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By A. J. Sedriks

ALTHOUGH the occurrence of a readily visible tarnish on the stress-corrosion fracture surfaces of titanium alloys tested in oxygenated nitrogen tetrox-ide solutions has been reported,' the possibility that the formation of this tarnish is a requirement for cracking to proceed does not appear to have been considered. It has been proposed that failure occurs in this system as a result of some electrochemical-mechanical process.2 However, recent studies3-6 of the stress-corrosion cracking of a brass in certain ammoniacal solutions, which also cause visible tarnishing, have led to the view that failure occurs by the repeated formation and fracture of a brittle surface film of cuprous oxide. The purpose of this note is to point out the similarities which exist between the tarnish which forms on a brass and that found on titanium alloys failed in nitrogen tetroxide, and to suggest, by analogy, that a similar tarnish-rupture mechanism may be operative in the latter case. The titanium alloy selected for the present study contained 5.2 pct Al, 2.5 pct Sn, 0.025 pct C, 0.16 pct Fe, 0.014 pct N, 0.012 pct H, 0.07 pct 0, and 0.002 pct Mn by weight. Vacuum-annealed alloy strips measuring 4 by 0.25 by 0.04 in. were used to prepare self-stressed test specimens. Each specimen was made from two strips by bending the end portions and spot welding them together to produce curved sections of uniform bending stress. (The exact details of preparing such specimens have been described by Lisagor el al.7) The curvature in the strips determines the ma-magnitude of the outer fiber stress, which in the present specimens was 100,000 psi (yield stress = 120,000 psi). The specimen surface in the spot-welded end regions was shot-peened to induce compressive stresses and thereby eliminate the possibility of stress-corrosion cracking in these regions. The test environment was nitrogen tetroxide, initially containing 99.5 pct N2O4, 0.1 pct H2O, and 0.08 pct C1, through which oxygen had been bubbled for 30 min. During testing the tetroxide was subject to an oxygen pressure of 250 psi. The duration of the test was 96 hr, and during this time stress-corrosion cracks propagated through some 50 pct of the thickness of the specimens. After testing, the tarnish was liberated from the fracture surface by immersion in a methanol-5 pct bromine solution, and then examined by electron dif- fraction and transmission electron microscopy using a JEM-7 electron microscope. The possibility that the bromine solution had affected the structure of the tarnish was investigated by an "in silu" examination of the stress-corrosion fracture surface using a reflection electron diffraction attachment designed for handling bulk specimens. Typical areas of the tarnish liberated by the me-thanol-bromine solution are shown in Fig. 1. Fig. l(a) reveals that the tarnish consists of individual platelets, and from Fig. l(b) it can be seen that the platelets are joined together to form a semicontinuous film, the boundaries of the titanium substrate grains being retained in the tarnish. Electron-diffraction patterns taken from these areas exhibited diffraction spots typical of a monocrystal. The diffraction pattern shown in Fig. 2 was taken from the central area in Fig. l(n). Monocrystal patterns obtained from areas containing numerous individual platelets can only be explained by assuming that their growth is governed by the titanium substrate (i.e., their growth is epitaxial). In other areas, the tarnish had folded over or became mechanically damaged, and these areas gave diffraction patterns consisting of "spotted" rings, enabling interplanar spacings of the tarnish lattice to be determined. These spacings, measured using a

Jan 1, 1968

[Separates of all the Technical Publications published in 1928 are available at Institute headquarters. All the papers are on file in public, university and technical libraries, and when so indicated in the list, may be found either in the TRANSACTIONS or in the special volumes issued by the Institute.; METAL MINING TECH- NICAL TRANS. PUBLI- TITLE AUTHOR MEETING VOLUME CATION AND PAGE* No. 50 The Eötvös Torsion Balance D. C. Barton New York Method of Mapping Geologic Feb., 1928 Structure 52 A Cartographic Correction for the C. A. Heiland New York Eötvös Torsion Balance Feb., 1928 61 Liquid-oxygen Blasting at Chuqui- H. C. Schultz, New York camata, Chile F. K. Middleton Hunter Feb., 1928 76, 108, 123 64 Working Methods of Practical Geo- Hans Haalck New York physics Feb., 1928 65 Experiments with Eötvös Torsion P. W. George New York Balance in the Tri-State Zinc and Feb., 1928 Lead District 74 Gravity Surveying in Great Britain H. Shaw New York Feb., 1928 75 The Computation of Eötvös Gravity E. Lancaster-Jones New York Effects Feb., 1928 82 Earth-resistivity Measurements in W. O. Hotchkiss, New York the Lake Superior Copper Country W. J. Rooney, Feb., 1928 James Fisher 83 Mining Methods and Records at the Roy W. Moore New York 76, 56, 90 United Eastern Mine Feb., 1928 98 Recent Results in Electrical Pros- Hans Lundberg New York specting for Ore Feb., 1928 101 Relation between the Oxygen Bal- G. St. J. Perrott, New York ance and Propulsive Strength of N. A. Tolch, Feb., 1928 Eight Gelatin Dynamites J. E. Crawshaw 102 Effect of Oxygen Balance of Gelatin G. W. Jones, New York Dynamites on the Gaseous Prod- G. St. J. Perrott Feb., 1928 ucts of Detonation 108 The Financial Report of a Min- Henry B. Fernald New York ing Company-Its Content and Feb., 1928 Meaning 116 What Duty to Support the Surface R. G. Bosworth New York Does a Subsurface Owner Owe? Feb., 1927 136 Comparison of Branch Raise and C. A. Mitke Los Angeles 76, 93, 103 Combined Shrinkage and Caving Sept., 1928 Methods 141 A Mining Company Balance Sheet G. F. Wolff New York Feb., 1928

Jan 1, 1927

By D. R. Spink

In the preparation of zirconium and hafnium metals, there are many indications that impurity levels control the physical and chemical properties of the metal. The purpose of this work was to develop methods of producing pure raw materials that could be reduced to highly pure metals. Early work by the Carbomcndum Metals Co. and others indicated that certain fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. We have developed workable fused salts along with a continuous and higly efficient scrubber design which can be used to produce very pure zirconium tetrachloride. Metal made from the purified tetrachloride has been shown to approach crystal bar metal in purity. Scrubber designs are discussed with recommended materials of construction. VARIOUS methods have been used to purify zirconium (and hafnium) tetrachloride. Most of these methods involve thermal degassing initially (the removal of more volatile compounds at temperatures below that where zirconium tetrachloride exhibits a significant vapor pressure) followed by a sublimation step (which conveniently leaves the nonvolatiles behind.) While these procedures effect definite purification, such processing is batchwise and does not result in optimum purification. Early work by The Carborundum Metals Co. and others indicated that fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. The objective of this work was to develop a continuous fused-salt scrubbing process that would yield high-purity zirconium and hafnium tetrachlorides. The term "fused salt" refers to the molten state of ionic compounds and as used here, specifically refers to alkali metal and alkaline earth halides. Fused salts, because of their many valuable properties, are becoming increasingly im- portant industrially. These valuable properties of the fused salts are: 1) stability at elevated temperatures; 2)low vapor pressure; 3) low viscosity; 4) ability to dissolve many different materials; and 5) good elctctrical conductivity. All but the last property enhances the use of fused salts as scrubbing agents for zirconium and hafnium tetrachlorides. Fused-salt scrubbing may be defined for our purpose as the intimate contact between a gaseous compound and a molten salt with the purpose of removing impurities from the gaseous compound. In this case, the gaseous compound is zirconium tetrachloride which submlimes at 331°C. When this gas is contacted with a molten salt, impurities such as aluminum, iron, and titanium are removed and the resulting product is considered fused-salt scrubbed. Zirconium and hafnium are sold to a purity specification. Generally speaking, normal production without scrubbing is capable of meeting specifications. There are, however, several considerations That make the knowledge of methods of additional purification highly desirable. These are: 1) the control of product analysis; 2) the production of a pure product for special applications; 3) the salvaging of off-specification material; and 4) the use of raw materials with higher impurity levels than 1 he present raw materials. You will note that items 1 and 2 are somewhat complementary to each other and that item 4 assumes that The present process has impurity removal limitations. To better understand the part that fused-salt scrubbing of zirconium tetrachloride plays in the manufacture of zirconium, Fig. 1 contains an illustrated flow sheet of the industrial production of zirconium metal. In referring to Fig. 1, we can point out the specific benefits derived from our ability to purify zirconium tetrachloride. Purification of the crude (hafnium-containing) zirconium

Jan 1, 1962

By J. D. A. Morrow

This discussion relates to the distribution of coal under the di , of the U. S. Fuel Administration beginning Apr. 1, 1918. At t' L a definite method of controlling and directing distribution was put int effect. Prior thereto, although some of the machinery utilized was in operation, especially in the few weeks immediately preceding' Apr. 1, distribution had not been effectively and comprehensively organized. The writer was called to the Fuel Administration by Dr. Garfield about the first of February, 1918, to assume general direction of the distribution of coal for the Fuel Administration, to develop the general plans, and to obtain practical men to assist in this work and in carrying through the program finally devised. A study of the situation and conferences with the Fuel Administrator and leading men in the business made it plain that it would be necessary to begin at the bottom, measure the undertaking, develop plans to meet the need thus shown, and build an organization to effect the distribution required. This work had to be done under war pressure in the midst of a bad coal shortage. The successful performance of such a task is always primarily a matter of putting competent men in the right places and giving them the power and opportunity to function properly together. In the Distribution Division of the U. S. Fuel Administration, the men who were chiefly responsible for whipping plans into practical form and then for carrying out these plans were A. W. Calloway, of Baltimore, President of the Davis Coal & Coke Co., who served as the Director of Bituminous Coal Distribution; S. Lovell Yerkes, of Birmingham, Alabama, Secretary of the Grider Coal Sales Agency, who assumed general charge of distribution while the new plans and organization were being perfected and then became the Assistant Director of Bituminous Coal Distribution; Warren S. Blauvelt, of Detroit, who was Director of Coke Distri. bution; A. S. Learoyd of New York, Director of Anthracite Distribution, in connection with the Anthracite Committee, consisting of Joseph P. Dickson, President of Dickson & Eddy, Chairman; S. D. Warriner, President of the Lehigh Coal & Navigation Co., and W. H. Richards,

Jan 1, 1920

By Charles L. Harness

STRONTIUM is an essential constituent of celestite (strontium sulphate), of the rarer strontianite (strontium carbonate), and of a few very rare minerals. Celestite is the chief ore but strontianite is more valued except for making the purest strontium salts, because of its ease of processing. The public knows strontium mainly as the source of the red flame in fireworks but it has many other uses. PROPERTIES The celestite of commerce is a massive mineral of varying texture: coarsely crystalline, fibrous, bladed, very fine grained or earthy. The color varies greatly with the nature of the impurities but the purer specimens are light blue (Latin, caelum, sky) or white. The strontianite of commerce is a massive mineral, more or less coarsely crystalline. The color varies with the impurities. Distinctive characteristics are effervescence with acids, density (3.68 to 3.71), and crimson strontium flame. A typical British celestite before World War II analyzed: SrSO4, 96.55 pct; SrCO3, 0.17; BaSO4, 0.25; CaSO4, 0.54; MgCO3, 0.15; R20,, 0.90; Si02, 1.38.10 A German strontianite analyzed: SrCO3, 90.9 pct; CaCO3, 7.5; BaCO3, 0.1; Fe2O3, 0.05; A1203, 0.1; SiO2, 0.04; S, 0.1; P, 0.005.10 ORIGIN AND MODE OF OCCURRENCE According to Clarke,9 strontia forms about 0.02 pct of the crust of the earth and is present in most igneous rocks, but in smaller quantities than barium. Under certain conditions, large masses of celestite are deposited from sea water with anhydrite. The presence of large amounts of celestite in some saline deposits and its absence in others suggests that the deposition of celestite depends on whether certain as yet undetermined concentrations of sulphate and chloride ions are reached in the brines. The most extensive of these sedimentary deposits are those of the Keuper (Triassic) in England, of the Zechstein (Permian) in Germany, and of various Cretaceous formations in Texas, Arkansas, and Utah. Of the deposits of southeastern California and western Arizona,

Jan 1, 1949

By Thomas L. Kesler

IF all of the 14 million tons of kaolin produced in Georgia through 1949 had been mined from a single deposit 20 ft thick, it would represent a mined-out area of less than 1 sq mile. This measure of depletion is in such strong contrast with the large size of the area shown in Fig. 1, from which most of the output has come, that there has developed an optimistic outlook concerning future supplies of kaolin equal in grade to that already mined. Dozens of mines are widely but not evenly distributed within this area, which consists mostly of parts of Twiggs, Wilkinson, and Washington counties. There are scarcely half a dozen kaolin mines elsewhere in the state that have been appreciably productive, although the areas in which they occur may have good possibilities. Most of the efforts to find new deposits, therefore, will be confined to the area shown in Fig. 1, for it is here that the industry has established its facilities, and prospecting is encouraged by relatively numerous outcrops and opened deposits of kaolin.

Jan 10, 1951

By Jean Howard

RECENT attempts to produce secondary recrystalli-zation in high-purity iron have given conflicting results. Coulomb and Lacombe1'2 did not find it but Dunn and Walter3,4 did. The latter workers have stated that (100) [001] and/or (110) [001] orientations develop depending on the oxygen content of the annealing atmosphere. This Technical Note records results which are in agreement with Dunn and Walter in so far as it shows that secondary recrystallization can be produced in high-purity iron, but does not confirm that both types of orientation are obtainable. Similar observations have been made on chromium-iron and molybdenum-iron, although when this technique is used on 3 1/4 pct Si-Fe, both types are obtained as in the work of Dunn and alter.' Pure iron strip was cold-rolled from sintered compacts prepared from Carbonyl Iron Powder-Grade MCP of the International Nickel Co. (Mond) Ltd. The powder contains about 0.5 pct 0, 0.01 pct C, 0.004 pct N, (0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni—that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The iron powder was (a) pressed at 25 tons per sq in. into blocks measuring 3 by 1 by 0.3 in., (b) deoxidized in hydrogen (dewpoint -60°C) by heating first at 350°C and then at 600° C until the dewpoint returned to -60°C at each temperature and (c) sintered in hydrogen (dewpoint -40°C) at 1350°C for 24 hr. (when dewpoint is referred to in this Note, it is the value as measured on the exit side of the furnace). The sintered compacts were cold-rolled to 1/8 in., annealed in hydrogen (dewpoint -60°C) at 1050°C for 12 hr and cold-rolled to 0.004, 0.002, and 0.001 in. with inter-anneals at 900°C for 5 hr and a final reduction of 50 pct. Final annealing of strip between alumina or silica plates at 875" to 900°C in hydrogen with dewpoints of -20°, -55" and -80°C produced secondary grains with the (100) in the rolling plane; the extent of secondary recrystallization was greatest when the dewpoint was -55°C. Annealing in a vacuum of 2 x 10"5 mm Hg at the same temperature produced no secondary recrystallization at all. With strip thicker than 0.002 in. very few secondary crystals developed whatever the conditions of annealing. Using a processing schedule somewhat similar to that described above, secondary recrystallization was produced in two bcc alloys of iron, viz. 80 pct Fe + 20 pct Cr and 96 pct Fe + 4 pct Mo. The former was reduced to final thicknesses of 0.001 to 0.004 in. and the latter to final thicknesses of 0.001 to 0.016 in. With the chromium-iron, a final anneal at 1250°C (found to be the most effective temperature for developing secondary crystals in the 0.004-in material) with a dewpoint of -25°C produced a greater degree of secondary recrystallization than with dewpoints of -50°C or -20°C. Secondary crystals developed in strips of all thicknesses from 0.001 to 0.004 in. Final annealing in vacuum produced no secondary crystals at all. For the molybdenum-iron a temperature of 1200°C was most effective. It was found that a dewpoint of -50°C during the final anneal gave better results than a dewpoint of -25 "C on the 0.008 in. material. Final annealing in vacuum gave slightly worse results than annealing in hydrogen with a dew-point of -50°C. Secondary crystals were developed in strips of all thicknesses up to 0.008 in. The experiments show that the extent of secondary recrystallization is a maximum for certain critical values of oxygen content of furnace atmosphere and annealing temperature, and that these values are different for different alloys. The thinner the material, the less critical these values are. The general conclusions are that secondary recrystallization can be obtained in high-purity iron, chromium-iron, and molybdenum-iron, using a processing schedule similar to that which will cause the phenomenon to take place in high purity 3 1/4 pct Si-Fe. Unlike the silicon-iron, however, only the (100) (0011-- orientation has been produced in these alloys, irrespective of the temperature of final annealing and the oxygen content of the furnace atmosphere. The information used in this Note is published by permission of the Engineer-in-Chief of the British Post Office.

Jan 1, 1962

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By W. B. Gogarty

With the use of polymer solutions in secondary recovery operations, the need has developed to understand the mobility control mechanism. This study investigated mobility control by considering both permeability and rheological effects. Experiments used a high molecular weight, partially hydrolyzed polyacrylamide polymer. Flow studies took place in reservoir and Berea cores having zero oil saturation. Effective size of the polymer flow unit was inferred from Nuclepore filter tests. Clay studies indicated the particle size capable of decreasing the core permeability. Flushed permeabilities measured the approximate core permeabilities with flowing polymer solutions. These permeabilities were considerably lower than original values. With mobility data and the flushed permeability, maximum effective viscosities were determined for polymer solution flow in a core. Effective viscosities showed that rheological properties play an important part in mobility control with polymer solutions. The study showed that permeabilities decrease and stabilize with polymer flow. At the lower permeabilities, high shear rates exist in the cores. Because of the pseudoplastic character of the polymer solution, the high shear rates caused low effective viscosities. This condition pointed to the inefficient use of the potentially high viscosity of the polymer solution at low shear rates. INTRODUCTION In the oil industry, a great deal of interest is being shown in the use of polymer solutions for secondary recovery and a number of polymer floods are being performed in the United States.1 Some of these floods have become commercial while others have been reported as failures. A number of floods are still in progress and remain to be evaluated. With the advent of polymer flooding, the need developed to understand the mobility control mechanism in porous media. Rheologically, the polymer solutions behave as pseudoplastic fluids. Investigators have studied the rheology for this type of non-Newtonian fluid in porous media?-6 Results have also been reported on the ability of polymer solutions to decrease mobility.7-10 Some investigators indicated that polymer solutions show a different rheological behavior in cores than on the viscometer.7,8 This study is representative of an initiatory investigation on mobility control with polymer solutions. Some effects are considered on a qualitative basis. Mobility control is considered from the standpoint of both permeability and rheology and, to the extent possible, permeability and rheological effects are considered separately. Results show that mobility control occurs from a reduced permeability caused by polymer retention and an effective viscosity determined by the average shear rate in the core. In this respect, rheological behavior is as important in mobility control as permeability. PROCEDURES A high molecular weight, partially hydrolyzed, polyacrylamide polymer was used in the investigation. Solutions of various concentrations were made with this polymer in different types of water. Some solutions used distilled water and others used tap water. The tap water contained approximately 500 ppm dissolved solids. As used in this paper, concentrations in ppm refer to parts by weight solute to one million parts by weight of solvent. In the tap water, calcium and magnesium accounted for from 60 to 80 ppm of the solids, the remainder being mostly sodium chloride. All solutions contained a bactericide, and anti-oxidants and antiprecipitants were added to the tap water. Capillary and concentric-cylinder* viscometers determined the rheological properties of solutions. The capillary viscometer is described elsewhere.6 Berea and reservoir sandstone were used as core materials for this investigation. Cores were 1 in. in diameter by approximately 2 to 3 in. long. Prior to mounting, the Berea cores were heat-treated for 3 hours at 850F. This treatment decreased the water-sensitivity of the clays in the cores. The reservoir cores were cleaned with solvent and

By W. O. Philbrook, K. M. Goldman, G. Derge

THIS is the third in a series of papers from the Metals Research Laboratory dealing with the transfer of sulphur across the iron-slag interface in a carbon-saturated system. The first paper' showed that the transfer obeyed first-order kinetics. The second' presented detailed evidence in support of the three-stage mechanism: FeS(Fe) FeS(slag) FeS(slag) + CaO(sing) ? CaS(slag) + FeO(slag) FeO(slag) + C ? Fe + CO. This emphasized the role of an iron-sulphur complex as the transfer agent across the interface and as an essential intermediate in the overall process. The present paper shows the influence on the process of the individual elements, carbon, silicon, manganese, and phosphorus, the alloying elements normally present and of interest in commercial blast furnace operations, aluminum, which has a pronounced accelerating influence, and nickel and copper, which are common minor impurities in the raw materials. The experimental methods and procedures for interpretation of data are the same as described earlier.1,2 Induction heated, graphite crucibles were used, and sulphur-free slag was added to the molten iron containing sulphur and the selected alloy. Slag samples were taken at regular time intervals and analyzed for sulphur and other components of interest. The authors wish to state specifically that these experiments were not intended to simulate industrial blast furnace operations. However, they do represent a study of the kinetics and mechanism of sulphur transfer at the slag-metal interface under specified laboratory control of the major variables in the system. It is believed that the results can be usefully applied to the blast furnace if consideration is given to the differences which are known to exist between the two conditions. A rigorous evaluation of the accuracy of rate studies is difficult. Recognized sources of error include sampling and analysis of both slag and metal, temperature measurement and control, selection of zero time, composition of the gaseous atmosphere over the reaction system, and extraneous sources of sulphur from the graphite crucible and reagent materials. In this study carefully standardized procedures were followed consistently in order to minimize the errors. It is believed that the reproducibil-ity of duplicate runs indicates that errors have been rendered negligible relative to the observed effects from intentional variables. For example, original experimental points for duplicate runs are shown in Figs. 1, 2, 7, etc. In most cases in this paper the drawn curves represent an average of at least two heats. The spread in sulphur values at a given time ranges from 0.02 to 0.08 pct, which is a small frac-tioi of the total values ranging up to 2 pct S in slag. In the systematic study of the influence of alloy additions, each element was added over a range of concentrations. The two slags used in this study were designated as "acid" or 1530 and "basic" or 1545. They had the nominal compositions given in Table I. Rates were measured in the temperature range 1500" to 1650°C. Data will now be presented to illustrate the various features of the study. Silicon The first alloying element examined was silicon, because its presence is unavoidable in any silicate slag system through the reaction y/2SiO2(slag) + xM?y/2Si(liq.Fe) + MxOy where M is any reducing agent such as iron or carbon. It is known that the attainment of equilibrium by this reaction is extremely slow and probably not reached in the blast furnace." The influence of silicon on the final stages of the sulphur reaction has also been studied.' It has been shown5 hat silicon increases the activity of sulphur in iron. For such reasons silicon may also be expected to influence the kinetics of the reaction. The observed effects will now be described. The general procedure was to melt 530 grams of ingot iron in a graphite crucible, 3 in. OD, 2 1/4 in.

Jan 1, 1955

By D. Y. F. Lai, R. J. Borg

Tracer diffusion of Fe59 has been measured in the a-stabilized Fe-1.8 at. pet V alloy from 700° to 1500°C. The activation energies are obtained in both the presence and absence of magnetic order. Furthermore, it is established that diffusion in the alloy is identical to that in pure iron and consequently the values of Do and Q accurately represent the temperature dependence for self-diffusion. The purpose of this investigation is to obtain an accurate estimate of the temperature dependence for self-diffusion in bee iron in both the presence and absence of magnetic order, and, in so doing, to establish the temperature range of the magnetic effect.&apos;" As the temperature interval suitable for diffusion measurements is severely limited in both bee phases of pure iron because of the intervening fee ? phase, the experiments were performed on an a-stabilized alloy containing 1.8 at. pet V. This alloy is bee over the entire range from room temperature to the melting point. Although there have been several independent investigations of self-diffusion of iron in a, iron,1, 3-6 there still exists considerable disagreement regarding the values of Do and Q for the paramagnetic region. The two systematic studies of diffusion in 6 iron6, 7 previously reported are also only in fair agreement; but in view of the extremely small temperature range available for diffusion studies, i.e., 1390o to 1535oC, this is not surprising. It is comparatively easy to obtain accurate values of Do and Q for the a-stabilized alloy inasmuch as measurements can be made over the entire temperature range -700o to 1500°C. However, in order to assume that these same values apply to pure iron requires careful comparison of the data in the a, and 6 regions in both the alloy and pure iron. We have made several measurements in the appropriate temperature ranges and are unable to establish any systematic difference between the diffusion coefficients of iron in pure iron and in the alloy. We therefore conclude that the values obtained for the alloy are truly applicable to pure iron; the complete evidence favoring this conclusion will be discussed later in this paper. EXPERIMENTAL The experimental methods will be given here only in barest detail since they have been thoroughly de- scribed elsewhere.l, 7 The alloy was prepared by induction melting and chill casting under argon. Diffusion samples were machined from the ingot and annealed in hydrogen for several days at 900°C to give an average grain diameter of 1 to 2 mm. The penetration profiles of the tracer were established by a sectioning technique, the residual activity being counted after the removal of each section. The tracer used is Fe59 which emits two high-energy ? rays of 1.098 and 1.289 Mev, respectively; these were detected by a ? scintillation counter equipped with a pulse-height analyzer. For the measurements in the temperature range -700o to 1130°C the samples were vapor-plated with Fe59, encapsulated in quartz under vacuo, and annealed in resistance-heated furnaces which are controlled to ±1°C. The specimens diffused at higher temperatures are prepared as edge-welded couples, the two halves being separated by a thin washer of the alloy to prevent sintering. The diffusion anneal is then carried out by inductive heating under a dynamic vacuum. The temperature is monitored pyrometrically. RESULTS The diffusion coefficients are obtained from the penetration profiles in the usual way using the error-function complement relationship. The results over the entire temperature range are shown in Fig. 1. In the linear region, 900o < t > 1500°C the least mean squares (lms) values of the diffusion coefficients are given by D = 1.39 exp[-(56.5 ± 1) x 103/Rt] cm2/sec [l] The average departure of the measured diffusion coefficients from the values given by Eq. [1]In order to determine whether or not the slope is truly constant over the entire range from 900" to 1500°C, the data are arbitrarily divided into two groups, the first containing values between -900" and 1133°C and the second between -1133o and 1500°C. The lms values for the two groups are given by Eqs. [2] and [3]: D = 0.519 exp[-55.7 x 103 /RT](900° to 1133°C) cm2/sec [2] D = 1.45 exp[-56.7x103/RT] (1133° to 1500=C) cm2/sec [3] Thus, there is no significant difference between the high- and low-temperature segments of the linear region. This not only assures us of the consistency of the values obtained by induction heating as compared to those obtained from the resistance-heated

Jan 1, 1965

By O. A. Cheadle, F. E. Lane

ThE computer program for arbitrary crystal systems reported by Camp and Clum&apos; has been modified to make it more convenient for hexagonal crystals. The program&apos; uses the Miller indexes (hkl) which can be confusing for hexagonal crystals while the modified program uses the Miller-Bravais indexes with four axes; e.g., the angles between the (110) planes, Fig. 1, are 0 and 90 deg but in the (hkil) system the angles between the (1150) planes are 0 and 60 deg. If a Laue photograph is taken of a crystal oriented with the prismatic planes nearly parallel to the film then the spots on the stereo graphic projection will be from high-index planes. The probable positions of the low-index planes, e.g., (0001) plane, can only be obtained from the intersection of zones and this is not accurate to 1 or 2 deg. The number of planes considered by the program (card 1)&apos; has to be limited to the ones of low index or the program time is excessive but a solution will not be obtained if one of the spots has an index that is not being considered. To overcome this problem the program1 was modified so that if no fit was obtained at *1 deg (card 3) of the tabulated angles then ±2 or ±3 deg was tried. If still no solution was obtained either due to one of the angles not being measured correctly to ±3 deg or because one of the spots was from a high-index plane, then the last spot was discounted and a fit tried for the remaining spots at i1 deg, and so forth. The minimum number of spots that the program will try to fit is five. If the limit on any individual index is 4 (card 1) and (h + k + l + 1) is six then twenty-three planes are considered and there are over 1000 interplanar angles. Many pairs of planes have very similar interplanar angles and with the errors previously mentioned the program will often produce several alternative solutions to a group of spots particularly at ±2 or ±3 deg. However without the program the alternative solutions would probably not have been found. If a large number of spots are used the number of possible fits is reduced. In the example shown in Fig. 2, if only spots which are on the film are used (case 1) the program gives six possible solutions, Table I. However if points 7 and 8 are also used (case 2) the program gives only one fit which also agrees with a standard projection of the crystal. In addition to time-saving the program ensures that a correct solution is obtained since it is unlikely that all the alternatives would have been gound manually; the first would probably be assumed to be the correct solution. The program has been used for zirconium crystals but is equally suitable for other hexagonal materials.

Jan 1, 1969

By AIME AIME

THE Seventh International Petroleum Exposition and Congress to be held in Tulsa, Okla., Oct. 4 to 11, inclusive, in true western spirit promises to be bigger and better than ever. The Exposition has become an established institution. It gives opportunity to petroleum engineers, technologists, and operators to see each year at one place what the tool makers and machinery manufacturers have to offer which is new or better. It has truly become a place "where men, methods and machinery meet." It is also a convenient focus for technical meetings of various kinds devoted to petroleum and natural gas problems. &apos;The Petroleum Division of the A. I. M. E. has for several years held its chief fall meeting at Tulsa just preceding the opening of the Es- position. This year our meeting will be on Oct. 2 and 3 and it will be held as usual at Hotel Mayo. The Mid- Continent Oil and Gas Association will, as usual, hold a meeting during the Exposition and this year the Petroleum Division of the A. S. M. E. will hold a three- day session, Oct. 6-8, in the auditorium on the Esposition grounds. In all, six technical sessions are planned by this Society, and aside from reports of committees some 20 technical papers are to be presented. Members of the Institute should attend its own meeting and stay over for as many days as possible for the other meeting at which they will hear and see much of helpful interest.

Jan 1, 1930

By J. R. Kyte, V. O. Naumann, C. C. Mattax

Imbibition and waterflooding tests at reservoir conditions show that conventional tests at room conditions sometimes lead to recovery estimates that are too low. Core samples which are of intermediate wettability at normal test conditions may be strongly water-wet at reservoir conditions. This was found to be true for samples from two of three reservoirs investigated. For the other reservoir, less difference was observed between the wettability of samples at normal test conditions and at reservoir conditions. Samples which became more water-wet at reservoir temperature and pressure also water flooded more efficiently at reservoir conditions. These results show that core analysis tests on intermediate wettability samples should be performed at reservoir conditions to obtain representative data. INTRODUCTION Throughout the oil industry, core analysis tests normally are performed using refined oils and at room temperature and pressure. This procedure has always been subject to question because the possibility is generally recognized that the reservoir environment may influence displacement behavior. Burkhardt, et al,&apos; have performed waterflood tests at reservoir conditions on East Texas cores. They found little difference between results obtained at reservoir conditions and results of conventional flooding tests at room conditions. As they pointed out, however, this situation might not be general since they obtained data on only one rock and crude-oil system. This paper presents data which demonstrate that it is sometimes necessary to perform core analysis tests in a simulated reservoir environment to properly represent the reservoir wettability and displacement characteristics. The work is specifically concerned with reservoirs which were thought to be of intermediate wettability on the basis of conventional test results at room conditions, i.e., core samples imbibed only small amounts of either oil or water and exhibited no decided preferential wettability characteristics. Tests were performed on cores from three such reservoirs to determine their behavior in the reservoir environment. lmbibition and waterflood tests were used to demonstrate the effect of reservoir environment on reservoir rock wettability and displacement characteristics. Results of tests performed at reservoir conditions were compared with results from conventional tests. Imbibition tests were performed on samples from all three reservoirs. Waterflood tests were performed on samples from only one reservoir. Fluid properties for the three reservoirs studied are shown in Table 1. Tests at reservoir conditions were performed using bottom-hole crude oil at reservoir temperature and pressure. The aqueous phase used in these tests was a synthetic brine approximating the reservoir brine composition. Conventional tests were performed at room conditions with refined oils and synthetic reservoir brine. The oil-to-water viscosity ratios were adjusted to the reservoir values. The cores used in all the tests were taken from the reservoirs using either brine alone or a bentonite-car-boxymethylcellulose mud without additives as coring fluids. Previous tests show that these fluids have no significant effect on the wettability of reservoir rock samples.1 The cores were preserved in brine at the wellsite to prevent wettability changes during shipment and storage. Wellsite imbibition tests have been performed on fresh samples from several reservoirs (including Reservoir A) and compared with later laboratory imbibition tests on samples preserved in brine. The comparison showed that the wettability of the preserved cores was the same as that of fresh, surfaced cores at the wellsite.2 IMBIBITION TESTS Conventional imbibition tests were performed on preserved cores using the apparatus and procedures described by Bobek, et al.2 A sketch of the apparatus for imbibition tests at reservoir conditions is shown in Fig. 1. The preserved samples were first centrifuged to expel excess water and then placed in a stainless-steel container which served

By J. L. Fitch, B. G. Hurd

The presence of gypsum in samples subjected to standard core analysis introduces serious errors in the measurement of water saturation and porosity. The magnitude of these errors, depending upon the type of analysis procedure used, has been evaluated experimentally and theoretically. Water-saturated pore volumes determined by vacuum distillation or retort procedures may be too high by as much as 48 per cent of the volume of gypsum present. The maximum error in this value determined by Dean-Stark extraction with toluene is 36 per cent of the gypsum volume. If pore space is measured by a Boyle&apos;s law type porosimeter the maximum erorr due to gypsum is 38 per cent of the original gypsum volume present. The conscientious core analyst may eliminate the errors caused by gypsum by either of two methods. He may apply suitable corrections for the water of crystallization removed from gypsum, or take special precautions to prevent dehydration of gypsum during core cleaning and alzalysis procedures. These alternatives are discussed and methods for obtaining reliable core analysis data are proposed. Gypsum (CaSO4 . 2H2O) occurs as a common mineral in many of the world&apos;s sedimentary basins. In addition to its presence as primary bedded evaporitic deposits, it is often found as secondary replacement zones and pore-fillings in host rocks. That it may cause false indications in porosity, both on neutron logs and in standard core analysis, has been generally recognized. False porosity interpretations from neutron logs result because the chemically bound water in gypsum attenuates neutrons as effectively as free water. Errors in core analysis result when gypsum is dehydrated prior to or during the analysis. Vacuum retort procedures used by many laboratories to determine fluid saturation and porosity effect a complete removal of water of crystallization from gypsum. The crystal water, distilled and collected with free water from the sample, is counted as water-sat11rated pore space. Dehydration of gypsum results in a decrease in volume occupied by calcium sulfate and a corresponding increase in pore volume. Thus, if gypsum is dehydrated by sample cleaning and drying procedures, subsequent porosity measurements with gas expansion or compression instruments will be high. The qualitative effect of gypsum on porosity determinations by retort procedures was discussed in a recent article by Bynum and Koepl3. They concluded that since false porosity was interpreted as being water saturated, determinations of oil content were not affected. Others in the industry, however, have pointed out that porosity values are often used with values of water saturation determined independently, e.g., from electric resistivity logs in making reserve estimates. Values of water saturation calculated from the formation resistivity using the Archie equation, S4= are actually low if values of are high due to gypsum. In this case, false porosity values due to gypsum could cause serious errors in calculations of oil-in-place. This investigation was made to determine quantitatively the effect of gypsum on porosity values determined by different core analysis procedures. EXPERIMENTAL PROCEDURES Dehydration of Gypsum The extent and rate of removal of water of crystallization from gypsum under conditions encountered in core analysis procedures were studied. Taken for the experiments were three types of relatively pure, naturally occurring gypsum, viz. selenite, satin spar and massive gypsum. Although all samples probably contained trace chemical impurities, each type lost the theoretical amount of water upon complete dehydration. An automatic recording thermobalance, similar to one described by Mauer2, was used to obtain dehydration rate data for samples heated in dry air. Water

By W. O. Brown

A laboratory investigation was conducted to determine quantitatively the extent to which connate water was contacted and displaced by invading flood water. In these experiments the connate water in unconsoli-dated sand packed columns was completely displaced by injecting water. The nature of this displacement was similar to that previously described for single-phase miscible fluid displacement studies, and thus the presence of a non-wetting immiscible phase did not appreciably change the nature of the displacement. The effects of water injection rate, column length, and oil viscosity on connate water displacement were investi-gated. It is concluded that the connate water in a reservoir is the water which actually displaces oil from the pores of the rock during a water flood. During a water flood the connate water forms a zone which separates the invading flood water from the continuous oil phase. The size and shape of connate water bank is chiefly dependent oil the oil viscosity and the column length. INTRODUCTION Water flooding is one of the most widely used techniques for the secondary recovery of oil. Presently, however, it is still not possible to recover all the oil in a reservoir by water flooding. The research described in this paper was conducted as part of a study to determine the conditions under which 100 per cent oil recovery could be attained by water flooding. The particular objective of this work was to determine if any chemical agent, regardless of its nature, placed in the flood water could be effective in influencing the mechanism of displacement of the oil by water. It has been known for many years that water does not displace all the oil in a reservoir because a portion of the oil is "trapped" and held immobile by capillary forces. This oil is trapped within the pores of a water-wet rock when it becomes broken into discontinuous globules. Initially, when oil is present at high saturations within the pores of a water-wet rock, the connate water forms rings around the points of contact of the sand grains and may even completely fill small cavities between grains, whereas the oil occupies the larger void spaces between the grains.&apos; Under these conditions, the oil in these spaces is in the form of irregular but continuous filaments, the diameters of which depend on the geometry of the sand pores. The filaments are formed by the oil contained in the small cells which are formed between the sand grains and are connected to their neighboring cells by channels or tunnels formed by pendular rings of water. At a high oil saturation, the oil filaments conform approximately to the shape and size of the cells and their connecting tunnels. Starting with this distribution, as the water saturation is increased the water layers in the small cavities and on the surface of the grains grow. As this occurs, the water rings grow and the diameters of the oil filaments decrease. When an oil filament is reduced to a critically small diameter, the filament breaks, and its tunnel fills completely with water. Any oil which remains within a cell after all its connecting tunnels have been water-filled is trapped as a discontinuous globule. Once the oil has become trapped, the capillary forces oppose distortion of the globules and may prevent their being squeezed through the water-filled tunnels. Only a very small pressure gradient is sufficient to keep oil moving as a continuous filament. On the other hand, once the filament has broken into discontinuous oil droplets a relatively large force is required to distort the surface of a drop and move it through a water-

Jan 1, 1958

By P. A. Toynbee, D. G. Wilson

The combustion performance of sub-bituminous slack coal is greatly improved by the removal of the smaller size fractions. Screening processes are not well suited to the size separation, at 1/8 in. or 1/16 in., with coals which are normally wet, and the use of an alternative size-separation device has been investigated. It is felt that this classifier might be applied equally well to other minerals in cases such as this, where precise size limits are not essential. Coal is dropped as a curtain onto a curved metal plate, shaped rather like a ski-jump. The smaller particles, slowed up in their free fall to the plate and also by contact with the metal, leave the plate with a lower horizontal velocity; they can be separated from the larger particles by virtue of their shorter trajectory. The principle of the classifier is obvious from the diagram (see Fig. 1) which shows also the positions, relative to the curved plate, of the point of coal feed and of the dividing plate which separates the streams of coal particles. The horizontal distance between the curved plate and the dividing plate is varied in the tests. It is designated in the general case, by X. Tests were carried out using slack coal with a free moisture content higher than that expected in any commercial operation. The results given in Table I. show the percentage recovery of upgraded product, and the cumulative screen analysis of both the upgraded and reject material, for three different positions of the dividing plate. The results show, for example, that the original coal can be upgraded, with a recovery of 80%, to reduce the minus 1/8 in. frac-

Jan 1, 1965

By Sidney H. Haughton

FOLLOWING the discovery of diamonds in 1870 and the Witwatersrand gold fields in 1886 South Africa changed from a predominantly pastoral country with a scattered white population into a land whose economy came rapidly to be based primarily on mining. The total value of the mineral output of the Union in 1944 was approximately $493,000,000, to which gold contributed 84 per cent. Gold furnished some 33 per cent of the Union Government&apos;s total revenue in that year, and approximately half the country&apos;s population obtained its livelihood directly or indirectly from the gold mining industry. In any review of the Union&apos;s mining activities and in any consideration of the country&apos;s future, gold mining must occupy a prominent place. It is generally conceded that the present structure is not properly balanced and that an economy based on a preponderance of a single nonpermanent factor possesses potentialities of serious instability.

Jan 1, 1946

By L. L. Peterson, W. C. Morgan

This paper discusses some of the problems involved in predicting the productivity of a shovel and truck fleet in a new set of operating conditions. More specifically, it concentrates on the problems of predicting the travel times on the haul and return portions of the truck cycle under new profile conditions and the prediction of the interaction effect between the shovel and truck at the loading point. The ability to calculate the travel times for a new road profile is not new. Additional corrections of these calculated times for expected actual operation can be made. In considering the interaction between the loader and the hauler, there are two approaches that can be taken. Probably the most accurate method of predicting the shovel-truck interaction is a simulation of the step-by-step operation considering the variation in cycle times of the shovel and trucks. This is usually called a stochastic simulation and requires input describing how these cycle times vary. However, by understanding the causes of this shovel-truck interaction it is possible to make sufficiently accurate predictions with much simpler methods. Haulage Cycle Established from Existing Operations For the purpose of this discussion let us assume that the problem involves trying to predict the productivity of a single shovel-truck fleet at some future time in an existing operation. Let us also assume for simplification that the new operation to be simulated has the same loading and pit conditions and the same dumping conditions as did the existing operation. Therefore, the only difference would be the difference in the hauling profile for the new operation. The problem then becomes one of predicting the change in the travel times on the haul and return portions of the cycle, and in determining the change in interaction between and the shovel and trucks with the new truck cycle times.

Jan 12, 1968

By W. J. Slatosky

As a means of effecting better control of endpoint temperatirres at the Jones & Laughlin basic oxygen furnace plant, a set of mathematical equations has been developed. The eqlutions are the product of a themlochemical anaysis of the process and aye designed to calculate the required scrap, lime, and hot metal additions in terms of a number of independent variables. Results of test heats have warranted adoption of this technique by the Prodrrction Department. BECAUSE of the autogeneous nature of the basic oxygen steel-making process, bath temperature can be controlled without an external fuel supply by charging the furnace with additions that are thermally balanced. The thermal requirements of the charge materials are such that, during the refining process, they throttle the heat generated by the metallurgical reactions in a manner designed to result in a speci-fied temperature at the completion of the heat. In the past, operating personnel at the basic oxygen furnace plant of Jones & Laughlin&apos;s Aliquippa Works relied on their experience and technical knowledge of the process to determine the quantities of charge additions needed to result in a finishing temperature in the range 2880"to 2920" F. (The charge consists primarily of 93 tons of scrap and hot metal plus an amount of lime sufficient to maintain a basicity ratio of 2.8 to 3.2). Estimates of these materials are based on a consideration of the effects on finishing temperature of 1) iron silicon content, having a variation of 0.8 to 1.8 pct; 2) iron temperature, ranging from 2250°to 2600°F; and 3)any excessive cooling of the furnace due to a production delay. The end temperature of the preceding heat also serves as a guide in that, if a heat was within the specified temperature range, the succeeding heat could be charged with materials of nearly the same proportions, provided the hot metal used in each of the two charges was of approximately the same temperature and composition. On the other hand, if a heat was outside the specified tapping range, or if the hot metal used in that heat was of different analysis and temperature from that of the iron to be charged, an adjustment in the proportion of additions is in order for the following heat. Due to the complex thermochemical behavior of the process and to the inexact and subjective nature of the described method of determining charge additions, consistently accurate temperature control was not to be expected. Therefore, those heats out- side the specified tapping range necessitated subsequent adjustments by either reblowing the cold heats for a suitable length of time so as to elevate the bath temperature to the desired level, or cooling hot heats with a proper amount of scrap. Because extra time is required to make these adjustments, production is delayed. In an attempt to devise a method for improving temperature control, an analysis of the thermochemistry of the process was undertaken. This, in turn, led to the development of a set of mathematical equations which enable the calculation of the quantities of scrap, lime, and hot metal needed to result in any specified tapping temperature range. The analysis was not intended to be a repetition of work done by others such as McMulkinl or ~hilbrook.&apos; It was meant to be an extension of their work so that charge additions could be calculated not in terms of silicon alone but, rather, as a function of all independent variables. This paper presents the derivation of these relationships, their effectiveness in controlling bath temperatures, and a method of utilizing them on an operational basis. The Heat Balance—The first step undertaken in the analysis of the problem was the enumeration of the pertinent variables. A list is presented in Table I where it is noticed that these quantities have been separated into the following three categories: important variables, variables considered as constants, and variables to be neglected. The breakdown was an arbitrary one designed to facilitate the analysis; otherwise, the mathematical treatment would have been exceedingly cumbersome and complex. Fortunately, experience has shown that these simplifying assumptions do not seriously impair the accuracy of the calculations. These variables along with the limiting assumptions listed in Table n were then used to write a heat balance of the process by applying the equation of continuity, Rate of Rate of Rate of Increase = Income - Outgo PI ] of Heat of Heat of Heat.

Jan 1, 1962