Search Documents

By R. D. Pehke, J. F. Elliott

The solubility of nitrogen in liquid pure iron has been measured as a function of pressure and temperature. Sieverts' Law is obeyed at all pressures up to 1 atm and the temperature coefficient of solubility is 8 x 106 %/°C. The solubility of nitrogen in liquid iron alloys has been studied by the Sieverts' method and by the sampling method. The solubility is decreased by Al, C, Co Cu, Ni, 0. Si atzd Sn, and it is increased by Cr, Cb, Mn, Mo, Ta, W, and V. Interaction coefficients eN, for the effect of these elements on nitrogen dissolved in liquid iron, are reported. 1 HE effect of nitrogen upon the properties of steel may be desirable or not, depending upon the composition, processing treatment, and the use of the product. To understand the behavior of nitrogen in the various steelmaking processes, it is necessary to have reliable fundamental data pertaining to the solubilities, rates of solution, and chemical reactions of nitrogen in steel, particularly in the liquid state. In an effort to extend our knowledge in these areas, an investigation of the thermodynamics and kinetics of the solubility of nitrogen in liquid iron alloys was undertaken. The thermodynamic aspects of the study are presented in this paper. The solubility of nitrogen in liquid pure iron has received the attention of several investigators whose results are summarized in Table I. Reasonable agreement among the more recent researches1-l8 is found for the solubility of approximately 0.044 wt pct at 1600°C and 1-atm pressure of N,, for the temperature coefficient of solubility being small but positive, and for adherence to Sieverts' law for pressures up to 1 atm. The solubility of nitrogen in a number of binary liquid iron alloys has been studied: Fe-A1,3 Fe-As,16 Fe-C,3, 71 18, 19, 20 Fe-Cr ,5,7, 10, 11, 15 21 Fe-Co,'4, '6 Fe-Cu,'6 Fe-Mn,10, 11, 18 Fe-Mo,13, 16 Fe-Ni,10, 11, 13, 15, 16 Fe-O,16, 17, l9 Fe-p,7 Fe-S,l6 Fe-Sb,16 Fe-Se,lg Fe-Si,4) 97 '77 187 19>2° Fe-Sn,16 and Fe-v.51 '3 A few ternary systems have been studied, most of which were reviewed by ~angenberg" who applied the methods suggested by WagnerPz3 Chipman,24 Darken and G~rry, and Morris and Buehl26 for predicting solubilities in multicomponent alloys. Langenberg22 and Humbert and Elliott15 compared the solubilities computed from simple binary alloy systems with experimental measurements of nitrogen solubilities in liquid iron containing two or more alloying elements. The interaction coefficients for nitrogen in

Jan 1, 1961

By Michael Tenenbaum

Selected characteristics of nonmetallic phases were determined in low-carbon sheet steels which had been produced by various refining; deoxidizing, and casting procedures. The results showed little influence of the refining process on the quantity, distribution, size, and character of the nonmetallic phases. The quantity of inclusions was governed by the deoxidation procedures. While the mode of casting influenced the internal structure and the pattern of inclusion distribution, it had little effect on the quantity of nonmetallics. The vast majority of inclusions were under 30 µ in diam, and there was little change in size distribution during hot and cold rolling. The composition and structure of the inclusions were expained an the basis of known equilibrium phase diagrams for the appropriate systems. Additional work is needed to explain some of the observations of this paper. HENRY Marion Howe's contributions to the metallurgical profession include his many writings, the wisdom that he imparted to his students, and the inspiration that he gave to the many scholars, teachers, and industrialists who knew him personally. It was Professor Howe's intimate colleague, Albert Sauveur,1 who, in the first Howe Memorial Lecture, could have been speaking for the metallurgist of our generation as well as his own when he wrote, "...how many of us on the point of going astray were called back to the right path by Howe's guiding torch?" More than a quarter of a century later, Francis Foley,2 one of the last in the Howe Lecture series who worked directly with the great man, delivered the ultimate tribute, "...truth, in its time is so hard to identify." While Professor Howe strove to be right, "he was content if he provoked the reader to take the next step along the path to greater knowledge." Like so many of my predecessors, I sought guidance for this lecture by referring to Professor Howe's two classic texts, Metallurgy of steel,3 and Metallography of Steel and Cast Iron: the former book interpreting the facts as he saw them near the start of his career, and the latter—published 26 years later—pointing to many fertile fields for metallurgical investigation. Those of us who harvest the fruits of Henry Marion Howe's contributions to the metallurgical profession now look with wonder at the tremendous legacy he has provided. It is rewarding to study his writings and to recognize the anticipation of such aspects of modern ferrous metallurgy as: 1) Direct reduction 2) Steelmaking reactions 3) The approaches and benefits of degassing 4) Solidification mechanisms 5) Habits and behavior of nonmetallic inclusions 6) Recrystallization phenomena 7) Slip and slip propagation 8) Dislocations 9) Discontinuous deformation 10) Microscopic and macroscopic segregation

Jan 1, 1970

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By Harry C. Gatos, Frank J. Bachner, Mario D. Banus

The portion of the Nb-Sn phase diagram between 75 and 79 at. pct Nb at temperatures near the liquidus has been investigated by melting alloys of known composition and examining the microstmc-tzlres resulting when these melts were quenched. The Nb-Sn samples were contained in magnesia sleeves, and were mounted in a high-pressure apparatus. It was shown that Nb3Sn me1ts by a peri-tectic decomposition and that the composition of the compound Nb3Sn at the peritectic horizontal lies between 77 and 78 at. pct Nb. Analysis of the phases present in the samples was accomplished by anodic staining techniques and an electron-microbeam analyzer. DURING the past several years a great deal of work has been devoted to the Nb-Sn system, and the bulk of this work has been primarily concerned with the intermetallic phase Nb3Sn. However, the melting characteristics of Nb3Sn have not been investigated because of the difficulty in maintaining known compositions due to tin losses by vaporization, and the added difficulty of containing Nb-Sn alloys without sample-container reaction at the high temperatures involved. This paper reports on the development of a technique for containing Nb-Sn alloys under pressure high enough to prevent tin losses at temperatures in excess of the liquidus. Using this technique, melts of known composition were made and a phase diagram near the liquidus is proposed based on the microstructures resulting when these melts were quenched. EXPERIMENTAL The Nb-Sn alloys weighing 0.7 g each were prepared in the form of cylinders. Niobium powder, -200, +325 mesh, and tin shavings with a minute amount of tin powder for a binder were mixed in the desired proportions and cold-pressed at 50,000 psi in a 0.150-in. die. This cylinder was then enclosed as shown in Fig. 1, and the entire arrangement mounted in a 2.6-in. pyrophyllite tetrahedron.' The desired temperatures (-2500°C) presented several problems in high-pressure container materials. Boron nitride, the usual sample holder, was found to react with niobium to form the nitride. However, MgO cans and plugs machined from refractory rods did not melt nor react with the sample. Thick tantalum contact disks were used to carry the large currents (~450 amps) to the graphite heater, since tantalum did not melt and had enough strength to prevent extrusion of the sample. It was further observed that the graphite heater and tantalum disks could not be in direct contact with the pyrophyllite because it melts and decomposes at these temperatures to kyanite and coesite (SiO2),2 the former reacting with graphite and the latter with tantalum to form the silicide. The use of a MgO outer sleeve

Jan 1, 1965

By J. F Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By J. F. Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By R. I. Jaffee, H. P. Nielsen

In recent years much attention has been given to high melting alloy systems. It has been of interest in this respect to investigate the alloys of platinum and tungsten, which were known from the literature to have very high melting points up to about 50 pct tungsten, but about which little had been published on the high-tungsten side of the system. Powder metallurgical methods were used throughout this investigation for the preparation of the alloys, utilizing electrical sintering techniques such as are used for tungsten and molybdenum. In the course of the work it was found desirable to determine fusion temperatures of the alloys, and it was possible from these and other data to draw a tentative constitutional diagram (solidus, mostly) applicable to the high-temperature part of the system. No attempt was made to determine solid solubility vs. temperature data, nor to investigate the lower temperature transformations in the solid state. Data on the microstructure, hardness, and a note on oxidation resistance of the sintered alloys were obtained. Past Work Miillerl determined liquidus temperatures of platinum-rich alloys to 50 pct tungsten, using a radiation method employing a photoelectric cell, and found that the melting points increased progressively from I771 C for platinum to 2350°C for the 50 pct alloy. Microscopic evidence by Miiller that complete solid solutions exist to 50 pct tungsten was not checked by Kremer2 who, according to Vines and Wise,3 found that "although the 8 pct tungsten alloy was a solid solution, the 26 pct tungsten alloy contained a eutectic or an intermediate phase." Hultgren and Jaffee4 using X ray methods found continuous solid solutions to at least 33.6 pct tungsten (35 at. pct) after annealing in vacuum for 6 days at I000 C. Vines and WiseS report work communicated to them by E. C. Rhodes on wrought alloys to 7 pct tungsten, which showed that tungsten hardened platinum extremely rapidly, and was one of the most potent hardeners of the binary additions to platinum. Considerable quantities of 4 pct tungsten platinum wire have been produced for grids in radar tubes and for aircraft spark plugs. Some of the alloy for the latter application is made by sintering, the remainder by smelting and casting. Materials The platinum powder used in this work was kindly supplied by the Research and Development Laboratory of the Owens-Corning Fiberglas Corp., Newark, Ohio. It was prepared from scrap platinum. After dissolving in aqua regia and evaporating almost to dryness, the solution was worked up several times with concentrated HC1. The resultant platinic chloride was diluted considerably, and metallic zinc was added, which precipitated the platinum in a very finely divided form. After dissolving the

Jan 1, 1949

By G. R. Speich, L. Zwell, H. A. Wriedt

HORNBOGEN1 has recently shown that it is possible to measure the degree of segregation accompanying cellular precipitation in ferritic Fe-Zn alloys by measuring the lattice parameter of the ferrite phase within the cell. In extending this work to study a wider range of composition and to evaluate the free-energy change accompanying the growth of the cells, the lattice parameter and the boundary of the a! phase in Fe-Zn alloys were redetermined to check the earlier work of Schramm.2 This appeared to be necessary since the Fe-Zn diagram has been drastically revised since the work of Schramm. Stadelmaier and Bridgers3 have recently shown that, contrary to prior belief: the y iron field is closed and the a phase boundary extends to an a + T + L peritectic at 782°C where peritectic a contains 42 at, pet Zn. The phase T in equilibrium with the a solid solution has a composition near Fe3Zn10 and a cubic 081 type structure.' The alloys were prepared by two different methods. In the first method carbonyl iron powder (400 mesh, 99.8 pet pure) and high-purity zinc powder (200 mesh, 99.99 pet pure) were mixed in a ball mill and then pressed in a die at 40,000 psi pressure to make compacts with a diameter of 5/8 in. and a thickness of l/4 in. These were sealed in evacuated quartz capsules, gradually heated to 1100°C over a period of 1 week (3 days at 600°C) 3 days at 800°C, 1 day at (1100°C), and then quenched in iced brine. For the alloys containing 23.4 and 30.1 at. pet Zn, the final homogenization anneals were performed at 1000" and 850°C) respectively, to prevent melting. In the second method, alloys were prepared by saturating high-purity iron millings (0.001 in. thick, 99.9 pet pure) in zinc vapor. For each alloy the impregnation was conducted at a fixed vapor pressure of zinc and a fixed temperature between 750' and 800°C. When saturated, the millings were quenched in water. The compositions of the alloys prepared by both methods are shown in Table I. The lattice parameters of the ferritic solid solutions were determined by comparing the 26 values of their 310, peaks (using Co Ka) or of their 211 , peaks (using Cr Ka) with those of corresponding peaks for high-purity a iron. The 20 values were measured at room temperature with an X-ray dif-fractometer (G.E.-XRD5). By using a fiducial value of 2.8664Å for the lattice parameter of pure a iron at 25oC,5 the lattice parameters of the zinc-bearing

Jan 1, 1964

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By J. V. Gluck

In the present paper," as in earlier publications, V1'2"1 the authors present experimentally obtained relations for the free energy of solution of oxygen in various metals as a function of temperature. The relations are linear and given in slope-intercept form. The authors give values for the "probable error" of the slope and intercept, citing Birge's method17 for obtaining these quantities. Birge discussed these methods as early as the period 1929-32.25726 In Ref. 25 the probable error is defined as "the numerical value which the true error is as likely to exceed as not", i.e., 50 pct probability. Ref. 26 is even more detailed and includes a lengthy discussion of the applicability of the Gaussian distribution to experimental data. However, the use of the "probable error" has come under some question. For example, Ezekiel'~ states that "the use of the probable error tends to make the results appear rather more accurate than the standard error". Moroney28 stated (in 1951) that "the term 'probable error' was used in former times to denote 0.67450 (50 pct confidence using the normal distribution)....the term, a poor one, is now very much obsolescent. It has been said that 'it is neither an error nor probable' ". Bennett and Franklin in 1954" in discussing statistical confidence levels mentioned that "the customary use of the 5 and 1 pct levels is not completely a matter of chance; these levels probably represent a balance between the desire to be correct and the desire to be specific. Also in most people's minds the borderline between something that could possibly happen and something that is not likely to happen is somewhere in this region. Certainly 5 or 1 pct confidence limits are to be preferred to limits such as the 'probable error' which has only a 50/50 chance of including the correct value." It may readily be seen that the 95 pct confidence level, which is given by 1.960 (assuming large sample size), thus corresponds to approximately three times the "probable error". Indeed, limits of one standard deviation correspond only to about 68 pct probability. Even if we triple the tolerances given by the authors in the equations of their Table 111, the deviations do not become excessive and would not detract from their excellent results. It could then be said with a high degree of confidence (95%) that the precision of the slope and intercept values is about *3-5 percent of their absolute levels rather than the 1-2 percent implied in Table 111. This is then compatible with an earlier suggestion of Gokcen~' of a probable accuracy of 5 pct in dissolved oxygen measurements by the technique employed. Alternatively, the authors could have

Jan 1, 1967

Sailing westward from the Society Islands in the fall of 1774, England's noted explorer Captain James Cook discovered New Caledonia-that long, linear island that has played such an important and varied role in the history of nickel. Upon his return to England the following year, Cook's announcement of this uncharted island generated governmental interest, but its distance from the Island Empire, the troubles in the colonies, and the difficulties with France combined to keep English interest indirect and in the background of the then-current events.

Jan 10, 1968

By John E. Murphy, Ernest L. Ohle

Hematite-magnetite ore bodies at Iron Mountain, Missouri, have produced nearly 9 million tons of iron ore concentrates since 1844. The ore minerals occur principally as open-space filling in fractured and brecciated andesite porphyry with very minor replacement of the wall rocks. The enclosing rocks are Precambrian in age and consist of a series of dacite, rhyolite, and andesite flows aggregating about 2000 feet in thickness. All of the ore is in andesite and the mineralization is Precambrian in age. The shape of the ore bodies, the breccia character of the ore, and the gangue mineralogy are believed to be unique. One of the two main ore bodies is crudely dome-shaped with a tendency for development of concentric mineralized shells; the other is an elongated lense in plan but hook-shaped in cross section. Both have strong linear elements striking northeast, east-west, or northwest. Various modes of origin for the structures and for the tension breccias have been suggested, but none is completely satisfactory. Hematite is the main ore mineral; magnetite is subordinate. Important gangue minerals are andradite, quartz, calcite, actinolite, apatite, epidote, and chlorite. Although some evidence favors injection of an iron-rich melt, other evidence suggests ore formation by a high temperature, water-rich solution.

Jan 1, 1968

By Richard J. Lund

Stock piling-and by that I mean well-organized stock piling on a substantial scale-is almost as old as the hills themselves. It was back in early Biblical times, as recounted in the Book of Genesis, that Joseph was charged by Pharaoh with the responsibility of stock piling food during the seven years of plenty to guard against the seven subsequent years of famine that were revealed by the Pharaoh's dream. And this same policy of storing up food or materials to provide for future anticipated emergencies can be traced repeatedly down through the ages. So our own efforts are anything but new. Our modern concept of stock piling-the purchase and storage of strategic materials to assure supplies needed in time of some future war- stems from our experience in World War I. In 1920, the War Department was charged by Congress with the responsibility of procuring all War Department supplies and mobilizing industry in the event of another war. During the two decades that followed there were many authoritative studies made of our deficient mineral problem, all of which pointed out the urgent necessity of stock piling certain strategic materials as a reserve against future war. One such study, made in 1925 through the combined efforts of the Mining and Metallurgical Society and the AIME, was done at the ex- press request of the War Department. Eight years later another more de-

Jan 1, 1949

By Albert J. Phillips

FOR the most part, recent changes in nonferrous physical metallurgy have been gradual and of a transition nature rather than abrupt modifications of existing methods. Development of new alloys containing vital constituents in what formerly would have been considered minute amounts has necessitated more precise control of metallurgical procedure than ever before. Realization of the remarkable effects of minute amounts of specific foreign elements in many alloys has brought about a revolutionary control in the selection of even the most commonplace raw materials. In addition, recognition of the widespread occurrence of precipitation hardness in metal systems, and the utilization of many of these, has emphasized not only the need for precise temperature control but also the necessity for considering the time factor in its effect upon properties in the treatment of most metals. These needs have caused the development and widespread installation of equipment that permits precision of control undreamed of a generation ago.

Jan 1, 1935

By A. P. Cohen, D. W. Fuerstenau

Methods of accounting for the feed size in analyzing the size distribution shift during comminution have been discussed in a number of papers.1,2,3 Based on experiments which charles2 performed with single Pyrex specimens, Schuhmann4 pointed out that the size modulus of an assembly of particles should be determined by the energy expended per unit volume (or mass), independent of the size of particle being comminuted. In this same paper, Schuhmann derived the Charles energy-size reduction relationship by considering that complex comminution operations can be considered to be the summation of many individual comminution events, each of which must be governed by Were 6wi is the mass of a particle receiving the impact, 6Ei is the energy delivered to the particle, ki is the size modulus of the product resulting from the impact, a is the distribution modulus of the assembly of particles, and A is a constant. Recent experiments on the compression loading of Pyrex spheres ranging in size from 1/8 to l-in. diam have shown that the size modulus of the fragments is determined by the strain energy at fracture per unit mass, independent of sphere diameter.' The objective of the present investigation has been to determine experimentally whether the size distribution of the product from such a complex comminution process as rod milling is determined only by the energy expended per unit mass independent of feed size. Samples of each Tyler sieve fraction ranging from 4x6 to 48x65 mesh were prepared from crushed Brazilian quartz crystals. One kilogram of each fraction was ground at 60 pct solids in an 8x9 1/4-in. mill containing 17.5 kg of rods (26 rods, 5/8-in.; 10 rods, 3/4-in.; and 5 rods, 7/8-in. diam). In each test, the mill was run at 77 rpm for 15 min. Size distributions were determined by a wet-dry sieving technique. Table I presents the size distribution of the products obtained by grinding each of the size fractions. Because the size distributions are so nearly alike, they are plotted in Fig. 1 by shifting each size distribution for the different feed sizes one screen fraction to the right. Thus, the lowest point in each size distribution represents 400 mesh and each of the other sieve sizes must be shifted accordingly. A single regression line was calculated by combining the data for the six tests, excluding the coarsest feed and the two finest feed fractions. 6 This regression line, which is given by (Y \0.88 where y is the cumulative percentage of material

Jan 1, 1962

By M. M. Neale

The pottery department has been aptly described as the "heart of the zinc plant," md every operator of a horizontal-retort plant is acquainted with the fact that good retort practice is the keystone of the smelting process. Since retorts and condensers are clay products, it is obvious that improvements in other branches of the ceramic industry should be observed for possible adoption in the pottery process for zinc smelting. Deaeration of clay bodies is one of the improvements that have become fully, established in many brick and pottery plants. Our investigation of a number of these installations always yielded the same answer—improved practice. Improvement in workability, elimination of laminations, less porosity, greater wet and dry strength, were among the claims put forth for this process. All of these features are exceedingly desirable characteristics in the manufacture of a zinc retort. A preliminary test, which involved truck transportation of deaired slugs over a relatively long distance, did show the value of many of these characteristics in forming the retort. Results from the standpoint of , longer retort life in the smelting furnace were not outstanding. The idea lay dormant for several years but was revived again in 1940, when it was decided to make whatever changes were necessary in the equipment for pottery manufacture to fully demonstrate the process. A number of the manu- facturers of machinery for clay work were asked to submit proposals, and the plan finally adopted was extremely simple and economical. Machine FOR DeaeRRATING Selection of the ''Straight-line'' principle for conversion of the "Wettengel" pug mill to a ''vacuum-extrusion" machine preserved some usable parts of the original equipment, such as the drive mechanism, and main shaft. The converted machine consists of a feed hopper, a compression and shredding zone, a vacuum chamber, and an extrusion barrel, as shown in Fig. I. In operation the clay mix travels from the feed hopper into the compression zone, where it is compressed and finally forced around the tapered cone into the vacuum chamber. As it enters this chamber the clay body is shredded into thin plates, for exFosure to the vacuum. The shredder consists of a hub mounted on the main shaft, to which are bolted segmental sections, each of which carries shredder knives. The compression zone and extrusion barrel function as seals for the vacuum chamber and the shredded clay mix is agitated thoroughly during its exposure to the vacuum. A vacuum pump, equipped with a 3-hp. motor, is attached to this chamber, and maintains 25 to 26 in. vacuum during operation of the mill. Changes in Practice Prior to the adoption of the deaeration process, our standard pottery practice called for double mixing in the combination 7

Jan 1, 1944

By Peter Allen, John R. Stuermer

COUNTRY RISK ANALYSIS A company operating in a foreign country assumes all the risks that it would at home. However, beyond these, it assumes risks that arise from the unique political economic, financial conditions of the foreign country which it operates. These risks are known as "country risks". The importance of these risks has grown appreciably in the recent past (particularly in the aftermath of Iran's revolution in the late 1970s and Mexico's debt rescheduling of 1982-83), and as a result, country risk analysis has become an increasingly useful management tool. Country risk analysis seeks to assess the probability that countries will service their aggregate foreign liabilities on time, as well as the probability that country conditions could inhibit the debt service capability of private sector debtors. This involves assessment of both the ability and the willingness of countries to meet their external liabilities in a timely fashion. "Ability" is linked economic and financial variables: principally, a country's economic structure, foreign exchange generating capacity and debt service burden. On the other hand, "willingness" is tied to political factors: mainly the economic/financial orientation of government policy and the stability of economic decision making. Ability: Economic, Financial Conditions and Prospects Judgement of a country's ability to meet foreign financial obligations begins with a detailed study of a country's external balance sheet which compares the country's foreign liabilities and assets. Table 1 below presents country balance sheets for Mexico, Korea and Indonesia. [TABLE 1 The External Balance 3-,-et 1983 (billions of dollars; Indonesia Mexico Korea Foreign Liabilities 31.1 67.6 40.5 By Source: Bank 13.1 75.5 26.3 Non-bank 18.0 12.114.2 Foreign Reserves 9.3 4.7 7.0] The large magnitude of Mexico's external debt (nearly $90 billion), compared to foreign assets of approximately $5 billion, illustrates the weakness of this country's external payments position, and the main reason that it has been unable to meet interest and principal payments and been forced to reschedule its foreign debt. On the other hand, the relationship between Korea's external liabilities and assets ($50.5 billion and $7 billion, respectively), is more favorable and helps explain why Korea has been able to meet debt service payments and maintain its access to the international capital markets. Indonesia has even a more favorable relationship between its foreign assets and liabilities, $31 billion and $9 billion, respectively, and its debt is mostly lower interest rate, non-bank debt, making for a less onerous debt service burden. After the balance sheet, the analysis turns to a comparison of the country's foreign exchange earning capacity and its prospective financing requirements, that is, the country's future earnings stream

Jan 1, 1985

By J. E. Breen, J. Weertman

The creep rate of polycrystalline tin was studied as a function of temperature and stress in constant stress experiments. The temperature was varied from room temperature to almost the melting point of tin. Activation energies were calculated from tests run at the same stress. It was found that on a log creep rate vs inverse temperature plot the experimental points did not fall on one straight line but on a line which changed its slope in the 90° to 160°C region. Two activation energies for the creep of tin can be calculated from the data: a value around 26,000 cal per mol at high temperatures and a value around 11,000 cal per mot at low temperatures. It is suggested that the discrepancies between the creep activation energies and those of self-diffusion can be accounted for if self-diffusion takes place predominately by Zener's ring mechanism rather than through vacancy or interstitial movement. SHERBY, Orr, and Dorn' and Dorn' have recently reviewed some of the data on high temperature creep of metals. -The data show that the activation energy of high temperature creep is approximately equal to the activation energy of self-diffusion. This same correlation has also been successfully made between the activation energy of grain boundary relaxation and that of self-diffusion.3,4 The metal tin does not fit into this simple picture. Its activation energies of self-diffusion differ appreciably from that of grain boundary relaxation and of creep. Fensham,5 from a precisely performed experiment, has determined that the activation energies of self-diffusion of tin are 10,500 and 5,900 cal per mol along the C and A axes, respectively. There are two energies because of the anisotropic nature of tin. Rotherham, Smith, and Greenough6 have shown that the grain boundary relaxation activation energy is 19,000 cal per mol (measurements made from room temperature to 100°C). Puttick and King7 found the same activation energy for grain boundary slip in bicrystals of tin (180° to 225°C region). Until recently, there was no high temperature large strain creep data on tin suitable for activation energy calculations. At rather small strains (up to 0.01), Tyte8 had made a series of measurements on tin from which activation energies can be calculated. In Fig. 1 are plotted some of his data on a log creep rate vs inverse temperature graph. It can be seen that Tyte's work indicates that at a relatively low temperature the activation energy is around 7,400 cal per mol but at higher temperatures the activation energy increases. Since Tyte measured the creep only for small strains, it is doubtful if a

Jan 1, 1956

Prospectors were digging silver in the Ray mine area in 1873, and by 1880 high-grade copper ore was feeding a 30-ton copper furnace. In 1910, D. C. Jackling and his associates organized the Ray Consolidated Copper Company, known in mining circles as Ray Con, to exploit the Ray orebody. For 50 years, all mining was underground and the Ray mine was known the world over for innovations in mining methods. It was the first to mine important tonnage (8,000 tpd) by block caving methods. The mill at Hayden, 26 miles (41.6 km) from the mine, kept pace with the new mining methods developed at Ray and in the early 1920's flotation replaced gravity concentration by the vanner machines. First mining by open pit methods began in 1950 and in January 1955 all underground mining was discontinued. The new primary crushing plant, installed in early 1967, featured design simplicity with a low capital cost. The 54 in. gyratory crusher was installed within a total height of 6 1 ft (18.65 m) from the truck dump road bed to the floor beneath the feeder-conveyor under the surge pocket. The crusher is fed by 120-ton trucks dumping from one side only into a 200-ton hopper equipped with a horizontal splitter bar to protect the crusher spider. The crushed ore pocket, of 120 -ton live capacity underneath the crusher, discharges to a 0 to 200 fpm (61.2 mpm), variable-speed, 72 in. by 80 ft long (1.83 m by 24.4 m) sloped belt feeder, probably a first in the industry. Wood-picking stations are provided on either side of the belt so that old mine timbers and tramp iron can be removed from the crushed ore and the wood can be dropped into Dempster containers located below the belt. Counter-weighted finger gates control the bed depth on the belt at 14 in. (356 mm) and a low- level radiation unit automatically maintains a minimum of a 3 ft bed (900 mm) of material on the belt directly under the surge pocket. The conveyor is skirted for its full length and is approximately 60 in. (1.52 m) wide inside its metal skirt liners. Ten impact idlers at 12 in. (305 mm) spacing are provided under the loading pocket and remaining idlers are spaced at 18 in. (457 mm). The belt is 1 ¼ in. (31. 8 mm) thick; and, while it has occasionally been damaged by tramp material, belt life averages 11 million tons. When the belt is changed, the coiled new belt is lowered into position onto one of two belt stands mounted over the feeder, the old belt is cut, and one end is attached temporarily to the new belt. The other end of

Jan 1, 1978