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By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.' This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970

By Earl Oliver

IN times like these, the A. I. M. E. and similar societies have their greatest usefulness. . . . Individuals and companies acting alone in the development of public opinion are merely voices crying in the wilderness. United and organized they make a great force that can and does influence public action. . . . What part, if any, then, shall the A. I. M. E. take in these great stabilization processes of civilization? Shall it help to give direction and force to scientific knowledge which comes within its field of activity or shall it merely develop more of it? . . . Is it the A. I. M. E.'s function to help bring system, order and direction out of this situation so that the world can again have forward economic movement, or should it rest on its oars until other agenciess develop that public understanding and direction so necessary for economic progress? As we understand the functions of the A. I. M. E. Petro¬leum Division, they are to discover and promote knowl¬edge for the benefit of society on the mining of oil and gas. To the individual member of the Petroleum Division, there are certain advantages of social and professional contacts, but the collective purpose is that described. And the individual is benefited by membership only as the Division measures up to the purposes of its existence. Consequently, the welfare of this Division and that of its members depends on the extent to which it keeps pace with the needs of society on matters relating to the mining of oil and gas.

Jan 1, 1932

By W. B. Humes

The use of high vacuum on a large industrial scale in the ferrosilicon process for the production of magnesium marks the coming of age of an important new metallurgical technique. The economical production of reactive metals, such as magnesium, which combine with all the well-known furnace atmospheres, has until recently been successfully carried out only by electrolytic methods. It is now apparent that, through the use of high vacuum, the distillation or sublimation of many metals can be done industrially at much lower temperatures, and hence in much simpler equipment, than heretofore has been thought possible. At the beginning of the present emergency, when the ferrosilicon process of producing magnesium was brought to the fore, little was generally known about vacuum engineering, practices, and techniques. In a comparatively short time, the available equipment has been adapted, new equipment designed and built, and a fund of know-how evolved to make possible the production of thousands of pounds of magnesium per day at pressures less than 1/ r0,000 of an atmosphere. Pilot-plant operations have been consistently maintained at pressures even as low 2s one micron (0.001 mm.). These low pressures, which previously were regarded as prohibitively costly or impossible to attain, have been demonstrated as economically feasible on an industrial scale. Necessity for Vacuum The main function of vacuum in the ferrosilicon process, and hence in most vacuum smelting processes, is to lower the temperature at which the metal may be distilled or sublimed from the reduction mixture. A secondary function is to protect the distilled metal from attack by the furnace atmosphere and to permit the formation of a dense condensate. In the ferrosilicon process, magnesium is formed by the reaction between dolomite and ferrosilicon: 2(Mg0-Ca0) -\- HFeSU / t=> aMg + MFe + (CaO)2-SiO2 The metal is distilled from the pelleted charge at a free air pressure of about 0.100 mm. of mercury (100 microns). This low pressure is not needed for the reaction, but rather serves to protect the metal vapor from the oxygen or nitrogen of the atmosphere and permits the formation of a condensate free of pyrophoric material. The reaction proceeds at air pressures as high as several millimeters of mercury, and evidence has been offered to show that the actual equilibrium pressure of magnesium at operating temperatures of 2I50°F. is somewhat higher. Experimentation indicates that the yield begins to decrease at pressures above 500 microns. While no real operating data are yet available on the relationship between

Jan 1, 1944

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES 'J. 1. IToffmon and B. T. Scribrer: I. Research h'atl. Bur. Standards, 1935, "01. 15, p. 205. 'W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. 'D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. 'K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. 'W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

By E. A. Nesbitt

THE important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent- magnet properties. In recent years great, advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,l an alloy of iron, cobalt, and molybdenum, the various iron- nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be .rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat- treatment, and at this time the ductility A of the alloy disappears. If the cast alloy is heat-treated without cold-working the magnetic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X l06. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold- worked in such a manner as to improve its energy product substantially, it is called Vicalloy II. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone In a variety of forms Vicalloy I or II is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age- hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of com- position are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. PREPARATION AND PROPERTIES OF VICALLY I The alloys were usually cast in graphite molds into bars ¾ in. in diameter and

Jan 1, 1946

Abel, Charles Edwin, Student, Univ. of California Los Angeles, Cal. '81 Ames, Marshall B., Blaine-Republic Co Republic, Wash. "81 Anderson, Norman John, Student, South Dakota School of Mines Rapid City, S. D. '82 Angst, Robert A., Jr., Student, Michigan College of Min. & Tech Houghton, Mich. '82 Apgar, James William, Student, Lafayette College Easton, Pa. '83 Armstrong, John R. Box 274, Neosho, Mo. '81 Armstrong, Robert H., Student, Lafayette College Easton, Pa. '81 Arnot, Paul H. 608 S. Acacia St., Compton, Cal. '81 Asel, Philip R., Student, Colorado. School of Mines Golden, Colo. '82 Atkins, William Robert, Student, Michigan College of Min. & Tech Houghton, Mich. '82 Augenthaler, Robert L., Student, New Mexico School of Mines Socorro, N. M. '82 Augustine, Robert W., Student, Alaska School of Mines College, Alaska. '82. Avery, Eugene A., Student, Montana School of Mines Butte, Mont. '82 Babcock, Norwood N., Student, South Dakota School of Mines Rapid City, S. D. '82 Baer, Jerome S., Student, Michigan College of Min. & Tech Houghton, Mich. '81 Baker, Robert C., Student, Pennsylvania State College.. 112 E. Beaver Ave., State College, Pa. '82 Baldwin, William C., Student, Univ. of Illinois Urban, III. '81

Jan 1, 1932

By Y. L. Yao

THE NaT1-type compound may be considered as the penetration of two diamond lattices in such a way that a superstructure of the bcc lattice is formed. Examples of the NaT1-type compound of lithium are LiZn, LiCd, LiA1, LiIn, and LiGa. Except for LiZn and LiCd, each molecule of these equiatomic compounds contains a total of four valence electrons. In LiZn and LiCd it was suspected (for example, see Ref. 1) that the fourth electron was withdrawn from the 18-shell of zinc or cadmium. An incomplete 18-shell would have to show strong paramagnetism. In 1955 Klemm and Fricke2 determined the magnetic susceptibility of LiZn, LiCd, LiA1, and LiIn (also NaTl and NaIn). The molar susceptibility of the outer electrons of LiZn and LiCd was found to be not strongly but weakly positive; that of LiAl and LiIn not negative but weakly positive. Thus they questioned the hypothesis about LiZn and LiCd in particular and the description of the NaT1-type structure in general. However, they did not determine the magnetic susceptibility of LiGa. This note is to report results for all five compounds of lithium. The starting materials are 99.9 pct pure lithium sticks containing less than 0.005 pct Na. 99.9 pct Zn, 99.9 pct Cd, 99.99 pct Al, 99.999 pct In, and 99.999 pct Ga. Weighed amounts of two components were wrapped in tantalum foil and placed in a graphite crucible. It was found that the tantalum sheath minimized the vaporization losses of lithium during melting. The sheath was easily stripped from the alloy rod and the tantalum in the alloy was barely detectable (less than 0.01 wt pct). The melting was performed in a resistance furnace under an argon atmosphere. Alloy specimens were annealed for 1 hr at 400°C in vacuum. The magnetic susceptibility at room temperature was determined by the Faraday Method, using the procedures previously described.' The results are shown in Table I. The interpolated values at 50 at. pct of Li and the average values at 48 to 52 at. pct of Li at 20°C determined by Klemm and Fricke2 are also shown. It is seen that the present value for LiZn and LiCd is slightly more positive but the present value for LiAl and LiIn is slightly less positive than their corresponding values. Also, it is noted there is an abrupt decrease of susceptibility of LiAl from 51.2 to 52.5 at. pct of Li. Klemm and Fricke2 found that the total susceptibility of LiZn, LiCd, LiA1, and LiIn is almost independent of temperature. slater4 gave a working expression for the diamagnetism of the atomic core as follows:

Jan 1, 1964

By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.' The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By H. R. Peiffer

Hardening of soft metals can be accomplished by dispersing finely divided hard particles in them. The dispersing of finely divided alumina in silver in the presence of oxygen yields a high strength material which is unusual in that its mechanical properties above the melting point of the continuous Ag-O alloy matrix are similar to other solids. The tensile strength is studied for two of these alloys, one of which contains 15 pct by weight alumina and the other 20 pct by weight alumina. The average fracture strengths above 960°C of these alloys were found to be 0.4 x106 dynes per sq cm and 3.8x106 dynes per sq cm respectively. The strengths appenred to be independent of temperature above 960° C. The creep behavior of the 20 pct alumina material was studied above 960°C. The initial creep rate, 6 , of this material can be represented by where s is the applied stress and E the activation energy for the process. This energy is of the order of 1.7 to 2.1 ev. HARDENING of soft metals by the addition of finely divided, hard particles has resulted in the production of materials with excellent creep resistance and with inhibited recrystallization.' It has been demonstrated that such composites have useful strength up to temperatures very near the melting point of the soft metals, but one might expect that the strengthening by the dispersed particles ceases to be of importance above the melting point of the softer phase. This, however, is not so.2 In this paper the strengthening of a liquid Ag-O solution by the presence of dispersed alumina is discussed and experimental data concerning the mechanical properties of such a material at temperatures above 960°C presented. EXPERIMENTAL PROCEDURE Specimens were prepared using powder metallurgical techniques. Finely divided silver oxide was mixed in the appropriate proportions with "Linde B" alumina. For these experiments the specimens contained 15 or 20 wt pct alumina in pure silver.* These alloys were used in these experiments since they were the ones that could be handled readily enough to yield experimental data. Silver oxide was used in preference to silver because it is readily available in a very finely divided form and because the presence of excess oxygen in the silver is important to the properties2 of the material. The powders were mixed wet, using alcohol as the medium, in an ordinary food blender until a uniform mixture was obtained. They were then dried and heated to reduce the silver oxide to silver. Only a fraction of the finely divided silver remains unoxi-dized upon removal from the oven since the finest particles of silver oxidize immediately upon contact with air. The remaining fine silver served as a binder during pressing. The mixture was then pressed at 20 tons per sq in. into shoulder-grip (reduced section 1/4 in. by l/4 in. by 1 1/4 in.) and rectangular bar specimens (l/4 in. by 1/4 in. by 2 in.). The green specimens were heated very rapidly in a globar furnace to 1000°C, held at temperature untic they had reached theoretical density and then furnace cooled. The strength of the two compositions at temperatures above 960 °C was determined by pulling shoulder grip specimens inside a furnace mounted on a tensile machine. Specimens were gripped by means of wires wrapped around the shoulders of the specimen. Temperatures were measured by means of a chro-mel-alumel thermo-couple placed in the vicinity of the specimen. Control of temperature (within ±°15C) was accomplished by means of a Weston Recorder-Controller. Before loading, specimens were held at temperature for approximately 15 min in order to insure uniform specimen temperature. The low loads were measured by a special load cell designed by Baldwin Lima Hamilton. All testing was performed on a FGT testing machine of the same com-pany. Creep studies were performed in bending utilizing rectangular specimens of the 20 pct alumina alloy. Specimens supported at both ends by knife edges of inconel were placed in a globar furnace, heated quickly to temperature, and the deflection of the beam measured optically as a function of time. The weight and size of the specimen were predetermined and the maximum stress on the beam calculated from

Jan 1, 1962

By AIME AIME

WHEN the present Chairman of the Coal Division, A.I.M.E. applied for membership in the Institute 28 years ago one of his endorsers was Howard N. Eavenson, with whom he has now been associated as a partner in a Pittsburgh consulting coal - mining engineering firm for 22 years. Back of that association was some ten years of operating work in Kentucky. Mr. Alford was born in Philadelphia on Dec. 11, 1887, and was educated in Quaker schools, graduating from Swarthmore with an A.B. in 1909, later receiving a B.S. and an E.M. from the University of Pittsburgh. In the summers of 1907 and 1908 he had his first taste of coal mining as a chainman for the U. S. Coal and Coke Co. in Gary, W. Va. Upon graduating in 1909 he got a job on the by-product coke ovens of the Illinois Steel Co. at Joliet, Ill., but a year later went to Kentucky as superintendent of the Shamrock mine of the St. Bernard Mining Co., by which company he was employed for the next ten years. Successively he was assistant chief engineer, chief engineer, and assistant to the president. His duties were varied, including all the engineering duties commonly associated with coal mining, both underground and on the surface, construction of washing plants, prospecting, reports on new properties, power plants, safety work, and labor relations.

Jan 1, 1942

By B. H. Kear, S. M. Copley

Stress-stvain curves are presented for Ni3Al (y') cvystals in several ovientations, deformed in tension and compression at constant displacement rate, at temperatures from 70° to 2000°F. Both the yield stress and wovk havdening increase with temperature, with the magnilude of the effect dependent on ovientation. The yield stress maximum occurs at 1500°F in [001], at 1400°F in [011], and at 1200°F in [111]. The suppression of the yield stress peak in [011] and [111] orientatiorzs is due to the onset of cube slip, rather than octahedval slip, a1 elerated temperatures. The temperature and orientalion dependence of work hardening in nominal single slip orientations corvelates with changes in the CRSS ratio for octahedral slip and cube slip, in agreement with a model for work hardening based on pinning of screw dislocalions by cross slip from an octahedral plane into a cube plane. It is concluded that the unique plastic properties of y' have a decisive influence on both ductility and strength characleristics of y +y' nickel-base superalloys. It has long been recognized that the strength of y + y' nickel-base superalloys depends on the precipitation of the y' phase [basically Ni3(Al,Ti)]. This paper presents new data on the strength characteristics of single crystals of simple y' (Ni3Al), and forms the first step in a systematic program aimed at elucidating the mechanisms of hardening in the complex commercial alloys. 1) EXPERIMENTAL PROCEDURE Single crystals of off-stoichiometric NiA1 were grown from the melt under vacuum by a modified Bridgman method. The melt was poured into a preheated alumina mold and crystal growth was promoted from one end by gradient cooling. The crystals were homogenized by annealing in hydrogen at 2400° F for 72 hr followed by furnace cooling. Chemical analysis of samples taken from several crystals gave an average composition of 88.2 wt pct Ni. Spectrographic analysis gave as the principal impurities in weight percent— Si (0.02), Mg (0.01), Fe (0.02), Ti (0.002), Cu (0.008), and Co (0.03). Tensile specimens with specifications as in Fig. 1 were prepared by a series of operations involving electrical discharge machining, precision grinding, and electropolishing. Compression specimens with dimensions 1/4 by 1/4 by -3/4 in. were prepared in a similar manner, except for the initial shaping operation using a precision cut-off wheel/two-circle goniometer unit to give selected crystal orientations. Specimens were deformed in a Baldwin-Wiedemann testing machine with furnace attachment, using a strain rate of 5 x 10-4 sec-1. The strain measuring device consisted of extension arms attached to the tensile grips (or compression plattens) at one end and leading out of the furnace to an LVDT at the other. Temperature was controlled by a thermocouple placed in contact with the specimen. According to the known phase diagram for the Ni/A1 system,' when an alloy of the specified composition is cooled from the melt, primary y (nickel solid solution) dendrites grow at the expense of the liquid phase, which becomes enriched in aluminum. At the eutectic composition the remaining liquid freezes as a two-phase mixture of y + y' (Ni3Al). Upon further cooling, a solid state transformation occurs, involving the precipitation of y' in the primary dendrites, and the complete transformation of the eutectic mixture to massive y'. The as-cast structure consists, therefore, of y + y' dendrites with interdendritic regions of massive y', i.e., transformed eutectic, Fig. 2. 2) DISCUSSION OF RESULTS 2.1) Stress-Strain Curves. Fig. 3 shows tensile stress-strain curves for crystals in orientations close to [001] deformed at temperatures from 70° to 2000°F. Both the yield stress and total elongation are strongly temperature-dependent. At 70°F, easy glide is absent, and the work hardening coefficient BIT - G/300. At T > 1500°F, the negative slope of the stress-strain curves is due to pronounced necking in the crystals. The yield stress maximum at 1500° F corresponds with a minimum in the ductility, Fig. 4. The extensive duc-

Jan 1, 1968

By H. D. Strain

Potash is a generic term used to describe a number of compounds containing the element potassium (K), which is one of the three major plant nutrients. Potash content of these compounds is commonly expressed as percentage potassium oxide (K20), and the market value of the products is usually dependent on contained K20. Most of the potash produced (approximately 95%) is used in agriculture as fertilizer. Potash products today are shipped by producing countries all over the world to meet the need for increased food production. WORLD POTASH RESERVES Apparent world potash reserves are shown in Table 15.2B.1 and total some 96 billion mt of recoverable potassium oxide. The Canadian reserves account for approximately one-half the known world reserves. The reserves shown represent the potassium oxide content of a variety of potash-bearing ores. The major ore is sylvinite (a mechanical mixture of KC1 and NaCl) from which KC1 or sylvite is recovered (63.2% K20 equivalent). Other ores, such as langbeinite (potassium, magnesium sulfate-22.7% K20) and carnallite (potassuim magnesuim chloride-17.0% K20) are also mined in various parts of the world, mainly for the potassium content. Theoretically, potassium is available in almost unlimited qualities from brines and saline waters. To date, the cost of recovery from salt brines has been greater than the costs by mining operations, but new technology could make brines and seawater an increasingly important source. POTASH PRODUCTION Potash production dates back to the 1860s in Germany, which was the only recorded producing country until 1912. By 1912 Germany was producing approximately 1 million tpy of K2O equivalent. Production began in France in 1913 and in the United States in 1915. World potash production and consumption are shown in Table 15.2B.2 for the years 1950-51 through 1967-68. In 1967 and 1968 the major potash-pro¬ducing countries in order of importance were those listed in Table 15.2B.3. By 1972 Canadian production had outstripped U.S. production. WORLD CONSUMPTION World consumption of potash for the years 1950-51 through 1967-68 is shown in Table 15.2B.2. Table 15.2B.4 shows total world consumption of potassium materials in 1967-68 by country. More than 70% of the world's potash is

Jan 1, 1976

By Frederick C. Hull, Robert F. Mehl, Robert A. Colton

IT is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth 12 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in 1939 3 Two types of process were described (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures, and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth Both cases are met in the formation of pearlite from austenite (Fig 1),2,3 the former, occurring near the knee of the S-curve has been named "grain-boundary transformation," and the latter, occurring at temperatures near AeI, has been named "group-nodule transformation " In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important''' to obtain data on the rate of nucleation and the rate of growth of pearlite Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the actors that affect hardenability, when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite 2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature,, and the degree of homogeneity of the parent austenite The studies are restricted chiefly to plain carbon commercial steels PREVIOUS DATA ON RAID OF NUCLEATION AND RATE OF GROWTH Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Mehl,1 and by Dorn, De Garmo and Flanigan22 It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc ), austenite grain size, and mode of formation of pearlite at the temperatures given

Jan 1, 1942

By D. W. Smith

The beta solid solution phases of the systems copper-zinc, copper-aluminum, copper-tin and silver-zinc are structurally analogous.' R. F. Mehl and 0. T. Marzke2 have shown that the a phase upon segregating from the 6 phase in the system copper-zinc takes the form of needles lying parallel to a [Ill] direction or some similar direction, such as [556], of the parent solid solution, and that the a phase upon segregating from the ß phase in the system copper-aluminum also takes the form of needles. By analogy they assume that in this case also the segregate needles lie parallel to the [ill] or [556] direction in the ß lattice. The purpose of this investigation is to determine whether the structures resulting from segregation of the a phases from the respective ß phases of the systems copper-tin and silver-zinc are analogous to those obtained by Mehl and Marzke in the systems copper-zinc and copper-aluminum. Segregation of the a Phase from the ß Phase in the Copper-tin System Preparation of the Alloy.—An alloy containing 74.92 per cent (by weight) of copper and the balance tin was chosen for this investigation. This alloy, as can be seen from a portion of the constitutional diagram, Fig. 1, of the system copper-tin by Hamasumi and Nishigori,3 with the proper heat treatment should segregate the « phase out of the a parent, solid solution phase. The alloy was prepared from high purity cathode copper (analyzing 99.98 per cent Cu) and Straits tin (analyzing 99.94

Jan 1, 1933

By W. W. Mullins

The development, by the mechanism of volume diffusion, of a grain boundary groove on an interface separating a solid phase and a saturated fluid phase is calculated under the following assumptions: 1) isotropy of the interfacial free energy 's, 2) applicability of the Gibbs-Thompson formula relating curvature and chemical potential, 3) a nearly planar groove surface. The groove profile is found to have a .fixed shape and linear dimensions that are proportional to (time)1/3. The constant of proportionality is evaluated and involves ?s in such a way that the latter my be evaluated from grooving kinetics. A grain boundary that intersects an interphase interface will tend to produce a groove along the line of intersection (Fig. 1). The ultimate motivation for the formation of the groove is the reduction in interfacial free energ that occurs as the grain boundary contracts. Smith has discussed the way in which the free energy of the interfaces determines their dihedral angles at the groove root and has given a detailed analysis of the effect of the dihedral angles upon the nature the microstructures developed in polyphase alloys. Herring2 has extended the considerations to the case in which the free energy of an interface depends on its orientation and has thus added torque terms to the condition for interface equilibrium. Although the grain boundary and the interphase interface may quickly achieve the proper equilibrium angles where they intersect, as determined by the balance of equivalent tensions and torques,"2 the groove will generally continue to grow (though with decreasing speed). Thermodynamically, this continued growth reflects the fact that the lowest free energy cannot be achieved until the entire grain boundary has been eliminated; mechanistically, the growth occurs in response to inhomogeneities of chemical potential that are caused by the constraint of fixed dihedral angles at the groove root. The latter point is illustrated in Fig. 1, which shows that atoms* near the groove are on the convex side of a cylindrically curved surface and therefore have a higher chemical potential than atoms on the flat interface beyond. Thus atoms tend to leave the curved groove shoulders and force the groove to deepen. When both phases are solid additional chemical potential gradient may arise from whatever strain fields are necessary to insure continuity of material across the interface. In the discussion that follows, this complication due to strain will not occur since we always assume one phase to be a fluid and the other a solid. The transport processes that may operate to permit growth of the groove are surface (interface)* diffusion, volume diffusion in the phase on either side of the interface, and evaporation-condensation when one phase is gaseous. (Also a melting-freezing process is responsible for groove enlargement on a solid-melt interface as discussed in Sec. VI). The theory of grain boundary grooving has been discussed in detail for the processes of surface diffusion and of one type of evaporation-condensation.3'4 The theoretical predictions for the mechanism of surface diffusion have been confirmed in an experimental study of grooving kinetics in copper.5 In this paper, the theory of groove development by volume diffusion will be presented. Volume diffusion can occur either by atomic migration in the solid S or by diffusion of S atoms in the fluid phase, or solvent, adjacent to the groove surface. As discussed in Sec. V, volume diffusion in the solid should be less important than surface diffusion in forming a groove. Apart from verifying this statement then, the main interest of the present analysis centers on diffusion in an external solvent. The solvent may be either a liquid (e.g., water, or-

Jan 1, 1961

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats of Formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 and the heats of solution of tellurium and selenium in liquid bismuth have been measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides have been measured in a constant temperature gradient calorimeter. The thermo-dynamic quantities are interpreted in relation to the stability of the compounds and the nature of the solid-liquid transition. THE selenides and tellurides of several elements of Group VB of the periodic system are of interest because of their electronic properties. The compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 are semi- conductors; they also have gained prominence in the fields of thermoelectricity and photoconductivity. However, little is known about their thermody-namic properties. As part of a research program on the thermo-dynamic properties of intermetallic compounds, the heats of formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 were measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides were measured in a constant temperature gradient calorimeter. The results, in addition to their intrinsic interest as thermodynamic quantities, contribute to an understanding of the stability of the compounds and the nature of the solid-liquid transition. 1) EXPERIMENTAL 1.1) Materials. Samples of the compounds SbzSe3 and Bi2Se3 were prepared by melting the elements in stoichiometric proportions in evacuated Vycor capsules followed by quenchinn in water. They- were then annealed in vacuum for 12 hr at 550°C. A sample of Sb2Te3, consisting mainly of one large grain, supplied by the Lincoln Laboratory,

Jan 1, 1964

By E. Teghtsoonian, K. G. Davis

Cobalt crystals of commercial purity have been tested in tension. Their resolved shear stress-shear strain curves are very similar in form to those for zinc, magnesium, and cadmium. There is an initial linear region for shear strains up to around 150 pct, the ratio of work hardening slope to shear modulus at room temperature being about 2 X x This is followed by an upturn, which is, PLASTIC deformation in metal single crystals with close-packed structures has been found strongly dependent on stacking-fault energy. The high stacking-fault energy hexagonal metals magnesium, zinc, and cadmium have been quite extensively tested, but up to now no data have been available for a comparable hexagonal metal with low stacking-fau1t energy' An however, smaller in magnitude for cobalt than for the other metals. Values for the critical resolved shear stress rise from 97 kg per sq cm at room temperature to approximately 170 kg per sq cm at -196 °C. The Cottrell-Stokes ratio is not constant either for variations in the strain rate or for temperature changes, its value decreasing with strain. investigation into the plastic deformation of cobalt, which has a very low stacking-fault energy, has therefore been undertaken. EXPERIMENTAL PROCEDURES Cobalt crystals in the form of rods 0.3 cm in diam were grown in an electron-beam floating-zone refiner at a rate of zone travel of 25 cm per hr. Details of the growing procedure are given in Ref. 1. The zoned cobalt rods had the following analysis:

Jan 1, 1963

By R. T. Hukki

The purpose of this paper is to present an analysis of the unit operation of grinding and the circulating load, of the unit operation of classification and the circulating load, and of the two superimposed into one operation to clarify the overall trend of events relating the circulating load to the capacity of the closed circuit grinding system, to the specific surface area of the final fine product, and to the energy consumption in the closed circuit grinding process. The capacity of the closed circuit is frequently, if not always, determined by the classifier, not by the mill." With these words a startling idea was expressed in 1934 by Dorr and Anable.1 Today, some 30 years later, grinding in closed circuit is universally accepted. The basic curve presenting the capacity factor versus circulating load by Dorr and Anable has obviously been so convincing that not a single authoritative investigation regarding its validity seems to have been conducted. The only major subject of discussion appears to have been the relative merits of the 'high' and 'low' circulating loads. It seems to be universally agreed that much still remains to be hoped for regarding sharpness of classification. BASIC CURVES FOR CONSTANT MILL LOADING Fig. 1 presents a series of basic curves for constant mill loadings in function of new feed rate and circulating load. The mill loading indicated by each curve is the sum of hourly tonnages of new feed and circulating load. For example, at point 0 where the new feed rate is 100 t/h and the circulating load 300%, or 300 t/h, the mill loading is 400 t/h. In closed circuit grinding, the new feed rate corresponds to the rate of finished classified material produced. Although at this stage the effect of classification is excluded in construction of the basic curves, the trend indicated by these curves is strongly in favor of closed circuit operation under relatively small circulating loads. A study of the curves reveals that, e.g., a mill operating under a load of 200 t/h at point P where the new feed rate is 50 t/h and the circulating load 300% will also operate under the same total load at point Q where the new feed rate is 100 t/h and the circulating load 100%. In other words, a reduction of circulating load from 300% to 100% would lead to doubling of the new feed rate and doubling of the rate of production of finished material, without a change in the total mill loading. The obvious question is, is it also possible by a reduction of the circulating load in a closed industrial grinding circuit to increase the production of finished classified material and, if so, how and to what extent? GRINDING TESTS BY DORR AND ANABLE In a series of open circuit grinding tests reported by Dorr and Anable1 limestone was ground at various feed rates in a 3-ft ball mill. The original data are reproduced in Table I. It can be seen that with the increased feed rate production of -65-mesh material increased and the energy consumption per unit weight of the -65-mesh product decreased in the reverse ratio. The data shown in Table I have been reproduced for our purposes in Table II for a scale corresponding to grinding in a large industrial mill. This reproduction

Jan 1, 1968