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By E. C. Nelson

An equation is derived for calculating approximately the solubility of nitrogen in an alloy steel over a temperature range from 1200" to 1900°C using data on the effects of alloys on the activity coefficient of nitrogen in iron at 1600°C. Calculated values are compared with experimental data. STUDIES involving the solubility of nitrogen in complex iron alloys have been aided by a system devised by Lanenberg for calculating the solubility of nitrogen in ternary and higher alloys of iron at 1600C using available data on the activity coefficient of nitrogen in binary alloys. Calculated nitrogen solubilities agree well with experimental determinations on complex alloys,' and the calculation procedure is useful when experimental data on specific alloys are not required. A method for extending calculations of nitrogen solubilities in alloy steels to temperatures other than 1600°C would be useful because of the paucity of experimental data in this area. Assumptions which must be made to permit this calculation introduce an element of approximation; however, the calculation is useful in cases where a large number of alloys and temperatures are under consideration, and the precision of experimental measurements is not required. The activity coefficient can be freed from the isothermal restriction of Langenberg's calculation if it is assumed that the solution is "regular". This is a reasonably good assumption for solutions of nitrogen in iron alloys, because usually they are dilute and the heat of solution is relatively small. The presence of large amounts of certain alloying elements would make this assumption less tenable.3 One of the properties of a regular solution is: when "f" is the activity coefficient of a solute and "T" is the temperature in OK. If the activity coefficients at temperatures T and T2 are denoted by subscripts 1 and 2 respectively: The activity coefficient of nitrogen in a complex alloy then can be calculated at any temperature from the sum of the effects of the other solutes on the activity coefficient of nitrogen at 1600°C. It will be convenient to incorporate this expression into an equation which will give directly the logarithm of the solubility of nitrogen at any temperature in the presence of alloys. Two constants, the solubility of nitrogen in pure iron at 1600 "C and the partial molar heat of solution of nitrogen in iron are required. The heat of solution value of 1400 cal at 1600 °C quoted by Kubaschewski and vans will be used. The accuracy of the calculation will suffer if the heat of solution should change materially with temperature. In the absence of experimental data on the temperature dependence of this quantity, it will be expedient to restrict the application of the calcula-

Jan 1, 1963

By Yang Tsang Woo

The method of making coke that has been adopted at the Kaiping and other collieries in northern China resembles, to some extent, the familiar bee-hive oven process of the United States, except that a kiln with permanent sides is used instead of a closed oven, and the products of combustion are drawn off at the bottom. In building coke-kilns in China, two circular holes, 8 ft. 6 in. in diameter at the bottom and 13 ft. in diameter at the top, are excavated in the ground, and connected at the bottom by a flue, as shown in Figs. 1 and 2. The sides and bottom of the kiln are lined with fire-bricks, and covered with a lager of fireclay, and a rectangular opening, 6 in. by 8 in., connects the bottom of each kiln with the main flue. Around the edge of the hole, and overlapping the lining, is a wall of fire-brick extending 2 ft. 6 in. above the level of the ground. An open space 5 ft. wide is left in this wall, through which the coal is carried into the kiln and the resultant coke removed. This space, of course, is bricked up during the time that the coking-operation is being carried on. The wall is pierced with nine flue-openings uniformly placed around the circumference, each interverliilg space in the wall being strengthened with a brick buttress, as is shown in Figs. 2 and 4. The floor of the kiln, as well as the main flue, is lined with fire-brick. Before charging the coal, it is first placed in shallow bamboo sieves, 2 ft. in diameter, and immersed in a trough 10 ft. long, and 3 ft. wide, fed with pit-water, in which it is washed by hand. Fig. 3 shows the manner in which the washing is done. From 25 tons of good "dust" coal, 22.5 tons of washed coal are obtained. When ready to charge the coal into the kiln, a temporary cone-shaped flue of fire-wood and lump coal is first built to a

Jan 1, 1906

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

Aclivilies of magnesium in liquid Alg-Si alloys have been delermined between 5 and 60 at. pcl Si, close to the melling point of Mg2Si, by an improved isopieslic melhod. Silicon specinrens, held in alumina crucibles and graplrile conlainevs of special design, were healed in a letrlpevalure gvadient and equilibrated with mag-nesilcrrl rapor in a closed lilanium system. The ther-madynamic Junctions were calculated and compared with the thermodyuamic properties of the other three mg- Gvoup IVB systems. Lattice paramelers of three Mg2X compounds were measured. The bonding in the Mg2X compounds is largely covalent with small and uarying amounts of metallic and ionic conlvibutions. The Mg-Si phase diagram1 has one congruent melting compound, Mg2Si, of essentially stoichiometric composition, two eutectics, and very limited terminal solid solubilities. Little information is available on the thermodynamic properties of this system. The free energy of formation of Mg2Si has been determined by the Knudsen cell technique2 in the range 572" to 680oC, by the transportation method3 between 858" and 950oC, and by the electromotive-force method4 in the range 400o to 600°C. Kubaschewski and villa5 and caulfield6 have measured the heat of formation of Mg2Si. An electromotive-force study of magnesium-rich liquid alloys was recently published by Sryvalin el al.7 The present investigation was undertaken to complete a general survey of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,a9,Mg-Sn,10,11 mg-Ge,12and Mg-Si. An isopiestic technique, previously developed for similar measurements on liquid Mg-sn11 and Mg-Ge alloys,12 was modified for the Mg-Si system. Specimens of the nonvolatile component, silicon, were contained in dense alumina crucibles placed inside covered graphite crucibles which were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure. The alumina crucibles prevented contact between the highly corrosive liquid Mg-Si alloys and graphite. The graphite cruci- bles effectively preserved the high-temperature equilibrium composition of the liquid alloys containing highly volatile magnesium on termination of the experiments during the quench to room temperature. EXPERIMENTAL PROCEDURE Silicon of semiconductor-grade purity (E. I. du Pont de Nemours and Co., Brevard, N.C.) and 99.99+ pct Mg (Dominion Magnesium Ltd., Toronto, Canada) were used. Graphite crucibles with press-fitted lids were machined from high-density (1.92 g per cu cm) rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The alumina crucibles had a purity of 99.7+ pct (Triangle RR grade, Morganite, Inc., Long Island City, N.Y.). In preliminary runs the liquid alloys were contained in graphite crucibles following the exact procedure developed for the Mg-Ge system.'2 These runs failed due to appreciable reaction between the molten Mg-Si alloys and graphite, and the results have been discarded. The procedure was then modified and the Mg-Si alloys were subsequently held in alumina crucibles. For most of the runs alumina crucibles of known weight and approximately 6.3 mm ID, 12.5 mm height, 1.0 mm wall thickness were loaded with weighed amounts of silicon and encapsuled in tightly covered weighed graphite crucibles 5/16 in. ID, 2 in. helght, 3/32 in. wall thickness). The graphite crucibles were machined from rods which were 85 pct of the theoretical density. These crucibles were therefore sufficiently porous so as to permit magnesium vapor to effuse through the silicon under the experimental conditions of approximately 970O to 1220°C and 1 day equilibration time. However, negligible magnesium was lost from the crucible during the quench due to the slow effusion rate through the pores of the graphite. The inner alumina crucible prevented the liquid alloys from contacting the graphite, and the very tightly fitting graphite crucible lids served to retain any magnesium vaporizing from the alloys inside the crucibles during the quenching step.12 The loaded silicon-alumina-graphite cells were positioned, one above another, on a 16-in.-long titanium thermocouple well and tied securely to the titanium tube with thin molybdenum wires held in grooves around the circumference of the graphite crucibles. A thin (0.005-in.) molybdenum strip prevented contact between the graphite crucibles and the titanium. This assembly was lowered into a titanium reaction tube (la in. ID, 16 in. long, $ in. wall thickness) closed on one end which contained a 11/2-in.-long cylinder of magnesium at the bottom. The inner titanium thermocouple well was positioned eccentrically in the large tube because of the eccentric mounting of the cells on the well. Appropriate modifications of the titanium cap"'12 were made to join the inner and outer titanium

Jan 1, 1968

By K. A. Jackson, J. D. Hunt

A new classification of eutectics is proposed, based on tlze entvopies of wzelting of the tuio eutectic phases. The clnssification was used to predict suitable tvansparent analogs of the metallic systems. Experimental confir?nation loas obtained for the theovetical shape of the lamellar solid-liquid interface, fov the fault mechanisms of lanzellar spacing changes, and for the development of low-energy solid-solid boundaries between the lamellae. An explanation is presented to account jov the irvegular and coinplex regular structures zrhich are found in some eritectic systems. FrOM experimental observations, single-phase materials can be divided into two groups according to their solidification characteristics, those that grow as faceted crystals and those that do not. acksonl' showed from thermodynamic reasoning that the type of growth depended on a factor a which was almost thg entropy of melting. Most nonmetals have high entropies of melting (a greater than 2) and grow with crystalline facets. Most metals have low entropies of melting (CY less than 2) and grow almost isotropically with no facets. The authors propose that eutectics may be classified in a similar manner. There are three groups of eutectics, those in which both phases have low entropies of melting, those in which one phase has a high and the other phase has a low entropy of melting, and those in which both phases have high entropies of melting. Lamellar or rodlike structures are formed in systems in which both phases have low entropies of melting. In these alloys dendrites of either phase may be formed, when the alloy is rich in the relevant component. Examples are Pb-Sn, Sn-Cd, Pb-Cd, Sn-Zn, Al-Zn. Irregular, Fig. 14((), or complex regular, Fig. 14(b), structures are formed in alloys in which one phase has a high entropy of melting and the other has a low entropy of melting. Examples are A1-Si, Zn-MgzZnll, Pb-Bi, Sn-Bi. When the alloys are rich in the low entropy of melting phase, dendrites are formed; when the alloys are rich in the high entropy of melting phase, faceted primary crystals are produced. These crystals are sometimes called hoppers or pseudodendrites. In this work the term dendrite will only be used to describe nonfaceted primary crystals. Dendrites are not formed during solidification in high entropy of melting single-phase materials. The third group of eutectics includes alloys in which both phases have high entropies of melting. Each phase grows with a faceted solid-liquid interface. Since most metals do not have high entropies of melting, metallic examples in this eutectic group are rare. However they may occur between some intermetallics and semiconductors or semimetals such as silicon, germanium, and bismuth. Attempts have been made to study eutectic solidification visually by watching the growth process.374 Since metals are not transparent, the observations had to be made on external surfaces. This difficulty can be overcome by using transparent analogs of the metallic systems. As was mentioned earlier, most single-phase compounds have entropies of melting greater than 2 and so grow as faceted crystals. Recently organic materials with entropies of melting less than 2 were investigated.' These materials grow in exactly the same way as the low entropy of melting metals. When the materials are pure, they grow with a solid-liquid interface parallel to an isotherm; when they are impure, cells or dendrites are formed. Since these materials are transparent, have low melting points, and even have cubic structures, they should be ideal for making up transparent analogs of the metallic eutectics. The purpose of the present work was to investigate these organic eutectics and to see whether this quite different series of eutectics could be classified in the same way as the metallic systems. The observations made on the organic alloys are also discussed with reference to the current theories of lamellar growth. Explanations are proposed to account for the structures formed in the other eutectic groups. EXPERIMENTAL Thin cells containing the organic alloys were uni-direction ally solidified on a specially constructed microscope stage.' Uniform growth rates were obtained by moving the cells, with a motor drive, through a fixed temperature gradient, so that the solid-liquid interface remained stationary with respect to the microscope objective lens. The cells were made by fusing two microscope cover slides 7/8 by 7/8 by 1/100 in. together on three sides, leaving a gap of 1 to 3 mils between the slides, and these were filled by surface tension. A preliminary investigation of the phase diagram between two components could be made very rapidly. One side of the cell was filled with component A and the other side with component B. Since only a small amount of mixing could occur every composition from pure A to pure B was present in the cell. When the cell was placed in the temperature gradient a pictorial representation of the phase diagram was obtained. Eutectics, peritectics, "interorganics", and solid -solid transformations could be readily detected. Fig. 1 shows part of a eutectic phase diagram. The Sample was first grown slowly then stopped. The two

Jan 1, 1967

By Luther Wagoner

HAVING given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and' believing it might be interesting to extend the work to include' some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S, steamer Albatross, and marked as follows

Jan 9, 1907

By H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500'C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the 'Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

By W. B. Heroy

ONLY through the mineral fuels can large amounts of energy be transported to great dlstances and stored for long periods for future use. Coal has the advantages over oil of greater safety of handling and smaller losses in storage. But oil is, in the present stage of technical advancement, the more economical source of liquid fuel for internal-combustion motors. No method for direct use of coal in such motors has been developed that can compete with petroleum products. The automoblle engine and the airplane motor are designed to make the most effective use of gasoline.

Jan 1, 1944

By James A. Lewis

It is the purpose of this paper to show the importance of sand characteristics, when combined with other physical data, in evaluating production obtained by secondary recovery operations, and to indicate the benefits to be gained from the application of these principles to primary production.

Jan 1, 1942

By James Norman, Benjamin S. Lindsey

Barite (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some binds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to I00 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaS04, II.II. per cent SiO2, and 2.85 per cent R2O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of non-metallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is separated. Laboratory Flotation Work Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coel for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1943

By Benjamin S. Lindsey, James Norman

Barite (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some binds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to I00 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaS04, II.II. per cent SiO2, and 2.85 per cent R2O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of non-metallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is separated. Laboratory Flotation Work Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coel for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1943

By John L. Burns

The object of this chapter is to present data concerning the effect of the introduction of relatively slight amounts of carbon and nitrogen into supersaturated solution in iron. The study is confined to the alpha temperature range of both the Fe-C and Fe-N systems. The age-hardening characteristics of these two systems are considered. These data are compared to those of other age-hardening alloy systems and a "classification" is essayed. A.—Relation of Lattice Parameter and Electrical Conductivity to Changes in Physical Properties Due to Aging of Fe-C Alloys Since Whiteleyl in 1927 showed that some of the iron carbide that is normally present in slowly cooled low carbon-iron alloys disappears on rapid cooling from just below the A, point, interest has been manifested in the possibilities of age-hardening in these alloys. Masing and Koch,~ and at the same time and independently, W. Koster,~ proved these alloys to be age-hardenable. A. A. Bates4 a little later also published an interesting paper on changes in physical properties due to the aging of low-carbon steels. Many other papers have appeared showing changes in physical properties in specific instances due to this same phenomenon.

Jan 1, 1934

By J. J. Arps

This paper is a study of the effect of temperature on the electrical resistivity of sodium chloride solutions based on the published resistivity and density data in the International Critical Tables. This temperature effect is of considerable importance in quantitative interpretation of electric logs, where it is frequently necessary to correct mud resistivities measured under surface conditions to temperatures existing at the bottom of the bore hole. An empirical approximation formula was developed for this conversion which has proved to be very useful and seems to provide results well within the range of accuracy of the data involved. This approximation formula states: sistivities of sodium chloride solutions at temperatures of t and t degrees Fahrenheit, respectively. INTRODUCTION Research by various investigators during the past 20 years has clarified the physical principles of the phenomena which cause the natural or spontaneous electric potential in rotary drilled bore holes. The basic relationship which is most commonly used reads: in which the SP deflection, as measured from the shale base line, is expressed in millivolts. K is a constant, which appears to vary between 50 and 110; the low value applying to shaly sands, whereas the higher values are more common in carbonate rocks. A good average value for K = 70. for which value there is considerable theoretical justification." In order to calculate the resistivity of the connate water R and to estimate its "equivalent salinity" (as NaCl) from an electric log by means of this SP relationship from a knowledge of the static self potential and of the resistiv- ity of the mud filtrate R it is necessary to first correct the resistivity of the mud filtrate measured under surface conditions to the resistivity of this same mud filtrate in the well bore at a different temperature. In order to make this temperature conversion for the mud filtrate the variation of the electrical resistivity of sodium chloride solutions with temperature is commonly used. Since some discrepancies were found in the charts ordinarily used for this purpose, it was felt desirable to make a new study of this relationship based on the published measurement data. Because of the fundamental nature of these relationships and as an aid to other workers in this field, an attempt has been made in this study to show every step in the calculations. CONDUCTIVITY VS MOL CONCENTRATION The most complete published reference on the temperature relationship of sodium chloride solutions of different concentrations is provided in the International Critical Tables.' The basic measurement data on the electrical conductivity of aqueous sodium chloride solutions, at different temperatures, as given in these tables, are reproduced in Table 1. The electrical conductivity values in this Table 1 are expressed as 10' times the specific conductivity k in ohm-'cm'l per unit of concentration in milligram mols per liter of solution C, or: RESISTIVITY VS MOL CONCENTRATION These conductivity values from Table 1 were first converted to the corresponding electrical resistivity values (R) , expressed in ohm-meters, as is conven-

Jan 1, 1953

"The reduction works of the Boston & Montana Reduction department, near the north end of this dam is one of the reduction plants belonging to the Anaconda Copper Mining Company, the other being at Anaconda. These works employ about 1,100 men and have a capacity of about 3,800 tons of crude ore per day. This plant is now being remodeled to embody results of experiments and investigations which have been made with a view to more economic.al treatment of ores. A brief description of the plant as it will be after the remodelling is as follows:Concentrator Department: Consists of six units or sections, each section treating from 550 to 600 tons of crude ore per day. This department is not being. remodelled at the present time. A concentrating process, however, has been developed and partially installed in the old mill, and an experimental section embodying this concentration process has also been installed at the concentrator at Anaconda."

Jan 1, 1913

By J. H. Smith, H. W. Paxton

X HE recent investigation of Butler, McCabe, and paxton' on the vapor pressure of manganese gas in equilibrium with Mn-Fe alloys has been extended to include the iron-rich solutions and alloys in the two phase equilibrium region. The study of the phase equilibrium by Kurnakov and Troneva2 and the extensive reviews of the Mn-Fe system by Hansen,3 and Hellawe114 are not in agreement with regard to the location and extent of the equilibrium between the solid phases of fcc y and complex P in the temperature range above the eutectoid temperature of approximately 975Kwhere 0 decomposes to y and bcc a. An evaluation of the existing equilibrium data is confronted with the conflicting results presented by various investigators who used techniques requiring a quenching treatment to retain the high-temperature equilibrium or encountered temperature hysteresis during thermal analyses. The difficulty of suppressing the transformation of the manganese-rich concentrations of the y-solid solution during quenching has been well etablished.' To avoid this uncertainty the phase equilibrium was investigated at temperature by measuring the partial pressure of manganese gas in equilibrium

Jan 1, 1962

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By J. H. East, E. R. Maize

INTRODUCTION PROBABLY no other type of equipment is now being introduced into American underground mines about which less is known and about which there is more misinformation than the Diesel mine locomotive. Any equipment installed underground brings with it hazards that were not present before, and it is the purpose of this paper to show that Diesel-powered equipment can be used with safety in underground mining if certain feasible but very important precautions are taken. Diesel locomotives are not new in underground mining, since they have been used successfully in European mines for at least 19 years, but their use in American mines is exceedingly limited; so far as is known, only five Diesel mine locomotives are operating at present in United States mines. Diesel locomotives were permitted underground in Great Britain for the first time in 1939, and the rapid increase in the number in use in those mines, testifies to their safety and efficiency. More than 1300 Diesel mine locomotives are in use in European mines, according to the latest statistics; these locomotives are employed in coal, iron, lead-zinc and mercury mines. So far as is known, the Diesel mine locomotive has not yet caused an explosion or mine fire, and has not been the cause of any fatalities from toxic gases in the mines in which it has been used. ADJUSTMENTS OF DIESEL ENGINES FOR UNDERGROUND USE A Diesel engine adjusted to work in an underground mine should not be confused with the same engine adjusted for use outside the mine. Adjustment of the air:fuel ratio for engines that are used on the surface is intended to give the maximum fuel economy, and little or no attention is given to the chemical composition of the exhaust gas produced. Many such engines are poorly adjusted and perhaps poorly maintained, with the result that the engine emits smoke in quantity as well as the disagreeable odor familiarly associated with Diesel engines. The air:fuel ratio in the case of Diesel engines operated on the surface is generally around 15:1; that is, 15 lb of air to burn 1 lb of fuel. Diesel engines adjusted to work underground usually have an air:fuel ratio of about 20:I, as at this ratio the minimum quantity of toxic gases is given off in the engine exhaust. Diesel engines operated underground must be maintained in better condition than similar engines used on the surface; otherwise, the smoke emitted in the exhaust becomes objectionable if not unendurable. Practically normal air is required for safe operation of Diesel engines underground or in confined places; failure to provide virtually normal air for Diesel engine operation is almost certain to result in trouble. Bureau of Mines engineers have determined that the air in which a Diesel operates in confined places should contain less than 1/2 pct of carbon dioxide and at least 20 pct of

Jan 1, 1947

By Paul Gemmill

Production was first recorded from the Pioche district in 1864, and it has continued to show an inherent ability to take on new life after periods of depression in the metal markets. Production from replacement leadsilver- zinc sulfide ore bodies in limestones of Cambrian age now accounts for several times the gross value of silver production from rich fissures in Lower Cambrian Quartzite. Aggregate production of some 6 million tons represents a gross value over $100-million. Future output is expected mostly to be from limestone replacement deposits of which the most productive are "channels" of ore up to several hundred feet wide and several thousand feet long with thicknesses from a few feet up to 50 feet. Such channels are restricted to the lowermost limestone bed of the district, about 250 feet above the basement quartzite. The "blotter-like" characteristic of this highly productive Jimesto~e bed in absorbing mineralization is believed to be, at least in part, due to lithology, including free carbon in the bed, which has created a unique set of conditions for delicately balanced mineralizing solutions that rejected any tendency to replace siliceous wall rock and were properly constituted for replacement of Limestone. All recognizable orogenic history is considered to be related to the Basin and Range faulting that created the mountain ranges. The faults developed after mid-Tertiary time and after widespread extrusives that are themselves involved in the faulting. Flat faults, formerly believed to be part of regional thrust faulting, are now interpreted as gravity slide faulting that can be shown to be large in magnitude and not simply local landslides. Large slide faults generally have concealed the great magnitude of mountain-bordering faults. Mineralization that accounts for ore is later than the faulting. Most faults are pre-mineral since they influence the shape of ore bodies, and some clearly have been offset by fault fissures containing ore. Post-mineral movement probably has been an important component of some large, initially pre-mineral faults. A single period of mineralization was begun by the introduction of large quantities of ironmanganese carbonate, and, in places, carbonate manganese with minor values in sulfides. Closely following the carbonate invasion, massive sulfides were brought in, usually replacing part of the carbonate body though in some places the massive sulfides replaced limestone that was not previously mineralized. Manganese mineralization is not a "halo" but leaks of manganese to higher formations and to the surface are the most significant exploration guides. The Pioche district is expected to be long lived with technological developments in ore treatment being important to the exploitation of low-grade manganiferous ores, while aggressive exploration is expected to find important quantities of bedded lead-silver-zinc ores of the massive sulfide type.

Jan 1, 1968

By R. H. Winn

In this paper a heterogeneous carbonate reservoir is considered as a succession of layers of formations of radically different porosities, permeabilities, water saturations, and rock matrix types; i.e., the heterogeneity is vertical rather than radial to the wellbore. Presumably each layer is more or less homogeneous. To determine the "net oil in place" in this reservoir it is desirable to know the porosity and water saturation of each layer. In addition, the section must be subdivided into that which will produce oil, that which will produce water, and that which will produce little or nothing. In numerous wells drilled in these reservoirs radioactivity surveys, guard electrode surveys, and caliper surveys have been made. These logs have been compared with core analysis data, when available, and the analysis of the surveys compared with production data. This study, still in progress, is intended to provide improved analytical techniques if such are possible. This paper is a progress report on the work. DETERMINATION OF POROSITY The neutron-gamma log has long been recognized as a measure of hydrogen concentration.1,2,3 In reservoirs that are free of clay, shale, or other hydrogen containing matrices, it has been accepted as a measure of porosity.4,5 Empirical methods to relate relative neu-tron-gamma intensity to porosity are often employed." To provide a more precise determination of porosity from the neutron-gamma log each instrument is calibrated immediately prior to each survey by a method which refers all tools to a hydrogenous cylinder. To insure stability a calibration check is made after each survey. These calibration records are printed as an integral part of the log that is recorded in standard counts per second. A detailed description of the calibration procedure is available in the literature.' The procedure employed insures that each Survey is numerically reproducible within the limits of statistical variation. To relate the standard neutron counts per second to porosity and hole size, records were made in test wells constructed of blocks of limestone. The porosities of the blocks were accurately measured and the blocks completely saturated with fresh water. Fig. 1 presents some of the results obtained in these test wells.' The lines shown in Fig. 1 were obtained by deriving an empirical equation relating the 11 points shown so that the relationship may be projected to larger and smaller hole sizes. A detailed description of the tool is available in the literature.' Field tests indicate that the tool is adjacent to the wall of the hole most of the time when the surveys are made in uncased holes drilled with saline muds. In this circumstance porosity may be calculated from Fig. 1 if the hole size is known. When fresh muds that form thick mud cakes are employed, the centralizing effect of the mud cake must be considered and the porosity determination is less reliable. In cased holes the combined effect of variations in hole diameter and the unknown eccentricity of the casing in the hole may make porosity determinations extremely unreliable. In any event, an accurate knowledge of hole size is essen-

Jan 1, 1958

The following is an incomplete list of members and guests who called at Institute headquarters during the period Jan. 10, 1918 to Feb. 10, 1918: K. Baumgarten, San Diego, Cal. J. A. Meyerovitch, Petrograd, Russia. F. J. Brine, Toronto, Ont., Canada. C. Naramore, Washington, D. C. W. A. Castleton, Salt Lake City, Utah. Orrin P. Peterson, Wausau, Wis. J. Ross Corbin, Boyerton, Pa. William H. Rea, Pittsburgh, Pa. W. M. Corse, Buffalo, N. Y. W. Murray Sanders, Tucson, Ariz. W. A. Deane, Summitville, N. Y. Edmund F. Saxton, Philadelphia, Pa. S. E. Doak, Philadelphia, Pa. William C. Schmidt, Humboldt, Ariz. F. G. Downs, Jersey City, N. J. G. J. Sielaff, Oakland, Cal. Albert H. Fay, Washington, D. C. A. D. Sproat, Bound Brook, N. J. F. Julius Fohs, Tulsa, Okla. J. A. Stader, Joplin, Mo. A. L. Gholz, Minneapolis, Minn. A. K. Stewart, Mine La Motte, Mo. Ruger W. Hay, Easton, Pa. Geo. W. Tower, Jr., New Rochelle, N. Y. Stanley C. Herold, Pittsburgh, Pa. Henry Traphagen, Toledo, Ohio. A. A. Holland, Montreal, Canada. H. E. Treichler, Chuquicamata, Chile. T. Z. Humphrey, Anaconda, Mont. Paul M. Tyler, Fairlee, Vt. H. M. LaFollette, LaFollette, Tenn. F. R. Van Campen; Seattle, Wash. J. B. Lain, Goldfield, Nev. Thor Warner, Phoenix, Ariz. J. R. Lashbrooke, Los Angeles, Cal. Clarence Woods, Narrows, Va. W. F. Lewis, Ewen, Mich. E. N. Zern, Pittsburgh, Pa. C. E. McQuigg, New Haven, Conn. Robert J. Anderson has resigned his position as chief chemist and metallurgist of the Cleveland Metal Products Co., Cleveland, Ohio.

Jan 3, 1918

By Philip M. McKenna

WHEN a new material becomes available to industry, it is useful to describe its properties as a guide to its most effective application; and when the new material may be produced in compositions having a series of graded properties, tests to select the combination of properties best adapted for various uses are helpful. The class of materials to be considered in this paper are hard tool materials produced by processes of powder metallurgy from hard carbide constituents and various matrices of iron, nickel or cobalt, or alloys of them with tungsten, or tungsten and carbon. The customary use of carbide hard alloys is for metal-cutting tools; although wire-drawing dies, lathe centers, follow rests, grinding rests, burnishers, rolls, extrusion dies, measuring gauges and micrometers, and a number of other tools are also made with these hard alloys as the essential wear-resisting parts. The properties and tests to be considered are those affecting these uses. In the development of tool materials since the industrial revolution we have had carbon tool steels, Mushet steel, high-speed steels, stellites, and now cemented carbide compositions. For an understanding of the latter category of materials their properties and uses relative to the older and more familiar tool materials will be considered. Hardness has been the property of greatest practical interest in tool materials. The word "hardness" is a generalized term lacking definite¬ness unless the specific test used is described. However, efforts to explain physical properties as a consequence of chemical bond, and distance between atoms in chemical compounds have been illuminating. This seems the most generalized attack on the problem, and is based upon the idea that atoms in a lattice are held together as the square of the valence and inversely as the square of the distance between the atoms. The compounds compared must all be of the same crystalline arrangement. It is interesting to note the values of the figure [V ] a number of

Jan 1, 1938