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ENROLLMENT of both undergraduate and graduate mineral engineering students rose approximately 11.8 pct over last year to a total of 12,830. Leading again in the enrollment climb was ceramic engineering which increased by about 21 pct. Approximated increases in enrollment of the other mineral engineering categories, in order, were: metallurgical 17.7 pct; petroleum 13.3 pct; geological and geophysical 3.3 pct: and mining proper, the lowest with 2.9 pct. Total ECPD school enrollment climbed to 242,405 -just below the 1947 peak, but 14.4 pct higher than 1955. Engineering enrollments have shown a general increase since 1951, and freshmen enrollments have climbed steadily since 1950.

Jan 5, 1957

[Trans. No,PlaceDate Vol. Page1 1. Wilkes-Barre, Pa*May, '71 13 2, Bethlehem, Pa Aug., '71110 3, Troy, N. Y Nov., '71.. 113 4. Philadelphia, PaFeb,, '72.. 117 5, New York, N, Y.*May, '72,, 120 6. Pittsburgh, Pa Oct,, '72,, 125 7. Boston, Mass Feb,, '73.. 128 8. Philadelphia, Pa,*May, '73., 23 9. Easton, PaOct., '73., 27 10. New York, N, Y Feb., '74,, 211 11. St. Louis, Mo,*May, '74.. 33 12, Hazleton, PaOct., '74., 38 13, New Haven, ConnFeb., '75., 315 14. Dover, N. J,*May, '75.. 43 15, Cleveland, 0Oct,, '75,, 49]

Jan 1, 1928

By Joseph William Pinder

Every millman engaged in the operations incident to the handling of crushing-rolls knows that in ordinary practice, when fine product is desired, the ore-materials delivered to the machine, divided into four sizes, may be estimated, approximately, as follows : Per cent. Papsing a 4-mesh screen,..40 2- " " ........30 " 3/4-inch-mesh screen,.. 20 Larger,...........10 This estimate refers more particularly to the requirements of medium-sized rolls and fine crushing. But, depending largely on the character of work to be performed, the coarser material is often larger and of a greater percentage, while the bulk is always more or less fine.

Jan 1, 1899

By Corale Brierley

The effect of hydrogen peroxide (H202) on growth and respiration of Thiobacillus thiooxidans and Thiobacillus ferrooxidans, organisms involved in acid leaching of copper sulfide minerals and uarnium oxides, was examined. Oxygen uptake and growth by T. thiooxidans were totally inhibited after contact with 0.82 mM H202. Complete inhibition of oxygen uptake by T. ferrooxidans occurred at 8.75 mM H202, and growth was inhibited after 6 hr exposure to 2.06 mM H202. Higher concentration of H202 can be used without detriment to thiobacilli if it is dissipated prior to reaching the oxidation pond or dump surface.

Jan 1, 1980

By K. Koneko, T. Nokoyama, S. Shibato

SEYBOLT et al.' have detected various silica films formed on a 3 pct Si-Fe alloy after heating at low oxygen potentials with the electron diffraction method, and they have made some observations on the H,0/H2 ratios required to form them. The purpose of this note is to describe the structure of the oxide film formed on either mechanically or electrolytically polished surfaces of a 3 pct Si-Fe alloy containing small amounts of manganese after heating at low oxygen potential. The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron, 76 pct ferrosilicon, and 76 pct ferromanganese, vacuum-in-

Jan 1, 1969

By W. J. Kroll

W. J. Kroll (Belgium)—Those who are acquainted with the metallurgy of our forefathers may have occasionally a good time when glancing at recent publications in which aged discoveries are unconsciously reported as novelties. We know very well, that oxygen blowing of iron has been described by old Bessemer. The author of the present article is, however, not aware of the fact that the process he describes, the fused salts scrubbing, was already used in the middle of the last century by St. Claire Deville in his attempts at making higher-purity aluminum from raw AlCl3 by sodium reduction. The same fact escaped the three investigators to whom the author refers. The technical grade AlC13 produced by St. Claire Deville from impure oxide, chlorine, and carbon (Oersted process) was contaminated with Sic4 and FeC13, which he removed on an industrial scale by various methods.' He sublimed, for instance, his chloride in contact with iron nails, or aluminum chips, or in hydrogen, which reduced the FeC13 to the less volatile FeCl2. He used also alkali-alkaline earth chlorides as a solvent for A1C13 and FeC13 in presence of iron as a reducing agent, and sublimed his purified AlC13 from solvent salts. The successors of Deville used also zinc or lead as a reducing agent. These methods were later used currently for the purification of BeCl2 and for collecting this compound in a salt bath, suitable for fusion electrolysis. More recently, the same Deville process has been described as applied to the purification of ZrCL4, as part of a method of extraction of ZrCL4 from silico zirconium, which later was reacted with FeC12 in a separate part of the equipment. According to the patent referred to3 the ZrCL4 is dissolved as a gas in a carrier salt such as alkali-alkaline earth chloride, from which it can be reclaimed in a purified form by distillation. A bath of NaCl/KCl is recommended in the specifications. The FeC12-FeC13 go in the salt solution in which raw ZrCl4 is introduced by bubbling, while Sic4 and Tic4 pass through the bath and escape in the atmosphere. purification by this salt-solvent method is thus well described. It may be worth while insisting on some minor details about which the author did not bother too much. One of these concerns the material of construction for the container. If iron is used, and if no other reducing agent is added, then it is the iron of the pot that acts as a reagent in the breakdown of FeC13 to FeCl2, and corrosion can be expected. This shows the importance of using extraneous large surface-reducing agents, of which there is a choice. Zir-

Jan 1, 1963

By R. S. Rickard

Chemical processing of ores has gained new im¬petus in recent years. The reasons are many. They range from the need to process ores that are difficult to beneficiate to the avoidance of pollution. Although many think of chemical processing as a hydrometallurgical operation there are other techniques. An example is chlorination. Chlorination, although examined and discarded by many investigators, is again being considered as a means of extracting uranium1, treatment of silver-lead ores2, and the recovery of base metals from pyrite cinder and ores3. Segregation roasting of copper and nickel ores, a process similar to chlorination, is another chemical treatment being revived.

Jan 1, 1970

By J. C. Jr. Vaughan

ALTHOUGH a considerable amount of practical importance attaches to systems involving gases and molten metals, little is known regarding the effects of alloy elements upon the solubility of gases in liquid iron. The solubilities of hydrogen1 and nitrogen2,3 in pure liquid iron are known and it has been shown that small amounts of silicon and aluminum3 exert only a small effect upon the solubility of nitrogen but greatly increase its rate of solution. This paper presents the results of a study of the Solubility Of nitrogen, at pressures approximately one atmosphere, in molten iron containing up to 1.5.5 per cent silicon.

Jan 1, 1939

By G. B. Craig, G. L. Montgomery

A simple technique has been developed which reveals glide dislocations in zone-refined aluminum as etch pits. The technique has been tested quantitatively by making dislocation counts on aluminum single crystals deformed in pure bending. The method has the advantage of being insensitive to the orientation of the surface under examination. A number of etchants which will reveal dislocations in annealed aluminum have been reported.'-' These etchants apparently depend on decoration of the dislocations by an impurity (probably iron) and cannot, therefore, be used to reveal fresh glide dislocations. In addition, it is unlikely that screw dislocations will be etched because of their small attraction for impurity atoms. Amelinckx6 has reported that glide dislocations located along slip traces can be revealed by fluo-rated aqua regia. This work indicated that dislocations themselves, irrespective of decoration by impurity atoms, are responsible for the etch pits. However, as a result of additional etching experiments, Wyon and Marchin7 concluded that dislocations alone are not sufficient to explain the localization of etch pits on slip lines in aluminum using chemical etch-pitting techniques. In addition, their results show that glide dislocations are revealed only on surfaces approximately parallel to a (100) axis and that not all slip systems are attacked. These observations have been confirmed by the present authors. The technique described in this article is insensitive to the orientation of the surface, and reveals dislocations on all glide systems. Fig. 1 shows a deformed region in the neighborhood of a scratch. Dislocations can be seen along three slip traces. In the present work, single crystals of zone-refined aluminum are polished for from 2 to 5 min in a chemical polishing reagent held at 100°C, as described by Herenguel and second:' H2Sol 60 pct H3PO4 30 pct HNO3 10 pet The samples are then coated with a thin oxide film by annealing in air at 450°C for 1 hr and cooling in the furnace. After deformation, dislocation etch pits are developed by immersing the specimen in the same polishing solution which is now held at a temperature of 50°C. The formation of small hydrogen bubbles indicates that etching has occurred. The sample is immediately removed from the solution. Prolonged etching results in enlargement of the pits and, in regions of high dislocation density, the overlapping and loss of resolution of individual pits. It is the experience of the authors that contact with iron will ruinously contaminate the reagent. With careful etching, dislocations separated by half a micron can be resolved optically and the method has been shown to be sufficiently sensitive to reveal dislocations produced during the pre-easy glide region of deformation, Fig. 2. A few examples of glide-dislocation configurations, as revealed by this technique, are shown in Figs. 1 to 4.

Jan 1, 1964

By D. A. Elgillani, M. C. Fuerstenau

In this paper, oxidation potentials measured in the presence of various concentrations of cyanide, ferro-cyanide, and ferricyanide and ethyl xanthate at various values of pH are related to flotation response. Eh-pH diagrams are presented to show that the formation of surface ferric ferrocyanide is probably responsible for depression when cyanide is added. The influence of cyanide on the depression of pyrite with xanthates as collector has been the subject of a number of investigations,'-6 and several theories on the mechanism of depression have evolved from these studies. Wark and Cox7 and Gaudin8 have suggested that the depressing effect is due to a competition of cyanide ion with xanthate ion for the surface. Cook and his colleagues9-11 have explained this phenomenon in terms of competition between hydrocyanic acid and xanthic acid. Sutherland 12 has shown that although both of these theories accurately describe the relation between pH value and cyanide addition at constant collector addition, they fail to describe the relation between pH value and the amount of collector required to cause flotation. Taggart 13 suggested that depression in these systems is due to the formation of a reaction product between ferric ion at the pyrite surface and ferrocyanide ion derived from solution. Majumdar4,6 has attempted to prove this hypothesis by measuring the contact angles of pyrite in the presence of 25 mg per liter ethyl xanthate and different concentrations of potassium ferrocyanide and ferricyanide. In all cases the contact angles were quite high up to pH 10. These results indicate that pyrite should not be depressed by either potassium ferrocyanide or ferricyanide. In view of these facts, Majumdar has assumed that the compound Fe(CN)2 forms at the surface. Gründer and Bornl4 have stated that depression may be due to the formation of the compound K2Fe(II)Fe(CN)6 at the pyrite-solution interface. This compound is thought to be an interaction product between the K2Fe(CN)6-2 ion from solution and the Fe++ ion at the pyrite surface and, accordingly, K4Fe(CN)6 should depress pyrite at least as effectively as KCN. This was proven experimentally, but there was no simple relation between the depression of pyrite and the concentration of either KCN or K4Fe(CN)6 in solution. In view of the many mechanisms that have been proposed for pyrite depression by cyanide, it is apparent that a clear understanding of the phenomena occurring in these systems is lacking. One reason for this may be the fact that the species responsible for pyrite flotation in the presence of xanthate is not the xan-thate ion but rather dixanthogen.15 Since the oxidation of xanthate to dixanthogen is dependent on the oxidation potential of the solution, it would seem that knowledge of these potentials would be a requisite to understanding the pyrite-xanthate-cyanide system. It is the object of this paper to measure both the oxidation potential and pH of the pyrite systems in the presence of various concentrations of cyanide, ferrocyanide, and ferricyanide and xanthate and to relate these values to flotation response. EXPERIMENTAL MATERIALS AND 'TECHNIQUES In the experiments discussed here, pure potassium ethyl xanthate was used as collector, and reagent grade potassium cyanide, potassium ferrocyanide, and potassium ferricyanide were used as depressants. Reagent grade HC1 and KOH were added for pH adjustment. Conductivity water, made by passing distilled water through an ion exchange column, was used in all experimental work. Two natural samples of pyrite were used in the investigation. Sample preparation for flotation included dry grinding with a mortar and pestle and sizing the product to 100 x 200 mesh. Prior to flotation, a 0.75-gm sample of pyrite was added to a solution containing a known amount of depressant at the desired pH value, and the system was conditioned for 4 min. Following this, a known amount of collector was added and the system was conditioned for another 4 min. The pH — termed flotation pH - was measured; the pulp was transferred to a Hallimond cell, and flo-

Jan 1, 1969

By Craig R. Barreft, Oleg D. Sherby

The steady-state creep characteristics of pure polycrystalline copper were studied in the temperature range 400" to 950°C and in the stress range 400 to 7000 psi. Tests were conducted in dry deoxidized hydrogen and all specimens exhibited high ductility before fracture. Two activation energies for creep were established as a function of temperature. Above about T/T, = 0.65, the activation energy for creep was 48,000 cal per mole whereas between 0.5 and 0.65 T, it was 28,000 cal per mole. The observed temperature dependence of the activation energy for creep follows the same trend as exhibited by the self-diffusion coefficient of copper in copper single crystals and silver in silver single crystals. It is therefore believed that the rate-cmtrolling mechanism in creep of copper in the stress and temperature range studied is diffusion-dependent and is probably associated with a dislocation-climb process. The low activation-energy region is attributed to enhanced volume difFusion from the presence of dislocations which act as short-circuit paths for diffusion. THERE is extensive experimental evidence1,2 that the activation energy for creep, Q,, for pure poly-crystalline metals tested at temperatures above one half the absolute melting temperature (0.5 Tm) is a constant and equal to the activation energy for volume self-diffusion, Qsd This equality is generally interpreted as meaning that creep in this temperature range is controlled by a dislocation-climb process. The existence of high-temperature creep activation energies not equal to the respective self-diffusion values has been suggested both theoretically3"5 and experimentally.6-8 Two examples of apparent nonequality between Q, and Qsd have been reported for the cases of silver7 and copper,' where activation energies for creep much lower than those for self-diffusion persist to rela- tively high temperatures (up to 0.6 T,). These observations suggest that dislocation climb may not be the only important process in the high-temperature deformation of these metals. That dislocation climb does indeed occur relatively slowly in these two metals due to their low stacking-fault energy has been suggested by many investigators.9-10 Although the creep behavior of copper has been studied extensively at low temperatures, the high-temperature activation energy for creep is not well-defined. The data of Feltham and Meakin8 indicated that Q, is temperature-dependent above one half the melting temperature, equaling a value of -30,000 cal per mole at temperatures up to 550°C and increasing to a value of -49,000 cal per mole at 700°C. No data has been reported above 700°C. The value of 49,000 cal per mole is very near the value of Qsd for copper reported by Kuper et al." as 47,100 cal per mole. In view of the lack of high-temperature creep data and the apparent temperature dependence of Q, for copper the present investigation was undertaken to determine the value of Q, over the temperature range of 400" to 950°C. It was hoped that such a study would clearly document the temperature dependence of Q, and yield significant information as to the nature of the rate-controlling creep mechanisms. MATERIALS AND PROCEDURES The material used in this investigation was high-purity OFHC copper. After rolling and recrystal-lization treatments spectrographic and chemical analyses showed only 0.0008 pct Ag, 0.0002 pctCa, 0.0002 pct H2, and 0.002 pct O2 as trace impurities indicating a purity of greater then 99.995 pct. Specimens were machined from cold-rolled sheet and the gage sections polished with 2/0 emery paper prior to annealing treatments. Annealing was done in both vacuum and dry deoxidized hydrogen atmospheres. No variation in creep strength was found as a result of the different annealing atmospheres. The final annealing temperature was either 700°, 800°, or 1000°C depending on the temperature range to be studied. These treatments resulted in average grain diameters of 0.03, 0.4, and 1.0 mm, respectively. The precise mechanical-thermal history of these

Jan 1, 1964

By J. Chipman, N. J. Grant, H. L. Bishop, H. N. Lander

Data of several studies on the equilibrium between molten iron and open hearth-type slags have been combined to determine some of the chemical reactions involved in steel-making. Effects of slag composition and temperature on the iron oxide activity, distribution of sulfur between slag and metal, and the carbon content of the metal are discussed. Also, an overall reaction for the equilibrium between sulfur and oxygen is presented. DURING the past 15 years, a number of significant equilibrium studies have been carried out between liquid iron and simple basic and acid slags in an effort to throw light on the chemical reactions involved in steelmaking. This paper is a summary of the experimental reports on investigations which have been conducted at the Massachusetts Institute of Technology, and of related work in other laboratories. The investigations summarized in this paper include the works of Fetters and Chipman1 and Taylor and Chipman,' which dealt with simple slags that are similar to those found in the open hearth. The sulfur determinations of the slag-metal tests of Fetters and Chipman as reported by Grant and Chip-man" are included. Also, the investigations by Win-kler and Chipman' and Grant and ChipmanQ f more complex slag systems are included in this summary. The experimental procedure is described in detail in each of these papers and will not be discussed. Since the previous reports have been somewhat independent, it is desirable to review and combine the data of the various investigations to determine, as accurately as possible, the reactions in the slag-metal systems of the open hearth. It is the object of this report to present the combined data in such a way as to enhance their utility and applicability. Oxidizing Power of Slags of the System (CaO+MgO)-Si0,-FeO in Equilibrium with Carbon-Free lron The slags selected to determine the iron oxide activity in equilibrium with pure liquid iron were those containing less than 2 pct each of P,O,, MnO, or A1,0, on a weight percentage basis. The method used to calculate activities of iron oxide in liquid slags was that developed by Taylor and Chipman.' The solubility of oxygen in molten carbon-free iron under pure iron oxide slags can be expressed by the following eauation —6320 log (pctO)-------------— + 2.734 [1] where T is the absolute temperature. The oxygen solubility values as determined from Eq. 1 were used throughout this study to calculate the iron oxide activity. The iron oxide activities of slags of various iron oxide contents are plotted in Fig. 1 as a function of the basicity, which is defined as the ratio (pct CaO + pct MgO)/pct SiO,, and are based on molecular percentage values of the components. The percent (FeO), is the total iron content in the slag calculated to FeO. Fig. 1 shows that as the basicity increases at constant mol pct (FeO),, the iron oxide activity increases rapidly and reaches a plateau which extends on the basicity scale from about 1.3 to 2.3; the iron oxide activity then decreases rapidly until a basicity of about 3.0 is reached, where it tends to level off. The solid portions of the curves represent the experimental data of Fetters and Chipman and Win-kler and Chipman. Their experimental heats were made in magnesia crucibles, and hence the slags were saturated with magnesia. The broken lines on the left represent the experimental data of Taylor and Chipman, who used a rotating crucible. In general, these slags contained less than 3 pct MgO. The absence of data for slags containing less than about 40 mol pct (FeO), and basicity ratios greater than about 2.5 made it necessary to calculate curves using ionic concepts of slags. The broken lines on the right, which disregard the solubility limits of di and tricalcium silicate and lime, were obtained by following the treatment of Flood and Grjotheim,"

Jan 1, 1957

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.' These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:' , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.' The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts' law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts' law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965

By L. D. Mullins, W. R. Bartlett, R. H. Barham, W. L. Wahl

This paper describes an electrical model and its applicution to the analysis of four reservoirs in Saudi Arabia. The model has 2,501 mesh points and represents 35,000 sq miles of the Arab-D member. Details of modeling such as mesh size, control problems and standards of performance in matching reservoir history are discussed. The particular performance match achieved for the Arab-D rnember is presented. Details such as permeability barriers, aquifer depletion and iwerference between oil fields are given. The performance match realized in the Abqaiq pool is presented in detail. INTRODUCTION The resistor-capacitor network and associated control equipment described in this paper comprise an electrical analog of a reservoir system. Similar equipment has been used to study the transient response of reservoirs for many years. The unique feature of the model and application to be described is the extremely large size of the model and reservoir system, and the detail observed in simulating the reservoir with the model. The Arabian American Oil Co. first became interested in analog computers for simulation of oil reservoirs in 1949. Since that time, several models have been developed, each more elaborate and refined so that the reservoir system might be more closely simulated. The current model is the latest in a series designed, built and operated by the Field Research Laboratory of Socony Mobil Oil Co. in collaboration with Aramco. It has been and continues to be used to study the regional performance of the Arab-D member limestone reservoir. The Arab-D member is one of the Middle East's most prolific producing horizons.. THE MODEL The theory of simulating a reservoir system with an electrical system has been presented in the literature.1-5 Therefore, this paper will not discuss the theoretical aspect of the problem except to point out the correspondence between the fluid system and electrical system, as shown in Table 1. In general, the complete model is made up of input devices, output devices, central control and a resistance-capacitance (RC) network. At times, the RC network alone is referred to as the "model". However, it should be evident from the text which meaning is attached to the word "model". A discussion of the equipment follows. THE RESISTANCE-CAPACITANCE NETWORK The RC network consists of 2,501 capacitance decades interconnected through 4,900 resistance decades. The components are arranged to form a rectangular network of 2,501 mesh points in a 41- X 61-mesh array. Imposing the mesh grid system on the continuous reservoir system divides the reservoir into discrete areal segments. These discrete segments may be of various sizes. More precisely, the mesh size need not be uniform throughout the model. The RC network is fabricated in two sections which are connected at the top. An inside view of the "tunnel" formed by the two sections is shown in Fig. 1. The height and width of the tunnel are shown in the figure. Numerals appear along the bottom and along the back opening of the tunnel. These numbers denote the x and y co-ordinate positions of mesh points. Fig. 2 presents a rear view of one-half the model. The length dimensions of the model, as well as a rear view of the capacitor decades, are shown in this figure. The control dials used in adjusting the resistance and capacitance values on the model can be seen in the enlarged portion of the model shown in Fig. 3. The electrical capacity at any mesh point can range from 0 to 1.0 microfarads set to the nearest tenth of a microfarad. The electric resistance connecting any two mesh points can range from 0 to 9,990,000 ohms set to the nearest 1,000 ohms. External capacitors may be added to any or all mesh points if the need arises. The values of electrical resistance and capacitance are adjusted manually by manipulating the two types of decade units. INPUT EQUIPMENT A considerable quantity of equipment is used to control the input to the RC network. These input devices are

By K. W. Smith, E. A. Thomas

Various grades of synthetic mullite have been developed in recent years to replace or supplement natural sources of mullite deriued from the mullite group of minerals consisting of sillimanite, kyanite, and andalusite. Raw materials and heat treating processes used in making synthetic mullite are described. Chemical and physical data are given for typical grades and crystalline structure is illustrated with micrographs. Use of synthetic mullite as a refractory material in the glass and metallurgical industries is discussed. Mullite (3A12O3.2siO2), the only stable compound formed in the alumina-silica system, is usually present to some degree in all aluminum silicate ceramic products. The formation of mullite is considered beneficial to give rigidity to the structure and is dependent upon the ratio of Al2O3 to SiO2 in the original composition, particle size, degree of mixing, firing temperature, cooling rate, and the presence of auxiliary glass-forming fluxes. Mullite may also be formed at the reaction interface of fire clay or alumina-type refractories in contact with glass or slag melts. The term synthetic mullite is commonly used today to identify a class of sintered and fused aggregates or grains in the alumina-silica system having a highly developed mullite structure but derived mainly from raw materials other than the sillimanite group of minerals. Within the past 15 years extensive research has been done to develop economical processes to form sintered synthetic mullite aggregate to replace calcined Indian kyanite in super-refractories. Severa1 brands of such mullite are now being produced in commerical quantity and finding extensive use in refractories. Based on the service results of such refractories in many applications throughout the metallurgical, ceramic, and glass industry these developments have been considered successful and suitable substitutes for Indian kyanite now appear assured. EARLY DEVELOPMENT The conversion of kyanite, sillimanite and anda-lusite minerals of the sillimanite group to mullite and their use in refractories and porcelain have been discussed quite extensively in the literature by peck,' Grieg,' Riddle and Foster,3 Bowen and Grieg,4 and others and will only be mentioned here for reference to compare properties with synthetic mullite. In 1928, curtis5 reported on the development of a high temperature gas-converter process for forming synthetic mullite. The raw materials were derived mainly from lumps of high alumina clay of the correct natural composition or blends of clays and alumina that was interground and briquetted to form a suitable charge to maintain a surface combustion firing within the converter. Curtis was, no doubt, the first to illustrate by micrographs in natural color the crystalline structure of mullite derived from kyanite and mullite derived by sintering clay and alumina mixtures at temperatures above cone 32 (3123°F) and by electric fusion. In 1937, sei16 was issued a patent covering the use of a mixture of alumina-silica minerals and alumina in the proportion to form a mullite-yielding material at temperatures in excess of 3100' F. During the period from 1930 to 1940, economic conditions were not favorable for the production of synthetic mullite mainly due to an adequate supply of good grades of Indian kyanite ore suitable for conversion to mullite. Uncertain conditions on availability of the Indian kyanite during the early stages of World War II fostered further study on the development of synthetic substitutes. In 1943, McVay and wilson7 reported on an extensive investigation of domestic substitute materials. Their work covered essentially the use of mixtures of electric furnace mullite, calcined topaz, and calcined domestic kyanite. Compositions were found that gave equivalent or better hot load strength than Indian kyanite in mullite-type brick compositions; however, the calcining of the topaz presented certain physical and chemical problems on the disposition of silicofluoride and hydrofluoric acid while the high cost of electric furnace mullite was a limiting factor. In this work it was pointed out that water-quenched fused mullite was found to be unstable on reheat and gave poor hot load strength due to excessive glass present whereas the slow cooled or annealed mullite contained large crystals of mullite and corundum with little glass and gave superior results.

Jan 1, 1961

By J. H. Swisher

In measuvements of the solubility of nitrogen in fer-rilic Fe-P alloys, tile nitrogen solubility is found to be Less in pIrospliorus-bearing alloys than in pure iron. The reduction in solubility is about 20 pct in a 1.0 wt pct P alloy at 1300°C and about 30 pct in a 0.23 wt pct P alloy at 440°C. Diffusion coefficient measurements at 1150 and 585°C show that phosphorus also decreases the nitrogen diffusivity in iron. In previous work on the Fe-P-N system, phosphorus was found to reduce the nitrogen solubility in liquid iron slightly.&apos; Indirect evidence for similar behavior in a Fe at low temperature was obtained by Dickenscheid and Brauner.&apos; These authors found that phosphorus reduces the height of the internal-friction peak due to dissolved nitrogen. The results of Dickenscheid and Brauner were confirmed by J. C. Swartz of this Laboratory in a single internal-friction experiment using the same specimen stock as in the solubility measurements described below. In the present investigation, the solubility of nitrogen in a fer rite-stabilized Fe-1.0 wt pct P alloy was measured in the temperature range from 800" to 1300°C. Additional experiments were performed in the temperature range from 440° to 585°C, using an Fe-0.23 wt pct P alloy and NH3-H2 gas mixtures. EXPERIMENTAL The experiments were performed in a vertical tube furnace wound with platinum wire. For experimental temperatures of 800°C and above, a mixture of 5 pct Hz in N2 was used as the reacting gas. The gas mixture was prepurified from oxygen by passage over platinized asbestos at 450°C, and subsequently over anhydrone to remove water. Flow rates of the gases were measured with capillary flow meters. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. The specimens used for the high-temperature solubility measurements were in the form of rectangular plates, 0.534 by 1.6 by 3.8 cm. The specimens were cleaned in trichloroethylene and annealed for 2 hr in hydrogen at the beginning of each experiment. In measuring the nitrogen solubility, the specimens were held in the reacting gas until equilibrated, then cooled in a water-cooled copper block at the bottom of the furnace. The time needed for equilibration at 1150°C was determined by measuring the average nitrogen content of the 1.0 pct P alloy as a function of reaction time. As will be described, the nitrogen diffusivity in the alloy at 1150°C is only slightly less than its calculated diffusivity in pure iron. At temperatures other than 1150°C, the reaction time used in measuring the nitrogen solubility was about twice the calculated equilibration time for pure iron at the same temperature. With a few exceptions, the procedure for the low-temperature solubility measurements was the same as that described above. The compositions of the NH3-H2 gas mixtures were determined by collecting gas samples from the gas train and analyzing them for NH3 by titration with HC1. The specimen thicknesses were less than those used for the high-temperature experiments, eg., 0.124 and 0.051 cm for measurements at 585° and 440°C, respectively. Nitrogen concentrations were obtained by chemical analysis, using the Kjeldahl method. The Fe-P alloys were made by adding ferrophos-phorus to electrolytic Plastiron (Type 104 A). Commercial ferrophosphorus, containing 3 pct Mn and 0.35 pct Si as the major impurities, was first purified by melting under an FeO slag. In a separate heat, the electrolytic iron was melted and vacuum-carbon-deoxidized prior to making the ferrophosphorus addition. The principal impurities and their concentrations in weight percent in the 1.0 pct P alloy are as follows: Mn, 0.01; Si, <0.01; C, 0.01; 0, 0.003; and N, 0.0012. The impurity levels in the 0.23 pct P alloy are con-

Jan 1, 1968

By A. J. de Witte

It has been observed that upon invasion of a sand containing oil or gas and connate water by mud filtrate the hydrocarbons are more rapidly flushed by the filtrate than is the connate water.&apos; In time, it appears that the following displacement pattern emerges: oil (or gas) is being swept ahead by connate water which, in turn, is pushed by invading fluid. Eventually the connate water may have "banked up" sufficiently to form a zone of appreciable thickness leading the invading front. In the extreme case, Fig. 1 shows how the situation will develop.&apos; Immediately adjacent to the borehole (radius r) there is a zone, the invaded zone proper, where the connate water has been flushed out completely and which contains only residual oil or gas and mud filtrate. This zone (extending out to a radius ri) grades more or less abruptly into the next (thickness A), which contains only residual hydrocarbon and connate water. Beyond it, again more or less sharply bounded, extends the virgin formation with the original interstitial water saturation Sw. The various saturations are indicated in Fig. 1. The three zones generally will be marked by resistivity contrasts owing to their different fluid contents. As the connate water is usually more saline than the invading fluid, the second zone having a high connate water saturation forms a concentric cylindrical ring or annulus of low resistivity R, around the borehole.&apos;,&apos; It will be referred to as the "low zone." Fig. 1 shows schematically the resistivity profile. It is clear that the phenomenon of a low zone could not occur in invaded water sands. The presence of a low zone, therefore, would be a qualitative indication of a hydrocarbon-bearing formation. Granted that the phenomenon is real, if it were pronounced enough to be detected, one might thereby have a means of locating oil or gas in the ground. This is the aim of the "displacement logging" method.&apos; In any case, the presence of a low resistivity zone will affect the reading of electric logs. Using conventional log interpretation techniques, one must be aware of this and, if necessary, correct for it. Whether correction or detection should be the goal will depend primarily on the magnitude of the effect. The type of log which is likely to be affected most is the induction log. The current pattern of an induction log is concentric with the borehole. Any concentric ring of low resistivity, therefore, will tend to become crowded by current lines. This zone of maximum current density will obscure the relative contributions to the current conduction by other portions of a bed making, for instance, the contribution of the virgin formation less significant and thus detracting from the value or the induction log as an R, reading device. The present note is intended to ascertain the maximum possible effect of a low zone in the extreme case portrayed by Fig. 1 on three commercially available types of induction logs, sc., 5 FF 27, 5 FF 40 and 3 F 60. Type 5 FF 27 or 5 PF 40 is currently run in conjunction with a 16 in. normal and SP log. This combination is gradually replacing the regular electric survey (two normals and one lateral) as a standard log in many areas. On the basis of the scheme of Fig. 1 (sharp boundaries between successive zones), the thickness of the low zone may be computed for various amounts of infiltration measured by the ratio of invaded zone diameter to hole diameter D,/d. Referring to Fig. 1, we can set up a material balance for the water displaced from the invaded zone proper and the water present in the low zone. The volume of connate water displaced from invaded zone upon flushing by mud filtrate is: V1 = e p (r2 - r2) ? Sw . where c = bed thickness ? = porosity Su, = original connate water satu-ration. The volume of water finally accu-mulated in the low zone is: Vz = e p [(r1 -?)2 - r2 4] ? Sw . where SW1 = 1 — Sor = "water" saturation in the invaded and low zones both. The volume of water originally present in the low zone is:

Jan 1, 1958

The curve of Fig. 3 for pyrite requires modification. There 11% a range of pH values from 6.2 to 7.8 for which no cyanide is required to prevent contact. From 7.8 to 11.3 a small amount of cyanide is required, with a sharp maximum of 20 mg. per liter at pH=9.6. The mistake arose from considering too few solution compositions (17 were considered) in constructing the curve. Subsequent work with other collectors indicates that the corrected curve is typical for such systems; it illustrates the further development of the dip in the pyrite curve of Fig. 5.

Jan 1, 1938

By E. C. Felton

At the Pennsylvania Steel Works, Steelton, Pa., a series of trials has been made with oil as fuel in steel-heating and open-hearth steel-furnaces with the following results : First Trial.—Hot 14-inch ingots, six to a charge, were heated in two Siemens&apos; heating furnaces in the blooming mill, the oil being put in first in March, 1888. The oil used had been partly refined, so that the paraffine and some of the naphtha were removed. During a run of six weeks the consumption of oil was about 61/2 gallons per ton of blooms, including the oil required to keep the furnace hot over Sunday.

Jan 1, 1889