Search Documents

By J. F. Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By E. Posnjak

IT is rather the general belief that acidified solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no. oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by, passing air for 3 hr. through solutions of Mohr's salt acidified with sulfuric acid." While this statement will be proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2. His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 1, 1927

By E. Posnjak

IT is rather the general belief that acidified, solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as. cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by passing air for 3 hr.. through solutions of Mohr's salt acidified with sulfuric acid." While this statement will bee proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2 His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 12, 1926

Aamot, Olav Crone, Research Engr., Guggenheim Bros. Labs., 3,771 10th Ave., New York, N. Y. '29 Abbott, Clarence E., V.P., Charge of Raw Materials, Tenn. Coal, Iron & R. R. Co., 1242 Brown-Marx Bldg., Birmingham, Ala. '04 Abbott, Louis Benjamin, Chief Engr., Consolidation Coal Co., Watson Bldg., Fairmont, W. Va. '15 Abeel, George H., Jr., Cons. Min. Engr 128/ S. Canon Dr., Beverly Hills, Calif. '18 Abel, Raymond L., Asst. Prof., Dept. of Pet. Refin., Univ. of Pittsburgh Pittsburgh, Pa. '28 Abel, Walter D., Cons. Engr 364 S. Cloverdale Ave., Los Angeles, Calif. '32 Abele, Louis T 1457 Euclid Ave., Zanesville, Ohio. '31 Abell, Leo M Sullivan Concentrator, Chapman Camp, B. C., Canada. '31 Abort, Robert H., Asst. Met., Research Lab., U. S. Steel Corp., Lincoln Highway, Kearny, N. J. '19 Abraham, W. E. V., East India United Service Club, 16 St. James' Sq., London, S. W. 1, England. '28 Abstain, Henry T., Engr. & Mgr., Profile-Tamarack Mines Co Yellow Pine, Idaho. '27 Acker, E. O'C., Met 128 East Washington Late, Germantown, Philadelphia, Pa. '86 Ackermat, D. E., Research Met., International Nickel Co., Inc. Bayonne, N. J. '35 Acres, T. H., Geol. Dept., Valuation & Pet. Engrg., Richfield Oil Co., 555 S. Flower St., Los Angeles, Calif. '29

Jan 1, 1934

By E. J. Rapperport, M. F. Smith

A presentation of the W-Ru constitution diagram is given. Techniques utilized in the determination of phase boundary values include electron micro-probe analysis of two-phased alloys and diffusion couples, as well as normal metallographic and X-ray methods. The primary features of the diagram are: 1) a terminal solid solution of ruthenium in tungsten with a maximum solubility of 23 at. pct Ru at 2300°C; 2) a terminal solid solution of tungsten in ruthenium with a maximum solubility of 48 at. pct W at 2205°C; 3) a o phase of maximum breadth about 6 at. pct based on the composition W3Ru2 which forms peritectically from the melt at 2300°C, and which decomposes eutectoidally at 1667 °C to form a twigs ten and 0 ruthenium; 4) a eutectic at 45 at. pct Ru and 2205°C with the products being o plus ß ruthenium. THE W-Ru diagram has previously been studied only in a cursory fashion. Raub and alter' obtained a 1400°C isotherm in which they observed no intermediate phases, and on which they established the limits of solubility as 36.5 at. pct W in ruthenium and about 1.5 at. pct Ru in tungsten. In addition, Obrowski2 found a o phase forming peritectically from the melt and existing only above 1650°C. Below this temperature the phase was presumed to decompose eutectoidally. The present work finds the diagram as given in Fig. 1. I) EXPERIMENTAL PROCEDURE The materials used for alloy preparation in determining the W-Ru constitution diagram were 99.9 pct pure ruthenium powder supplied by Baker Chemical Co., and 99.9 pct pure tungsten powder from General Electric Co. Typical analyses of these elements are given in Table I. Initial alloys at 10 at. pct intervals were prepared from the metal powders by the following method. Powders sufficient for 25 g of the alloys were weighed out with an accuracy of 0.1 mg and blended mechanically. After blending, the powders were compacted, in a steel die, at approximately 30,000 psi. The compacts were sintered in an electric vacuum furnace in order to remove adsorbed gases and to achieve partial densification prior to arc-melting. Vacua of 10-4 mm Hg or less were maintained in sintering as the furnace temperature was raised to approximately 2000°C. Sintering times ranged from 10 to 20 hr. The sintered compacts were arc-melted under a protective atmosphere of purified helium. Melting was conducted on a water-cooled copper hearth, utilizing a nonconsumable tungsten electrode. In the melting process, each alloy was turned over and re-melted on opposite sides from four to six times to ensure complete melting and to eliminate gross in-homogeneities. The arc-melter used had a vacuum capability of 5 X 10-6 mm Hg, and a leak rate of about 20 -liters per hr. Chemical analysis techniques for refractory metal-platinum group metal combinations are not well-established; therefore, composition control and determination depended principally upon weight-loss observations and calculations. This consisted in weighing each alloy after sintering and after arc-melting, and calculating the maximum and minimum composition values, assuming the total weight losses to be first all tungsten, and then all ruthenium. Since composition uncertainty was directly related to weight loss, care was taken to minimize losses in handling, compacting, and melting. Prior to homogenization and equilibration the as-arc-melted alloys were analyzed in several

Jan 1, 1964

By Harvey Cline, Donald P. Ferriss

THE violent outgassing of commercial tungsten and other refractory metals when melted in an electron beam zone refining apparatus1"3 is dealt with experimentally by one or both of two approaches. One is to provide a suitable emission current control1,2 the other is to purify the metal in the solid state before melting.4 The first of these is usually sufficient, but the authors chose also to investigate the source of the troublesome gases and to devise means of solid-state purification. Some further insights into the use of tungsten as a structural material at temperatures near its melting point were also revealed in the course of the work. One may speculate on the causes of gas formation in tungsten at high temperature by inferences from the literature and an examination of the impurities in commercial wire. Davenport5 observed microporosity in both tungsten and molybdenum filaments heated to several hundred degrees below their melting points. Studying the function of oxygen in molybdenum welds, Perry, Spacil, and wulff8 attributed similar porosity to the disproportionation of Moo2 to molybdenum metal and Moo3. Tungsten dioxide also disproportionates7 above 2000oC to yield WO3 vapor at considerable pressure. Commercial tungsten contains some 5 to 20 wt ppm O and a similar concentration of carbon depending on the details and precautions of processing. Therefore, evolution of CO is also a strong possibility as a source of gas at high temperatures. Furthermore, even for activities in the order of 0.01, it may be calculated that the pressure of CO at 3000°C would be over 4000 psi, which is in excess of the tensile strength of tungsten at this temperature.9,10 Powder metallurgy tungsten contains some 0.02 pet Fe and 0.002 to 0.005 pet of the elements Ni, Si, Al, Ca, Mn, Mg, and Mo; at temperatures over 2800°c, therefore, these elements will exhibit appreciable vapor pressure, though small compared to that of WO3 and CO. Some of these impurities may react to form high-pressure monoxides such as SiO and A10. Finally, dissolved and occluded nitrogen is an ever-present source of high-pressure gas. Commercial Type 218, General Electric filament wires, 0.025 in. diam, were heated by resistance in 10 -4 mm of Hg and in argon or hydrogen at pressures from 50 µ to atmospheric. For temperature determinations in vacuo, the Jones - Langmuir8 current-temperature relationship was employed. For gaseous atmospheres, the burn-out temperature was assumed to be the same as in vacuo so that a small, constant correction could be made for temperatures below burn-out conditions (i.e., local heating to failure). Several dozen experiments may be summarized by pointing out some structural observations. At 3050oC in 1 atm of A, porosity is very evident after 30 min, as shown in Fig. 1. For the section in Fig. 2, failure occurred 200°C below the melting point and many voids have grown in the grain bound-

Jan 1, 1962

By M. K. Foster

Ten horizontal retort zinc blocks of a modified Hegeler design are in operation at Nueva Rosita, Coahuila, Mexico, and produce approximately 170 t of spelter daily, or 62 000 t/year. A block consists of two furnaces of 448 retorts each, making 8960 retorts as the plant complement. Each furnace block is fired with natural gas and air maintaining the combustion mixture in the furnace always slightly reducing. No attempt to recover energy through waste heat boilers is made. The spelter moves to market by rail and truck either in palletized bundles weighing approximately 1060 kg, as loose slabs weighing 26.5 kg each, or as 1088 kg ingots. At present 46% of the metal is exported and 54% is consumed domestically in Mexico. The present day trend toward equalized or alloyed spelter, as well as special shaped castings results in sales of 35% of the entire plant's production. Sulfuric acid is also produced by the Contact Process using vanadium pentoxide as the catalyst. The plant is basically a Monsanto contact system, producing approximately 68 t of 100% sulfuric acid daily. Both 98.5% sulfuric acid and 20% oleum are available. All of the acid made is consumed in Mexico. Shipments are made in 26,900 dm3 tank cars.

Jan 1, 1970

By J. B. Morrow

BITUMINOUS COAL production for 1937 up to Nov. 27, was 400,000,000 ions, an increase of 3.43 per cent over the comparative period in 1936. The in- crease in consumption, however, was not so great as the increase in production. Stocks of coal, mostly in the hands of consumers, on Nov. 1 were 57,000,000 tons, compared to 44,400,000 tons at the same periods in 1936. The prospects were that both production and consumption for December, 1937, would be lower than for the corresponding month of 1936. , Anthracite production for the period ending Nov. 20 was 43,900,000 tons, com- pared to 48,500,000 tons for the corresponding period in 1936, or a decrease of 9.5 per cent. Production of mechanically loaded coal in. 1936 was approximately 57,000,000 tons, an increase of 17.5 per cent over

Jan 1, 1938

By K. Leutwyler, H. L. Bigelow

Jan 1, 1966

By C. W. Spencer, J. Singer

A PARTIAL phase diagram for the As-Te system is given in Hansen.' The only compound reported is As2Te3, melting at 362°C. Stoichiometric quantities of reagent-grade elements were reacted in evacuated quartz and directionally cooled. The resulting ingot consisted of very thin threadlike crystals from which only very small single-crystal fragments were isolated. A powder diffraction diagram disclosed nonisomorphism with the analogous V-VI compounds insofar as these have been reported; Sb2S3, As2S3, Bi,S,, and Bi2Te3 data in the ASTM index of powder patterns, together with the single-crystal data on Sb2Se3,2 were used for the com- parison with the observed spacings. Single-crystal data confirmed the uniqueness of the As2Te3 structure. Single-crystal Weissenberg diagrams have so far yielded the following data: As2Te3 is monoclinic, space group C-m (OkO data still lacking), a = 14.4A, b = 4.05A, C = 9.92A, ß = 97". The cell volume is about 5802. The set of isomorphous ortho-rhombic cells of Sb2Se3, Sb2S3, and Bi2S, are apparently related to As,Te, in having one lattice constant close to 4.0 and with cell volumes as large as 540A8. Assuming Z = 4 for As2Te3 also, the density is calculated as 6.1 which agrees well with a roughly determined value of 6.0. A complete structure analysis is under way.

Jan 1, 1956

By B. W. Dyer

In 1924, the Crescent Eagle Oil Co., while drilling the salt section of the Paradox formation in Grand County, Utah, encountered a salt that did not appear to be sodium chloride. This salt was analyzed and showed the presence of potash minerals, both sylvite (KCl) and carnallite (KMgC12.6H2O). Because of the high potash content of the sample, there was considerable speculation: (I) as to whether the hole had been salted, and (2), if not, the extent, richness, and the depth at which the deposit occurred. The discovery caused a large amount of activity in the area. During the next few years, 68 potash prospecting permits were issued by the Government, 24 under the Act of 1917 and 44 under the Act of Feb. 7, 1927, each including about four sections of land. Several holes, all shallow, were drilled for potash. A number of holes were drilled for oil into the salt horizon and the cuttings collected at the oil wells were examined petrographically and chemically. The shallow test holes were not sufficiently deep to reach the potash horizon and revealed nothing of value, but several of the oil test holes gave some indication of where potash might be found. Location and Geology of Deposits The potassium and magnesium salts have been found in various places from the Denver and Rio Grande Western Railroad tracks about seven miles west of Thompsons, in eastern Utah, to Cane Creek, a tributary of the Colorado River— a distance north and south of about 35 miles. In this locality, there appear to be five separate deposits: the Crescent Eagle area, which is in T. 22 S., R. 19 E.; the Salt Valley area, in the vicinity of the north-south line of T. 23 S., between R. 20 E. and R. 21 E.; the Seven Mile area, in the eastern part of T. 25 S., R. 20 E.; the Cane Creek area, on the Colorado River, in T. 26 S. and T. 27 S., R. 20 E. and R. 21 E.; and the Salt Wash area, in T. 22 S. and T. 23 S., R. 16 E. and R. 17 E. (Fig. I.) The Crescent Eagle and Salt Valley areas are in the Salt Valley anticline, some of the wells being in the fault graben and others outside. Structurally, the Salt Valley anticline is very complex, and can be described in general terms as a northwesterly plunging collapsed anticline about 15 miles long. In the Crescent Eagle area, the valley graben is about 1 1/2 mile wide and the salt probably forms a plug, the apex of which is in the vicinity of the Crescent Eagle well. Owing to the complex structure, there has been every opportunity for flowage in the salt to cause local thinning or thickening of beds. The regular succession of formations in the general area* is: Cretaceous Mancos Dakota Jurassic Morrison Summerville Entrada Carmel

Jan 1, 1948

By B. W. Dyer

In 1924, the Crescent Eagle Oil Co., while drilling the salt section of the Paradox formation in Grand County, Utah, encountered a salt that did not appear to be sodium chloride. This salt was analyzed and showed the presence of potash minerals, both sylvite (KCl) and carnallite (KMgC12.6H2O). Because of the high potash content of the sample, there was considerable speculation: (I) as to whether the hole had been salted, and (2), if not, the extent, richness, and the depth at which the deposit occurred. The discovery caused a large amount of activity in the area. During the next few years, 68 potash prospecting permits were issued by the Government, 24 under the Act of 1917 and 44 under the Act of Feb. 7, 1927, each including about four sections of land. Several holes, all shallow, were drilled for potash. A number of holes were drilled for oil into the salt horizon and the cuttings collected at the oil wells were examined petrographically and chemically. The shallow test holes were not sufficiently deep to reach the potash horizon and revealed nothing of value, but several of the oil test holes gave some indication of where potash might be found. Location and Geology of Deposits The potassium and magnesium salts have been found in various places from the Denver and Rio Grande Western Railroad tracks about seven miles west of Thompsons, in eastern Utah, to Cane Creek, a tributary of the Colorado River— a distance north and south of about 35 miles. In this locality, there appear to be five separate deposits: the Crescent Eagle area, which is in T. 22 S., R. 19 E.; the Salt Valley area, in the vicinity of the north-south line of T. 23 S., between R. 20 E. and R. 21 E.; the Seven Mile area, in the eastern part of T. 25 S., R. 20 E.; the Cane Creek area, on the Colorado River, in T. 26 S. and T. 27 S., R. 20 E. and R. 21 E.; and the Salt Wash area, in T. 22 S. and T. 23 S., R. 16 E. and R. 17 E. (Fig. I.) The Crescent Eagle and Salt Valley areas are in the Salt Valley anticline, some of the wells being in the fault graben and others outside. Structurally, the Salt Valley anticline is very complex, and can be described in general terms as a northwesterly plunging collapsed anticline about 15 miles long. In the Crescent Eagle area, the valley graben is about 1 1/2 mile wide and the salt probably forms a plug, the apex of which is in the vicinity of the Crescent Eagle well. Owing to the complex structure, there has been every opportunity for flowage in the salt to cause local thinning or thickening of beds. The regular succession of formations in the general area* is: Cretaceous Mancos Dakota Jurassic Morrison Summerville Entrada Carmel

Jan 1, 1948

By T. D. Yensen, R. K. McGeary

While we have not been primarily interested in the determination of hydrogen in the alloys that we have been dealing with, we arc very glad to cooperate in this symposium on sampling and analysis for hydrogen, as we can never tell when we may find it desirable to perform such analyses. Vacuum-fusion Method Our primary interest has been oxygen and carbon, in the analysis of which we think we have become very proficient. Our oxygen-analyzing apparatus is of the vacuum-fusion type (Fig. I). This employs Dr. Derge's type of graphite cruciblc and slit sleeve, with graphite powder between, for heat insulation (Fig. 2) supported in a clear quartz bulb connected to the Pyrex glass system by means of a carefully made ground joint. The latter is kept cool by means of an air blast from a circular copper tube surrounding the joint. The crucible is heated by high-frequency induction and the 24 one-gram samples successively dropped in from the horizontal tube at the top by means of a magnet. The gases (H², CO, N2) are passed through the CuO catalyst held at 300°C. (converting CO to CO²I, H² to H²O) and the CO² and H2O frozen out in the main liquid air trap, while N2 is evacuated. At the end of the operation, shown by the termocouple vacuum gauge indicating a pressure of 10-4 mm. Hg, the analyzing system is isolated by means of the mercury cutoffs, and the CO² and H2oare determined by transferring first the CO2 and then the HzO to the small trap at the right. This is done by placing liquid air on the small trap, then removing the liquid air from the large trap for one minute, which is sufficient to evaporate the Co2 and transfer it to the small trap. The CO2 is then measured by closing the mercury cutoff at the extreme right, removing the liquid air from the small trap, warming it up to room temperature, adjusting the mercury level to one of the three marks on the glass tube (corresponding to three volumes calibrated so that I mm. Hg of CO² corresponds to 0.001, 0.002 and 0.010 mg., respectively, of oxygen) and finally reading the pressure. Liquid air is now replaced on the large trap, the mercury cutoff at the right opened, transferring the COz back to the large trap. The cutoff to the pumps is then opened, the liquid air removed for one minute, thus evacuating the CO², the pumps again cut off and the H2 O transferred to the small trap as before, except that it is now necessary to warm the large trap with a Bunsen burner in order to evaporate all the H2O. This requires about three minutes, as the inner tube must be heated to at least 100°C. In order to prevent H²O from being adsorbed on the glass walls, the glass tubing beyond the catalyst (i.e., to the right in Figs. I and 3) is kept heated to about 150°C. by means of Nichrome ribbon as shown in Fig. 3. For a I-gram sample the above amounts of oxygen (0.001, 0.002 and 0.010 mg.) 35

Jan 1, 1945

By Fred W. Stiefel

THIS paper covers the operation and maintenance of Diesel locomotives underground on a portion of the Delaware River Aqueduct.[t] This part of the tunnel is 15 miles long, with shafts 14 ft. in diameter spaced about 5 miles apart. These shafts (2, 2a and 3) are 825 ft., 1551 and 840 ft. deep, respectively. The grade of the tunnel is almost level, except for the 12,100 ft. north of shaft 2, which has a grade of 2.31 per cent. The tunnel is circular, 17 to 19 ft. in diameter. It lies at a depth of 400 ft. below sea level, with a maximum over-burden of 2400 feet. The tunnel driving was carried on in six headings, using 15 storage-battery locomotives, each of 13 gross tons and having a maximum speed of 8 miles per hour. The longest haul was 3 miles, which proved to be the maximum distance for which storage-battery locomotives could be employed economically for the amount of material to be moved. One locomotive was used for switching cars at each heading, one for switching cars at the bottom of each shaft and one on the main-line haul from the heading to the shaft. The maximum amount of material hoisted in one shaft from two headings when 104 ft. of tunnel was driven in 24 hr. was 1000 cu. yd., or about 2000 tons of rock in place. The total quantity excavated was 750,000 cu. yd. (1,500,000 tons of rock). The tunnel-lining operations using concrete presented a problem of hauling a maximum distance of 5 miles in the tunnel. The concrete-placing equipment had a capacity of about 2000 cu. yd., or 4000 tons in 24 hours. Experience had shown that storage-battery equipment could not handle this quantity of material within the time required at the distance of 5 miles. Trolley-locomotive haulage was considered dangerous and expensive, and would cause interference because transmission equipment would be required. Therefore the performance of Diesel locomotives of 160 hp., with a speed of 18 miles per hour, in comparison with that of other types of locomotives, was studied. CHOICE OF LOCOMOTIVES In deciding upon the type of locomotive to be used for the 5-mile haul, four alternatives were considered, as follows: I. To purchase additional storage-battery locomotives with the necessary batteries over the 6 locomotives and 12 batteries available. 2. To convert the existing battery locomotives to the trolley type. 3. To purchase new trolley locomotives. 4. To purchase Diesel locomotives. PROPOSITION No. I The 90-hp. storage-battery locomotives available (each weighing about 12 tons), when hauling a load of 64 tons, with a drawbar pull of about 1900 lb. on a level track, developed a speed of 8 miles per hour and could make five round trips in 8 hr. with a

Jan 1, 1942

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.'-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968

By H. F. Yancey

AT the annual meeting of this Institute held two years ago a new method, of estimating the grindability of coal was described, based on experimental work carried on by the Bureau of Mines at its Northwest Experiment Station. Since that time, several organizations concerned with the testing or utilization of coal as pulverized fuel have adopted and used the method in determining the grindability of several hundred samples of coal. In addition, a series of comparative tests of this method and three others has been carried out in five laboratories under the auspices of Committee D-5 of the American Society for Testing Materials. As a result the Committee has recommended that the Bureau of Mines method, designated as the "ball-mill method," and the Hardgrove method2, previously advanced, be accepted as tentative standards3. Since the ball-mill method was originally developed and published, an opportunity has been presented to apply it to a larger number of coals and to study intensively some of the principles upon which the method is based. This paper presents a resume of these further studies and includes a comparison with the Hardgrove-machine method. Trial runs were also made with another procedure recently proposed-the C.I.T. roll-test method4.

Jan 1, 1936

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;',' however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3' The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962

By T. F. Witherbee

Discussion of Mr. Baker's paper, read at the Lake Superior Meeting, September, 1904. MR. T. F. WITHERBEE, Durango, Mexico (communication to the Secretary*) : Mr. Baker's paper is very instructive in that it shows how furnace-derangements sometimes originate from apparently slight causes. In 1896 a similar burning through of the lining occurred at the Mayville furnace of the Northwestern Iron Co., Mayville, Wis., in exactly 38 days from the time the furnace was blown in. At that time I attributed it to the fact that the bell was carried several inches to the front side of the furnace, the length of the versed side of the arc described by the lever, thus dumping a little more of the charge on the back side, which made the front side of the furnace-charge more open and consequently increased the circulation of the furnace gases through it. After reading Mr. Baker's description, I believe that possibly a little more ore was charged on the back side of the hopper, due to the fact that it was nearest to the elevator. This unequal charging, however, was unconsciously done, as the fillers were both honest and faithful. The illustration of the burned lining of Furnace No. 1, given in Fig. - of Mr. Baker's paper answers very well for the Mayville furnace. It shows that in both cases the destruction of the lining was largely due to faulty construction, in that there were no cooling-plates in the angle of the bosh and in one or two courses of brick above it, where I believe they are-more in demand than anywhere else in the furnace. The presence of these cooling-plates at the angle of the bosh would have obliged the current of the hot gases to turn the corner and would have prevented them from following the angle of the bosh com¬pletely through the lining and shell.

Mar 1, 1905

By R. G. Davies

Isothermal annealing of quenched Fe3Al reveals that the superlattice forms by the nucleation and growth of ordered domains. The activation energy for isothermal ordering and initial domain growth is -29 keal per mole, which is thought to he the activation energy for vacancy migration. Domain growth, in the absence of excess vacancies, has an activation energy of -100 keal per mole. A maximum in the hardness is observed when the structure consists Of ordered domains, -35-4 in size, growing into a short-range ordered matrix and, also as a function of degree of order, S, with an infinite domain size at S = 0.4 to 0.5. It is proposed that both maxima are due to a transition from deformation by unit dislocations to deformation by superdislocntions. FE-AL alloys containing more than -23 at. pet Al, when quenched from above the critical temperature for the Fe3A1 type of order, always contain the maximum possible amount of FeAl (B2) type of order' (see Fig. 1). Thus when the Fe3A1 superlattice forms, in a 25 at, pet A1 alloy, it does so from an imperfect FeAl structure. The formation of the Fe3Al superlattice has been the subject of several recent X-ray,1, 2 electrical-resistivity,3"6 and dilatometric3 investigations. McQueen and Kuczynski3 concluded that the isotherma1 ordering of Fe3Al, after quenching from 800°C (T,, the critical temperature for order, is 55O°C), takes place by the nucleation and growth of ordered domains. However, Feder and Cahn4 found that the isothermal ordering was complex but more like a homogeneous nucleation process than a nucleation and growth process. Lawley and Cahn2 reported that the degree of order is a continuous function of temperature which is a characteristic of a homogeneous nucleation process. Thus, the evidence is conflicting as to the nature of the Fe3Al ordering reaction. Lipson7 was the first to suggest that ordered domains should exist in the Fe3A1 structure since, as

Jan 1, 1964

By Martin F. Littmann

Inclusions of MnS and Fe3C have been introduced into single crystals of 3 pct Si-Fe to study their effects on recrystallization behavior and textures after cold rolling and annealing. The presence of MnS in (110) [001] and (111)[112] crystals inhibited primary grain growth and promoted secondary recrystallization but did not alter the texture significantly after annealing at 1200°C. The presence of Fe3C in (llO)[OOl] and (100)[001] crystals caused a refinement of the primary re crystallized grain size but did not promote secondary recrystallization. THE texture behavior of single crystals of 3 pct Si-Fe during deformation and recrystallization has been studied by numerous investigators. The early work of Dunn&apos; followed by Decker and Harker2 involved relatively small cold reductions. More detailed studies of Dunn3&apos;4 and of Dunn and Koh5&apos;6 involved a reduction of 70 pct and recrystallization at 980°C for several crystals. Walter and Hibbard7 studied a greater variety of initial orientations and sought to relate the textures to those of polycrystalline material. Attention was focused on the nucleation process during early stages of annealing and on surface energy effects in studies by Walter and Dunn8 and by HU.9&apos;10 One of the most extensive investigations has been reported by T. Taoka, E. Furubayashi, and S. Takeuchi.11 Most of this work has been conducted using relatively pure crystals with minimal amounts of precipi-tate-forming elements such as carbon, oxygen, sulfur, and nitrogen. Recently, however, S. Taguchi and A. Sakakura have observed that AIN precipitates can alter the recrystallization textures of rolled (100)[001] crystals.12 The present studies were initiated to determine effects of MnS and Fe3C precipitates on recrystalli-zation and grain growth behavior of rolled single-crystals of 3 pct Si-Fe. Both of these types of inclusions play significant roles in the recrystallization behavior leading to the formation of the (110)[001] or cube-on-edge texture in commercial grain-oriented silicon iron. It is well known that (110)[001] primary grains are formed by recrystallization of (110)[001] or (11 l)[ 112] crystals after cold reduction of about 60 pct or more. Crystals of these orientations, therefore, were selected for study of the effect of MnS in-clusions on grain growth. On the other hand, a major component of the texture of cold-rolled, polycrystal-line 3 pct Si-Fe is the (100)[011] orientation. The function of Fe3,C inclusions is of interest for this orientation. EXPERIMENTAL PROCEDURE The single crystals used are listed in Table I and were obtained from commercial Si-Fe alloy processed to produce (110)[001] and (100)[001] texture by secondary growth. The cube-on-edge material was 0.59 mm thick. Suitably large (110)[001] crystals 25 mm wide were selected and their orientations were determined using an optical goniometer. Etch pits for texture determination were formed by a ferric sulfate solution. The other crystals used in the study with (100)[001], (100)[011], and (111)[112] orientations were obtained from sheet which contained large grains developed from secondary recrystallization by a surface-energy driving force.13 Most crystals had a (100) plane very nearly parallel to the sheet surface and the rolling direction could be selected readily. The same sheet also contained a few crystals with (111) planes parallel to the sheet surface, these also being a result of growth by surface energy. The crystals selected from the sheet were about 25 mm wide and 0.25 to 0.28 mm thick. As shown in Table 11, the crystals already contained about 0.070 to 0.10 pct Mn. Inclusions of MnS were incorporated into crystal 36 in the following manner. The crystals were first sulfurized by holding them Table I. Initial Orientations of Crystals Crystal No. Initial Orientation Thickness, mm Special Treatment 34 (I10) [00l]* 0.59 None 36s (110) [001] 0.59 Sulfide precipitates added 30,40 (111)[Ti21 0.28 None 43s (III) [Ti21 0.28 Sulfide precipitates added 37 (100) [Oll] 0.30 None 37C (100) [01I] 0.27 Carbon added 41 (100) (01I] 0.25 None 41C (100) [OI11 025 Carbide precipitates added 42 (100) [OOl] 0.25 None 42C (100) [001] 0.25 Carbide precipitates added *Tilted 4 deg to r~ght about R.D. Table II. Compositions of Crystals Special Treatments Base Analysis ~ ______________________£________________Crys- Crystals Pct Si Pct C Pct Mn Pct S Pct N Pct Al tal Pct C Pct S 34.36 2.93 • 0.099 <0.005 - 0.0014 36S 0.011 30.37 to 42 2.78 0.0057 0.070 0.001 0.0008 0.0011 43S 0.022 37C 0.029 -41C 0.028 -42C 0.026 *Estimate 0.004 pct. Oxygen estimated <0.003 pct on all samples

Jan 1, 1970