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By Bernt Ellingsaeter, Terkel Rosenqvist

IN the silicothermic reduction of magnesia, burned dolomite is treated with high grade ferrosilicon in an evacuated steel retort at temperatures between 1150° and 1200°C. The following reaction is assumed to occur MgO + CaO + 1/2 Si (Fe) - Mg(g) +- & Ca,SiO, + Fe with the equilibrium constant on the basis of thermodynamic data for the substances involved and assuming unit activity for all solid constituents, Kubaschewski and Evans' calculated the magnesium pressure as a function of temperature logp,, (mmHg) = 15.06-1.61 T- log T- 13,16O/T. Pidgeon and King," who measured the magnesium pressure by means of a flow method, found values about three times the calculated ones. This may be caused by uncertainties in the thermodynamic data, but may also be caused by the formation of other reaction products, such as Ca,SiO,, which is known to be the stable silicate in equilibrium with lime. Whatever the exact reaction may be, it is evident that as long as all other factors are maintained constant the magnesium pressure will vary with the silicon activity, viz: p,, = &,. (p,,) ", where (p,,)" is the magnesium pressure by the reduction with silicon of unit activity. In the present investigation, p,,, was therefore measured for various grades of ferrosilicon and their silicon activities were calculated. The experimental method was similar to that used by Pidgeon and King. Briquettes of burned dolomite and Fe-Si alloys were placed in a 1 in. heat resistant steel tube and were heated to 1200°C. By means of a flow of purified hydrogen, the magnesium vapor was swept into a condenser filled with steel wool. From the amounts of hydrogen used and magnesium condensed the magnesium partial pressure was calculated. First a tube of 28 pct Cr steel, and later a tube of Kanthal D (a ferrous alloy with 22.6 pct Cr, 2 pct Co, and 4.5 pct Al), was used as a heat resistant tube. The latter tube showed the best heat resistance. The dolomite used had the following composition: 43.6 pct MgO, 55.5 pct CaO, 0.2 pct K,O + NalO, 0.2 pct Fe,O,, and 0.3 pct insoluble. The ferrosilicons were prepared from 98 pct Si of technical grade (0.7 pct Al, 0.3 pct Ca, and 1 pct Fe) by melting with various amounts of electrolytic iron of high purity. The alloys thus obtained were analyzed on their iron and silicon contents, which added up to between 99 and 100 pct. The amounts of reactants were chosen so that there would always be an excess of the oxides, and the average decrease in silicon content during the experiments would be about 1 pct. Most of the reaction occurred in the part of the reaction mixture facing the gas flow. The change in the silicon concentration in the part facing the condenser was, therefore, negligible. To facilitate the reaction, about 1 pct fluorspar was added to the briquette mixture. Fluorspar does not enter the reaction, but is known to act as a

Jan 1, 1957

By James A. Crookston, William D. Fitzpatrick

Committee C-8 of the American Society for Testing and Materials defines "Refractories" as "Material, usually nonmetallic, used to withstand high temperature," and it defines the term "Refractoriness" thus, "In refractories the capability of maintaining the desired degree of chemical and physical identity at high temperatures and in the environment and conditions of use." The ability to withstand high temperatures is critical to classifying a material as a "refractory." However, as the foregoing definition of "refractoriness" implies, the refractory material may be subjected to and is expected to resist not only high temperatures but a variety of other destructive forces incident to its use. These include abrasion, impact, thermal shock, chemical attack, and high level loads at high temperatures. The various industrial applications of refractories represent an infinite variety of combinations and degrees of severity of these destructive forces, including high temperatures. Naturally, such a variety of application conditions leads to a need for a wide variety of refractory products to satisfy those conditions. The number of refractory products available is great enough that some form of classification is necessary to a discussion of refractories. Refractories may be classified in several ways, but the most suitable one is based on their general compositions and to lesser degrees on their physical condition and distinctive properties. The primary types of brick include aluminosilicate brick (fire clay and alumina), basic brick (magnesia and chrome ore, alone and in various combinations), silica brick, insulating brick, and special refractories (carbon, Sic, ZrO,, zircon, borides, and nitrides). Brick are, of course, preformed and are usually heat treated at high temperatures before use, but are in some instances unburned and/or chemically bonded, including the relatively new class of tar-bonded magnesia and/or dolomite brick. In addition to preformed refractories, another broad category includes the so-called specialty refractories, which are usually made in the same types as itemized for brick-bonding mortars and high temperature cements, hydraulic setting castables or refractory concrete, plastic firebrick, and ramming mixes. Refractory grains, such as fire clay and high alumina calcines, dead-burned magnesite and periclase, and dead-burned dolomite are also considered refractory products. Brick are also classified on the basis of physical dimensions, as standard sizes and special shapes. The standard sizes are those which are of definite shape and design and are designated as 9 x 4 ½ x 2 ½ in. and 9 x 4 ½ x 3 in. straights and series. All other brick of non- standard sizes are referred to as special shapes. These come about as a result of a particular need for a given furnace or for a particular application.

Jan 1, 1975

By Charles F. King

THE only investigations on record of the reactions occurring during the Bessemer blow are of charges containing a large percentage of manganese, with the exception of two partial analyses by Snelus and Barker of the. English method, where a low percentage of manganese was used. They do not give the analysis of the spiegel, nor do they report any graphitic carbon after the first stage of the process. Both report only traces of manganese after the first stage until the addition of spiegel. The slags corresponding to the samples of metal were not analyzed.

Jan 1, 1881

By R. P. Heuer, Paul M. Tyler

THE literature on refractories, although fairly extensive, is so scattered through books and periodicals as to be difficult of access to the general reader and most of the individual papers serve merely to illuminate some particular phase of the industry. Two general treatises by American authors8.16 are available, also the somewhat older works by a well-known British authority, 12,13 but these make their appeal to the technically minded ceramic engineer. Another small group of publications deals with the use of refractories, mainly in the iron and steel industry.1, 3,5,6,11,15 Raw materials utilized by the refractories industry have been covered by sundry books and articles. For the relatively nontechnical reader and economist, however, there appears to be no single review that purports to describe the industry as a whole. Furnace linings and other products that are classed as "refractories" are designed primarily to withstand high temperatures but this important property is by no means the only requirement; a suitable refractory material must likewise withstand slagging (chemical' action), abrasion (physical wear), and spalling, as well as the various other stresses and physical phenomena induced by heat, of which softening or incipient melting is only one phase. Nevertheless, subject to these highly practical considerations, the definition of a refractory material is based upon temperature resistance. Broadly speaking, any material that shows obvious signs of fusion after being heated slowly to 1500°C (2732°F) cannot be classified as a refractory material. The characteristic properties and requirements of refractory materials are conveniently summarized in Fig 1, prepared on the American Refractories Institute Fellowship at Mellon Institute, Pittsburgh, Pennsylvania. Most of the factors of service and properties of refractories given in this chart are interdependent and are greatly affected in degree by the functions of temperature and time. The factors in the chart are believed to cover the commoner questions.

Jan 1, 1949

By Z. T. Bieniawski, E. Unal, H. Reginald Hardy

INTRODUCTION Rock bolts are a major means of support in underground coal mines in the United States. However, two of the most crucial problems facing the mining engineer today are that of finding a well defined and standard method for testing the anchoring ability of rock bolts, and of selecting the most suitable type of rock bolt and bolting pattern for a particular mine or specific mine section (Anon., 1982). Such selection requires not only an understanding of the behavior of the rock mass and the rock-bolt unit itself, but also a knowledge of the basic mechanisms by which rock bolts provide support while they interact with the rock mass during various field loading conditions. A recent study in this area has shown the inadequacy of present methods used in selecting and testing of rock bolts and the lack of clearly defined guidelines for safe and economical design of bolting patterns (Bieniawski, et al., 1980). The present paper describes a research study aimed at developing laboratory instrumentation and associated techniques for the evaluation of bolt-rock interaction. The instrumentation system developed, procedures followed during various experiments, and typical results from a series of studies carried out on mechanical bolts are presented. DEVELOPMENT OF THE ROCK BOLT TESTING FACILITY General A block diagram of the experimental facilities are shown in Fig. 1. The system consists of three main sections. The first

Jan 1, 1982

By C. W. Sherman, N. J. Grant

The correlation of the high temperature chemical properties of slag-metal systems with some easily measured property of either slag or metal at room temperature has been the goal of both process metallurgists and melting operators for many years. There are several rapid methods for estimating various constituents in steel in addition to the conventional chemical methods which are quite fast, but these do not reveal the nature of the slag as a refining agent, which is of primary interest to the steelmaker. Furthermore, there are several methods for examining slag, the three principal ones being slag pancake, petrographic examination, and the previously mentioned chemical analysis. The main objection to the last two is the lime required to make a satisfactory estimate of the mineralogical or chemical components. The objection to the first is the inadequacy of the information obtained. A new technique has been developed by Philbrook, Jolly and Henry1 whereby the properties of slags are evaluated from an aqueous solution leached from a finely divided sample of slag. It is known that the pH or hydrogen ion concentration (of saturated solutions that have dissolved certain basic oxides, notably calcium oxide) will indicate a pronounced basicity. Philbrook, Jolly and Henry devised the pH measurement technique in order to supply open hearth operators with a fast, reasonably accurate method of estimating slag basicity. They offered the method as an empirical observation and made no claims as to its theoretical justification. The results were presented as an experi-metally observed relationship which applied over an important range of basic open hearth slags. They found that, in plotting the measured pH against the basicity, the best relationship existed between the pH and the log of the simple V ratio, CaO/SiO2. Extensive investigation also showed that there were several variables in the experimental technique that influenced the results and necessitated following a standard procedure to obtain reproducible pH readings. These variables were: 1. Particle size of the slag powder used. 2. Weight of sample used per given volume of water. 3. Time of shaking and standing allowed before the pH was measured. 4. Exclusion of free access of atmospheric carbon dioxide to the suspension. 5. Temperature of the extract at the time the pH was measured. In subsequent investigations of the pH method by Tenenbaum and Brown2 and by Smith, Monaghan and Hay3 the general conclusions of Philbrook's work were reaffirmed. It was the object of the present investigation to extend the technique to a point where it could be used to evaluate slags of all types. Experimental Results PARTICLE SIZK OF SLAG POWDER A large sample of commercial blast furnace slag of intermediate basicity (V-ratio 1.15) was selected for the study. The slag had been put through a jaw crusher until all of it passed through a 20 mesh screen. Five fractions of this crushed material were separated, -20 to +40, -40 to +60, -60 to +100, -100 to +200, and -200 mesh. A representative sample of 0.5 g was removed from each fraction and the pH determined using the method of Philbrook. Check pH analyses on the sample fractions varied due to the different amounts of shaking. To eliminate this variable, a mechanical shaker was employed. In order to know the exact time of contact between the slag and water, it was found necessary to filter the extract at the end of the shaking period. Using the mechanical shaker and a filtering apparatus, similar runs were made on the five fractions for contact times of 5, 10, 20, and 40 min. Random checks gave reproducible results within 0.02 pH. The data are plotted in Fig 1. It can be seen from the plot that each slag fraction is hydrolyzed to an extent that is roughly proportional to the surface area exposed to the water. The (—100 to +200) mesh material changed very little in pH after 10 min. shaking time. The curves are symmetrical and lie in proper relation to one another. The —200 mesh curve appears to be somewhat flatter than the others, but this can be attributed to the portion of very fine material that is not present in the other fractions. The closeness of the (-100 to +200) mesh curve to the —200 mesh curve and the fact that a —100 mesh sample would contain amounts of slag down to 1 or 2 microns in diam were considered sufficient reasons for selecting a —100 mesh sample as representative of the whole sample of slag for the purposes of this investigation.

Jan 1, 1950

By N. A. Ziegler

THE chief difficulty in determining oxygen in steels is its tendency to form a variety of compounds. Almost every element, found as an ingredient in steels, maybe expected to be present as an oxide. Some of these oxides have widely differing properties, and consequently behave differently when attempts are made to reduce them by the vacuum fusion method. As I pointed out in a paper published in the Transactions of the A.S.S.T., Vol. 20, No. 1, many experimenters are spending considerable time and effort in attempting to deter¬mine the degree of completeness of the above reactions, and hold different opinions on the matter. In studying this subject the following table, taken from Hodgman and Lange's "Handbook of Chemistry and Physics" may be used as a guide.

Jan 1, 1933

Resistant Tape A new oil-resistant tape for rapid insulation build-up on splices in large power cables has been announced by Minnesota Mining & Mfg. Co. Designated Scotch brand electrical tape No. 25 is made of synthetic rubber providing greater dielectric strength and resistance to high temperatures. The chemical-resistant qualities of the tape make it suitable for use in oil drilling, mining and underground [ ] cable operations, while the 40-mil thickness and extreme stretch (1500 pct breaking point) make possible smooth insulation wraps on irregular surfaces. Dielectric strength is 15,000 v and 10,000 v at 500 pct elongation. It has an electrolytic corrosion factor of 1.0 and an insulation resistance of 100,000 megohms. Circle No. 1 Hydra-Lift The Pitman Mfg. Co. announces that is now has in production a new model of the Pitman hydra-lift, recently-developed crane with hydraulically-powered boom that can be mounted on the frame of any truck, 1 ½ tons or larger. According to the manufacturer, the new model hydralift model B features a variety of improvements over the original production model, introduced late in 1950. Changes incorporated in the new model, according to officials, not only have resulted in improved crane, but also have given the unit a new profile which distinguishes it sharply from the original model. The two chief improvements in the new model are: a big increase in the unit's safety margin and the fact that it is now shipped almost completely preassembled, cutting the time and cost of installation. Rated capacities of the hydra-lift are based on the tipping factor of a 1 1/2 ton truck, with outriggers down, and thus have not been increased. Circle No. 2

Jan 1, 1952

By AIME AIME

FEATURES of the second fall meeting of the Petroleum Division for 1941, held at the Ambassador Hotel, Los Angeles, Oct. 29-30, were the forum on the Paloma Plan on Thursday after- noon, the large attendance from east of the Rockies, and the dinner on Wednesday evening sponsored by the Southern California Section and at which President Suman spoke on the strategic minerals and metals situation. The attendance was large and the technical fare uniformly good ; the presiding officers had the proceedings well in hand at all times and kept things humming. Some- times it was necessary to taper off the discussion because of pressure on time. All this was due to careful groundwork before the respective sessions. These presiding officers deserve citation: L. W. Huebel, Howard Pyle, E. K. Parks, Carlton Beal, E. G. Trostel. R. W. French, Jr., John Dodge, and H. N. Marsh. The Los Angeles local commit- tees and the Southern California Section deserve much credit for the arrangements, which were recognized by suitable resolutions at the end of the meeting.

Jan 1, 1941

By J. W. Borough

THE electrical conductivity of pure copper is markedly decreased by small amounts of impurity in solution. The magnitude of this effect has been very carefully determined by numerous investigators who studied a wide variety of impurity elements. Much of this work is summarized in an excellent review by Pawlek and Reichel.' The case of zinc impurity in copper is an exception to the above in that there has been no well-documented study of the effect using high-purity starting materials. The values for the effect of zinc on conductivity, which are usually taken from unpublished work by Skowronki, indicate that zinc in low concentration has no effect whatever in lowering the conductivity of pure copper. This effect, if true, is unusual since it is generally known that even in lowest concentration, impurities exert an effect on conductivity which is proportional to the amount dissolved. It is more reasonable to suspect that in the original work on the effect of zinc some of the zinc was oxidized out of solution during specimen preparation. The following experi- and calculated d-spacings based on the unit cell dimensions of Baenziger et al. Since the single crystal studies of Baenziger et al. were limited to (hk0) and (hk 1) data, it was not possible to Compare all the intensities of the powder and single crystal patterns. However, the strongest reflections of both studies, the (321) reflection, agree very well when the appropriate multiplicity factor is used. Good agreement was also found in a number of other reflections of lesser intensity. Despite the precautions taken in annealing the U6Fe powder, an appreciable amount of UO, was detected in the powder pattern after heat treatment. The powder pattern reported by Groganoand Clews is given in Table I. Except for the 3.15A line, which is the strongest line of UO,, their pattern, as far as it goes, compares favoEably with the data from this study. Gordon and Kaufmann have reported a diffraction powder pattern purported to be U, Fe but it bears very little resemblance to the patterns of Table I. ments were carried out to redetermine the effect of zinc on conductivity using high-purity starting materials and processing conditions capable of producing oxygen-free alloys. Materials used in the experiment were ASR 99.999 pct Cu and Cumingo 99.999 pct Zn. Four 1 lb melts were prepared with identical procedure in argon atmosphere with crucibles made from Speer No. 580 graphite. The compositions were 0.0, 0.1, 0.3 and 1.0 pct Zn. Standard No. 14 wire (0.064 in. diam) was made from these melts as follows. The 1 pct Zn sample was first reduced 94 pct by cold swaging with five annealing treatments of 800o for 10 min in hydrogen between swagings, and then reduced 94 pct to the

Jan 1, 1962

By T. G. Digges, C. L. Vold, M. R. Achter

A study was made of the effect of the growth conditions on the perfection of single crystals of niobium (columbium). Dislocation densities, determined by means of double-crystal diffractometer measurements , were not greatly affected by the method of crystal preparation but could be reduced by annealing treatments. However, the size, sharpness, and tilt angles of the substructures, observed with X-ray reflection macrograph, were sensitive to variations in growth procedures as well as to subsequent thermal treatments. Although the dislocation density was the same in both types, there were more low-angle bound-aries in crystals grown by zone melting than in those prepared by strain anneal. Mechanisms to account for these observations are discussed in terms of dislocation movements. A planned study of the structure-sensitive properties of refractory metals required the use of single crystals of a high degree of structural perfection and, for ease of handling, of large cross section. It appeared that the strain-anneal technique could satisfy both of these requirements. First, crystals grown in the solid state have been reported to be more perfect than those obtained from the melt.' Second, the diameters of rods which may be produced by zone melting should have a theoretical limit determined by specific gravity, thermal conductivity, and surface tension, while the diameter of strain-annealed rods is limited only by practical considerations. Previously it was shown that niobium (columbium) single crystals of 1 in. diam2 may be grown by strain anneal, compared to the 0.5 in. maximum diameter achieved by zone melting, as reported for molybdenum by Belk.3 The current research was undertaken to investigate and optimize the effect of various process variables on the perfection of 1/4 and 1/2-in.-diam niobium single crystals grown by strain annealing and to compare their perfection to those grown by zone melting. Characterization of these crystals was more conveniently accomplished by means of X-ray than by metallo-graphic techniques. EXPERIMENTAL PROCEDURE Specimen Preparation. Zone-melted crystals of 1/4 in. diam were produced by the standard electron-beam zone-melting technique. The swaged and cleaned rods were outgassed, in the solid state at a temperature near its melting point, at a rate of 12 in. per hr, and single crystals were grown by making two molten passes at 2 in. per hr. By maintaining a zone length of 4 to % in., very uniform single crystals several inches long were obtained. For the strain-annealed crystals, an induction heater was used, in preference to other types of heating, to take advantage of the good penetration of large sections. A five-turn coil, 1 in. long, operating at 10 kc and powered by a motor generator, was contained in a vacuum chamber. The rod, suspended from the upper end, was raised through the coil for both recrystallization and crystal growth. In preliminary work single crystals of the same material were also grown with single and multiturn coils powered by a 450-kc generator. A vacuum of 2 X 10-6 Torr was maintained at temperatures up to 2400°C. Starting with electron-beam-melted ingots of 21/2 in. diam, the analysis for which is given in Table I, the material was cold-swaged to the desired cross section of 1/4 and 1/2 in. diam and then recrystallized. The rods were then strained in a tensile machine and converted to single crystals by passing through the induction coil. As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and smallman,4 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point in the poly crystalline portion. Finally, it is returned to the chamber and growth is continued "around the corner". This procedure has certain limitations. If the bending operation exceeds the critical strain, recrystallization may take place. Also, the amount of bending which can be imparted to the rod is limited by coil geometry, and up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. In preparation for X-ray examination, single crystals were sectioned and planed by means of the spark-erosion technique. To obtain the maximum reflected intensity, the (110) plane was exposed for examination. They were then etched 3 to 5 min in a mixture of con-

Jan 1, 1967

By Horace Pops, J. F. Libsch

THE discovery of SAP alloys (sintered aluminum powders) by lrmannl has stimulated investigations in other alloy systems.23 Not only do such alloys have good room-temperature properties, but they maintain high strength after prolonged service at elevated temperatures. In addition, they show high structural stability, including unusually high recrystallization temperatures. These characteristics are secured by dispersion hardening. For this investigation, Zn-ZnO alloys were selected. Practically, the fact that commercially pure zinc recrystallizes near room temperature prohibits strengthening and hardening by cold deformation and therefore limits the application of zinc where mechanical strength is important. Similarly, the poor

Jan 1, 1961

By Georges Ranque

THIS paper by. Georges Ranque is an attempt to reason out the conditions of formation and stability of inclusions and to establish an operative process capable of eliminating or minimizing them. The paper consists of two parts; one in which the author considers the laws of physical chemistry and physics that apply to liquid slag-metal systems and one in which he describes a practice based on the theoretical considerations. Such a paper is bound to contain controversial points and it is therefore your speaker's intention to present Mr. Ranque's side of the picture to the best of his ability without regard for any thoughts or criticisms of his own. RISING VELOCITIES OF INCLUSIONS Most nonmetallic inclusions have densities ranging from about 1.7 to s, while liquid steel has a density of about 7. Under these conditions, ferrostatic pressure should cause the inclusions, being lighter, to rise from the bath and be eliminated. This rising tendency is expressed by Stokes' law, from which may be calculated the rising velocity of a spherical particle in a liquid medium whose density and viscosity are known.

Jan 1, 1947

By E. von Maltitz

In his highly interesting paper, Piping and Segregation in Steel Ingots,' Prof. Howe emphasizes the effect of successive phases of internal pressure in the ingot in the evolution of gas, and the consequent formation of blow-holes. From his statements in other places, it may be inferred that he does not here intend to ignore the other variable factor, temperature, but rather to discuss this one more particularly. At all events, it is my purpose not to engage in controversy with Prof. Howe, but, rather to contribute, towards the complete elucidation of this important subject which we all desire, my own views and experience. If, in doing so, I specially emphasize other factors than pressure, I need not be understood as denying what I do not think it necessary to discuss fully. Nor, in presenting my own original conclusions, need I be understood as claiming to be the first who ever reached or announced them. Many things are asserted or suggested upon inconclusive evidence; and to confirm such tentative propositions may be as valuable a service as to overthrow them. In the following passage, Prof. Howe adduces analogies, based upon the behavior of charcoal and of water, respectively, which seem to me questionable : "In general, the solvent power falls as the pressure falls ; and in general it rises as the temperature falls. Thus, to heat a solid, for instance charcoal, may expel part of its dissolved gas ; and a tumbler of water drawn cold from the faucet gradually evolves gas, as it stands and warms up on the sideboard." (p. 72.) Charcoal is a solid body, which has the property not only of absorbing gases in large quantities, but also of expelling the thus absorbed gases upon heating. A comparison between charcoal and iron as to the absorption of gases is scientifically not possible; the gas-content of charcoal is partly due to the

Jan 1, 1908

By R. J. Colony

MINING geology does not lend itself - very readily to a review embracing "improvements in methods," as perhaps do shop practices or laboratory procedures. The "methods" used in mining geology are simply the application of geology to mining; winning the ore, the handling of material, mechanical appliances, all belong strictly to mining proper, and have no place in a review of geology as applied to mining. A comprehensive review would necessarily cover a .very broad field, which could be subdivided into many -parts. Only a few of these can be discussed here. .Those that have been suggested to the chairman indude :

Jan 1, 1930

By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;' the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

By G. Derge, Lo Ching Chang

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By G. Derge

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By C. S. Brooks

Several of the commonly used methods for deter-mination of effective grain densities of minerals have been evaluated for accuracy and precision, and their applicability to various types of petroleum reservoir minerals tested. Consideration was given to the effect of consolidation, swelling clay, and wettability on these grain-density determinations. Procedures with helium displacement, a modified low-pressure Boyle's law porosimeter, and liquid displacement (water, n-decane, and n-octanol) were tested. The helium-displacement procedure was used primarily as an independent reference for which the effects of fluid-solid interaction, e.g., adsorption and wettability, were negligible. The procedures with the Boyle's law porosimeter and with liquid displacement are the methods in common use. Minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The number of samples tested, while not large, was adequate to permit application of statistical methods. Grain-density measurements on calcite (Iceland spar) provided a basis of comparison for the accuracy and precision of the procedures under investigation for a material with a high degree of chemical and physical homogeneity and for which fluid-solid interactions were at a minimum. Liquid-displacement procedures (water or n-decane) provided the greatest reliability and precision for measurement of the grain densities of the limestone tested. Gas-displacement procedures (helium or Boyle's law porosimeter) provided the greatest reliability and experimental convenience, if not the greatest precision, for the measurement of the grain densities of the swell- ing clay, Wyoming bentonite, and the shah sandstones which -contained appreciable amounts of swelling, in-terstitial clays. These experiments were designed to evaluate the applicability of the grain-density procedures in common we to some of the less tractable minerals—tight limestones, shaly sandstones, and swelling clays. The results should provide a useful basis for a selection of the method most suitable for application to the various petroleum reservoir minerals encountered and especially for use in the estimation of formation porosity. INTRODUCTION These experiments were undertaken to evaluate the accuracy and precision of several commonly used methods for determination of effective grain densities of minerals, and to test their applicability to various types of petroleum reservoir minerals. Consideration was also given to the effect of consolidation, clay, and wettability on these grain-density determinations. Procedures used included measurements with helium displacement, with a modified low-pressure Boyle's law porosimeter, and with liquid displacement (water, n-decane, and n-octanol). The minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The accurate determination of the porosity of petroleum reservoir formations, in particular those of low porosity, has received much attention. Both bulk-volume and grain-volume measurements necessary in the evaluation of porosity have been examined by many investigators with the objectives of improving both the accuracy and the precision of these determinations. In this investigation statistical criteria for selection of the most reliable and suitable procedure for use with a given type of mineral are demonstrated. The grain-volume measurement procedures appear to be the most susceptible to improvement.

Jan 1, 1958

By AIME AIME

MANY producers have held that the only workable quicksilver ore is easily recognized by its .cinnabar content. In most cases this is true. A noticeable exception is a. particular opalite deposit where part of the ore now being mined in considerable quantity shows only the yellow mineral, calomel, or its alteration products. This mineral, on exposure to the sunlight, quickly becomes coated with gray or black layers that may be removed by scraping to reveal the yellow mineral beneath. The blackening of this mercuric chloride on exposure to sunlight shows reaction to form metallic mercury, which is usually plainly present in this class of ore.

Jan 1, 1929