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By J. E. Warren

In their analysis of Eqs. 29 and 30, the authors correctly deduce the following behavior limits for the "differential capacitance model". 1. When the rate group a is sufficiently large, the model reduces to that implied by Eq. 1, i.e., the simple convection-diffusion model. 2. When the rate group a is sufficiently small, the model reduces to that implied by Eq. 1 with 1 replaced by 1, i.e., the simple convection-diffusion model with a total pore volume equal to that occupied by the mobile fluid in the original model. Unfortunately, the authors' solution, Eq. C-1, to the transformed versions of Eqs. 29 and 30 does not exhibit the same limiting behavior. For example, as a approaches zero, Eq. C-1 reduces to the solution to Eq. 1 or, equivalently, the solution to Eqs. 29 and 30 for sufficiently large values of a. Therefore, it can be concluded that Eq. C-1 is not a general solution to Eqs. 29 and 30; this conclusion can be easily verified by substitution. I suggest that the correct form of Eq. C-1 is the following: It is generally realized that accounting for dispersion effects is an extremely tricky business; therefore no one should criticize the pragmatic approach of Coats and Smith who proceeded by accessible theory, made use of some available phenomenology, and who then took the trouble to check the consequences, against their own carefully undertaken experimental results. Here I should like to defend three assertions: (1) Coats and Smith copy the error of previous authors in the formulation of the so-called simple diffusion model (which error is then retained in their differential capacitance model); (2) improving the fit between data and the predictions of an arbitrary model by increasing the number of parameters is a triviality unless the parameters are disposable by being independently determined; and (3) existing experimental procedures lack sufficient resolution to clarify some current theoretical uncertainties. Taking first the view that all theoretical approaches (whether constructed by statistical, finite difference, or continuum arguments) tend to reduce to the same model form as fixed by the number and nature of the disposable parameters, one notices that the "finite-stage" model of Deans1 is equivalent to the Coats and Smith so-called differential capacitance model for the pertinent case where a

Jan 1, 1965

By G. F. Tagg

In an earlier paper1, the author described a method of interpreting earth-resistivity curves, based on the theoretical investigation of a single horizontal underlying stratum. If the four-electrode system of Wenner is employed, the resistivity in a homogeneous soil is given by the formula where a is the electrode separation and R is the resistance of the earth between the two inner electrodes. If the earth is not perfectly homogeneous, the application of this formula gives an apparent specific resistance varying with the electrode separation. In the special case of the single horizontal underlying stratum, there is a surface layer of thickness h and resistivity p1 and a lower layer, extending to infinity, of resistivity pz. It has been shown by Lancaster-Jones2 that the apparent resistivity obtained by an application of equation 1 is related to the true resistivities, the depth h and the electrode separation a by an expression of the formhere pa is the apparent resistivity and F is a function (actually an infinite series), of the ratio h/a, and a reflection coefficient k = (p2 — p1)/(p2 + p1). For given values of h/a and k, the right-hand side of equation 2 can be calculated, and curves drawn showing the relationship between pa/p1, h/a and k. Such a set of curves for the case when p1 > p2 is given in Fig. 1. When pl is less than pz it is more convenient to use conductivity instead of resistivity. Hence, if oa = the apparent conductivity = lip, and a1 = the conductivity of the upper layer = l/pl, it follows that GeophyGical prospecting by earth-resistivity methods is frequently applied to investigation of structural problems in geology. Fig. 1 indicates a scheme of the general arrangement used in these methods of measurements. The battery (or generator) E is connected with two "current electrodes" I1 and I2. The current of intensity J, supplied by this battery, passes through the earth between these elcc- trodes. A potential difference U will be measured between two other electrodes V1 and Vz, called "potential electrodes." According to the configuration of electrodes (Fig. I), the resistivity of a homogeneous soil results from the formula

Jan 1, 1940

By Walter S. Weeks

THE process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. Case 1 If compressed air is allowed to expand to the atmospheric pressure through an orifice in an sir line that is supplied by a running compressor, no cooling results except the negligible one due to the Joule-Thompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected. Symbols P1 Absolute pressure in pipe line, lb. per sq. ft. P3 Atmospheric pressure, lb. per sq. ft. V1 Volume occupied by 1 lb. air in pipe. V3 Volume occupied by 1 lb. air at P3. Cv Specific heat of air at constant volume, B.t.u. per lb. per deg. F. Cp Specific heat at constant pressure, B.t.u. per lb. per deg. F. T1 Absolute temperature of air in pipe, deg. F. T3 Absolute temperature of air outside after expansion and mixing and coming to rest. J Mechanical equivalent of heat (778 ft. lb.) R Gas constant for air, ft-lb. per deg. F. = 53.3. Formulas Consider 1 lb. of air moving out of a pipe. The air behind it does work on it to the extent of P1V1 ft-lb. This work is really done by the thrust of the piston of the compressor and does not come from any energy that exists in the air in the pipe. The pound of air contains

Jan 1, 1937

By LOWELL LAWRENCE

MAGNETITE minim and milling in the Eastern States continued at a low rate of production during 1934. The year's output was 50 per cent greater than in 1933, but when one considers that the 1934 output was only 1.5 per cent of the combined plant capacities of the eastern iron ore producers, the far-reaching effect of unrestricted importation of foreign ores and pig iron is apparent. The Chateaugay Ore and Iron Co., at Lyon Mountain, N. Y., produced 1.00,136 gross tons of concentrated and sintered ore up to Nov.1, when operations were closed clown. At Mineville, the Witherbee, Sherman Corp. confined its productivity to part-time operation of its Old Bed and Harmony mines front May 1 Lo Oct. 27. This period of activity was brought about by the use of Mineville ores in the recent blast made by the Green Island furnace at Troy, N. Y. The Forest of Dean property at Fort Montgomery, N, Y., has continued closed down during the year.

Jan 1, 1935

By AIME AIME

I would like to ask Bob Merrill whether he considers that horizontal concave curvature of a slope has any stabilizing effect, such as Jenike 1 suggested several years ago. The stabilizing effect is due to the restraint offered to radial movement by the curvature. We found in laboratory tests that if we constrained the rock with the same stresses as those measured in the pit then it would sustain a maximum stress about two or four times greater than when the same rock type was unconstrained. We are therefore definitely of the opinion that a constrained situation in a slope is favorable towards stability.

Jan 1, 1967

Geological Survey of Ohio, Columbus, Ohio. Wilbur Stout, State Geologist. A complete list of publications will be sent upon request The present Geological Survey of Ohio is the fourth organization of this kind in the state The first Survey issued two reports, dated 1838 (not now available), the second, from 1869 to 1888, issued two reports, 75 cents and $1, respectively, and five volumes on geology, $1.25 to $3 50. The third organization, 1890 to 1900, issued a report for 1890, $1, and vol. 7 (1893), $150 Since 1900 the present organization has issued a number of Bulletins, most of which deal with the geology of some part of the state, as follows: Bulletin 10, The Middle Devonian (1909), 25 cents, 14, Columbus Quadrangle (1911), 30 cents; 15, Devonian and Mississippian of northwestern Ohio (1912), $1; 17, Conemaugh Formation (1912), 60 cents, 22, The Dunkard Series (1920), 60 cents; 23, Camp Sherman Quadrangle (1921), 50 cents; 24, Wayne County (1921), 50 cents, 28, Columbiana County (1924), $1, 30, Delaware County (1926), 75 cents, 31, Vinton County (1927), $1; 35, Jefferson County (1930), $1. Other bulletins on Ohio geology and resources of most interest are.

Jan 1, 1933

By J. S. Hromatko, L. J. Gurevich

In the course of the examination, at the BureLu of Standards, of fusible tin boiler plugs for the Steamboat Inspection Service, it became evident that an investigation should be undcrtaken to determine the precautions necessary in the manufacture of acceptable plugs. The results of the tests of these plugs show that their manufacture has improved, though at present not all of the plugs tested are, satisfactory. Table 1 gives the result of tests of some 1500 plugs from about 100 makers. Records of the tests show that several of the makers were able to produce satisfactory plugs with every pouring. The Steamboat Inspection Service has the following specifications for fusible plugs: "Fusible plugs for use in boilers of steam vessels under the jurisdiction of the Steamboat Inspection Service shall be made of bronze casing with the bore tapering continuously and openly from end to end, and filled from end to end with tin not less than 99.7 per cent. pure and to contain not more than 0.1 per cent. of lead and not more than 0.1 per cent. of zinc. The small end of the bore may be countersunk not more than 1/32 in. in depth and width, but no recess, thread, or cavity other than this countersink shall be allowed." Table 1.—Thirty-"five-mdh Testing Record of Fusible Plugs Causes of Rejection Inspection Period June-November, 1916.................. 311 32.8 47.2 3.8 11.5 15. 1 10.9 1 1.9 4.5 December, 1916-May, 1917............. 318 71.4 28.6 2.2 4.4 12.8 5.9 i ... 2.8 June-November, 1917.................. 228 73.0 27.01 ... 9.6, 5.2 9.6' ... 0.8 December, 1917-May. 1918............. 214 72.028.0 0.9 0.4 11.6 7.0 ... 7.9 June-November, 1918...............250 70.7 29.3 ... 2.0 20.0 5.2 ....2.8 December, 1918-April. 1919............ 23378.121.9 7.2 1.2 1 4.7 3.0 ... 6.0 Total 35 months....................1544.69.7 30.3 2.3 4.8 11 0 6.9 0.3 4.1

Jan 1, 1921

BARBOUR, PERCY E., Deputy Supt., (Captain), New York State Troopers; Captain, 22nd Regiment, N. Y. N. G. BARLING, 1i. B., 1st Lieutenant, Engineer Officers' Reserve Corps. CHAPMAN, R. H., Major, Engineer Officers' Reserve Corps. DUNN, THEODORE S., 1st Lieutenant, Engineer Officers' Reserve Corps. DWIGHT; ARTHUR S., Major, Engineer Officers' Reserve Corps. FORBES, CARROLL R., Captain, Engineer Officers' Reserve Corps. GOODSPEED,. G. E., JR., 1st Lieutenant, Engineer Officers' Reserve Corps.

Jan 7, 1917

By W. Denham Verschoyle

IN designing a pocket instrument whereby any given horizontal or vertical angle may be closely approximated, the following points should be kept in view, if general utility is aimed at 1. The instrument should be light and compact, so that it can be carried in the pocket, or in a sling. 2. It should be capable of observing any angle whatever, horizontal or vertical. 3. Since time is often an important consideration in making a preliminary survey, it should be capable of giving the horizontal and vertical angle at one observation. I do not know of any instrument that will fulfill these requirements, except the one here described. Where the depression- or elevation-angle of the distant object, whose bearing is required, exceeds 50 or 60 degrees, it becomes difficult or impossible with a prismatic compass, for instance, to obtain accurate results; and since it frequently happens, particularly in mining, that much work requires to be done beyond that limit, it is obvious that an instrument which can be used to observe a high angle just as easily as a low one, if not absolutely a necessity, will at least be a great convenience. How this " pocket transit " attains to the required degree of universality will be understood from the diagram, Fig. 1, in which B is a beveled, graduated circle, attached to and freely revolving about the center of the magnet A. Light falling on B is reflected through a window in F (the compass-box), along the line AC, and is again reflected back to the eye at D by the prism C. By a simple arrangement, the sight-line DCE can be completely revolved in the vertical plane DE, which is normal to AC. It is clear, then, that no matter through what vertical

Jul 1, 1907

By W. J. Garmoe

Distinct areas of mineralized and non-mineralized brecciated rock are found in the Ontario Unit of the United Park City Mines. These breccias contain an appreciable fraction of the present ore reserves and probably will become even more important as deeper levels are developed. Three ages of breccia have been recognized in the Ontario Mine to date: ( 1) Pre-mineral breccia that may or may not be mineralized, (2) early post-mineral breccia with mineralized fragments, and ( 3) late post-mineral breccia that is younger than and cuts through ( 1) and (2) above. These age ,relations are known from detailed underground mapping. Locally, both pre-mineral and post-mineral breccias have sufficient lead-zinc-silver content, either as matrix or fragmental material, to constitute ore. Ore-grade breccias occur throughout a vertical range of over 1000 feet and are found in both the Humbug and Deseret formations from above the Ontario 1300 level to below the Ontario 2200 level. The mineralized breccias, which are difficult to distinguish on mine maps, are not well delineated by underground workings, and their horizontal outline and vertical extent are not known beyond the immediate mining areas. The greatest amount of truly mineralized breccia is exposed on the 2200 level.

Jan 1, 1968

By C. D. Hall, F. E. Dollarhide

Fluid Ioss agent.s for crude oil and for water have been studied in dynamic tests. A treatment using a spearhead with a fluid loss agent followed by plain fluid appears feas ible in crude oil, but not in water. An equation for spearhead depletion shows that spurt loss relative to fracture width must be low, if the portion of spearhead fluid in the treatment is to be small. The presence of colloidal matter in crude oils aids the fluid Ioss agent. Unlike in kerosene, where flow limited the agent deposition, in crude oils the filter cake continually formed and leak-off declined. The volume-time relation varied somewhat for different crudes, but was best described by a square root of time function. Spurt loss was inversely proportional to agent concentration. After the fluid loss agent initiated the filter cake, the crude oil colloids built on it effectively. A 2-minute or a 5-minute spearhead with double the normal agent concentration gave the same fluid Ioss curve as the same concentration did for a 30-minute test. The agents tested in water gave fluid Ioss plots on which, for the first few minutes, volume was proportional to the square root of time, but later became proportional to time. For fracture area calculation the customary square root of time function is a satisfactory approximation. Leak-off rates and spurt losses were higher in water systems than in oils. The spurt Ioss tended to be inversely proportional to concentration. In spearhead tests, the filter cakes were not eroded by water flow. However, the rather high spurt loss values make spearhead treatments impractical for water-based fluids. Introduction The effects of dynamic testing conditions on the performance of fluid loss agents in kerosene have been studied previously.' We have extended the work to include crude-oil- and water-based fracturing fluids. An understanding has been gained of the mechanisms of formation and functioning of the filter cakes of fluid loss agents. The practical aspects of evaluating performance of agents in relation to fracture area calculations also are considered. The feasibility of using the fluid loss agent in a spearhead stage of the treatment is examined further for both types of fluids. Experimental Procedure The dynamic fluid loss tests were performed in an apparatus similar to the high-pressure apparatus described in a previous publication.' A fracturing fluid was circulated over a rock surface located in a closed pressurized loop. The fluid flowed axially over the cylindrical surface of a core 2 in. in diameter X 3.5 in. long, mounted (with the flat ends sealed off) in a pipe, with 0.117 in. annular clearance. The filtrate was collected in a central hole in the core and led through valves to graduated cylinders. Provision was made for changing quickly the circulating fluid during the test (spearhead runs) without interrupting the filtration pressure. The only modifications were to add heating tapes and water jackets for the tests with crude oils, all conducted at ISOF, and to change all parts exposed to the test fluid to stainless steel for the tests with water-based fluids. The latter tests were made at room temperature, 80F. Three crude oils were tested. A mixed crude, obtained from a local refinery, contained a considerable amount of light ends. For safety reasons, it was stripped to 250F vapor temperature before use in the fluid loss tests. The other two oils were used as obtained from lease tanks. One was a greenish-brown, 37" API paraffinic crude, and the other was a black, 32" API asphaltic crude. The fluid loss agent for oil, here designated for brevity as Agent A, was Adomite@ Mark II*, a granular solid commercial agent, the same as previously tested in kerosene.' Three different compositions of fluid loss agents were tested in Tulsa tap water. Agent B was adomit& Aqua*, a solid commercial fluid loss agent, comprising clays and hydrophilic gums principally derived from starch. Agent C was a mixture of three parts of Agent B with two parts of silica flour. Agent D was Dowel1 J137, a mixture of guar gum and silica flour. The test cores were cut from contiguous blocks of Berea or Bandera sandstones. For the oil tests, the cores were oven dried, evacuated, saturated with kerosene, and the kerosene permeability was measured. The cores used with the water-based fluids were pretreated by saturating with 3 percent calcium &loride solution to minimize pemeability damage by the fresh water due to clay migration. The

Jan 1, 1969

By D. M. Waldorf

Steam permeability measurements have been made in the laboratory on several samples of natural reservoir materials. The steam temperatures and pressures were selected to simulate conditions which might exist in a reservoir during the injection of steam. For each sample tested, the experimental permeability to superheated steam was comparable to that measured with air and no evidence of plugging was detected. Some samples were exposed to water at various temperatures and plugging was found to occur in materials which contained significant quantities of monmorillonite clay. Temperature had little effect on the degree of plug-ning between 75 and 325 F. The measured pemeabilities tended to increase slightly with temperature, but the changes were small compared with the initial loss of per~neability on wetting. Sequential pemzeability measurements were made on two samples using air, water, steam, water and air, in that order. Both samples were water-sensitive and plugged extensively after the initial injection of water. Upon exposure to superheated steatm the samples dehydrated and their permenbilities to superheated steam were comparable to those initially measured with air. The remaining measuretnetzts with water and air confirmed that the water plugging was reversible and that the samples were not seriorrsly damaged during the tests. INTRODUCTION The swelling of water-sensitive clays during water floods has long been recognized as a potential source of reservoir damage. The recent extensive application of steam injection and stimulation has compounded this problem since both hot water and steam (as well as fresh water at reservoir temperatures) are, at sume time, in contact with the producing zone adjacent to the bore of a steam injection well. The purpose of this paper is to present data which compare the sensitivity of some natural sedimentary rock samples to water at various temperatures, and to super-heated steam. Some properties of montmorillonite clay are briefly reviewed, and comparisons are drawn between empirical data and the predicted behavior of the montmorillonite known to be present in the samples. PROPERTIES OF MONTMORILLONIT E CLAY Water initially adsorbs on dry N a -montmorillonite clay in discrete layers in the interlaminar space between clal platelets. The platelet spacing, which is 9.6 A (angstroms) for a dehydrated clay, has been observed to expand in discrete steps to 12.4, 15.5, 18.4 and 21.4 A spacings, indicating the formation of four discrete layers of regularly oriented water molecules.' The first two layers are easily formed by hydrating a dry sample to equilibrium in an atmosphere with carefully controlled humidity. The formation of the higher layers is more difficult. The usual X-ray diffraction patterns of the more highly hydrated samples indicate a gradual increase in the average spacing betwcen 15.5 and 19.2 A, followed by a discontinuous expansion to 31 A when the weight ratio of water to dry clay is between 0.5 and 1.2.' Platelet expansion above 31 A proceeds monotonically as the moisture is increased and no regular arrangement of the platelets ib observed. Water-sensitivity in sedimentary rocks is usually associated with Na-montmorillonite clay when it is in the noncrystal-line state. Mering3 found that the average lattice spacing of sodium montmorillonite hydrated at 68 F and 70 per cent relative humidity was 15.5 A, and that the spacing, at 92 per cent humidity was 16.5 A. The water adsorbed at the higher humidity has the same free energy as liquid water at 65.6 F. Kolaian and Low' used a tensiometer to measure the thermodynamic properties of water in diffuse suspensions of montmorillonite clays relative to pure water. They observed that water in suspensions as dilute as 6 per cent clay became partially oriented when left undisturbed. The bonding associated with this orientation was not extensive because the free energy difference between the water in suspension and pure water was only a few millicalories per mole. They also found that the measured free energy difference decreased rapidly with temperature and became negligible above 100 F. This evidence indicates that montmorillonites contained in sedimentary rocks would dehydrate to a crystalline structure when exposed to superheated steam, and that the rock permeability measured with steam would be equivalent to that measured with air. The effect of elevated temperatures on the swelline of montmorillonite clays in aqueous suspensions has not been investigated. The Gouy-Chapman diffuse-ion-layer theory has been used to predict the swelling pressure of clay suspensions in dilute salt solutions at room temperature with reasonable success. theory also correctly predicts the direction of the thermal response of Na-mont-morillonite swelling pressures in dilute salt suspensions, 9 Over the temperature range of 33 to 68 F, an increase in

Jan 1, 1966

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram' shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By J. H. Swisher

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

Jan 1, 1968

By W. F. Chiao, R. B. Gordon

Tile sharp-yield point found in magnesium crystals in the solulion-treated and aged condition is studied by dislocation internal-friction experiments. The results show that the sharp yield is not file to the sudden release of pinned dislocations hut is movc likely due to the rapid multiplication of an initially small number of dislocations. Recovery or the dislocation internal friction after deformation is also studied. This yecovery results from the re-pinning of dislocations by a solute, presumably nitrogen, which moves with a relatively small activation energy. SHARP-yield points, when they occur, are a striking feature of the stress-strain curve generated during a tensile test. Although commonly associated with steel, sharp yielding has been found in a variety of metallic and nonmetallic crystalline materials. In particular, sharp-yield points have been found in zinc"' and cadmium3 containing nitrogen. With this background, Geiselman and Guy4 investigated the tensile properties of magnesium single crystals containing nitrogen to see if sharp yielding also occurs in this system. They found that sharp yields did indeed occur in solution-treated and aged specimens tested at elevated temperature but were not able to give conclusive proof that the sharp yield was caused by nitrogen, a yield drop being observed even in their purest crystals. Sharp-yield points have also been found in various polycrystalline magnesium alloys.7'8 In the study of the sharp-yield phenomenon it is desired to observe the behavior of dislocations in the earliest stages of the deformation process. Internal-friction experiments are useful for this purpose because dislocation damping is sensitive to the mobility of free-dislocation segments. At low strain amplitudes the damping, A, due to the the forced vibration of dislocation segments of average length L is ? =KAL4 [1] where A is the dislocation density and K, if the applied frequency is well below the resonant frequency of the dislocation segments? is a constant for the sample under observation.5 Dislocation damping, because of the fourth-power dependence on L, is particularly sensitive to the creation of free-dislocation segments during deformation. Since sharp yielding is associated with the sudden release of pinned-dislocation segments, marked changes in the dislocation damping are expected at the yield point.6 The use of the dislocation-damping observations to help elucidate the incompletely understood mechanism of yielding in magnesium is the primary objective of the experiments reported here. PROCEDURE Many investigations have shown that very marked and rapid changes occur in the dislocation damping of of a deformed material as soon as the straining is stopped.5 It was quite essential, then, for the purpose of this investigation, to make the damping measurements during the deformation of the samples. This can only be accomplished through the use of the ultrasonic-pulse method. In this method traveling sound-wave pulses are used and, in contrast to resonating-bar methods, only the sample ends are set in vibration. Thus, the sample can be gripped along its sides in the tensile-test machine without disturbing the damping measurements. In the pulse method, the decrease in the amplitude of a sound pulse is measured as it travels back and forth through the sample. If A is the amplitude after traversing a distance x and A. is the initial amplitude, A=Aoe-ax [2] and a is called the attenuation. It is commonly measured either in units of cm-I or as db per µ sec. The observed attenuation in a metal sample is due to a number of causes. These include scattering by grain boundaries and impurity particles, thermo-elastic damping, diffraction effects, stress-induced ordering of solute atoms, and dislocation damping. The total observed attenuation in a given sample usually cannot be resolved into these various components, but changes in a due solely to changes in dislocation damping can be accurately determined, provided the experiment is arranged so that all other sources of damping are held constant. It is desired to reduce the extraneous sources of attenuation to a minimum and for this reason the experiments are done on single crystals of high purity. Magnesium crystals offer the further advantage that, when properly oriented, only a single set of slip planes is active during deformation. Crystal Preparation. The method of sample preparation is similar to that of Geiselman and Guy.4 The starting material was high-purity, sublimed magnesium rod supplied by the Dow Chemical Co. Melting under Dow 310 flux was used to reduce the nitrogen content of the starting material: the fluxing was done under an argon atmosphere and the

Jan 1, 1965

By Glenn A. Keep

THIS paper is not an announcement of the successful conclusion of the Cerro de Pasco Copper Corporation's pacos-pyrite problems, but merely a description of the commercial-scale, intermittent-roasting operations conducted by the writer, J. H. Lucas and others of the staff. It was prepared by request, for presentation at the February meeting of the Institute. The results obtained in Peru confirm the 1-ton-a-day experiments completed about three years ago at Kearny, N. J. by C. C. Gordon and Mr. Lucas, where it was first demonstrated that a mixture of about 80 per cent. pacos ore with 10 per cent. pyrite ore and 10 per cent. salt could be roasted intermittently in a small 1-ton-a-day Holt-Dern furnace without extraneous fuel, producing porous calcine that could be leached rapidly. Mr. Keep and his staff, by successfully introducing improvements in the construction of the commercial furnace and in their handling of material, have established beyond doubt a low cost for roasting. The other steps in the process of treating pacos and pyrite ores have not as yet been demonstrated as sufficiently conclusive to warrant their acceptance for a permanent plant. Cerro de Pasco Ores The ores of the Cerro de Pasco Copper Corpn. at Cerro de Pasco, Peru, are situated at an altitude of 14,000 ft. The town and mines are served by the Cerro de Pasco Railroad, which operates between Cerro de Pasco and Oroya, the site of the company's copper and lead smelters. Table 1.—Average Analysis of Cerro de Pasco Ores Pacos Ore Pykite Ore Silver, oz............................................... 10.3 12.0 Gold, oz................................................ 0.007 0.01 Lead, per cent........................................... 1.7 1.8 Copper, per cent......................................... 0.19 0.27 Zinc, per. cent........................................... 1.4 1.02 Iron, per cent........................................... 13.4 34.45 Silica, percent.......................................... 61.8 24.5 Alumina, per cent....................................... 2.5 0.62 Lime, per cent........................................... 1.5 0.20 Manganese, per cent..................................... 0.42 0.09 Sulfur, per cent,.......................................... 1.1 34.2

Jan 1, 1929

By Edward Steidle

THAT veterans are crowding the colleges is no longer news; 78 per cent of the 1916-47 enrollment in mineral industries curricula in the United States were veterans, but the rapid comeback from an estimated 1262 total mineral industries students in 1944-45 to 11,422 in 1946-47 is almost astonishing. The figure, which includes 1008 graduate students, is a substantial increase over the previous top record of 9619 in 1938-39. A small part of the increase is caused by the larger number of women entering the field, of whom there were c 9 in 1916-47. Petroleum leads the curricula with 34.5 % of the enrollment, metallurgy is second with 28%, and mining is third with 18%. Table 1. shows all curricula offered and those accredited by ECPD. Using the Mississippi River as a dividing line, 31 colleges in the East and 27 in the West offer curricula in the mineral industries.

Jan 1, 1948

By Wolfgang Gartner

METALLURGISTS engaged in the pulling of single crystals of germanium and silicon, and their zone purification and zone levelling for transistor and diode production, have found that the lifetimes of minority carriers in low resistivity samples tend to be shorter than in high resistivity material, although equal care is taken in the crystal preparation. In other words, it is more difficult to obtain long lifetimes in single crystals of low resistivity semiconductors. It is the purpose of this note to point out that this phenomenon follows directly from the Hall1 and Shockley-Read' theories of lifetimes in semiconductors." In general, the recombination mechanism may be very complicated,' but experiments seem to indicate that the simple formula2 for the lifetime of excess carriers given by n0 + n3 Pn + P1 T = Tpo,------------------+ Tjpu ----------------------- [ 1 ] nu + pn na+ + Pa is a good representation of the situation prevailing in transistor grade semiconductors. In this formula, no and pa are the equilibrium densities of electrons 6+ - E./ET and holes, n1 = N,e is the number of electrons E1- E2/KT in the conduction band, and p1 - N,e is the number of holes in the valence band, both for the case in which the Fermi level falls at the trap level, E1. N,. is the effective density of states in the conduction band; E1, the recombination level; E1, the lower edge of the conduction band; k, Boltzmann's constant; T, absolute temperature; N,., effective density of states in the valence band; and E,., the upper edge of the valence band. t,.,, denotes the lifetime of holes injected into highly n-type material, and The indicates the lifetime of electrons injected into highly p-type material. Eq. 1 holds for nondegenerate semiconductors in which only one recombination level is active and the charge in the recombination centers is neglected. It is further assumed that the number of injected ex-

Jan 1, 1957

By David Cole

AT the time flotation appeared upon the metallurgical horizon in Arizona, the writer, under the direction of Dr. Ricketts, was engaged in remodeling and enlarging the No. 6 Concentration Plant of the Arizona Copper Co. at Morenci, and the work had been in progress nearly a year before the Inspiration experiments with flotation had disclosed the revolution in concentration that was at that timè impending. The simplified flowsheet worked out for the remodeling of the Morenci plant had been based upon the removal of the freed metal in a minimum number of stages by treatment upon tables equipped with Butchart riffles, the latter being adapted to accomplish both classification of feed and removal of the metal at one operation, substantially as described in my previous paper.1 The scheme of treatment for the slime was based upon the well-known fact that after copper sulphides, such as chalcocite and chalcopyrite, etc., are reduced to a certain extremely fine state of comminution they are definitely beyond the reach of separation upon any of the concentrating devices then known. By using drag-belt classifiers (which served as conveyors as well as separators), the overflow would be of the usual "slimes" class. Experiment had shown that when these drag-belt overflows were, properly diluted (that is, to about 5 to 7 per cent. solids in the feed under treatment) . the very fine sand, and especially the very fine but still granular sulphide particle's, would, if given a short distance to fall, quickly settle out in prime condition to yield an excellent recovery on vanners; a further valuable feature would be that the very fine non-separable final overflow tonnage might be discharged direct to tailing, thus conserving space requirements so as to permit within the old building, without embarrass-ment, the increase of capacity required.

Jan 9, 1916

By AIME AIME

The following persons have been proposed for election as members or associates of the Institute during the period, March 16 to May 1, 1907. Their names are published for the information of members and associates, from whom the Committee on Membership earnestly invites confidential communications, favorable or unfavorable, concerning these candidates. A sufficient period (varying in the discretion of the Committee, according to the residence of the candidate) will be allowed for the reception of such communications, before any action upon these names by the Committee. After the lapse of this period, the Committee will recommend action by the Council, which has the power of final election. The names of candidates were formerly published in the various circulars of the Institute, issued from time to time to the members. Hereafter, they will appear regularly in the Bi-Monthly Bulletin, each number of which will contain the names received since the issue of the preceding Bulletin.

May 1, 1907