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By A. M. Hall

Sulphur, even in small amounts, may often be harmful to nickel and high-nickel alloys, causing impairment of mechanical strength and destruction of malleability and ductility, as shown by Merica and Waltenberg.l,2 It may act either in the form of nonmetallic inclusions produced in the liquid state during furnacing or as reaction products resulting from its diffusion into the solid metal. In recognizing the action of this element, ability to identify its various forms by means of the microscope is often of considerable importance, especially when direct quantitative methods are inapplicable. Of the sulphur compounds associated with nickel and high-nickel alloys, the sulphides that may be found in malleable nickel, Monelt and Inconel are an important group. These sulphides were investi- gated by metallographic methods in order to provide descriptive data by which to identify them. The nominal compositions of malleable nickel, Monel and Inconel are given in Table I. The term "sulphide" is employed here in a very general sense, to designate a substance in which sulphur and one or more metallic elements are combined. The term includes any combinations of compounds and solid solutions. Method of Investigation Three groups of small laboratory melts were made, one group to represent each of the three types of alloy under investigation. Within each group, a number of ingots with a sufficient variety of chemical analyses were prepared so that the effect of each of the elements entering the complete commercial alloy could be isolated and observed. In most cases, to facilitate metallographic study by exaggerating the number and size of the resulting sulphides, somewhat greater amounts of the minor elements were added than are present in the commercial alloys. Likewise, considerably more sulphur was added than is normal, but not enough to complicate the system. Transverse sections were cut at a point one third of the distance from the butt to the head of each ingot, polished and examined with an inverted stage metallo-graph equipped with a combination polar -izing-analyzing vertical illuminator. The light source was a tungsten-mercury vapor arc lamp.

Jan 1, 1943

By John A. Putnam, Morrough P. O’Brien

DATA on the physical and thermodynamic properties of hydrocarbons have been made available in recent years but the formal method of applying these data to flow in porous media appears not to have been fully developed. By making usual thermodynamic assumptions and employing existing data on permeability to two-phase flow, Darcy's law may be applied to obtain the flow characteristics for representative combinations of flowing medium and geometry. The numerical examples presented herein are based on hydrocarbons for which complete physical and thermodynamic data are available under equilibrium conditions. INTRODUCTION Thermodynamic data are obtained in the laboratory under equilibrium conditions and their application requires the assumption that equilibrium also exists during flow. This assumption is at least usual in engineering analyses, though not easily justified in many instances, and will be followed here. In regard to hydrocarbons, laboratory experience in determining the pressure-volume-temperature relationships indicates that gas-liquid mixtures must often be stirred vigorously for periods of 15 to 20 min. before reaching equilibrium. On the other hand, boiling and condensation are known to occur on solid surfaces and the large surface exposed to the flowing substance by a porous medium may bring about rapid approach to equilibrium. For the purpose of providing at least a guide to experimentation and a standard for later comparison with experimental results, it will be assumed that the phases present in cross sections perpendicular to the direction of flow are in thermodynamic equilibrium. Another assumption usually made in the solution of problems of flow in porous media is that the fluid remains at a constant temperature; i.e., isothermal flow. This assumption is arrived at by considering the porous medium and surroundings to be an infinite heat source and the rate of heat flow to be infinite at a boiling front. Its validity depends in large measure upon the character of flow, the number of components, and the physical and thermodynamic properties of the fluid. However, the assumption of isothermal flow represents a limiting case. The other limit can be represented by the assumption that the fluid is thermally isolated; i.e., irreversible adiabatic. The thermodynamic process characterizing the actual flow of a given fluid system probably lies somewhere between these two limiting cases and might be thought of as a flow system in which the confining walls are maintained at a constant temperature. For isothermal flow the solid material of the porous media is considered as the infinite heat source capable, without loss in temperature, of giving up heat to the fluid as the latter tends to cool by expansion. For the thermally isolated system, the solid material is considered to give up no heat to the fluid. In the intermediate case the impervious walls confining the porous media are at constant temperature from which heat is transferred along various paths, solid and fluid, throughout the porous media. It would appear that an actual petroleum-

Jan 1, 1941

By H. Q. Golder

With the development of open-pit mines of ever increasing depth, the stability of the pit slopes in soil and rock is of growing economic importance. How is it, considering the newness of the problem that we know anything at all about the stability of man-made slopes? How much do we know and how did it all begin? We can make a reasonable estimate of the stability of a slope in soil, but we know as yet woefully little about slopes in rock because the problem is much more complex. It is only with the development of the capacity of the computer to handle wearisome calculations that any but the simplest of stability problems in rock have become possible of solution. But what we do know is a guide of immense value in the design of slopes in rock. But remember that the computer is a great elevator; it takes everyone's feet off the ground! So our study began with soils and what is now known as "Soil Mechanics", which is a translation of the German term "Bodenmechanik". It is a pity that the title of Terzaghi's book "Erdbaumechanik" was not used instead. But here the task of the translator is difficult because English lacks the facility of German to string together several words and make a new one whose meaning is unequivocal. Thus, we have the three German words 'Erde' 'Bau' and 'Mechanik'. 'Erde' means "earth" in almost all the English senses including "soil". 'Bau' and 'bauen' convey the meaning of building and construction, and 'Mechanik' means "mechanics" which includes statics and dynamics and the 'mechanics of materials', etc. So that a correct translation of the German is a phrase like "the mechanics of construction with, in or on, earth or soil." However we are stuck with 'Soil Mechanics' and that is where it all began. Now this study or subject did not begin with 'Terzaghi' although his contribution to the subject is unquestionably greater than that of any other single person. Every scientific discipline has its 'classical problem' and that of soil mechanics is 'the earth pressure problem' and it began in the 17th century. In fact, it probably began before this with the introduction of gunpowder to Western Europe in about the 15th century, but the first known reference to the problem was by Vauban, a distinguished French military engineer who lived from 1633 to 1707 and who gave rules for the dimensions of retaining walls from 6 to 80 ft. in height. The soil properties were not mentioned by Vauban probably because the rules were intended to be applied to fortifications only, but Poncelet (1840) claimed that Vauban's rules were based on a theory, and not simply on military and practical

Jan 1, 1972

By Frederick N. Rhines

BECAUSE of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding 'their occurrence, even though the fundamental mechanisms involved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpret the next. It is the purpose of the present paper to present, by means of examples drawn from practice, a brief survey, of the ways in which gas-metal diffusion serves and obstructs the purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with but brief mention of parallel cases. THE NATURE OF GAS-METAL DIFFUSION The term "gas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to- regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. No element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By E. J. Pasierb, H. W. Paxton

Mavkers ill a diffusion couple in the iron-chromium system move towards the high chromium side indicating Dcr > DFe at the marker composition. By a combituztion of measurements of D& and D a: a function of composition, this is also shown independently. DFe is calculated as a function of composition. and shown to be in reasonable agreement with measured values by other workers. MEASUREMENTS of marker movements in diffusion couples have been used from time to time to demonstrate that a vacancy or interstitial mechanism may be operative. Since there is a possibility that ring diffusion1 may be operative in chromium, the present experiments are of interest in showing some non-ring mechanism in iron-chromium alloys around the equiatomic composition. EXPERIMENTAL PROCEDURE The movement of markers originally at the interface between 1-in. sq sections of pure Cr (6 mm thick) and outer slabs of 30 Cr-70 Fe alloy was followed as a function of time at temperatures from 1150" to 1425"C, in a Kanthal-wound furnace. Temperature control was +5°C over extended periods. The analyses of these alloys are given in Table I. Selection of suitable markers presented a considerable experimental problem; the eventual solution was to draw quartz rod down to 0.01 cm and seat this in V-grooves 0.01 cm deep on each side of the chromium prior to welding. A preliminary experiment in which the groove was machined in the alloy gave identical results. Welding was accomplished by passing a heavy current through specimens under moderate pressure in a helium atmosphere. This method produced good welds with a planar interface as shown by subsequent metallo-graphic investigation. Any markers which did not adequately fill their groove and showed subsequent contamination from the atmosphere during heat treatment were not considered reliable. The composite sample was ground and metal-lographically polished on the four sides perpendicular to the interface. Fiducial marks (deep milled slots) were made outside the diffusion zone to check on total volume change. All necessary measurements were made on a metallograph reading to +0.0005 cm. The samples were wrapped in tantalum foil and given diffusion anneals for times to 200 hr in carefully purified dry hydrogen in a sealed McDanel porcelain tube. Chromium-zirconium chips were introduced near the specimen as an additional getter. The specimens were cooled relatively slowly after the diffusion anneal to preserve the McDanel tube but no significant error in effective time at temperature was thereby introduced. At least 1 mm was ground off the surface before measurements were taken. It was observed that the grain size following short diffusion anneals was several mm and was appreciably larger in the 30 Cr alloy than in the pure Cr. No significant grain boundary penetration was present as indicated by the etch limit. The results are presented in the next section. Measurements of D were made by standard sectioning techniques with chemical analysis. Machining difficulties limited the

Jan 1, 1961

By P. B. Queneau, J. E. Litz, T. P. McNulty

I. INTRODUCTION Modern hydrometallurgy has its roots in such notable successes as heap leaching for recovery of copper, cyanidation of gold ores, the Bayer process, the Oxland process for tungsten, electrorefining of copper, roast/ leach/electrowin process for zinc, and production of yellowcake from lowgrade uranium ores. Metallurgical testing techniques, sampling and analytical procedures, operating and maintenance practices, and improved methods and materials of construction which were pioneered in these processes have promoted the extension of hydrometallurgy into other applications. Periodically, new tools such as solvent extraction, resin ion exchange, and flocculants have opened new avenues to hydrometallurgists. Conversely, pursuit of more complex mineralization, the rising costs of energy and environmental quality preservation, and declining ore grades continue to create new challenges. For much of this century, it can be fairly said that practically any hydrometallurgical development moved the frontier of technology. The 1970's and 1980fs, however, have seen a significant maturing of hydrometallurgy's role in process metallurgy. Simplistically, this maturing seems to derive from a growing awareness of the strengths and weaknesses of hydrometallurgy and a determined effort to capitalize on the strengths. For example, many of us were among those revolutionaries of the 1960's and 1970's who taught that "chemical smelting" was the answer to the treatment of all sulfides. We now recognize, however, that only in very special cases can hydrometallurgy offer economic advantage over the generally less energy-intensive pyrometallurgical systems. The maturing of hydrometallurgy does not, however, signal stagnation. Important innovations are being studied and developed in most extractive areas, and a number are approaching or have achieved commercialization. From our company's perspective, that of an organization dealing with the development of the most economic solutions to metallurgical problems, innovation must be defined as the commercially successful reduction of an idea to practice. There appears to be no shortage of ideas, nor has there ever been a shortage. Many ideas now being implemented were conceived decades ago, but reduction to practice was foiled by the lack of such technology as responsive process control and economical materials of construction capable of withstanding highly corrosive or erosive environments. Commercialization of a new process is a particularly challenging undertaking. Even if technical risks are reduced to a minimum through careful and thoughtful process development, there are inevitable uncertainties in feed characteristics, variable costs, and product prices. Commercialization takes courage, both on the part of innovators who may be staking their careers or reputations and of investors who may face financial disaster in the event of project failure. This paper discusses innovative programs and recently commercialized processes which either have been discussed in the literature or disclosed to Hazen Research staff in private nonconfidential conversations with contacts in industry. Regarding this latter category of information, relative ease of communication has resulted in many of our observations being of North American origin.

Jan 1, 1985

By Lassi Klemettinen, Ari Jokilaakso, Dmitry Sukhomlinov, Pekka Taskinen

The solubilities and distributions of molybdenum and iridium in iron silicate slag and copper-iron mattes were studied using an equilibration-quenching technique and subsequent direct phase composition analyses by EPMA (Electron Probe X-ray Microanalysis) and LA-ICP-MS (Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry). The equilibrations were carried out on a wide matte grade interval, ranging from 55 wt-% Cu to 75 wt-% Cu, in pSO2 = 0.1 atm at 1300°C. The results in equilibrium with a solid iridium-molybdenum alloy indicated an iridium solubility of 150–500 ppmw in the sulphide matte, depending on the matte grade, and a molybdenum solubility of 100–600 ppmw. Iridium was distributing predominantly in the sulphide matte with the distribution coefficient of 10+3 - +4 but molybdenum deported predominantly in the slag with Lm/s(Mo) = 0.02–0.1. The effects of alumina and lime additions in the smelting slag were also examined. INTRODUCTION Iridium is a highly siderophile element (HSE), which means that it is incompatible with the sulphide forming elements and possesses a small solubility in mattes, such as copper- and nickel-iron sulphide melts. Molybdenum behaves only modestly in that way (Walker & Li, 2008; Righter et al., 2017). They both are known to be trace elements accompanying copper and nickel sulphide ores. No solubility data, however, are available for them in copper-rich sulphide mattes. Geochemical data on the behaviour of Ir and Mo deal mostly with low-iron silicate systems, e.g. basaltic melts, and high-sulphur sulphide solutions and mattes (Ertel et al., 2008; Fonseca et al., 2007). They also indicate that Ir and Mo dissolve in silicate melts primarily as oxides and not as electrically neutral metal species. Most geological data of iridium focus on high-sulphur systems of the monosulphide composition and typically Fe-Ni mattes where copper is a trace element (Fleet et al., 1996; Sattari et al., 2002). Direct solubility measurements for mattes and iron-lean silicates have also been made using pure Ir or an Ir alloy as the saturation phase (Borisov & Palme, 2000; O’Neill & Eggins, 2002; Makovicky & Karup-Møller, 1999; Ertel et al., 2008; Mungall & Brenan, 2014). A recent summary about the solubilities of HSE’s in iron- and sulphur free silicates is available in Laurenz (2012). The thermodynamics of molybdenum partitioning between oxides and Fe-S-O melts was studied by Mengason et al. (2011). Their results indicate strong accumulation in the iron-rich sulphide in reducing conditions (pO2 = 10-9.6 atm in Ni-NiO equilibrium at 1050°C). Molybdenum dissolves in iron-lean silicate melts as MoO3 species in oxygen pressures above the Fe-FeO equilibrium and as MoO2 in more reducing conditions (Farges et al., 2006; Righter et al., 2017).

Jan 1, 2019

By C. Stansfield Hitchen

THE introduction of the logarithmic sector method of quantitative spectrography by Scheibe and Neuhäusser in 1928, and the subsequent .modification and improvement of the method by Twyman and Simeon, would seem to have marked yet a further advance in quantitative spec-trum analysis and its industrial application, inasmuch as it offers a simple means of eliminating some of the uncertainties inherent in the older methods based upon mere visual comparison of line intensities. In their recent admirable review of the position and capabilities of industrial spectroscopy, Brownsdon and van Someren1 say: Ways and means of facilitating the comparison of line-intensities so as to give them numerical values are helpful, and of these a logarithmic sector rotating in front of the slit appears to he one of the most promising; . . . the success recently experienced by the author in using this method for the examination of steels and solutions of metallic salts prompted him ,to investigate its possible use in estimating the impurities commonly present in crude and refined tin. The results of this investigation are submitted in the present paper. Details of a number of spectrographic analyses of tin for various impurities have already been published. Thus, Schweitzer2 describes the spectrographic examination of tin for lead, bismuth and cadmium, and was able to distinguish between such atomic percentages as 0.01, 0.05, 0.10, 0.30, 0.60, 1.20, 3.00 and 10.00. Negresco3 investigated the bismuth content of tin over a range of from 0.0005 to 35 per cent. Meggers, Kiess and Stimson4 compare spectrographic and chemical analyses of tin metal for copper, lead, iron, zinc, silver, nickel and bismuth. They stress also the value of spectrum analysis in the examination of tin used for boiler plugs, where the requirements that only minute quantities of impurities shall be present render the chemical analysis both tedious and difficult.

Jan 1, 1933

By P. S. Rudman

The solubility limit and the diffusivity of carbon in molybdenum have been obtained by duffising carbon into molybdenum rods from a Mo + Mo2C powder mixture. The solubility limit was taken as the long-time asymptotic limit of the rod composition. The diffusiv-ity was obtained from fractionally saturated rods from the rate of change of the average composition. Compositions were determined by chemical analysis. The solubility limit obtained is: WhILE the Mo-C system is important in refractory alloy technology neither the solubility limit nor the diffusivity of carbon in molybdenum is unambiguously known. In Fig. 1 the Mo-C phase diagram is presented. The heavy lines, the terminal solution solubility limit, and the eutectic temperature are results of the present investigation and will be discussed in detail later. However, it is readily seen that the previously published solubility limit determinations, Few and Manning1 and Fromm and ROy2 differ by up to an order of magnitude. The general form of Fig. 1, the Mo2C field, and a eu- tectic temperature -2200°C are due to an early Investigation by Sykes et a1.3 Although they did not determine the solubility limit, they did establish that the maximum at the eutectic temperature was about 1000 ppm. The only other prior data found on the solubility limit is from a lattice-parameter study by Speiser et a1 .,4 from which it can be concluded that the maximum solubility is greater than 1800 ppm. There does not appear to be any data oh the diffusivity of carbon in molybdenum. However, Samsonov and Epik5 have determined, from the rate of growth of an MozC layer, the diffusivity of carbon in Mo2C, and this has been erroneously interpreted, for example by ~c~eil,' as applicable to diffusion of carbon in molybdenum.

Jan 1, 1968

By M. J. McPherson

Having worked on the thermodynamics of air/liquid-water mixtures passing through the surface fans of deep mines, I find this paper of great interest and congratulate the authors on producing it. There are two matters, however, deserving discussion. First, the authors have described the classical theory of fog formation with fogging occurring at "supersaturation." In fact, the process of fog formation begins well below 100% humidity. The more strongly hygroscopic nuclei in the atmosphere will attract water molecules and begin to grow at a relative humidity perhaps as low as 70%. The process is a dynamic one with both condensation and evaporation taking place throughout the mixture on microscopic liquid surfaces. As saturation is approached, the rate of condensation accelerates rapidly producing the familiar reduction in visibility. Hygroscopic nuclei are present in all natural atmospheres and under the appropriate conditions of pressure and temperature, will produce clean fogs. However, if the air is polluted by particulates from combustion or other processes then the resultant coagulation with growing liquid particles may produce dense (and sometimes photochemical) smogs. It is this process that is likely to occur in underground mines when moist air is cooled below dew point. Second, the authors have summarized very well the individual measures that might alleviate the problem. In particular, I agree that neither heating nor refrigerating the air, by themselves, provides a satisfactory solution. However, there is a combination of these that provides a neat and effective control of fog formation. This involves a small, self-contained refrigeration unit within a duct but without the usual external heat rejection facility. The air is cooled below dew point and, hence, dehumidified on passing over the cold evaporator coils. The heat from the condenser is rejected back into the air down-stream from the water eliminator, as shown in [Fig. 1]. The duct configuration can be designed to create good mixing at the outlet.

Jan 1, 1984

By Will H. Coghill

In this investigation, the low-grade red iron ores of Alabama were examined by the use of "heavy solutions."' Ores are generally ground preparatory to concentration and as long as the concentrators make suitable products the effectiveness of the grinding is likely to be unquestioned; but when suitable products are difficult to make, an investigation becomes imperative. In such a case a dissection of the ore might be made to find the cause of the trouble. Such a condition of unsuitable products exists in the low-grade red iron ores of Alabama. They are difficult to concentrate. To be sure it might be said that the concentration of iron ores is a new thing and that the ore-dressing methods are undeveloped, but a glance at the industry reveals an abundance of methods and devices for almost all imlaginable conditions. Concentrating machinery has not been tested in this investigation. When the properties of the ores have been gleaned, the machinery may be used more effectively. Alabama Low-grade Red Iron Ores The Bureau of Mines has undertaken by laboratory methods to select the best means of concentrating the low-grade iron ores of Alabama. These ores constitute the parts of the ore bed left by selective mining. If more of the ore bed could be included in the current output, the mining cost would be reduced and longer life of the district would be insured. This advantage would be reflected by added permanence of churches, homes, schools and every undertaking in the commonwealth. The red ores chosen for this study of effectiveness of grinding are too low in lime to meet the requirements of the blast furnace. If lime is

Jan 1, 1927

By Olga K. Karakasi, Angeliki Moutsatsou, Ioanna Kavallari

"The present study focuses on the amelioration of the behaviour of high calcium fly ash (HCFA), investigating its application in a new environmental field: oil spill clean up. High calcium fly ash is a by-product of electric power plants, produced annually in large quantities, whose greater amount is landfilled. Some of its properties, such as its chemical and mineralogical composition, its fine particle size, its porosity, floating ability and hydrophobic character make it an attractive material for this purpose. Researches showed that when added to an oil spill, it forms a semi-solid phase, which allows the quite total removal of the oil, but it is not stably retained on the surface. In order to ameliorate its floating ability, the decrease in its specific gravity by mixing with a lighter material is investigated. In the present study the mixing with two materials, already used in oil spill clean up, sawdust and a polymer, has been examined. Addition of 15-25% w/w sawdust to HCFA results in a material with better performance than HCFA or sawdust alone: it has a satisfactory floating ability and allows total removal of oil. Addition of the polymer, however, has resulted in no significant amelioration of the oil sorption behaviour of HCFA, probably because no affinity between HCFA and polymer has been achieved.IntroductionCoal fly ash is a by-product of coal combustion in electric power plants, produced worldwide in huge quantities, approximately 500 million tones annually. High calcium fly ash (HCFA) is classified to class C presenting a (Al2O3 + SiO2 + Fe2O3) > 50%. The production of lignite fly ash in Greece comes up to 13 million tones annually, of which only 12% is used in construction applications, the other being landfilled [5, 6].Besides its limited application worldwide as a construction material, research is focusing on the development of new environmental applications, such as waste stabilisation and solidification, soil and water environmental improvement [9, 12]. For the application of fly ash in further environmental fields several chemical modifications have been applied, in order to improve its properties. Extensive research has been focused on the conversion of both coal and lignite fly ash to zeolite and its further application in environmental field, such as the uptake of inorganic (heavy metals and ammonium [8, 11]) or even organic compounds (methylene blue [15]) from waste water streams, or the use as molecular sieves, to adsorb water molecules, SO2 and NH3 from gas streams, due to the high cation exchange capacity and porosity of the produced zeolithic material. Furthermore, lignite fly ash has been combined with sodium silicate solution, prepared by treatment of rice husk ash, and tetrapropylammonium bromide, to synthesise hydrophobic zeolite ZSM-5 [4]."

Jan 1, 2008

By W. D. Robertson, D. A. Koss, A. J. Goldman

THE significance of the hcp (E) structure, which appears when Fe-Cr-Ni alloys (stainless steels) are transformed martensitically, has been the subject of considerable study and speculation.'-7 It has been proposed that the hcp structure is an intermediate phase in the transformation: fcc (austenite) — hcp (E) -bcc (0, martensite). However, recent studies by transmission electron microscopy6,7 have indicated that the hcp structure may be a consequence of the large shear strain (10 deg) associated with the fcc to bcc transformation. That is, the transformation to a bcc structure is accompanied by extensive dissociation of dislocations in the parent austenite, which has a low stacking-fault energy.'-'' X-ray diffraction analysis of the transformed alloy reveals a pattern of lines corresponding to an hcp structure, together with the parent austenite and the bcc product. The fact that the hcp structure is observed only in association with the bcc product in these alloys1'4'6'7 lends support to the conclusion that the hcp structure is a secondary product of the transformation. But, the evidence is circumstantial and more definite resolution of the two possibilities mains to be obtained. If the hcp structure is an intermediate product of the transformation, as in 1) above, then two distinct Ms temperatures should be observed, Ms and To evaluate this possibility, three different techniques that are particularly sensitive to the structural changes accompanying such transformations have been used in an attempt to detect two transformation temperatures in an Fe-15.1 Cr-11.7 Ni alloy: 1) high-sensitivity differential thermal analysis, 2) the temperature dependence of resonant frequency (elastic moduli), and 3) internal friction of cylindrical specimens vibrating in either longitudinal or torsional modes. To obtain the necessary sensitivity, a differential thermal analysis technique was developed for the purpose, Fig. 1. The differential temperature between a nickel standard and the specimen was amplified to produce a sensitivity of 0.02OC (0.7 v) in temperature difference. The specimen and the standard were surrounded by a copper block and the entire assembly was immersed in a solution of methyl and ethyl alcohol, freezing point, - 140OC, which provided the necessary thermal stability to reduce temperature fluctuations to negligible proportions. A cooling rate of about 1.5OC per min was obtained by bubbling liquid nitrogen through the liquid bath. In order to calibrate the experiment with respect to the evolution of heat in the transformation from fcc to hcp structures, differential cooling curves were obtained for an Fe-19.8 Mn alloy, which transforms martensitically to E.'"-' a Ms(e) temperature of 145°C was clearly defined by a temperature

Jan 1, 1964

By R. S. Archer

In the microscopic examination of aircraft-engine parts made of heat-treated alloy steels, the writer has been forcibly impressed by the failure of the usual etching processes to disclose any but gross defects in heat treatment. It seemed particularly desirable to bring out the grain size of the steel, which is indicated in the ordinary etching processes chiefly by the change in orientation of structure from grain to grain. After various attempts, a fairly successful method has been found, which is here presented in the hope that it may be of use to those who have occasion to examine these steels in the hcat-treated condition. The specimens worked with have been mostly chrome-nickel steels heat treated (that is, hardened and tempered) to a Brinell hardness of around 300. A few experiments with other specimens will be referred to later. Briefly, the method employed consists in etching the steel about 10 min. in a fresh solution of picric acid in ethyl alcohol, and then rubbing off the smudge of carbonaceous matter on moist broadcloth. Different samples of almost identical analysis, heat treatment, and physical properties (including resistance to impact) respond quite differently to this treatment. In some, the grain boundaries are developed quite readily, while in others, especially in those whose grain is unusually fine or in which the final hardening heat has not quite obliterated the previous crystallization, the results are more obscure. The exact time of etching to secure the best results also differs for various samples, and the greatest success is usually attained by a process of "tinkering." Such a process is illustrated in a series of micrographs, the first six of which were taken at a magnification of 300 diameters. The properties of the steel are as follows: Carbon, per cent............... 0.42 Brinell hardness.............. 293 Nickel, per cent................ 1.35 Yield point, pounds per square Chromium, per cent............. 0.90 inch........................ 131,000 Copper, per cent................ 0.025 Maximum strength, pounds per Manganese, per cent............ 0.74 square inch................. 144,500 Phosphorus, per cent............ 0.024 Elongation in 1 in., per cent... 28 Sulfur, per cent................ 0.036 Lod impact, foot-pounds...... 51 Reduction of area, per cent...... 57.3

Jan 1, 1920

By William S. Hannan, H. Rush Spedden

Flotation may be defined as a process whereby mineral particles are concentrated by selective adhesion to air-liquid interfaces. The process involves attachment of desired mineral particles to air bubbles, and removal of the mineralized air bubbles from the surface of the pulp as a mineral concentrate. Problem Although great strides have been made in understanding the principles of flotation, one part of the process which has not been adequately explained is the mechanism by which selected mineral particles become attached to air bubbles. A glance at the froth of an operating flotation cell demonstrates adequately that use of proper reagents and conditions mill result in such attachments; but how such attachment takes place is not definitely known. A better knowledge of this factor might lead to improved flotation practice either through altered machine design or the application of scientific innovations. Direct observation of the behavior of mineral particles and bubbles in an operating cell does not appear promising because of the complexity of the system. For this reason, conclusions concerning the problem must be deduced from theoretical considerations or from observation of simplified systems designed to reproduce conditions thought to exist in an operating cell. Present Theories Two mechanisms have been recognized as fundamental in particle-bubble attachment: gas precipitation and direct encounter. It is a simple matter to demonstrate in the laboratory that attachment can be brought about by either mechanism. As to the relative importance of the two in a particular flotation system, however, there is a divergence of views. Taggart1 states, Under exceptional circumstances sufficient force and time to effect attachment may conjoin in an ore pulp undergoing agitation, and a preformed bubble adhere to a collector-coated mineral particle, but the occurrence is rare. . . . Pulp-body froth flotation effects selection in the body of a conditioned pulp by causing gas bubbles to precipitate from solution in the liquid phase preferentially at the surfaces of collector-coated particles, and to cling to these particles, Gaudin2 states that, within the pulp body of an agitation machine, attachment of mineral particles to air bubbles occurs as a consequence of contact between the two. This theory has been supported by theoretical reasoning and much circumstantial evidence. Perhaps the most interesting bit of evidence in favor Of this theory js the difficulty in the flotation of fines. If attach-

Jan 1, 1949

By M. J. Dry, G. B. Harris

"This paper presents basic chemistry and operating conditions for the hydrolysis of ferric chloride into solid hematite and gaseous hydrogen chloride, and shows how this unit operation can be applied in chloride hydrometallurgy to regenerate strong hydrochloric acid and reject iron without also rejecting valuable metals such as nickel, copper and cobalt. Two examples are used to illustrate the hydrolysis technology and compare it to existing technology. The first is the regeneration of spent steel pickling acid, comparing hydrolysis to conventional pyrohydrolysis. The second example is the processing of a hypothetical low grade nickel laterite, comparing the novel chloride hydrolysis route to conventional sulphate HPAL technology.INTRODUCTION Whilst, in many respects, the control and removal of dissolved iron from chloride leach solutions can resemble the manner in which it is done in sulphate systems, chloride chemistry additionally offers the ability to achieve the same objectives in different ways (Harris, 2014). Conventionally, iron is oxidised to its ferric state (if necessary) and then precipitated with a base, usually magnesia where the feed is a laterite and lime where it is a sulphide, since calcium will precipitate sulphate formed during leaching. One method for controlling iron is to form FeOOH, either ß-FeOOH (akaganéite), a-FeOOH (goethite), or a mixture thereof (Fillipou and Choi, 2002). However, if akaganéite is formed, the precipitate will contain a significant chloride component (as high as 7% Cl), leading to chloride losses and difficulty in satisfactorily disposing of the residue. Washing chloride from akaganéite is almost impossible due to the propensity of the solids to undergo peptization. The conventional approach requires the addition of a base, but it is based to some extent on controlled supersaturation precipitation (Demopoulos, 2009), which produces a more uniform and crystalline material and is far more attractive than, for example, the turboaeration process proposed by Great Central Mines in their chloride copper process (Raudsepp & Beattie, 1986)."

Jan 1, 2016

By R. V. Riley

IN the metallographic examination of the alloys of iron and silicon, several investigators1-' have reported on the occurrence of an unusual type of etched structure, particularly in the alloys of higher silicon content. This, the so-called "barley shell" structure, has been observed with iron-silicon alloys over a wide range of silicon content, and under certain circumstances it can be seen upon the micro-sections of pure iron. The barley shell structure may be demonstrated most easily with iron-silicon alloys in the range 8 to 20 pct Si after etching in a hydrofluoric acid base etchant. Two etchants which produce the structure are: Corson's reagent, which is 2 parts hydrofluoric acid, 1 part nitric acid, and 2 parts glycerol; and picric acid reagent, which is 1 part hydrofluoric acid and 1 part saturated solution of picric acid in alcohol. Both when freshly prepared and used for etching commercial silicon-iron alloys containing 14 to 16 pct Si, invariably produce the barley shell structure shown in Fig. la. It is now well known that the barley shell structure is a pseudomorph and the true structure of an alloy of this composition consists of a single phase of silico-ferrite together with graphite as shown in Fig. lb. Lower silicon alloys and even pure electrolytic iron may also be etched in the above reagents to give the barley shell provided the etchant has been either: 1—Stored in contact with glass or silica, or 2—used previously for etching an iron containing silicon. Pure iron etched in perfectly pure hydrofluoric acid base etchants free from silicon contamination gives a normal structure free from the barley shells. Therefore, although the hydrofluoric acid in the reagent primarily is responsible for the barley shells, silicon, or its compounds, also must be present, either in the etching reagent or in the specimen. It was of considerable interest to the author to read the paper by Wachtell,? in which the barley shell etch was deliberately used for the identification of the boundaries of high and low silicon areas in diffusion experiments made upon laminate bars of compacted and sintered pure iron and ferrosili-con powders. This method of utilizing the barley shell etch is novel and in the hands of the investigator gave a useful differentiation between the high and low silicon areas in those specimens. For the reasons already given, however, the technique is not to be regarded as of universal application. Misleading results might be obtained, for example, if two or more specimens were etched in the same etchant. Fresh pure reagents only must be used each time. Provided this is done and the investigators are well aware of the limitations of the method, then the barley shell pseudomorph can be made of limited use in distinguishing between higher and lower silicon areas in a microspecimen of a ferrous material. The greatest of care must be exercised in the interpretation of the results which may be regarded as qualitative only and may, in fact, not be specific to silicon alloys.

Jan 1, 1952

By G. L. Oldright, T. B. Brighton, C. M. Dice

The base bullion from the lead blast furnace contains varying amounts of the impurities left in the smelter feed by the concentrator, regardless of the method of smelter operation. These impurities may be held in part in mechanical suspension rather than being present as true alloys. However, usually there is little free space in the crucible in which to separate these drosses before the bullion is taken from the lead well. When such a dross is melted in a laboratory crucible and allowed to cool, the products obtained are lead bullion, speiss, and matte in well separated layers. Typical analyses of layers are: Analyses. Per Cent Element Bullion Speiss Matte Pb.............................................. 92.0 41.2 38.3 Cu.............................................. 2.4 36.3 40.6 As............................................... 4.0 16.5 4.3 Sb............................................... 0.7 0.2 0.4 S................................................ 0.6 1.9 13.1 Fe............................................... 0.0 0.0 0.0 Totals......................................... 99.7 96.1 96.7 The absence of iron in these products drossed from the blast-furnace bullion proves that the impurities for the greater part are not simply finely divided blast-furnace speiss or matte that has been dissolved or dispersed in the lead, but are held in solution by the liquid metal and rise to its surface as infusible compounds when the temperature of the bath is lowered. In general, the drosses made locally are metal sulphides and arsenides and not oxidized compounds. The large content of metallic lead also does not seem to be retained because of oxidized compounds

Jan 1, 1937

By William A. Johnson, Robert F. Mehl

It is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process of freezing is a simple example of this, as Tammann pointed out years ago.1 Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain12-8 that the formation of pearlite from the eutectoid decomposition of the solid solution austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Karnop and Sachs, and others9-11 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decomposition by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect—the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.12 Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939

By William A. Johnson, Robert F. Mehl

It is now recognized that several important types of reactions in metallic systems proceed by the formation of nuclei and the growth of these nuclei. The process of freezing is a simple example of this, as Tammann pointed out years ago.1 Tammann held that the rate of freezing is determined by a rate of nucleation, expressed as the number of nuclei formed per unit volume of unfrozen liquid per second, and a rate of growth of these nuclei, expressed as the linear rate of radial growth in units of length per second. For isothermal freezing the conception is simple; for ordinary freezing, extending over a range of temperature, it is not as simple, for the values of the two constants must change with change in temperature. There is ample evidence that the postulated mechanism is correct even though a quantitative derivation of the rate of isothermal or of ordinary freezing in terms of the two constants has been lacking. In recent years other reactions have been found to proceed in a similar fashion. It has been well established, particularly by Bain12-8 that the formation of pearlite from the eutectoid decomposition of the solid solution austenite proceeds in such a way, and Polanyi and Schmid, Tammann and Crone, Karnop and Sachs, and others9-11 have shown that the process of recrystallization proceeds in a similar way. Isothermal reaction rates have been determined for eutectoid decomposition by a number of investigators. Bain's2-8 work on the formation of pearlite from austenite is especially valuable in this respect—the type of isothermal reaction curve obtained, as illustrated in Fig. 13, showed an initial slow rate, accelerating to an intermediate maximum rate which then decelerated to the completion of the reaction; similar curves have been obtained by Wever and his collaborators.12 Other eutectoid decompositions show similar behavior: for example, the decomposition of the beta eutectoid in the copper-aluminum system, studied by Smith

Jan 1, 1939