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By I. D. Shah

A roasting procedure for synthetic copper sulfide which results in a reproducible transient melting at 450° and 470°C is described in this paper. Possible causes for this melting phenomenon are suggested, and also a procedure to avoid it during the roasting. This melting is believed to be responsible for the occasional occurrence of stickiness in the commercial roasting of copper sulfide concentrate. Many workers have studied the roasting of copper sulfides, but only Lewis et al. have reported that fusion and, in some cases, fusion with "boiling" occurred in the neighborhood of 450°C. The DTA and TGA apparatus, the materials used in this investigation, and the discussion of chemical reactions occurring during the CuS roasting are described in an earlier publication. CuS, in the form of either pellet or powder, was heated at 280° to 330°C in a flowing air or 30% 02: 70% N2 atmosphere. Heating was continued at this temperature until no further weight increase due to sulfates formation was observed on the TGA thermogram. This is believed to be due to the inability of SO, to diffuse out from the sulfate layer on the surface of the pellet, thus halting the sulfate-forming reactions. Hereafter, the sample oxidized in this manner will be referred to as "partially oxidized CuS." X-ray analysis and microscopic examination of a polished cross section of a partially oxidized CuS pellet showed the following order of layers starting from the center of the pellet: Cu2S, Cu2O, CuO • CUSO4, and CuSO4. A bare thermocouple inserted in the center of a partially oxidized CuS pellet (2.5 g) did not indicate any noticeable change in the temperature of the pellet when melted at 450° to 470°C in an inert or oxidizing atmosphere. During the preparation of a partially oxidized pellet, the temperature of a CuS pellet increased by 50°C due to the exothermic formation of sulfates in air at 320°C. The endothermic peak associated with the melting phenomenon at 450°C is shown in [Fig. 1.] A CuS pellet (0.2 g) was oxidized in flowing air (150 cc per min) at 10°C per min up to 320°C and held there for about 2 hr. Then, N2 replaced air and heating was continued up to 500°C. The exothermic peak at 320°C represents an overall formation of sulfates, and an endothermic peak at 450° to 470°C represents the melting phenomenon. To observe the melting visually, a small (50 mg), partially oxidized CuS pellet was heated (in static air) in a hot-stage microscope. The melting phenomenon was observed on an auxiliary TV screen. The sample

Jan 1, 1976

By R. D. Russell, R. M. Farquhar

ISOTOPIC tracers have become an important aid in following the progress of chemical processes in the laboratory. It has recently been found possible to utilize a system of naturally existing isotopic tracers to obtain information about the geo- logical history of lead ores. Common lead, such as is found in lead deposits, is a mixture of four stable isotopes having atomic weights 204, 206, 207, and 208. Of these, the last three are identical with the lead isotopes produced as stable end products of the radioactive decays of uranium and thorium: the first, lead-204, is not known to be produced on the surface of the earth by any process. Since uranium and thorium occur in the surface regions of the earth in amounts comparable with lead, and since the half-lives of uranium and thorium isotopes are of the same order as the age of the earth, they produce the radiogenic lead isotopes in amounts com- parable to the amount of nonradiogenic lead present. Every significant exposure of a sample of lead to uranium and thorium will therefore lead to the permanent alteration of the lead isotope ratios in that sample.

Jan 5, 1957

By Paul A. Farrar, Felix Ermains, Harold Margolin

The systems Ti-Crand Ti-Vhave been reinvesti-gated in the region up to 40 wt pct alloying addition using both conventional and rapid quenching techniques. The Ti-Cr eutectoid temperature was determined to be at 667° & 10° C and 14.5 wt pct Cr. The solubility of the Cr in a Ti was found to be less than 1 pctat 700"C. The P transus of the Ti-V system was found to be depressed to 510°C at 40 wt pct V and the solubility of V in a Ti was found to be less than 2 wt pct at 700°C. Investigation by a. d. McQuillan1-3and m. k. McQuillan4 on the systems Ti-Co, Ti-Cr, Ti-Cu, Ti-Fe, Ti-Mn, Ti-Ni, and Ti-V has cast doubt as to the position of the ß/a + ß boundaries in many of these systems. Their investigations were carried out using hydrogen pressure and/or rapid quenching experiments, as opposed to the conventional quartz capsule techniques employed by most other investigator.'" By these methods, the ß/a + ß boundary was found to be lower than that obtained by conventional techniques in all except the Ti-Fe system. In the latter, the ß/a + ß boundary was essentially the same as the boundary obtained by conventional technique.7' On the basis of rapid quenching results in the Ti-Cr system, M. K. McQuillan4 placed the eutectoid temperature below 550°C whereas other investigations using conventional techniques had placed the eutectoid variously as between 650' and 700°C,5 between 675' and 700°C,6 between 650" and 675°C,7 at 670°C,8 and above 625"C.la9l3 In order to check these results, a reinvestigation of four of the systems was undertaken using both conventional and rapid-quenching techniques. The Ti-Fe and Ti-Mn systems will be dealt with in anoth er paper, with only the Ti-Cr and Ti-V systems being discussed here. EXPERIMENTAL TECHNIQUES Alloys employed for the delineation of the systems under investigation were prepared from iodide titanium sheet capsules containing the alloying materials,

Jan 1, 1962

By Maurice Ewing, L. Don Leet

Assuming that wave velocities in seismic prospecting increase as a continuous linear function of the depth, the authors have derived formulas for computing, from two time-distance observations, the amount of velocity increase, depth of penetration and a graphical determination of the path of the vibrations, and have discussed the ground, reflected and refracted waves. The application of the formulas is illustrated numerically. Earlier Investigations Observations of the energy propagated from the center of an earthquake disturbance have been used to give information about the velocities and paths of elastic waves in the interior of the earth. One method of accomplishing this depends on the use of the times of transmission. Herglotz(7) § and Bateman(3) obtained a solution of the integral equation involved, which determines the velocity of propagation at any point as a function of the distance from the center of the earth, with no assumption as to the manner in which the velocity of the disturbance varies with depth below the earth's surface. The expressions on which the value of the time and the form of the ray of propagation depend contain an unintegrable definite integral, involving the velocity as an unknown function of the distance from the center of the earth. Wiechert and Zoppritz(15) obtained a manageable form for this function by assuming a law of variation which required a constant curvature form for the path within each of a succession of concentric spherical layers of the earth. C. G. Knott(9) worked out the problem for the first time by an absolutely rigorous method from the data of observation (Zoppritz-Turner tables), without making any assumptions as to the functional relationship connecting the speed of propagation and the distance from the earth's center. His method is a numerical solution of an integral equation, giving each velocity and the corresponding distance from the center of the earth in figures.

Jan 1, 1932

By D. C. Jillson

BRIDGMAN1,2 melted metals in a graphite or hard glass tube and lowered the tube through a furnace to make it cool from one end only. Because of the difficulty of eliminating all vibration of the mold, others have raised the furnace instead. Neither way seems as desirable as a setup with no motion of either the mold or the furnace. A furnace in which both the shape and the slope of the temperature gradient could be controlled and varied over a wide range and in which such a gradient could be moved from one end of the furnace to the other, freezing the specimen from one end to the other, at any desired rate, all by means of isolated external control, seemed to offer definite advantages. In addition to eliminating the possibility of vibration due to moving parts, it might also give better control over the direction and rate of heat flow. Such an apparatus was assembled and is shown schematically in fig. 1. Equipment Furnace: A clay-carborundum tube of 3 1/2 in. ID with a % in. wall thickness was used as the core. This had a main winding of No. 12 B.&S. gauge Nichrome V with some compensation for heat loss at the ends. Taps to this winding were made at points 12 in. from each end. Fig. 2 shows details of this winding and of the two end windings. Each end winding was wound over Micanite over the main winding. No. 15 B.&S. gauge Nichrome V was used for these, and again taps were supplied at two inter-mediat,e points on each. The tube was supported in an 18 in. OD black iron shell with brick insulation. The input to each of the windings was regulated by means of a variable transformer. Temperature Regulation: A chromel-alumel thermocouple located near the furnace wall in the center of the furnace was connected with a Celec-tray controller, type PIC, 300" to 900°C range, which opened and closed a shunt across an external variable resistance in the main winding circuit. An "anticipatory response" device also was incorporated to minimize the cyclic effect of the control mechanism. Eleven survey couples in a common pyrex glass protection tube were located near the furnace wall and spaced 2 in. apart. The couple leads went to a common reference junction box where they were connected to copper leads from a selector switch which, in turn, was connected to a type K potentio-meter. This arrangement permitted rapid temperature surveys. The knob on the controller dial was replaced with a threaded brass spool turned at a controlled rate by a thin iron wire one end of which was attached to a gear train and the other to a small weight heavy enough to prevent slipping of the wire on the spool. The gear train, driven by a 1-rpm Telechron motor, contained a series of different sized interchangeable gears and threaded drums permitting a range of travel speeds from 0.10 in. per hr up to a hypo-

Jan 1, 1951

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson' measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans' and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner's data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By J. V. Emmons

IT has long been known that the outside skin of tool steel frequently exhibits properties widely different from the interior of the mass. Within the last few years it has been generally recognized that many of these properties were clue to surface decarbonization. The origin and effects of this altering of the composition have been but little studied. C. M. Johnson' arrives at the conclusion that, in annealing, "the most active agent in surface decarbonization is the rust or scale (present on the surface), which is actually reduced to metal at the expense of the carbon in the steel to which it adheres." W. H. Hatfield in his admirable paper, The Chemical Physics Involved in the Decarburization of Iron-Carbon Alloys,' has given us the most tenable theory of the removal of carbon from iron. While Mr. Hatfield's work has been principally clone in connection with the annealing of white cast iron to produce malleable castings, it is frequently applicable to the decarbonization of tool steel. The following equations which he proposed have been fully borne out by the author's experiments: 2Fe3C + 2CO2 = 3Fe2 + 4C0 2C0 + 02 = 2C02 Continuous 2C02 + 2Fe3C = 3Fe2 + 4C0 It is the purpose of the author to show, in a quantitative manner, the effect of various treatments in eliminating the carbon in tool steel. Some of the phenomena of the decarbonized surface will also be described, as well as the practical problems they present to. the manufacturer and user of tool-steel products.

Jan 9, 1914

By Davis Baker

The direct-metal cars or ladles of the Maryland Steel Company have a capacity of 18 tons when filled within 12 inches of the top. On account of this large capacity, the formation of skulls in these ladles is by no means as rapid as in smaller ladles; but a skull once formed is a very unwieldy piece of metal to handle, and especially to remove from the ladle. We have found it cheaper to clean ladles often rather than make very heavy skulls. We aim to keep the ring of chilled metal that forms on the surface of the iron chipped off, so that the skull shall form principally at the bottom until it becomes so thick as to render the ladle unfit for service. Sometimes it happens that a ladle may be held for several hours filled with molten metal. This invariably leaves a large amount of chilled metal in the ladle. Frequently the skull will weigh several tons, and will be of the full size of the ladle inside, with a top crust, having perhaps a hole 12 inches square, through which the molten metal was poured. In order to remove skulls that cannot be easily chipped out with a bar, we use what may be called a skull-extractor, consisting of a hydraulic cylinder mounted in the center of a heavy cast-iron plate, standing vertically on a suitable foundation. Figs. 1 and 2 show the construction and operation of this apparatus, Fig. 1 being a view of the extractor with pistons extended to full stroke, and Fig. 2 a view with ladle in position and pistons about to commence the stroke. in both figures, A is the hydraulic cylinder, B the vertical cast-iron plate, and C the foundation. The water-pressure, admitted through the pipe, P, is 750 pounds per square inch, and the inside diameter of A is 14 inches. There are two pistons: D, fitting the bore of the cylinder, and E, 84 inches in diameter, moving inside of D. Both pistons move together when

Jan 1, 1893

By D. C. Hilty, W. Crafts

J. Chipman—It has been my privilege to discuss this work with the authors on several occasions and to observe at first hand the experimental methods employed. I wish, therefore, to emphasize certain points which they have mentioned only briefly with regard to the experimental techniques. The rotating induction furnace as here employed interposes liquid metal between slag and refractory thus preventing the two nonmetallic parts of the system from reaching equilibrium with one another. It is therefore impossible for the metallic phase to be completely in equilibrium with both the slag and the crucible. The metal also acts as a partially permeable membrane allowing certain components, including oxygen, to diffuse from slag to crucible. This transfer results in building up on the face of the crucible a layer of material whose composition is in part dependent on that of the bath. Reactions between the layer and the solid refractory are slow, as evidenced by the rather good life of the crucible. Hence it seems probable that the layer is more nearly in equilibrium with the metal than with the underlying crucible material and that, once it is established under a bath of a given composition, its further reactions with that bath are slow. Additions to slag or bath may be followed by changes in the layer; and time must be allowed for virtual completion of such changes, before it can be assumed that slag and metal are in equilibrium. We may judge from the results reported that, in general, this was the case and that the data represent at least quite close approximations to slag-metal equilibrium. Data on deoxidation and on oxygen solubility are no better than the analytical methods employed. The vacuum fusion method as used by the authors seems entirely adequate for the samples analyzed. I have had frequent occasion to compare results with their laboratory, always with very satisfactory agreement. The determination of aluminum at very low concentrations is perhaps an even more difficult procedure. Here also the colorimetric method used has been worked out with great care and is undoubtedly the most dependable method available. The discrepancy between observed and calculated deoxidation or solubility lines is not to be explained as the result of experimental errors, either in the sampling or analysis of the metal. Nor is it to be blamed upon inaccuracies in the several kinds of indirect data upon which the calculated results were based. It is true that both the observed and the calculated lines admit of some uncertainty as to their exact locations, but the uncertainties are small compared to the wide gap which separates the two lines. The authors have pointed out the real cause of the discrepancy. In all of their experiments the solid phase was not Al2O3 but a mixed oxide containing iron and aluminum. This suggests an extension of the calculated values to include equilibrium with the spinel FeO . A12O3. The free energies of FeO and A12O3 are known, that of the spinel is not. However, it cannot differ greatly from that of its component oxides for even in the more stable spinel, chromite, the free energy of formation from the oxides is less than 10,000 cal. For purposes of calculation we shall call this free energy X and solve for values of X lying between zero and 10,000 cal. The other data required are taken from the forthcoming revision of "Basic Open Hearth Steelmaking" and are given in the following equations in which underlined symbols indicate elements dissolved in liquid steel and the standard concentrations are 1 pct. ?F° at 1600°C, cal ?LA = 2 Al + 3 O; + 107,200 FeO = Fe + 0; + 5,460 FeO + A12O3 = Fe + 2A1 + 4 0; + 112,660 — X The corresponding equilibrium concentrations are shown in fig. 21. The line marked A12O3 corresponds to the first equation, those marked FeO . AL2O3 correspond to the last, with X = 0, 5000 and 10,000 cal, respectively. The two upper lines represent the data of Hilty and Crafts and of Wentrup and Hieber. The points are the observations of Hilty and Crafts in the presence of 0.50 pct Mn.

Jan 1, 1951

By Charles Trotter

AN instrument has recently been developed for determining the inclination and azimuthal direction of boreholes. This instrument is known as the Tro-Pari Instrument and is the invention of C. Trotter and G. Pajari of Sudbury, Ontario. DESCRIPTION The instrument is characterized by a unit mounted in gimbals and provided with a clockwork mechanism to clamp a compass to indicate azimuthal direction and simultaneously to clamp the unit in its plumb position to indicate inclination (Fig I). By means of a timing ring suitably calibrated in 5-min divisions, the unit may be set to lock after a lapse of time sufficient to allow the placing of the instrument at the desired point in the drill hole where readings are to be taken. The maximum time lapse obtainable with the instrument designed for use in EX or AX size holes is 1 hr 30 min which is considered to be ample time to lower to the greatest depths that may be drilled with this size of equipment. Larger sizes could be developed for larger diameter holes such as BX and NX sizes or the larger oil-well sizes and a correspondingly greater time lapse could be provided for. Up to the present time only the EX-AX size has been built. OPERATION Assuming a borehole is to be surveyed at 1000-ft depth and assuming it will take 30 min to lower the instrument to this depth, the timing ring is rotated through seven divisions which represent a time lapse of 35 min (5-min leeway) and is then returned to its zero position. This operation imparts energy to a spring which drives the clockwork mechanism. Simultaneously the compass needle is freed to swing to its magnetic north-south position and the encased mechanism is freed to hang plumb within a semicircular portion of the frame which is graduated in degrees after the fashion of a protractor. This semicircular protractor portion has a V-shaped notch at each degree division of its inner periphery. The instrument, now in its free position, is inserted in a bronze container made to suit the size of hole to be surveyed (Fig 2). Soft rubber washers are provided within the container to prevent undue shock. The container is connected to the drill rods with three 5-ft lengths of brass or aluminum alloy rods separating it from the steel rods in order to prevent distortion of the magnetic field. The assembly is then lowered to the desired point where readings are to be taken and is allowed to remain at rest until a period of time has elapsed slightly in excess of the time for which the timing ring was set. In the example cited above, when the 35 min has elapsed the compass needle is locked in its north-south position and the protractor locking pin is extruded and locks in the V notch opposite its plumb position. The device may now be removed from the borehole and it will remain in this locked position in spite of jarring or shak-

Jan 1, 1947

By Charles Trotter

An instrument has recently been developed for determining the inclination and azimuthal direction of boreholes. This instrument is known as the Tro-Pari Instrument and is the invention of C. Trotter and G. Pajari of Sudbury, Ontario. Description The instrument is characterized by a unit mounted in gimbals and provided with a clockwork mechanism to clamp a compass to indicate azimuthal direction and simultaneously to clamp the unit in its plumb position to indicate inclination (Fig I). By means of a timing ring suitably calibrated in 5-min divisions, the unit may be set to lock after a lapse of time sufficient to allow the placing of the instrument at the desired point in the drill hole where readings are to be taken. The maximum time Lapse obtainable with the instrument designed for use in EX or AX size holes is I hr 30 min which is considered to be ample time to lower to the greatest depths that may be drilled with this size of equipment. Larger sizes could be developed for larger diameter holes such as BX and NX sizes or the larger oil-well sizes and a correspondingly greater time lapse could be provided for. Up to the present time only the EX-AX size has been built. Operation Assuming a borehole is to be surveyed at 1000-ft depth and assuming it will take 30 min to lower the instrument to this depth, the timing ring is rotated through seven divisions which represent a time lapse of 35 min (5-min leeway) and is then returned to its zero position. This operation imparts energy to a spring which drives the clockwork mechanism. Simultaneously the compass needle is freed to swing to its magnetic north-south position and the encased mechanism is freed to hang plumb within a semicircular portion of the frame which is graduated in degrees after the fashion of a protractor. This semicircular protractor portion has a V-shaped notch at each degree division of its inner periphery. The instrument, now in its free position, is inserted in a bronze container made to suit the size of hole to be surveyed (Fig 2). Soft rubber washers are provided within the container to prevent undue shock. The container is connected to the drill rods with three 5-ft lengths of brass or aluminum alloy rods separating it from the steel rods in order to prevent distortion of the magnetic field. The assembly is then lowered to the desired point where readings are to be taken and is allowed to remain at rest until a period of time has elapsed slightly in excess of the time for which the timing ring was set. In the example cited above, when the 35 min has elapsed the compass needle is locked in its north-south position and the protractor locking pin is extruded and locks in the V notch opposite its plumb position. The device may now be removed from the borehole and it will remain in this locked position in spite of jarring or shak-

Jan 1, 1949

By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert's measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith's8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert's6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert's a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

By T. Egleston

THE works of the Ore Knob Copper Company are situated in the county of Ashe in the northwestern part of the State of North Carolina, about ten miles from the Virginia line, at an elevation of 4600 feet above the sea. The nearest railroad station is at Marion, Smythe County, Virginia, about forty-five miles distant. The roads from the railroad to the works have been constructed by the company for the transportation of their material, and are very hilly, and in certain seasons of the year in bad repair. Transportation is therefore always limited and never easy, although it is done by contract at a very low price. The main difficulty with the transportation is not so much its cost as the fact that it puts a limit to the production of the works. These unfavorable conditions make it necessary for the owners of the mine to smelt their ores and to send to market nothing except the metal, which alone will bear the cost of transportation. The mine was opened previous to 1860, but has only been worked systematically during the last five or six years. The vein is a fissure vein from ten to twenty feet in thickness in the gneiss of the

Jan 1, 1882

By T. Egleston

The works of the Ore Knob Copper Company are situated in the county of Ashe in the northwestern part of the State of North Carolina, about ten miles from the Virginia line, at an elevation of 4600 feet above the sea. The nearest railroad station is at Marion, Smythe County, Virginia, about forty-five miles distant. The roads from the railroad to the works have been constructed by the company for the transportation of their material, and are very hilly, and in certain seasons of the year in bad repair. Transportation is therefore always limited and never easy, although it is done by contract at a very low price. The main difficulty with the transportation is not so much its cost as the fact that it puts a limit to the production of the works. These unfavorable conditions make it necessary for the owners of the mine to smelt their ores and to send to market nothing except the metal, which alone will bear the cost of transportation. The mine was opened previous to 1860, but has only been worked systematically during the last five or six years. The vein is a fissure vein from ten to twenty feet in thickness in the gneiss of the

Jan 1, 1882

By Harrison Souder

MAGNETITE mining and milling in the Eastern States showed continuing improvement during the year. Some of the smaller mines remained idle, but the larger operations responded promptly to the improved situation in the iron and steel industry. The output of ore for 1936 was over twice that for 1935. A number of improvements were made in mine plant and equipment, and operating forces were increased and maintained at near normal. The coming year should see additional mines started up and production increased at the larger properties.

Jan 1, 1937

By G. R. Speich

The distribution of carbon and the type of substructure in iron-carbon martensites containing 0.02 to 0.57pct C has been studied in the as-quenched condition and after tempering at 25" to 700°C by using electrical resistivity, internal friction, hardness, and light and electron microscope techniques. in marten-sites containing less than 0.2 pct C, almost 90 pct of the carbon segregates to dislocations and to lath boundaries during quenching; in martensites containing greater than 0.20 pct C, appreciable amounts of carbon enter normal interstitial positions located far from defects. Tempering martensites with carbon contents below 0.20 pct at temperatures below 150°C results in additional carbon segregation to dislocations and to lath boundaries but no carbide precipitation whereas -carbide precipitation occurs in martensites with carbon contents exceeding 0.2 pct. Above 150°C, a rod-shaped carbide (either Fe3C or Hagg) is precipitated in all cases. At 400°C, spheroidal Fe3C precipitates at lath boundaries and at former aus-tenite grain boundaries. At 400" to 600"C, recovery of the martensite defect structure occurs. At 600" to 700°C, recrystallization of the martensite and Ost-waW ripening of the Fe3C occur. The effects of the carbon segregation that occurs during quenching and the subsequent substructural changes that occur during tempering on martensite tetragonality, hardness, and precipitation behavior are discussed. A mathematical analysis of carbon segregation during quenching is presented. RECENT studies of the strength of low-carbon martensitel-4 emphasize the importance of carbon segregation to the martensite lath boundaries and to the dislocations contained between them during quenching. Unfortunately, very few studies of the tempering of low-carbon martensites have been conducted, so the exact nature of this segregation is poorly understood. In fact, most early tempering studies5,6 were restricted to carbon contents greater than 0.20 pct. Moreover, these studies did not determine the amount of carbon segregated to the martensite substructure during quenching so that the initial state of the martensite was not established. Aborn7 studied the precipitation of carbide in low-carbon martensite during quenching but did not establish whether carbon segregation occurs prior to carbide precipitation, nor did he study the subsequent tempering sequence in detail. In the present work we have used electrical resistance and internal friction measurements, supplemented by electron transmission microscopy to establish the carbon distribution in as-quenched specimens. Specimens thin enough to avoid carbide precipitation (but not carbon segregation) were employed. The redistribution of carbon on subsequent tempering below 250°C was followed by measurements of elec- trical resistance. Additional studies were made on specimens tempered at 250" to 700°C to elucidate the overall tempering behavior of low-carbon martensites, including the formation of cementite and recrystalli-zation of the martensite. EXPERIMENTAL PROCEDURE Eight iron-carbon alloys with 0.026, 0.057, 0.097, 0.18, 0.20, 0.29, 0.39, and 0.57 wt pct C were prepared as 8-lb ingots by vacuum melting. Typical impurities in wt ppm were 40 Si, 20 Mn, 30 S, 10 P, and 10 N. These alloys were hot rolled to 3 in. plate at 1095°C) (2000°F). The hot-rolled plates were surface ground to remove scale and the decarburized layer, then cold rolled to 0.010 in. sheet. Specimens cut from the sheet were austenitized for 30 min at 1000°C (1830°F) in a vacuum tube furnace in which the pressure did not exceed 2 x 10-3 torr. Chemical analysis of specimens after austenitization indicated no decarburization at this pressure. Immediately before quenching, the furnace was filled with prepurified helium. The specimen was then pushed rapidly through an aluminum foil gasket, which sealed the bottom of the furnace, into an iced-brine bath (10 pct NaC1, 2 pct NaOH). The quenching rate at the M, temperature is about 104'c per sec for 0.010 in thick specimens, as calculated from Newton's law of heat flow2 using a heat transfer coefficient of 25 ft-'. This quenching rate is sufficiently high so that all the alloys transformed completely to martensite throughout the entire 0.010 in thickness and no carbide precipitation occurred in the martensite. All specimens were immediately transferred to liquid nitrogen after quenching and stored there until needed. Tempering below 250°C (480°F) was done in silicone oil baths thermostatically controlled to *;"C. Tempering above 250°C was done in circulating air furnaces or lead pots with the specimens contained in evacuated silica capsules. Electrical resistance was determined by measurement of the potential drop across both a standard resistance and the specimen, connected in series. All resistance measurements were made in liquid nitrogen (77K, -196°C) to minimize thermal scattering of electrons and thus maximize the contribution of impurity scattering to the resistance. Specimen dimensions were 5.10 by 0.19 by 0.025 cm. Although the precision in the electrical resistance measurements was +0.1 pct, the electrical resistivities could only be measured with an accuracy of +5 pct because of uncertainty in the specimen dimensions. Internal friction measurements were performed in an inverted pendulum apparatus at vibration frequencies of either 1.9 or 66 Hz. The specimen dimensions were 5.10 by 0.375 by 0.025 cm. Hardness measurements were made with a Leitz-Wetzlar microhardness machine with loads of 100 g. Specimens were examined by light microscopy after etching in 2 pct Nital and by electron transmission microscopy after preparation of thin sections by electrolytic thinning in a chromic-acetic acid solution.

Jan 1, 1970

By M. J. Coolbaugh

Mining potash at depths of 3000 ft or more beneath thick water-bearing sediments in Saskatchewan presented a unique challenge to the North American mining industry. Potash is known to flow under pressure, but the knowledge of its flow characteristics at great depths was inadequate for safe design of mine workings and for assured protection from water above the salt formations. At the 3000-ft. depth of the Canadian mines, the potash is stressed beyond its elastic limit, and therefore mining design must deal primarily with its behavior as a plastic material. Recognizing that careful study would be required in order to assure safety and stability of mine workings in deep potash, IMC initiated an extensive rock mechanics investigation of structural properties of potash and salt under high-stress conditions. This presentation consists of a brief review of the development of some methods of testing potash in the laboratory and in the field; some of the rock mechanics concepts and principles derived; and their application to potash mine design. The mining of potash more than 3000 ft beneath the water-bearing sediments in Saskatchewan presented the unique challenge of designing stable mine workings and assuring protection from overhead water in a material that was believed to flow plastically, but whose behavior as a plastic material was not sufficiently known. Under the stress conditions ordinarily encountered in mining, most rocks behave as elastic materials; that is, they compress slightly under pressure, and rebound when the pressure is released. Salt and potash, however, are different. Even under the relatively low pressures encountered at shallow depths, these materials become slightly plastic and yield to stress by flowing.* The plastic properties become more pronounced at greater depth and pressure, and the question arises as to whether or not the plastic flow will be rapid enough and exert enough pressure to destroy underground structures or interrupt the mining process. It was found, however, that not only was there an insufficiency of information about the behavior of potash and salt, but conventional methods of testing these materials, such as determining the modulus of elasticity, Poisson's ratio, and uniaxial compressive strength, were inapplicable because of the high stress conditions prevailing at the 3000-ft depth. Potash under high pressure, for example, has practically no modulus of elasticity, its stress-strain relationship varies with time, and its compressive strength depends upon the degree of confinement. Elasticity and Stress/Strain Relationship: Fig. 1 shows a standard stress/strain chart for potash as made by the Department of Mines in Canada. Typically, when stress is applied to a hard-rock specimen, the specimen contracts, then expands to its original shape when the stress is withdrawn. This chart illustrates, however, that potash under stress yields to the stress by flowing, and does not expand when the stress is withdrawn. When the applied stress was held constant for 30 min, beginning at points A and C, the strain continued to increase and the potash flowed to points B and D, respectively. Points B, D, F, and H show that the potash did not return to its original shape when the stress was released. Thus it can be observed that potash has practically no elasticity and that the amount of strain depends upon the length of time that the stress is applied. Compressive Strength: The conventional method of determining the compressive strength of hard material is to find the maximum pressure that long slender specimens of the material can withstand without failing. As illustrated in Fig. 2,* line B, a standard 2-in. cube of potash subjected to a conventional type of uniaxial compressive test will exhibit a strength of about 5000 psi. However, the compressive strength exhibited can be made to change by changing the conditions under which the test is made. For example, if teflon plates lubricated with graphite are inserted between the press and the specimen, thus minimizing end constraint, the compressive strength is only about 2500 psi, shown in line A. If a specimen is cut in half, changing the width-to-height ratio to 2 : 1 instead of 1:1, and then tested without lubri-

Jan 1, 1968

By B. W. Frazier

At a recent meeting of the North of England Institute of Min ing and Mechanical Engineers, during a discussion upon the com pression of air, attention was called to an apparent anomaly in the phenomena attending the compression. At a subsequent meeting this apparent anomaly was explained by Prof. Herschel, and all the facts observed shown to be strictly in accordance with the laws of thermodynamics. Upon reading the report of the discussion in the published transactions of the society, it occurred to me that an attempt to determine mathematically the amounts of energy (whether in the form of heat or of work) expended and absorbed in compressing air, and causing it to perform work by expansion, might prove of use to some who have not access to any treatise upon the application of the laws of thermodynamics to the compression of air, and who have not the time or the inclination to make such application for themselves. The apparent anomaly noticed was this: If air be compressed, and at the same time, by the sufficient application of a cooling medium, kept at a constant temperature, the indicator diagrams in the

By Edwin F. Brush, John Chipman

Published data on the activity of carbon in binary and ternary austenite at 1000°C are reviewed. The composition variables are . The coefficient, Vj, has the value for substitutional elements but may be assigned a ualue -1 for silicon to effect a simplification on the mathematical treatment. The activity coefficient PC = is obtained from gas equilibrium data. For the ternary systems studied the Henrian activity coefficient is given by the expression: The principle advantage in cornparison with the analogous expression in terms of atom fractions is found in the fact that for most systems the final term and in many the last two terms are zero. Values of the interaction parameters are tabulated and the graphical comparison of the equation with experirt~ental data is sho,wn in several figures. The thermodynamic properties of the solid solution, austenite, are of considerable importance in the heat-treatment of alloy steels and in other aspects of ferrous metallurgy. Early studies embodied in the Fe-C diagram have been extended to include other binary and some ternary diagrams. Our best hope of obtaining a useful thermodynamic treatment of reactions in complex alloy steels will not be found in quaternary and quinternary phase diagrams but in determinations of activities and interaction relations among the several solute elements. The foundation for such a development was laid by smith' in his early studies of the activity of carbon in Fe-C alloys and his subsequent work on Fe-C-Si, Fe-C-Mn, Fe-C-Ni, and Fe-C-Co solid solutions.2"4 Other observers have also made noteworthy contributions and these will be discussed and correlated here in the light of a somewhat simplified mathematical treatment of solute interactions. Fe-C AT 1000°C In a recent review of the thermodynamic properties of binary Fe-C austenite it was shown that the simple mathematical treatment employed by smith' was capable of describing all the published results on this solution. The treatment utilizes the atom ratio, yc = nC/nF,, rather than the atom fraction. The activity of carbon is proportional to the equilibrium gas ratio, either measured on a scalk in which the activity of graphite is taken as unity or, alternatively, aC may be set equal to yc at infinite dilution. In either case the ratio aC/y = (PC, the activity coefficient. It was found that the experimental data of smith1 and those of Diin-wald and wagner; Bungardt, Preisendanz, and Lehn-ert,' and Scheil, Schmidt, and Wiinnings at temperatures of 800" to 1200° C as well as reliable data on the solubilities of graphite and cementite could be represented by the equation for which graphite is the standard state: The data on alloyed austenite have been obtained at 1000°C. For this temperature, the "Henrian" activity coefficient (which is unity at infinite dilution) is: FOr an interstitial solute such as carbon in austenite it has been shown by statistical mechanicsg that the activity in the infinitely dilute solution is proportional to the ratio of the number of lattice sites occupied by carbon to the number of yet unfilled lattice sites. A variable zz proportional to this ratio serves as a useful measure of concentration:" in which b is the number of lattice sites provided by each atom of solvent; in austenite b = 1. The Henrian activity approaches zz at infinite dilution and the ratio a is the activity coefficient. The effect of a change in concentration is then given by: It has been shown further that in some systems the derivative in Eq. [4] remains constant over a wide range of concentrations. In such a case second-order terms become negligible and the Henrian activity coefficients is:

Jan 1, 1969

[America,-Dear, G. C. Anniston.-Klugh, B. G. Auburn. *Poor, R. S. Bankhead.-Armstrong, W. D. Bessemer.-Creveling, J. G. Lindstrom, W. A. McKenzie, W. C. Mitchell, F. R. Birmingham.-Abbott, C. E. Armstrong, G. R. Austin, W. W., Jr. Ball, T. L. Beard, A. H. Benjamin, F. S. Blackburn, E. C. Blair, A. J. Blair, C. S. Blair. H. W.]

Jan 1, 1946