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By John Wulff, J. H. Hollomon

The opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was re-deposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May16 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to a1pha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,a in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As2O3),

Jan 1, 1942

By C. Atkinson

A method is described for the numerical solution of the diffusion equation with a composition-dependent diffusion coefficient and applied to the radial growth of a cylinder; the radial growth of a sphere, and the symmetric growth of an ellipsoid. Sample applications of the method are made to the growth of particles of proeutectoid ferrite into austenite. RECENTLY&apos; we described a method for numerical solution of the diffusion equation with a composition-dependent diffusion coefficient for the case of the growth of a planar interface. In this paper we extend this method to describe the radial growth of a cylinder, the radial growth of a sphere, and the symmetric growth of an ellipsoid. In the latter case, limiting values of the axial ratios of the ellipsoid reduces the problem to one of a cylinder, a sphere, or a plane depending on the axial ratio. A check on these limiting values is made in the results section. In all of these cases we consider growth from zero size. A natural consequence of this assumption as applied to the sphere, for example, is that the radius of the sphere is proportional to the square root of the time. This is consistent with the condition that the radius is zero initially, i.e., grows from zero size. It may be argued that it is more realistic to consider particles which grow from a nucleus of finite initial size; even in this case the analysis of this paper is likely to be applicable. This can be seen if a comparison is made of the work of Cable and Evans,2 who consider a sphere of initially finite size growing by diffusion in a matrix with a constant diffusion coefficient, with the results of Scriven3 for growth from zero size. This comparison shows that the rates of growth in each case differ trivially by the time the particle has grown to about five times its initial size." This investigation is a generalization of those of Zener,4 Ham,5 and Horvay and cahn6 to the situation often encountered experimentally, in which the diffusion coefficient varies with concentration. First let us consider each of the cases separately. I) GROWTH OF SPHERICAL PARTICLES FROM ZERO SIZE In this case the differential equation in the matrix depends only on R, the radius in spherical coordinates, and can be written: ? 1 <^\ ^13D . , dt U\dRz + R 3Rj + dR dR [ J where C is the composition, t is the time, and D is the diffusion coefficient which depends on c. The boundary conditions will be: c = c, at the moving interface in the matrix, c = c, at infinity in the matrix (and at t = 0, everywhere in the matrix), c = X, is the composition in the spherical particle. Each of the above compositions is assumed constant. In addition there is the flu condition at the moving interface which can be written: , dR0 ~/3c dt \dR/H =Ra where R,, which is a function of t, is the position of the moving interface. We make the substitution q = RI~ in [I] reducing this equation to: & - m - *ws) »i where we have written D = D,F(c) or simply D,F, and Do = D(c,). Thus F[c(q0)] = 1 where q, = ~,/a is the value of the dimensionless parameter q evaluated at the interface. Multiplying Eq. [2] by dq/dc and integrating, we find: where the lower limit of the integral has been chosen so that dc/dq — 0 as c — c,, thereby satisfying the boundary condition at infinity. We require, then, to solve Eq. [3] subject to the condition c = c, when q = q, (this follows from putting R = R, at the interface) together with the flux condition which can be rewritten in terms of q as: Eqs. [3] and [4] together with the condition c = c, at q = q0 enable us to find 77, and the concentration profile c = c(q). Numerical Method. We treat Eq. [3] in the same way as we did the corresponding equation for the planar interface problem&apos; i.e., by dividing the interval c, to c, into n equal steps so that: cr = ca -rbc [5] where r takes the values 0, 1, ... n and we call no,, q1, ... nn the values of n corresponding to the compositions c,, c,, ... c,.

Jan 1, 1970

By T. I. Moore, L. A. Painter

THE electrolytic zinc plant of the American Zinc Co. of Illinois was described by Davidson&apos; in 1944. Since then, improvements as well as expansion of the plant facilities have been made. In order to increase the production of high grade zinc which was needed for war purposes, an expansion program designed to double the slab zinc capacity was started in 1942 and completed in March 1943. This expansion was propagated by a contract between the American Zinc Co. of Ill. and the Defense Plant Corp. The contract included the facilities of the Fairmont City, Ill., property of the American Zinc Co., where a suspension-type roaster with contact acid plant, cadmium distillation furnace, Waelz oxide and densifying plant, and horizontal retort furnaces were installed. The expanded Monsanto, Ill., plant and the additional facilities of&apos; the Fairmont plant were designed to integrate the metallurgical treatment of zinc concentrates for the production of special high grade zinc at Monsanto with the production of acid, cadmium, high grade zinc from furnace skimmings and the Waelz treatment of leach residue at Fairmont. In general, the original flowsheet was not changed, except for the addition of the filtering, drying and reclaiming of leach residue, and the treatment of purification cake for the recovery of copper, cadmium sponge, and zinc. Fig. 1 is a flow diagram of present operations. The original plant facilities, desi-gned for 50 tons daily production of slab zinc, had some units which were more than adequate. Therefore, in expanding the facilities to 100 tons per day, it was not necessary to double all operating components. Table I gives the comparison of the changes made in the unit operating components for the original facilities, 1941, the 1943 expansion, and the 1951 facilities. During the past 11 years a number of improvenients have been made resulting in: 1—an increase in slab production, 2—higher recoveries on the calcine treated, 3—better quality of slab zinc produced, 4—higher current efficiencies, and 5—less man hours Table I. Changes in Operating Facilities Operating Unit 1941 1943 1951 Calcine unloading (pneumatic), 10 tons per hr 12 calcine unloading track hpr. and elev., 60 tons per hr 1 Calcine storage, tons 1,000 2,000 2,000 Leach tanks, 35 vol. tons. No. 3 5 6 slurry mixing 6x6 ft stainless tank, No. 1 Ball mill. 4.5 rt x 16 in. conical. No. 1 CLassifier duplex, No. 1 1 Thickeners. 50 it diam. No. 2 9 2 Filter thickeners, sq ft &apos;-- Moore filters, sq ft 5.760 11,520 Drum filters, 10 ft diam x 16 ft, No. 3 3 Rotary arlers, No. 1 2 1st stage Cu-As purificatlon tank. 90 vol. tons, No. 3 Solution heaters, No. 3 Filter press, 30x30 bronze, No. 4 Zinc dust purification tanks, 45 vol tons. No. 3 5 4 Filter press, 36x36 bronze, No. 3 5 3 Cadmium recovery plant: Process tank. No. 5 2 Cake roaster, 20 ft diam x 4 hearth. No. 1 Filter press, 24x24, No. 4 1 Sponge wash box, 4x6 ft, No. 1 Evaporative cooling unit (vacuum), No. 1 Purified storage tank, vol. tons 400 400 400 Cell acid storage, vol. tons 400 400 400 Electrolytic cells, No. 180 372 372 Cell room ventilation, cu ft per min 35,000 125,000 125,000 Cell cooling water. gal per min 1,500 2,300 2,300 Deep well 16 in. x 95 ft, 1500 gal per min, No. 2 3 3 Melting and casting furnace, 130 ton. No. I Furnace fume scrubber unit, No. 1 Dross drums, No. 2 Dross roaster, 8 ft diam x 8 hearth, No. 1 Electrolysis power conversion, kw 6,250 23,750 23,750 Power transformers, 13,800/440, kva 1,000 1,500 2,000 Steam boilers fire tube, 15 psi, lb per hr 12,000 18,000 18,000 Steam boilers water tube. 125 psi, Ib per hr 30,000 Air compressor, 2 stage. 300 cu ft per min. 100 psi, No. 1 2 Air compressor, 1 stage, 300 cu ft per min, 20 psi, No. 1 Vacuum pumps, 18x7, 720 cu ft per day, No. - - . Vacuum pumps, 24x11, 1.633 cu ft per day, No. 3 3 Building area, sq ft 60,854 113,568 115,000 per ton of metal produced. In the summer of 1944, the "reverse" leaching process was placed in operation and since it has been described,&apos; no further description will be given. Other facilities and changes which have contributed to the process improvements were the scrubbing of fume from the melting and

Jan 1, 1953

DESIRABLE as it is to summarize what has been set forth in preceding chapters, the task can only be approached with great hesitation. What follows represents the personal views of the author at the moment of writing, reserving the privilege to change them on more mature reflection or in the light of further evidence. With that reservation they may be stated somewhat as follows. Education for the mineral industries falls into two categories; general education and technical vocational, using the word vocational not in its usual sense but to signify preparation for specific activities, in which sense a law school is a vocational school. Even at the beginning, as indicated in the first chapter, mineral industry education was partly general and partly technical and that relationship still persists, because technical education requires a firm basis of general education. Our general American system is to provide free public general education through the twelfth grade, or completion of high-school work, though there are already many technical vocational high schools, and even in a community where nearly all the young people are preparing for entrance to college there will be some who wish to qualify for employment at the end of the high-school course, or even on completing junior high. Our educational system, therefore, has not only to provide education for those who intend to proceed beyond the twelfth grade but also for those who, for a variety of reasons, may wish or be forced to cease full-time education at any level between the first and twelfth grades. This study has been chiefly concerned with the problem of what kind and how much technical education to provide for those who have completed the twelfth grade and who wish to make their living in the mineral industries. The obvious fact that the mineral industries employ all sorts of trained persons,

Jan 1, 1941

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By A. J. Lynch, W. J. Whiten

Extensive research, ,development and plant application work has been done on automatic control systems for wet grinding and sulphide flotation circuits during the past twenty years. The result is that there is a good understanding of the process mechanisms, the effects which changes in different variables have on these processes, the procedure for design of control systems to satisfy particular objectives and the problems in the implementation of control systems. There is also an appreciation of the problems which are still to be solved. These are reviewed briefly in this paper. Other processes used for the beneficiation of fine particles have been studied in lesser detail. The control of dry grinding, coal flotation and gravity separation are mentioned briefly in this paper.

Jan 1, 1980

By A. U. Seybolt, V. A. Phillips

Binary iron alloys containing 1 pct of Al, Cr, Mn, Mo, Si, Ti, or V, and 0.4 pct C, 1 pct Cr steels with and without 1.2 pct A1 or 2.0 pct Ti additions, were ion-nilrided at 550° to 600° in N-H mixtures. Nitriding increased the inicrohardne ss of all the binary alloys except those containing manganese or molybdenutn, and also hardened the heat-treated steels if aluminum or titanium urns present. Transmission electron microscopy revealed particle formation in all casts where hardening occurred. Electron diffraction gare positive identifications for ALN, CrN, and a, Si3N4 in the binary alloys, and AlN and CrN in the aluminum- cold chromium-bearing steels, respectil&apos;uly. Cubic VN with a, = 4.13A was tentatively identified. Particles, apparently of CrN, also formed in the base steel but did not increase the hardness very much. Chromium and vanadium formed nitride platelets on {001}° matrix planes, while titanium gave clusters <15A diam. Aluminum nitride precipitated at grain and subgrain boundaries, and within the grains. Silicon gave profuse precipitates of several Morphologies at grain boundaries and cubical particles within the grains. No effect of the alloy carbides on nitride precipitation was observed in the heat-treated steels. THE nitriding of steel has been a well-established commercial process for about 40 years, but in spite of this comparatively long period of use there have been few studies aimed at understanding the process. Most studies, like the early but very competent work of Jones and organ&apos; and nones.&apos; were concerned with establishing the pertinent engineering variables of steel composition, gas composition, temperature, and time. As far as the present authors are aware, there have been no studies of the composition, size, shape, or distribution of the nitrides formed in the nitriding of steel. Noren and Kindbom3 did, however, examine a few nitrided steels by surface replica electron microscopy, and were able to show the presence of car-bonitrides and AlN and TiN nitrides. pitsch4,5 and Hrivnak6 examined nitrided pure iron by transmission electron microscopy. Baird7 found manganese nitrides in Fe-1.6 pct Mn when nitrided at 650°C, using the same technique. In the present work, emphasis was placed on transmission electron microscopy because of its inherently better resolution, using principally binary alloys of iron containing 1 pct of alloying element. In addition, a few simple 0.4 pct C steel compositions were examined to investigate possible carbonitride formation. It was not anticipated that all of the added elements would form nitrides under the conditions used, but it was considered desirable to obtain direct experimental evidence on this point. It would be considerably easier to ascertain the presence of alloy nitrides by examining appropriate binary alloys in preference to relatively complex steels. The work reported here could have been done using orthodox ammonia-nitriding procedures, but an operating ion-nitriding equipment was available, and was therefore used for specimen preparation. EXPERIMENTAL DETAILS 1) Materials. Binary alloys were made up from vacuum-melted electrolytic iron with 1 wt pct additions of Cr, Ti, V, Al, Mn, Mo, and Si of about 99.9 pct purity. In addition, three steels were similarly made up—a basis steel with 1 wt pct Cr and 0.4 wt pct C and two steels with further additions of 1.2 wt pct A1 or 2.0 wt pct Ti, respectively. The materials were vacuum-melted and cast as 11-lb heats into tapered square molds of about 2 by 2 in. average cross section. The castings were forged and hot-rolled to 11/4 in. rounds. Discs of 4 in. thickness by about 1 in. diam were machined from the rods. Some of these discs were hot-forged and hot-rolled to about 0.020 in. thick, sand-blasted, and then cold-rolled to about 0.003 in. thick. At this point, the surface was cleaned by light etching with HC1, then washed, dried, and vapor-degreased prior to nitriding. 2) Ion-Nitriding Procedure. The type of ion-nitriding equipment used here is similar to that described by Jones and Martin.8 Briefly, a mixture of nitrogen and hydrogen at 5 mm total pressure is placed in a vacuum chamber with a dc potential of 450 to 500 v applied between the work (cathode) and the grounded metal vacuum enclosure (anode). Nitrogen ions are accelerated to the work where a thin layer of Fe4N forms on the surface and thus sets up a nitrogen concentration gradient. This causes nitrogen atoms to diffuse into the surface layers of the alloy forming a finely divided dispersion of alloy nitrides, causing hardening of the surface. In the work to be reported here. the nitriding was carried out at 550° to 600°C to be consistent with commercial nitriding practice. The temperatures cited are those measured by a thermocouple located under a platform on which the work was sitting. Except where otherwise stated, the mixture used in nitriding the binary alloys contained -2.0 pct N, balance hydrogen. The nitrogen concentration in the nitriding gas mixture used for the binary alloys was purposely kept lower than normally used in nitriding steels. 10 to 20 pct, in order to minimize Fe4N formation. In this way only the alloy nitrides would be present as a second phase. However, in the case of steels which would contain a- carbide phase along with as

Jan 1, 1969

By George Stanley Scott

Many requests for information as to the possibility of washing coals to some predetermined percentage of ash or sulfur have suggested that the producers aim to satisfy some degree of purity set by the user of the fuel, rather than to attain the greatest economic benefit to all concerned. This paper is written to show that the highest economic purity of washed coal can be determined from washability studies of the raw coal, costs of mining and washing coal, and data on the effect of ash and sulfur on the value of the coal for the particular use for which it is intended. Coke fob Blast-fuenace Use For purposes of illustration, we take the case of coal washed for coke to be used in the iron blast furnace. The method outlined can be made general in its application by substituting for the figures used here the actual operating figures for the particular case under consideration. In general, it costs the blast-furnace operation from 8 to 25 c. per ton of pig iron to slag out each 1 per cent. of ash introduced into the blast furnace by the coke. This figure depends on which one per cent. of ash is removed, and decreases with decrease in ash. When blast furnaces and coal mines are considered as a whole, the figure decreases to zero and then becomes negative, on account of low recovery of washed coal. Various figures1 have been given by different investigators. These figures necessarily differ, not only on account of the differences in operating costs but on account of the difference in the respective fuels as well. For the purpose of this paper, which, as explained, is to point out a method of attacking a certain problem, the figures used in the exposition of the method are of secondary importance. It is apparent that no universally applicable figures can be used, because there are none. Each plant has its own coal,2 its own operating cost, and its own conditions.

Jan 1, 1930

By H. R. Gardner

The heat treatmmt of plutonium was studied using the Jominy end-quenching technique commonly used for determining the hardenability of steel. Plutonium specimens were end-guenched from temperatures in each of the ß, y, d, d&apos;) and E phases. One series of specimens with a low-iron content, 165 pprn Fe, and another gvoup with a high-iron content, 678 pprn Fe, were used in order to study the effect of a Pu-Pu,Fe eutectic network on the hardness and micro-structure. Hardness traverses indicated no significant variations in hardness with either cooling rate or quench temperature. Metallographic studies indicated major effects on microstructure. Grain size was found to vary markedly with quenching temperature and cooling rate. It was determined that the Pu-PueFe eutectic network could be modified extensively by heat treatment, including spheroi -dization in the y phase and 6 phase below 413°C. An unidentified spheroidal inclusion was observed to go into solution in the delta and higher temperature phases. 1 HE element plutonium is unique among metals in that it has six allotropic forms in the solid state.&apos; These have been designated&apos; as the a, ß, y, d, d&apos;, and phases. The respective phase transformations occur at approximate temperatures of 122", 210°, 319°, 450°, and 480°C with a melting point at 640°C. With this number of phase transformations it becomes pertinent to consider the effect of heat treatment and cooling rate in the various phases on the microstructure and hardness of plutonium. To determine; the effect of a wide range of cooling rates, the Jominy end-quenching technique was applied to cylindrical plutonium specimens. In addition, since the presence of iron in amounts greater than 500 pprn is common in plutonium and results in a network of the Pu-Pu6Fe eutectic, it was decided to study heat treatment effects on two bomb reduced plutonium buttons with different iron contents. A low iron button containing 165 ppm Fe and a high iron button containing 678 ppm Fe were selected for this comparison. EXPERIMENTAL PROCEDURE Experimental Material. The cylindrical bars for Jominy quenching were cast from button stock in vacuo in MgO coated graphite molds. Metal pouring temperature was approximately 950°C and the molds were preheated to 300°C. The castings were machined to 0.5 in. diam. by 2.5 in. long cylinders. Chemical analysis and density data for the two groups of Jominy specimens containing different iron contents are presented in Table I. Except for iron, heats 19-12-1 and 20-2-1 are comparable within the limits of analytical accuracy. Representative specimens from the low-iron and high-iron bars were taken for metallographic examination. The low iron specimen was found to have extensive microcracking, Fig. 1. In addition, numerous unidentified spheroidal inclusions were present, Fig. 17. The average grain size of the low-iron plutonium is 0.068 mm, Fig. 4. In the high-iron plutonium, a Pu-Pu6Fe eutectic network is prominent, Fig. 7. The average size of the network is 0.100 mm. Unidentified spheroidal inclusions were also common in the high-iron plutonium. The average grain size of the high-iron plutonium is 0.036 mm. Experimental Technique. A Jominy end-quenching fixture was fabricated for glove box use. A 2.5 in. water height was used with an orifice of 0.250 in. ID. The orifice to specimen distance was maintained at 0.5 in. Annealing temperatures of 160°, 265°, 400°, 465°, and 535°c were chosen for the study of the effect of quenching from ß, y, d, d&apos;, and e phases on microstructure and hardness. During quenching, cooling curves were obtained from the Jominy specimens at distances from the quenched end of 1/16, 1/8, 3/8, 3/4, 1-1/4, and 2 in. Cooling rate calculations were made from the cooling curves for temperature intervals of 100° to 110° 160" to 170°, 330" to 340°, 420° to 430°, and 490° to 500°c. These temperature intervals were chosen

Jan 1, 1962

By R. J. Arsenault

The yield drop that occurs in tantalum, Cu-AZ. and Ag-Al was investigated as a function of strain rate and at several temperatures. From the strain-rate dependence of the yield drop an activation volume was calculated and found to agree with that obtained from differential strain-mte tests. The temperature dependence of the yield drop can he explained in terms of the parameter temperature divided by activation volume. The yield drop is attributed to the rapid multiplication of dislocations during their motion. THE yield-point or yield-drop (upper yield stress minus the lower yield stress) phenomenon has been the subject of numerous investigations1-9 in both bcc and fcc metals. Also, there is no dearth of theoretical explanations10-20 to account for the yield-point phenomenon. The present explanations can be divided into two categories: the concept of dislocation locking and subsequent unlocking and the concept of multiplication of dislocations due to their motion. The Vottrell10,11mechanism of locking and unlocking, as applied to bcc metals, is the best known of the three proposed locking mechanisms. The two additional mechanisms, short-range order (SRO)7,16,17 and Suzuki-type locking,14,15 have been employed to account for the existence of yield points in fcc metals. The experimental evidence supporting the locking of dislocations, especially in bcc metals, is well-established. The dependence of the yield point on interstitial concentrations,&apos; the kinetics of strain aging,2 and the observations by electron-transmission microscopy18 are some of these experimental results. The number of experimental observations supporting dislocation locking in fcc metals is not as extensive as in bcc metals. The unlocking of dislocations, which actually is supposed to account for the yield drop, is by no means well-established by experimental results for either bcc or fcc metals. The similar temperature dependence6 of the yielding and plastic flow is one of the experimental factors that cannot be explained in terms of the unlocking of dislocations. The mechanism based on the rapid multiplication of dislocations has been proposed by several investigators. 18-20 Johnston and Gilman19 have proposed a detailed model of yielding, which was later employed by Hahn21 to predict quantitatively the yield drop in iron. This mechanism was discussed in a previous paper22 and several limitations were pointed out. In the same paper it was shown that an activation volume could be obtained from the strain-rate dependence of the yield drop and that a correlation existed between the activation volumes obtained from the yield-drop tests and from differen-

Jan 1, 1964

By J. E. Ostberg, G. Phragmen, A. Hultgren, S. Wohlfahrt

Detailed study was made of a number of rimming ingots, both low and high carbon, and especially upon effects of superimposed air pressure. Requirement to suppress core bubbles is between 10 and 15 atm; at 6.5 atm freezing was in semikilled manner and at 3 atm, steel was of rising type. Probable mechanism of freezing under various conditions is discussed. AN earlier paper&apos; reported an investigation made by a committee for studying rimming steel ingots appointed by Jernkontorets in Stockholm. The present paper is the outcome of some further work done by the same committee. Since the characteristics of ordinary rimming steel are connected closely .with the amount of gas liberated during freezing and since this amount of gas is governed by the pressure, it was considered of interest to ascertain in what manner and to what extent definite pressures applied to the top of the liquid steel in the mold would affect the solidification process and the consequent structure of a rimming steel of ordinary composition. The experiments were made at the Domnarfvets Steel Works. The steel was made according to normal practice in a 4-ton Rennerfelt electric furnace. Ferromanganese was added in the furnace; no aluminum was added, with one exception. Analyses of the four heats are given in Table I. The top-poured ingots measured about 12 in. sq x 48 in. and weighed about 1300 lb. One or two ingots of each heat were allowed to solidify under pressure, using a special device for admitting compressed air to the upper closed part of the mold, as shown in Fig. 1. A heavy plate sealed with asbestos was bolted to the top of the mold. The plate had a tapered aperture for pouring. Immediately after pouring the hole was closed by a wedged plug, and compressed air was admitted through a hole in the plug. Because of some delay in applying the plug, full pressure was not reached immediately. The pressure was adjusted to the desired value as indicated by a manometer. In order that the interior of the ingot might have the benefit of the pressure, the freezing of the top crust was delayed by a refractory lining applied to the top part of the mold, Fig. 1. Ingots were also cast from each heat without applied pressure, and with and without refractory lining at the top. Axial sections of ingots were cut either of the whole ingot or of some part of it of special interest; sections were polished and usually etched.&apos; To facilitate description of structures the following terms may be used for different types of ingots solidified under gas evolution: 1. Box-hat or boot-leg ingot: Abundant gas evolution during casting and during rimming; no rim holes. 2. Normal rimming ingot: Lively gas evolution during rimming; usually rim holes in lowest part of

Jan 1, 1952

By Donald Barton

Geophysical methods of prospecting taken as a whole do not seem to offer much promise to a young man planning to enter them in the future. They have come to stay, to be sure, and they will continue in at least moderate use for a long time. Domestic use of those methods presumably is at a maximum at the present time. Geophysical pros-pecting is expensive; the effects of the law of diminishing returns in efficiency in finding prospects can already, be recognized. Small oil companies, independent oil operators, and royalty buyers have been doing much geophysical work. But in face of the increasing costs of discovery of prospects and in face of the probably decreasing favorability of the prospects discovered, I expect to see a sharp drop in their use of geo-physics within the next 10 years. The major oil companies and the larger small oil companies will continue to use geophysics indefinitely, but it seems doubtful whether the very extensive domestic campaigns of a few companies will be maintained for many years, certainly not for 10 years. The use of the geophysical methods in foreign countries has not yet reached its peak, and probaby will continue to increase for several years. That peak level of activity will probably be held for 10 years, although the site of maximum activity will shift from country to country; by the end of 25 years from now, I should expect the foreign use of the methods to have leveled off to one-fourth to one-half the peak level. Foreign service in geophysics does not seem to offer an attractive career, except for men of exceptional disposition. Young men just out of college, who are willing and who can afford to spend three or four years having a fling at adventure before settling down, will find it attractive, but when their tour of foreign service is over, they probably will have harder work finding a job than when they were seniors, and their foreign experience will count for little, except for further foreign service. A few men, mainly the higher men, will have headquarters at civilized or semi-civilized cities and towns or at permanent oil-company towns, and can

Jan 1, 1938

By Carl Pierce

The writer of this article has not attempted to write a technical paper; on the contrary, he has tried to express in "steel-plant English," for steel men, a viewpoint drawn from his practice and experience. It is not his thought that it shall be taken as the "last word" in the making of this class of steel, or that good rimming steel cannot be made by any other practice. The paper was written to serve as the basis of a discussion from which it is hoped much benefit may be derived. The paper deals only with rimming steel made by the open-hearth process, and with the lower carbon steels, such as sheet and tin bar, rivet stock, skelp, etc., although good rimming steel as high as 40 to 50 carbon can be made by having good open slags and giving proper attention to working and tapping temperatures. Definition of Rimmed Steel Rimmed steel is sometimes called open or effervescing steel to differentiate it from killed or partly killed steel. It is steel made by a process which permits the free escape of gases from the metal in the molds. In passing up through the metal, the gases keep it in a rolling action from the walls of the mold inward. The top of the ingot rims in as the metal chills and the walls of the ingot get thicker, the center part remaining fluid until it reaches a pasty condition when it is covered with a cast-iron cap. The Charge In making up a charge for rimming steel, clean stock of a known composition must be selected, special attention being given to the analysis of the materials. The silicon in good rimming steel must be eliminated to a trace, therefore it is advisable to have a uniform amount going into the charge. Too much silicon gives a raw melting heat from which rimming steel is unlikely to result. For this reason a charge containing not to exceed 40 per cent. pig iron and 60 per cent. scrap, with no iron ore, is preferred to the Monell type of charge in which as high as 65 to 70 per cent. pig iron is used with a proportional amount of iron ore for the removal of the excess silicon and carbon. The silicon content of pig iron varies so much from day to day in the average blast-furnace practice that there is danger of getting too much of this element in the latter mixture when

Jan 1, 1926

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970

By G. R. Leverant, C. P. Sullivan

To evaluate the effect of a dispersion of nondeform-able, incoherent, second-phase particles on high-strain cyclic deformation and fracture, recrystallized TD-nickel (Ni-2ThO2) and a commercially pure nickel, Ni-200, were fatigued under strain control at total strain ranges varying from 0.009 to 0.036. Relative to the Ni-200, the slip at the surface of the TD-nickel was more wavy and discontinuous due to the presence of the thoria particles. This made crevice formation (incipient cracking) within slip bands more difficult in TD-nickel than in Ni-200. Both materials cyclically hardened to a constant (saturation) flow stress which increased with increasing plastic strain amplitude. Cellular substructures were developed in both materials during cycling. The cell size in TD-nickel was controlled by the thoria particle distribution and was independent of plastic strain amplitude over the range investigated. The cell size in Ni-ZOO was larger than that in TD-nickel at similar plastic strain amplitudes and was a function of plastic strain amplitude. These results, together with the cyclic stress-strain curves for both materials, are discussed in terms of a model for fatigue strain accommodation at saturation recently proposed by Feltner and Laird. NUMEROUS fatigue investigations have considered the interrelation of slip character, dislocation substructure, and cracking in pure metals and solid-solution alloys. However, except for the studies of the low-strain fatigue of internally oxidized copper alloys1 and cast, dispersion-strengthened lead,&apos; little is known about the effects which small, incoherent, nondeform-able, second-phase particles have on cyclic deformation and cracking processes. Effects due to the particles alone are often obscured by a dislocation substructure introduced during thermomechanical processing of dispersion-strengthened metals. In the present study, recrystallized TD-nickel and a commercially pure nickel, Ni-200, were employed to evaluate the effect of a thoria dispersion on high-strai fatigue deformation and cracking at room temperature. I) MATERIAL AND EXPERIMENTAL PROCEDURE The TD-nickel was supplied by DuPont as a 5/8-in.-thick stress-relieved plate which had been subjected to a proprietary schedule of thermomechanical treatments, and the Ni-200 as 3/4-in. bar which was subsequently annealed for 2 hr at 850°C in argon resulting in an average grain diameter of 0.05 mm. The compositions of these materials are given in Table I. The microstructure of the TD-nickel consisted of elongated grains parallel to the primary working direction with an average width of 0.16 mm, Fig. l(a). Many fine annealing twins were present indicating that the starting material was in a recrystallized condition; this supposition was confirmed by the absence of of any extensive dislocation substructure, Fig. l(b). Sheetlike stringers parallel to the rolling direction were occasionally seen both within grains and at grain boundaries. Some approximately spherical particles about 2 in diam, which may correspond to exceptionally large thoria particle aggregates, were also present. The average Young&apos;s modulus of the plate material in the rolling direction was 21.8 X 106 psi which is consistent with a {100}<001>recrystalliza-tion texture3&apos;* being prominent. In transmission microscopy, the 2.3 vol pct of thoria particles generally appeared to be uniformly distributed although some clusters, 0.1 to 0.3 in diam, of larger particles were observed as previously reported for TD-nickel sheet,5 and stringering of particles was present in some areas as welt. The average diameter of the thoria particles was 450A with a calculated mean planar center-to-center spacing of 2100A, as determined by quantitative metallographic analysis.= The 0.2 pct offset yield stress was 36,000 psi which agrees with the value predicted by the modified Orowan relation7 for edge dislocations bowing between thoria particles of the size and spacing observed in the present investigation. Fig. 2 illustrates the specimen design employed for the axial high-strain fatigue testing. Adapters were screwed onto the threaded portions of each specimen so that testing could be performed in the same manner as that reported for buttonhead specimens.8 Stressing was coincident with the working direction for both materials. The gage section of each specimen was electropolished and lightly etched prior to testing. The total strain was controlled, being varied between zero and a maximum tensile strain ranging from 0.009 to 0.036. In addition to these tests, a circum-ferentially notched TD-nickel specimen was cycled over a total strain range of 0.0075. The same strain

Jan 1, 1969

By Albert Sir Kitson

THE manganese ore deposits of the Gold Coast, British West Africa, occur in very ancient rocks, of both sedimentary and metamorphic types. In. certain respects, they strongly resemble those of India and Brazil, as contrasted with those of Tertiary age in Georgia. Viewed from the present condition of the maganiferous rocks, the oldest deposits are in the sediments. Later than these are the progressively metamorphosed representatives of these sediments; youngest are the products of decay and degradation with the concentration of manganese oxide of both areas. The oldest occurrences are in argillaceous and siliceous phyllites and slates, which show only a moderate amount of metamorphism. They belong to a series which also includes mudstones, sandstones, grits, conglomerates and subordinate limestones, with tuffs and lava-flow&apos;s largely of basic types. To this series I have given the name Birrim. Its age is unknown, for no definite fossils have been discovered in it. As the characteristics of these non-fossiliferous strata at many places are the same as those of strata in many parts of the world that are suitable for the preservation of fossils and that contain them, it is assumed that the Gold Coast deposits are pre-Cambrian. These rocks of the Birrim series have normally a northeast-southwest strike and are folded, but not to any very great degree except in certain belts. From the Eastern Province of the Gold Coast they may be traversed across their strike for more than 600 miles to the extreme northwestern corner of the Northern Territories. Thence they probably extend much further into French Territory.

Jan 1, 1927

By L. L. Newman

PUBLIC UTILITY GAS PRODUCTION IN 1802, William Murdock first used retort coal gas to light his house and the Boulton and Watt plant where he was employed. For the next three quarters of a century coal served as the principal raw material for the manufacture of city gas for general distribution. Coal continued to hold its predominant position for another half century after Prof. Thaddeus C. Lowe developed the first practical method of enriching water gas with cracked-oil vapors in an integrated operation. This position, however, was no longer maintained through the medium of direct carbonization of coal in retorts but as a result of using anthracite or coke as the generator fuel in carburretted water-gas machines. The early water-gas machines were extremely crude and the consumption of both oil and generator fuel was very high. However, the cost of installation was considerably lower than for any coal-gas system having the equivalent gas-making capacity, the labor involved was small, and the water-gas machine could be started up and shut down quickly. It thus proved very useful as standby equipment and in taking peak loads from the coal-gas plants. The flexibility of the water-gas machine, furthermore, made it possible to change the candlepower of the gas readily to suit the required conditions. Later, when calorific value replaced candlepower as the standard of gas quality, the water-gas machine was found to be equally flexible in keeping the city gas under complete and convenient control. No basic improvements were made in the Lowe carburetted water-gas process until 1898, when means were added to provide for regular reversals of the flow of steam through the fuel bed. By judicious proportioning of the quantities of up-run and down-run steam, it became possible for the operator to control the hardness and position of the clinker to a degree that previously had been unattainable. Also in 1898, the first by-product coke plant in America to supply city gas was built at Everett, Massachusetts. Later many other by-product plants, of greatly improved design and capacity, were built, but not primarily for city-gas production, chiefly because of the relatively high investment cost per unit of gas made. Cheaper plant construction has been the subject of serious study, and some progress is expected, but other factors, such as plant life,

Jan 1, 1953

By H. R. Reed

THE cost of hoisting with electricity in deep mines is a matter about which little information has been published. This paper makes a detailed study of such costs and presents the information in a series of curves. In particular the curves show the cost of hoisting ore from depths varying from 500 to 7000 ft. Vertical with the shaft at 70° incline for the double cylindroconical and double cylindrical drums, the hoists operating balanced, using Ward Leonard and Ilgner-Ward Leonard control, and designed for most economical operation from each depth. Operation with the double cylindrical drum is expanded to cover hoisting from 2000 to 5000 ft. using equipment designed for 5000 ft. and from 4000 to 7000 ft. using equipment designed for, 7000 ft. Additional curves are included to show the ratings of the necessary hoist motors, energy input per hoisting cycle and size of flywheel in tons for complete equalization when the Ilgner-Ward Leonard system is used, also hoisting efficiency. The duty imposed on a mine-hoist motor fluctuates between wide limits during a cycle of operation. The demand on the motor may vary from a large horsepower value&apos; near the beginning of the cycle to a small or a negative demand near the end of the cycle. Such factors as tonnage to be raised per hour, depth of shaft, and balanced or unbalanced opera-tion have such a marked effect on the operating cycle and vary to such an extent for different mines that no set of rules can he formulated for quickly determining the size of the motor required. The duty cycle from which the motor rating is (derived must he determined for each case according to the conditions of the proposed hoisting operations. The motor torque required at the cardinal points of the duty cycle is determined from the moment or torque in pound-feet necessary to raise and lower the load and ropes, accelerate and retard the load, ropes, drum, etc. The torque diagram depends largely upon the type of drum. Two different types of drums, if used on exactly the same duty cycles, may have widely different peak demands and capacities of hoist motors. The essential feature in the design of hoisting drums and in determining

Jan 1, 1937

By L. C. Brown, E. B. Hawbolt

The formation of grain boundary precipitates has been studied in Ag-5.64 wt pcl Al alloys at 688°C. Large-grain specinzerzs were used and the boundary misorientation measured by X-ray diffraction. At low-angle grain boundrrries Primary sideplates form. u)hile abore a 17-deg misorientation lenticular precipitates predominate. Growth of the lenticular precipitates was studied on individual grain boundaries using a statistical technique. The thickening and lengthening rates appeared to be independent of &apos;pain boundary misorientation, indicating that grain boundary diffusion was not significant in this system. The precipitates grew urith constant shape, with both the length and thickness increasing parabolically with time. The parabolic lengthening rates were unexpected since previous theory and experimerztal results had indicated linear growth. By approximating the shape of the precipitate to that of an oblate spheroid grouling with constant shape an equivalent diffusion coefficienl was calculated. The zlalue obtained was in good agreement with nleasurements obtained fron, diffusiorz couples. IF a single-phase alloy is heated or cooled to a temperature such that the phase becomes supersaturated, there is a tendency for a second phase to precipitate from it in order to remove the supersaturation. Precipitation takes place initially on grain boundaries due to preferred heterogeneous nucleation, but subsequently Widmans kitten plates may form in the grain interiors if the grain size and supersaturation are sufficient. The type of grain boundary precipitate formed depends on the nature of the boundary. Aaronson1 and clark2 have shown that grain boundary misorientation can be characterized by the simple parameter R, where and X, Y, and Z represent the minimum rotations about three orthogonal axes required to bring the two lattices forming the grain boundary into coincidence. The maximum value for R is 60 deg. In using this parameter the orientation of the grain boundary itself is, of course, neglected. However it was found in both Fe-si3 and A1-Ag2 that the precipitate shape depended only on the parameter R. Clark found that the vast majority of precipitates formed were allo-triomorphs— lens-shaped precipitates that grew along the grain boundaries. At low-angle boundaries, however, (R < 15 deg) Widmanstatten sideplates nucleated at the grain boundaries and grew into the adjacent grains. It has been reported that the rate of growth of grain boundary precipitates is controlled by diffusion within the supersaturated phase.&apos; The theories which have been developed for growth rates have assumed the diffusion coefficient constant over the composition range of the supersaturated phase. This is a fairly good approximation if the composition range involved is not large. Thickening rates have been calculated using the theory developed by Zener4 and by Frank5 for the growth of planar precipitates. A parabolic growth law

Jan 1, 1968