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By William C. Peters

"A large proportion of the earth's surface is blanketed by young sedimentary formations and by recent lava flows. How many Guanajuatos lie concealed beneath the rhyolitic capping of the Sierra Madre of Mexico? How many Kirkland Lakes are under the drift cover of the Canadian Shield? How many Wilunas are still hidden by the alluvium of the desert of Western Australia? How many ore deposits lurk underneath the basalt-covered plateaus of the Columbia River region? If erosion at Goldfield, Nevada, had stopped 100 feet higher, probably no ore would have been exposed. How many Goldfields are still awaiting discovery?" --Hugh Exton McKinstry, 1948

Jan 1, 1969

By Howard S. Avery

The wear resistance of an alloy in heavy mill liner sections may be quite different from that of the same alloy in small balls and other light sections. This fact was established by means of a well standardized laboratory test that was validated for ball mill service. The salient properties of mill liner alloys, including austenitic manganese steels, medium alloy hardenable steels, and abrasion resistance cast irons are described, critically compared, and quantitatively ranked in terms of mill liner service. Where they are tough enough the high-chromium and other martensitic cast irons (e.g. Ni-Hard) promise maximum economy, but their section sensitivity is a limitation. To overcome this an extensive research program studied over a hundred experimental alloys, ranking them for heavy section abrasion resistance by means of the laboratory test. Computer analysis of the results provided a parabolic formula in terms of composition, the apexes of the parabolas providing optimum wear resistance. From the extensive family of parabolas one apex was selected for intensive study in experimental liners, pilot plant production, development of quality controls, and finally full scale production. This is a 19% chromium iron critically alloyed with nickel and molybdenum and hardened by heat treatment. It has excellent resistance to various types of abrasion, but its chief advantage is in heavy mill liner sections, where it has about 25% better abrasion resistance than the best of the quality controlled chilled Ni-Hards. It is also tougher. After production problems were solved, a number of ball and rod mill tests were arranged on a guaranteed performance basis. Two of these, representing about 138,000 pounds of mill liner castings, have recently confirmed in service the superiority that was predicted by the laboratory tests.

Jan 1, 1969

Reports on process control computer projects at the Kamioka Plant are summarized from the Japanese technical literature (see references). Fluidized Bed Roaster and Sulfuric Acid plant1 A small process control computer (Yokogawa CCS-200 with an OKITAC 5090P 8K central processor) was installed in the Kamioka smelter in the summer of 1964. A year-and-one-half installation project followed, which successfully brought the roaster and acid converters under computer control. The process plant consisted of two 130 RPD fluosolids roasters and two Monsan to acid units. The roasters are charged with lead-zinc concentrates with SO2 from the roaster processed to sulfuric acid. The computer system provides the following functions: 1) log data from the plant--the input is taken from 50 analog signals, 130 high-low digital alarm points, and 50 analog high- low alarm points; 2) set-point control on 18 control loops; 3) direct digital control (DDC) on eight control loops for which conventional controllers were difficult to adapt due to abnormal loop characteristics or delay times; 4) execution of a safe shut-down procedure

Jan 1, 1969

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;''2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.' The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969

By A. M. Mirani

The Mine Planning System consists of two parts: 1. A Sales Forecast (Sales Planning) 2. A Production Planning. The mathematical methods of the sales forecast are the exponential smoothing and a method with Markov-Chains. By these methods the quantity of material (ore, coal) will be calculated for the time planned. These quantities constitute the points in the production-planning. In the production-planning , special kinds of networks are used for calculating the resources-equipment required, labor and costs. A special routine optimizes the sequence of the mining areas within the mine on the basis of the lowest costs. The resources can be limited. The activities will be shifted when the demand exceeds this limit. The basis of the production-planning are computer files, in which the geological data and economical evaluations are stored.

Jan 1, 1969

By D. S. Kingery

Experiments initiated by the Bureau of Mines on August 26. 1969, and recent work of others, have demonstrated the effectiveness of ventilation for controlling concentrations of respirable coal mine dust. Substantial reductions in dust concentrations have been attained by increasing the volume and rate of air movement across the face and by controlling the airflow pattern. Ventilation experiments conducted by the Bureau using high-pressure fans as auxiliary ventilation units showed that lace-generated dust could he effectively controlled in five mines employing continuous mining machines. Additional data was obtained on industry installations in two mines using similar ventilation systems. By maintaining an airflow approaching 100 fpm across the entry, the experimental system reduced the concentration of respirable dust by factors as great as 6.4. In all mines where the system was used the face-generated dust concentrations were reduced to below 3 mg/m3. Total respirable dust in two cases was above the 3 mg/m value because of the dust content of the intake air. In some mines. depending upon the type of coal being mined and other dust control factors in use, it was possible to Obtain concentrations of less than 2 mg/m Although the technology for the application of the dust control system investigated is readily available, it is evident that additional engineering studies should he made in each mine where the system is to be applied.

Jan 1, 1969

By A. Mitchell

An approximate phase diagram has been developed for the CaF2-CaC2 system, indicating a eutectic point at 1240°C, Ncac2 = 0.13, and no detectable solid solution in either phase. The liquidus line is shown to correspond to a simple c22- ion in solution. A thermo-chemical study of&apos; the reaction between carbon-saturated Ni-Ca alloys and CaC2-CaF2 liquids indicates that lhe Raoullian activity coefficient of CaC2 in dilute solution in Cap2 al 1500°C lies between 8 and 10. Some effects of the stabilily of Cap2-CaC2 solutions at high temperatures on electroslag remelting praclice are outlined. THE alkaline earth acetylides. MIIC2, have a reasonably high thermochemical stability at high temperature in the solid state,&apos; with the exception of magnesium, which forms an unstable acetylide at low temperatures (-500°C) and a carbide, Mg2C3, in the range 700&apos; to 1000°C. The acetylides of calcium and barium have been shown to have limited solubility in their respective chlorides,&apos; and further these solutions contain the acetylide as a C: ion.&apos; The equivalent magnesium solutions have not been studied. Although calcium "carbide" is used as a desulfuriz-ing reagent in steelmaking. and is possibly present as an acetylide-oxide phase in very basic electric arc practice slags, the acetylide ion appears to be substantially unstable in a silicate slag.* As a conse- *This instability arises from equilibria in the reaction: CaC2 + CO = (Ca0) + 3C where the low intrinsic solubility of CaC2 in silicate lattice, and the low activity of CaO in a silicate solution where CaO/Si02 < 1, combine to give a very small equilibrium concentration of CaC2 in solution in such silicate slags at temperatures in the region of I 500°c, even under carbon-saturated conditions. Under highly basic conditions, a liquid CaO-CaC2 phase may separate from the silicate system quence of this, the possibility that reactions involving CaC2 in silicate solutions are of importance to general steelmaking practice is remote. However, in operations involving a slag primarily based on a halide, or alkaline earth oxide, we must take into account the possibility that CaC2 will appear in quantities sufficient to significantly affect both the chemical and physical properties of the slag. The work outlined below presents a study of the CaF2-CaC2 system intended to provide sufficient data to allow an estimate of the importance of this system to electroslag remelting and welding practice. However, we should indicate at this point that there will be other processes, e.g., heat treatment, flux cleaning of castings, fused salt electrolysis, and so forth, where alkaline-earth halide fluxes are in contact with carbon, graphite, or carbides, and where halide-acetylide solutions must be taken into account. EXPERIMENTAL 1) Structural Studies. In view of the difficulty ex-perienced in handling CaC2 prepared from calcium turnings and propane gas at 700°C, it was decided to use solutions prepared directly in the equilibration apparatus, Fig. 1. The starting materials were: a) Ni-Ca-C alloy, prepared by adding calcium to liquid nickel held under calcium fluoride in an induction-heated graphite crucible; b) calcium fluoride, prepared by fusing calcium fluoride powder (British Drug House "EXTRA PURE") calcium fluoride in an induction-heated graphite crucible, in air, followed by electrolysis between graphite electrodes at 1 amp cm-2 density, for 10&apos; coulombs per g CaF2. This procedure decomposes the CaO produced by hydrolysis during the fusion step, replacing it by CaC2; Ca2+ + 2e-Ca*(l) Ca*(l) + 2C(gr)-(CaC2)caF2 O2- -2e-O*(g) O*(g) +C(gr)-CO(g) This results in a composition of between 2 and 5 wt pct CaC2 in CaF2. Fifty grams (in lumps) of this material were placed in a graphite crucible, together with Ni-Ca-C alloy (averaging 20 wt pct Ca), and the equilibration apparatus assembled. The alloy reacted with the crucible at high temperature to give CaC2, which dissolved in the calcium fluoride solution to give the desired composition. Cooling curves were plotted manually for these liquids, with rapid stirring and CaF2 seeding to minimize supercooling, and using a Pt/Pt 13 Rh thermocouple calibrated on the freezing points of nickel and copper. This gave a reproducibility of ±0.l°C. and an absolute accuracy of the thermocouple of ±l°C. An example curve is shown in Fig. 2, with the CaF2 end of the binary system in Fig. 3. The CaF2-CaC2 ingots were crushed, under dry nitrogen, and sampled for chemical analysis and X-ray examination. Analytical details are given in the Appendix. Powder diffraction data indicated that the only phases present in all samples examined were calcium fluoride and tetragonal (Types I and 111) calcium acetylide,4 with no evidence of solid solutions or compound formation. 2) Thermochemical Studies. The apparatus used to obtain activity data on CaC2 in these systems is shown in Fig. 4. It consists of an arrangement whereby the graphite crucible and its contents (CaF2-CaC2. Ni-Ca-C) can be rapidly cooled without exposure to air. Trial experiments to determine an equilibration time by ap-

Jan 1, 1969

By R. Ward Grosz

The Robinson mining district in east-central Nevada is itself a century of study in the changing economics of the mining business. It began as a boom and bust area. In the district today, just west of Ely, Nev., the hills are pockmarked with the tunnels and shafts sunk in a frantic scramble for gold and silver before the turn of the century. But as the economics of dwindling reserves, rising costs, and changing markets were stamping out the efforts of the gold and silver seekers, copper took over as the king of the Robinson district. Today, Kennecott Copper Corp. has four open pit mines in the district and is planning a fifth. From these mines, Kennecott produces nearly 40,000 tpy (tons per year) of copper. In its hundred years of history, the district has produced more than $1 billion in mineral values, a richer treasure than that from the more famed Comstock Lode of Virginia City, Nev. Prospectors had reported copper outcroppings in the Robinson district as early as 1872. But the first significant copper orebody was not discovered until 1901. In that year, Dave Bartley and Edwin Gray exposed the top of the porphyry orebody that would become the Ruth mine in a shaft at a depth of 120 ft. Subsequently, other larger orebodies were discovered nearby which have resulted in this area being one of the leading copper producers in the country for some 60 years. Following a period of development and exploration, the Ruth mine started production in 1915 and continued as a prosperous underground mining operation until 1948. The mining industry in Nevada experienced the same increasing cost of labor and supplies that all other mining areas had to contend with, and by 1948 the Ruth mine was no longer profitable. The mine was closed down on August 8 of that year. Now, two decades later, the mine is to produce again. The key factor in the case history of

Jan 1, 1969

By E. S. Fisher, L. C. R. Alfred

The elastic anisotropy factors, c4,/c6,, c3,/cll, and c12/cl,, for hcp metal crystals vary significantly among the dgferent unalloyed metals. Significant variations with temperature are also found. The effects of elastic anisotropy on the dislocation in an elastic continuum with hexagonal symmetry have been investigated by computing the elasticity factors for the self-energies of dislocations in fourteen different metals at various temperatures where the elastic moduli have been reported. For most of the metals the effects of the orientation of the Burgers vector, dislocation line, and glide plane are small and isotropic conditions can be assumed without significant error. Significant effects of anisotropy are, however, found in Cd, Zn, Co, Tl, Ti, and Zr. The elasticity factors have been applied in the calculations of dislocation line tensions, the repulsive forces between partial dislocations, and the Peierls-Nabarro dislocation widths. It is predicted that the increase in elastic anisotropy with temperature in titanium and zirconium makes edge dislocations with (a), (a + c), and (c) Burgers vectors unstable in basal, pyramidal, and prism planes, respectively. The probability of stacking faults forming by dissociation of Shockley partials in basal planes also decreases with increasing c4,/c6, ratio, when the stacking fault energy is greater than 50 ergs per sq cm. The widths of screw dislocations with b = (a) in titanium and zirconium increase very significantly in prism planes and decrease in basal planes as c4,/c6, increases. The effects of elastic anisotropy on various dislocation properties in cubic crystals have received considerable attention during the past few years. In the case of cubic symmetry the departure from isotropic elasticity depends entirely on the shear modulus ratio, A = 2c4,/(cl, —c12); i.e., the medium is elastically isotropic when A = 1. Foreman1 showed that an increase in the ratio A produces a systematic lowering of the dislocation self-energy for a given orientation and Poisson&apos;s ratio. ~eutonico~, has shown that large anisotropy can have a marked effect on the formation of stacking faults by the splitting of glissile dislocations in (111) planes of fcc and (112) planes of bcc crystals. ~iteK&apos; made similar calculations for (110) planes of bcc metals. Both studies of bcc metals showed that the large A values encountered in the alkali metals tend to reduce the repulsive forces between Shockley partial dislocations. In fcc metals, however, A does not vary over the large range encountered in bcc metals; consequently, the effect of A on the forces between Shockley partials is masked somewhat by the differences in Poisson&apos;s ratio between metals. The effect of A on the line tension of a bowed out pinned dislocation has also been investigated for cubic crystals, first by dewit and Koehler5 and more recent- ly by Head.6 In both cases the line energy model is applied and the core energy is not taken into account, thus making the conclusions somewhat tenuous with regard to the physical interpretation. Nevertheless, the fact that a large A decreases the effective line tension is clearly evident and the tendency for large A to produce conditions that make a straight dislocation unstable (negative line tensions) also seem evident. Head, in fact, shows visual microscopic evidence that stable V-shaped dislocations occur in 0 brasse6 For hcp metals the definition of elastic anisotropy is more complex and, furthermore, significant deviations from an isotropic continuum are found among a number of real hcp metals, especially at higher temperatures. The present work was carried out to survey the effects of elastic anisotropy on the elasticity factors, K, that enter into the calculations of the stress fields around a dislocation core. Some isolated analytical calculations have previously been carried out for several hcp metals but they are restricted in the dislocation orientations and temperature.8&apos;9 The present computations are based on single-crystal elastic moduli that have appeared in the literature and consider various orientations requiring numerical computations. The results are then applied to survey the effects of temperature on the dislocation line tension and dislocation splitting in hcp metals. PROCEDURE Anisotropy Factors. The degree of elastic anisotropy in hcp crystals cannot be described by a single parameter, such as the A ratio in cubic crystals. The following three ratios must be simultaneously equal to unity in order to have an elastically isotropic hexagonal crystal: The magnitudes of these ratios at several temperatures, as computed from the existing data for the elastic moduli of unalloyed hcp metals, are given in Table I. There are no cases of complete elastic isotropy, but the large anisotropy ratios encountered in the cubic alkali metals are also missing. There are, however, several significant differences among the hcp metals, the most notable being the relatively small A and B ratios in zinc and cadmium and the differences in the magnitudes and temperature dependences of A. It has been noted that the temperature dependence of A has a consistent relationship to the occurrence of the hcp — bcc tran~formation. For cadmium, zinc, magnesium, rhenium, and ruthenium, A is less than unity at 4&apos;~ and, with exception for rhenium, decreases with increasing temperature. In the case of rhenium, A has essentially no temperature dependence between 923&apos; and 1123"~, so that it is clear that A does not approach unity at higher temperatures. Cobalt is similar to the above-mentioned group of metals in that it also does

Jan 1, 1969

By K. R. Carson, J. Weertman

An attempt is made to ascertain the mechanism of tangle and cell formation and its dependence upon dislocation-interstitial carbon interactions. The strain-hardening behavior of single crystals of 3.25 pct Si-Fe was determined at 300° and 425°K and under conditions of both continuous and interrupted tensile strain. Significantly enhanced hardening was observed in crystals deformed at the elevated temperature, and it was further accentuated by interrupted straining. Transmission electron microscopy was used to study the resultant dislocation structures. Strain aging was found to aid tangle and cell formation at 425°K, but at both temperatures embryo tangles formed solely from primary glide dislocations, presumably by a process involving cross slip and "mushrooming". IN the course of plastic deformation all bcc metals and alloys develop a dislocation structure characterized by loose-knit groups of tangled dislocations. With increasing strain the tangles become more tightly knit and grow larger; finally a three-dimensional cellular substructure is formed:1 This process has been observed with the transmission electron microscope.&apos;-l7 However, most investigations were confined to the study of nearly pure polycrystalline metals at relatively low temperatures. At intermediate temperatures, 0.17 to 0.14 Tm where T, is the melting temperature in degrees absolute, the mobility of interstitial impurities such as carbon is high enough to permit migration to nearby glide dislocations but is still low enough so that a significant drag force is exerted.18,19 it is also in this temperature range that a hump occurs in the curve of work-hardening rate vs temperature for iron. Analogous plots for tantalum" and columbiumzo show a definite upward trend in the work-hardening rate. Keh and Weissman1 have pointed out that this behavior may be explained solely on the basis of changes in the dislocation configuration: at low temperatures the dislocations tend to be relatively straight and uniformly distributed, but at intermediate temperatures tightly knit tangles and cellular substructure appear. The interference of these tangles with glide dislocations causes the observed increase in the work-hardening rate. This explanation appears reasonable, yet one might ask what factors cause tangle formation to be so favorable at intermediate temperatures. It seens likely that the strong dislocation-interstitial interactions which are known to occur in this temperature range are at least partly responsible," with the magnitude of the effect being proportional to the interstitial concentration. The purpose of the present work is to study the relationship between tangle formation and strain hardening in a bcc metal in the temperature range 0.17 to 0.4 Tm. Particular emphasis was placed upon a study of the effects of interstitial-dislocation interactions. Single crystals of 3.25 pct Si-Fe containing about 200 ppm of C in solid solution were used in the investigation for the following reasons: 1) The mobility of interstitial carbon in 3.25 pct Si-Fe is negligible at 300°K but increases rapidly at slightly elevated temperature22. Hence, differences between the flow curves and dislocation structures of crystals deformed at 300°K, 0.17 T,, and crystals deformed, say, at 425°K, 0.24 Tm, should be appreciable because of the enhanced dislocation-carbon interactions at the elevated temperature. This effect was accentuated in some samples by interrupted straining, thereby introducing a certain amount of aging. 2) Near room temperature, slip in suitably oriented 3.25 pct Si-Fe single crystals is largely confined to the (110) planes.23&apos;24 Dislocation structures formed under conditions of single glide are the least complicated and their method of formation is the most easily discernable. 3) Dislocations in Si-Fe can be tightly locked with carbon atmospheres by a low-temperature aging treatment. The subsequent thinning of samples to foil thicbess causes little or no rearrangement in the dislocation structure.25 EXPERIMENTAL PROCEDURE Large single-crystal sheets of 3.25 pct Si-Fe were donated by Dr. C. G. Dunn of the General Electric Research Laboratory, Schenectady, N. Y. The orientations of the sheets were determined and slabs 1.0 by 0.25 by 0.05 in. were cut such that the desired tensile axis corresponded to the long dimension. The slabs were mechanically polished and subsequently decar-burized by heating at 1000°C for 3 days in a flowing wet-hydrogen atmosphere. A carbon content of about 200 ppm was introduced by heating at 805°C for 25 min in a flowing atmosphere of dry hydrogen containing heptane vapor. Shaped copper tools were then used to spark-machine at 0.125 by 0.50 in. gage length onto each slab. Vacuum annealing at 1225°C for 2 days followed by a quench into the cold end of the furnace to retain carbon in solid solution concluded the soecimen preparation. Continuous tensile flow curves for crystals of severa1 orientations Were obtained both at 300&apos; and 425°K. A strain rate of 6.67 x 10-4 Per set was used in these and all other tests. Crystals oriented for single glide, B and D in Fig. 1, were subjected to a 3.5 pct plastic elongation to insure uniform slip along the gage length; they were then immediately subjected to interrupted strain cycling as indicated in Fig. 2(a). Each cycle consisted of unloading to 1.5 kg per sq mm, holding

Jan 1, 1969

By Clarence O. Babcock

Model pillars of limestone, marble, sandstone, and granite with length-to-diameter (L/D) ratios of 3, 2, 1, 0.5, and 0.25 (0.286 for granite) were tested to failure in axial compression to determine to what extent an increase in end constraint increased compressive strength. Adjustable steel rings, mechanically tightened about the ends of test specimens to create a radial prestress of 3,000 or 5,000 psi prior to the application of axial load, increased end constraint more than was possible in previous tests using solid steel rings. (Solid rings, epoxy-bonded to the ends of dogbone specimens, increased compressive strength compared with that of straight specimens without ring constraint.) During the loading cycle, additional end constraint was produced by lateral expansion of the specimens against the rings. The effect of the end constraint was to increase the compressive strength 55 to 58 percent for the shorter pillars of dogbone shape compared with the compressive strength of straight pillars with the same L/D ratios without ring constraint. Most pillars with L/D ratios of less than 2 were made stronger by end constraint. Pillars with an L/D ratio of 3 did not benefit significantly from end constraint. When the results from compression testing of straight specimens of rock in the laboratory are used to design mine pillars in situ, the pillars will be larger than necessary if the horizontal compressive stress is several thousand pounds per square inch greater than that resulting from the weight of the overlying rock alone. The L/D ratio can be increased by a factor of 1.76 for ratios in the range 0.25 to 3 and still provide the same compressive strength. The safety factor applied with straight specimen test results should also be acceptable for use with constrained pillar test results.

Jan 1, 1969

By E. T. Turkdogan

The activity of sulfur was determined as a function of composition of ferrous sulfide by equilibrating with hydrogen sulfide-hydrogen gas mixtures at 670° , 800°, and 900". The present results supplement the available data over the composition range from 36.6 to 39.5 pct S. The X-ray lattice spacing measurements made are in accord with the available data and indicate that the limiting composition FeSl.008 may be taken for the iron-iron sulfide equilibrium. The growth rate of ferrous sulfide on iron was measured by reacting iron strips or blocks in hydrogen sulfide-hydrogen gas mixtures. Owing to the slow approach to equilibrium between the gas phase and the surface of the sulfide layer, The sulfidation experiments were carried out for several days. It is shown that the growth rate ullimately proceeds in accordance wilh the parabolic rate law. From the parabolic rate constants and the thermodynamic data on iron sulfide the self-difiusivity and chemical diffusivity of iron in ferrous bisulfide are evalualed. The self-diffusivity of iron thus derived zs found to increase with increasing sulfur content. THE ferrous sulfide known as "pyrrhotite" is a non-stoichiometric phase having a wide composition range from about 50 to about 58 or 60 at. pct, depending on the sulfur activity. RosenQvistl studied the thermodynamics of this phase over wide ranges of temperature and composition. Hauffe and Rahmel&apos; and Meussner and ~irchenall~ studied the parabolic rate of sulfidation of iron in sulfur vapor. By using markers, these investigators showed that the iron cations were the predominant diffusing species in iron sulfide. This is confirmed decisively by the self-diffusivity measurements of condit4 who showed that the self-diffusivity of sulfur in ferrous sulfide is several orders of magnitude lower than the self-diffusivity of iron. Although much has been learned from these studies about the Fe-S system, further research on this subject was considered desirable for better understanding of the physical chemistry of iron sulfide. This work was confined to the study of the kinetics of sulfidation of iron in hydrogen sulfide-hydrogen gas mixtures. The results of this study are given in two consecutive parts. Part I, the present paper, is on the parabolic rate of sulfidation of iron and the diffusivity of iron in ferrous sulfide. The second paper, Part 11, is on the kinetics of the surface reaction between hydrogen sulfide and ferrous sulfide. EXPERIMENTAL Three types of experiments were carried out: i) equilibration of ferrous sulfide with gas of known E. T. TURKDOGAN, member AIME, is Manager,Chemical Metallurgy Division, Edgar C. Bain Laboratory for Fundamental Research, U. S. Steel Corp., Research Center, Monroeville, Pa. Manuscript submitted March 6. 1968. ISD sulfur potential; ii) X-ray studies of ferrous sulfide; and iii) measurements of the parabolic rate of sulfidation of iron. Equilibrium Studies. About 1 g of iron powder or foil. contained in a small recrystallized alumina crucible ind suspended from a calibrated silica spring, was reacted with a hydrogen sulfide-hydrogen mixture of known ratio until no further change in weight was observed. %hen the gas composition was changed and the new state of equilibrium was established after several hours of reaction time. The composition of the sulfide was obtained from the initial weight of the sample and the weight after equilibration. X-Ray Studies. The lattice parameters of some of the equilibrated samples were determined using the General Electric XRD-5 diffractometer with a cobalt tube (no filter) set at 40 kv apd 10 ma; the CoK, radiation was taken as 1.79020A. Observed 220 and 311 diffraction peaks of silicon served as an internal comparison standard to correct for possible misalignment of the goniometer. The lattice parameters of the sulfide phase were calculated from the corrected Bragg angles of the 110 and 102 peaks. Rate Studies. In the initial experiments attempts were made to measure the parabolic rate of sulfidation by measuring the gain in weight of a thin iron strip, -0.05 cm thick, suspended from a silica spring in the reacting atmosphere. The preliminary experiments showed that this technique was not reliable for the measurement of the parabolic growth rate of the iron sulfide layer. In the subsequent experiments the data on growth rate were obtained by measuring, on a microscope stage, change in the thickness of the sample after reaction for a specified time in a hydrogen sulfide-hydrogen mixture of known sulfur activity. For each reaction time a new sample was used. Precision-machined iron blocks, 0.5 by 2 by 5 cu cm, were de-greased and annealed in hydrogen for several hours prior to the sulfidation rate measurements. The experiments were carried out at 670°, 800°, and 900°C in gas mixtures having the ratios, and 1.0 for periods of times from a few hours up to 8 days. Apparatus and Materials. A vertical globar tube furnace with a 3-in.-long uniform temperature zone was used. The glass tube fittings were fused on the zircon reaction tube, 1.5 in. diam. The temperature was measured with a Pt-10 pct Rh/Pt thermocouple placed in the hot zone of the furnace inside the reaction tube (an alumina thermocouple sheath was used). A separate thermocouple was used for the temperature controller which maintained the furnace temperature constant within about 2°C. Anhydrous liquid hydrogen sulfide and oxygen-free dry hydrogen from gas tanks were used in preparing the gas mixtures by the constant head capillary flow-meters. In all cases volume flow rate was 1000 cu cm per min at stp, corresponding to a linear velocity of about 6 cm per sec at 800°C; under these conditions

Jan 1, 1969

By R. H. Schutz

This publication lists the respiratory protective devices approved by the Bureau of Mines as of December 31, 1968, and the names and addresses of their manufacturers. The purpose of this publication is to inform the public about approved equipment for safe use in mines and mineral and allied industries.

Jan 1, 1969

By J. D. Forrester

In striving to develop this discussion about "Manpower for Industrial Mineral Industries" two fundamental classes of manpower are encountered. These are: 1) The Labor Force, comprised of unskilled and semi-skilled, nonprofessional personnel who participate in conducting economic, mineral deposit operations and; 2) The Professional People involved in the science, engineering, and management of such industrial enterprises. The commentary given here will be directed primarily to a review of the characteristics of the second or latter class. To pursue successfully a career as a scientist or engineer in today&apos;s industrial and social complex, it is necessary that technical knowledge must have been acquired by training and study in an institution of higher learning. Also, to act effectively, the individual must have achieved some degree of specialzation, although this element often is developed to most notable degree by post-graduate exposure and experience. In addition, and especially in the case of "management," it is desirable, indeed it is even necessary, that an individual recognize and appreciate the fundamental humanistic-sociological controls, and their nuances, as these elements exist to shape his total environment.

Jan 1, 1969

By Dale E. Walker

The Captain mine came into being under the following circumstances: 1) Commonwealth Edison had need for fuel for the generation of electricity in their Chicago service area. 2) Southwestern Illinois Coal Corp. had an ample supply of coal in the Illinois No. 6 and No. 5 seams. 3) The Gulf, Mobile & Ohio R.R. had a one-line transportation system with the capability of transporting coal from the Captain mine to Commonwealth Edison. These fortuitous conditions permitted an effective three-way partner- ship to develop. Commonwealth Edison had built a new generating station at Joliet, Ill., across the Illinois River from the existing station, to supplement their power-generating capacity for the Chicago area (Fig. 1). The annual requirement of the Joliet station is approximately 4.5 million tons of coal. From large reserves of coal in the No. 6 and No. 5 seams, Southwestern Illinois Coal Corp. contracted to supply Commonwealth Edison with approximately 6 million tons annually from its Captain mine. The logical carrier was Gulf, Mobile & Ohio, whose mainline travels through this coal field and also passes by the Joliet station on its way to Chicago. This railroad has been moving Southwestern&apos;s coal from the Streamline mine for more than 30 years. The basic ingredients of timing, scheduling, moving, and handling were adopted by the three parties, the precise details being worked out jointly. To do this, each group had to know its requirements exactly. The initial schedule was drawn up and tentatively approved, with each party taking a hard look at its own requirements and commitments to make certain that the schedule could be met on a normal daily basis. With only minor changes, the final schedule was adopted, each participant feeling that it had a sufficient factor of safety to maintain steady operation. Each party agreed to help the other in time of emergency. When a delay occurs in any part of the operation, the other

Jan 1, 1969

By G. W. Weems

The Bureau of Mines used the Burnett method and apparatus to determine the compressibility factors for helium and carbon dioxide mixtures at 0°, 10°, 20°, 23°, and 35° C and to pressures of 900 psia. Tables of compressibility factors and approximations of the virial coefficients are presented for seven binary mixtures as well as for helium and carbon dioxide. The results compare favorably with existing data.

Jan 1, 1969

By Jerome E. Grader

Special-purpose analog computers are being profitably applied in the process industries to perform miscellaneoas online computing functions in situations where conventional measurement and/or control hardware cannot perform a required task satisfactorily. This paper will discuss the application of such equipment in the mining industry. It is divided into two parts, beginning with a description of operation of the hardware, followed by a discussion of several applications of the computers to mining industry control problems.

Jan 1, 1969

By O. P. Quist, S. H. Carpenter

The internal friction of single-crystal LiF has been investigated as a function of crystal orientation, while simultaneously applying a static compressive load. Three different crystal orientations were used, these being samples with the (100), (110), and (111) directions along the sample length. Results show the internal friction measured to be similar in appearance but different in magnitude for the (100) and (110) samples. With both orientations, application of a static stress caused an increase in the amplitude-independent damping, which recovered with time. The amplitude-dependent damping was found to first decrease with load up to the yield stress and then increase rapidly. Samples of the (111) orientation were found to have no measurable internal friction even when loaded up to 3.0 kg per sq mm. These results are discussed in terms of current theories of internal friction in ionic crystals. This paper presents the results of an investigation of the dislocation mobility and dislocation motion in high-purity single-crystal LiF at applied stress levels up to the yield stress. Internal friction measurements of the dislocation damping while simultaneously applying a static compressive load was the experimental technique used. LiF crystals much prefer to slip on the (110) set of slip planes. However, with a suitable stress distribution they can be forced to slip on the {100} set of slip planes.&apos; For both sets of slip planes the slip direction is the same, namely (110). The object of this investigation was to try and learn more about the dynamical properties of dislocations on the different slip systems in LiF crystals. EXPERIMENTAL PROCEDURE Dislocation damping was measured, in terms of the log decrement, using a five-component marx2 composite piezoelectric oscillator. The apparatus used allows one to measure the dislocation damping while simultaneously applying a static compressive load on the sample. A schematic of the apparatus used is shown in Fig. 1 and a complete discussion of its construction and operation is given elsewhere.3 All measurements were made at room temperature with a longitudinal resonant frequency of approximately 50 kc per sec. Damping measurements were made using longitudinal vibrations with strain amplitudes from up to 10. Static loads up to 3.0 kg per sq mm were applied to the sample while the damping was being measured. Samples used in this investigation were high-purity single crystals of LiF purchased from the Harshaw Chemical Co. All samples were approximately of an in. square and were hand-ground in length to one-half wavelength to match the resonant frequency of the driver and gage quartz crystals. Samples of three different crystallographic orientations were used, namely, crystals with the (loo), (110), and (111) direction parallel to their length. The magnitude of the damping is a direct measure of the area on the slip planes swept out by dislocations during a complete oscillatory cycle. With a sample of the (100) orientation the maximum applied shear stress, due to longitudinal vibrations, is on the (110) slip planes with zero shear stress on the (100) slip planes. Thus, damping measured from a (100) sample is due entirely to dislocation motion taking place on the (110) set of slip planes. Similarly, for a sample of the (111) orientation there is zero shear stress on the (110) set of slip planes and the damping measured from a sample of this orientation is due entirely to dislocation motion on the (100) set of slip planes. Samples of the (110) orientation will have a component of shear stress on both sets of slip planes and

Jan 1, 1969

By Michel David

One of the most important questions that arises in ore estimation can be stated as follows: What is the error when one extends the grade of a sample to a certain volume? The theory of regionalized variables, with the concept of extension variance, provides a response to that crucial question for any kind of sample extended to any volume. For the usual "extensions" encountered in current mining practice, some simple results can be derived from that theory which was initiated by Dr. G. Matheron. These results have been applied to a stratiform lead-zinc deposit for which several estimations of grade, tonnage and related precision have been made for a series of grid sizes such as might be used in a progressive exploration program.

Jan 1, 1969

By R. E. Siemens

The Bureau of Mines sought to correlate the variation of structure-sensitive superconducting properties with microstructure in selected Cb-Hf alloys and to compare the experimental results with those predicted by the GLAG theory. Alloys in wire and rod form were evaluated by critical temperature, critical current, magnetization, resistivity measurements, and optical and electron microscopy. In the absence of an external magnetic field, the current carrying capacity of columbium was greatly reduced with addition of up to 85 wt pct Hf, but a large increase in Ic occurred for Cb-90 wt pct Hf. Favorable Ic-H behavior was observed in cold-drawn alloys containing 25 and 57 wt pct Hf. Correspondingly, a maximum in Tc occurred at 10-25 and 90 wt pct Hf. Four- or five-hour heat treatment at 600° C resulted in maximum Ic values and maximum hysteresis in magnetization. Dislocation pileup, polygonization, and fine precipitates, responsible for flux pinning, are listed in order of their effectiveness as pinning sites. Sites having an average separation of 1,500 to 3,000 A and a diameter of 1,000 A or less were most effective in influencing Ic-H and M-H behavior. The resistive critical fields increased smoothly to a maximum of 80 k0e between 60 and 65 wt pct Hf. Highfield, mixed state, reversible paramagnetism was observed in some alloys; however, the GLAG theory was in good agreement with experimental results for the majority of the composition range studied.

Jan 1, 1969