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By M. R. Tek, K. H. Coats, D. L. Katz

A large number of boundary value problems encountcred in unsteady-state heat transfer, fluid flow through porous media, neutron diffusion and mass transfer involve the solution of a linear, parabolic partial differential equation commonly refcrred to as the diffusivity equation, where U is the dependent potential variable. K is the diffusivity (hydraulic, thermal, neutron, etc.) and 1 is the time variablc. Solutions to Eq. I are available in the literature for a wide variety of initial and houndary conditions. The great majority of these solutions are ohtained for geometric boundaries corresponding to linear. cylindrical or spherical flow models. A typical engineering application where the solution to Eq. 1 is required is the calculation of underground water encroachment across the boundaries of oil or natural gas reservoirs, In this particular area of application, the reservoir boundary is invariably approximated by circular geometry. However. the areal shape of many reservoirs can be better approximated by elliptic rather than circular boundaries. Thus the need for a general method of solving the diffusivity equation in elliptic coordinates arises in this problem as well as in other engineering applications involving elliptic boundaries. The solution to the diffusivity equation usually in volves the Error Function for the linear flow model, Bessel functions for the radial flow model and trigonometric or Legendre functions for the spherical flow model. It is well known that the general solution to the diffusivity equation in elliptic coordinates involves Mathieu functions. The significance of Mathieu functions in the analytical treatment of the diffusivity equation in elliptic coordinates is discussed in the literature However, these references do not providc analytical solutions useful in practical engineering problems. The objectives of this papcr are the development of the equations describing the unsteady-state liquid flow through a porous medium with an elliptic inner boun- dary, the development of a numerical method of solving these equations and, finally, a comparison of the water encroachment quantities calculated from the elliptic flow equation with those calculated from the radial flow equation. While the specific problem treated in this paper relates to unsteady-state liquid flow through a porous medium, the basic equations and computational techniques devcloped will apply equally well to problems occurring in the other areas of engincering interest mentioned previously. The solution given here is limited to a single case in which thc outer boundary encloses an area 100 times that of the inner boundary. DESCRIPTION OF THE FLOW MODEL Fig. 1 shows the flow model upon which the calcu lations presented in this paper are based. The inncr and outer houndaries of the flow model are represented by two confocal ellipses with major and minor axes, respectively, equal to 2a1, 2b1, and 2a, and 26,. The height of the elliptic cylinder flow model is denoted by 17. The following assumptions are employed in the development 01 the equations governing the unsteady-state liquid flow through the described flow model. 1. Uniform porosity and permeability throughout the flow model

By C. O. Tarr, G. V. Smith, R. F. Miller

METALLURGISTS have long recognized that the Fe3C type of carbide is not a stable phase in steel and that, given sufficient time, it will decompose with formation of graphite, at least at temperatures below about 2050°F.1 This slow graphitization has never been of much concern to users of hypoeutectoid steels, for in such steels it occurs only during prolonged exposure at elevated temperature. In 1935, Kinzel and Moore2 reported complete graphitization of the carbide of a 0.1 5 per cent carbon steel that had been in senrice for about 26,000 hr. at a temperature of about 1100° to 1200°F. In discussing this paper, both Mathews and Sauveur reported graphitization of slightly hypereutectoid steels. In an extensive investigation of graphitization of high-purity iron-carbon alloys, Wells1 produced graphite at 7o0°C. (1290°F.) in an alloy containing as little as 0.13 per cent carbon, and showed that graphite may precipitate either directly from austenite or from decomposition of Fe3C, also that the rate of graphitization tends to increase with increase of temperature, at least up to a certain point, and with the presence of graphite nuclei. Jenkins, Mellor and Jenkinson,3 studying the structural changes in carbon steels ranging from 0.17 to 1.14 per cent carbon during stress-rupture tests at elevated temperature, obsenred graphite in an aluminum-killed 0.40 per cent carbon steel after fracture in 4340 hr. under a stress of 17,900 lb. per sq. in. at 840°F. and in many of the steels after stress-rupture test at 1200°F. Unstressed samples of 0.60, 0.86 and 1.14 per cent carbon steels graphitized almost completely in 360 hr. at 1200°F., while samples of 0.90 and 1.10 per cent carbon steels were somewhat graphitized, and steels containing 0.24, 0.40 and 0.57 per cent carbon showed no sign of graphite. Their results indicate that graphite precipitates the more readily the higher the carbon content, though this tendency is influenced to some extent by deoxidation practice, and that graphitization is accelerated by plastic deformation. In a recent study of the graphitization of 0.4 and 0.6 per cent carbon steel strip, made by M. A. Hughes,4 it was found that at 1200°F. graphite appeared after 72 hr. in aluminum-killed but not in silicon-killed steel, and that the rate of graphitization was increased by slow cooling from 1600°F. and by cold-working prior to annealing. In creep tests of normalized o. I 5 per cent carbon steel killed with 2.5 lb. of aluminum per ton, at the U. S. Steel Corporation laboratory at Kearny, spheroidization and some graphitization were found after 3000 hr. at 1000°F. under a stress as low as 15m lb. per sq. inch.

Jan 1, 1944

By P. W. Bakarian, John C. McDonald

Three magnesium alloys were processed in various ways to exhibit a wide variation in the ratios of yield strength and tensile strength in the rolling direction compared to the cross-rolling direction. Basal-plane pole figures were prepared from several specimens. A fair correlation was observed between the property ratios and the ratio of percent of poles oriented in the cross-direction quadrants compared to the percent oriented in the rolling-direction quadrants of the pole figures. THE modes by which magnesium crystals deform are such as to lead to marked preferred orientations in all forms of wrought products. The effect of the active modes at room temperature, coupled with these orientations, is often to produce a lower compressive yield stress compared to the tensile yield stress. The phenomenon is due to easy twinning in compression, and has been well-related to the preferred orientations as described by basal-plane pole figures of the hcp magnesium single crystal. The literature contains some information on the variation with test direction of the tensile properties of sheet, but no quantitative relationship to the observed pole figures has been established. These effects have been reviewed in the few com- prehensive treatises in English which have been written on magnesium technology and metallurgy.1°3 Roberts presents several pole figures, but no tensile-property data in the plane of the sheet. Raynor has no pole figures, but quotes Frommer's4 results. The information in Beck's compendium more or less parallels the results of Jones and powell.5 In both a Mg + 1.5 Mn alloy and a Mg + 4.6 A1 alloy, cold rolling was found not to change the general situation of higher properties in the cross-rolling direction,* than in the rolling direction. Thomas'6 X-ray studies of Jones and Powell's specimens did not permit correlation of properties and preferred orientation. Ansel and Betterton7 report tensile and compressive properties on three other alloys as a function of degree of cold rolling, plus a recrystallizing anneal. As rolled, there was a change in anisotropy with degree of reduction, but all alloys were reasonably isotropic in tension when annealed. X-ray diffraction photograms illustrated the kinds of orientations present, but were not correlated with the properties. Bakarian8 has described a method of determining quantitatively a preferred orientation, and illustrated the method by applying it to pure magnesium and two of its alloys. This method was used in the present work as a basis for correlating the strength properties with the texture.

Jan 1, 1965

By R. M. Waterstrat, E. C. van Reuth

BINARY- alloy phases having the A15-type crystal structure have been described as occurring at a simple and more or less invariant stoichiometric composition (A3B) which corresponds to the relative number of atoms occupying each of the two crystallographi lattice sites in this structure.1,2 It is frequently assumed, therefore, that each crystallographic site is occupied exclusively by one kind of atom. In most cases, however, there have been insufficient experimental data to establish whether atomic ordering is, in fact, complete. Recent studies have shown that binary A15-type phases are sometimes stable over an appreciable composition range3''* and, occasionally, the composition range of stability does not even include the "ideal" A3B stoichiometric composition.5-7 We have observed the existence of nonstoichiometric A15-type phases in the binary systems Cr-Pt and Cr-Os. This has not been reported in previous work on these alloy systems.1,8-11 A series of alloys, each weighing approximately 30 g, was prepared by are-melting in an Ar-He atmosphere using 99.999 pct Cr, 99.999 pct Os, and 99.99 pct Pt as starting materials. Each alloy was melted four times with a total weight loss of less than 1 pct. The stoichiometric (A3B) alloys were sealed in evacuated quartz tubes and annealed at 1200°C for periods of time ranging from 3 days to 2 months. Examination of the alloy microstructures revealed that little change had occurred over this time interval and it was therefore assumed that the microstructures were fairly representative of equilibrium conditions. No evidence of contamination was observed although there was apparently some loss of chromium which was confined to a thin layer at the surface of the specimens. The quartz tubes were quenched from the annealing temperature into cold water. X-ray diffraction and metallographic examination of the stoichiometric alloys revealed an estimated 10 to 30 pct of second phases which were tentatively identified as phases previously reported in these binary-alloy systems.8-11 A second series of alloys was prepared by mixing -325 mesh metal powders having a nominal purity of 99.9 pct and compressing these mixed powders in a cylindrical die at a pressure of 43,000 psi. These alloys, each weighing 15 g, and some of the arc-melted alloys were annealed in a high-temperature vacuum furnace heated by tantalum strips at a pressure of 10-8 Torr and were rapidly cooled by turning off the furnace power. X-ray and metallographic examination of both series of alloys served to establish the composition ranges of the A15-type phases. Although some chromium losses occurred during the vacuum annealing, they were largely confined to a thin layer on the outer surfaces of the samples. It was established that the A15 phases occur in the Cr-Pt system at 21 ± 1 at. pct Pt after 1 week at 1200°C and in the Cr-Os system at 28 ± 1 at. pctOs after 1 day at 1400°C (see Table I). We also observed that an arc-melted stoichiometric (A3B) alloy in the Cr-Ir system was single-phase (A15-type) in the "as-cast" condition in agreement with previous work.8,13 In addition we obtained a sample of the Cr-Os A15-type phase from Argonne National Laboratory. This alloy contained less than 1 pct second phase12 and was submitted to a density measurement. The density measurement yielded a value of 11.14 g per cu cm in comparison to a theoretical value of 11.25 g per cu cm calculated using the observed lattice constant (4.6806Å) of this alloy. The uncertainty in measurement was 0.1 pct but the sample may have contained some cracks or minor imperfections which could account for the low experimental value. We have also studied the atomic ordering in these phases by means of integrated line intensity measurements using thick, flat, rotating powder samples and CuK a radiation in an X-ray diffractometer. We have obtained order parameters of 0.90 for the Cr-Pt phase, 0.89 for the Cr-Ir phase, and 0.64 for the Cr-Os phase using the formula: where s is the usual Bragg and Williams order parameter, ra is the fraction of chromium atoms in A sites, and FA is the fraction of chromium atoms in the alloy. The values obtained are estimated to be accurate within ±4 pct. If the unusually small value for the order parameter of the Cr-Os A15 phase were due to the existence of lattice vacancies on the "B-atom" sites, then a density of 10.04 g per cu cm would be expected in contrast to the observed value of 11.14 g per cu cm. We, therefore. conclude that the fraction of lattice vacan-

Jan 1, 1967

By M. D. Banus, M. B. Bever, A. K. Jena

Measurements of the heat effects on addition of various solid phases of InSb to a solution calorimeter have confirmed the existence of a new high-pressure plzase InSbQII), which was jormed at 37 kbar and 623°K. The heats of formation of InSbQ), InSbfl), and InSb(111) have been measured and the heats of transjormation of InSb(1) to InSb(1l) and InSb(Iii) and of 'InSb(ll) to InSb(iiI) at atmospheric pressure and 78°K have been determined independently. Other thermodynamic properties of these phases, the phase boundary InSb(i)/InSb(ll), and the relative positions of the triple points are calculated. The pressure-Dolume term is shown to be more critical than the internal energy difference in making the phase InSbQ) less stable than InSb(II) at high pressures. Observations on partially transformed specimens suggest that the transformation of' metastable InSb (III) takes place in the two steps InSb(lll) — InSbQI) and InSbQI) — InSb(l). The compound InSb can exist as several phases depending on the temperature and pressure. The phase InSb(I), which is a semiconductor having the zinc-blende structure, transforms into the phase InSb(11) at a pressure of about 23 kbar and room temperature.'-3 The phase InSb(II) has the 6 tin structure,4-6 is metallic, and becomes a superconductor below 2.lok7 An orthorhombic phase of InSb has been reported to occur above a pressure of approximately 30 kbar at room temperature.' This phase is also a superconductor below about 3.4k9 The phase InSb(I1) is retained at atmospheric pressure if it is quenched to 78°K under pressure,6,7 but tends to transform at higher temperatures and does so explosively above approximately 210ok,7 A value of the heat of transformation of InSb(1) to InSb(II) at 210°K and atmospheric pressure has been reported.' A concurrent publication'0 reports evidence for a new solid phase InSb(III), which was formed by annealing InSb above 58 1°K at 37 kbar, above 560°K at 52 kbar, and above 473°K at 65 kbar. Specimens of InSb(II1) had a superconducting transition temperature of 4.lo ± 0.1oK. X-ray diffraction patterns also indicated the presence of a new phase. In this communication, thermodynamic properties of the phases InSb(I), InSb(II), and InSb(II1) are reported and discussed. The phase boundary InSb(I)/InSb(II) and the relative positions of the triple points are calculated. 1) EXPERIMENTAL 1.1) Preparation of Specimens. Specimens of the high-pressure phases of InSb were prepared in a belt-type high-pressure chamber by a tichnique described in detail elsewhere.'' Charges of 0.6 to 0.8 g of Cominco semiconductor grade InSb were used. The temperatures were measured with a chromel-alumel thermocouple, the hot junction of which was within 0.5 mm of the specimen. The specimens were heated under a pressure of 37 kbar for 1 hr at 723°K (which is well above the liquidus) and quenched to room temperature. One set was annealed at 523°K and another set at 623°K for 20 to 24 hr. These annealing temperatures were chosen because 523°K was below and 623°K was above the temperature of the transformation of InSb(II) to InSb(1Tl) at 37 kbar.10 The specimens were then cooled to 125°K by passing liquid nitrogen through the jacket of the belt die before the

Jan 1, 1968

By D. K. Crampton

The object of this work was to obtain and correlate information on effect of internal stress in variously drawn tubes on several properties. Also, a simple approximate method of comparing types of stress distribution in such variously drawn tubes was sought. There is also included some work on comparison of single and polycrystalline materials and effect of different types of operation and preferred orientation. Preparation of Material A series of tubes was drawn to study the effect of the type and degree of final reduction on various physical properties and the approximate distribution of stress intensity across the tube wall. The material used all came from a single heat of 70-30 brass melted in a regular production Ajax-Wyatt induction furnace. The analysis of the metal as cast was: copper, 70.36 per cent; lead, 0.04; iron, 0.02; zinc, balance. The material was cast in "shells" with 4 in. outside diameter and in. wall thickness. It was drawn part way down according to the usual standard mill schedule and then by suitable individual schedules to finish by a variety of types and degrees of drawing to the same final cases in every instance; namely, 0.750 in. outside diameter by 0.080 in. wall thickness. The exact final draws, together with the percentage area reductions, diameter reductions and gage reductions are given in Table 1. In fabricating these tubes, rather unusual precautions were observed to insure the elimination of ail variables not under immediate study. All intermediate anneals were carried out at about 1200" F. down to the so-called "cut-in size"; namely, 17/16 by 3/16 in. From this point on, all anneals were made at from 1050' to 1100" F. The greatest care was used all through to have the tubes as free from minor surface defects as possible. When such defects were visible on intermediate sizes they were carefully filed out. On the final draw to 3/4-in diameter the die was aligned with the greatest possible precision in order to insure as straight a tube as possible

Jan 1, 1933

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

Jan 1, 1971

By K. Reinhardt

The idea of burning blast-furnace gases directly in gas-engines, instead of under steam-boilers, as had previously been done, was first put into practice barely ten years ago, almost simultaneously in Great Britain, Germany and Belgium. The pioneers of this movement made their first experiments with small engines. After these experiments had given satisfactory results, and it had been shown that the thermal value of the poor blast-furnace gases, in spite of defective scrubbing, could with safety be directly transformed into mechanical work in the gas-engine, there very soon arose a considerable demand for gas-engines of large power, similar to the large steam-engines employed in metallurgical works. In face of these sudden requirements, the gas-engine builders were placed in a difficult position; for up to that time the gas-motor was considered as suitable for small engines only, and it was generally believed that the limit of size had been attained with 100 to 150 effective h.p. in a single cylinder. Manufacturers of gas-motors, however, did not underrate the advantages offered by this new field for their manufactures, and it so happened that in Germany the Berlin-Anhaltische Masch-inenbau-Gesellschaft, of Dessau, was the first to undertake the construction of a 600-h.p. two-cycle gas-engine, with two cylinders of the Oechelhauser-Junkers type, for the Hoerder Mining & Smelting Company. The engine was started in 1898, and, with a few improvements and alterations, is still working satisfactorily. This engine worked with astonishingly high effciency, considering the period. The builders were therefore

Jan 1, 1907

By C. R. Keyes

Discussion of the paper of C. R. Keyes, presented at the Chattanooga meeting, October, 190S, Bulletin No. 26, February, 1909, pp. 119 to 166. E. R. BUCKLEY, Flat River, Mo. (communication to the Secretary*) :-Some statements in the paper of Mr. Keyes relative to the nature and formation of the Ozark lead- and zinc-deposits seem to me erroneous and misleading, and I respectfully present the following criticisms, placing Mr. Keyes's original statements in quotations. Referring to the Ozark dome: (P. 127.) "It is a region that has been repeatedly upraised and planed off, until in the middle portion the oldest known' rocks only are exposed." Does he mean that the St. Francois mountains, which have always been considered as lying on the eastern flank of the Ozark dome, are the middle of the dome? Or does he mean that the Cambrian rocks of the generally-accepted middle are the oldest known rocks ? Certainly not the latter, and if the former, his idea of the middle of the dome is not in accord with that of others who are familiar with the region. (P. 138.) " . . . the ore-deposits are definitely associated with, or localized by, geologic structures of some kind that .produce in effect basins in which' the underground waters are impounded, or their flow retarded." This statement does not appear to be altogether consistent with the facts, since the ore- bodies of the Joplin district, as the rule, occur in those parts of the Mississippian formation which have a tendency to accel¬erate the flow of ground-water rather than retard it. I might name the open, breeciated ground near Joplin, Webb City, and Oronogo as especially noteworthy illustrations. The ore-bodies, everywhere, occur in positions where there must have been a free and copious circulation of dilute lead- and zinc-solutions in the presence of reducing constituents. The inequalities in the distribution of the ore-deposits are

Oct 1, 1909

By B. L. Averbach

THE rolling process may be considered as a case of a nonhomogeneous plastic flow. In such a heterogeneous deformation there is no direct general solution, and the plastic deformation varies from point to point as a function of the coordinates. It is practicable to determine these plastic strains only at the conclusion of the rolling process, and the local strains can be studied by observing the deformations produced in a suitably placed grid system. Strains at the surface of a bar after rolling have been reported by MacGregor and Coffin,' but the strain distributions within the bar have not been previously observed. Siebel² has investigated the plastic deformations resulting from wire-drawing by splitting the wire along its axis, milling a grid coordinate system on the inner plane surfaces, and binding the .wire together so that it would pull through a die as a single unit. This method was possible because of the rotational symmetry of the die. In the rolling process, however, such a system was not readily applicable. This paper describes another method of including a grid system, and reports some preliminary data on the plastic rolling strains within a square bar. Experimental Procedure 2.1 mm wide (144 network squares per sq in.) was punched from a thin lead sheet with a steel die and supported in a brass mold by thin copper wires. Pure tin was then poured around the grid to form a solid bar, with the network securely imbedded at. a given position. This bar was then machined to a square 15.2 mm (0.60 in.) wide, and then radiographed. The lead grid was quite adherent and sufficiently ductile to follow the deformation of the bar faithfully. The network lines also remained sharp enough to maintain a high radiographic contrast, and the tin bar, with the grid included, could withstand considerable deformation at room temperature without splitting at the interface. In order to fill the mold, it was necessary to cast the tin at 260-280°C and during pouring the lead grid was supported at short intervals to prevent warping. Some shrinkage cavities were encountered, but only bars which were free of shrinkage in the network region were used. This method is similar to the one employed by Steinberg" in an investigation of the strain distribution in a tensile specimen. Before rolling, the machined bars were radiographed in two directions to obtain accurate initial dimensions of each square and to observe whether the grid was straight and correctly positioned. The rolling was performed in a small hand mill with 2 in. diam rolls at room temperature, and a 20 pct reduction based on the original height was employed. The rolls were clean and no lubricant was used. Halfway through the bar, at the center of the network, the rolls were reversed and the bar extracted. These bars were then radiographed again

Jan 1, 1951

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.' 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-'. 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 Rclssell Gibson, F. S. Turneaure

The tin deposit of Monserrat; Bolivia, consists of one major vein 1600 m in length. The ore is unusual because of the notable quantity of teallite, even though cassiterite is the principal tin mineral. The deposit, formed at shallow depth under a wide range in temperature, may be classed as xenothermal. Polished sections reveal a complex history of replacement, with low-temperature minerals deposited before high-temperature minerals.

Jan 1, 1950

By Charles M. Cooley

A NOTED Prospector Passes-Stories of the grizzled old prospector that discovered what turned out to be a famous and highly profitable mine, only to die in poverty through the shenanigans of "the Interests," are legion. It is pleasant, therefore, to be able to report that the discoverer of one of Canada's most famous mines was more fortunate.

Jan 7, 1953

By J. M. Vonfeld, V. D. Hanson, W. K. Heinlein

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion No. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and - 3/8-in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3/8-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 1/4 in., and 11/4x3/8 in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into 3/8x0 which is cleaned in the fine coal plant and 3x3/8 for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1952

By R.J. Anderson

Roughly, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term and refers to the contractio~l in volume of a metal or alloy on passing from the liquid to the solid state. Patternmaker's shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring temperatures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment, and technical knowledge of men experienced in the production of castings.

Jan 1, 1923

By R. J. Anderson

Roughly, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term and refers to the contractio~l in volume of a metal or alloy on passing from the liquid to the solid state. Patternmaker's shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring temperatures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment, and technical knowledge of men experienced in the production of castings.

Jan 1, 1923

By W. R. Ingalls

In reviewing the history of the metallurgy of zinc, I shall pass hastily over what is only of antiquarian interest. That has been excellently treated by Dr. Bernhard Neumann in "Die Metalle" (1904) and has been described briefly in my "Production and Properties of Zinc" (1902), in my "Lead and Zinc in the United States " (1908), and in other metallurgical works of more or less the same date. In this present monograph, I have it in mind to confine myself mainly to technical practice, especially to that of the last 75 years, prior to which period advance was slow and of no great moment. The ancients made brass by the cementation process, i.e., embedding copper in a mixture of calamine and carbon and heating, whereby zinc oxide was reduced and zinc was vaporized and combined with the copper. Zinc was isolated by some of the alchemists, who named it and knew something of its properties, but made no use of it. Long before then, however, zinc was produced in India. Later it was produced in southern China. Possibly the Chinese obtained their knowledge from India. The Chinese in remote places still produce small quantities of zinc. I have seen photographs of their furnaces; or pots, for they hardly deserve the dignity of being called furnaces. I imagine that they are the same that were used centuries ago, for I cannot conceive of anything more primitive. Anyway, it is certain that the idea of a commercial production of zinc in Europe was imported from the Orient, where the metal was known in commerce as Speauter and Spiauter, whence speltrum and finally our term spelter. Tutanego and Tuteneague are other old names. Dr. Isaac Lawson went to China about 1730, expressly to discover the method of its production. What connection there was between Isaac Lawson and John Champion we do not know, but the latter obtained in 1739 a patent for a process of distillation downward and at some time between 1740 and 1743 erected a works at Bristol and actually began the manufacture of spelter. A production of 200 tons per annum is mentioned. In about the year 1766, Rishop Watson visited the Champion works and saw the process in operation, which previously had been

Jan 1, 1937

By Gordon H. Geiger, J. Bruce Wagner

Electrical conductavity and therrnoelectvic nzeasuretnents on synthetic hematite slabs with 0.01 to 0.90 at. pet Ti and with 0.30 at. pet Ca were made. Additions of titanium and of calcium both increased the electronic conductivity with titanium yielding greater n-type behavior and calciurn p-type behavior. Reduction studies of hematite to magnetite in CO-CO2 atmospheres between 600° and 900°C initially exhibited linear kinetics. These linear rates were increased by additions of titanium and decreased by calcium. IN recent years many studies have been reported in the literature on the kinetics of the reduction of hematite and magnetite to iron. In addition, Hansen and Josephl and Schenck and Schultz2 have reported studies on the reduction of hematite to magnetite, the first step in total reduction to iron. In order to evaluate the results of the studies of over-all reduction in terms of the actual mechanism of the reaction and to define further the important factors in the rate- controlling mechanism of the magnetic roasting reaction, the following experiments were undertaken. Specimens of undoped hematite and hematite containing titanium or calcium in solution as doping agents were reduced to magnetite in CO-CO2 mixtures. In addition, electrical-conductivity measurements were correlated with the reduction kinetics using concepts of defect solid-state chemistry. EXPERIMENTAL Fisher certified Fe2O3 powder was used to make specimens for both the electrical and kinetic studies (see Table I for analysis). Doping with titanium and calcium was accomplished by adding TiO2 and CaO powders to the Fe2O3 powder. The powders were mixed in a Waring blender for minimum times of 1/2 hr. Satisfactory blending was achieved based on comparison of analyses of individual specimens af- ter reduction. The specimens were formed in a steel die using opposed punches with a rectangular opening 10.0 by 40.0 mm. The Fe2O3-TiO, platelets were pressed cold at 16,000 psi. They were sintered for approximately 16 hr at 1075°C in air, in accordance with information in the literature3, 4 on the time and temperature needed to obtain solution of the titanium in the hematite. The Fe2O3-CaO mixtures were first cold-pressed at 20,000 psi and sintered for 3 hr at 1225°C to insure solution of CaO. This material was then ground to -325 mesh in a 6-in. ball mill and the resulting powder was used to make platelets in the same manner as above. The sintered platelets were usually between 1/16 and 1/8 in. thick. They were ground on a carborundum wheel and polished on 2/0 paper. Typical dimensions of the kinetic-study specimens were 1.6 by 0.8 by 0.05 cm, and a typical weight was 0.3 g. Conductivity and thermoelectric specimens were approximately the same size, but were subjected to further sintering in order to ensure maximum densification. Finally, all specimens were measured to the nearest 0.0005 in. and weighed on a Mettler H-15 balance to the nearest 0.0001 g and the density calculated. The average density of the specimens used for the reduction studies was 4.87 g per cc, or 7.1 pet total porosity. The standard deviation ranged from 0.14 to 0.063 g per cc within a composition group. In the present study, the apparent surface area as measured with a micrometer was taken as the true surface area. The chemical analyses for calcium and for titanium within a group showed maximum variations of 50.04 pet from the average values used in Figs. 9 and 11. In order to suspend the specimen from the balance for the kinetic studies, a hole, 0.03 in. in

Jan 1, 1965

By A Andersen

DURING an investigation of the copper-rich portion of the copper-silicon-iron system as part of an extensive research program on P.M.G. alloys, which was begun in 1937 in the research laboratory of the Phelps Dodge Corporation, it became apparent that the binary copper-silicon system below 7 per cent Si needed revision, therefore an investiga-tion was undertaken. Both X-ray methods and microscopic technique were employed. Despite the many investigations that have the clarification of this sys-tem as their object, no two successive reports on the system have agreed in placement of the alpha-phase solubility limit, and uncertainty about the secondary phase first to appear has been voiced several times.3,4,5 It was therefore not surprising, when T. Isawa's6 and M. Okamoto's7 works were reported at the time we were finishing up our experimental work, to find essential disagreement between their results and ours. But when C. S. Smith's latest work on the copper-silicon system8 was published just as we were finishing our laboratory report, it was indeed gratifying to find that the latter's diagram and ours checked in all essen-tial features, except the temperature of the peritectic line above 830° C. Many attempts were made to retain the beta phase during the present investigation, but none was successful. Isawa,6 however, reports that he has been able to obtain X-ray photograms of the beta phase. The structure, he states, is body-centered cubic with a lattice constant of 2.848 A.. at 7.2 per cent Si. Okamoto7 and Smith8 both use the designation Kappa for the hexag-onal phase, and to avoid confusion this designation will be adhered to in the present paper.

Jan 1, 1939