40-42 33-35 13.5-16.0 41.0 Sn 0.5-1.5 Si 0.75-1.25 3.75-4.25 Pb 1.0 Ni 16.0 Properties Tensile, lb. per sq. in.. 55,000-60,000 65,000-70,000 85,000-95,000 85,000-95,000 Yield, lb. per sq. in.d.. 30,000-35,000 35,000-40,000 65,000-70,000 65,000-72,000 Elong., per cent in 2 in . 15-20 20-30 8-12 10-20 Brinell hardness 120-130 120-130 160-180 160 Specific gravity 8.47 8.50 8.15 8.45 Properties reported by Fox.2 b Trade name of Brastil, Doehler Die Casting Co., similar to Webert Alloy, 3,4 American Brass Co., and Tombasil Alloy,5 Ajax Metal Co. c Trade name Tinicosil, Titan Metal Manufacturing Co. Melting point (liquidus) of the yellow brass is given by Herb' as 1650° F., of the high-silicon Brastil (with 4.5 to 5 per cent Si) as 1600° F., and of the nickel silver as 1675° F. d Criterion not stated.

Jan 1, 1939

THE first session of the Institute was held on Tuesday evening, September 16th, in the William Molson Hall, of McGill University, Dr. T. Sterry Hunt, Chairman of the Local Committee of Arrangements, in the chair. Dr. Hunt introduced Monsieur S. Rivard, Mayor of Montreal, who spoke as follows : GENTLEMEN: We welcome you with pleasure to our city, and we are proud to find that you have deemed it worthy of your visit. I understand that your association was founded in 1871 with some thirty courageous members, and that so valuable has it been esteemed, and so attractive was it found, that nearly one thousand have now enrolled their names as members and associates. But we must regard your profession as dating back to the stone age and mingling therewith ; how remote that is none of us can tell. Much of civilization is due to the discovery of metals, and the magnitude of our works to their widespread abundance. If you have not accomplished what the alchemists aimed at, which was to turn the ruder materials into gold, you manage, by your subtle skill, to turn stones into gold value. Europe has long since been-dug into and perforated with shafts and galleries in search of metals, and great wealth, and power, and comfort have arisen there-from ; but by an increase of knowledge, and more than European enterprise and energy, America is following rapidly in the race, and by means of natural advantages of a geological character has out-stripped the Old World. We are pleased to see you, gentlemen, as an evidence of the unity of this continent. Maps may have various delineations, but the veins and arteries of commerce and the nerves of science knit all together into one social organism with the same vital functions. We live here on the margin of the world, and can claim but a modest share in. the great works of modern times, but such as we have that can interest you we gladly offer for your observation.' Our Victoria Bridge may he considered appropriate, for without mining engineers to precede the civil and mechanical, no bridge would be there to-day. In truth, the same may be said of all works of metal, and of all that are executed by tools and machinery made of metal. The Mont

Jan 1, 1880

By Thomas Varley

IN THE congressional act establishing the Bureau of Mines one of the functions outlined was "to assist I the industry in the prevention of mineral waste." This had not only to do with the waste in mining but in milling and metallurgical practices, including smelting. The organization of the Bureau of 'Mines includes many divisions, each working in a particular field and charged with certain investigative work. The metallurgical division has the above duties under its immediate supervision, and the station located at Salt Lake City is directed by the chief of this division: There are ten experiment stations of the Bureau of Mines, located in various parts of the country, most of them being housed at state universities under cooperative agreements. Considerable care was exercised in locating the stations and in choosing the particular type of work to be investigated at each place. Inasmuch as the Bureau was designed to serve and cooperate with the industry it is only natural that the investigative work be of interest and importance to the territory immediately adjacent to the respective stations.

Jan 1, 1925

By W. S. CAYPLESS, H. O. Hofman, E. E. HARRINGTON

I. INTRODUCTION. LIME-ROASTING is a term proposed by Ingalls 1 for the operation of forcing air under pressure through a mixture of galena and lime at the kindling-temperature with the object of oxidizing lead and sulphur and of fritting or fusing the charge. If, finely-divided galena were treated in this manner without the addition of lime, the heat set free by the oxidation of part of the lead and the sulphur would be sufficiently great to fuse undecomposed sulphide, and thus stop desulphurization. Besides the chemical action that the addition of lime, limestone or gypsum to the charge may have, the admixture has the physical effect that it keeps the particles of galena separated from one another and accessible to the oxidizing effect of the air. At present, three methods of lime-roasting are carried out on a working-scale, the Huntington-Heberlein, the Carmichael-Bradford and the Savelsberg2 processes. In the last, which interests us here, an 8-ton charge is made up of galena, limestone and perhaps some siliceous or ferruginous flux; the whole is crushed to pass a screen with 3-mm. holes and moistened with 5 per cent of water. It is fed gradually into a bowl-shaped converter, 6.56 ft. in diameter, supported by trunnions attached to a truck. On the .bottom the converter has a grate with blast-inlet beneath. In starting, the truck with the converter

Jan 1, 1907

By Paul E. Rosten

Introduction This papers describes some of the latest improvements that have been incorporated or planned by the Cleveland-Cliffs Iron Co. to reduce operating costs and improve pellet quality. The Cleveland-Cliffs Iron Co. operates and manages mining, beneficiation, and pelletizing operations in Michigan, Canada, and western Australia. This paper deals with the grate-kiln pelletizing operations at Republic, Humboldt, Tilden, Empire, and Pioneer in Michigan, and the Adams and Sherman in Ontario, Canada. Table I characterizes each operation in regard to location, ore type, pellet capacity and date that pellets were first produced. All of the operations with the exception of Pioneer and Tilden, utilize downdraft-two-pass grate cycles of drying followed by preheating. Pioneer utilizes an all-downdraft, three-pass grate cycle which consists of three drying zones followed by the preheat zone. The Pioneer and Tilden cycles have been described previously (Lindroos and Koski, 1966; Villar and Dawe, 1975; Koski, 1977). Tilden utilizes a three-pass grate cycle with a stage of updraft drying, followed by two downdraft drying stages. Recuperation systems which supply hot gases to a drying zone from second stage cooling were designed and fur¬nished for Tilden I. Tilden II will be identical. Empire IV will also be furnished with a recuperation system. The Adams grate¬kiln system was retrofitted with a recuperation system. This paper will summarize some of the efforts that are in effect or planned for grate-kiln pelletizing systems to: (1) reduce operating and maintenance costs, (2) reduce energy requirements, (3) improve product quality, and (4) meet environmental standards.

Jan 1, 1981

By Pei-Yung Huang, Carle R. Hayward

IN order to understand more fully the actual state of copper lost in copper reverberatory slags, a systematic study on the various reactions between certain metallurgically important copper compounds and synthetic copper reverberatory slags was undertaken by the authors in the Massachusetts Institute of Technology from 1942 to 1945.1 This paper, being only a part of the work completed, is published first because it furnishes the first experimental evidence of the formation of copper ferrite from reactions between cuprous oxide and copper reverberatory slags. CHOICE OF SLAG COMPOSITION The choice of the composition of the synthetic reverberatory slags to be used was much deliberated. Commercial copper reverberatory slags, neglecting minor constituents, average:2.3 45 to 47 pct FeO; 38 to 42 pct Si02; 5 to 6 pct CaO; 5 to 6 pct A1203. Since the ternary system CaO-FeO-SiO2 has been much more thoroughly studied4 and is much simpler than the quaternary system CaO-FeO-Si02-A1203, it was decided to use calcium oxide only instead of calcium oxide and alumina in the synthesis of the slags. Fortunately the composition of the average copper reverberatory slag with calcium oxide substituted for alumina lies in the region of the phase diagram clarified by the investigators. A survey of the phase diagram (Fig I) suggested two compositions: (I) the com¬position near the invariant point S, which is made up of 46 pct ferrous oxide, 37 pct silica and 17 pct calcium oxide; (2) the composition near the invariant point K with 45.5 pct ferrous oxide, 43 pct silica and 11.5 pct calcium oxide. Composition S has the advantage that the percentages of ferrous oxide and of silica almost exactly coincide with those of the average reverberatory slags, and that of the lowest melting point (1093° ± 3°C) in the whole ternary system. The calcium oxide content, however, obviously is high. Since we have already substituted calcium oxide for alumina, and since calcium oxide is more basic than alumina, the resulting slag is decidedly too basic. Composition K has a slightly higher melting point (1105° ± 3°C) and a higher silica content, but this is preferred because the slag is saturated with respect to tridymite and thus should not corrode siliceous refractories. Besides, it is less basic than composition S. The final slag composition, therefore, was chosen to

Jan 1, 1947

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."' These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11'74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By W. A. Tiller, W. C. Johnston

A high-temperature electromagnetic stirrer is described in which heating and stirring are accomplished by independently controlled power sources. The appavatus is suitable lor use at temperatures up to 1700°C in a variety of ambient atmospheres. Some typical examples of the homogenizatimz capabilities of the system are given. THERE are few processes in solidification that are not markedly affected by motion in the melt during freezing. In many instances, the mechanisms are diffusion-controlled, and the transport in the melt may be greatly accelerated by deliberately stirring the melt. In zone-refining, stirring1 assists the removal of rejected impurities from the interface, so the process proceeds at a faster rate. The transition from a planar to a cellular interface is caused by constitutional undercooling in the melt ahead of the interface: and stirring delays its onset. Stirring is valuable for homogenization of melts: and chemical reaction with sluggish kinetics may be accelerated. Finally, it has been observed that grain refinement is related to motion in the melt. Fine grain castings are usually produced by the addition of catalysts to the -melt,' catalysts which are thought to act simply as hetereogeneous nucleation centers. Even here motion is important. Richards and Rostoker 5 applied ultrasonic vibration to a solidifying A1-Cu alloy which had been innoculated with a catalyst and found that the grain diameter fell linearly with the amplitude, the peak acceleration and the power input to the melt from the transducer. Finally, mechanical and electrical stirring alone have been used to generate a fine-grained structure.6,7 Johnston ef a1.' have carried out a series of systematic investigations of grain refinement by electromagnetic stirring in a number of low melting point alloys. They found, for example, that the number of grains per unit volume in Pb-Sn alloys could be increased several orders of magnitude by stirring an undercooled melt at the moment of recalescence. In general, a relation AT .H = constant prevailed for a given grain size, where AT was the undercooling of the melt and H the field strength. In more recent work, deliberate homogeneous nucleation of slightly undercooled melts established that the mechanism of refinement must be one involving crystal fragmentation and subsequent multiplication, rather than a "shower" of nuclei effect.9 It is the purpose of this note to describe a stirring device suitable for use up to 1700°C. At low temperatures mechanical stirring and direct-current methods are feasible, but at high temperatures the problem of a protective atmosphere and of electrode corrosion rules out such procedures. The most convenient method for high temperatures is to use externally generated ac fields for both stirring and heating. With rf induction heating alone, considerable stirring and agitation can be achieved, but in general the penetration of field into the melt is small, and the stirring cannot be controlled independently of the heating. In the present experiments, separate power sources of different frequencies for heating and for stirring were used. A susceptor design was chosen so that the 450 kc rf heating field was completely absorbed in the susceptor. The stirring frequency, 400 cps, hereafter called the af field, was chosen so that a high penetration of the melt proper was achieved. EXPERIMENTAL APPARATUS The apparatus, Fig. 1, consists of a quartz tube and end plates, surrounded by an rf induction coil and six equally spaced af stirring coils, four of which are shown in full and a fifth in section. Each af stirring coil is a transformer of which the secondary is a single-turn water-cooled copper loop and the primary is composed of two 10 amp-117 v Variac cores as shown. These cores are cooled by forced air, as each of the six pairs will carry maximum currents of 15 amp for short periods. Each set of Variac windings are connected in series, but opposite sets are connected in parallel with a three-phase 400 cps 400-v source. By properly phasing the coils in this way, a rotating field is produced. Capacitors C1, C2, and C3 in Fig. 2 are used to match this inductive load to the generator. Fig. 3 shows a cutaway view of the quartz tube. The sample (1 in. diam by 1 in. high) is placed in a tapered alumina crucible. An axial W-26 pct Re thermocouple, enclosed by a protection tube, is provided. The cruci-

Jan 1, 1968

By William T. Folwell

The Lucky Friday mine east of Mullan, Idaho, is an outstanding example of a property in the Coeur dlAlene district where a small and insignificant-appearing silver-lead-zinc vein at the surface has changed at depth into a large vein of great importance. The Lucky Friday vein has little if any surface expression and above the 1200 level the ore shoots are small and discontinuous. Between the 1200 level and 2450 level, the lowest developed level, the main ore shoot has shown remarkable improvement on each succeeding lower level, and today the mine is one of the major lead-silver producers in the Coeur d'Alene district. History: The Lucky Friday property is on the north side of the South Fork of the Coeur d'Alene River in sections 25, 26 and 35, T. 48 N., R. 5 E., Hunter mining district, Shoshone County, Idaho. This is about one mile east of the town of Mullan, which serves the eastern portion of the Coeur d'Alene district. The southern part of the property is crossed by a branch line of the Northern Pacific Ry. and by U. S. Highway 10. This highway is the principal road crossing the panhandle of Idaho and connects the district with Spokane, Wash., on the west and Missoula, Mont., on the east. The main portal and surface plant of the Lucky Friday mine is at an elevation of 3365 ft, only a short distance above the valley floor and a few hundred feet from U. S. Highway 10. so the mine is readily accessible for year-round operation. The property is comprised of six claims, known as the Lucky Friday group, owned outright by the Lucky Friday Silver-Lead Mines Co. There are four patented claims, Good Friday, Lucky Friday, Northern Light, and Lucky Friday Fraction No. 2 (Mineral Survey No. 3028), and two unpatented claims, Hunter and Creek. In addition, Lucky Friday owns an undivided one-half interest in the Hunter Creek property. which adjoins the Lucky Friday group on the north: a 90 pct interest in the mineral rights in the Jutila Ranch (160A), which adjoins the Lucky Friday group on the east; and a 60 pct interest in the Lucky Friday Extension claim group, which adjoins the Lucky Friday group on the west. The company also has a long-term mining lease on the Hunter Ranch, which adjoins the Lucky Friday group on the west. The claims of the Lucky Friday group were located between 1899 and 1906. The Lucky Friday Mines Co. was organized in 1906 and did considerable exploration work by surface trenching and shallow underground workings, only to see the property sold by the Shoshone county sheriff to satisfy labor claims totaling $2000 in 1912. Another firm, Lucky Friday Mining Co., bought the claims in 1914 and spent 12 years driving what is now known as the tunnel level crosscut. This tunnel intersected a vein previously exposed in a higher tunnel, but it was only a few inches wide. The vein was followed a short distance westerly but was so unpromising that the work was discontinued in favor of extending the main crosscut tunnel several hundred feet north. No ore was found and all work was discontinued. The property was held in such low esteem by the firm that it let taxes amounting to less than $15 a year go delinquent for nine years. Then the property lay idle for two more years until in 1938 John Sekulic, a Mullan service station operator, took a lease, with a $15,000 purchase option, on the advice of an old miner who had worked in the mine. Sekulic re-opened the tunnel level crosscut and explored the vein with an easterly drift for about 200 ft. The vein was too narrow to be of commercial value but was believed interesting enough to warrant further exploration at depth. Lacking funds to explore the vein at depth, Sekulic tried to get the district's larger operating companies to take over his lease and option. They were not interested because of the lean tunnel level showing and the fact that the property lay between the White Ledge fault on the north and Osburn fault on the south, an area which geologists always considered unworthy of exploration. Sekulic then organized the present company and assigned his lease and option to it for stock. This was in 1939. Enough stock was sold locally to finance sinking of a shaft 100 ft from the tunnel level east drift. The vein at this additional depth still was not commercial but showed some improvement. Treasury stock was offered at 5 to 10C a share

Jan 1, 1959

By James R. Holden, Frederick E. Wang

Through both single-crystal and powder X-ray diffraction methods, ten A6B23-type compounds have been confirmed to exist between lanthanides (A) (plus scandium and yttrium) and manganese (B); A = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The formation of a compound of this type is shown to he extremely atomic size-sensitive; hence it can be classified as a "size-factorH compound. The "enveloping effect", a geometrical consideration observed in its crystal structure, is proposed as the reason for the A6B23-type compound being size-sensitive. The approximate ideal geometrical ratio of the radii R/r is 1.31 while experimentally A6B23-type compounds have a radius ratio lying within the range 1.2 to 1.4. FLORIO t al.' characterized the structure of Th6MnZ3 as fcc, space group Fm3m, with 116 atoms in the unit cell. Since then, a number of isotypic binary compounds, and recently Gd n,,' have been confirmed to exist. The fact that strontium and barium form A6Bz3-type compounds with magnesium strongly suggested the possible existence of Ba6Liz3. However, investigation3 showed the compound Ba6LiZ3 to be absent. Since both strontium and barium are group 11-a elements and are therefore "open metals",6 the nonexistence of Ba6LiZ3 can hardly be explained satisfactorily by valence-electron considerations. On the other hand, the consistent atomic-radius ratio, (R/r),* observed for the known A6Bz3-type compounds,3 strongly suggests that the formation of compounds of this type is atomic size-sensitive. Therefore, one is tempted to explain the nonexistence of Ba6LiZ3 entirely on the basis of the atomic-size difference between strontium and barium. However, this approach is not entirely without objection. Atoms are not rigid spheres and are known to vary in size within certain limits.7 Since the atomic-radius difference between strontium and barium (0.07 to 0.09A) is within these limits, it is reasonable to assume that the size difference would have a negligible effect on the formation of Ba6LiZ3. This view is further supported by the fact that the radius ratio, R/r, in other known "size-factor" compounds is observed to range widely—for example, from 1.08 to 1.45 for ABz-type compounds (C15, MgCuz type)' and from 1.37 to 1.58 for AB5-type compounds (D2d, CaZn5 type).g The present investigation was undertaken in order to find a more satisfactory explanation for the non-existence of Ba6LiZ3 and, consequently, a better understanding of the nature of the A6Bz3-type compound. The primary objectives are to confirm the previous conclusion3 that the A6B23-type compound is indeed a "size-factor" compound and subsequently to determine the atomic-radius ratio range in which the A6Bz3-type compound can exist. In order to achieve these objectives, stoichiometric A6Bz3 alloys, where manganese (B) was alloyed with various lanthanide elements (A), were selected for investigation. The atomic-radius ratios of lanthanide elements with manganese range from 1.26 for Lu/~n to 1.46 for Eu/Mn. This radius ratio range includes and exceeds the range of all previously reported A6Bz3-type compounds—1.32 for Th/Mn' through 1.38 for Sr/Li. Furthermore, the atomic-size difference between successive elements of the lanthanide series in order of atomic number) is of the order of 0.01A (europium and ytterbium are exceptions). The series of lanthanon-manganese alloy systems is ideally suited to a precise determination of the limits of allowable atomic-radius ratio for A6Bz3-type compound formation. EXPERIMENTAL PROCEDURE The lanthanide metals, in ingot form, supplied by Michigan Chemical Corp. (St. Louis, Mich.) and Nuclear Corp. of America (Burbank, Calif.), were guaranteed by the suppliers to be at least 99.9 wt pct pure (traces of silicon, calcium, and other minor constituents present on occasion, not to be more than 0.05 wt pct) as shown by spectrographic analysis. Manganese metal, in polycrystalline form, was redistilled from the commercial, chemically pure grade and was analyzed to be at least 99.95 wt pct pure. In all cases, the atom ratio between the two elements in each charge was A (rare-earth meta1):B (manganese) = 6:23 and a constant weight, 3 g, of

Jan 1, 1965

By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson' obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock' used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

By F. M. Morris

A large reserve of thick coal in southwest Virginia was developed by Clinch-field Coal Co. in 1957-1958 to produce a nominal rate of 1500 tph raw coal. Operation features coal cleaning in transit. Refuse removed averages 35 pct. Evolution of plant from initial conception to completion is discussed, selection of means applied is explained, and performance to date us design expectation is described. The long-range plan calls for ultimate handling capacity of 40,000 tpd raw coal with anticipated clean coal capacity of 26,000 tpd on a three-shift basis. From a materials handling viewpoint, the Moss No. 3 operation is principally of interest as an ensemble. Generally speaking, it uses time-tested equipment and ideas but some of these are employed on a scale that may be new in the industry. At present about 20,000 tpd of raw coal are being handled. This is expected to increase to 40,000 tpd as soon as business conditions justify it. The purpose of this paper is to discuss the evolution of the plant as to materials handling practices, to describe briefly the equipment and methods used, and to comment on performance in certain areas. The subject divides itself naturally into four phases: 1) operations at the mines, 2) transportation from mines to plant, 3) raw coal handling into the plant, and 4) transportation of refuse away from the plant. OPERATIONS AT THE MINES The coal reserves for Moss 3 are in southwest Virginia where Dickenson, Russell, and Buchanan Counties come together. This area contains about 15 square miles and over 100,000,000 tons of coal. Here the No. 4 (Tiller) and No. 5 (Jawbone) seams of the Norton Formation lie so closely together that for practical purposes, they constitute one seam of coal. This seam, which is called the Thick Tiller, varies from 10 to 18 ft in thickness and underlies Sandy Ridge, a mountain cresting between 2400 and 3300 ft above sea-level. At 18-ft seam height (which is considered to be the maximum practical mining height) the parting between seams will be about 3 1/2 ft thick and each bench of coal will be about 7 ft thick. Depending on the amount of impurities in the seams Drover. total reject in this height coal may approximate 50 pet by wt. It will average about 35 pet for the property as a whole. The first move in developing this resource was made in 1953 when contour maps of several square miles around Duty, Va., including all the known outcrop, were made by photogrammetry. At this time, it was felt the prospective operation would be served by the Clinchfield Railroad and a photogrammetric route survey was made by this railroad from Haysi to Duty. Study of the resulting maps indicated only one site—adversely owned—which might accommodate the size washing plant to be erected. Water resources of a dependable nature seemed nonexistent. In 1954 bulk washability tests were made on the Tiller Bench at the Moss No. 1 preparation plant. The tests indicated this portion of the seam, mined separately, would wash to 4 pet ash with good recovery. Also in 1954, development of Moss No. 2, south of Sandy Ridge, was begun. This mine is in the Tiller Seam where it is about 100 ft below the Jawbone Seam. The reasons for developing a mine in the normal Tiller Seam before tackling the Thick Tiller seemed compelling: Railroad service could be established quickly, communications were better (though not good!), more was known of the seam (it had been mined in the years 1911 to 19241, and there was no essential property to be acquired. After some legal skirmishing, the Norfolk & Western Railroad was granted the right to serve the new mine. Three decades earlier the old mine had been served by the Clinchfield Railroad. The event which triggered active development of Moss 3 was the Appalachian Power Co.'s decision in 1956 to build a 450,000-kva power plant on Clinch River at Carbo. This solved the problem of marketing the steam coal which inevitably must be a product of a mine in the Thick Tiller. Management promptly decided to build the preparation plant at Carbo where an excellent site was owned; where railroad service existed; where telephone service could be obtained; and where roads, bridges, and water supply were tolerable.

Jan 1, 1961

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967

By Harry A. Lipsitt, Douglas Y. Wang

A fatigue study in completely reversed axial tension-compression has been perforried on high-purity titanium and on three high-purity alloys of titanium. The alloys each contain approxi7nately 0.75 at. pct of a single interstitial element; carbon, nitrogen, and oxygen, respectivley. The results corroborate a previously published theory which proposed that strain aging under alternating stress was responsible for the fatigue limit behavior of certain alloys. The present data indicate that in these alloys an increasing strain-talline aging effect under alternating stress is provided by oxygen, carbon, and nitrogen, respectively. CURRENT research on the nature of the fatigue limit in metals suggests that the presence of a fatigue limit in metallic materials is a manifestation of strain aging that occurs under alternating stress.lm5 A comprehensive theoretical model based on the above hypothesis has been developed to explain the existence of a fatigue limit.' This model also provides increased insight into several other fatigue phenomena as under stressing, overstressing, and coaxing effects. The theory, as well, provides equal understanding for those cases where no real fatigue limit is observed. Briefly, this theory assumes that the S-N curve for a pure metal is a smooth function of the applied stress, and the effect of adding an element that is soluble (or forms a precipitate) in the pure metal is simply to shift the S-N curve to the right. If the added element confers the power to strain age, the result is a further shift of the S-N curve, this time upward and to the right. Since strain aging is not expected to be a strong function of stress, and since damage per cycle is known to be quite stress dependent, it is to be expected that there will be some limiting lower stress at which the strengthening due to strain aging will balance the damage due to crack propagation. This stress is the fatigue limit. The position of the fatigue-limit knee was thought to be a function of the magnitude of the strain-aging effect on both the finite and infinite life portions of the S-N curve. Although the strain aging hypothesis seems to be reasonably valid for bcc materials,2'6 it needed to be tested for both fcc and cph metals. This report is the first of a series concerning the fatigue-limit behavior of titanium with varying amounts of the interstitial solutes (C, N,, and 4) that are known to cause static strain aging in titanium. Yield-point effects have been reported for polycrys-talline high-purity titanium alloys containing either carbon, nitrogen, or oxygen.7'9 These effects were observed at testing temperatures in the range 100 to 300'. In addition yield-point and strain-aging effects have been reported for single crystals of titanium containing 0.1 wt pct C plus N.' These yield points were observed over a wide temperature range, but no room-temperature aging occurred. Aging at 180' was required to cause the return of the yield point. The magnitude of the yield phenomena in titanium containing interstitials is not expected to be as large as is observed in bcc metals because of several factors. Titanium has a very high chemical affinity for oxygen and nitrogen. The thermodynamic stability of solutions of oxygen or nitrogen in titanium is recognized. Lattice parameter measurements of titanium containing arbon, oxygen,1° or nitrogen" show that the "c" parameter is expanded more than the "a" parameter, but that up to about 2 wt pct this results in an insignificant change of the axial ratio 'c/a." Ehrlich" has shown that the sites occupied by interstitial atoms in titanium are spherically symmetrical and therefore a lattice expansion, at a constant c/a ratio, results in a simple dilation of the interstitial site. Such a dilation involving no shear has been shown to react only with edge components of dislocations.13 This causes only a weak pinning action. Shear stresses would be anticipated locally when only one of the two interstitial positions was occupied. The carbon atom will cause a symmetrical distortion of the lattice whereas the oxygen and nitrogen atoms have, in addition, the previously mentioned chemical affinity of titanium for these elements. These factors will result in a considerably smaller reduction of free energy upon the association of interstitial atoms with dislocations, and therefore a much weaker pinning than has been observed for the bcc metals. These considerations would lead to the hypothesis that of the interstitial elements considered here carbon would cause the strongest pinning effect in titanium where the amount of interstitial in solution is constant. This hypothesis will be borne out in the analysis of the present results.

Jan 1, 1962

By B. M. Larsen, T. E. Brower

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

Jan 1, 1952

By T. Watanabe, S. Karashima, H. Oikawa

Creep tests of a! iron and its solid-solution Fe-Mo, Fe-Co, and Fe-Si alloys with bcc structure were conducted under constant stresses in ferromagnetic and paramagnetic temperature regions above 0.5T,(T, is the absolute melting temperature). It was found their high-temperature creep behavior changed in the vicinity of the magnetic transformation temperature, that is Curie temperature, TC. In the ferromagnetic region below the steady-state creep rates were lower than those expected from the extrapolation of the data in the paramagnetic region, the amount of decrease being affected by solute addition. Also, activation energies for steady-state creep were different in the two temperature regions. The observed changes were concluded to be due to the effect of ferromagnetism on diffusion. It is well-known that plastic deformation of metals and alloys in the temperature region where mobility of atoms becomes high enough is controlled by atomic diffusion." Many experimental results394 on fcc and hcp materials have been reported to confirm this view. In bcc metals and alloys, not much basic investigation of creep deformation has been performed. In particular, experimental work on iron5-&apos; and its alloys, covering a quite wide temperature range is extremely scarce. On the other hand, the effect of ferromagnetism on diffusion has recently been demonstrated in a iron and its alloys;&apos; it has been made clear that diffusion rates in ferromagnetic temperatur~e region are significantly lower than those expected from diffusion measurement in the paramagnetic region. Therefore, it is concluded that the magnetic effect influences the high-temperature creep behavior in a! iron and in its alloys. The present authors have conducted creep experiments on a iron and its solid-solution alloys over a very wide temperature range, and have demonstrated the magnetic effect. A part of the result has already been reported elsewhere.26 In this paper, the experimental results will be described in detail. While the manuscript was in preparation, a similar magnetic effect on creep deformation of a iron was reported by Ishida . Though their experiments covered an extremely wide temperature range, the creep stresses varied from several thousand psi to several ten thousand psi with decreasing temperature. Consequently, it may be said that there remain some questions concerning their results. I) EXPERIMENTAL PROCEDURE The materials used in the experiments were pure iron and its alloys; they were prepared by vacuum melting (10"" mm Hg) electrolytic iron (99.9 pct), molybdenum powder (99.9 pct), ultrapure silicon, and cobalt pellet (99.5 pct) in alumina crucibles. The ingots were hot-forged to plates 10 mm thick and 50 mm wide, and then were hot-rolled at about 700°C into sheets 1 mm thick. Creep specimens, 5 mm in width and 15 mm in gage length, were machined from the sheets. They were annealed at temperatures which were well above their respective recrystallization temperatures. The chemical compositions of the metal and alloys are shown in Table I together with their heat treatments. High-temperature creep tests by the use of a lever-type creep testing machine were carried out in argon atmosphere under constant tensile stress. In order to keep &eep stress constant within about *0.5 pct, stress change due to specimen elongation was compensated by tensile force of a stainless-steel bellows which was inserted between the loading lever and lower specimen grip with the assumptions of a linear relationship between change in cross section and strain and uniform strain along the section. Beyond the limit of compensation by the bellows, small amounts of load were removed after appropriate strains. The testing temperatures were maintained to within i2"C of the reported values. Creep deformation was auto-graphically recorded at the upper (moving) specimen grip using a linear differential transformer which was held by a stainless-steel rod mechanically connected to the lower specimen grip. It was also directly measured with a dial-gage reading to -& mm. 11) EXPERIMENTAL RESULTS AND DISCUSSION 1) Creep Curves of a Iron and Its Alloys. Creep curves of a! iron, Fe-Si, Fe-Co, and Fe-Mo (<2 at. pct Mo) alloys usually consisted of three stages, that is transient (primary), steady-state (secondary), and accelerating (tertiary) stages. An example is illustrated in Fig. 1 for a! iron. However, in Fe-Mo alloys with more than 2 at. pct Mo, an inverse transient creepZ8 was observed as indicated in Fig. 2. The inverse behavior, which varied with the amount of molybdenum, may be due to the substructure* in the annealed specimen as was sug-

Jan 1, 1969

By G. A. Swanquist, E. M. Morales

INTRODUCTION The idea of water management and control at the Church Rock Mill operations began to take shape in February 1979. At that time, we were already investigating the feasibility of decreasing the fresh water requirements so that the solids would become the limiting factor in tailings impoundment utilization. The area for solution evaporation could be kept at a fraction of the normal requirements under the standard process of full water usage. The Church Rock Mill is an acid leach circuit followed by solids/liquid separation with thickeners in counter current decantation, and solvent extraction. Following the normal design of acid leach circuits, reuse of tailings solution was not incorporated in the original mill process design. INITIAL WATER CONTROL INVESTIGATIONS The investigations to decrease the fresh water requirements centered around modifying the grinding circuit from the present semi-autogenous grinding (SAG) mill in closed circuit with hydrocyclones, to open circuit grinding with a rod mill. The open circuit grinding with the SAG mill and rod mill in series had the potential of decreasing the water requirements for grinding and leach dilution by approximately 50% or 1.4 m3/min (300 gpm). The grinding pulp density would be maintained at 70 to 72% solids, and the leach dilution to 50% solids would be accomplished with acid tailings liquor recycle. In such a grinding circuit arrangement, the SAG mill would provide the primary or coarse grind, and the rod mill would be used for the fine grind. By the SAG mill and rod mill series grinding method of water control and other secondary water controls in various places downstream from the grinding circuit, the required necessary evaporation area was estimated at 120 acres of liquid surface. A second method of water control at grinding was investigated. A two-stage cyclone classification circuit appeared to have a good potential of achieving the same water reduction at a much lower capital and operating cost. However, in retrospect, this would not have been a viable method since a high slime recycle load would have been established hindering classification. The use of reagents to neutralize the acid tailings solution was not considered seriously at that time, since it would have materially increased operating costs, although it would have also allowed more tailings solution recycle and consequently, less fresh water usage. However, with the tailings solution deposition area available at that time, it was not then necessary to incur the high cost of neutralization. The control expected by the series grinding of semiautogenous and rod mills would have been sufficient to maintain a water consumption/evaporation equilibrium well in line with the available land area. IMPLEMENTATION OF NEUTRALIZATION OPERATIONS During the summer of 1979, the UNC Church Rock Mill experienced a tailings dam breach which resulted in a prolonged mill shutdown. Upon resumption of operations at the end of October 1979, tailings deposition was restricted to a small portion of the tailings impoundment area. Figure 1 shows the general tailings area and the limits of the present deposition area in the central part including the borrow pits. These borrow pits had been excavated to provide materials for tailings dam construction. Immediately after resumption of operations, it became evident that it would be necessary to control the quantity of liquid to be evaporated because of the small confined area available for tailings solution deposition and to maximize the deposition time in the tailings area. The water control required had to be exercised on a large scale, and to be in operation as quickly as possible. An obvious solution was to reuse the tailings liquor in mill process. Immediate steps were taken to install the necessary equipment for tailings neutralization on an interim basis. Anhydrous ammonia was selected as the primary neutralization reagent since it was the quickest system that could be placed in operation. Previous laboratory tests indicated fair results with ammonia neutralization. Such a system required a minimum of installed equipment and handling. INITIAL NEUTRALIZATION OPERATIONS Actual neutralization operations began on November 26, 1979. The raffinate solution which normally would have been discarded was pumped to a 3.7 m (12ft) diam by 4.3 m (14ft) tank for reagent contact, see Figure 2. At this tank, anhydrous ammonia was added directly from the tanker trailers and controlled at pH 7.0 nominally. Agitation was provided by air sparging. The neutralized product formed a highly viscous slurry in the grinding circuit which resulted in pumping and cyclone classification problems.

Jan 1, 1982

By G. M. Willis, F. L. Hennessy

The oxygen pressure in equilibrium with silver and Ag2O-B2O3 melts has been measured between 800&apos; and 900°C, to obtain the thermodynamic properties of the liquid. The compound Ag20. 4B20:1 appears to exist in the liquid, which shows marked heat content and entropy effects. A KNOWLEDGE of the thermodynamic properties of binary liquid silicates, borates, and phosphates would be of considerable assistance in the interpretation of the behavior of multi-component metallurgical slags. However, the literature contains comparatively few studies of the thermodynamics of binary slags. The system Ag20-B,O, attracted our attention as it was known to give a single liquid phase,&apos;,&apos; in which high contents of silver could be obtained (up to 61 pct Ag according to Foex2). Further, it would be expected that the partial pressure of oxygen over melts in equilibrium with metallic silver could be used to determine the activity of Ag2O in the Ag,O-B,O, system. In many respects, it may be expected that the reaction of a basic oxide with boric oxide would be analogous to its reaction with silica. Liquid immiscibility frequently occurs in both borate and silicate systems. With B2O3 and SiO reaction with a basic oxide presumably involves a breakdown of the three-dimensional network of the acid oxide by reaction with oxygen atoms common to more than one silicon or boron atom. Ag2O-B2O3 was therefore investigated as a model of a slag system in the hope that its thermodynamic properties would assist in understanding those of other systems. Several methods for determining the activity of a component in a slag have been described in the literature. Chang and Derge" used high temperature electromotive force measurements to obtain the activity of SiO2 in CaO-SiO2 and Ca0-Al203-Si02 slags, but the cell reaction in their work is not clear. low has used rate of volatilization and vapor pressure measurements combined with phase diagrams to obtain activities in the systems KO-SiO,, Na,O-SiO, and Li,O-SiO," and PbO-SiO26 Taylor and Chipman7 extrapolated their results for the distribution of FeO between liquid iron and CaO (+Mg0)-FeO-SiOl slags to obtain the activity of FeO in the binary FeO-SiO2 system. In principle, one of the most direct methods for obtaining the activity of a metallic oxide in a phase is by comparison of the equilibrium oxygen pressure for the system metal-pure oxide with that of metal oxide-containing phase. Schenck and othersa have studied the stabilization of Ag2O on combination with other oxides (MO,) in the solid state by measurements of the oxygen pressure in systems of the type Ag-Ag,O-xM0,-MOy-0, (gas). Schuhmann and Ensio" have determined the activity of FeO in iron silicate slags in equilibrium with solid iron, using CO/CO2 mixtures to establish known partial pressure of oxygen. Although the method gives the activity of FeO without ambiguity, the slag is not a binary system, and interpretation of the results in terms of the hypothetical binary system FeO-SiO, is not possible. If a metal is solid at temperatures at which the properties of the slag containing its oxide are to be studied, this method has the considerable experimental advantage that the metal can be used as the container for the slag, and contamination by contact with refractories is avoided. In this work, crucibles for Ag2-B,O, melts were made from silver, and the liquid brought to equilibrium with definite pressures of oxygen gas. The oxygen pressure PO, thus fixes the activity of Ag20 in the liquid silver borate. For the reaction at a given temperature. is substantially constant, is directly proportional to the square root of the equilibrium oxygen pressure. Varying the oxygen pressure changed the silver oxide content of the liquid and it was possible to obtain the activity of Ag2O over a range of composition. Experimental Procedure In principle, the method consisted of bringing melts in silver crucibles or boats to equilibrium at a fixed temperature under a definite pressure of oxygen and analyzing the glass after solidification. Materials: B2O3 glass was prepared from A.R. quality boric acid by fusion in platinum. The silver

Jan 1, 1954

By R. M. Hudson, P. E. Perry

Weight-gain data obtained by nitriding low-carbon sheet steel in an amrnonia CNH,) atmosphere indicated that the process obeyed a parabolic rate law. The calculated actization energy for nitriding in the range 964" to 1268°F agreed reasonably well with published data. At 1358"F, rate data indicated that the activation energy decreased. Weight-gain data obtained by uszng mixtures of NH3 -Nz at 1268°F containzng jrom 10 to 100 zol pct NH3 also obeyed a parabolic rate law. The rate of &apos;nitriding increased with an increase in the NH3 content of the gas Mixture. It is well-known that steel heated in gas mixtures containing ammonia (NH3) takes up much larger quantities of nitrogen than steel heated in nitrogen, both gases having a total pressure of 1 atm;&apos; this phenomenon can presumably be attributed to the catalytic decomposition of NH3 on the steel surface to furnish nascent (monatomic) nitrogen. This process was studied bv Brunauer. Jefferson, Emmett, and Hend-ricks at furnace temperatures of 752" and 831°F2 using mixtures of NH3 in Hz. Englehardt and wagner3 reported that, at a furnace temperature of 914°F and under their experimental conditions, both nitriding and denitriding were controlled by the rate of gas-metal reactions at a steel surface rather than by the rate of diffusion of nitrogen in iron. The present study was undertaken to obtain information on the kinetics of nitriding low-carbon steel strip at higher temperatures so that practical rates for short-time strip-annealing treatments could be estimated. Variables studied included time: temperature, and NH, content in the annealing atmosphere. Mechanical and chemical characteristics of steel nitrided in this manner will not be considered in the present article. MATERIALS AND EXPERIMENTAL WORK The samples used were from a commercial low-carbon steel, 0.0244 cm thick, in the cold-reduced condition. The chemical composition of this steel is given in Table I. Panels were cut to 5.1 by 17.8 cm, degreased in toluene, and weighed just before treatment. Four specimens were nitrided under each of the experimental conditions. A study was made of the nitriding rate of steel in a 100 vol pct ammonia atmosphere, 740 mm pressure, at five specific temperatures within the range 964" to 1358°F. The nitriding rates of steel in ammonia-nitrogen gas mixtures containing 10, 18, 26, 50, and 100 vol pct ammonia, 740 mm total pressure, at 1268°F were also determined. All atmospheres used were dried by successively passing them through drying towers packed with soda lime and with Linde Molecular sieve Type 4A. Quoted gas compositions refer to those entering the furnace. Specimens were held in the constant-temperature zone of a vertical annealing tube furnace for times of 14, 3, 5, 10, or 15 min. Gas flow rates were maintained at 3.8 cu ft per hr, which was nineteen volume changes per hour for the system used. The rate of flow was selected to provide a high level of free NH3 for cracking on the steel surface where the ammonia gas is most effectively used as a nitriding agent. The vertical annealing tube furnace consisted of a Hevi-Duty tube furnace with a 2 1/2-in.-ID mullite ceramic high-temperature tube. The constant-temperature zone (controlled within 10°F) was about 10 in. long. After each specimen was degreased, a hole was punched in one end, for attaching the specimen by hook to a chain so that it could be lowered into or raised from the high-temperature portion of the tube by means of a power-driven winch. A stainless-steel access port with O-ring seals was connected by suitable glass-to-metal seals to the cool upper portion of the furnace tube. After the weighed specimen was placed in the access port, the furnace tube was evacuated to approximately 10"3 torr, and then the system was flushed thoroughly with the atmosphere under study. When the gas flow rate and constant-temperature zone of the furnace were established, the specimen was lowered into the constant-temperature zone. The atmosphere flowed from the top to the bottom of the vertical furnace tube and was then vented. For all these runs, during the first 3 min of the time the specimen was in the constant-temperature zone of the furnace the specimen was heating up to the tempera-

Jan 1, 1970

By W. J. Schuster

Safety in coal mines depends largely upon adequate training of the foreman. Although management must provide modern and safe equipment and at all times keep mines in first class condition from a safety viewpoint, final results will be determined by the quality of supervision. HANNA COAL CO., Division of Pittsburgh Consolidation Coal Co., operates three large underground mines in eastern Ohio. The section of Pittsburgh No. 8 coal seam in which these mines are located varies in thickness from 52 to 64 in. It is immediately overlain by a stratum of shaly material 12 to 15 in. thick locally known as draw slate, which is structurally very weak and which disintegrates rapidly upon exposure to atmosphere. Immediately above the draw slate as it is normally found is a band of extremely high ash material 6 to 12 in. thick known as roof coal or rooster coal, and above this is a stratum of conglomerate material varying from 4 to 10 ft in depth. Overlying the conglomerate is a relatively thick stratum of limestone, the first stable material above the Pittsburgh coal seam in eastern Ohio. With the method of full-seam mining that has been adopted, draw slate is shot down, loaded with the coal, and removed in the preparation plants. The roof coal then becomes the permanent roof. The major problem in mining the No. 8 seam in eastern Ohio is control of the roof. Since the strata above the draw slate contains no material with a structure firm enough to provide self-support, the roof begins to sag in a relatively short time after the coal and draw slate have been removed. The problem thus becomes one of getting temporary safety posts under this roof as quickly as possible to prevent a break or separation from occurring either in the roof coal or in the conglomerate above it. Haulage System The Pittsburgh No. 8 seam in eastern Ohio is relatively level, with only minor local dips. Throughout the Hanna Coal Co. mines, entries are generally 12 ft wide. Rooms are driven on a 60" angle on 30-ft centers and are 22 ft wide. No attempt is made to extract the 8-ft pillars between. The entire length of main line haulage is gunited in one mine, and a major portion in another. Two of the mines have single-track main haulage roads with passways. The third, a new mine, is double-tracked, and the roof is supported by steel crossbars, 60 lb or heavier, spaced on 4-ft centers and lagged. In recent years timbering on main line and secondary haulage roads has been accomplished by one of two methods: 1—crossbars are supported on a small section of post set in a hitch hole in the rib, or 2—or a hole is drilled in the rib about 12 in. below the roof, of sufficient depth to fasten securely a short length of 40-lb rail, the bottom of the rail facing the roof, on which a short post is set directly under the crossbar. At present the hitch-hole timbering method is favored. At two of the mines the main line haulage locomotives are 26-ton, 8-wheel units. These locomotives are of the axleless type, each wheel being individually mounted on the frame. The motorman&apos;s compartment is encircled by 3-in. armor plate for the protection of the occupants. At the third underground mine conventional 15-ton locomotives are being used. However, these locomotives have been completely rebuilt in the company&apos;s shops. Equipment has been streamlined and quarters have been provided for two people, who are protected by heavy steel plate in much the same way described above. This modernization program has been completed on all secondary haulage locomotives at the three mines, and the company is well on the way to similar equipment of the 6-ton section locomotives. The following additional features have been included in their modernization: 1—additional support for the motors to prevent their falling to the middle of the track and derailing the locomotives should a break occur in the suspension bar support; 2—installation of additional bracing to prevent brake rigging from becoming displaced and causing derailments; 3—enclosure of all electric wiring in conduit or raceway; 4—provision of an enclosed compartment for the storage of re-railers, jacks, and other equipment, so that they need not be carried on the outside of the motor; and 5—redesign of the end of the locomotive opposite the operator&apos;s compartment to prevent anyone&apos;s mounting from that direction. It is interesting to note that some

Jan 1, 1955