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By Herbert Hoover

YOUR committee asks that I speak today on the relations of the engineering profession to public affairs. That takes in a lot of ground. This being a cheerful occasion, I will assume that I should exclude the engineer's function as a taxpayer. This being a nonpartisan occasion, I will assume that I should not refer to his voting emotions in 1940. Perhaps what was in the minds of your committee was the application of engineering thought to the confusions of the times. That is also a lot of ground. I fear, however, its boundaries disappear in mirages and rainbows on all sides. Now any entry of the engineer into public affairs involves his breaking into the fields of the sociologists, the economists, and the politicians. However I don't know why, seeing the difficulties these professions are having, they should not welcome a little help.

Jan 1, 1939

By Walter Harvey Weed

In a previous paper upon the enrichment of mineral veins by later metallic sulphides,? the writer has shown that certain masses of rich ores, such as are found in many mines, either near the water-line or as bonanzas in depth, are of secondary origin, and are due to a leaching of lean ore and the concentration of the material by reaction between the solution and the unaltered ore below. The geological and mineralogical evidence is believed to form an adequate basis for a chemical and physical explanation of the phenomenon. In the present paper the writer will give a brief synopsis of this theory, and will apply it more particularly to deposits of the precious metals, laying special emphasis upon the dependence of such enrichments upon the presence of iron sulphide (as pyrite, etc.) in the primary ore, and upon structural features which control the circulation of the enriching solutions below the water-level. It is believed that many, though not all, of the bonanzas arid pay-shoots of rich sulphide ores, especially those carrying gold and silver, which are encountered in ore-deposits, are of such secondary origin. Apparently it is essential that the occurrence and structural relations of such ore-masses should be understood, as the success of the mine is often dependent upon the finding and extraction of these ores. A legitimate deduction, too, is that such ore-deposits decrease in value With depth. As my own studies have been mainly in Montana, my illustrations must be drawn from the ore-deposits of this and adjacent States, with such as I have noted in hurried visits else-

Jan 1, 1901

By J. C. Fisher

Martensite transformations in steels and other alloys are characterized in part by the absence of composition changes during the growth of a new phase. Transformation occurs rapidly, and there is insufficient time for long range diffusion or partition of alloying elements to take place; martensite reactions in alloys thus are similar to phase transformations in single component systems. A fundamental understanding of martensite transformations in steels is impossible without knowledge of the free energy change upon transforming austenite (face centered cubic iron containing alloying elements) to ferrite (body centered cubic iron containing alloying elements) of the same chemical composition. The present paper assembles the best information available concerning the influence of temperature and composition on this free energy change. Most of the material has been taken from the work of Johansson,' Mehl and Wells,2 Zener3,4 and Smith;5 and indirectly, through these authors, from the work of Austin.6 In agreement with the generally accepted viewpoint, martensite is assumed to be an ordered solution of carbon in ferrite of the same composition as the parent austenite; only at high temperatures and low carbon concentrations is the carbon in ferrite distributed at random. The properties of the disordered solution are estimated by extrapolating the known properties of iron-carbon solid solutions into the range of supersaturation, and the free energy change associated with ordering is estimated from the theory developed by Zener. By incorporating Smith's recent thermodynamic measurements and Zener's theory of ordering, the present analysis modifies previous estimates of the free energy change associ- ated with martensite transformations. Consider a two component system consisting of a solvent A and a solute B. Let Na and Nb represent mol fractions of A and B respectively, let aa = raNa and ab = YbNb represent activities, and let superscripts 1 and 2 refer to phases 1 and 2. The partial molal free energies of A and B in phases 1 and 2 can be summarized as follows: free energy standard state Fa' - Fao1 = RT In an1 pure A' Fa2 - Fa2 = RT In aa2 pure A2 Fb1 - Fbo = RT In ab1 pure B Fs2 - FB2 = RT In aB2 pure B. The free energy of a gram atom of phase 1 is* AF1 = Na'Fa1 + Nb'Fb1 and that of phase 2 is AF2 = NA2FA2 + NB2Fb2. A martensite transformation from phase 1 to phase 2 requires Na1 = Na2 = Na and NB1 = NB2 = Nb, and the free energy change per gram atom accompanying transformation is AFi-2 = NA(Fa2 - Fa1) + Nb(Fb2 - Fb1) = NA[RT In (aA2/aA1) + AFa1?2] + Nb RT In (aB2/aB1) = Na[RT In (ra2/ra1) + AFa1?2] + Nb RT In (TaVTB1). [1] where yn2, yn1, yB2, yB1 are activity coefficients, and where Ma'+* is the free energy change upon transforming a gram atom of pure A from phase 1 to phase 2 at the temperature in question. For martensite transformations in plain carbon steels, A = iron (Fe), B = carbon (C), 1 = austenite (7). 2 = ferrite (a), and Eq 1 is AFr ?a= NFe[RT In (rf.a/rfer) + AFF.r?a] + TVc RT In (eca/rc1)- L2] Nothing is known concerning the values of yFea and yca for carbon concen- , trations in excess of 0.025 pct. However, the approximation rf.7 = 7f." = 1 cannot be appreciably in error for small carbon concentrations, and Eq 2 reduces to Afr-a = NfeFfer?a1 + NC RT In (rca/rcr)- [3] Johanssonl and Zenera have calculated MFfr?a from the specific heat measurements compiled by Austin.6* Their calculated values agree closely, and are summarized in Table 1. The activity coefficients relative to graphite for carbon dissolved in iron vary with temperature according to the relationships d In rcr/d(1/T) = AHcr-R dlnyca/d(l/T) = AHCa/R where AHc? and AHca are the heats of solution of graphite in y and a iron. Assuming the values of AH to be independent of carbon concentration and temperature, In rCr = AHcr/RT + I1 In rca = AHCa/RT + 12

Jan 1, 1950

By C. W. Chen

MARTENSITE transformations in ß Cu-Al alloys have been studied by Greninger1 and other investigators. According to Greninger, the parent phase ß1 an ordered body-centered-cubic structure obtained from ß phase by suppressing the eutectoid decomposition, transforms into an ordered hexagonal-close-packed phase in composition containing 12.9 to 14.7 pct Al. The M, temperature decreases with increasing aluminum content; for the alloy containing 14.5 pct Al, for example, the ß1??' transformation occurs below room temperature. More recently, Kurjumow2 studied the transformation in ß Cu-Al alloys with the addition of nickel. His report stimulated new interest in the subject due to the observation of completely reversible transformation without hysteresis in the transformation temperature ranging from 10° to —10°C. In the present paper some characteristics are described of the transformation of Cu-Al-Ni alloys that were partly studied by Kurjumow. Experimental Procedure High purity copper (99.999 pct) and aluminum (99.99 pct) and electrolytic nickel were used in the preparation, by the Bridgman technique, of single crystal specimens which contained aluminum and nickel of 14.5 and 0.5 to 3.0 pct, respectively. Polished surfaces were prepared mechanically. Specimens were then chemically etched to remove distorted material, homogenized at 1000°C for several hours, and quenched drastically to room temperature in a 10 pct NaOH bath to produce the parent phase ß1. The transformation was studied under a microscope and, in some cases, recorded by means of motion pictures. A device similar to that designed by Greninger and Mooradian3 was used to cool and reheat the specimens. Results and Discussion When the specimens were cooled below room temperature, the ß1 to ?' transformation began at 10°C with the appearance of ?' crystals In relief, Fig. la. As the specimen temperature dropped further, the transformation continued, either by the growth of the ?' crystals, with the ß1 — ?' interface moving into the ß1 phase, Fig. 1c and 1d, or by the formation of new ?' crystals, Fig. 1b. As a consequence of the former process, banded structure is observed as a common feature of the low temperature phase. According to the theory of the formation of martensite by Wechsler, Lieberman, and Read,' the bands of ?' phase are probably twin-related, as is the case in the diffusionless phase change of In-T1 alloys,5 but this was not revealed by X-ray tech- niques. New ?' crystals, in needle form, often emerged suddenly across the ?' bands during the transformation. These acicular crystals then grew, both in length and in width, see Fig. 2a through 2d. The transformation on cooling is completed at about -35°C. Upon heating, the reverse transformation started at —10° C, in a manner nearly opposite to the transformation on cooling, and completed at 35°C. There was no noticeable change in the transformation temperature when the nickel content was varied within the limits previously mentioned. Through control of the specimen temperature, the transformation can be started, stopped, or reversed at will. This phenomenon has frequently been observed in the martensite transformation of many nonferrous alloy systems. Other systems are Au-Cd6 and In-Tl.5 ow-- ever, in the latter systems, the transformation is accomplished by single interface motion if the specimen composition is homogeneous and the temperature gradient in the specimen is uniform and sharp, whereas in the Cu-Al-Ni specimens, only multiple interface transformation is observed. The speed of the interface motion appears to be a functionof the rate of temperature change and the temperature gradient across the specimen length. In one case, in which the temperature increased at the rate of 10°C per min and there was no temperature gradient along the specimen axis, the speed of the disappearance of a ?' plate was determined, by the study of the motion pictures made, to be 26 µ per sec. Quench markings were observed on the polished surfaces of specimens. The markings were grouped into one or more sets of different orientations, and were parallel in each set. The ?' plates formed in subsequent transformation were parallel to the markings, indicating that the ?' plates and the quench markings had the same geometric relation-ship to the ß1 matrix. The quench markings on two intersecting surfaces of a specimen were therefore used in the determination of the habit plane of transformation, by the trace method suggested by Barrett.' Results obtained from five sets of markings in three specimens indicate that the habit plane is an irrational plane about 2" from one of the {221} planes. This is very close to the habit plane (3" from 221 planes) of ß Cu-Al alloys containing more than 13.0 pct Al.1 The martensite transformation of Cu-Al-Ni alloys is reproducible. No sluggishness was found between consecutive transformation cycles, although a slight difference in the distribution pattern of the ?' plates was observed, compare Figs. Id and 2d. The transformation can be strain-induced. This characteristic has been tested by a simple method. When a specimen was elastically strained slowly in a vise, ?' plates were gradually produced in the same fashion as during transformation on cooling, This test was done at room temperature, and thus above the M,

Jan 1, 1958

By Oliver Bowles

DISCUSSIONS of trade and commerce are generally more comprehensive today than in the past; the problems are approached with a vision unrestricted by national boundaries, and broad enough to comprise the entire world. The extent to which the limited viewpoint that has characterized past ages is yielding to an economy of world-wide scope is exemplified by the Atlantic Charter which blazes a trail in the direction of trade principles that aim to preserve the interest of each individual country in the commonwealth of nations. Its fourth article promulgated the principle that all nations should have access on equal terms to the trade and to the raw materials of the world which may be needed for their economic prosperity. Future developments in reciprocal international trade may have some effect upon the flow of nonmetallic minerals but such effects are not likely to be great because tariffs and trade policies have not affected that flow profoundly in the past. Nevertheless conditions may change and new problems may arise demanding important decisions. Sudden changes are not to be expected, but rather an orderly evolution in which national interests will merit due consideration in establishing broader policies.

Jan 1, 1945

By Willis Carrier

PARTICULAR interest in the ventilation of deep mines, especially those in South Africa, has been created by a very complete system of cooling of the world's deepest mine, the Turf shaft of the Robinson Deep ill Johan-nesburg. The writer visited this mine in January, 1936, and again in 1937. During these visits and subsequently, a considerable part of the theory involved in rock cooling in tunnels was developed and this has been checked by practical observations of the rates of rock cooling made within mines. The purpose of this paper is to set forth the method of attack of the mine problem. The cooling or air conditioning of mines by the use of mechanical refrigeration was not wholly new 1-5 when the Robinson Deep installation was made. The first mine to be cooled was the Morro Velho mine, in Brazil. The first installation in this mine was put into operation in December 1920, the refrigerant being ammonia.5 The surface cooling gave considerable benefit but it proved inadequate as greater depths were reached, therefore in 1929 two centrifugal refrigerating machines were installed at the 6000-ft. level. These were used in conjunction with the surface cooling system to furnish additional cooling at the lower levels. This later installation used Carrene as a refrigerant. This nonflammable refrigerant, having a boiling point of 104° at sea level, insured reasonable safety, since all parts of the machine operated At subatmospheric pressure. Very favorable reports have been received on the effectiveness of this installation, but no recent data are available. An interesting feature of that plant is that the condenser water is cooled by spraying it into the exhaust air from the mine at the base of the ventilation upcast, which permits the water to be cooled within a few degrees of the wet-bulb temperature of the air entering the upcast, and the only water that has to be supplied for condensing purposes is that lost by evaporation, or about 0.5 per cent of the volume circulating through the condenser. This plan affords an ideal means for the removal of the heat load from the refrigerating system, and of course also from the mine itself. In many mines, however, especially those in South Africa, there is no

Jan 1, 1938

By E. Swartzman, G. C. Behnke

THE free-swelling index, a numerical value for the free-swelling properties of coal, is being used to an increasing extent in specifying coal for burning in various types of equipment. The empirical standard ASTM method for determining this index uses, as a source of heat, a gas burner which requires frequent calibration because gas pressures are not constant, relatively small changes in gas pressure resulting in rather wide variations in the temperature attained in a crucible and thus in the resultant size of the coke button. Furthermore, the quartz crucibles specified for the test are not standard equipment, and relatively small variations in dimension and wall thickness from those specified often result in rather wide variations in the resultant size of the button. A method of analysis to be satisfactory not only for a scientific laboratory but also for use in industrial control laboratories under varying conditions should employ equipment which is rugged, easily calibrated, and readily replaceable by standard materials. Gas is not universally available as is electricity, and it is generally easier to calibrate and control a simple electric furnace or heater than a gas burner, the voltage not usually fluctuating to the degree that gas pressure does. Quartz crucibles are fragile, and the size specified in the test is not normally used for any other purpose in the laboratory. Although more expensive, the 15-cc platinum crucible, available in all laboratories where volatile matter in coal is determined by the standard ASTM method, is sturdy and standard and easily replaced. Because of these considerations, a modification of the standard method has been developed which employs a standard laboratory 350-w cone heater and standard 15-cc platinum crucibles. The results of numerous tests conducted with such apparatus show conclusively that the free-swelling index values as judged by the buttons produced with this equipment are exactly the same as those obtained by the standard gas burner method. Thus it is suggested that this electric cone heater method employing standard 15-cc platinum crucibles be considered as an alternative to the ASTM method, Designation: D720-46. The free-swelling index of coal is determined by means of the ASTM method, D720-46. This method, which is an adaptation of the crucible swelling test for coal of the British Standards Institution, consists of heating 1 g of coal in a special covered quartz crucible in a regulated gas flame for a period of not less than 2.5 min in which time the temperature of the inner surface of the bottom of the crucible reaches a temperature of 82025°C. The residual coke button is then compared in size and shape with a series of standard profiles shown in Fig. 1 and designated by number from 1 to 9 in increasing order of size. As the method is empirical, it requires rigid standardization of the apparatus and repeated calibration of the gas burner. The dimensions of the low form quartz crucible recommended must be rigidly adhered to as small variations in diameter or wall thickness result in variations in the rate of heat transmission and thus in the resultant size and shape of the coke button. The gas burner must be calibrated almost every time a new set of determina-

Jan 1, 1952

By Leland L. Mink, Roy E. Williams, C. Daniel Kealy

The passage by Congress of Public Law 92-500 (the 1972 Water Pollution Control Act amendment) has placed a new emphasis on the need for methods to minimize the escape of water from tailings ponds. Presumably tailings pond seepage will fall under the jurisdiction of the act. This paper is designed to explain some of the problems caused by leakage from tailings ponds and to present a method by which leakage can be minimized if not eliminated. Ground-water pollution in one case studied by the authors results from leaching of old jig tailings that are intermixed with the upper part of a sand and gravel aquifer. Anomalous concentrations of zinc, lead, and cadmium occur in ground water and soil samples taken from the portion of the sand and gravel aquifer containing the old jig tailings. Analysis of water samples from a tailings pond located in the area indicates that the pond water is not the source of the heavy metal concentrations found in the down-gradient ground water. However, leakage from the pond and water from the pond's decant system combine with natural ground water to compound the problem by raising the water table into old jig tailings which cover the upper portion of the aquifer. The ground water which discharges from this aquifer causes a statistically significant decrease in the quality of the receiving stream water. The shallow ground water contains oxygen; therefore, corrective measures include lowering the water table to depths below the old jig tailings which cover the aquifer at ground level. This, in turn, implies elimination of ground-water recharge by subsurface leakage from the pond. A laboratory study and a mathematical model study have revealed that seepage from such ponds can be minimized by a carefully designed and managed peripheral tailings discharge system. The process involves maintaining the slime zone and the free-water surface near the center of the pond so that the slimes retard downward and semilateral movement of pond water. The free-water surface must not be allowed to extend out over the nonslime portion of the tailings during or after pond operation. Mathematical model output reveals that this method can hold the subsurface discharge rate to as little as 110 gpd per acre of pond water area. The technique should be applicable to any tailings pond system in which the loss via seepage of poor quality water must be minimized or where recharge of ground water by losses from a tailings pond must be minimized, regardless of the reason.

Jan 1, 1974

By J. W. Evans

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

Jan 1, 1954

[ ] Utilizing tendencies for low grade ores in the Sudbury District of Ontario to cave after higher grade ore has been mined, International Nickel Co., of Canada, Ltd., is recovering millions of tons of nickel-copper ore once regarded as submarginal. Inco is working lower grade ore than ever mined before from its underground operations because of the caving method and metallurgical practices. In the caving method, blocks containing as much as 1.5 million tons of ore are undercut. As ore from the undercut block is withdrawn, the block to be mined breaks away and starts to disintegrate as it moves downward. Inco is also using the blasthole method, using explosives to break slices of harder, tougher ore from solid material. Inco has built a new concentrator at one of its most recent shafts for handling the increased tonnages of low grade ore. The concentrator presently has a 10,000-ton per day capacity, and is scheduled to be increased to 12,000 tons. Hoisting from the mine is by push-button control and the ore is milled on the spot. A 7 ½ -mile pipeline carries bulk concentrate to reduction plants at Copper Cliff. Giant crushers, weighing 165 tons each, have been installed underground. Twenty-ton electric locomotives haul ore to the crushers. The expansion program is expected to lift total annual production of nickel in the free world to 375 million pounds annually, an increase of 150 million pounds. Inco is presently mining more than 1 million tons of ore per month from combined surface and underground operations.

Jan 1, 1952

By J. R. Kyte, L. A. Rapoport, R. J. Stanclift, S. C. Stephan

Experimental studies covering a wide range of core materials and fluid properties have been conducted to determine the mechanism of oil displacement by water in a partially gas-saturated porous medium. In all instances, the presence of a gas phase was found to have a beneficial effect in reducing residual oil saturations. The practical significance of this benefit is discussed, and a simplified procedure is outlined for evaluating the effects of free gas on water flooding by means of short core tests. INTRODUCTION In addition to oil and water, reservoirs subjected to water flooding frequently contain, also, a gas phase. Common engineering procedures account for the presence of this "free gas" only from the viewpoint of volumetric balance, implying that the only role of the gas consists of providing "fill up" space. It is usually visualized that during the initial stages of the water invasion, the oil, moving ahead of the water, displaces part of the gas and that subsequently the remaining portion of the gas phase is totally compressed and dissolved in the advancing oil bank. Thus, consideration of a two-phase, water-oil flooding mechanism supplies an adequate basis for predictions of oil recovery if the pressure build-up caused by the flood is sufficiently great, so as to reduce the free gas saturation to a negligible value in any portion of the reservoir by the time that portion is reached by the advancing flood water. In many in- stances, however, waterflooding operations are carried out when the reservoir pressure is still relatively high SO that the pressure build-up associated with the water flood may not result in complete dissipation of the gas phase. Under such circumstances it is necessary to ascertain whether or not the presence of free gas has an effect on waterflood behavior and, if so, to account for any such effect in the evaluation of field operations. The difficulties encountered in attempting to arrive at a comprehensive picture of the displacement mechanism of oil by water in the presence of free gas stem from the fact that most of the published data on this subject were obtained under conditions that were either not clearly representative of those existing in a reservoir or not sufficiently controlled to permit evaluation of the effects specifically caused by the gas phase. Some of the most precise data found in the literature were obtained in tests using a "static" gas phase created prior to each water flood by circulating oil through partly gas-saturated cores until a "trapped," residual gas saturation was established throughout the system.' Other investigations were conducted under more representative conditions where the gas phase was free to move during the water flood: but in most cases the results of these tests were obscured by auxiliary phenomena which arise from the compressibility and solubility of the gas and preclude quantitative conclusions.2,3,4 Prior to water flooding, a reservoir usually contains oil and gas, distributed in a manner in which both are free to move. Thus, the principal objective of the present studies was to determine the type of displacement mechanism occurring when water invades a porous medium containing oil and a "mobile" gas phase. Further-

Jan 1, 1957

By Raymond B. Ladoo

NONMETALLIC minerals (excluding fuels) arid their primary products produced annual in the United States have a value in excess of one billion dollars, or more than that of the metals, yet the lack of expert knowledge of some of the fundamental technical and economic aspects of this most important and complicated business is astonishing. This paper will deal with the economics of this non- metallic mineral field-the business of making money from producing these minerals. The incentive behind all business activity in a capitalistic economy is to make money-to plan so that each dollar invested in property, plant, equipment, services, and so on will return more than a dollar plus simple interest. Of course, business has social, civic, and national duties and responsibilities, but the fulfillment of these is largely dependent upon financial success.

Jan 1, 1939

By Ulick Evans

I SHOULD like to commence by saying how much I appreciate the honor which the American Institute of Mining and Metallurgical Engineers has done me in inviting me to visit your country, and to deliver this lecture before you. In choosing a subject, and in deciding what to include and what to omit, I have endeavored to discuss as far as possible work carried out recently in Europe with which you may not be unduly familiar. It would be poor return for your hospitality, and a mistaken sort of compliment indeed, if I were to load the lecture with accounts of researches carried out in your own country-researches with which you are probably better acquainted than I. Not that I have in any way excluded work done on this side of the Atlantic from my survey; one would indeed find it difficult to write on this, or on any other branch of science, without mentioning American work. But I have endeavored as far as possible to concentrate on aspects of the case which will, I hope, be comparatively fresh to you, and I feel fairly certain that this will be in accordance with your own wishes. If a strip of iron is heated strongly at one end, the other end remaining cold, there is produced over the heated portion a layer of oxide scale, the thickness of which diminishes steadily with the distance from the hot end. Somewhere in the middle of the strip, the thickness of the oxidized layer will become comparable to the wave length of light, and over this region the thin films give rise to a series of beautiful interference tints, commonly known as "temper colors." The colors are caused by the fact that two trains of light waves are reflected respectively from the outer and inner surfaces of the oxide film, and the possibility arises that the "crests" of one series of waves may coincide with the "troughs" of the other, thus diminishing the intensity of the light of some particular wave length. The state of affairs in this part of the strip is shown diagrammatically in Fig. 1, in which the film thickness is enormously exaggerated, of course, in comparison with the length of the strip; the

Jan 1, 1929

By S. C. Lindsay, D. J. I. Evans

With each year that passes hydrometallurgical processes are being more widely used to recover base metals from ores and concentrates. Generally these processes involve liquid-solid separation of metal-bearing liquors from barren residues. This may be done by countercurrent decantation, thickening and filtration, or filtration or centrifuging only. Choice of method is governed by chemical and physical characteristics of the pulps; cost of labor, power, materials, and waste disposal; and even by the amount of capital available when building plans are under way. Since all these controlling factors change with time and location and with technological advances, the separation method must be re-evaluated when new plants or expansion programs are contemplated. At the Sherritt Gordon refinery in Fort Saskatchewan, Alberta, an ammonia pressure leaching process recovers nickel, copper, and cobalt from the nickel concentrate produced at Lynn Lake, Manitoba.' Pregnant liquors are separated from the barren leach residues in a thickener-filter liquid-solids circuit. The decision to use this type of separation was based on a summation of economic factors during the pilot plant and design stages. Although countercurrent decantation was not incorporated in the refinery flowsheet, the problems solved in thickening the leach residues and the experience gained in operating the commercial plant are pertinent to countercurrent decantation, particularly where it is applied to slow-settling leach slurries or slurries having a relatively high vapor pressure of a valuable, obnoxious, or poisonous vapor. The nickel sulfide concentrate is leached under pressure with air and ammonia to dissolve the nickel, copper, and cobalt and most of the sulfur, leaving a residue of iron and siliceous material to be discarded.2,3 During a subsequent distillation stage to recirculate part of the ammonia used for leaching, copper is recovered from the solution as a high-grade sulfide. After further purification to remove traces of copper and undesirable sulfur compounds, the nickel is precipitated by hydrogen under pressure at an elevated temperature. The cobalt, together with unreduced nickel, is precipitated as a mixed metal sulfide by hydrogen sulfide for eventual cobalt recovery. The end solution is then evaporated to produce a crystalline ammonium sulfate byproduct. As shown in Fig. 1, the nickel concentrate is leached in a continuous, two-stage, countercurrent circuit. In the first stage, or adjustment leach, the fresh concentrate is partially leached (60 pct) in the liquor produced in the second stage, or final leach. This system is necessary to produce a solution suitable for treatment in the copper sulfide precipitation step. Both stages are carried out at 170" to 180°F under a total pressure, with air, of 100 to 120 psig in large, horizontal, water-cooled autoclaves. The autoclaves are divided by overflow weirs into four compartments to give a certain amount of staging during leaching. In each compartment a relatively slow-speed (100 to 150 rpm) agitator maintains the nickel concentrate in suspension. Adjustment leaching, carried out in two autoclaves in parallel, is followed by a thickener-filter liquid-solids separation. Final leaching is done in two parallel trains of three autoclaves using aqueous ammonia to extract metal values from the adjustment leach residues. This too is followed by a thickener-filter circuit. Here the residues are repulped once with aqueous ammonia and twice with process water and refiltered after each repulping stage, to insure a maximum recovery of soluble metal, before being discarded to the tailings pond. The adjustment leach is followed by a seven-disk Dorr-Oliver American filter, with an agitator in the filter boot to keep the residues in suspension. Agitators have also been installed beneath the four ten-disk filters following the final leach thickener. Slurry Characteristics: A typical analysis of the Lynn Lake nickel concentrate, produced by differential flotation,' is given in Table I. The concentrate comprises 35 to 49 pct pentlandite, (Fe, Ni)S; 3 to 6 pct chalcopyrite, CuFeS,; 1 to 4 pct pyrite, FeS2; and 24 to 42 pct pyrrhotite, Fe1-2S (where x varies between 0 and 0.2) together with various siliceous minerals such as actinolite, hornblende, and talc. During leaching, the sulfur in the pentlandite, chalcopyrite, and part of the pyrrhotite is successively oxidized through the thiosulfate and poly-thionate radicals to sulfate and sulfamate." Simultaneously the nickel, copper, and cobalt are converted to soluble ammine complexes and the iron in the pentlandite, chalcopyrite, and part of the pyrrhotite is oxidized to a spongy hydrated iron oxide. The hydrated iron oxide is readily broken down by the agitation needed to sustain the concentrate in suspension and to maintain a satisfactory mass transfer of the oxygen from the air to the slurry. Table I shows typical chemical, screen, and

Jan 1, 1961

By Geoffrey Gilbert

A study of specimens shows that the key to both oxidation and enrichment at Duck-town is the behavior of pyrrhotite, which is in part dissolved and in part replaced by marcasite. Enrichment takes place chiefly at the expense of marcasite. THE material that forms the basis of this paper was collected in the spring of 1922, during a ten-day visit to Ducktown by the writer in the company of Prof. L. C. Graton. The time available for the work was far too short to allow anything like a thorough study of the deposits, and structural and stratigraphic questions, though they have an important bearing on the origin of the primary ores, were necessarily left untouched. Attention was focussed on the zone of oxidation and enrichment; and by devoting most of our time to the upper levels, open pits, and old workings, and examining the deeper levels only thoroughly enough to obtain a fair idea of the nature of the primary sulfide ore, we were able to make a reasonably complete survey of the various orebodies. With this field work for a background, the writer later made a study, in the Harvard laboratories, of the specimens obtained during the visit. As some of the facts brought to light by this study appear to be new, it seems worth while to set forth the outstanding features and a proposed explanation of them. Much of the Ducktown material that is obviously of greatest significance, as regards oxidation and enrichment, is soft and crumbly. Notwithstanding the desirability of gaining from such material all possible information as to its mineral composition and textural relationships, but little has heretofore been learned regarding it; but, by suitable preparation of this material in connection with the present study, it has been possible to examine it under the microscope without any disturbance of its texture and about as satisfactorily as if it were hard, fresh ore. The information thus gained has contributed measurably to the results set forth in this paper.

Jan 3, 1924

Charles H. Morgan, Worcester, Mass. (communication to the Secretary): In connection with Mr. Douglas's mention of the continuous charcoal kiln used at Kopparberg, some further data concerning this important invention may be of interest. Before giving these, however, I will say a word or two concerning other features of Swedish practice. In 1894 I spent two days at Soderfers with Mr. Tom Bergendal, the manager of the works, and was specially interested in the gas-producers and wood-drying kiln, illustrated in the paper contributed to our Transactions by Mr. Odelstjerna in that year.* The wood-drying kiln is, however, quite different in design and construction from Ljungberg's charcoal kiln. In the summer of 1894 it was discovered that by placing the gas-producer as close as possible to the open-hearth furnace, and working the producer hot, ordinary weather-dried wood, still containing a considerable percentage of moisture, could be used to advantage in the melting-furnace. Hence, the dryingkiln was needed for wet wood only. One of the iron-works of the Udeholm Go. was the first to adopt the Lundin saw-dust gas-producer and condenser, enabling them to make gas from saw-dust containing 45 per cent. of moisture, and convey the gas from the condenser through wooden pipes to the Siemens steel-melting furnace.† This sawdust gas gave very satisfactory results in iron-works; but the proprietors experienced much trouble by reason of the pollution of rivers by the tar-water from the condenser. On my visit, in 1894,I found that the Udeholm Co. had put in for their steel-melting furnaces the same wood-gas producers

Jan 1, 1899

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.'-' This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,' by the copper-decoration technique,' by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18'19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965

By N. Parlee, V. C. Kashyap

The solubilities of nitrogen in liquid iron and liquid Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys were measured by the Sieverts method. Measurements were made at 1600° to 1800°C on binary alloys up to 20 pet Ni, 10 pet V, 10 pet Mo; and on ternary alloys containing 0 to 3 pet V with 0 to 5 pet Mo. The results on liquid iron confirm that Sieverts' law is obeyed in the range 50 to 750 mm pressure. The measured solubilities and their temperature coefficients are in general agreement with other modern authors. The logarithms of the activity coefficients of nitrogen in the binaries are approximately linear functions of the pet of alloying element. A method suggested by Wagner, Chipman, and others for predicting gas solubilities in complex alloys from solubility data on binaries was applied to the Fe-Mo-V alloys. Reasonably good agreement was obtained between calculated and experimental solubilities. NITROGEN'S solubility in liquid iron has been studied by a number of investigators. It is reasonably well established that the solubility of nitrogen follows Sieverts' law at least up to 1 atm partial pressure and that the solubility increases gradually with temperature. The solubility of nitrogen in Fe-X binary liquid systems has been investigated in only a few cases. Only the systems Fe-Cr,3-5, 7 Fe-V,3 Fe-Mn,3, 5 Fe-Ni,3, 5 Fe-Si,B, H Fe-C, L, H and Fe-P4 appear to have received any study. The only work on liquid Fe-V was done by Brick and Creevy.3 This was limited to 13.5 pet and 26.5 pet V, but no exact temperatures were recorded. No work whatsoever appears to have been done on liquid Fe-Mo alloys and even work on Fe-Ni alloys is rather scant. The work on liquid ternary systems is still more limited, and the only publication available appears to be that of Wentrup and Reif,7 who studied the Fe-Cr-Mn and Fe-Cr-Ni alloys. Rassbach, Saunders, and Harbrecht17 have reported work on the solubility of nitrogen in stainless steel but this was not a systematic study of any particular system. Commercial alloys usually contain several alloying elements. Thus, it often becomes important to be able to predict the nitrogen solubility in systems containing two or more added elements without the necessity of making measurements. Wagner,14 Chipman," Darken and Gurry," and Morris and Buehl 14 have suggested means by which this may be accomplished, and Langenberg14 has recently applied one of these methods to nitrogen solubility in complex liquid alloys. This paper reports the results of nitrogen solubility determinations on Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys and compares calculated and experimental solubilities in the ternary alloy. Attempted measurements on Fe-Cr alloys were not successful by the experimental method employed. Experimental Method The general method of solubility measurement was that of Sieverts.' The apparatus and procedure were essentially the same as used by Liang, Bever, and Floe."' The equipment consisted of a small vacuum furnace heated by a 6 kw induction unit, gas measuring apparatus, and a gas purification train. The crucibles used were Norton Alundum with alumina sand around them for insulation. The crucibles were charged with 100 to 200 g of material, about 180 g or nearly filling the crucible being found most satisfactory. Hot volumes were determined with argon and ranged from 95 to 130 cu cm (stp). Temperature measurements were made with a Leeds and Northrup optical pyrometer which was calibrated periodically against the melting point of iron in the same apparatus."-'* Good quality nitrogen, hydrogen, and argon gases were further purified and dried in standard purification trains. The sources of the high purity iron and other alloying elements used were as follows:

Jan 1, 1959

The objective of the mission was basically to study the utilization of engineers and engineering technicians and their interrelationship in the Soviet Union. Beginning with their graduation from the engineering institutes and technicums, we hoped to learn how the graduates started out in industry, what their training on the job was, what sort of work they did, and how they worked themselves up within their profession. However, it turned out that, as our host was the Ministry of Higher and Secondary Education, most of our visits were to educational establishments. Our itinerary covered Moscow, Leningrad, Kharkov, Rostov, Baku, and Tashkent, with a side trip to Samarkand. In all, we visited 13 technical institutes, three technicums, and five industrial plants or enterprises, as they are called there. Our trip was one of only four weeks. Our observations were limited by the few cities and enterprises we were permitted to visit. Nevertheless, we did come back with some definite impressions and conclusions which we feel should be of interest to engineers, educators, and those concerned with the relative economic and technical power of the USSR and the U.S.

Jan 9, 1960

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958