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By Chikao Nishiwaki

INTRODUCTION The Japanese dependency for mineral raw materials from foreign sources increased rapidly within the 20 years since the Korean war. During this 20 year period Japan has attempted to industrialize and develop her economy while depending mostly on heavy import of nearly all kinds of mineral raw materials. She has fabricated them using energy generated mostly by mineral fuel that are also imported. Fabricated goods are either used domestically to accelerate more fabrication industry or exported after adding more refinement or fabrication. In this paper iron ore as a major raw material for the Iron and Steel industry, three major base metals, copper, zinc and lead, and petroleum as a major energy source have been selected as examples to represent the general features of various kinds of mineral raw materials that are imported. Among other important mineral commodities for which Japan dependa upon foreign sources are: Aluminium, nickel and cobalt, potash and phosphorous 100 percent dependent and tin, tungusten, chromium and molybdenum over 95 percent dependent. IRON ORE Statistics for the important iron and steel raw materials, namely iron ore, coal and scrap iron are shown in Tables 1, 2 and Fig. 1. Iron ore is by far the most important and basic among these three commodities. There has been practically no steel or iron imported as a metal into Japan during this period. Iron ore, including aggregate such as pellets, and metallurgical coal are mostly transported in large ore cargo boats to the port where very efficient port facilities unload them directly at the steel mill site. As a result

Jan 1, 1976

By Theodore Swann

DURING recent years, there has been a material increase in the use of ferrophosphorus in the steel industry. It has been observed, when rolling sheets, that those made of Southern iron did not have to be rolled at as high a temperature as the others and, consequently, did not stick together. The reason was found to be the phosphorus content of Southern iron. It was therefore thought that an addition of phosphorus to sheet steel of other than Southern origin would give the same result as the use of Southern iron. At first, this addition was made by intro¬ducing phosphate rock in the blast furnace and reducing it together with the iron ore; but, because of the necessity for only small quantities of this grade of iron, the process was not satisfactory. The manufacture of ferrophosphorus was then introduced, so that additions might be made to the open-hearth furnace or ladle. Ferrophosphorus was first manufactured in the blast furnace. This method, however, can only economically produce a grade of product up to about 20 per cent. To produce a higher grade, it would be necessary to charge a larger proportion of phosphate-bearing material; and as the rate of absorption by the iron is low, there would be an increased loss of phosphorus oxides. This feature makes the production of a higher grade ferrophosphorus in the blast furnace uneconomical. The use of high-grade ferrophosphorus in the steel requires a smaller addition and involves, besides the economies in handling, an additional economy in transportation. The alloy with a higher percentage than 20 per cent. can be made only in the electric furnace. In the ordinary operation of the electric furnace in the production of ferrophosphorus, an alloy may be produced containing 26 per cent. phosphorus; this is the limit, for it does not seem possible to produce a higher phosphorus alloy even if large excesses of phosphatic materials are used. The reasons for the difficulty in raising this percentage of phosphorus are not known. The compounds Fe3P, containing 15.6 per cent., and Fe2P, containing 21.7 per cent. phosphorus, have been studied and it appears as if the alloy produced, containing percentages of

Jan 10, 1924

By C. F. Willis

The problem of the curtailment of forces in large numbers does not often come to employment departments and is, therefore, a problem that many departments are not prepared to handle intelligently. Those companies that are able to measure the individual efficiency of each man would probably lay off men according to their individual ability, irrespective of dependents, citizenship, or other considerations. During the war when labor was scarce, the business of the employment manager in industry was hiring men and carefully placing them where they were best fitted to work. The careful selection of employees had developed to a considerable extent before the war, and was becoming a recognized science. In the last few months, however, the cancelation of copper contracts, the accumulation of large stocks, the necessary curtailment of production because the copper could not be sold, and the lack of any immediate prospects of' the copper market opening, have led to a universal reduction of forces, and the problem that industry now confronts is that of discharging rather than employing. The problem has been aggravated by the cancellation of contracts in many war industries with the consequent turning loose of hundreds of thousands of men, a great amount of unemployment, and the return of the soldiers and sailors. The problem has now become one of reduction of working force with the least hardship and the least injustice, and yet caring for the soldiers, sailors, and marines who have been in the service of the government for nearly 2 years, and are now returning to their pre-war positions. The Copper Queen Branch of the Phelps Dodge Corpn., operating at Bisbee, Arb., found it necessary, like all of the other copper companies of the country, to reduce its force materially. In making this reduction it was, after due consideration, decided to classify employees with respect to dependents, length of service, and citizenship. The question of individual efficiency or workmanship was not considered. Copper produced to sell at 26 c. a lb. has been selling at under 15 c., and very little copper is being sold at all. Practically every copper producer in the country has enormous stocks on hand, and it would be profitable,

Jan 1, 1920

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By M. J. Saarivirta

A high-purity copper-zirconium alloy system was imesti-gated. The zirconium content of the alloys studied varied from 0.003 to 0.23 pet. The solid solubility of zirconium in copper and some physical and mechanical properties of the alloys have been determined. By proper heat treatment, Cu-Zr alloy can develop a high electrical conductivity and resistance to softening at temperatures up to 500°C (930°F). This combination of desirable properties makes this alloy superior, to other com-merzcrrl copper base alloys for- use in the electrical conductor field. DEMAND for high conductivity copper alloys that retain their mechanical properties at elevated temperatures is growing rapidly. At present, copper-base alloys such as copper-silver and copper-chromium are used where these characteristics are required. As an example, commutators in electric motors are often made of these alloys. However, the life at elevated temperature of commutators made of copper-silver alloys is much shorter than the life of the same part made of copper-chromium and copper-zirconium alloys. Copper-silver alloys are subject to creep and subsequent failure when the service temperature exceeds several hundred degrees centigrade. Use of copper-chromium alloys has been known for the past several years, but little information is available in the literature concerning the properties of alloys in the copper-zirconium alloy system. Some work had been directed toward determining the solubility of zirconium in copper as well as determining properties of the Cu-Zr alloys. These investigations have revealed the superior high-temperature and electrical conductivity properties of copper-zirconium alloys over copper-chromium alloys. The United States Metals Refining Co., Carteret, N. J. has recently produced OFHC R copper-zirconium alloys for experimentation and evaluation. Because OFHC R copper contains no appreciable oxygen, no harmful oxides are formed and the full benefit of Zr as an alloying addition is obtained. This paper describes the results of this work. It contains room-temperature and some high-temperature data which have been obtained after various processing techniaues. Actual elevated temperature properties are being determined and will be reported in a separate paper. Preliminary results obtained at elevated temperatures suggest that the Cu-Zr alloy is superior to other high conductivity copper-base alloys. WORK PROCEDURE The high-purity oxygen free (OFHC R) copper-zirconium alloys with zirconium content ranging from 0.003 to 0.23 pct were cast into 4-by 4-in. wirebars by both continuous casting and conventional casting methods. Zr was added in the form of a master alloy containing 30 pct Zr and 70 pct Cu. Castings were analyzed for zirconium and nine bars containing various amounts of zirconium were selected for this study. The results of analyses and the sample numbers are given in Table I. Typical analyses of OFHC R copper are also shown. The following properties were studied: A) Solid solubility of zirconium in copper. B) Effect of zirconium on properties of copper. C) Effect of combined working and heat treating on properties of Cu-Zr alloys. The solid solubility of zirconium in copper was determined by metallographic techniques. Specimens for this phase of the investigation were hot rolled at 900oC (1650oF) to 0.250-in. rod. The rolled rods were cut into 2/3-in. long specimens and solution annealed at 950 °C (1740°F), 980°C (1795 °F). and 1020 °C (1870 °F) for 6 hr and quenched in water. In order to find the solid solubility limits at lower temperatures, the homogenized specimens were reheated at various temperatures for 1 hr and quenched. The physical and mechanical properties were determined on 0.250 in. rod, 0.132- and 0.081-in. wires. The wires were cold drawn from the 0.250-in. rods after they were solution annealed at 980 °C (1795°F) and quenched in cold water. Mechanical and electrical properties were determined on cold drawn and

Jan 1, 1961

By J. W. Spretnak, V. Kandarpa, G. W. Powell, R. A. Erickson

Neutron-diffraction pattens were obtained at room temperature from two austenitic manganese steels, oxc wth n carbon content of 1.23 zct PC/ and the olher 0.63 wt pct. Analysis of the data showed that the curOan atols (ions) occupy tile octaheadral site. any of the cavbon is in the tetahedral site, tile concentration is too strzall lo be detecled by tzeulr-on d$facton. AS part of a long-range investigation of eutectoid decomposition, a study of the structure of austenite has been undertaken in order to characterize as best as possible the parent phase in the Fe-C system. Austenite is a solid solution of carbon atoms in fcc iron, the carbon atoms being located in interstitial positions. Of the two kinds of interstitial sites, octahedral (0, +, +) and tetrahedral (4, a, $), in this lattice, the larger octahedral sites are usually considered as the probable position of carbon. The strain energy involved in pytting a neutral carbon atom (covalent di; ameter 1.54)' into a tetrahedral site (diameter 0.56A) is considerably greater than that associated with p2tting carbon into the octahedral site (diameter 1.08A). Dayal and arkeen' observed the migration of carbon in iron under the influence of an electric field indicating tha tye carbon is ionized. pe ionic radius of C'4 is 0.15A and that of C" is 0.29. Consequently, it is conceivable that carbon ions could occupy the tetrahedral sites if one considers only the strain energy. Size considerations alone do not provide a complete explanation for the formation of the interstitial solid solutions, however. because metals such as copper, zinc, and cadmium do not appear to form interstitial solid solutions in spite of their large interstitial sites. Evidence which suggests partial ioni-zation of the carbon in austenite has also been obtained by Speiser, Spretnak, and alor who derived formu- lae relating the observed change in lattice parameter to the effective diameter of the solute atom. Assuming the carbon occupies the octahedral site. they computed the effective diameter of carbon to be 1.33A whereas the covalent diameter is 1.54A. petch5 concluded from powder X-ray diffraction experiments that carbon atoms occupy the octahedral sites. His conclusion was based on the general trend observed in the intensity of the diffraction lines as the carbon content of the austenite was increased. However, the major difficulty associated with application of X-ray diffraction to this particular problem is the relatively poor scattering power of carbon. Williamson and smallman' utilized X-ray diffraction to study the line broadening caused by the strain field about carbon atoms inferrite: these investigators concluded that at least 85 pct of the carbon in ferrite occupies the octahedral (0: 3, B) site rather than the larger

Jan 1, 1967

By L. K. Jetter, C. J. McHargue

The use of axis charts for representing the texture of cold-rolled thorium sheet was compared with conventional pole figures. Four texture components were deduced from the axis charts and shown to be consistent with the pole figures. It was shown that consideration of the pole figures alone could lead to an apparent component which is the average of two actually present. It was also shown that the spread about the "ideal" textures and the amount of material associated with each could be readily obtained Fom the axis chart method. BECAUSE of the crystallographic nature of the deformation mechanisms in metals, plastic flow results in the alignment of certain crystallographic directions with the primary flow directions. In the study of the "preferred orientation" thus developed, one wishes to discern the distribution of the crystallographic directions with respect to some reference direction, usually a direction related to the fabrication procedure, such as the rolling direction. The pole-figure method, introduced by ever,' involves the plotting of the distribution of the poles of some family of planes on a stereographic projection which places the reference direction(s) at the north pole and/or in the center. By noting the angles between the reference directions and concentrations of poles on several such pole figures, one can deduce the crystallographic directions which are aligned with the reference directions. If the preferred orientation is relatively simple and well-developed, one to three pole figures may be sufficient for obtaining the desired information; if there are several texture components, more pole figures may be needed. A significant improvement in the method of representing the textures in wires and rods resulted from the introduction of the "inverse pole figure" or axis-distribution chart by Harris.2 Such a chart gives directly the distribution of the reference axis relative to the standard stereographic projection. There has been widespread acceptance of this method for the representation of fiber textures, and methods have been proposed for converting observed diffraction intensities into axis densities.2-6 The suggestion by Mitchell and Rowland3 and Jetter, McHargue, and williams5 that sheet textures could be represented as distributions of rolling, normal, and transverse directions have been criticized on the basis that they offer no significant advantage over a combination of two ordinary pole figures and that it has not been proved that sheet textures can be treated as quasi fiber textures.6 If the purpose of a texture determination is to study some property which is related to the orientation of a particular crystallographic plane or direction, then conventional pole figures certainly are sufficient. For example, the distribution of the slip planes in face-centered cubic metals (the (111) pole figure) serves to indicate the variation in mechanical properties of sheet. On the other hand if the study is directed at an understanding of the factors influencing texture formation, it is desirable to know not only the preferred orientation but the kind and degree of spread from it and the relative amounts of material in each component, if there are more than one. Axis charts give this information as well as the orientation distributions. Consider the procedure for deducing a texture component from a pole figure for the (111) planes

Jan 1, 1961

By J. A. Singmaster

A REPORT that it did not pay to use present-day galvanized iron on account of the short life of the material, accompanied by proofs of the state-ment in the form of a tabulated history of the first costs of various kinds of building materials and their main-tenance expense, started an investigation of modern galvanized products. At the very outset it was apparent that our experience with galvanized products was by no means unique. Correspondence with the State Agricultural Depart-ments, the Agricultural Experiment Stations, the County Agents and State Granges all over the United States brought a mass of complaint on this same score. Visits to large buyers of galvanized sheet and wire revealed the same condition coupled with an ever-increasing use of substitutes for galvanized iron. We believe, therefore, that the title of this article is fully warranted by the experience of the consuming public. A study of the proceedings of the various societies having to do with the testing and use of sheet iron and steel products revealed a tremendous amount of work on the life of the base metal itself. Great stress was laid on differences in life of various types of iron and steel, the difference amounting at best to months rather than years. Very little recent attention has been paid to a study of the life of the zinc coating and the causes of its present-day lack of durability. There have been some real exposure studies published, how-ever, which show that the weight of the zinc coating determines the protection afforded by the galvanizing, which is of far greater influence on the life than the base-metal composition. An interesting paper was published by the Phillipine Journal of Science in 1916, entitled: "Galvanized Roofing in the Phillipines," a contribution from the Bureau of Science of the Phillipine Island Government. The author, Mr. Arguelles, found on 18 old galvanized sheets, after from 30 to 35 years' exposure, from 2.3 to 4.1 oz. of zinc per sq. ft. of sheet and sums up the study by saying: Of the various factors influencing the durability of galvanized iron which have been studied with a view towards accounting for the difference in behavior of old and modern sheet, it appears evident that the greater weight of zinc per unit of area on the former accounts for the greater durability.

Jan 10, 1922

By C. H. Li, R. D. Carnahan, R. J. Stokes, T. L. Johnston

When silver chloride deforms by pencil glide at temperatures of 26ºand 72°C, grain size has no effect upon the proportional limit and the material necks down to a knife edge under tension. At -196ºC, deformation takes place on fewer slip systems to produce straight slip traces, the flow stress becomes sensitive to grain size and fracture occurs by cleavage from an intergranular source without any reduction in area. THERE are significant differences between the appearance of the slip bands formed in silver chloride and in the alkali halides at room temperature. The bands in sodium chloride, e.g., are fine and geometrically straight, whereas in silver chloride they are coarse and wavy.' Such differences in the slip behavior prompted us to inquire what the effects of grain boundaries might be on the mechanical properties of these solids. As an introduction to a general study of ionic poly-crystal behavior, we have investigated the effect of grain size on the stress-strain relationships in silver chloride at different temperatures. We have chosen silver chloride chiefly because polycrystals can be easily prepared free from cracks and macroscopic voids by conventional techniques. Moreover, as we shall see, the slip behavior can be readily modified by changing the temperature. It will be shown that the effect of grain size on the yield stress of silver chloride is strikingly dependent upon the temperature of deformation and that this temperature effect comes about through a change in the number of slip systems which operate at the onset of plastic flow. EXPERIMENTAL PROCEDURES Polycrystalline tensile specimens were made by recrystallizing cold-rolled AgCl sheet. Thirty-gram quantities of AR grade silver chloride powder were melted in a low heat capacity furnace, cast into cylindrical forms 3/4 in. in dim and approximately 1 in. in length and then extruded with a 16:l reduction ratio into rods 3/16 in. in dim. Extrusion temperatures were varied from room temperature to 350°C. In order to impart various degrees of cold'work to the extruded rod. All extrusions were then cross rolled to sheet 0.040 in. in thickness at room temperature and machined to form tensile specimens having a gage length of 0.750 in. with a width of either 0.250 or 0.145 in.* Annealing was carried out in an air oven at 200°C for periods up to 20 hr. specimens having average grain diameters ranging from 0.024 to 0.40 mm were prepared by varying the extrusion temperature and annealing time in the conventional manner. To obtain specimens with grain sizes larger than 0.40mm, lightly deformed thin prisims of silver chloride single crystals (supplied by Harshaw Chemical Co.) were recrystallized. Grain size determinations were made by an intercept method and revealed that the grains were equi-axed. Laue back-reflection X-ray patterns showed little tendency to form a preferred orientation texture. Specimens which were to be used for the slip band studies were polished by immersion in fresh boiling concentrated NH,OH for 60 sec. They were then etch polished for 10 sec on each side by hand lapping on a stationary velveteen lap wetted with a dilute Hypo solution (5 g of Kodak Acid Fixer in 100 cc H20). Finally the specimens were rinsed in warm water and alcohol, blown dry and carefully mounted in the tensile machine for testing. Tensile tests were performed at three temperatures, namely, 26º, -72º, and -196°C. A screw-driven hard tensile machine was used at a constant strain rate of 0.006 in. per in. per min. Loads were determined with a light- proof ring fitted with A-18 strain gages and extensions were measured with a 0.0001 in. dial gage. Constant level baths of alcohol with dry ice and liquid nitrogen were used to maintain the two lower test temperatures. EXPERIMENTAL RESULTS Reproducibility—In view of the light sensitivity and reactive nature of silver chloride, it was necessary to determine whether reproducibility depended upon either exposure to light or to the condition of the surface. However, during the course of the work it became clear that variation of laboratory lighting

Jan 1, 1962

By C. F. Jackson

THE work of, the Mining Methods Committee is now well under way. Following discussions previous to and during the February meeting, an Outline for Papers on Mining Methods was prepared, and over a thousand copies have now been distributed to committee men, to section secretaries and to members who have indicated any interest in the subject. The objective of the committee is to prepare a symposium on mining methods which will be of real practical value to the operator and engineer in the solution of every-day mining problems. It is planned to cover the entire field of mining in such a way that the different branches of mining, such as coal and ore (iron, copper, lead, zinc and precious metal) can benefit from the experience of the others at points where they have problems in common.. It is realized fully that each of these branches of mining possesses its own peculiar problems, but at the same time, there are prob-lems in connection with each, where the experience in others should be of value. The committee proposes to proceed along the following lines: 1. To present a general classification of mining methods, showing their inter-relationship, and at the same time .provide a common language for the discussion of mining methods and a nomenclature that will have the same meaning wherever used. A com-plete set of illustrations will accompany the classi-fication to make clear the terminology adopted and to show graphically the inter-relationship of methods. 2. To show the relationship between the physical characteristic of the deposit, the economic consider-ations and the. mining method., It is not proposed to treat this subject as a mere academic problem, but to secure reports from every mining company of impor-tance in this country, which will show what methods or modifications and combinations of methods have actually been applied and the physical conditions and economic considerations which have led to the adoption of these methods in each case. The Mining Methods Committee has drawn up an Outline for Papers on Mining Methods to be distributed among mining engineers and operators, giving in detail the information desired. This outline is the result of several months of careful thought and is a composite of the suggestions of many engineers and mining company officials from all parts of the United States.

Jan 7, 1922

By Robert H. Hafner, Irvin R. Kramer

IN recent years considerable interest has been shown in surface-alloyed metals, particularly those of chromium (chromized steels), which have excellent corrosion [ ] resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high temperatures of 1200° to 1400°C. (2200° to 2550°°F,) caused excessive grain growth and warpage, Louenstein and Ulmer2 packed iron castings in ferrochromium and com- [ ] mon salt, and heated for approximately three hours at 930° to 1040°C. (1700° to 1900°F,). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900° to 1000°C., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a chromized layer, 0.004 in, thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1942

By S. E. Szasz, E. J. Moore, B. F. Whitney

An accurate value of formation water resistivity R, is essential in calculating formation porosity and fluid saturation from electrical well logs. In the cases where R, has not been measured directly, it must be obtained from other data, e.g., the SP curve. This paper deals with another approach: how to calculate R, from the chemical analysis of the formation water. INTRODUCTION It is known that the resistivity of aqueous solutions of pure salts depends on their concentration and on the temperature; the concentrations are given in MPL (mg of solute per liter of solution), or sometimes in ppm (mg of solute per kg of solution): MPL = ppm X specific gravity. Values for different pure salts are available in the literature, but not for solutions of mixtures which are of practical interest. The major component of the dissolved material in almost all formation waters being sodium chloride, it is customary to express the resistivity of formation waters in terms of equivalent sodium chloride concentration, i.e., the concentration of a solution of pure NaCl which has the same resistivity at a given temperature as that of the formation water under consideration. Thus, the problem of calculating R, from the chemical anaylsis can also be stated as how to convert the other constituents of the solute into equivalent NaCl concentration. Salts dissolved in water are at least partly dissociated into ions, and do not conserve their identity. If known amounts of several salts are dissolved in water, the solution does not necessarily contain the same salts in the original proportion, but perhaps some other combination of the ions, along with free ions in solution. This is why the chemical analysis of formation waters is often given in terms of ions, as if all dissolved salts were completely dissociated. Our problem then boils down to how to convert the concentrations of the various ions to equivalent concentrations of Na' and C1-. Dunlap and Hawthorne' have proposed to convert the concentration of all other ions to equivalent Na' and C1-concentrations by means of constant multipliers; e.g., 0.95 for Ca"; 2.0 for Mg"; 0.27 for HCO 3-; 0.5 for SO, -, etc. Their factors were based on measurements made at 68F on 26 formation water samples from the Texas Gulf Coast, ranging in concentration from 1,500 to 75,000 ppm. The Dunlap method is widely used in electric log interpretation, and is often extrapolated beyond its original concentration range. A comparison of R, values calculated by this method and values actually measured on formation water samples has shown large discrepancies, especially at higher concentrations. Therefore, two new methods were developed at Sinclair Oil Corp.'s Tulsa Research Center to calculate equivalent sodium chloride concentration from the chemical analysis of formation water samples. FUNDAMENTAL CONSIDERATIONS The resistivity of a solution, or its reciprocal the conductivity, at a given temperature is determined by the charge, concentration and mobility of the ions actually present. Monovalent ions such as Na' or C1- always carry the same charge. Compounds of polyvalent ions, however. may show incomplete dissociation, e.g., NaSO; + Na' instead of SO,-- + 2Na'. This happens especially in more concentrated solutions. Only very dilute solutions are completely dissociated, as assumed in the chemical analysis report. At higher concentration, the degree of dissociation depends not only on the nature and concentration of the particular salt under consideration but also on the nature and concentrations of the other solutes. Mobility of the ions depends on the viscosity of the solution. It also depends on the degree of hydration of the ions, which in turn is a function of the nature and the charge of the ions and also of the amount of free water available per ion, i.e., the total ionic concentration. The net effect is that the conductivity increases slower than proportional to the concentration, even if a solution contains only one salt such as NaC1, and is different for different salts (Fig. 1). Conductivity can even decline with a further increase in concentration, e.g., if additional salt is little dissociated but ties up some of the free water and/or causes an increase in viscosity. In solutions containing more than one salt, the contribution of one salt to the total conductivity depends not only on the fractional concentration of this same salt, but also on the concentration of all other solutes. A perfect method would give the conductivity or resistivity of a solution as a function of the concentrations of all solutes present. This is so complicated as to be impractical, and a simpler method must be found which is of acceptable accuracy. The Dunlap method, on the other hand. is too simple because it askmes that at any concentration the contrih-

Jan 1, 1967

By OWEN H. PERRY

One of man's primary tools is the ordinary screen. Whether of mesh or punched plate, it is fundamental in principle, primitive in its origin, and common in its application through all the world; and yet the screen goes only a part of the way toward the completion of its job of separating materials according to size. It will give a practical and continuous separation according to "size," as generally understood (accurate according to the breadth), but the accurate and continuous separation as to thickness is not a practical function of the screen. Still, all through history, the thickness of particles of material must have been important to many people; therefore, one would expect that some standard method of sizing for thickness would long since have been evolved and that equipment applying that method would be readily available to any in¬dustry. This, however, seems not to be so.

Jan 1, 1949

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

By D. F. Gibbons

THIS investigation was undertaken in order to gain further information on the mechanism of plastic deformation of iron at temperatures between room temperature and 77.2°K, and also to contribute to our understanding of the low temperature brittleness phenomenon that occurs in both the tensile and impact tests. It was decided to study as pure an iron as possible and to use the tensile test in order to simplify the problem as much as possible. Two series of iron were used throughout the investigation: iron A, obtained from the National Research Corp. and supplied as gas-free, high purity iron; and iron B, obtained from Fast' and produced by melting iron under purified hydrogen. Typical analyses of samples of both irons, after fabrication, are given in Table I. The main difference in composition of these irons is in their nickel and oxygen contents. Nickel has a very large solid solubility in iron. However, oxygen has an extremely small solid solubility. An attempt was made to reduce the oxygen content still further by remelting under purified hydrogen. This was successful in reducing the oxygen content to -0.0006 pct. However, no results on tests of this iron are included, since difficulty was encountered in fabricating the ingot. Wire specimens 1 mm in diameter were used for the investigation. The wires were produced from the ingots, as supplied, by cold rolling and swaging, with intermediate vacuum anneals at 700°C. Care was taken to reduce preferred orientation in the wires to a minimum by keeping the percentage of reduction in area between anneals of 30 to 40 pct. X-ray transmission photographs showed no indication of preferred orientation. The final grain size of iron A was 20 to 24 grains per linear mm and of iron B, 16 to 18 grains per linear mm. All specimens were tested in the decarburized and denitrided condition unless otherwise stated. The procedure was to pass hydrogen, saturated with water vapor at 26oC, over the specimens at 730°C for 2 hr. The specimens were quenched in iced water and then annealed in a vacuum of - 5x10-6 mm Hg for one day at 560°C to remove hydrogen. Higher temperatures were used for the vacuum anneal but this temperature was found to be quite satisfactory in removing hydrogen. The specimens were slow-cooled after the vacuum anneal. Where it is stated that the specimens were carburized, the specimens were given an identical decarburizing treatment and then carburized by passing hydrogen, saturated with pure n-heptane vapor at 0°C, over the specimens at 730°C. The specimens were then homogenized at 730°C for 2 hr in dry hydrogen. After the carburizing treatment the specimens were given the same vacuum anneal as for the decarburized specimens. The carbon content was determined from the maximum value of the internal friction carbon peak.2 Apparatus Fig. 1 shows a diagram of the tensile apparatus, with half the cooling coil removed. The cooling coil enabled temperatures from 200" to 77.2oK to be obtained. The apparatus was designed to fit a standard Tinius Olsen Universal tensile machine. The apparatus consisted of the rigid plate A which carried two carefully machined hooks H. These hooks attached the plate firmly to the moving crosshead of the tensile machine. The lower grip B was rigidly suspended from the plate A by three stainless steel rods. The upper grip C was joined to the upper grip of the tensile machine by the stainless steel rod E. The lower part of the apparatus was surrounded by a Dewar vessel, which was made a sliding fit inside the brass collar D. The specimen was held in a clamp which fitted into the grip, forming a ball and socket joint (see inset a). This was to attain as nearly pure

Jan 1, 1954

By C. C. Herrick

The vapor pressure of indium has been measured by the torque-effusion technique, as a function of temperature between 1102o and 1422oK. For liquid indium, the vapor pressure (in atmospheres) can be represented by the equation -R In P = 5.782 x104/T - 25.29from 1000o to 1422oK. Extrapolation yields a calculated normal boiling point of 2329°K and a heat of vaporization at 298 oK of 58.09 kcal per mole by the third-law method and of 58.39 kcal per mole by the second-law method. Calculations indicate that the free-energy functions of Hultgren are to be preferred to those of Guruich. BECAUSE of the potential uses of liquid metals, it is important that convenient experimental methods be developed which will lead to a sufficient body of thermodynamic data so that reasonable estimates of properties of liquid metals can be made. Indium is particularly well-suited to investigation, since it remains liquid over a long temperature interval, it alloys readily, suitable containers for it are easily procured, and relatively few investigations of its thermodynamic properties in the region above 1000°K have been made. PREVIOUS RESEARCH The first determination of the vapor pressure of indium was made by Anderson,' using the Knudsen method and silica-lines stainless-steel cells. Kohlmeyer and spandau2 determined the normal boiling point, and a mass-spectroscopic investigation has been made by Lyubimov and Lyubitov.3 (Unfortunately, only an equation representing the data of the latter investigators has been available to us.) Hultgren et al.4 and Gurvich5 have published discordant tables of the free-energy functions for indium. EXPERIMENTAL METHOD The torsion-effusion principle has been described amply in the literature.8,7 With this method, one observes the angular deflection induced by effusion of vapor from a multihole effusion cell which is suspended from a filament producing a small rotational restoring force. The pressure within the effusion cell can be computed from the relation ziaifiai where k is the torsion constant of the filament, 6 is the observed angular deflection, and ai, fi, and qi are the area, force factor, and moment arm of the ith effusion orifice. The force factor f is analogous to the Clausing factor,' and corrects for the reduction in effusive force attributable to the finite geometry of the effusion orifice. Schultz and Searcy' have tabulated the force factors for various tube geometries. EXPERIMENTAL APPARATUS The physical arrangement employed in this study is shown in Fig. 1. The furnace elements are six Globar heat rods with 15-in. hot zones. Temperature is maintained to * 1°K by a Beck mechanism driving two 26-amp Powerstats in parallel. A Pt (Pt, Rh 10 pct) thermocouple serves as the sensing element. Four inner tubes act as vibration isolators; the air pressure required for maximum isolation was determined empirically, and is maintained by a solenoid valve. The tungsten fiber, 9 by 0.002 in., is joined to an 0.008-in. tungsten wire or graphite rod via a machined lightweight chuck.

Jan 1, 1964

IN speaking, on the subject, "Engineer-Citizens," at the Lehigh Valley Mineral Industries Conference dinner, on April 26, at Easton, Pa., George Otis Smith, Director of the United States Geological Survey and President of the American Institute of Mining and Metallurgical Engineers, said in part: "It would be carrying coke to Connellsville to bring to the Lehigh Valley the idea that mineral resources are the foundation of national prosperity. Unfortu-nately, however, this obvious, fact is not everywhere recognized. Too many of our economists, journalists, statesmen and other dopesters of present business con-ditions stress the human factor so strongly that they overlook the material with which men work out their destiny. To them the financial psychology of Wall Street and the political logic of Capitol Hill and the business commonplaces of Main Street all loom far larger than the geology of the Lehigh Valley or the engineering triumphs of Bethlehem, or, the creative thinking at Lehigh and Lafayette. "The present situation in the industrial and .business world is a complex of interacting causes and reacting effects not easily itemized and entered on our trial balance sheet. But, chief among the liabilities of today is the excess of production capacity in most branches of industry. The farmer has no. monopoly in his desire for relief. Whether your professional connections are with steel or cement, coal or oil, copper, or zinc, you; know too well that for, the moment America is over-engined, and you keenly realize the ever-present hazard of industry speeding up regardless of the curves or grades just around the corner.

Jan 5, 1928

By Robert C. Stephenson

Large deposits of titaniferous magnetite occur associated with anorthosite and gabbro in the Lake Sanford area, Essex County, New York. The ore, gabbro, and anortbosite show consanguineous relations. Anorthosite grades through gabbroic anortbosite into gabbro but is locally intruded by gabbro. Structural and petrographic evidence suggests that gabbro was differentiated from anorthosite by filter pressing. Field and laboratory study of ore occurrences indicates that an ore residuum concentrated in the gabbro through magmatic segregation' by normal crystallization and flowage. Ore occurs as bands which grade into gabbro, and also as large masses which replace anorthosite. Ore in the gabbro is finer grained and richer in ilmenite than ore in anorthosite. Introduction The Lake Sanford area lies in the heart of the Adirondack Mountains, in the southeast portion of the Santanoni Quadrangle (Fig. I), and there are four ore bodies in the area immediately surrounding Lake Sanford. The area lies 30 miles by highway from the railroad at North Creek. The deposits were discovered in 1826, and from then until 1858 iron was produced in small quantities. They were idle from 1858 to 1906. Between 1906 and 1913, extensive development work was carried on. These early attempts to produce iron ore were thwarted by transportation difficulties and by the titanium content of the ore, which, ironically, has been the element responsible for the present development. In 1941 the National Lead Co., Titanium Division, developed the Sanford Hill ore body and is now producing ilmenite and magnetite concentrates.18 The Defense Plant Corporation is extending the railroad to the property from North Creek and is building a sintering plant to treat the magnetite concentrate. Investigations OF the Deposits* Early studies of the Lake Sanford titaniferous magnetite deposits were made by Emmons in 1842,l2 by Kemp, in 1897-98'0 and by Newland in 1908.22 Singewald26 and Osborne23 considered these deposits along with numerous other titaniferous magnetite deposits in 1913 and 1928, respectively. None of these reports entailed a detailed study of the ore occurrence in this area. The present study was begun in 1940. Seven months were spent in the field, and considerable time was spent in labora-

Jan 1, 1949

By Robert C. Stephenson

Large deposits of titaniferous magnetite occur associated with anorthosite and gabbro in the Lake Sanford area, Essex County, New York. The ore, gabbro, and anortbosite show consanguineous relations. Anorthosite grades through gabbroic anortbosite into gabbro but is locally intruded by gabbro. Structural and petrographic evidence suggests that gabbro was differentiated from anorthosite by filter pressing. Field and laboratory study of ore occurrences indicates that an ore residuum concentrated in the gabbro through magmatic segregation' by normal crystallization and flowage. Ore occurs as bands which grade into gabbro, and also as large masses which replace anorthosite. Ore in the gabbro is finer grained and richer in ilmenite than ore in anorthosite. Introduction The Lake Sanford area lies in the heart of the Adirondack Mountains, in the southeast portion of the Santanoni Quadrangle (Fig. I), and there are four ore bodies in the area immediately surrounding Lake Sanford. The area lies 30 miles by highway from the railroad at North Creek. The deposits were discovered in 1826, and from then until 1858 iron was produced in small quantities. They were idle from 1858 to 1906. Between 1906 and 1913, extensive development work was carried on. These early attempts to produce iron ore were thwarted by transportation difficulties and by the titanium content of the ore, which, ironically, has been the element responsible for the present development. In 1941 the National Lead Co., Titanium Division, developed the Sanford Hill ore body and is now producing ilmenite and magnetite concentrates.18 The Defense Plant Corporation is extending the railroad to the property from North Creek and is building a sintering plant to treat the magnetite concentrate. Investigations OF the Deposits* Early studies of the Lake Sanford titaniferous magnetite deposits were made by Emmons in 1842,l2 by Kemp, in 1897-98'0 and by Newland in 1908.22 Singewald26 and Osborne23 considered these deposits along with numerous other titaniferous magnetite deposits in 1913 and 1928, respectively. None of these reports entailed a detailed study of the ore occurrence in this area. The present study was begun in 1940. Seven months were spent in the field, and considerable time was spent in labora-

Jan 1, 1949

By G. A. Beske, P. Hilsch, J. Wulff

The effects of the growth precipitates on the su-perconduching properties of an Al- 15 al. pel Zu alloy have been studied using magneization, transition lem-perature, and residual resistivity measurements. Aging at 230C for 1/2 to 11 he produces an increase in Hfp, Ike field of first penetration, and tut increase in trapped flux. The upper critical field, Hc2 remains constant for such aging tunes. Aging at 200°C produces a decrease in Hfp and an increase in trapped flux. The transition temperature remains constant at Tc - 1.227° ± 0.02°K for aging at 220°C for tims of from 1/2 to 10 hr, and for aging at 200°C it remains constant at Tc. = 1.18° i 0.02°K for times from 1/2 hv to 26 hr. The observed behavior indicates that the superconducting matrix when aged at 220°C behaves tike a type U su-perconducior, but when aged at 200°C behares like a type I superconductor. The magnetization changes after aging can be attributed to the growth and clutnge in distribution of the precipitate in a matrix of fixed composition. IT has been realized for some time that the superconducting properties of alloys are highly structure-sensitive. This is evident in the work of Mould and Mapother1 who examined the properties of an aluminum alloy. Precipitation effects have also been briefly mentioned in other studies.2-4 Bonnin and coworkers5 have observed a sharp inc rease in trapped flux in an A1-Mg alloy when the residual resistivity reaches a value that indicates it is a type II superconductor. Recently Blanc, Goodman, and Nemoz5p have reported on precipitation effects in A1-Ag alloys. Detailed studies of precipitation in Pb-Sn and Pb-Cd alloys made by Livingston6 serve to show that the upper critical fields are enhanced by quenched-in solute. Furthermore. at various stages in the precipitation process? the upper critical field is determined largely by the remanent solute. The observed magnetic hysteresis and trapped flux in such alloys result from the interaction between precipitate and the flux filaments in the mixed state. The flux trapping appears to depend largely on the precipitate distribution and is greater if the superconductor is type II than if it is type I. To examine the effect of precipitation in another alloy system, particularly one in which the composition of the superconducting phase does not change significantly during the course of precipitation, the Al-Zn system seems interesting, especially in view of the transition temperature and resistivity studies of Chiou and seraphim.' Furthermore, the recent detailed electron-microscope studies of an Al-Zn alloy by Richards and Garwood8 provide a guide for relating superconducting properties to changes in structure. For these reasons, magnetization, transition temperature, and residual resistivity measurements for varying times of heat treatment at two temperatures were made with a -15 at. pct Al-Zn alloy. The results are reported in this paper. I) EXPERIMENTAL The alloy used was prepared by Cominco Products Inc. from 99.9999 A1 and 99.999 Zn. It was chill-cast, swaged, and drawn to 0.125-in.-diam rod. The analyzed composition was 15.6 at. pct Zn (31.1 wt pct). A jeweler's saw was used to cut the 0.125-in.-diam rod into the 0.875-in. lengths needed for magnetization measurements. The ends of the cylinders were slightly beveled to remove the sharp edges. A portion of the original 0.125-in.-diam rod was drawn into 0.010-in.-diam wire and used for transition temperature measurements. Specimens were suspended from wires within a vertical furnace during heat treatment. All were homogenized at 500°C for a minimum of 3 days and subsequently solutionized for times in excess of 6 hr. The solutionizing temperature was held constant to +3°C. Individual specimens were homogenized, quenched, and aged several times and no effects indicating loss of zinc were noted. The suspended specimens were quenched by cutting the wires and allowing the specimens to fall into a silicone oil bath held at the aging temperature. They were then isothermally transforked by aging in the same bath used for quenching. After aging for the required time (approximately 10 min aging was necessary before the upper critical field reached a fixed value), they were briefly (1 to 2 sec) dipped into an acetone bath at room temperature to remove adherent oil and then immediately transferred to liquid nitrogen where they remained until inserted into the helium bath (usually within an hour). The temperature of the aging bath was held constant to +3°C for longer aging times. The cryostat used for the measurement of superconducting properties consisted of outer and inner dewars for liquid nitrogen and liquid helium, Stokes 6-in. booster diffusion pump and Stokes Model 212 mechanical pump, temperature controller to measure and control the temperature of the helium bath, and a superconducting solenoid with inserted search coils to provide the magnetic field and measure the magnetic moment of the specimens. A schematic diagram of the cryostat is shown in Fig. 1. An ultimate temperature of 0.85°K was reached with this apparatus. The temperature controller used is similar to the one described by Blake and chase.' A 0.5 pct Allen-Bradley carbon resistor and a nichronle heater (200

Jan 1, 1968