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By Sherwin F. Kelly

The need for geophysicists to adopt a uniform mode of expressing the electrical resistivity of geological formations has been stressed by Dr. A. S. Eve.1 The present paper is to emphasize the point he raised, to bring the weight of disinterested authority to bear on the matter, and to urge the adoption henceforth, save in exceptional cases, of a standard expression for resistivity; all in the hope that the needed reform will thus actually be brought about. The general definition of the resistivity of a material is the resistance in ohms between two opposite faces of a unit cube of that material. No account need be taken here of the cases in which the unit volume is not a cube, and the units of length and cross-section are different, encountered principally when dealing with metallic conductors such as wires. The idea of the resistance of a unit volume of earth or rock has found expression in geophysical literature in a number of forms and with a variety of units. Fortunately, the metric system has been adhered to in most cases, so ordinarily the meter or the centimeter, usually the latter, has been the measure chosen. The resistivity is then the resistance of a cube of the given rock, or soil, one centimeter on an edge. This is far from always being the same thing, however, as the resistance of a cubic centimeter. A long thin wire could contain a cubic centimeter and have a high resistance, whereas the same volume formed into a flat plate would have an entirely different, and quite low, resistance between faces. Consequently, it is not proper to express resistivity in ohms per cubic centimeter, inch, etc., as has been done occasionally by some writers. In an effort to emphasize the idea of cubic volume, some geophysicists, the writer among them, have used the phrase, ohms per centimeter cubed. This is a graphic way of picturing the measure, but is not in favor among highly qualified authorities. In this connection, an appeal was made to the U. S. Bureau of Standards for advice, and the Director, George K. Burgess, kindly replied in detail as to the practice adopted by his Bureau: 'I.., such expressions as 'ohms per centimeter cubed' or any similar expressions are objectionable, because they certainly carry the implication that the resistivity is found by dividing ohms resistance by the volume in cubic centimeters." Actually, of course, resistivity is found

Jan 1, 1932

By Sherwin Kelly

THE need for geophysicists to adopt a uniform mode of expressing the electrical resistivity of geological formations has been stressed by Dr. A. S. Eve.1 The present paper is to emphasize the point he raised, to bring the weight of disinterested authority to bear on the matter, and to urge the adoption henceforth, save in exceptional cases, of a standard expression for resistivity; all in the hope that the needed reform will thus actually be brought about. The general definition of the resistivity of a material is the resistance in ohms between two opposite faces of a unit cube of that, material. No account need be taken here of the cases in which the unit volume is not a cube, and the units of length and cross-section are different, encountered principally when dealing with metallic conductors such as wires. The idea of the resistance of a unit volume of earth or rock has found expres-sion in geophysical literature in a number of forms and with a variety of units. Fortunately, the metric system has been adhered to in most cases, so ordinarily the meter or the centimeter, usually the latter, has been the measure chosen. The resistivity is then the resistance of a cube of the given rock, or soil, one centimeter on, an edge. This is far from always being the same thing, however, as the resistance of a cubic centimeter. A long thin wire could contain a cubic centimeter and have a high resistance, whereas the same volume formed into a flat plate would have an entirely different, and quite low, resistance between faces. Con-sequently, it is not proper to express resistivity in ohms per cubic centi-meter, inch, etc., as has been done occasionally by .some writers. In an effort to emphasize the idea of cubic volume, some geophysicists, the writer among them, have used the phrase, ohms per centimeter cubed. This is a graphic way of picturing the measure, but is not in favor among highly qualified authorities. In this connection, an appeal was made to the U. S. Bureau of Standards for advice, and the Director, George K. Burgess, kindly replied in detail as to the practice adopted by his Bureau: ." . .' such expressions as ohms per centimeter cubed' or any similar expressions are objectionable, because they certainly carry the implica-tion that the resistivity is found by dividing ohms resistance by the volume in cubic centimeters." Actually, of course, resistivity is found

Jan 1, 1932

By Rudolph G. Wuerker

THE scarcity of values of tensile strength of rocks has been explained by the lack of successful testing procedures. In the case of mine rock a description is given' of the difficulties encountered in testing a cylindrical specimen, such as a core, by conventional methods. Over a period of years the following method has given definite and reproducible results with the weakest as well as with the strongest rocks. It does not completely supersede the use of cores with special fixtures but is a supplement in all cases where cores cannot be obtained, as from soft rocks, or in cases where it is less expensive to prepare test specimens by cutting them out of the rock instead of drilling cores. Principle and equipment are the same as for the test for tensile strength of hydraulic-cement mortar.' The test specimen, Fig. 1, has the shape of a briquet. While in the original cement mortar test the briquet is cast in a special mold, it is prepared from rocks in different ways, depending on how easily they can be cut and shaped. Soft rocks, which cannot be core-drilled with a carboloy or diamond bit, are simply hand-cut. Only two dimensions need be watched. The first is the 1-in. diam at the narrowest cross-section of the briquet. The other critical measure is the radius of curvature of the waistline, as the roller supports in the grips have a fixed distance. This radius is ground out of the solid by means of a carborundum grinding wheel having a 3/4-in. radius. Medium hard rocks can be core-drilled with a carboloy bit. The resulting core can be used for nondestructive sonic testing first, and after that for any destructive test. By using an EX-bit and by carefully placing the coreholes, preferably by using a tenplate such as shown in Fig. 1, it is possible to obtain from the rock a punched sample from which numerous tensile briquets can be made. The outside radius of the EX-bit differs from the radius of curvature of the briquet by 1/8 in., but this still permits placing and aligning the specimen in the grips. In the case of bedded rocks the core might have bedding planes normal to the plane of the briquets, and rocks can be tested in any arrangement of the bedding planes desired. Hard rocks, limestones, igneous, and metamor-whic rocks can only be diamond-drilled or diamond-cut. Here the method of getting the tension briquets by accurate placing of EX-drill holes is especially economical. The tops of the briquets made from hard rocks cannot be rounded; they are straight cuts made with a diamond cut-off saw and rounded off on a polishing wheel. Results: As long as specimens broke over the waistline the results were considered acceptable. Further statistical treatment of the tests' showed a satisfactory percentage of standard deviation. The tensile strength values obtained by this method do not represent true values because of the stress concentration caused by the curvature of the side of the piece and because of the closeness of the grips. The ratio of maximum to average stress at the plane of failure has been determined to be about 1.75." All tensile strength values listed in Table I are corrected accordingly. To avoid this stress-concentration, if there are a sufficient number of cores, tensile strength can be measured by imbedding the cores in mortar in the two outer briquets in the gangmold.4 Strain-Measurements: The applicability of the briquet specimens for strain observations was tested in the case of sandstone and shale. Two element Rosette SR-4 strain gages were used. Young's modulus and Poisson's ratio, both in tension, were computed and found to be different from those in compression, determined during the same test series and from the same rock, see Table I. References 1 L. Obert, S. L. Windes. and W. I. Duvall: Standardized Tests for Determining the Physical Properties of Mine Rock. U. S. Bur. Mines R.I. 3891 (1946). 2 Test for Tensile Strength of Hydraulic-Cement Mortar, ASTM Standard C 190-44. S F. O. Auderegg, R. Weller, and B. Fried: Tension Specimen Shape and Apparent Strength. Proc. ASTM 11939) 39, pp. 1261-1269. 4 API Code 32.

Jan 1, 1956

By Edwin M. Chance

EDWIN M. CHANCE, Wilkes-Barre, Pa. (communication to the Secretary*).-I have read with great interest Mr.. Liebermann's paper reporting dynamometer tests of mine cars and wish to express my appreciation of this investigation. The coal-mining industry needs just such precise study of the problems with which it is confronted.

Jan 10, 1916

By H. M. Chance

The Choctaw coal-field is a direct westward extension of the Arkansas coal-field, but its coals are not like Arkansas coals, except in the country immediately adjoining the Arkansas line. From the base of the coal-bearing rocks up to the top of the coalmeasures, I find a total thickness of at least 8500 feet. This great mass of coal-bearing rocks consists of an alternation of slates, shales, sandstones and coal-beds, with their accompanying under-beds of fire-clay. Only one small bed of limestone was observed. This occurs near the middle of the series; it is about eighteen inches thick, and quite arenaceous. The formation is naturally subdivided by seven or eight thick beds of sandstone, varying from 50 to 200 feet in thickness, the outcropping edges of which form a series of more or less bold " hogback " ridges, the interbedded shales and slate forming the intervening valleys. The base of the coal-series is a massive sandstone, ranging from 100 to 200 feet or more in thickness, lying immediately beneath the Grady coal-bed, which is the lowest known coal. In the district embraced between. the Missouri, Kansas and Texas railroad and the Arkansas State line, this sand-rock usually forms a bold semi-mountainous ridge. This is the ridge through which the St. Louis and San Francisco railroad passes at Bryan station, where the Grady coal-bed is opened and worked, from which point it can be traced westward without difficulty, passing about three miles north of Le Flor on the same railroad, thence west to the " Little Narrows " (which is merely a gap in the ridge), 'and beyond to a point two miles west of the Thompson-McKinney place, where it swings abruptly north for a mile or more, only to resume immediately its westward course, forming for some miles the northern boundary of the valley known as the " Boiling-Springs Prairie," beyond which it trends somewhat

Jan 1, 1890

By William D. Klopp, Joseph R. Stephens

A substantial reduction in the 300°F ductile-to-brittle transition temperature for unalloyed chromium was achieved in alloys from systems which resemble the Cr-Re system. These alloy systems include Cr-Ru, Cr-Co, and Cr-Fe. Transition temperatures ranged from -300° F for Cr-35 at. pct Re to -75°F for 0-50 at. pct Fe. The ductile alloys have high grain gvowth rates at elevated temperatures. Also, Cr-24 at. pct Ru exhibited enhanced tensile ductility at elevated temperatures, characteristic of superplas-ticity. It is concluded that phase relations play an importarlt role in the rhenium ductilizing effect. The ductile alloys have compositions near the solubility limit in systems with a high terminal solubility and which contain an intermediate o phase. The importance of enhanced high-temperature ductility to the rhenium ductilizing effect is not well understood although both may have common basic features. CHROMIUM alloys are currently being investigated for advanced air-breathing engine applications, primarily as turbine buckets and/or stator vanes. The inherent advantages of chromium as a high-temperature structural material are well-known1 and include its high melting point relative to superalloys, moderately high modulus of elasticity, low density, good thermal shock resistance, and superior oxidation resistance as compared to the other refractory metals. Additionally, it is capable of being strengthened by conventional alloying techniques. The major disadvantage of chromium is its poor ductility at ambient temperatures, a problem which it shares with the other two Group VI-A metals, molybdenum and tungsten. For chromium, the problem is further amplified by its susceptibility to nitrogen em-brittlement during high-temperature air exposure. In cases of severe nitrogen embrittlement, the ductile-to-brittle transition temperature might exceed the steady-state operating temperature of the component. The low ductility of chromium would make stator vanes and turbine buckets prone to foreign object damage. The present work was directed towards improvement of the ductility of chromium through alloying, with the anticipation that any improvements so obtained might be additive to strengthening improvements achieved through different types of alloying. The alloying additions for ductility were selected on the basis of the similarity of their phase relations with chromium to that of Cr-Re. The reduction in the ductile-to-brittle transition temperatures of the Group VI-A metals as a result of alloying with 25 to 35 pct Re is well established.a4 the temperature range -300" to 750° F. This phenomenon is commonly referred to as the &apos;<rhenium ductilizing effect"; this term is also used to describe systems in which the ductilizing element is not rhenium. Other alloy systems which have recently been shown to exhibit the rhenium ductilizing effect include Cr-Co and c-Ru.= In order to explore the generality of this effect, alloys were selected from systems having phase relations similar to that of Cr-Re, primarily a high solubility in chromium and an intermediate o phase. The following compositions were prepared: Cr-35 and -40Re; Cr-10, -15, -18, -21, -24, and -27 pct Ru; Cr-25 and -30 pct Co; Cr-30, -40, and -50 pct Fe; Cr-45, -55, and -65 pct Mn. Seven other systems were also studied which partially resemble Cr-Re. These systems have extensive chromium solid solutions or a complex intermediate phase, not necessarily o. The compositions evaluated include the following: Cr-20 pct Ti; Cr-15, -30, and -45 pct V; Cr-2.5 pct Cb; Cr-2.5 pct Ta; Cr-20 pct Ni; Cr-6, -9, -12, and -15 pct 0s; Cr-10 pct Ir. The compositions of alloys in these systems were chosen near the solubility limit for the chromium-base solid solutions, since in the Group VI-A Re systems, the saturated alloys are the most ductile. These alloys were evaluated on the basis of hardness, fabricability, and ductile-to-brittle transition temperatures. In addition to the studies of alloying effects on ductility, an exploratory investigation was conducted on mechanical properties at high temperatures in Cr-Ru alloys EXPERIMENTAL PROCEDURE High-purity chromium prepared by the iodide deposition process was employed for all studies. An analysis of this chromium is given in Table I. Alloying elements were obtained in the following forms: Commercially pure powder — iridium, osmium, rhenium, and ruthenium. Arc-melted ingot — titanium and vanadium. Electrolytic flake — iron, manganese, and nickel. Sheet rolled from electron-bearn-melted ingot — columbium and tantalum. Electron-beam-melted ingot — cobalt. Sheet rolled from arc-melted ingot — rhenium. All alloys were initially consolidated by triple arc melting into 60-g button ingots on a water-cooled hearth using a nonconsumable tungsten electrode. The melting atmosphere was Ti-gettered Ar at a pressure of 20 torr. The ingots were drop cast into rectangular slabs and fabricated by heating at 1470" to 2800° F in argon followed by rolling in air. Bend specimens measuring 0.3 by 0.9 in. were cut from the 0.035-in. sheet parallel to the rolling direction. The specimens were annealed for 1 hr in argon, furnace cooled or water quenched, and electropolished prior to testing. Three-point loading bend tests were conducted at a crosshead speed of l-in. per min over

Jan 1, 1969

By George B. Lee

DURING The Two Years In Which The New Reduction-Works Of The Copper Queen Consolidated Mining Co. Have Been In Operation At Douglas, Ariz., There Has Developed A Remarkable Condition In Regard To The Corrosive Action Of The Water Used To Cool The Jackets Of The Blast-Furnaces. Were It Not For The Many Contradictory Features, It Might Pass As One Of The Unavoidable Troubles Due To The Composition Of The Water. This Water, Obtained From Wells 600 Ft. Deep, Is Also Used In The Steam-Boilers, And Its Composition, As Shown By The Following Analysis, Does Not Indicate The Presence Of Any Ingredient Which Would Explain The Corrosion Grains Per U. S. Gal. Silica, 0.861 Iron Oxide And Alumina, 0.223 Calcium Carbonate, 0.2111 Calcium Sulphate, Magnesium Carbonate, Sodium And Potassium Sulphates, . 14.850 Sodium And Potassium Chlorides, 9.732 Sodium And Potassium Carbonate, 6.452 32.409 The Jackets Are Made Of Inner Plates 0.5 In. Thick And An Outer Plate I In. Thick, With 3-In. Stiffeners Between The Inner And Outer Plates. In From 10 To 12 Months The Inner Plates Have Been Reduced By Corrosion To A Thickness Of From 1/8 To 1/16 In., While The Outer Plate In The Same Time Is Reduced By Less Than 1/16 In., And The Stiffeners Show Very Little Corrosion. The Plates Are Pitted And Eaten Away In Some Places More Than In Others. There Is Practically No Scale Found On The Jackets, But When Cleaned Considerable Iron Oxide Is Found In The Bottoms. With An Action So Marked, Serious Trouble Would Be Expected In The Boilers, But, On The Contrary, A Recent Inspection By a

Mar 1, 1908

By W. P. Blake

The mining district and the town of Tombstone are situated in Cochise County, Arizona Territory, at the northwest end of the Mule Pass range of mountains, in longitude 110°, and latitude about 31 40&apos; N,, upon the right bank of the San Pedro River, from which the town is distant 9 miles east.. It is also 24 miles south of Benson station on the Southern Pacific Railroad of Arizona, and about 40 miles north of the Mexican line. Its altitude above the sen is 4600 feet. The Dragoon Mountains rise across a valley to the northeast, and the Huachuca Range similarly upon the southwest. The country is open, without timber, and the surface, where the mines are opened, is in general gently rolling, and accessible to wagons by. natural roads. The first locations were made in the pear 1878 by the Scheffelin brothers and Richard Gird, the latter being well known among the pioneers of Arizona as a surveyor and miner, who contributed largely to our knowledge of the geography of the Territory in early days,

Jan 1, 1882

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.&apos; Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts&apos; Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg&apos;s method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By William M. Huang, T. Carl Shelton

There are undoubtedly many factors that affect the emission of gas from coal but the permeability of coal to gas flow would seem to be fundamental. However, there is very little information on coal permeability to gas flow available in the U.S. at the present time, despite the fact that such knowledge would appear to be significant in any degasification effort. Studies made recently in the mining engineering laboratories at Virginia Polytechnic Institute have determined values of permeability on one-inch cubes of selected coals. COAL PERMEABILITY The permeability values given in this paper are based on adaptations of Darcy&apos;s Law formulated by Henry Darcy in 1856 from experiments with fluid flow in porous media.&apos; Using air as the gaseous fiuid, they were obtained by employing similar methods as are used to determine the permeability of petroleum and gas reservoir rock specimens.

Jan 5, 1962

By W. A. Tiller, J. P. McHugh

HE majority of liquidus and solidus surfaces in phase diagrams have been determined by the conventional cooling- and heating-curve techniques.&apos; These techniques have two main shortcomings: 1) the solidus may be in considerable error due to the difficulty involved in completely homogenizing the solid and 2) the determination of liquidus and solidus in more than a two-component system does not enable one to determine tie-lines connecting the specific equilibrium solid and liquid compositions. However, in a recent paper by one of the authors,&apos; a method was suggested whereby the liquidus and solidus surfaces plus tie-lines in an n-component system may be determined. This method utilizes a controlled solidification technique and assumes that interface equilibrium exists during freezing. The present work was undertaken with a twofold purpose; first, to determine the liquidus and solidus lines in the pseudo-binary system Bi2Te3-Bi2Se3 by heating- and cooling-curve techniques and, second, to determine the partition coefficients of Te and Se in the BizTe3-,Sex system by controlled solidifica- tion techniques. The two sets of results can be compared to test the accuracy of the controlled solidification method. EXPERIMENTAL I—The starting materials for this study were 997999 pct Bi, Te, and Se, obtained from the American Smelting and Refining Co. The compounds BizTe, and Bi2Se3 were each prepared by melting together stoichiometric amounts of the elements, followed by twelve zone-refining passes. This produced homogeneous bars of the compounds for use in the phase-diagram studies. The apparatus used to obtain heating and cooling curves is illustrated schematically in Fig. 1. The alloy samples were located in a graphite crucible placed in a stainless steel canister. The canister was supported in a heavily lagged pit furnace by a device which oscillated the canister about its vertical axis at a frequency of about 3 cycles per sec during heating and cooling-curve runs. The graphite crucible was designed to minimize the thermal coupling of the sample to the furnace. A thin graphite sleeve separated the alloy sample from the stainless steel tube that housed the thermo-

Jan 1, 1960

By M. R. Tek, L. K. Thomas, D. L. Katz

Threshold displacement pressures are needed to determine how much overpressure can be used in storing natural gas. An experimental technique for determining threshold pressures by displacing water with gas from samples saturated with water is presented. Threshold pressures for eight low permeability samples were measured. Threshold pressure data obtained in this work, plus data on higher permeability samples reported in the literature, are correlated with porosity, permeability, surface tension and formation resistivity factor. Mercury injection pressures also were measured and correlated with air-water threshold pressures. Threshold pressures were found to be independent of time. An aerial photograph of gas emerging from the top of a core shortly alter its threshold pressure has been exceeded shows that the gas bubbles are uniformly distributed across the face of the core. Channeling will occur, however, when an increased gas phase permeability is reached, A porous medium can be re resealed alter its threshold pressure has been reached, provided it has not been desaturated below a fixed saturation. Its new threshold pressure will be lower than when the sample is 100 percent saturated with water. INTRODUCTION The degree of overpressure in excess of the discovery pressure that a gas storage reservoir can withstand is determined by the ability of its caprock to contain gas, providing the pressure does not exceed the structural limit of the reservoir. The retention of gas in a reservoir by a caprock saturated with water is a result of the capillary forces acting at the gas water interface. Without the presence of water in a caprock, gas would leak out of the reservoir at a rate determined by the permeability of the caprock to gas. The ability of a caprock to contain gas is expressed in terms of its threshold displacement pressure, which is defined as the minimum pressure needed to initiate the displacement of a wetting phase by a nonwetting phase from a porous medium 100 percent saturated with the wetting phase. The gas industry must be able to predict how much "overpressure" a gas reservoir can withstand before leakage occurs by gas displacing water from caprock overlying the reservoir. This is of economic importance since the storage capacity of a gas reservoir is proportional to its pressure. The discovery pressure for most reservoirs is found between the upper and lower limits1 shown in Fig. 1. Discovery pressures in excess of their hydraulic pressure gradient are attributed to the compaction of an isolated shale formation by the overburden.2.3 The lower limit of 0.433 psi/ft corresponds to the weight of the overburden, the gradient of the rock itself. Somewhere between

Jan 1, 1969

By H. M. Chance

Jan 1, 1887

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By John C. Sawyer

The mechanism of catastrophic oxidation of chromium and 446 stainless steel is examined. Data are presented to show that accelerated oxidation of these two materials, as caused by lead oxide, can occur in the absence of a liquid layer contrary to presently accepted theory. An alternate theory is proposed in which the rate of accelerated oxidation is a function of the rate at which lead oxide destroys the protective oxide formed on the base metal. An example of the application of the theory is given for the catastrophic oxidation of chromium in the presence of lead oxide. WHEN stainless iron-, nickel-, or cobalt-base alloys are heated in air to moderate temperatures in the presence of certain metallic oxides, oxidation will proceed at an accelerated rate. This phenomenon, often called "catastrophic oxidation", is most pronounced for the stainless steels. With these alloys the condition is so severe that large masses of oxide will form on the surface of the alloy in 1 hr or less at temperatures of 1200o to 1700oF. While a number of oxides are known to cause this effect, PbO, V2O5, and Moo3 are the most familiar, having been the subject of one or more investigations which have appeared in the literature.1-7 In presenting the results of these investigations, many of the authors have offered possible explanations to account for the more rapid rate of oxidation observed; however, the liquid layer theory as proposed by Rathenau and Meijering 2 has been the most commonly accepted mechanism. The liquid layer theory proposes that a low-melting oxide layer is formed on the surface of the alloy as the result of the interaction of the alloy oxide and the contaminating oxide. When the temperature of oxidation is above the melting point of the oxide on the surface, a liquid layer will form and oxidation will proceed at an accelerated rate. At temperatures below the melting point of the surface oxide, oxidation will proceed more slowly in the normal manner. It is argued that the rates of diffusion of oxygen and metal ions through the liquid layer are extremely rapid thereby accounting for the high rate of oxidation. Various experimental data have been presented to show that the temperature at which accelerated oxidation first becomes apparent coincides with the melting point of the eutectic oxide which would be present on the surface. Some exceptions have been observed, e.g., silver will oxidize in the presence of Moo3 at temperatures below the lowest melting eutectic; on the other hand, stainless steel will not be catastrophically oxidized at 1500oF in a molten bath of PbO and SiO2. In reviewing the various theories which have been used to explain catastrophic oxidation, Kubaschewski and Hopkins 8 favor the liquid layer theory, but note that, ".. .as experimental observations are not altogether in agreement with this theory (liquid layer theory), one should consider it a necessary but not a sufficient condition." In contemplating the liquid layer theory, it appears that sufficient evidence has not been presented to establish the theory beyond question. As a means of further clarification, a program of research was undertaken to determine in greater detail the mechanism of accelerated oxidation as caused by lead oxide. The first part of the program deals with a comparison of the oxidation of both AISI 446 stainless steel and chromium metal in the presence of lead oxide, vs the oxidation of these two materials in air alone. These comparisons are made at a number of different temperatures, most of which are below the melting point of the surface oxides. The second part of the program is concerned with a presentation of an alternate theory of accelerated oxidation exemplified by the system Cr-PbO-Air. PROCEDURE AND RESULTS Several experimental methods are commonly used to follow the progress of oxidation. One of these, the weight-gain method, was chosen for this work. This procedure requires that a specimen of the alloy be weighed, oxidized for a given period of time at an elevated temperature, and reweighed—the difference between the two weights being noted. The weight gain of the specimen represents the amount of oxygen acquired from the atmosphere to transform a portion of the specimen to oxide. In those cases where there is a tendency for the specimen or oxide to volatilize at the testing temperature, additional data must be collected so that a correction factor can be determined. This factor must be applied to the weight change in order to ascertain the actual amount of oxidation which has taken place. The specimens used for this work were 1 1/2 in.

Jan 1, 1963

By C. C. Templeton, S. S. Rushing

Methods previously developed for the study of air-liquid displacements in microscopic capillaries (inner diameters of 3 to 40 microns) have been used to investigate oil-water displacements in capillaries initially filled with water. Displacement calculations assuming perfect displacement and no capillary pressure hysteresis yielded oil effective viscosities smaller than the macroscopic viscosities. For a given liquid pair, the oil effective viscosity decreased both with decreasing capillary size and with increasing oil-water viscosity ratio. This behavior can be explained by the existence of an annular water film (20 A to 260 A thick) on the capillary wall. When the capillary was first filled with oil, the ratio of the oil effective viscosity to the normal oil vircosity was highest for the first water displacement and decreased with subsequent displacements. Sometimes the oil effective viscosity ratio during the initial water displacement was greater than unity. INTRODUCTION In a previous paper1 a technique was described for studying air-liquid and liquid-liquid displacements in very small capillaries of uniform diameter, in the hope that such microscopic data would further the understanding of the nature of multiphase fluid flow through porous media. That paper contained comprehensive data for air-liquid displacements in Pyrex capillaries, with a few data for oil-water displacements in capillaries initially filled with water. The purpose of this paper is to present more complete results for oil-water displacements in capillaries initially filled with water, and to describe for the first time such observations in capillaries initially filled with oil. In this way the effect of the wetting history of the system upon the displacement process may be studied. METHODS The basic techniques employed were described in the previous paper.1 The measuring procedure and the working equations will be briefly summarized here and a few modilications will be pointed out. For the present study, temperature control within 0.l °C was obtained by placing the microscope and its immediate accessories in a thermostated air bath made of a steel frame covered with plexiglas. The water and oils used in this work were the same as in the previous paper,1 with the addition of "Medium Mineral Oil, U.S.P. supplied by the Harshaw Scientific Co. When the first liquid was introduced into the horizontal capillary, the air-liquid static capillary pressure Poc was measured along the observable length of the capillary. From the relation Poc = 4y cos 0/d, the capillary diameter d could be calculated from Poc if the "microscopic" air-liquid boundary tension, To = y cos On, was taken as equal to its known "macroscopic" value. This calculation involves assuming that cos 6 = 1 and that capillary size or the resulting high interfa-cial curvature has no effect on surface tension, or y cos 6, as was verified by our work, and also by that of Cohan and Meyers on air-liquid-solid systems. For several capillaries these calculated diameter values were compared with values measured visually with a filar micrometer eyepiece. For a given capillary the average values for the two methods agreed within 1 or 2 per cent, but the visual values were less reproducible than the calculated values. Further the calculated values were much less subject to personal bias and took into account any slight ellipticity that might be present. Hence diameters calculated from air-liquid Poc data were used throughout this paper. The second liquid was introduced in such a way that a single spherical interface separated the two liquids. Displacements were always made with a constant pressure, Pt, between the ends of the capillary. The times (t) at which the interface passed certain

Jan 1, 1957

By E. Heaton Hemingway

DURING the past year, the Watertown Arsenal has been interested in the occluded gas and oxide content of certain ordnance steels in order to determine, if possible, whether some of the peculiar failures in their physical properties might not be traced to these causes. For the purpose of best accomplishing a study of this nature, it was decided to heat the various samples of steel in a vacuum for definite periods of time at high temperatures and carefully examine the quantity and composition of the gases evolved. By the use of a fused quartz tube fitted with a water-cooled, ground-glass stopper, it was possible to maintain a vacuum at a temperature of 1000° C. for 10 hr. without perceptible leakage being evidenced as measured by a McLeod gage. The silica tube was connected with an evacuating system so constructed that the volatilized gases could be removed from time to time and a low vacuum of 0.002 to 0.0010 mm. of mercury continuously maintained. At no time during the period of heating or in the removal of the gases did the evacuated system come in contact with rubber stoppers or any rubber connections, making contamination from such a source impossible. In other words, the only volatile products that could be obtained must necessarily have come from the steel itself or from the glass and fused quartz system or from the mercury used as a sealing agent. In the earlier experiments, the steel treated was in the form of turnings, but this practice was discarded because the weights of the turnings before and after being heated were widely inconsistent, even when taken from the same piece of steel. This discrepancy developed largely through variation in the amount of metal volatilized with the gases; this metal could always be seen in the form of a ring where it condensed in the cooler portion of the tube either in the amorphous or crystalline condition. Because of the frequency in occurrence and the variation in the manner of deposition, this material was roughly analyzed and found to consist for the most part of iron. At the same time two samples of steel that had been

Jan 8, 1920

By Orlando E. Romig

As metals and alloys are composed of an aggregate of allotriomorphic crystals or grains, each possessing an individual orientation, the physical characteristics of a metal or an alloy are closely related to the properties of the individual crystals. The preparation and study of single metallic crystals are, therefore, matters of considerable importance. The advent of the X-ray spectrograph as a valuable metallurgical tool has magnified the importance of this subject, because the interpretation of some X-ray spectrographs is difficult unless single crystals are used in these studies. Previous Work The first paper, as far as the writer knows, on the behavior or preparation of single crystals of metals is by Baker.&apos; He describes the behavior of extruded wires of sodium and potassium. These wires, when pulled in tension, instead of showing the usual conical fracture common to most metals, had a chisel-shaped fracture when they were broken. I and 11, Fig. 1, have a similar fracture. Baker checked his results by preparing single crystal wires from molten sodium and potassium and observing their properties. He pre- pared the wires by filling glass tubes, under oil, with the molten metal. The surfaces of the strained wires showed slip bands of remarkable clearness of which photographs are shown in his paper. He concluded that these wires were single crystals and "that the portions of the metal brought into play are cubes. Such cubes, when placed so that a plane through two opposite edges was parallel to the axis of the wire, would allow of lateral contraction by faces gliding over one another in one direction only and not in the direction at right angles."

Jan 1, 1927

By Lucien Eaton

VENTILATION in the iron mines of the Lake Superior region in nearly all cases is natural; that is, it is induced by the difference in elevation between different outlets in the mine and by the difference in temperature of the air in the mine and that outside. This difference in temperature is frequently augmented by placing a steampipe in the upcast shaft; but aside from this, artificial aids to ventilation have been rare until - recent years. In some of the older mines, as at the Cliffs Shaft mine at Ishpeming, Mich., in the 80&apos;s, fans have been used when there was only one opening to surface, but their use was abandoned as soon as a natural circulation of air started. In recent years, the Newport mine at Ironwood, Mich., was the first to use positive mechanical ventilation. The installation was not large enough, however, to give definite results, reliance being placed largely on natural ventilation. With the coming of warm weather in the spring of 1914, the necessity of positive mechanical ventilation at the Lake mine of the Cleveland-Cliffs Iron Co. at Ishpeming, Mich., became evident. The workings of the Lake mine are under the bed of old Lake Angeline, which was pumped out in 1894, and the mine had been in operation for 6 years prior to that date making a total of 26 years of continuous operation. The total production, up to 1914, amounted to over 8,000,000 tons. The ore was first mined by square-set rooms and pillars, but this was later changed to top slicing and caving. Both methods required the use of large amounts of timber, probably 80,000,000 board feet in all, practically all of which remained in the timber mat. The slow oxidation of this timber was one of the principal causes leading to the installation of mechanical ventilation. The mine was served by only one working shaft, called No. 4, a second outlet being provided by a raise to the surface from the old workings on the south side of the mine. This raise was the "down cast;" but it was very small and the drifts and raises leading to it were too small and crooked to permit an adequate amount of air to enter the mine, especially during the warmer weather. Measure-

Jan 8, 1920