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By J. T. Eash, E. M. Wise

Many of the platinum metal alloys are hot-forged in the early stages of reduction from ingot and substantial quantities of platinum alloys are commercially employed at very high temperatures in ammonia oxidation units, orifices for forming glass rods and fibers and as cathodes in long-life thermionic amplifiers. They are used also for electrical heating resistors, safety blowout disks, thermocouples and crucibles. The tensile properties at elevated temperatures are important in many of these situations but data on the subject are limited. Creep data also are important, but will not be covered at this time. Scope and Conclusions Tensile tests were carried out at room temperature and elevated temperatures up to 1100" C. on previously well annealed samples of platinum. palladium and several of their important alloys with compositions shown in Table 1. The results are presented graphically in Figs. 1 to 4. The tensile strengths of platinum and the platinum-base alloys (with the exception of the 10 per cent rhodium-platinum alloy) at 1100" C. are from 16.6 to 18.8 per cent of the strengths of the same alloys (well annealed) at room temperature. The strength ratio of the 10 per cent rhodium-platinum alloy is 22.3 per cent, which is appreciably higher than that of the other materials tested. The tensile strengths of palladium and the palladium alloy at 1100" C. are from 10 to 11.2 per cent of the room-temperature values. The elongations of platinum and its alloys tend to increase at temperatures above 600" to 800" C., while the two samples of pure palladium show a maximum at 600" C.

Jan 1, 1938

By P. LaRochelle, K. Y. Lo, A. L. Tamuly Phukan

In many civil or mining engineering works, the stresses and deformations of natural or excavated slopes due to the combined effect of self-weight and initial stresses are of interest. Because of the mathematical complexities of this problem, however, no complete exact solution exists for the simplest case, that of assuming the stress-strain relation of the rock to be perfectly elastic. Efforts have therefore been directed toward numerical and experimental technique. The stresses within an elastic slope have been obtained by LaRochelle,1 using the photoelastic and finite difference method to determine the difference and sum of principal stresses. Subsequently, Finn,2 Hoyaux and Ladanyi,3 and Duncan and Dunlop4 attempted to solve the same problem by using the finite element method. The problem was also investigated by Brown and Goodman5 and Brown and King6 who emphasize the importance of the effect of loading or unloading procedure on the stress distribution within the slope. Although the geometry of the slope and the boundary conditions involved are identical or similar, the results obtained by these various authors by no means agree. It is therefore necessary to review briefly the results of elastic analysis in order to lend credence to the methods used in the solution. Although the stress-strain behavior of some rocks may be reasonably approximated by the elastic modrl, other rocks generally exhibit an elasto-plastic behavior with strain hardening or strain softening as shown in Fig. 1. Experiments show that for most rocks, the stress-strain relationship is approximately linear from the origin to the point P (neglecting the small concave region under low stresses). At P, the curve deviates

Jan 1, 1970

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By A. L. Titchener, M. B. Bever

FROM their investigation of the martensitic transformation in Cu-Zn alloys, Greninger and Mooradian' concluded that there was no critical temperature at which martensite formation began in this system. Recent unpublished work by Gen-evray With two compositions of brass revealed the existence of a critical temperature, which is a function of composition and stress. In the work reported here the temperature range of the martensitic reaction was studied as a function of composition in high purity Cu-Zn alloys. The specimens were about 4 in. long with a diameter of 1/16 in.; their compositions are given in Table I. They were heated under vacuum for 5 min at 5" to 10°C below the temperature of incipient melting, and quenched into brine at about — 10°C. Specimens of alloys C, D, E and F were obtained with little or no precipitated a phase. Many attempts yielded only three usable specimens of alloy B, and even these contained appreciable amounts of a. All efforts failed to preserve metastable p in alloy A (containing 38.02 pct Zn and 0.002 pct each of Pb and Fe). The transformation was studied by measuring the electrical resistance during continuous cooling and heating of each specimen at similar rates. The cooling media were alcohol with dry ice from room temperature to — 78°C and a bath of petroleum ether and methyl cyclohexane (75:25), cooled by liquid nitrogen, from —78" to about —150°C. Readings were also taken at —195 °C in liquid nitrogen. Fig. 1 illustrates a typical experiment. The relative resistance is obtained by assuming the known

Jan 1, 1955

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc. When Mr. Carnegie made. his gift which made possible a home for the engineering societies, a separate corporation was organized to act as a holding company and to manage the common property. This was long known as the United Engineering Society, but the name has now been changed to one which more nearly reflects the real function of the corporation. It holds title to the Engineering Societies Building and to various funds placed in its charge and is managed by a Board of Trustees, of which three are chosen by each of the four societies, American Institute of Mining and Metallurgical Engineers, American Society of Mechanical Engineers, American Institute of Electrical Engineers and American Society of Civil Engineers, which have equal and undivided interests in the property. The land and building cost two million dollars. During the year 1934, the Constitution and Bylaws of The United Engineering Trustees, Inc., were thoroughly revised and a better organization of its functions was effected: The Engineering Foundation and the Engineering Societies Library were made "departments" of the United Engineering Trustees. The Founders Societies share in the property which it holds, and estimated at the present time, as follows: Real estate,. $1,993,793; Depreciation and Renewal Fund, $401,000. The U.E.T. has endowment funds amounting to $1,086,893. The A.I.M.E. trustees are W. D. B. Matter, Jr., A. L. Queneau and Albert Roberts.

Jan 1, 1939

By George Hunt

THE first practical treatment of wood to prevent decay was devised early in the 19th century. At that time the oaken navy of England, when the nation was fighting for its very existence, seemed doomed to annihilation by the swift ravages of decay. The acute situation inspired a desperate search for preventive measures and resulted in the development of the Burnett, Bethel and Kyan processes for impregnating wood with zinc chloride, coal-tar creosote and mercuric chloride, respectively. In the century that has elapsed, their use has spread throughout the world and the three original preservatives are used today in enormous quantities. Meanwhile, improved processes have been developed, new preservatives discovered, and the practice of impregnating wood to make it last longer has attained a position of major importance in the field of structural materials. USE OF PRESERVATIVES BY THE RAILROADS In the application of wood preservatives in the United States the railroads have been the leaders for the past 50 years or more. Having found that decay is the chief cause of the early destruction of wood and that preservative treatment is the remedy, they have treated their ties and timber in increasing amounts(1)?-in 1925 about 220;000,000 cubic feet. By preservative treatment the Santa Fe Railroad saves annually 1,500,000 ties in its 18,000 miles of track, and many other railroads effect similar savings. (2) In like manner the life of wooden bridges and trestles,(3) poles, marine piling, water tanks and other wooden railroad structures has been greatly increased, reducing the amount of timber required annually to maintain them.(5),(7)

Jan 1, 1927

By F. W. Osterwald, C. R. Dunrud

A continuously recording seismic network was constructed in 1962 by the U.S. Geological Survey to locate epicenters and record incidence of bumps (bounces, rock bursts) that occur in the bituminous coal mines of the Book Cliffs coal field near Sunny-side, Utah. The coal is mined because of its value as coking coal, although these bumps may be a hazard to life and property. Daily records of tremors caused by bumps for 1 3/4 years indicate that a seasonal pattern, as well as a daily pattern, exists for the number of bumps that occur in a given period. Maxima occur in May and June and November and December. Marked increases at 5-day to 9-day intervals are superimposed on these seasonal maxima. The largest bumps commonly occur during seasonal maxima when the rate of occurrence suddenly decreases and the amplitude of the individual bumps increases. Knowledge of this pattern may lead to prediction of general locations and periods of increased hazard from bumps. Experience to date has shown that prediction of precise times and locations of hazardous bumps is not possible, and may never be; primarily because even a small bump can be a hazard to life and property. Some bumps or bump sequences are actually composites, consisting or two or more discrete bumps a few tenths of a second to a few seconds apart. Violent and spontaneous releases of coal and rock from faces, ribs and roofs of mines (termed bumps or bounces by miners) are a common hazard to life and property in the coal mines located in the Book Cliffs near Sunnyside, Utah (Fig. 1). These bumps

Jan 1, 1965

By H. A. Doerner

PROPOSALS to use hydrocarbon or natural gases for the reduction of zinc from oxide materials may be traced back through Patent Office files to the early years of the present century. Natural gas at rates cheap enough to compete with solid fuels has been available at or near one major zinc district for more than a decade. That the seemingly meritorious and economically interesting applications of these proposals have not devel-oped into workable processes for direct production of zinc by natural gas cannot be completely ascribed to the proverbial conservatism of the zinc industry. It is possible to produce spelter commercially in normal times from zinc oxide and carbonaceous reducing agents without having a very precise understanding of the chemistry of the process. The reduc-tion by hydrocarbons is not, however, in this class, and the technical complexity of this reduction metallurgy and chemistry prohibits solution of the inherent difficulties by the "hit and miss" methods that are some-times thought to be practical. In a thermodynamic study of the chemistry of zinc smelting, Maier1 made a preliminary study of the chemistry of the use of methane for reducing zinc oxide by thermodynamic means, pointing out that the following reactions, the limits of which could be theoretically predicted, were important: ZnO + CH4 = Zn(gas) + CO + 2H2 [1] CH4 = C -I- 2H2 [2] ZnO + CO = Zn(gas) + CO2 [3] ZnO + H2 = Zn(gas) + H2O [4] Other possible reactions, not discussed in the reference quoted, are: CO2 + CH4 = 2CO + 2H2 [5] H2O + CH4 = CO + 3H2 [6]

Jan 1, 1933

By C. W. Hoffman, W. R. Hinken

Probability sizing, a fairly recent development in the field of particle separation, is now under investigation to determine its value to the mining industry. The method employed is probability sizing through a vibrating network of decreasing screen openings. While probability sizing is not new, the possibility of using it for coarse, highly abrasive ores at high tonnage rates has only recently appeared to merit practical consideration. The advantages of probability sizing vs. conventional screening methods are: (1) reduced space requirements for a high capacity unit, (2) fewer moving parts, (3) more versatile product sizing selection, (4) reduced maintenance requirements, and (5) lower power consumption. Screening is a necessary part of virtually every crushing circuit. At some stage in the process, particle separation becomes a controlling factor in the operation. The basic type of screen in use today is the vibrating unit, which usually employs a mechanical vibrator of one type or another to obtain sizing and material transportation across the screen surface. The vibrating screen has its limitations and inherent problems. Operators must live with: (1) high maintenance — worn rods, screen cloth, spacers, cross members, chutes, etc., (2) low capacity in relation to floor space requirements, (3) extreme noise levels, (4) high power consumption, and (5) structural problems in the screens and supporting steelwork. All plant operators have become tolerant of these drawbacks through the years, and little innovation has been developed in screening. The vibrating screens in use today incorporate improved metals, more efficient power sources, better lubricants, and increased manufacturing skill, but the basic machine itself remains unchanged. Screening is a relatively small part of most plants' operating expenditures and gets relatively little attention from research and development. The HiProb sizer is a new approach to the problem of particle separation on a high tonnage basis. Developed by Dr. Fredrik Mogensen (president of Fred-rik Mogensen, A. B. of Djursholn, Sweden), this unit has found its primary acceptance in the sizing of wet or dry materials in the fine ranges. Climax has been working cooperatively with Mine and Smelter Supply Company, the United States licensee, on the adaptation of the sizer to obtain consistent recovery at a high tonnage rate on a — 3/8-in. separation. This was a new application for the sizer and opened up a whole new field of problems. Dr. Mogensen's machine utilizes the control of normal probability of falling particles and is designed to eliminate some of the undesirable features of vibrating screens mentioned earlier. The machine is light, compact, consumes less power than conventional screens and has a low noise level. PRINCIPLES Probability sizing is a process designed to allow solid particles to segregate with a high ratio of the materials reporting into their respective size fractions with a minimum amount of misplaced particles. Sizing is defined in this paper as segregation of dry solid particles into fractions of comparable sizes. Probability is usually estimated as the ratio of the number of ways an event might occur vs. the total number of allowable ways. The probability process described depends upon the fact that particles falling through a network will segregate across the sizing surface even though all openings are larger than the particles. The degree of segregation is dependent upon the particle size and the trajectory applied by the sizing network to each falling particle. Specifically, the process utilizes a maze made up of screen cloth to control the path of a particle in free fall as illustrated in Fig. 1. The usefulness of this probability sizing process is dependent upon the degree of efficiency of an effective maze. Primarily, a maze must be extremely flexible to meet the multi-faceted nature of solid particles and, at the same time, the degree of control must be reproducible so that a desired separation is predictable. Dr. Fredrik Mogensen has formulated a maze that is not only flexible and easily controlled, but, mote importantly, easily adaptable to a working machine.

Jan 1, 1970

This excellent, concise paper by Dr. Iwasaki on the principles of selective flocculation for iron ores discusses many of the principles and problems which have occurred in our bench and pilot plant test-work. The use of sodium tripolyphosphate in combination with sodium silicate as a dispersant is very effective. However, this may cause a problem with the environmental groups as phosphorous is a nutrient. We have also established that the lower the Ca level in the pulp solutions the greater the dispersion. We have found that ores from the same geological strata, having the same general mineralogy and iron content will sometimes have widely different degrees of dispersion. There was-no difference in the gross mineralogy but the solubility of the Ca and SO ions was much less in the ores most easily dispersed. Research efforts should be directed towards a more practical means which would more easily enable one to predict the amount of dispersant required for the various ores. With regard to water quality we have found that waters having higher contents of SO4 and C1 ions hinder dispersion. This could be a method of controlling too much dispersion by the addition of sulfate or chloride ions. This would require further investigation. We have had no trouble with agitation speeds of up to 925 rpm in conditioning starch with the dispersed pulp prior to selective flocculation. We have found about 0.3Lb/LT of starch to be sufficient for selective flocculation on our ores. The increasing of the starch to 1.25Lb/LT has had no effect on the metallurgy of the selective floccula-

Jan 1, 1979

By R. F. Marande, R. S. Busk

THE magnesium-aluminum-zinc system contains most of the magnesium-base alloys used commercially, although in practice the ternary, alloys are usually modified by the addition of a small amount [ ] of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the object of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.1 [ ] All alloys reported were made in 15-lb. melts, superheated to 1700°F. for 15 min., cooled to 1400°F. and poured in sand molds. The test bars produced had a ½ in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. CONSTITUTIONAL DATA Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By Walter Weeks

LITTLE study has been made of the pressure changes and energy losses that take place when an air current is divided into splits which subse-quently unite. The discussion and the experiments that are described in this paper deal with the division of an air current into square splits of equal size, the area of each of the splits at the downstream junction being one-half the area of the main duct. APPARATUS AND SYMBOLS The duct system shown in Fig. 1 was built of Y4-in. redwood and made as smooth as possible.The section of the top over the splits and the zone of mixing was of plate glass to permit observation of the stream lines. FIG. 1-DUCT SYSTEM. Static pressures were measured by means of pinhole tubes and a precise inclined manometer. Measurements of rates of flow were .made by determining the drop in pressure through concentric square orifices in the splits. The air was supplied by a fan operated by a direct-current motor that received its current from a motor generator set. Delicate rheostats in the armature. of the motor. made possible the perfect control of the fan speed, which was indicated on an electrical tachometer. Vanes to straighten the. flow were placed at the head of the main duct.

Jan 1, 1933

By George J. Bancroft

INTRODUCTION. IT is unnecessary to repeat here the contents of many valuable contributions to this subject which have appeared in the Transactions and in the publications of the U. S. Geological Survey. As a basis for the further suggestions of this paper, the following are the most important: 1. The investigation of J. R. Don,1 showing the gold of certain Australasian veins to have been deposited by ascending solutions, and not by lateral secretion. 2. The theory of Prof. Posepny,2 distinguishing the vadose from the deep circulation, and ascribing the origin of certain classes of ore-deposits to ascending solutions of the latter class. 3. The theory of Prof. Van Hise,3 as to the underground circulation and the primary enrichment of veins thereby. 4. The paper of Prof. J. F. Kemp,4 showing that ore-deposits are largely the products of " expiring vulcanism." Many of Prof. Kemp's, ideas have been widely adopted by mining men. 5. The theory of secondary enrichment, so lucidly expounded by Mr. S. F. Emmons.5 This theory, dealing with, the rearrangement of ore-bodies after primary mineralization, has been generally adopted, and seems to me to have been as completely proved as the nature of the case permits. There are two facts which I think should be constantly borne in mind in formulating a theory of the genesis of ore-

Jan 1, 1913

By A. F. Banks

INTRODUCTION Selective flocculation as a method of desliming potash flotation plant feed has been in commercial use since November, 1974.l It was installed to replace a 1ess efficient mechanical desliming process. While most plants operating in the Saskatoon area of Saskatchewan were designed for 4% to 5% insolubles in practise the quantity and quality of the insoluble materials in the ore has been variable. The variability of the ore has contributed to less than optimum efficiency in the desliming and consequently, the potash flotation circuits. This lower than expected efficiency contributed to the commercialization of a patented process2 through large scale pilot plant testing. Referring to published information and experience, the application of selective flocculation-flotation of slimes to sylvinite ores will be compared with the more conventional mechanical methods of desliming. THE ORE The ore beds being mined in the Saskatoon area of Saskatchewan have proven to be much less uniform than originally thought (Figure 1). The insoluble content of the plant feed is variable in both quantity and quality due to two factors, the presence of disturbances and the structural weakness of the mud seams immediately above the ore beds. Some alteration of the insolubles in the vicinity of disturbances has made them more difficult to liberate and makes ore from the disturbed areas less amenable to treatment.

Jan 1, 1980

By H. W. Morse

INTRODUCTION THE experimental work on the oxidized copper ore at the New Cornelia mine at Ajo, Ariz., ended on Jan. 12, 1916. On that date final decision was made on the general nature of the process to be used in the 5,000-ton leaching plant, and on many of the details, as far as experience on a40-ton scale could decide them. With the approval of the Board of Directors and the General Manager, John C. Greenway, we have compiled what seem to be the most interesting data on the results obtained during the experimental period. The most important part of the data resulted from the operation of a 1-ton and a 40-ton plant at Ajo. Experimental work on Cornelia oxidized ore dates back to April, 1912, and has been going on nearly continuously since that time. A good many variations from the original idea have been tried, but the process finally decided upon is in principle and in all of its details a simple one. The history of the leaching work on this ore has been brought down to about a year ago in papers presented to this Institute by Stuart Croasdale1 and Dr. L. D. Ricketts.2 The present paper will, therefore, deal principally with the results obtained during the last year of the work.

Jan 9, 1916

By James A. Roberson

THE mechanical behavior of molybdenum has become a matter of considerable interest in recent years because it has a reasonably high strength at high temperatures. Various aspects of its fatigue behavior have been investigated previously,1-3 and the results can be summarized as follows. Recrys-tallized molybdenum exhibits a fatigue limit which decreases continuously with increasing temperature. The ratio of fatigue-limit stress to ultimate tensile stress is high (0.6 to 0.8) and reasonably constant. The present work was undertaken to determine the effect of variations in environment on the fatigue of molybdenum stressed in fully reversed axial tension compression. In order to provide a basis to which these data could be compared, a complementary series of fatigue tests were made in vacuum. All of the specimens used were made from one mill lot of unalloyed molybdenum which had been vacuum-arc melted, worked down to 1-in.-diam bar, re-crystallized, then warm-worked to 5/8 in. diam. The interstitial content by weight was as follows: C—0.022 pet, 02-0.0026 pet, Hz-0.0001 pet, and N20.0002 pct. The average grain diameter in the transverse direction was about 0.035 mm, and the average grain length was about 0.15 mm. Typical tensile-test data are shown in Table I. None of the specimens tested exhibited an upper yield point.

Jan 1, 1965

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan' presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner's contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-' demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann' and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,' who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By O. F. Walker, W. C. Hahn, V. A. Johnson, J. D. Wood

The diffusion coefficients of zinc in single-crystal zinc and carbon in single-crystal and poly crystalline nickel were measured by means of radioactive tracer techniques both with and without the application of ultrasonic vibrations under conditions such that the temperature of the sample was closely controlled. The results of this investigation indicate no enhancement of diffusion in any of the samples. It is suggested that previously reported enhancement may have been due either solely to temperature increases caused by ultrasonic vibrations or in combination with changes in the boundary conditions. A number of observations have been reported in the literature in which it has been implied or inferred that the application of ultrasonics enhances diffusion (see, for example, Refs. 1-5). The present study was undertaken in an attempt to observe this effect under carefully controlled conditions, particularly with regard to measurement and control of the temperature of the sample. Two different types of systems were studied; these were the self-diffusion of zinc and the diffusion of carbon in nickel. EXPERIMENTAL For diffusion with ultrasonic energy applied, the samples were included as part of a resonant ultrasonic system operating at 58.5 kcps. The ultrasonic generators used were rated at 100 and 250 w and could be tuned over a frequency from 10 to 100 kc. A PZT (lead titanate/lead zirconate) ceramic transducer provided the driving vibration. This system requires no metallurgical joining of the specimen to the acoustical transmission line since the ultrasonic driver and the follow-up section clamp the specimen in position by means of a constant pressure of 50 lb developed by an air cylinder. The ultrasonic driver and follow-up section, both made of titanium, were 4 in. in length from clamping point to the end in contact with the specimen. Using the relationship given by Mason,6 A = V/f, the resonant wavelength, A, in titanium is calculated to be 3.3 in. at a frequency, f, of 58.5 kc, taking the velocity of sound in titanium, V, as 1.95 X 105 in. per sec. The 4-in. driver and follow-up section, therefore, are each 4.0/3.3 =1.21 times the resonant wavelength. Clamping pressure must be applied at stress nodes of the transmission line in order to preserve resonance. Therefore, a specimen length of 0.58 times the wavelength in the specimen was required to place the clamping pressure application points at stress nodes exactly three wavelengths apart. A stress antinode was contained in the center 3 in. of the specimen. A small PZT ceramic disc attached to the follow-up section provided an output voltage proportional to the intensity of the standing wave. This output voltage was monitored on an oscilloscope and the ultrasonic system was tuned to resonance by varying the frequency until the output signal was a maximum amplitude. The amplitude of the output signal was maintained constant throughout the diffusion anneal. A split cylindrical stainless-steel chamber, which was purged with argon prior to and during the runs, was placed around the specimen. The chamber in turn was surrounded by a movable furnace whose temperature could be controlled to 7C. Heat exchangers were used to cool the driver, follow-up section, and ultrasonic transducer. Great care was taken to obtain the true specimen temperature in all cases. Several different methods were tried; the most successful was that in which the thermocouple was held in contact with the midlength of the specimen by means of an asbestos insulating pad and wire straps. In the case of zinc, single-crystal specimens of 99.999 pct purity were used. The samples were 0.25 by 0.25 in. square and of the proper length for resonance, that is 1.1 in. long with the c axis parallel to the long dimension of the specimen for the case of diffusion perpendicular to the c axis and ultrasonic motion parallel to the c axis, and 1.9 in. long with the c axis perpendicular to the long dimension of the specimen for the case of diffusion parallel to the c axis and ultrasonic motion perpendicular to the c axis. In each case, one of the rectangular faces was electroplated with a thin film of zinc containing Zn The constant pressure used to clamp the specimen in place in the ultrasonic system caused some deformation in some of the samples. For these samples the deformation was concentrated in either end of the specimen; thus, for all samples (both zinc and nickel) the center in. was cut from the specimen after the diffusion anneal to be used for sectioning and counting. The nickel single-crystal samples, of 99.999 pct purity, were used in the form of rods 0.25 by 0.187 by 2.07 in. long with the (100) direction parallel to the rod axis. The polycrystalline nickel samples of 99.97 pct purity had an average grain diameter of 0.007 in. and were used in the form of rods 0.25 by 0.125 by 1.87 in. long. The direction of ultrasonic motion was parallel to (100) direction (bar axis) for the single-cqstal samples and parallel to the bar axis for the polycrystalline specimens. A thin film of c14 suspended in methanol was applied to the diffusing face of the specimen. Two specimens were butted together lengthwise for each diffusion anneal to minimize oxidation. After diffusion, a precision lapping device similar to the one described by Goldstein7 and a radiation detector were used to obtain a plot of specific activity vs penetration distance for each specimen. (A scintil-

Jan 1, 1969

By Thomas Clagett

THE Pocahontas coal field comprises the area in Tazewell County, Va., and Mercer and McDowell Counties, W. Va., in which Nos. 3 and 4 Pocahontas seams of bituminous coal are mined. It is a mountainous region with ridges rising 300 to 1000 ft. (91 to 305m.) above the very narrow valleys and, except for some poorly kept farms along the tops of the ridges and the area occupied by the mining and coking plants and villages, is wooded throughout. First shipments were made from Pocahontas in 1883. There are now, about 100 mines, 95 per cent. of which are drift mines. At the end of 1920, approximately 298,000,000 gross tons of coal had been produced and 35,000 acres of coal mined. No. 3 seam is from 4 to 10 ft. (1.2 to 3 m.) thick, but the change is gradual and the thickness fairly uniform in any particular locality. It has a streak of bone, about 2 in. (5 cm.) thick, io which the coal adheres on both sides. In parts of the field this bone is replaced by hard slate, usually from 2 to 4 in. thick. The seam has a slate or fireclay bottom and a draw-slate top. No. 4 seam is from 65 to 80 ft. (19.8 to 24 m.) above No. 3 seam, and of minable section only in the western part of the field. It is from 3 to 8 ft. thick and has two streaks off bone, each from 1 to 2 in. thick. It has a fireclay or slate bottom and is overlaid by from 4 to 24 in. of a laminated coal and slate, locally termed "black rash," which is separated from the coal seam by about 3 in. of slate. This "black rash" averages about 25 per cent. ash, but contains some clean coal. The coal in both seams is quite soft. Cleavage sufficiently well defined to exert an influence on the mining is rare. Overlying strata are slates, shales, and sandstones, the sandstones predominating, extending from .30 to 1000 ft. above No. 3 seam. The strata directly above the. draw slate of No. 3 seam, or "black rash" of No., 4 seam, and up to the first sandstone are usually slates or shales, about 10 ft. thick over the

Jan 5, 1922

By Harold B. Janzen, M. A. Nobles

Campbell and Martin1 described a new exploratory logging tool which was developed as the result of a new concept of the phenomenon that takes place when a porous formation containing mobile hydrocarbons and irreducible interstitial water is invaded by mud filtrate. They postulate that invasion will create a bank of interstitial water between the flushed zone and the undisturbed formation. This postulate was confirmed by Wyllie.' Thus, if R,, is greater than R, and mobile hydrocarbons are present, the resistivity profile with increasing radii from the borehole is high:low:high, as shown in Fig. 1. If mobile hydrocarbons are absent, the bank of interstitial water is indistinguishable from the undisturbed formation and the resistivity profile, when R is greater than R,, is high:low, as shown in Fig. 2. The zone containing the bank of interstitial water and residual oil was named the "low zone". Campbell and Martin conducted extensive electrolytic wedge and resistivity analog model studies to select a logging system that would reflect the presence or absence of the low zone. The system they selected was that of a family of lateral curves. The model studies indicated that the presence of a low zone could be detected in approximately 60 to 70 per cent of the producing sand reservoirs with a family of lateral curves provided that the sonde effectively occupies 90 per cent of the diameter of the hole. These studies were conducted with D, = 5d. The presence or absence of the low zone is best determined by a plot of the apparent resistivity vs spacing as shown in Figs. 3 and 4. A dip or inflection in the profile that repeats at successive depth intervals is considered diagnostic. To reduce the shunting effect of the hole and mud, a sonde of insulating material that is surrounded by a series of flexible rubber bumpers was designed. The bumper efficiency is considered to be the ratio of the bumper diameter to the hole diameter. Field tests conducted by Campbell and Martin on 10 wells with a tool that provided for station readings indicated that dips or inflections could be detected in 19 out of 25 known producing zones. INSTRUMENT DEVELOPMENT Halliburton developed a logging system to simultaneously and continuously record eight lateral curves. The instrumentation is described in the literature.' The original logs made