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By Ziebell, Howard A.

THE Washington magnesite deposits, located in the hilly and mountainous northeastern part of Washington, occur as massive lenses in a sedimentary series made up of dolomite, shale, and quartzite, into which basic dikes have intruded. The ore pattern resembles a series of disconnected chain links extending approximately 25 miles in a south-west direction. Magnesite in this district is all crystalline and closely associated with dolomite, talc, serpentine, and basic dike rock. All deposits which have been developed are near the surface so that quarry-bench mining has been possible. For over twenty years hand sorting magnesite ore at the quarry face was standard practice. Ore cars were hand trammed on 30-lb rail systems which led from the face to ore passes or raises for the magnesite ore and to the waste dumps for disposal of the rejected waste material. This system was somewhat modified by the use of Dempster Dumpster trucks. The ore was, however, still sorted by hand from the calcium and silica bearing waste rock. Power equipment. consisting of one 3/4-yd electric shovel, was

Jan 1, 1949

By GERALD A. WARING

ALASKA'S coal consumption is now about 130,000 tons annually. About one-quarter of this amount is used in the southeastern part of the territory and in settlements on the western coast and comes from Seattle and from British Columbia mines. About 60,000 tons is sub-bituminous coal from the Healy River mine in central Alaska, and is used mainly at Fairbanks, sixty miles to the north, for heating and the development of electric energy, for the city and the gold-dredging operations of the Fairbanks Exploration Co. The remaining 40,000 or 50,000 tons is bituminous coal from Matanuska Valley, in the south-central part of the territory. These coal deposits extend intermittently for about forty miles along the valley, which trends eastward from the upper end of Cook Inlet.

Jan 1, 1934

By Sherwin F. Kelly

THIS is intended as a simple review of the principles and practice of geophysics, so will not be of interest to the geophysicist, who is hereby warned of its elementary character. The engineers for whom it is written are those who, having glimpsed the formidable formulas and discussions of the geophysicists, give all publications on the subject a wide berth. For a few years now the geo-physicists have had a tendency to be ingrowing at their meetings, going deeper and deeper into theory and instrument construction, and forgetting to present the topics that would interest the practicing engineer who desires merely to know how geophysics can help him, not why.

Jan 1, 1934

By F. W. Glaser, W. Ivanick

A pressure-sintering method was used to produce binder-free and very dense TiC specimens. Some physical properties of these TIC bodies were determined and found to compare favorably with those of certain cemented Tic grades. It was also observed that the hot transverse rupture strength of TiC bodies remained substantially the same regardless of the amount or type of binder material used. STUDIES of the structure and physical properties of refractory materials have been intensified recently because of the urgent need for nonstrategic materials that retain their strength at high temperatures. Research aimed at determining and improving the physical properties of cemented carbides and borides has been accelerated with a view toward possible use of such materials in connection with turbine blades, rocket nozzles, and other high temperature applications. On the hypothesis that the strength requirements in connection with some of the above applications could be met only by proper choice of cementing agents for such refractory materials, the literature describing the physical properties of borides or carbides was reviewed. However, with a few exceptions,'-" references were found only to compositions containing at least one or more auxiliary binder metals. Cobalt and nickel are among the most frequently employed cementing agents. The melting point of Tic (approximately 3250°C) and therefore the sintering temperature, at which notable densification of a cold pressed Tic powder compact could be expected in the absence of a liquid binder phase, is relatively high. The present study makes use of a high temperature, pressure-sintering procedure, recently described by one of the authors in connection with the sintering of binder-free ZrB,," to produce dense bodies of sintered Tic—free of any cementing agent. During the course of this sintering study, some physical properties of dense Tic bodies produced by this method will be discussed. Materials, Preparation of Samples, Testing Methods The procedure for the forming of Tic powder consisted of mixing graphite and TiH, powders in stoi-chiometric proportions, and heating this mixture in a H, atmosphere and carbon crucible by high frequency, to temperatures ranging between 1900° and 2100°C (3452" and 3812°F). The powdered carbide was then comminuted and screened to the desired particle size. Table I shows the chemical analysis of the two grades that were employed for the production of samples during this work. Bodies of Tic, approximately 2.5xlx0.5 cm were produced in graphite molds that were heated by direct conduction. Sintering was carried out at temperatures for time intervals ranging from approximately 0 to 30 sec under a constant pressure of about 1.3 tons per sq in. An alternate method for the production of samples consisted in cold pressing the individual Tic grades at pressures ranging from 4 to 10 tons per sq in. and sintering in a hydrogen atmosphere in graphite crucibles heated by high frequency induction. Sintering temperatures ranged from 2600° to 2900°C (4715° to 5255°F). Electrical testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp at room temperature. Cross-sectional areas as well as densi-

Jan 1, 1953

By B. Amadei

INTRODUCTION Laboratory studies on the deformability and strength of intact rocks generally involve the uniaxial compression test, the standard triaxial compression test and direct or indirect tension tests. If [al ,a2 ,a3] are principal stresses [(al>a2>a3)] with compression taken as positive and tension taken as negative, the applied stress field for each one of these tests can be represented as shown in Fig. 1. However, for most in-situ conditions, such as those that exist at any point around an underground excavation, the stress field is truly three-dimensional or multiaxial [(al+ a2+a3)] and none of the tests shown in Fig. 1 can be used to predict the mechanical behavior of the rock. There are special cases for which one of the three principal stresses vanishes. Biaxial loading of rocks in-situ takes place, for instance, when rocks deform and fail in plane stress conditions. This can occur in a free unloaded surface of a rock structure such as in the wall of an underground excavation or a rock slope. Parallel to the free surface, the stress field components can be both compressive [(al>a2>0)], both tensile [(O>a2>a3)], or mixed, one component being compressive and the other one tensile [(U~>O>U~)]. The purpose of this paper is to present the results of 25 true biaxial tests that have been conducted on cubical specimens of Indiana Limestone using the multiaxial cell available at the University of Colorado at Boulder. The tests include uniaxial compression and tension, biaxial compression and combined biaxil compression- tension. Flexible fluid cushions and brush bearing platens were used for compressive and tensile loading respectively in order to minimize loading end effects on the test specimens. The paper begins with a review of previous investigations on the multiaxial behavior of rock. Then, test results are presented in terms of

Jan 1, 1984

By A. W. Ruff

In the last ten years large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now-prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. In the last ten years, large gains have been made in the field of blasting. These gains have been both in the theoretical and in the practical application of explosives. One of the most publicized changes in the practical application of commercial explosives is the now prevalent use of ammonium nitrate and fuel oil. The new water-compatible mixture of ammonium nitrate and TNT should also have a large field of application. Most of the theoretical gains have been concerned with the actual rock breakage obtained with explosives. EXPANDING-GAS-BUBBLE THEORY There has been an outstanding change in the conception of how an explosive produces rock failure. The early theory which explained rock breakage was correct for some of the first force-producing agents such as quicklime. When a drillhole was filled with quicklime and water added, the material expanded and steam was generated. The expanding material and the steam exerted a slowly increasing pressure on the sides of the drillhole. The force broke the rock by splitting. Because a great quantity of gas was produced by the deflagration of gunpowder, the same process of the gas pressure splitting the rock was assumed to take place. Even after 80 years of use, the rock-breaking action of all high explosives was thought to be caused entirely by the expanding gas bubble which tore and split the rock. Fig. 1 shows a vertical section through an exploding spherical charge of high explosive. It illustrates the early theory which attributed the entire breakage to the expanding gas bubble. The basic idea of this theory is that the breakage started at the explosive charge and progressed toward the free face. REFLECTED-WAVE THEORY me expanding-gas- bubble theory has gradually been replaced by the reflected-wave theory. The reflected-wave theory explains rock failure by explosives in the following manner: The enormously high gas pressure in the drillhole produces fracturing of the rock on the sides of the drillhole. The fracturing around a 1 1/2-in. diam drillhole is usually confined to an area with about a 6-in. diam. In the fractured area, the pressure of the gas is reduced until the force on the walls is no longer capable of fracturing the rock. Although the gas pressure does not continue to fracture the rock, the pressure imposes a high impact stress on the wall rock. In addition, a pressure or seismic pulse is produced in the rock. The pulse is probably entirely a compression pulse when originally produced in the rock. But, with distance, part of the energy of the compression pulse is transformed into a tension pulse which follows the compression pulse. The explosive charges and burdens used in conventional mine blasting are such that the tension pulse of the original wave is probably too small to be considered in a practical evaluation of the theory. The compression pulse is transmitted through the rock with no associated fracturing.

Jan 1, 1961

By Herbert M. Wilson

We of the employer class represent labor in the social organization and in industry just as truly as do those who labor only with their hands, and, because our labor is chiefly with our brains, the duty is all the more imposed upon us to use those gifts in which we excel in helping steer a clear course through the turbulent waters in which we are now enmeshed. Only their selfish engrossment in the daily tasks they were employed to perform could possibly have permitted the great majority of the intelligent and industrious German people to become terrorized by a handful of the idle, the vicious, and the criminal, whom the elections to the National Assembly showed to be in as pitiful a minority as they are in Russia, in this, and in other countries. It is the leisure unemployment of the I.W.W.'s, the Bolsheviki, and the Sparticans that has enabled them to devote their whole time to a concerted and aggressive struggle against the great majority of those of the world's workers who are unorganized, and who are therefore even in opposition one to the other. In union there is strength, and this was never better illustrated than by these conditions. The great fallacy of our previous attitude toward social and industrial problems has been the belief that labor, by which we commonly mean organized or physical labor, is something antagonistic to and having a different object in life from that great body of unorganized laborers who work with their brains. Our difficulty has been our lack of will or opportunity to think. The hurry of our daily struggle to earn our livelihood under the nerve-racking pressure of modern civilization has left us no opportunity for quiet thought and study. The physical laborer, and above all the laborer in the mines, on the other hand, has all his hours of toil in which to think over, in all their varied aspects, those problems that concern his immediate, personal well-being. As a result he has arrived at perhaps a more true appreciation of the facts of life in their relation to social and industrial conditions than we. Have we not too readily adopted the view that, as the managers of industry under the direction of capital, it has been our duty to think and act in opposition to labor, rather than to realize that we also are laborers, have like aspirations, and should participate in a free and aggressive solution of these problems rather than leave their solution

Jan 1, 1919

By George W. Riter

(Canal zone meeting, November, 1910.) A DISTINGUISHED engineer, the active head of a large mining company, has said that surveying attains the dignity of a profession only in the hands of a few men-the few who know how to keep notes that will be understood by even a novice without further word of explanation. Of all mine-records, survey notes are perhaps the most important. The maps made from them serve as a working-guide, and as framework for other data ; and when, from any cause, access to underground workings is shut off, the surveyor's record often becomes invaluable. So seldom does a surveyor have a chance to check underground surveys by making a closure, that he is compelled to rely on the precision of each step of his work for the accuracy of the final result. When data are fully recorded on the spot, the notes, even in the hands of second parties, become evidence of the care and precision with which the surveying was done. It is worth a great deal to be able to pick up the work of a former surveyor where it was left o$; and to be able to carry it forward without retracing from the beginning. The purpose of this paper is to describe the survey-note system of a mine now under my direction, in which underground surveys had to be relied upon entirely for the proper division of rich ore-bodies between neighbors, thereby placing a premium on accurate surveying and permanent records. In survey-work, it soon turns out that paper is the least item of expense, and that little is gained by trying to economize note-book space. For many purposes it is best to record notes on cards or loose-leaves, which may be left in the office at the end of the day's work, and need not be carried into the mine again, there to become smeared with grime and grease. With the loose-leaf or card system, all notes relating to the same local-

Apr 1, 1911

By Y. C. Liu, R. H. Richman

The effects of gel,manium and tin on the deformation and 9-e-crystallization textures of copper have been explored in detail with in the copper-rich terminal solid solutions. Addition of solute to copper produces a change in deformation texture from the copper type to the 70 :30 brass type. This transition has been measured quantitatively The types mid proportions of recrystal-lization components have been determined as a function of com-position, and correlation of recrystallization components with specific deformation components is discussed. On the basis of information available in the literature, it has been suggested that the effect of solute elements on the recrystallization texture of copper

Jan 1, 1961

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith's graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970

By Willard P. Ward

Having been engaged during the past year in the manufacture of ferro-manganese in a blast furnace, I have imagined that some further information on this subject might be of interest to that large number of members of the Institute who are engaged in the iron and steel industries. The great question of the economical production of good steel, ingot metal, or homogeneous iron (we scarcely know now what to call it) from good materials, and at reasonable prices, has, thanks to the intelligence and energy of a few American engineers, been successfully solved in this country. Nearly all first-class railroads, and many that would not rank so high, have adopted the Bessemer rail. Martin boiler-plates are rapidly gaining ground, in competition with

By H. M. FRENCH

ARC welding can be defined as a process whereby two A pieces of metal are brought together, heated to a molten state by the heat of an electric arc, and fused into one piece. There are several kinds of arc welding: the metallic arc, the carbon arc, the atomic hydrogen arc and the shielded arc methods. A short description of each, together with its major applications, will serve to distinguish between them. Metallic arc welding involves an arc drawn between a metal electrode and the material to be welded, called the work or the "parent metal." It may be further subdivided into hand and automatic welding, depending on whether the electrode is fed to the arc by hand or by motor drive. This form of arc welding can be applied to most welding operations. Exceptions to its use consist of applications where very thin metals are to be welded; where it is desired to join the work with- out adding metal; or where extreme ductility may be required:

Jan 1, 1930

By H. C. Kenny

THE annealing or softening temperature of cold-worked copper is appreciably increased by almost unbelievably small amounts of silver. As indicated by some data in this paper, the softening temperature of high-conductivity, tough-pitch copper may be increased from 200° to 350° C. by the addition of only 15 oz. per ton (0.052 per cent) of that element. Because it has this higher annealing temperature as compared with the silver-free metal, silver-bearing copper finds considerable use in industry. For example, when hard-rolled copper is used in operations that involve soldering or tinning, silver-bearing copper insures against loss of strength, whereas silver-free copper becomes "dead soft." Yet-though several investigators, beginning with Caesar and Gerner1 in 1916, have shown that small amounts of silver do definitely raise the softening temperature of copper-data are lacking on the problem: What is the specific influence of different amounts of silver on this tem-perature? It was to help in filling this gap in the knowledge of what might be termed "alloy coppers" that the data given herein were obtained. The softening of cold-worked copper depends, of course, on a number of factors, of which the composition of the material is only one. Other highly important factors are the degree to which the material is cold-worked and the time it-is held at the annealing temperature. The method of cold working and the grain size of the metal produced are also signifi-cant. All these variables were taken into account in the investigation reported here, and the influence of silver on the electrical conductivity and on the working was also considered.

Jan 1, 1934

By C. A. Stetefeldt

In May and June, 1885, I was engaged in examining the goldores of Las Minas, in the State of Vera Cruz, Mexico, with a view of finding a cheap and efficient method for extracting the gold. The following minerals could be plainly seen in the ore : magnetite, pyrites of iron, pyrites of' copper, quartz, and garnet. Neither galena nor zinc-hlende mere visible, but the ore contained a trace of lead, and in some samples of ore from the Muertos mine, 1.19 per cent. of zinc mas found. Antimony and arsenic were not present. Native gold could scarcely be seen in specimens of' the ore, and it only appeared—mainly in extremely fine particles—after pulverizing and washing. Magnetite was in every instance the most prominent mineral, its quantity varying between 43 and 67 per cent. Determinations of copper and sulphur showed that from 3.5 to 7 per cent. pyrites of copper, and from 3 to 22 per cent. pyrites of iron were present. The gold-value of the ore varied between 0.3 oz. and 0.8 oz. per ton. I do not speak of specimens, but of average samples of large quantities of ore put through the battery. In ore that had been crushed through a No. 40 screen, the gold appeared, in part, as free gold, the rest being thoroughly mixed with the magnetite and pyrites, both minerals containing about the same percentage of gold. If this free gold was brought in contact with pure quicksilver it (lid not amalgamate readily, even if the quicksilver was charged with sodium amalgam.

Jan 1, 1886

By R. W. Jenkins, O. J. Neslage

The need for mechanized drilling to decrease mining costs has resulted in the development of the jumbo from column-and-bar drill carriages to hydraulically controlled jib jumbos. Resultant savings from use of improved jumbos have been high enough usually to retire the machinery investment within a year. The jib jumbo unit has been applied successfully to development and preparation programs and flat-bedded stopes, and an even wider field is forecast for its use.

Jan 1, 1950

By B. K. Parekh, W. M. Goldberger

A novel process is proposed for continuous removal of ash and unreacted solids which become suspended in the oils obtained during coal liquefaction. The proposed method uses water in direct contact with the oil under conditions which cause the suspended residue solids to transfer from the oil to the water phase. Separation of the phases yields a product oil essentially free of suspended solids. The water is cooled, clarified or filtered by conventional low-cost systems, and recirculated. The paper describes experimental work leading to development of the novel concept and includes the result of batch experiments that establish the feasibility of the process.

Jan 1, 1980

By E. W. Davis

Iron-ORE beneficiation methods are determined largely by blastfurnace requirements. There are still many millions of tons of direct furnace ore in the Lake Superior district and blast furnaces are designed and operated for the most efficient use of this material. Beneficiated ore must be so prepared that existing furnaces may use it without alteration in design or radical changes in practice. Many attempts have been made to develop new furnaces or processes for smelting iron-ore concentrate not suitable for blast-furnace use, but these processes have gained little importance. It is, therefore, the endeavor in beneficiating iron ore to make a product that will give at least as good results as direct furnace ore in existing blast furnaces. The term "beneficiation," as applied to iron ore, does not necessarily mean concentration, but more accurately means "dressing up" the ore so that it is more acceptable to the blastfurnace operators. In modern blast-furnace practice the structure of the ore is quite as important as the chemical analysis. Certainly, the higher the iron content and the lower the silica, phosphorus and sulfur, the more desirable the ore bccomcs; but if the structure is bad, that is, if the blast-furnace gases can penetrate the charge only with difficulty, the ore is undesirable regardless of its analysis. This means that the ore should be as uniform in size as possible and free from fines, and also that the individual particles of ore should be pervious to the reducing gases of the furnace. Structure and purity are the primary requirements for a furnace ore and structure is just as important as purity. Iron-ore beneficiation processes can be divided, therefore, roughly into two main classifications: (1) processes that primarily improve the structure, and (2) processes that primarily improve the chemical analysis. During the past 10 years approximately 25 per cent of the ore shipped from the Lake Superior district has been beneficiated. Of this about half has been crushed and screened, a simple operation that primarily improves the structure but in some cases also improves the analysis slightly. The other half of the shipment of beneficiated ore, amounting to an average

Jan 1, 1935

By Eric J. Bradshaw

For several hundred years the petroleum industry has flourished in Burma and at the close of the eighteenth century there were over five hundred producing wells in the Yenangyaung field. These were laboriously dug by hand and were exceedingly primitive, yet even today a small part of India's total production is obtained from hand-dug wells. The Indian Empire, the cradle of the oil industry, today produces but an unimpressive fraction of the world's supply of petroleum, not because the size of her contribution has diminished, but because it has remained more or less stationary while other countries have far outstripped her during the prodigious increase in the world's production of petroleum in recent years. Though for the past 10 years the total production in India has been remarkably constant, it has become increasingly difficult to maintain this output and at any rate from the older fields a slow decline may be anticipated unless new productive horizons are discovered. Production figures for the 10 years 192&1929 (the last year for which figures are available) are given by fields in Table 1. Crudes of Burma and Assam The bulk of India's production comes from the Yenangyaung and Singu fields, from which the crudes are very similar, the only important difference being that the oil from the Singu-Yenangyat structure contains a higher percentage of lighter fractions. The Burma crudes resemble that of the Panhandle of Texas and have a high content of solid paraffin, though strictly speaking the oil is of mixed base with a low content of asphaltum. With the exception of the negligible production from Sabe, the Burma crudes do not require dehydration; the sulfur content is very low and is innocuous. A small amount of naphthenic acids occurs in the kerosene and intermediate oil fractions while the lubricating fraction is practically free from acid. The ash content is low and the average A.P.I. gravity of mixtures of Yenangyaung and Singu oil is 36.4. Burma crudes require only light refinery treatment and practically dl the fractions are merchantable. Part of the gasoline supply is stripped

Jan 1, 1931

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen's experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964

By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948