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By Henry M. Howe

This paper may be regarded as a report of progress of an investigation into the influence of prior exposure to different high temperatures, under different conditions, on the properties of steel after it has been cooled completely. The following are the chief divisions: II.—Experiments on toughening manganese-steel by sudden cooling. III.—A study of the critical points of common or carbon-steel, chiefly by examining the spontaneous retardations which occur in heating and cooling it, and by examining the ductility of pieces of steel which have been cooled suddenly from different temperatures by quenching them in water or brine. IV.—A brief note on Osmond's theory. V.—A study of the critical points by examining the ductility of pieces of steel which have been cooled slowly from different temperatures at, above, and below them. VI.—A description of the furnace used, with notes on thermoelectric pyrometry. It remains to throw further light on the questions studied by ascertaining the condition of the carbon and the hardness proper, and by studying the microstructure and the fracture of the many pieces treated. I hope to present later the results of experiments in some of these directions. With few exceptions, the experiments have been performed in my private laboratory. I tender sincere thanks to my assistant, Mr. William Haskins, S.B., on whom most of the labor has fallen, for his zealous and intelligent co-operation; to the Sterling Steel Co. for their extra hard steel, Series 17; and to Mr. Joseph Hartshorne and the Pottstown Iron Co. for their soft basic steel. Series 8, 9,10, and 18 were supplied by Messrs. Spaulding, Jennings & Co., of the West Bergen Steel Works; to them also my thanks are due. The temperature of the pieces treated has been very carefully

Jan 1, 1894

By A. D. Brokaw

The so-called "paraffin dirt" of the Gulf Coast oil fields has been considered an indication of the possible presence of oil and gas, and not a few wells have been brought in solely on the basis of such evidence. In a sense, it may be empirically justified as evidence of the presence of oil or gas, though it cannot be said to be infallible. If the writer is correctly informed, its association with oil and gas was pointed out by Lee Hager some years ago, and while it is commonly mentioned by geologists and operators in conversation, no discussion seems to have found its way into print. The present interpretation is based on laboratory study rather than on field investigation, and is put forth with the hope of stimulating discussion which shall lead to more complete understanding. The term "paraffin dirt" has been applied to soils with a peculiar texture, which has been described as "curdy" or "rubbery." When moist, the material breaks much after the fashion of "green" cheese. It is rubbery under compression, but does not resemble rubber in tenacity or cohesion. When dry, the material ranges from hard clods to a horny mass of high tensile strength. The shrinkage in drying is very great, especially in the hornlike matter. The moist material ranges in color from dark brown in the specimens rich in organic matter to grayish in specimens containing more inorganic matter. All of the specimens studied were readily attacked by molds, which in some cases grew in great profusion on the samples. Samples exhibited a rather characteristic "swampy" or "mucky" odor when wet, and a characteristic odor of humic soils when moist. If the material is brought into suspension in water, very fine sand settles out and may be recovered by successive washing and decantation. The sand is almost entirely quartz, but contains occasional fragments of feldspar—more or less kaolinized and iron-stained. Practically all of the sand passes through a 100-mesh screen and the grains are extremely sharp —possibly below the limit of rounding. A flocculent mud, of clay and organic matter, remains in suspension for days. Some material is taken into solution in the water, imparting a slight tendency to froth when vigorously shaken. The results of partial analyses of four samples of "paraffin dirt," and, for comparison, one of a coastal plain soil are given in Table I.

Jan 1, 1920

By George Asmus

Closed front, or open front for blast-furnaces, has been for a number of years a much discussed question among the furnace-men in every country where iron is made. As blast-furnaces are costly structures, and as the whole question is one of economy, I hope to be excused for entering a little into details. The "fore-hearth" is a prolonged opening in the lowest part of the hearth, from two to three feet wide, four to six feet long, and two to three feet high. It is a more or less fire-proof box, cooler than

The greatest mining center in the state of Utah is the incorporated town of Bingham about twenty-five miles southwest of Salt Lake City. The principal industry of this vicinity, prior to the early fall of 1863, was lumbering and the first saw-mill in the state was built near the mouth of Bingham Canyon. Early in the fall of that year. George B. Ogilvie discovered gold and shortly afterward the first mining district in the state was organized. Some writers place the discovery of gold in the canyon in the late fifties. If this be so, however, the matter was kept extremely quiet because no mining was engaged in until after Ogilvie's discovery. Bingham was a placer mining camp, producing about one million dollars' worth of dust and nuggets from placers up and down the canyon and in Bear Gulch until early in the seventies, or about ten years after the discovery of gold, when a large body of argentiferous lead ore was discovered and soon after heavy shipments were made from a half dozen or more properties.

Jan 1, 1925

By AIME AIME

WHEN H. I. Smith joined the Institute back in 1908, he was an instructor in mining and metallurgy at Penn State the college from which he had graduated the year before with a B.S. degree. He had not gone far afield for his education, for he was born, February 15, 1984 at Finleyville, Pa., a small village some fourteen miles south of Pittsburgh and without doubt famous chiefly as H. I.'s birthplace. The summer that he graduated he took a trip to the copper mines Arizona and Mexico and en route worked for four weeks for the Portland Gold Mining Co. at Cripple Creek, Colo., as a mucker and trammer. The next summer he roamed farther afield mines and metallurgical works in Europe. Wishing to see more of Arizona, he left the Penn State faculty early in 1909 and went out to Wenden in that State to become mining engineer and assistant superintendent of something called the Corona Copper Co., with 72 mining claims and a one-mule-powered whim for a hoist. When that job folded he helped build the Santa Fe railroad from Parker. Ariza., to Danby Cialif., and then came back to Pennsylvania to enter Government services as a junior mining engineer with the Bureau of Mines.

Jan 1, 1943

By H. J. French

At the request of a committee of the Engineering Division,' National Research Council, a study of the properties of boiler plate at various temperatures up to about 900' F. (482" C.) has been instigated. The following is a report of preliminary tests made on two grades of 1/2-in. plate and includes a description of the apparatus used in the determination of the proportional limit. Detailed reference to- the many published investigations in connection with the properties of steel at various temperatures will be omitted from this report. Suffice to state that results obtained for variation in tensile strength, elongation, and reduction in area with temperature are in substantial agreement with the effects now generally considered to be correct. Comparison of proportional limit values with results obtained by other investigators will be found in the conclusions. Materials Used The steels tested were $1/2-in. (12.7 mm.) open-hearth boiler plate of firebox and marine grades. The specified tensile strength and the analysis for each are shown in Table 1. In the manufacture of this material, a

Jan 1, 1922

By H. J. French

At the request of a committee of the Engineering Division,' National Research Council, a study of the properties of boiler plate at various temperatures up to about 900' F. (482" C.) has been instigated. The following is a report of preliminary tests made on two grades of 1/2-in. plate and includes a description of the apparatus used in the determination of the proportional limit. Detailed reference to- the many published investigations in connection with the properties of steel at various temperatures will be omitted from this report. Suffice to state that results obtained for variation in tensile strength, elongation, and reduction in area with temperature are in substantial agreement with the effects now generally considered to be correct. Comparison of proportional limit values with results obtained by other investigators will be found in the conclusions. Materials Used The steels tested were $1/2-in. (12.7 mm.) open-hearth boiler plate of firebox and marine grades. The specified tensile strength and the analysis for each are shown in Table 1. In the manufacture of this material, a

Jan 1, 1922

By William E. Harris

Time and experience have demonstrated that by means of the Waelz process zinc, lead, cadmium, arsenic, antimony, bismuth and tin can be volatilized satisfactorily. In this way difficult gold ores are being treated to allow for the recovery of the precious metal. Iron ore containing zinc is being treated to remove the zinc and recover the iron. In Germany, thallium is being recovered in commercial quantities from the zinc oxide fume; indium, germanium and gallium are also concentrated to a degree warranting recovery, even though these rare metals are only recognizable in the ore by means of the spectroscope. The physical, chemical or mineralogical condition of the raw material affects very little the applicability of the process. The name Waelz is derived from the German word Waelzen, meaning a "trundling motion," which very aptly describes the movement of the charge through the slowly rotating kiln. The recovery of zinc and lead by volatilization in a rotary kiln has its origin in a process patented in 1910 by Edward Dedolph, of British Columbia. The Dedolph patent was taken over by the Metallgesell-schaft of Frankfurt-on-Main, Germany, which in cooperation with the Griesheim-Elektron, now a part of a large industrial combine, introduced certain improvements (Ohlmer, Specketer patents), but without bringing the process to a state suitable for large-scale operations. The war temporarily stopped all work on the process, and it was not until after the war that the Krupp Grusonwerk, of Magdeburg-Buckau, Germany, quite independently of the Metallgesellschaft, instituted research work in this field of metallurgy, which in 1923 led to the Waelz process proper. The Krupp Grusonwerk and the Metallgesellschaft A.G. later on collaborated, and by their joint efforts further developed and perfected the Waelz process, which they are marketing together as "Waelz-Gemeinschaft." The process is capable of treating a varied type of material; for instance, oxidized and sulphide zinc ores, calamine (zinc carbonate ore) waste dumps, jig tailings, jig slimes, table concentrate slimes, brass ashes, zinc-bearing iron ores (where the iron sinter is the real objective and the zinc oxide a by-product), electrolytic-zinc leach residues, zinc muffle residues and works sweepings, lead-furnace slags, tin ores and slags, anti-

Jan 1, 1937

By Carville E. Sparks, Rollin Farmin

Edward Thomas (U.S. Bureau of Mines, Washington, D. C.)—This excellent article on an ingenious and successful installation of wooden rock bolts loses much of its effectiveness through an attempt by the authors to establish the general adaptability of this type of support. Possibly because they have only local experience as a guide, they imply erroneously in the first paragraph that the Bureau of Mines has been opposed to wooden bolting, although later in the article reference is made to a Bureau publication on the subject. In 1947 the Bureau of Mines decided to sponsor experiments in roof bolting in coal mines because the experience of the St. Joseph Lead Co. had indicated that this type of roof support appeared to be a roof-fall accident-prevention measure that might be adopted and also effect economies in operating cost. Justification for this belief has been borne out, particularly in coal mining. This program has been carried out under the following general program: 1—The Roof Control Section of the Bureau of Mines has advocated and initiated underground experiments under controlled conditions with many different ideas related to rock bolting since 1947. In no instance has cooperation in developing an idea been refused, no matter how ridiculous it may have seemed at first glance, if it has been requested by a mining company. 2—The Bureau of Mines has no police powers over the selection of roof-support devices and seeks none. 3—At the request of an operator, the Bureau of Mines will make comparative tests on various types of bolts underground and will submit resultant data for the operator's consideration. 4—Wherever possible, the Bureau publicizes successful installations, so that others may benefit from this experience; however, it is careful not to discriminate between manufacturers of bolts or bolt-installation equipment. Unsuccessful experiments probably should also be publicized, but from a practical standpoint it is usually not feasible. In other words, the role of the Roof Control Section of the Bureau is in line with the original purpose for which the Bureau was first organized: to serve industry through gathering, analyzing, and disseminating factual data. It would seem to be logical that the starting point for any experimentation on roof bolts in coal mines should be the time-proved practice of the

Jan 1, 1955

By Charles H. Fulton

The process of crushing ore in cyanide solution was first used at the Crown mine, New Zealand, in 1897, by Mr. F. R. W. Daw; and, two years later, Mr. John Hinton tried it experimentally at the old Dakota plant, Central City, South Dakota. To Mr. Hinton belongs the credit of introducing this important modification in the Black Hills, this being its first successful application in the U. S., and its results have been so satisfactory that it has become established as the proper manner in which to treat the dense oxidized siliceous ores of this district. Five mills are now crushing ore in cyanide solution, namely, the Horseshoe, 120 stamps (60 in operation); the Dakota, 30 stamps; the Maitland, 40 stamps; the Hidden Fortune, 60 stamps; the Lundberg, Dorr & Wilson, one 6-ft. Monadnock roller-mill; and several others intend to adopt this practice. The dry-crushing process still holds its place for the treatment of the more porous and open siliceous ores; and two mills continue to dry-crush dense siliceous ores. Character of the Ores. The occurrence of the ores of the Cambrian strata in the northern Black Hills has been frequently described.' In practice they are classified, according to their appearance, into " red " and " blue " ores, the former being oxidized and the latter unoxidized. At the present time, usually the red ores only are treated at the mills, although occasionally small quantities of blue ore, which have become intimately mixed with the red in mining, are included. Generally the extraction of values by the direct treatment of raw ore is from 70 to 75 per cent. for red ores, and from 25 to 50 per cent. for blue ores. The ores consist mainly of a siliceous matrix containing, as a +1SOUTH DAKOTA SCHOOL OF MINES, RAPID CITY, SO. DAK.

Jan 1, 1905

By A. T. Stroebel, J. A. Goodwin

Diatomite deposits, the skeletal remains of tiny aquatic plants called diatoms, are found in many parts of the world. Only a few of these deposits are of commercial value. Open pit mining is used in nearly all deposits now being worked. Processing methods range from simple drying, crushing, sizing and packaging to carefully controlled and highly sophisticated calcining and air classification procedures, employing the latest control and testing techniques. The major uses of processed diatomite are infiltration as filter aids and fillers and extenders.

Jan 1, 1983

Gerald Sherman, Bisbee, Ariz. (written discussion*) .—The fact that, after a change in the hours of labor, as much work is found to be done in 8 hr. as was accomplished in 10, probably results from the more rigid examination of operating methods that is made when the management faces new and more difficult conditions. Although A better working pace will prevail, most of the gain will result from economies of plan and only a part of it from the improved effciency of labor. The Iabor of shoveling is so severe that it may be easily believed that a working period of less than 7 hr. will give maximum results, but there arc many other occupations about a mine in which this is not true, and in which the rate of accomplishment is in proportion to the time employed, up to 9 or 10 hours. Mr. Harley's study of shoveling has becn thorough, and demonstrates the benefit of investigation and education even in such simple work, but his reference to methods of payment opens a subject even more important in mine management. The efficiency of labor may be excellent, but unless a method of equitable payment accompanies it, the result will be only temporary. With strict but sympathetic supervision, a good average day's work can be obtained; but with the exception of those unusual men who cannot be restrained from working to their limit, an average daily wage does not bring out the remarkable performance of which many men are capable. There is also a considerable variation in the average amount accomplished, dependent on the supply of Iabor. This can readily be shown by any labor record that covers several periods of shortage or superabundance of labor. An increase in the daily wage in the time of labor shortage does not necessarily bring out an increased day's work; there is usuaIly a decrease in labor efficiency at such times regardless of the wage, whenever a daily rate is used. Rewards to individuals for exceptional performance appearing as an increased rate of pay cannot be made in a large organization without bad feeling. In a small organization, an individual's ability may be so well recognized that different rates of pay can be applied. Exceptional work can only be obtained by a method of payment based on the valuable results accomplished. As a basis for such payment, an

Jan 1, 1920

By S. Atak, M. C. Fuerstenau

Clean quartz cannot be floated with a high molecular weight sulfonate as collector at any pH. Good flotation is achieved from pH 6 to 12 when Pb is added at low additions of sulfonate. The active species of lead responsible for flotation is shown to be Pb(OH), which in the presence of sulfonate forms precipitated lead-hydroxy-sulfonate, the apparent collector in these systems. The ratio of collector to metal ion addition is critical for flotation to be effected at a given value of pH. At low Pb++ additions, the constant, k, k = (hydroxyl activity)/(sulfonate addition)', must be equalled or exceeded for flotation to result. Similarly, at high additions of Pb ++, k1 = (hydroxyl activity)/(sulfonate addition) " must be exceeded. Previous work has shown that clean quartz cannot be floated at any pH with a high molecular weight sulfonate as collector.'" Flotation can be effected, however, when a polyvalent metal ion is added to the system in a pH region in which the metal ion is hydrolyzing to its first hydroxide complex. Although the basic phenomenon responsible for activation is apparently metal ion hydrolysis, the amount of collector added in relation to the amount of metal ion is critical. In fact, Schuhmann and Prakash,3 and Gaudin and Rizo-Patron4 have demonstrated that this ratio of collector addition to metal ion addition determines whether any flotation is possible at a particular value of pH. The object of this paper is to explain and quantify the relationship between collector and activator additions as a function of pH. For this work, Pb++ was selected as activator, and a high molecular weight sulfonate was chosen as collector. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate (mol wt 450) was used as collector. Reagent grade n-amyl alcohol was added as frother, and pH adjustments were made with KOH. Lead was added to the systems as the chloride salt. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample

Jan 1, 1965

By M. E. Grimes

A method of predicting uranium extraction rate in underground bacterial leaching of as-blasted ore has been developed. The method is based on the hypothesis that extraction is directly proportional to the volume of a piece of ore that is penetrated by the leaching agent, and that each piece of ore, regardless of size, has been penetrated radially from the external surface to the same depth at a given leaching time. Consequently, given an initial size and assay distribution, extraction should be predictable for a given penetration. Two laboratory bacterial leaching tests under simulated stope leaching conditions were carried out for a periods of 89 and 96 weeks. On completion, the residual ore was screened and analyzed. The information so obtained was employed to provide an elapsed time base for the penetration model, from which predictions of future extraction were made. The finding of solubilized uranium trapped within apparently sol id ore pieces was unexpected. However, it is not recoverable except after crushing, and hence does not affect calculations of underground leaching .

Jan 1, 1974

By Charles Y. Clayton

A study of the literature shows that the greater part of research work on annealing of cold-worked iron has been for the purpose of studying the effect on grain-size and properties other than hardness. No reference has been found of experimental work of the same nature as that explained in this short paper. The material used throughout was Vismera iron, an iron containing 0.03 carbon and made several years ago by the Inland Steel Co. One-half inch stock was cut into cylinders % in. long. The cylinders were then compressed for 60 sec. in a Reihle testing machine under loads as indicated below: CoMPressiON, Average Length, Series Pounds Inches 1 10,000 0.693 2 15,000 .599 3 20,000 .501 4 25,000 .426 5 30,000 .378 6 35,000 .351 7 40,000 .311 Fig. 1 shows these cylinders after compression. Each series consisted of 17 specimens lettered 0, B, C, D, E, F, G, H, I, J, K, L, M, N, P, Q and R. One specimen of each series was reserved for study of the properties in the cold-worked condition. The other specimens were annealed in a Hump furnace for 1/2 hr. at the following temperatures: TEmpeRa- TempeRa- Letters tuRe,° C. LettERs tuRe °C. B............................... 250 J.............................. 650 C............................... 300 K............................. 700 D............................... 350 L.............................. 750 E............................... 400 M............................. 800 F................................ 450 N............................. 851 G............................... 500 0. . :........................... 900 H............................... 550 P.............................. 950 I................................ 600 Q............................. L000

Jan 1, 1926

By R. O. Williams

A recent article by Chernock, Singer, Mueller, and Beck 1 which supports the use of the integral of I sin $ d$ for comparing fiber texture data does not settle what happens to I sin ø as ø approaches zero, where I is the diffraction intensity for poles oriented 0 deg from the fiber axis. They indicate that they believe that it should approach some constant value (that is, I increases without bound) and the fact that in reality it does not was a result of the diffraction

Jan 1, 1960

By P. E. Busby, C. Wells, M. E. Warga

Fundamental data on the rate of diffusion of boron in austenite and solubility of boron in the a and y phases of iron and steel have been obtained from deboronizing experiments and provide partial explanations for some of the phenomena observed in boron steels. The rate of diffusion of boron is about the same as carbon in austenite. The solubility of boron in austenite at normal heat-treating temperatures is less than 0.001 pct. A partial tentative Fe-B phase diagram in the important low boron concentration ranges and an equation representing the diffusion of boron in austenite are presented. A LTHOUGH a search of the literature revealed ALTHOUGHthat boron diffusion had not been studied quantitatively and systematically prior to 1948, a few qualitative observations which were made by following the diffusion of boron into iron packed in ferro-boron1-3 suggest that boron obeys normal diffusion laws and that the rate of diffusion increases with increasing temperature. The claim of Cornelius and Bollenrath1 that boron does not appear to influence the rate of carbon diffusion has recently been substantiated by Wells, Batz, and Mehl.4 Calculations based on data from the paper by Campbell and Fayv indicated that the diffusion coefficient (D) for boron in iron at 900°C is approximately 3x10 sq cm per sec; a value of 2x10-7 sq cm per sec at 1038°C has been reported by Digges et al in connection with decarburizing experiments on a commercial boron steel containing 0.43 pct C. During the period 1948 to 1950 several diffusivity constant (D) values for the diffusion of boron in the y phase of iron and steel and a number of solubility values for boron in both a and y phases were reported. It was concluded tentatively as a result of Metals Research Laboratory studies that D values for boron in y and a phases are about the same as for carbon in the comparable phasesa and that carbon up to 0.4 pct did not affect the rate of diffusion of boron in y iron above 1000°C within the limits of experimental error. Whether saturation of the y or a phases with carbon would significantly affect rates of diffusion of boron through them was then and still remains in doubt. The best estimate of Q (activation energy) was reported to be about 25,000 cal, somewhat lower than that for carbon in y iron. The solubility of boron in y iron at 1000°C was thought to be higher than 0.004 pct B but not as high as a more recent analysis of available data shows it to be. The solubility of boron in a iron at 700°C was reported to be 0.0004 pct B, but it would not have surprised the authors if the true solubility value is actually lower than this. Breaks in diffusion curves which were not understood when first obtained prior to 1950 have now been recognized as indicating solubility limits, and these are included in the present paper. Experimental Procedure Two methods were employed in an effort to determine diffusion coefficients (D) for boron in austenite. Early experiments involved the use of welded couples prepared in accordance with the procedure of Wells and Mehl,' but when the results of these experiments proved to be unsatisfactory for calculating D values, studies were continued by means of deboronizing experiments. In both cases, boron analyses following the diffusion anneal were carried out spectrographically and all D values were computed using the Grube solution of Fick's law. The precision of the spectrographic method used proved to be about equal to that reported by Corliss and Scribner" —average deviation from the mean about 5 pct of the amount present when the boron content is 0.003 pct. Concentration-penetration curves obtained from spectrographic analyses of welded couples generally indicated that practically no boron was transported across the weld interface during the diffusion anneal. Furthermore the concentration-penetration

Jan 1, 1954

By J. C. M. Li

The steady state shape of a shrinking cylindrical grain boundary of miform boundary energy is shown to be circular. This is based on the principle of either the minimum rate of entropy production or the minimum thermokinetic potential. The circular shape corresponds also to a state of minimum (not maximum) velocity. The steady state shape of a grain boundary moving between two inclined surfaces is a circular cylindrical arc whose position and curvature will be afjected by the nature of the surfaces. The minimum thermokinetic potential is the only valid criterion in this case. THE preceding paper1 reports an interesting experiment in which it is shown that a grain boundary moving between two inclined surfaces assumes a circular cylindrical arc whose axis nearly coincides with the line of intersection of the two surfaces. The driving force is well defined since it is the energy of the grain boundary itself. The velocity of the grain boundary is found not to vary linearly with the driving force. Several interesting questions arise: 1) What principle determines the shape of a moving grain boundary? 2) What is the effect of the inclined surfaces? 3) How do we understand the nonlinear velocity-driving force relationship? It is attempted in this paper to discuss the first two questions based on irreversible thermodynamics and in a following paper to discuss the third question based on dislocation theory. STEADY STATE SHAPE OF A SHRINKING LOOP (A CYLINDRICAL GRAIN BOUNDARY) In irreversible thermodynamics, there are two criteria for the steady state. One is the minimum rate of entropy production2 which is based on the symmetry of phenomenological coefficients and is applicable to linear force-flux relations with constant coefficients. The other is the minimum thermokinetic potential3 which is based on the integrability of a certain Pfaffian differential equation and is applicable to nonlinear systems with variable coefficients. In the case of a shrinking grain boundary loop (a two dimensional version of a cylindrical grain), the flux of atoms across the grain boundary can be taken as the local boundary velocity v measured perpendicular to the boundary (the number of atoms transferred per unit area per second is equal to the product of atom density and the velocity of the boundary). The local thermodynamic driving force can be taken as y/p with y being the grain boundary energy (invariant with respect to the orientation and curvature of the grain boundary) and p being the radius of curvature. Such driving force can be understood by considering the loop as an elastic string with tension y. As shown in Fig. 1, across a length ds along the loop, the direction of y changes by an angle d@ which is ds/p. Because of this change of direction, the tension exerts a force perpendicular to the curve equal to yd@. The force per unit length is then y/p. According to the experimental observation, the velocity v is a power function of y/p, where M is the velocity at unit driving force and 'n is a constant. The rate of entropy production per ds along the loop is vyds/pT, where T is the temperature. For a given length L of the loop, the total rate of entropy production is The thermokinetic ptentia13 has only a differential definition and its existence depends on the integrability of this definition. In this case, Eq. [3] happens to be a total differential and the thermokinetic potential can be defined as which turns out to be the same as the rate of entropy production, Eq. [2], except for a constant factor n + 1. Strictly speaking, since the flux-force relation is not linear, the rate of entropy production may not be a minimum at the steady state. However, because of the proportionality between Eqs. [2] and 141, the state of minimum thermokinetic potential happens to be the same as that of minimum rate of entropy production. The steady state shape thus can be obtained by minimizing either integral [2] or [4] for a given L.

Jan 1, 1970

By Alan J. Strauss

The Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. This paper reviews the properties of the pseudobinary solid solutions formed by these compounds, including the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and energy band structure. Particular emphasis is placed on the Pbl-xSnxTe and Pb1-xSn,Se alloys with rocksalt structure, because of current interest in these malerials for generating and detecting infrared ,radiation. ThE Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. Some of the physical and electronic properties of these compounds, including their melting points1-8 and energy gaps,4'9-12 are listed in Table I. Four compounds (SnTe, PbS, PbSe, and PbTe) have the cubic rocksalt (Bl) structure. At room temperature GeTe has a rhombohedra1 structure closely related to the B1 structure, into which it is transformed at about 400°C. Four compounds (GeS, GeSe, SnS, and SnSe) have the orthorhombic B29 structure. In samples which have not been intentionally doped with impurities, the electrical conductivity is due primarily to electrons or holes produced by the ionization of donor or acceptor lattice defects associated with deviations from stoichiometry. Undoped samples of PbS, PbSe, and PbTe may be either n type or p type, depending on whether they contain excess lead or an excess of the Group VI element, respectively, but only p-type samples of the other compounds have been reported. This paper will review the properties of the pseudo-binary solid solutions formed by the nine 1:l compounds. The topics to be considered include the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and band structure. Particular emphasis will be placed on the Pb]-xSnxTe and Pbl-xSnxSe alloys with B1 structure, which are promising materials for generating and detecting infrared radiation in the 8 to 14 µm atmospheric window and beyond. MUTUAL SOLID SOLUBILITY The extent of mutual solid solubility in the pseudo-binary systems has been investigated for fourteen of the eighteen ternary systems (in which the two terminal compounds have a common element) and for nine of the eighteen quaternary systems. In most cases, X-ray diffraction measurements made at room temperature were used to determine the structure and lattice parameter(s) of the phase(s) present in samples of various compositions prepared by freezing from the melt. In many investigations, including the extensive studies of Krebs and co-workers,13'14 the samples were annealed at elevated temperatures before X-ray measurements were made. In some cases, metallographic examination and thermal analysis have also been employed. The results for the ternary and quaternary systems are summarized in Tables II and III, respectively. (The original references should be consulted for the annealing temperatures.) The solubility of one compound in the other is at least 5 mol pct in all cases, and is often much larger. Complete solid solubility has been observed in all systems so far investigated in which the terminal compounds have the same structure, although in the PbS-PbTe system complete solubility is limited to elevated temperatures. Thus complete solid solubility occurs in five systems where both compounds have the B1 structure (SnTe-PbTe, PbS-PbSe, PbS-PbTe at temperatures above 805°C, PbSe-PbTe, and SnTe-PbSe) and in three where both compounds have the B29 structure (GeS-SnS. GeSe-~n~e-, and SnS-SnSe), as well as in two involving GeTe and a compound with B1 structure (GeTe-SnTe and GeTe-PbTe). On the basis of thermal analysis data, complete solid solubility at sufficiently high temperatures has also been reported for the GeSe-GeTe2 and SnS- pbS22 systems. This seems unlikely, however,

Jan 1, 1969

By F. D. Mahone

Much crude oil, as produced from the well, carries varying amounts of water, which may be present as free water in globules sufficiently large to settle out, in time, if the fluid is allowed to stand, or as an emulsion formed by myriads of minute water particles, each surrounded and entrapped by a film of oil through which it cannot break under the action of gravity alone. Such an emulsified mixture of oil and water is commonly termed "cut oil." When such an emulsion is subjected, under proper conditions, to the influence of a high-potential alternating-current field, the minute water particles rupture the enveloping oil films and coalesce into larger water droplets this procedure continuing until all the water is freed into drops of such size that they readily settle out. This action has been photographed by the micro-moving-picture camera; under the microscope, the breaking-up of the emulsion, as described, is seen to be accomplished in a few seconds. The low power requirements of the process, from records of commercial plants, substantiate the theory that the action is that of a multitude of electrical condensers in series, rather than that of a number of conducting paths. The minute water particles serve as the metallic elements, or plates, of the condensers and the separating oil acts as the dielectric. Such surface charges as the particles may have are removed, and the intervening oil is broken, probably electrically by the voltage and mechanically by the attractive force between adjacent oppositely electrified particles. The principle of breaking up an emulsion under the influence of an alternating electric field was discovered by F. G. Cottrell and Buckner Speed, through experiments conducted, at the University of California, which resulted in a plant being installed on the property of the Lucile Oil Co. in the Coalinga field, California, early in 1909. This plant was able to reduce 14-per cent. emulsion to less than Pper cent. with commercial success. Standard Cottrell Apparatus The present standard Cottrell apparatus consists essentially of the electric treater and a settling or trap tank. The treater is a galvanized-iron tank approximately 3 ft. in diameter and 10 ft. high, which con-

Jan 1, 1924