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By W. L. Fink, M. S. Hunter, R. H. Brown

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.' The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when

Jan 1, 1941

By M. S. Hunter, W. L. Fink, R. H. Brown

Early workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.' The method was subject to such limitations (e.g., the difficulty in attaining electrochemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilibrium electrode potentials in molten salts.2"4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the determination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metallurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temperature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and introduces considerable difficulty, especially at the higher temperatures. Apparently, no consideration has been given heretofore to the metallurgical use of irreversible electrode potentials that exist when a specimen is immersed in a suitable aqueous solution at room temperature. The apparatus and the method required for such measurements are very simple, and if the results of such measurements could be demonstrated to be reproducible they might be very valuable in studying the structure of alloys. The method would not have the scope of that developed by Seltz and his co-workers because no thermodynamic quantities could be calculated from the data. However, the utility and the simplicity of the method might warrant extensive use for the determination of phase fields and similar applications. Theory of Irreversible Potentials A brief review of the theory of irreversible potentials will be given before showing how to interpret the potential readings in terms of alloy structure. It is known that heterogeneity of a metal surface in an electrolyte will produce points of different potentials, with the result that current flows between these points and electrochemical reactions occur. The points at which oxidation reactions are localized are known as anodes, and those at which reduction reactions are localized are known as cathodes.6, 7, 8 For the benefit of those who are not familiar with the terms anode and cathode as applied to a primary cell, the potential difference between anode and cathode of such a cell can be measured when

Jan 1, 1941

By D. Moradkhani, S. M. Javad Koleini, M. Abdollahy, F. Soltani

"The objective of the study was to determine the type and distribution of rare earth elements (REEs) in the phosphate flotation concentrate from the Esfordi flotation plant in central Iran, in order to understand their leaching behaviour. Samples of the concentrate were prepared and analysed using XRF, XRD, ICP, and EMPA. The Ce, Nd, La, and Y contents were 5608, 2227, 1959, and 679.7 mg/kg, respectively. The main REEbearing minerals in the concentrate are fluorapatite, monazite, and xenotime. Apatite is the chief mineral of the concentrate and the ratio of apatite to monazite is greater than 60. From EMPA analysis, monazite contains a much higher proportion of REEs than apatite, but more than 50% of the REE content of the concentrate is in apatite, as this is the main mineral constituent of the concentrate. During the leaching of REEs in the phosphoric acid production process, more than 99% of the total rare earth values report to the large amounts of phosphogypsum (CaSO4·2H2O) formed during the dissolution reaction. Accordingly, two process options are suggested for treating the Esfordi concentrate. In the first option, the concentrate is treated with 98% H2SO4 at 200–300°C. After digestion and water leaching, phosphorus and REEs are precipitated out of solution. In the second option, the concentrate is treated in a pre-leach stage. The process residue from the pre-leach stage is then subjected to acid digestion at elevated temperature for phosphoric acid production.IntroductionThe rare earth elements (REEs) comprise a set of 17 chemical elements in the periodic table, specifically the 15 lanthanides plus scandium and yttrium. REEs and alloys that contain them are used in devices such as computer memory, rechargeable batteries, cell phones, catalytic converters, magnets, fluorescent lighting, and many more (Krishnamurthy and Gupta, 2004). China supplies about 94% of the REE demand, with the remaining 6% coming from Russia and Estonia, the USA, India, Malaysia, and Brazil (Zhanheng, 2011). Increased industrial development in China has prompted the Chinese government to limit annual export quotas to approximately 35 kt of rare earth oxides (REOs), while non-Chinese annual demand is expected to reach 80 kt by the year 2015. This constriction of supply is being met by the development of many new rare earth mining projects, each of which has its own unique mining and processing challenges (Jordens, Cheng, and Waters, 2013). One of these projects is the Esfordi phosphate project, which is located in Yazd Province in central Iran. The concentrate from the Esfordi flotation plant contains 1.2–1.5% REEs."

Jan 1, 2017

By Phillip B. Bucky, Fred D. Wright

The present known petroleum reserves are limited, and unless important new fields are discovered the Nation will be dependent, in the not too distant future, upon imports or upon synthetic liquid fuels to supplement domestic petroleum supplies. As a national defense measure, it would appear desirable to develop a substitute source of liquid fuels within the borders of the country if new discoveries of petroleum should Prove disappointing. Congress undoubtedly had this in mind when it passed the Synthetic Liquid Fuels Act (78th Congress, approved April 5, 1944). The act directed the Bureau of Mines to construct and operate demonstration plants for producing synthetic liquid fuels from coal and oil shale, and from forestry and agricultural products. As a part of this program, the Bureau of Mines has built a demonstration plant at Anvil Points, near Rifle, Colo., for retorting the oil shale, and has developed a mine to supply the plant with oil shale. At the beginning of mining operations, the physical qualities of the oil shale, which would have a bearing upon the selection of mining methods and practices for exploiting the deposits, were largely unknown. A comprehensive mining-research program has been set up to determine the best methods and practices to follow to obtain the lowest overall practicable mining cost for producing the oil shale on a large scale. Unusually low mining costs will be necessary for shale oil to be produced commercially. Consideration now is being given to exploiting a series of flat-lying beds 70 ft thick by a room-and-pillar method of three benches with the advance heading at the top. This report is one of a series giving the results obtained in research on mining problems, The structure and physical qualities of the oil shale indicate that the 70-ft interval of the oil-shale measure can be safely mined in open stopes; studies indicate that this method would be the most economical one to use.' As labor will be a major item of expense, the largest equipment that could be operated efficiently in the workings would be required to obtain the lowest practicable mining Cost. It Was therefore desirable to know the maximum safe span of unsupported rooms and the size of pillars necessary to support the overburden. This paper describes the work done at the Columbia School of Mines Barodynamic Laboratory in determining the maximum safe unsupported roof spans and the minimum safe pillar dimensions for the oil-shale mine at Rifle, Colo.

Jan 1, 1949

By M. S. Moats

"The effects of commercial copper electrorefining additives (glue and thiourea) on the electrochemical removal of bismuth are of importance in copper production. It was found that Bi(III) electrodeposition occurs readily from acidic sulfate solution via a diffusion-controlled quasi-reversible reduction. The diffusion coefficient of Bi(III) was measured and found to be less than reported values of copper in similar solutions. The presence of thiourea and/or glue was found to accelerate or de-polarize Bi(III) reduction on stainless steel as compared to the inhibition or polarization of Cu(II) reduction. The additives also inhibited the dissolution of the Bi-Cu co-deposit during cyclic voltammetry. During short term deposition studies, the additives increased the concentration of Bi in co-deposited Cu-Bi products from solutions with low concentrations of Cu (<2 g/L). Bi deposition was significantly suppressed by increasing the Cu(II) concentration in the solution. The formation of a copper layer on the stainless steel electrode appeared to significantly suppress the reduction of Bi(III). This study demonstrates that glue and thiourea depolarize the deposition of bismuth on stainless steel. Therefore, the additives could be used to improve Bi impurity removal during third stage liberation.INTRODUCTIONThe production of high purity copper has been steadily increasing due to the wide application of the metal and its alloys in electrical and electronic products, infrastructure construction, industrial machinery and equipment, general products and transportation (Moskalyk et al., 2003). Most high purity copper is manufactured from copper sulfide mineral concentrates and/or scrap via a pyrometallurgical process followed by electrorefining (Navarro et al., 1999). During the electrorefining process, cast anodes of 99-99.5% purity are electrochemically dissolved into an acidified copper sulfate solution while high purity copper (>99.99%) is plated on stainless steel blanks or copper starter sheets (Davenport et al., 2002). The control of cathode deposit growth (purity and morphology) while maintaining a high current efficiency is of significant importance for copper refining (Ilkhchi et al., 2007). At typically applied current densities for industrial copper electrorefining, mass and charge transfer play important roles in the quality of cathodic products (Hiskey et al., 1998). If the real current density at some surface points is substantially higher owing to uneven current distribution, then rough spots can and will grow faster leading to nodules (Suarez et al., 1992). Nodulated deposits tend to capture solution and anode impurities (slimes) resulting in unacceptable cathode quality (Afifi et al., 1987). Furthermore, these nodules can grow until they eventually contact the anode leading to short circuits and current efficiency reduction (Ilkhchi et al. 2007)."

Jan 1, 2016

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By W. F. McKechnie

"Southern Africa is generally thought to be well explored, with only limited potential for major new diamond discoveries. However, Chiadzwa in Zimbabwe and reports of a significant new kimberlite find in Angola are testimony to the dangers attached to an attitude that ‘there is nothing left to find’.Since the major discoveries in the central interior of South Africa in the 1870s, diamond exploration in the region has been led by market and political factors that influence the key exploration drivers of opportunity and value proposition. Unexpected new discoveries by new players always impact on existing producers and, from time to time, denial of opportunity through political or protectionist policies has inhibited investment in exploration.Entrepreneurial exploration appetite in southern Africa will be tempered by the potential value equation and security of investment. Overlaid on this, developments in diamond recovery technologies provide opportunity to reinvigorate current mines and old prospects previously considered too difficult or costly to exploit. Position on the cost curve will remain a key factor for survival in an increasingly competitive environment. IntroductionThe diamond industry in southern Africa boasts a history of 150 years of discovery and mining, forming the cornerstone of development of the core, modern economies at the southern tip of Africa.Since the discovery, in the 1860s and 1870s, of the secondary diamond placers and primary diamond-bearing kimberlite deposits in the central interior of the then Cape Colony and Orange Free State, southern Africa has endured as the pre-eminent diamondproducing region in the world. Notwithstanding periodic competition from significant new discoveries in other parts of the globe and the paucity of recent, new discoveries in the region, its ranking is unlikely to change in the short to medium term.In a geological context the region contains the Kaapvaal-Zimbabwe and Angola-Kasai cratons, identified in terms of Clifford’s rule as areas inherently prospective for diamonds, being underlain by portions of the Earth’s crust that are tectonically stable and older than 1.5 billion years (Clifford, 1992). Although the Democratic Republic of Congo (DRC) would, in a geographic context, be considered to be part of Central Africa, for the purposes of this review it is included in southern Africa since northeast Angola and the adjacent parts of the DRC form part of the same geological terrane and diamond production from both countries needs to be considered together. Historical and current diamond production from the northeastern parts of the DRC around Kisangani is not considered to be significant and its inclusion in the overall numbers for the DRC does not materially affect the overall picture presented here."

Feb 1, 2019

By D. Malhotra, K. Purdy, G. Ramadorai

INTRODUCTION Today, flotation is clearly the dominant mineral concentration method. Since it is a relatively selective process, it is used for almost all sulfide minerals. A recent U. S. Bureau of Mines study indicated that approximately 225 million metric tons of sulfide ore was processed in 67 plants in the United States in 1980 (USBM Staff, 1981). There were over 100 plants processing copper ores in the world (Bassarear, 1985). Sulfide ores containing lead, zinc, copper, molybdenum, precious metals, cobalt, nickel, and iron are generally separated and concentrated by flotation. This chapter briefly reviews the plant practice related to the recovery of the above-mentioned sulfide minerals with emphasis on chemical reagents used for the production of marketable-grade products. PROCESSING OF SULFIDE ORES It is beyond the scope of this chapter to review the milling data for operating plants which have been extensively covered in literature (Tveter and McQuiston, 1962; Rausch and Mariacher, 1970; Weiss, 1985; Crozier, 1979). However, the following generalizations can be made regarding the processing of sulfide ores: 1. The primary grind is targeted to produce as coarse a product as necessary to provide an economic degree of liberation. 2. The concentration process, generally flotation, is designed to produce a concentrate consisting predominantly of valuable minerals and a middling fraction which may require further grinding to produce an optimum release of minerals. 3. The chemical reagent suite (collectors, frothers, etc.) for the separation of sulfide minerals from gangue minerals is generally complex. Total reagents used in the flotation process can be as high as six to eight, as is the case for lead and molybdenite separation from complex sulfide ores. 4. Chemical reagents are generally expensive because of the high selectivity for sulfide minerals. The process flowsheet is dependent on several factors, including ore grade and mineralogical composition. Generic process flowsheets for processing different sulfide ores have been developed for discussion in this chapter. However, there appears to be a consistent relationship between the reagent combination choice and the mineralogical composition of the ore (Tveter and McQuiston, 1962). These are covered in detail in the following sections. LEAD AND ZINC Galena (PbS) and sphalerite (ZnS), which commonly occur together, are the only minerals of lead and zinc, respectively, in most primary deposits. Feed ore grades are typically 1 to 5 percent Pb and 1 to 10 percent Zn. Very often economic quantities of copper and precious metals, silver and gold, also occur with these base metals.

Jan 1, 1986

By John V. Beall

The Mining Engineering Handbook is written primarily for persons interested in the economic extraction of minerals. Not everyone referring to this book will be knowledgeable about mining and, therefore, this section is intended to explain to interested persons the scope of mining as well as fulfilling the title of "Mining&apos;s Place and Contribution" among the industries of society. 1.1-MINERALS, ROCKS AND ORE In the year 1971, the number of known elements amounted to 104. Fifteen of these have been made only in the laboratory, others may have persisted from the primitive atmosphere, but, by and large, elements originated from magmas or igneous rocks of the outer rocky shell of the earth. Only eight elements constitute 98% by weight of the earth&apos;s crust. These are oxygen, 47%; silicon. 28%; aluminum, 8%; iron, 5%; and sodium, magnesium, potassium and calcium, less than 4% each. These common elements and the other less common ones are the building blocks of minerals, of which there are over 2,000 varieties. According to Webster: "A mineral is an inorganic substance occul.ring natura!ly in the earth and having a consistent and distinctive set of physical properties and a composition that can be expressed by a chemical formula. The term is sometimes applied to organic substances, such as coal." Thus, minerals are precise combinations of elements. Rocks, as distinct from minerals, are composed of assemblages of minerals. When minerals are found in sufficient concentration to warrant extraction by mining, the mineralized area is considered an ore deposit. The definition of ore is mineral that can be extracted from the ground at a profit. The economic connotation is implicit in the word ore. Since most of the useful elements compose such a small percentage of the earth&apos;s crust, the occurrence of ore deposits as we know them would not have transpired had not geologic processes concentrated the elements (see Sec. 4). 1.2-DEFINITIONS OF MINING TERMS Extensive coverage of the many descriptive terms used in mining may be found in a good mining glossary, such as is available from the Superintendent of Documents (see Sec. 35), but for convenience a number of the more common definitions are given here. Mining may be defined, as by A. B. Cummins, as the act, process or work of extracting minerals or coal from their natural environment and transporting them to the point of processing or use. Mining techniques are applied to extracting metallic minerals, such as ores of gold, copper, lead or zinc; to fuels, such as coal, anthracite, lignite and tar sands; and to nonmetallic minerals, such as lime-

Jan 1, 1973

By Scott Turner

The settlers of a new country necessarily suffer at first from the lack of accumulated stocks of metals - in-use that are possessed in older countries . Our American colonists were at first compelled to import their metals in manufactured forms , and it must have proved difficult to produce an exportable surplus of commodities with which to pay for them . These circumstances stimulated a search for domestic ore deposits . Various discoveries resulted , so that as early as 1628 , we find the colonists importing two craftsmen from England to establish iron -works in Massachusetts to beneficiate local ores . In 1648 , an iron -works at Lynn was producing metal at an annual rate of 400 tons . Later on , the colonial iron industries became of importance , some metal being actually exported to England . The people of this country thus early became convinced of the necessity for domestic mineral production . It is now little realized how persistent were their efforts to - make mineral discoveries , before the gold- rush to California ; the extraordinary success of our subsequent mineral explorations has overshadowed the earlier record . Precise and complete accounting of our mineral production , having the character of national bookkeeping , is available only for the series of years beginning with 1880 , when commences the official record that is provided by the Government publication called Mineral Resources of the United States . In the period of 52 years , from 1880 through 1932 , the value of mineral production of the United States amounted to more than 122 billion dollars . Only 12 billions of this total were produced in the 21 years , 1880-1900 , while nearly 110 billions were produced in the first 31 years of the present century . Of this 110 billions , over 53 billions were produced in the most recent decade , 1921- 1930 , the production of the previous decade , 1911-1920 , having been only 37 billions , though it included the war period ; that of the decade 1901-1910 was 16 billions . In 1931 , the total value of mineral products of the United States was $ 3,180,000,000 , compared with an average annual value of $ 5,556,000,000 during the previous five - year period , 1926-1930 . The decline in 1931 from that average was therefore 43 per cent . As to the three great groups of mineral commodities , metals fared worst , with a decline of 55 per cent in the value of their production , while the value of fuels declined 39 per cent , as did that of the nonmetals group .

Jan 1, 1933

By John S. Brown

As a part of a symposium on the relations of structure to ore deposition, in February 1938, the writer presented some tentative opinions derived from his experience with a number of important lead-zinc replacement deposits. These ideas were set forth, as a basis for discussion and a stimulus to further inquiry, in a mimeographed leaflet that read as follows: Intimate acquaintance with a number of lead and zinc deposits in metamorphosed limestones seems to indicate the existence of certain common features from which can be established some general principles governing the localization of ore in this type of formation. It is suspected that these principles can be applied, with modifications, to mineralization in unmetamorphosed limestone. In metamorphosed formations, some observed rules are as follows: 1. Bands or masses of pure limestone are very resistant to replacement by ore solutions, and are likely either to contain no ore or to resist replacement until near the end of mineralization. The reason for this apparently is physical, not chemical, since microscopic data indicate that when ore is deposited by far the greater part of it substitutes for carbonate. The chief factor is believed to be a lack of porosity in massive limestone that has undergone flowage and recrystallization. 2. Masses of intensely siliceous or silicated rock are likewise unfavorable ore receptacles. This seems to be accounted for by two factors: (a) chemical unsuit-ability or resistance to replacement, and (b) physical resistance to small-scale brecci-ation, which might faeilitate the opening of effective channelways for solutions. Some low-grade ore may occur, however, and also sporadic fracture fillings. 3. The optimum condition for ore reception appears to be found in bands or areas containing carbonate and silicates (or quartz) intimately mingled in something like equal proportions. In this situation movement is likely to result in mixed flowage and fracture, producing a finc-textured porosity that admits solutions freely and provides access to an abundance of replaceable carbonate. Cleavage cracks in some minerals such as diopside are believed to facilitate the penetration of solutions. 4. Certain minerals or assemblages are regarded as favorable impurities in a limestone and others as unfavorable. Original quartz, and subsequently developed diopside, and perhaps garnet, are typical favorable pre-ore gangue; in general rather equidimensional, brittle minerals. Tremolite, biotite, and probably wollastonite, are typical unfavorable pre-ore gangue; in general highly elongated and somewhat flexible minerals likely to develop under strong shearing stresses. 5. Tentative opinion is that the ratio of lime and magnesia in a limestone is of little or no importance.

Jan 1, 1941

By M. Cohen, S. A. Kulin

AT a recent symposium on thermodynamics in physical metallurgy1 two opposing theories of the austenite-martensite transformation were presented. Both theories agreed that this type of reaction involves a nucleation process which requires activation and that the activated nuclei develop into the well-known martensite plates with tremendous speed. However, there were essential differences in the two points of view concerning the nature of the nucleus and the mechanism by which the nucleus propagates. According to Cohen, Machlin, and Paranjpe,&apos; the nucleus is a strain center with sufficient elastic energy to initiate a cooperative displacement among the atoms of the parent phase when a sufficiently low temperature is reached. This displacement propagates as a wave in shear-like fashion to transform the austenite into martensite without benefit of diffusion. On the other hand, Fisher, Hollomon, and Turnbull3 regard the nucleus as a solute-poor region (in the austenite) of a size which becomes supercritical relative to coherent growth into martensite when an appropriately low temperature is reached. This growth process is taken to be an atom-by- atom transfer from the receding austenite lattice to the advancing martensite lattice through the coherent interface that exists between the two phases. The present paper is not conceded with the divergent views as to the nature of the nucleus but describes some critical experiments which differentiate between the two proposed mechanisms of propagation. Fisher&apos; has summarized the latter issue in the following way: According to the cooperative displacement theory, the speed of formation of mar-tensite plates should not be decreased by lowering the temperature, and martensite should form with extreme rapidity at very low temperatures; whereas with the alternate growth process, the speed of the martensite transformation should be retarded at very low temperatures, decreasing to zero at the absolute zero. The atom-by-atom growth mechanism predicts a marked slowing down of the reaction rate with decreasing temperature because the rate of self-diffusion in the austenite is involved in this picture. For example, Fisher, Hollomon and Turn-bull5 estimate that the activation energy for this growth process in steel is (0.34)2(0.36)* times the activation energy for self-diffusion in y-iron. The two most recent determinations of the latter quantity are 67,900" and 74,2007 cal/mol, which may be averaged as 71,000 cal/mol. This, in turn, gives a value of 3000 cal/mol for the activation energy of the atom-by-atom process, and hence the rate of growth should vary as e 8,000/RT where R is the gas constant

Jan 1, 1951

By John S. Brown

As a part of a symposium on the relations of structure to ore deposition, in February 1938, the writer presented some tentative opinions derived from his experience with a number of important lead-zinc replacement deposits. These ideas were set forth, as a basis for discussion and a stimulus to further inquiry, in a mimeographed leaflet that read as follows: Intimate acquaintance with a number of lead and zinc deposits in metamorphosed limestones seems to indicate the existence of certain common features from which can be established some general principles governing the localization of ore in this type of formation. It is suspected that these principles can be applied, with modifications, to mineralization in unmetamorphosed limestone. In metamorphosed formations, some observed rules are as follows: 1. Bands or masses of pure limestone are very resistant to replacement by ore solutions, and are likely either to contain no ore or to resist replacement until near the end of mineralization. The reason for this apparently is physical, not chemical, since microscopic data indicate that when ore is deposited by far the greater part of it substitutes for carbonate. The chief factor is believed to be a lack of porosity in massive limestone that has undergone flowage and recrystallization. 2. Masses of intensely siliceous or silicated rock are likewise unfavorable ore receptacles. This seems to be accounted for by two factors: (a) chemical unsuit-ability or resistance to replacement, and (b) physical resistance to small-scale brecci-ation, which might faeilitate the opening of effective channelways for solutions. Some low-grade ore may occur, however, and also sporadic fracture fillings. 3. The optimum condition for ore reception appears to be found in bands or areas containing carbonate and silicates (or quartz) intimately mingled in something like equal proportions. In this situation movement is likely to result in mixed flowage and fracture, producing a finc-textured porosity that admits solutions freely and provides access to an abundance of replaceable carbonate. Cleavage cracks in some minerals such as diopside are believed to facilitate the penetration of solutions. 4. Certain minerals or assemblages are regarded as favorable impurities in a limestone and others as unfavorable. Original quartz, and subsequently developed diopside, and perhaps garnet, are typical favorable pre-ore gangue; in general rather equidimensional, brittle minerals. Tremolite, biotite, and probably wollastonite, are typical unfavorable pre-ore gangue; in general highly elongated and somewhat flexible minerals likely to develop under strong shearing stresses. 5. Tentative opinion is that the ratio of lime and magnesia in a limestone is of little or no importance.

Jan 1, 1941

By John L. Lamont, Walter Crafts

ADEQUATE hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test1 and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann&apos;s principle2 for calculating hardenability from chemical composition; and Field&apos;s conversion3 from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollenback,5 Burns, Moore, and Archer,6 and Burns and Riegel.7 The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependent only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1945

By W. E. Rice

The ceramic industry has to do with forming or molding articles of clay, and imparting to them their characteristic properties of permanence, strength and color by subjecting them to heat treatment in kilns. This heat treatment is commonly known as "firing" or "burning." The art of firing clay ware antedates the industrial use of coal; hence wood was the fuel first used, and the earliest kilns were built to burn wood. The majority of the clay ware produced today is fired in periodic kilns that are essentially enlarged structures similar to the earliest enclosed kilns; a kiln consists of a large chamber 16 to 32 ft. dia. (or rectangular) in which the ware is charged and fired either in direct contact with flame or hot gases from the fuel, or in saggers which shield the ware from direct contact with the gases. The fuel is burned in a number of small furnaces built in the thick wall that encloses the chamber; these furnaces are from 16 to 36 in. wide and from 3 to 5 ft. long; some of them have horizontal or sloping grates, but many have no grates; the last are called "dead-bottom" furnaces. The temperature necessary to mature the charge in the kiln varies for different clays; for some it is as low as 1800°, and for others as high as 2700" F. Wood was an ideal fuel for the low temperatures that were used in early kilns; it burns freely and produces a long, clean flame, which promotes uniform distribution of the heat in the kiln; it does not coke and so restrict the passage of air through the fuel bed; the ash does not melt in the fuel bed to form clinker; and the ash that is carried into the chamber and deposited on the charge does not contain iron and sulfur to discolor the clay. The extent of the ceramic industry now precludes the general use of wood in kilns, so that today this industry is one of the large users of bituminous coal, burning more than eight million tons annually in kilns. Manufacturing plants usually are at or near the source of clay, with deposits of coal suitable for kilns occurring near the clay. The cost of coal is the largest single item of expense in the manufacture of clay ware, and, because all coals are not equally suitable for the process, the careful selection of coal is important. In this selection the desidera-

Jan 1, 1932

By M. Bhattacharya, A. Dutta, P. Barat

"Pinning of dislocations at nanosized obstacles like precipitates, voids and bubbles, is a crucial mechanism in the context of phenomena like hardening and creep. The interaction between such an obstacle and a dislocation is often explored at fundamental level by means of analytical tools, atomistic simulations and finite element methods. Nevertheless, such studies fail to predict the effect on the overall plasticity on account of insufficient information about the underlying statistics of this process comprising a large number of dislocations and obstacles in a system. Here we propose a new statistical approach, where the statistics of pinning at idealized spherical obstacles is explored by taking into account the generalized size distribution of the obstacle along with the dislocation density within a three-dimensional framework. The application of this approach has been demonstrated for dislocation pinning at nanovoids in neutron irradiated type 316-stainless steel.IntroductionPresence of nanoscale obstacles like precipitates, voids and bubbles play a crucial role in determining the deformation behavior of a crystalline solid on account of the interactions between the line defects and such localized obstacles. In the context of the glide motion of dislocations, the obstacles can offer resistance to a moving dislocation, thereby causing a hardening effect [l-3]. In some other cases, inclusions like voids and bubbles can affect the rate of dislocation climb through diffusive [4] and non-diffusive [5] mechanisms. Over the last few decades, numerous studies have been performed to gain an insight of the dislocation-obstacle interactions at a fundamental level. These include the interactions responsible for the hardening effect, in addition to those pertaining to the non-conservative motion of dislocations.Although the elementary mechanisms of the various dislocation-obstacle interactions have been vastly explored and understood by means of analytical theory and numerical simulations, it remains difficult to quantitatively understand their effects on the macroscopic deformation behavior. This is due to the fact that their influence on the gross plastic deformation of a bulk sample would be the collective outcome of a large ensemble of such interactions. As a result, it becomes infeasible to predict the bulk deformation behavior of a material until the statistics of pinning of the dislocations at the localized obstacles is available. In the context of precipitate hardening, some well known attempts to extract the pinning-statistics were made by Friedel-Fleischer [6] and Mott [7] by analytical means, which were later tested through simplified 2-dimensional in-silica modeling [8]."

Jan 1, 2014

By L. A. Cornish, J. W. van der Merwe

"The hydrofluoric acid (HF) industry in South Africa uses normalized mild steel (SA 516 Gr 70) for the storage and distribution of its technical-grade product (70% HF). The technical-grade acid is split from the anhydrous hydrogen fluoride (AHF) product during distillation just after HF is produced, in a stainless-steel-lined kiln, from the reaction of calcium fluoride (CaF2) with sulphuric acid (H2SO4). Uniform corrosion of the storage tanks is mitigated during commissioning by contacting the steel with 70% HF. A corrosive reaction takes place (2H+ + 2F- + Fe - H2 + FeF2) to form scale inside the tank which diminishes the attack of the steel by fresh HF, thus prolonging the service life expectancy of the vessels. This iron fluoride scale in the vessel grows continually, resulting in corrosion of the vessels continuing at a predictable rate (approx.0.5 mm/a) since the first commissioning of the tanks at Necsa in 1993. In early 2012, an increase in the average corrosion rate of the tanks to 3 mm/a measured at and below the liquid band in the storage vessels was noted. Three months later the corrosion rate had increased to 30 mm/a, just before the first leak from the tank was detected. The tanks were decommissioned shortly afterwards and an investigation revealed that the rapid corrosion was due to the presence of increased levels (>50 ppm) of nitric acid (HNO3) in the tanks, which attacked the fluoride layer protecting the steel.The oxidation characteristics of high concentrations of HNO3 with low concentrations of HF on stainless steel surface treatment are well documented. The effects of low levels of nitric acid on the corrosion of steels in sulphuric acid are also known, but no suitable published data currently exists on corrosion by high HF concentrations with low HNO3 concentrations. Establishing the rate and mechanism of corrosion by HNO3 (0.1 to 1%) in 70% HF is currently a high priority for the HF industry in South Africa and will become increasingly important in the near future due to depleting fluorite reserves and cheaper, but less efficient, processes producing H2SO4 with higher impurity levels, which were not anticipated in the original plant design. The aim of this study is to simulate the corrosion conditions in the plant on a laboratory scale in order to establish the corrosion characteristics of the steels used in the HF plant, which are increasingly exposed to the HNO3 impurities that tend to concentrate in the final technical-grade HF acid product."

Jan 1, 2016

By C. W. Phillips, R. S. Busk

With most cast metals the grain size may vary within wide limits, depending upon the conditions at the moment of freezing. These conditions are subject to control in magnesium-base alloys, by proper melting and superheating techniques, enabling production of quite uniform and fine-grained castings, almost independent of section thickness. However, such variations of grain size as do exist, in common with all metals, are reflected in corresponding changes in mechanical properties. It is the intent of this paper to present data giving the relationship between grain size and mechanical properties. Data are also included on the combined effects of grain size and micro-porosity. In addition, a short discussion of factors influencing the grain size of sand castings is included. Measurement OF Grain Size By grain size is meant the statistical distribution of volumes occupied by the individual crystallites in a metal section. Since this is almost always impossible of direct measurement, several methods of estimating and expressing the size have been evolved. Most exact methods make use of the microscope. This involves study of a single plane cut at random through the metal. What is seen in the microscopc are polygons, each the cross section of a grain. The diameters or areas of these polygons are then measured and the grain size is expressed as an average diameter, number of grains per unit area, average area per grain, or, rarely, average volume per grain. Rutherford, Abom, and Bain3 have discussed extensively the errors involved when using a plane section to estimate volume. They clearly point out that the tendency is to underestimate the true grain size because of the nature of the measurcment. The A.S.T.M. recommends that measurement be made by comparison with a standard chart, by means of Jeffries&apos; planimetric method4 or Heyn&apos;s intercept method. The Society recommends that the notation be in terms of the number of grains per unit area (as is the grain-size number used for steel) or as an average diameter, expressed in inches or millimeters (as for copper and brass). The method of measurement used for this study was comparison with a standard chart, which has been described by P. F. George.5 The chart was constructed by photographing at Ioo diameters a uniform specimen with an average grain diameter of 0.003 in. The average diameter of this specimen was determined by numerous measurements, using both the Jeffries and Heyn methods. The other grain sizes were then obtained by appropriate enlargemcnt of the master sample. Careful comparison of the chart method with other methods on identical samples indicates that though the differences be-

Jan 1, 1945

By J. Gordon Parr, D. H. Polonis

High purity alloys of titanium and iron, made by a technique of levitation melting, have been investigated with particular reference to martensite formation and decomposition in the hypoeutectoid range. A preliminary study has been made of the occurrence of the phase corresponding to the structure Ti2Fe. MANY of the previous investigations of Fe-Ti alloys have been made using Kroll sponge as a source of titanium; and the subsequent heat treatments to which alloys have been subjected has, on occasion, led to further contamination. Worrier,&apos;,&apos; who suggested a part of the equilibrium diagram for the binary system, and Wallbaum and coworkers,3-5 who worked largely with iron-rich alloys, all used Kroll sponge. Van Thyne, Kessler, and Hansen,6 in their determination of the equilibrium diagram, used iodide titanium for alloys up to 30 pct Fe. Duwez,7 who measured the M. temperature of titanium binary alloys with many solute elements, used iodide titanium in all cases except in his work on Ti-Fe alloys for which he used Kroll sponge. The investigation of the supposed phase Ti2Fe by Rostoker8 nvolved the use of iodide titanium. A section of the constitutional diagram, after Van Thyne et al., is reproduced in Fig. 1. Frequently too much stress is placed on the effect of contaminants in equilibrium and nonequilibrium systems, but there is no doubt that titanium alloys are extremely susceptible to interstitial atoms. Consequently, the main purpose of the work to be described was to determine those features of phase transformations in pure Ti-Fe alloys that were considered of importance in commercial heat treatments. For, although commercial alloys may not be of high purity, the investigation of a system uncomplicated by traces of impurity is a desirable starting point. Another incidental feature, the occurrence of Ti2Fe, was also investigated. The entire study was carried out using powders obtained from alloy ingots, for diffusion reactions are often more rapid in small particles than in bulk specimens. The frequently adopted practice of ascertaining phase constitutions by X-ray analysis of powders, and relating these to the microstructures and mechanical properties of bulk specimens, is considered by the authors to be open to criticism. In the martensite reactions in the Fe-Mn system, for example, it has been shown- hat similar phase distributions in solid and powder may result in different hardness values and appearance under the microscope; and it is possible that similar anomalies might occur in the Ti-Fe system. Consequently, in order to

Jan 1, 1955