Search Documents

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.' The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By George S. Rice

STUDIES of ground movement and subsidence caused by mining necessarily chiefly deal with causes and effects of making extensive excavations underground with spans beyond the strength of the un- supported or temporarily timbered roof or hanging wall. Perhaps no other phase of engineering is so de- pendent for results upon the assemblage of what may be called "experience data." That this is the case is cot surprising when one considers the number of variables involved in any at- tempted mathematical formula to determine the angle of draw or the angle of permanent slope of the rocks in any particular case. It is not like dealing with construction materials in which, through testing of. small specimens, in conjunction with the tests of large built- up specimens, relative stresses and strains may be deter- mined and formulas closely approximated for still larger constructions.

Jan 1, 1931

By Grimes, J. A.

EXTENSIVE discovery 'and rapid exploitation of orebodies within the past half century have attracted many able geologists to the mining industry and furnished them a wealth of data from which to develop theories concerning ore genesis. By tosting and elimillating theories which are not sufficiently sup- ported by fact, or which are based on inaccurate observation of field data, the trend of geological opinion has . moved strongly in certain directions until, at the present time, large numbers of geologists subscribe to a broad concept of .ore genesis that I would summarize as below:

Jan 1, 1928

Jan 1, 1942

Jan 1, 1911

Jan 1, 1906

By John V. Beall

Cutting costs and increasing safety with new ideas is the byword with The Cleveland-Cliffs Iron Co. on the Marquette Range in Michigan. Among the new ideas being tried out are mechanical shaft mucking, prefabricated lagging to replace timber poles, Carset bits in shaft sinking, and rubber tired guide wheels on the ore skips. Plans are being made to stockpile ore with conveyor belts during the winter. In sinking the Mather "B" Shaft a 3/8-yd clamshell-type bucket is used for mucking. The clamshell is opened and closed by means of a verticallymounted hydraulic ram actuated by 5000 psi oil pressure. An Ingersoll Rand-type hoist is used to raise and lower the clamshell. The hoist is controlled by one member of the crew on the floor of the shaft. When the bucket is raised, the men swing it over the muck pile to the desired position and then it is lowered on to the broken rock. The 1400-lb weight of the bucket causes it to sink into the broken rock and it digs as the ram closes the bucket. The hydraulic ram is operated by a man on the lowest shaft steel set who controls a specially designed oil pump which supplies oil pressure. The clamshell is emptied.

Jan 1, 1949

By AIME AIME

WITHOUT frills, but with an admirable program of technical papers and discussion, many opportunities for social contact, and all New York for a playground, the 142d Meeting of the Institute will make the Engineering Societies Building a lively place from Feb. 20 to 23. Prices are down, even in New York. Come and forget the depression listening to the stories of old friends. Hear at first hand what is going on in your professional world. The fare is varied, of wide appeal. The program on the opposite page has been arranged carefully to minimize conflicts between the subjects in which you are interested. If it is not possible to come for all four days, check over the sessions that are most important to you. No changes in the scheduling are likely.

Jan 1, 1933

[ ]

Jan 1, 1938

Jan 1, 1933

For the year ending February, 1918 PRESIDENT PHILIP N. MOORE ST. Louis, Mo. PAST PRESIDENTS WILLIAM L. SAUNDERS NEW YORK, N. Y. L. D. RICKETTS, NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS, NEW YORK, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND,.. NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 3, 1917

Jan 1, 1890

Jan 1, 1902

The Institute has no available copies of Bulletin No. 7, January, 1906, and Bulletin No. 105, September, 191.5. The sum of 30.50 per copy will be paid for these Bulletins.

Jan 6, 1917

For the year ending February, 1917 PRESIDENT L. D. RICKETTS, 1............... NEW YORK, N. Y. PAST PRESIDENTS BENJAIMN B. THAYER.1 ............... NEW YORK, N. Y. WILLIAM L. SAUNDERS,P ................ NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 .....,...... ., .... NEW YORK, N. Y. TREASURER GEORGE C. STONE,l. ................ NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, .... .,. .......... NEW YORK, N. Y

Jan 9, 1916

Jan 1, 1920

By Philip E. LaMoreaux

Fluoride, generally less than 0.5 ppm, is present in ground water from rocks of Paleozoic age and older, in northern and eastern Alabama. Some of the water-bearing formations in the Coastal Plain area of the State yield water with as much as 6.8 ppm fluoride.

Jan 8, 1950

By Denis Yeung, B. H. G. Brady

A hybrid finite element-boundary element code with eight noded isoparametric finite elements and three noded boundary elements is described for plane strain and linear isotropic elasticity. In the direct formulation of the Boundary Flement Method, quadratic variation of geometry and displacements, and linear variation of tractions with respect to the element intrinsic coordinates are used. The boundary element region is treated as a "super-element" in the finite element sense.

Jan 1, 1982

By W. G. Jewitt

YELLOWKNIFE, the most northerly Canadian gold mining district, is once more in the throes of a boom. Touched off by spectacular and well-publicized diamond-drilling results on the property of Giant Yellowknife Gold Mines, Ltd., mining companies and the general public are competing for mining claims and for the shares of companies owning mining claims in the area, with little regard for values. Such a stock-market boom has various unfortunate consequences but undoubtedly one beneficial result is that considerable amounts of money are made available for serious development. The Yellowknife mining area lies on the north shore of Great Slave Lake, in the Northwest Territories, at a latitude of approximately 62°30' north. The topography is a low-relief phase of that usual in the Canadian Laurentian shield. Roughly, one third of the surface is lake-covered, one third muskeg or overburden, and one third is bare

Jan 1, 1944