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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

ROESLER MAX-Geology of the Iron-Ore Deposits of the Firmeza District, Oriente Province, Cuba. Discussed by William Kelly, J. T. Singewald, Jr., B. L. Miller, J. D. Irving, L. C. Graton, C. P. Berkey 439 SINGEWALD, J. T., JR., AND MILLER, B. L.-The Manganese Ores of the Lafayette District, Minas Geraes, Brazil. Discussed by L. C. Graton, J. T. Singewald, Jr., F. Lynwood Garrison HARDER, E. C.-Manganese Ores of Russia, India, Brazil, and Chile. Discussed by J. T. Singewald, Jr., E. C. Harder 454 SCHRADER, FRANK C.-Geology and Ore Deposits of Mohave County, Arizona. Discussed by J. C. Anderson McDOWELL, J. SPOTTS-A Study of the Silica Refractories. Discussed by J. W. Richards, H. D. Hibbard, W. F. Rochow, J. B. Umpleby-: 460 PHALEN, W. C.-The Conservation of Phosphate Rock in the United States. Discussed by E. G. Spilsbury 462 NORTON, S., AND LEFEVRE, S.-The Magnetic Concentration of Low-Grade Iron Ores. Discussed by G. C. Foote, J. L. W. Birkinbine, F. L. Nason 462

Jan 4, 1917

By Maxwell Gensamer

Jan 1, 1960

By Frank Rieber

EVERYONE is familiar with the story of the poor Indian and his leaking tepee. He couldn't repair the leak while it was raining, naturally. And when it wasn't raining, where was the incentive? Even if this traditional Indian was apochryphal, his counterparts are certainly alive today, and operating on a world-wide scale. - A recent issue of the Wall Street Journal, for example, carried an impassioned letter from an old cocoa planter, who wants the world to know why the price of cocoa has gone skyrocketing. For years, he says, British and American interests have bought cocoa at the cheapest possible price and, incidentally, from growers willing to sell at that price. Between them, they didn't put enough money back into the business, either to fight disease in the cocoa groves or to plant new cocoa trees. Until new trees are planted and come into bearing, we will be paying exorbitant prices for our cocoa, and getting less of it.

Jan 1, 1948

By Joseph Hyde Pratt, Douglas B. Sterrett, CHAPEL HILL

I. DESCRIPTION. MONAZITE is one of the minerals which, for a long time, was considered rather rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas and Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals, cerium, lanthanum, and didymium (Ce, La, Di)PO;. There is nearly always present a varying but small percentage of thoria, ThO2, and silicic acid, SiO, which are very probably united in the form of a thorium silicate, ThSiO4 Some monazites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent. ; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellow in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a conchoidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that were 6 in. in length. The more perfect crystals are, however,

Jun 1, 1909

By W. C. Winegard, A. Galibois, C. J. Beingessner

The effects of solutes on the distribution of two-dimensional configurations of grains in zone-refined tin have been studied. When solutes with partition coefficients (ko) greater than unity are added, three-sided pains become more prevalent and the growth law changes. It is shown by electron-Probe micro-analysis that a solute buildup occurs ahead of a moving grain boundary when ko > 1. It has been found recently1, 2 that solutes with partition coefficients greater than unity have a larger retarding effect on grain growth than solutes with k, less than unity. ko is defined as the ratio of the concentration of solute in the solid to the concentration of solute in the liquid with which the solid is in equilibrium. Niessen and winegard2 have suggested that this effect is probably due to the complex shape changes which occur during the process of grain growth and that no theory based on single boundary motion3-5 can explain the results. They suggested that the dissociation of the unstable fourfold junction was delayed in alloys where ko was greater than 1 because the boundaries at the junction had to move into a region of high solute concentration. If indeed this mechanism were correct, it was felt that not only would the dissociation of fourfold junctions be affected by the solute buildup ahead of the boundaries, but the collapse of three-sided grains would be impaired. These combined effects would naturally lead to a modification in the distribution of the number of sides per grain seen on a two-dimensional section. The present investigation was undertaken to test these hypotheses by examining the grain-growth process in detail. EXPERIMENTS The Distribution of Grain Configurations in Zone-Refined Tin as Seen on a Two-Dimensional Section. Following the method of Bolling and Winegard,6 zone-refined tin was cast into button-shaped specimens and, subsequently, plastically deformed under a drop hammer at room temperature. The resulting flat coin-shaped samples were annealed at 200°C, some for 50 sec and others for 100 sec. The specimens were then examined to determine the distribution of the number of sides per grain, i.e., the num- ber of crystals adjacent to any particular grain in the section. For simplicity, the grains were classified as three-sided, four-sided, and so forth; this concept is schematically illustrated in Fig. 1. As indicated by smith,' it was necessary to examine every grain within an enclosed area to obtain a proper distribution of the relative frequency of each type. The distributions for the two annealing times are illustrated in Fig. 2. The total number of grains examined is also indicated on the figure. It is evi-

Jan 1, 1965

By T. R. Ingraham

When aluminum sulfate was decomposed in an evacuated apparatus and the sample cooled, Q alumina was found. The thermodynamics of the decomposition reaction were resolved by measurements of the total pressure of SO3, SO2, and O2 generated over the sample at various temperatures. The results were correlated with other published data to calculate the rmges of thermodynamic stability of the various compounds involved. The thermal decomposition of aluminum sulfate was studied by Wijhler, Pluddeman, and Wöhler1 and by Warner and Ingraham.2 The results of both studies were critically reviewed by Kellogg,3 who observed that "each set of data shows considerable scatter and strong curvature on a plot of log pso3 vs 1/T".3 He agreed with Warner and Ingraham2 that both the discrepancy in the two sets of results and their curvature may arise from the indefinite properties of the particular form of A12O3 which is formed during the decomposition. While studying the thermal stability of other sulfate systems, we had noted the presence of nonequilibrium oxide properties in both the cobalt4 and manganese5 systems, but neither had shown any appreciable curvature on a logPSO, vs 1/T relationship, and the data from both systems agreed reasonably well with prior work. It therefore seemed reasonable to reexamine the technique which had been used in our earlier work on aluminum sulfate.2 The principal difference was that a tightly compacted pellet had been used for the earlier aluminum sulfate work, whereas a loose powder, contained in a platinum boat, was used for our work on other sulfate systems. In addition, a better technique had been developed for dehydrating the samples. From work done on the nickel system,6 we had become aware of the highly protective nature of some sulfate layers on their oxjdes, and hence of the necessity of providing a large surface area of P3e sample when equilibrium was to be attained in a reasonable time. That observation suggested that perhaps a steady state, rather than equilibrium, had been reached in the earlier work on aluminum sulfate. This paper reports a repetition of the experimental work with large, finely divided samples of anhydrous aluminum sulfate. APPARATUS AND PROCEDURE The apparatus used in the experimental work was described in earlier papers.2,7 The source material was Anachemia reagent-grade Al2(sO4)3 - 18H2O which was first partly dehydrated by heating at 400°C for 48 hr and then completely dehydrated by repeated baking of an aluminum sulfate-oleum slush to dryness at 450°C. ? Alas was prepared by decomposing some of the sulfate in a muffle furnace at 800° C overnight. Approximately equal amounts of the 7) alumina and aluminum sulfate were used in the experiments. The finely divided samples were handled under dry box conditions, and in addition some of the aluminum sulfate was decomposed in the apparatus while it was under vacuum, to ensure its complete dehydration prior to sealing the apparatus. The samples were heated to a series of constant temperatures on both increasing- and decreasing-tem-perature programs. Two to three days were required to obtain steady readings of the total decomposition pressure on an increasing-temperature program, and 5 to 6 days on a decreasing-temperature program. Three samples were examined on both programs. Within experimental error, the results for each sample and each program could not be distinguished.

Jan 1, 1969

By W. H. Boyer, J. W. Gabelman

The concept of metal zoning has long been recognized (Spurr, 1907, 1923; Emmons, 1924, 1926; Lindgren, 1933; Rateman, 1950), although it has been considered indistinct for most epithermal districts. The geometric relation of barren zones of hydrother-mally altered rock to ore deposits was emphasized in the work of Lovering (1941, 1949, 1950), Sales and Meyer (1948, 1949, 19501, Burbank (1941, 1950), Schwartz (1939, 1950), and Kerr (1947). Lovering (op. cit.) and Sales and Meyer (op. cit.) emphasized the consistent presence of barren alteration envelopes enclosing individual ore bodies, particularly of the vein type. Schwartz (1950) noted a difference between the distribution of alteration zones described by Lovering and by Sales and Meyer, as compared with those associated with the porphyry copper deposits of the Southwest. The disseminated deposits of the Southwest usually occur within large bodies of altered rock whereas most veins do not. In the following discussion the mineralization process is conceived of consisting of two distinct phases: pre-ore nonmetallic alteration and metallization. In the present investigation the position, size, and shape of all known hydro thermally altered areas and the position, size, and metal type of all known ore deposits were plotted on base maps of southwestern and west-central Colorado (Figure 1). The maps indicate a generally consistent geometric relation between altered and metallized areas. The addition of alteration to the pattern of metal deposits establishes a temperature zoning pattern of much greater clarity than that formed by the epithermal metal deposits alone, and allows a more precise definition of mineral belts. The center of strongest mineralization is indicated to be the area of greatest barren alteration, and metal deposits are grouped about it both under structural control and crudely in response to temperature zoning. The combination of an area of strong alteration and associated marginal clusters of metal deposits is defined as a mineral district. The strong similarity in individual deposits, in groups of different types of deposits, and in the alteration-metallization relation in districts throughout the region implies that a single metallogenic province is represented in southwestern and west-central Colorado. The occurrence of deposits in Tertiary voi-canics indicates a late Tertiary metallogenic epoci., although an early Tertiary epoch is known locally as at Ouray. Patterns formed by mineral districts can be

Jan 1, 1961

By A. Mitchell

An approximate phase diagram has been developed for the CaF2-CaC2 system, indicating a eutectic point at 1240°C, Ncac2 = 0.13, and no detectable solid solution in either phase. The liquidus line is shown to correspond to a simple c22- ion in solution. A thermo-chemical study of&apos; the reaction between carbon-saturated Ni-Ca alloys and CaC2-CaF2 liquids indicates that lhe Raoullian activity coefficient of CaC2 in dilute solution in Cap2 al 1500°C lies between 8 and 10. Some effects of the stabilily of Cap2-CaC2 solutions at high temperatures on electroslag remelting praclice are outlined. THE alkaline earth acetylides. MIIC2, have a reasonably high thermochemical stability at high temperature in the solid state,&apos; with the exception of magnesium, which forms an unstable acetylide at low temperatures (-500°C) and a carbide, Mg2C3, in the range 700&apos; to 1000°C. The acetylides of calcium and barium have been shown to have limited solubility in their respective chlorides,&apos; and further these solutions contain the acetylide as a C: ion.&apos; The equivalent magnesium solutions have not been studied. Although calcium "carbide" is used as a desulfuriz-ing reagent in steelmaking. and is possibly present as an acetylide-oxide phase in very basic electric arc practice slags, the acetylide ion appears to be substantially unstable in a silicate slag.* As a conse- *This instability arises from equilibria in the reaction: CaC2 + CO = (Ca0) + 3C where the low intrinsic solubility of CaC2 in silicate lattice, and the low activity of CaO in a silicate solution where CaO/Si02 < 1, combine to give a very small equilibrium concentration of CaC2 in solution in such silicate slags at temperatures in the region of I 500°c, even under carbon-saturated conditions. Under highly basic conditions, a liquid CaO-CaC2 phase may separate from the silicate system quence of this, the possibility that reactions involving CaC2 in silicate solutions are of importance to general steelmaking practice is remote. However, in operations involving a slag primarily based on a halide, or alkaline earth oxide, we must take into account the possibility that CaC2 will appear in quantities sufficient to significantly affect both the chemical and physical properties of the slag. The work outlined below presents a study of the CaF2-CaC2 system intended to provide sufficient data to allow an estimate of the importance of this system to electroslag remelting and welding practice. However, we should indicate at this point that there will be other processes, e.g., heat treatment, flux cleaning of castings, fused salt electrolysis, and so forth, where alkaline-earth halide fluxes are in contact with carbon, graphite, or carbides, and where halide-acetylide solutions must be taken into account. EXPERIMENTAL 1) Structural Studies. In view of the difficulty ex-perienced in handling CaC2 prepared from calcium turnings and propane gas at 700°C, it was decided to use solutions prepared directly in the equilibration apparatus, Fig. 1. The starting materials were: a) Ni-Ca-C alloy, prepared by adding calcium to liquid nickel held under calcium fluoride in an induction-heated graphite crucible; b) calcium fluoride, prepared by fusing calcium fluoride powder (British Drug House "EXTRA PURE") calcium fluoride in an induction-heated graphite crucible, in air, followed by electrolysis between graphite electrodes at 1 amp cm-2 density, for 10&apos; coulombs per g CaF2. This procedure decomposes the CaO produced by hydrolysis during the fusion step, replacing it by CaC2; Ca2+ + 2e-Ca*(l) Ca*(l) + 2C(gr)-(CaC2)caF2 O2- -2e-O*(g) O*(g) +C(gr)-CO(g) This results in a composition of between 2 and 5 wt pct CaC2 in CaF2. Fifty grams (in lumps) of this material were placed in a graphite crucible, together with Ni-Ca-C alloy (averaging 20 wt pct Ca), and the equilibration apparatus assembled. The alloy reacted with the crucible at high temperature to give CaC2, which dissolved in the calcium fluoride solution to give the desired composition. Cooling curves were plotted manually for these liquids, with rapid stirring and CaF2 seeding to minimize supercooling, and using a Pt/Pt 13 Rh thermocouple calibrated on the freezing points of nickel and copper. This gave a reproducibility of ±0.l°C. and an absolute accuracy of the thermocouple of ±l°C. An example curve is shown in Fig. 2, with the CaF2 end of the binary system in Fig. 3. The CaF2-CaC2 ingots were crushed, under dry nitrogen, and sampled for chemical analysis and X-ray examination. Analytical details are given in the Appendix. Powder diffraction data indicated that the only phases present in all samples examined were calcium fluoride and tetragonal (Types I and 111) calcium acetylide,4 with no evidence of solid solutions or compound formation. 2) Thermochemical Studies. The apparatus used to obtain activity data on CaC2 in these systems is shown in Fig. 4. It consists of an arrangement whereby the graphite crucible and its contents (CaF2-CaC2. Ni-Ca-C) can be rapidly cooled without exposure to air. Trial experiments to determine an equilibration time by ap-

Jan 1, 1969

By Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.&apos; Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-&apos;. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By J. L. Tomlinson, B. D. Lichter

Electrical resistivities 01 liquid Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi alloys were measured using an electrodeless technique. The resistivities ranged from 50 to 160 microhm -cm, temperature dependences were positive, and no sharp peaks in the composition dependence of the resistivity were observed. On the basis of these observations, it was concluded that the alloys are typical metallic liquids. The electron con-cent9,ation was calculated from the measured resis-tizlity and available thermodynamic data using a model which attributes electrical resistivity to scattering by density and composition flzcctuations. A correla-tion was shown between the departure of the electron concentration from a linear combination of the pure component valences and the value of the excess integral molar free energy. Calculation of the temperature dependence of the electrical resistivity showed a need for more detailed thermodynamic data in these systems and led to suggestions for improvement in the concept of residual resistivity in the fluctuation scattering model. THE electrical resistivity of liquid metals provides information regarding interatomic interactions and their effects upon structure. In this experiment an electrodeless technique was used to measure the electrical resistivities of liquid alloys of Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi, and the results were used with thermodynamic data to calculate a parameter which reflects the tendency toward localization of electrons due to compositional ordering. It was found that the resistivities of these alloys are generally metallic in magnitude and temperature dependence. The electrical and thermodynamic properties are discussed in terms of the fluctuation scattering model&apos;22 which supposes that the electrical resistivity arises from scattering due to a static average structure and departures from the average due to fluctuations in density and composition. Further, this model is compared with the pseudopotential scattering model of Ziman et al.3-5 EXPERIMENTAL PROCEDURES Alloy samples were prepared from 99.999 pct pure elements obtained from American Smelting and Refining Company (except tin which was obtained from Consolidated Smelting and Refining Company.) J. L. TOMLINSON, Member AIME, formerly Research Assistant Division of Metallurgical Engineering, University of Washington, Seattle, Wash., is now Physicist, Naval Weapons Center, Corona Laboratories, Corona, Calif. 0. D. LICHTER, Member AIME, is Associate Professor of Materials Science, Department of Materials Science and Engineering, Vanderbilt University, Nashville, Tenn. This work is based on a portion of a thesis submitted by J. L. TOMLINSON to the University of Washington in partial fulfillment of the requirements for the Ph.D. in Metallurgy, 1967. Manuscript submitted May 31, 1968. EMD Weighed portions were sealed inside evacuated silica capsules, melted, and homogenized before the resistivity was measured. The resistivity of a liquid alloy was measured by placing the sample inside a solenoid and noting the change in Q. According to the method of Nyburg and ~ur~ess,~ the resistivity of a cylindrical sample may be determined from the change in resistance of a solenoid measured with a Q meter as T7--5--W =R7JT^ =&apos;Kc-lm(Y) [1] where L, R, and Q = wL/R are the inductance, series resistance, and Q of the solenoid. The subscript s refers to the solenoid with the sample inside; the subscript 0 refers to the empty solenoid. Kc is the ratio of the sample volume to coil volume and y = 2 [bei&apos;0(br)-j ber&apos;o(br)~\ br\_bero(br) +j bei0 (br) expressed with Kelvin functions which are the real and imaginary parts of Bessel functions of the first kind with arguments multiplied by (j)3&apos;2. The argument of the function Y is hr where r is the sample radius and b2 = po~/p, i.e., the permeability of free space times 271 times the frequency divided by the resistivity in rationalized MKS units. Since Eq. [I] cannot be solved explicitly for p, values of Kc. lm(Y) were tabulated at increments of 0.1 in the argument by. A measurement of Q, and Q, determined a value of Kc . lm (Y) and the corresponding value of br could be read from the table. From the known r, uo,, and w, the resistivity, p, was determined. The change in Q was measured after letting the encapsulated Sample reach equilibrium inside a copper wire solenoid. The solenoid was contained in an evacuated vycor tube in order to retard oxidation of the copper while operating at high temperatures and heated inside a 5-sec-tion nichrome tube furnace capable of obtaining 900°C. Temperature was determined with two chromel-alumel thermocouples, one in contact with the solenoid 30 mm above the top of the sample and the other inserted in an axial well at the other end of the solenoid and secured with cement so that the junction was 2 mm below the bottom of the sample. Temperature readings were taken with respect to an ice water bath junction, and the voltage could be estimated to the nearest thousandth of a millivolt. The lower thermocouple was calibrated by observing its voltage and the Q of the coil as the temperature passed through the melting points of samples of indium and tellurium. The upper thermocouple reading was systematically different from the lower thermocouple reflecting the temperature difference due to a displacement of 60 mm axially and 6 mm radially. Calculations show that the gradient over the sample was less than 2 deg. Q was measured by reading a voltage related to Q from a Boonton 260A Q meter with a Hewlett Packard

Jan 1, 1970

Jan 1, 1969

By R. G. Davies

WeERTMANI has shown that the high temperature steady state creep rate, i, in lead and indium-base alloys obeys an equation of the form where AH is the activation energy, o the applied stress, n the stress exponent, and R and T have their usual meanings. He observed a variation in n from 4.5 for pure metals to 3 for concentrated alloys, which he interpreted as due to Change in creep mechanism from the climb of dislocations in pure metals to a micro-creep mechanism in the alloys. The Cottrell-Jaswon microcreep mechanism of the moving dislocation taking its impurity atmosphere with it was considered to be the most likely process, although short-range order and the segregation of solute atoms to a stacking fault will also give a stress exponent of 3. Steady state creep has been investigated in a Au - 27 at. pct Cu alloy at temperatures above 1/2 TIM where TIM the absolute melting temperature. As the oxidation resistance of this alloy is excellent all tests were carried out in air with a furnace built to give a temperature variation of less than 1°C along the 60 mm gage length. A lever-arm arrangement applied the stress with a load being adjusted between each creep test to maintain a constant stress. As each test produced less than 0.5 pct creep strain, the variation in stress during the test was negligible. The creep strain was measured by a transducer at the end of one of the alloy-steel grips, with the out of balance potential being finally recorded on a variable speed chart recorder. A typical creep curve is shown in Fig. 1. The results, Fig. 2, confirm that n is nearer to 3 than to 4.5; the creep mechanism could be any of those given above. The activation energy, AH, which is independent of stress, is consistent with a diffusion controlled process; the activation energies for the self-diffusion of gold and for the diffusion of gold into Copper are both -45 kcal per ml., There is now considerable evidence, that, when the steady state creep is dependent upon diffusion, irrespective of the actual creep mechanism, the activation energy is independent of the stress. The author would like to acknowledge the financial assistance provided by the International Atomic Energy Agency, Vienna, and the Argentine Atomic Energy Commission.

Jan 1, 1962

By C. G. Cheriton

The Bathurst mining district is located near the town of Bathurst on the north shore of the province of New Brunswick in eastern Canada. This region is the northeasterly extension of the Appalachian mountain system. The area is heavily forested and covered with a fairly uniform layer of glacial gravels and boulder clay. The relief is low, increasing to a few hundred feet in the north west and several hundred feet in the extreme southwest. Thus, rock outcrops are scarce and occur mostly along streams and ridges. These factors made conventional prospecting difficult and resulted in the district becoming an excellent place for the application of regional geological studies, air photo techniques, airborne and gound geophysical methods and soil sampling. Late in 1952, The Brunswick Mining and Smelting Company discovered a very large base metal sulphide body presently known as their No. 6 orebody. Early in 1953, another and even larger sulphide body was discovered and is known as the No. 12 ore body. Mining exploration was very active thoughout 1953 and in 1954, The American Metal Company discovered the orebodies which have been developed into The Heath Steele &apos;Mines. The location of these deposits is shown on figure one. In the latter part of 1954, The Anaconda Company became interested in the district and decided to make a geological study of this new and promising base rrietal area. The following paper presents the story of the application of modern geological and geophysical techniques, leading to the discovery of a large sul-nhidp liodv. The Bathurst district is generally underlain by the Tetagouche group of Middle Ordovician rocks.

Jan 1, 1961

By W. J. Kroll

Jan 1, 1960

By E. T. Turkdogan, L. S. Darken

Using the quadratic formalism, thermodynamic equations are derived for the composition dependence of the heat and entropy of mixing. The applicability of these equations is confirmed by available experimental data on the activities and heats of mixing for binary metallic systems of Group ZZB elements. In a recent paper arkeen&apos; introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. That is, in the terminal region, which may extend to as much as 60 at. pct, the logarithm of the activity coefficient, log y,, of component 2 is a linear function of (1 - N,)&apos; where N2 is the atom fraction of component 2. Similarly, for the other component, log yl is a linear function of (1 - N,)&apos;. A number of iron-base binary liquid alloys were shown to obey this quadratic formalism. arkeen&apos; extended this formalism also to any corner of a ternary system and showed that the activity coefficients of the components 1, 2 and 3 (1 is taken as the solvent) can be represented by quadratic terms involving five parameters, four of the binaries and one for the ternary system. Numerous examples given by arkeen&apos; demonstrated the general applicability of the quadratic formalism to iron-base systems over a wide composition range. In this paper further examples are given of binary liquid systems (Group IIB elements, Zn, Cd, and Hg) and of several solid solutions, again demonstrating the appropriateness of this concept. A further purpose of this paper is to extend the quadratic formalism to the enthalpy and excess entropy of binary metallic solutions and to test the equations so found using available experimental data. QUADRATIC FORMALISM FOR HEATS AND ENTROPIES OF MIXING OF BINARY METALLIC SOLUTIONS The following equations, reproduced from Darken&apos;s paper, are for the two terminal regions of binary systems. at infinite dilution and a&apos;s are temperature dependent parameters to be determined from the experimental data. Although the quadratic formalism is an assumed representation of the data, Eqs. [I] to [4] are thermo-dynamically consistent with the Gibbs-Duhem relation and satisfy Raoult&apos;s and Henry&apos;s laws as limiting cases. As pointed out previously,&apos; the following form of the Gibbs-Duhem equation facilitates the integration in general but particularly in regions I and 11, where each of the derivatives is constant. The partial molar enthalpy of solution i, (and i; the value of i, at infinite dilution) are related to the activity coefficients y, and y," by the thermodynamic relation Differentiating Eq. [l ] with respect to 1/T and substituting the above thermodynamic relation gives for region (I) It is reasonable to assume that over a temperature range of experimental interest, the enthalpy of mixing is essentially independent of temperature, implying from Eq. [7] that the derivative da,,/d(l/) is also independent of temperature. On the basis of this argument, the temperature dependence of a has the form where £ and S have the units of enthalpy and entropy respectively; they are characteristic parameters for a terminal region of a binary system, e.g. for region (I), C12, S12 and for region (II), d:,,, S2,. Using this equation gives for dff ,/ d(l/), From Eqs. [7] and [9] an expre_ssion is obtained for the composition dependence of L,. Similar calculations are made for El and the results are summarized below for the two terminal regions. For region (I), The corresponding expressions for the molar heat of solution, AHM, are readily obtained from the above equations for the two terminal regions: For region (I),

Jan 1, 1969

By Charles Y. Clayton

A study of the literature shows that the greater part of research work on annealing of cold-worked iron has been for the purpose of studying the effect on grain-size and properties other than hardness. No reference has been found of experimental work of the same nature as that explained in this short paper. The material used throughout was Vismera iron, an iron containing 0.03 carbon and made several years ago by the Inland Steel Co. One-half inch stock was cut into cylinders % in. long. The cylinders were then compressed for 60 sec. in a Reihle testing machine under loads as indicated below: CoMPressiON, Average Length, Series Pounds Inches 1 10,000 0.693 2 15,000 .599 3 20,000 .501 4 25,000 .426 5 30,000 .378 6 35,000 .351 7 40,000 .311 Fig. 1 shows these cylinders after compression. Each series consisted of 17 specimens lettered 0, B, C, D, E, F, G, H, I, J, K, L, M, N, P, Q and R. One specimen of each series was reserved for study of the properties in the cold-worked condition. The other specimens were annealed in a Hump furnace for 1/2 hr. at the following temperatures: TEmpeRa- TempeRa- Letters tuRe,° C. LettERs tuRe °C. B............................... 250 J.............................. 650 C............................... 300 K............................. 700 D............................... 350 L.............................. 750 E............................... 400 M............................. 800 F................................ 450 N............................. 851 G............................... 500 0. . :........................... 900 H............................... 550 P.............................. 950 I................................ 600 Q............................. L000

Jan 1, 1926

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.&apos; They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,&apos; it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,&apos; the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:&apos; = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By F. C. Langenberg, J. Chipman

Jan 1, 1959

[Contents AH-Metal Mining and Industrial Minerals Pipeline Transportation of Phosphate. (Paper by I. S. Tillotson, R. B. Burt, and J. A. Barr, Transactions AIME, 193, 273; Mining Engineering. March 1952. Discussion by Howard Howie.) 1066 B-Minerals Beneficiation The Effect of Zinc Deleading Operations on Lead-Zinc Selectivity at the Parral and Santa Barbara Mines. (Paper by C. L. Boeke an G. C. Gunther, Transactions AIME, 193, 495; Mining Engineering. May 1952. Discussion by I. M. Symonds, L. H. Lange, Norman Weiss, H. S. Wildman, C. F. Zeuch, E. H. Crabtree.) 1067 Jaw Crusher Capacities, Blake and Single-Toggle or Overhead Eccentric Types. (Paper by D. H. Gieskieng, Transactions AIME, 190, 971; Mining Engineering. November 1951. Author s supplement.) 1069 Screened Ore Use for Fine Grinding at Lake Shore Mines. (Paper by Bunting S. Crocker, Transactions AIME, 193, 499; Mining Engineering. May 1952. Discussion by Fred C. Bond, J. Myers, Norman Weiss, Harlowe Hardinge, Oscar Johnson, L. E. Djingheuzian.) 1069 The Third Theory of Comminution. (Paper by Fred C. Bond, Transactions AIME, 193, 484; Mining Engineering. May 1952. Discussion by Milton C. Shaw and Donald R. Walker; R. J. Russell.)1071 Flotation Rates and Flotation Efficiency.t (Paper by Nathaniel Arbiter, Transactions AIME, 190, 791; Mining Engineering. September 1951. Discussion by Gregoire Gutzeit and Porter Clements.) 1074]

Jan 1, 1952