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By Willis Burns

I. INTRODUCTION. These notes are submitted, not as a discussion of the modern practice of electrolytic-copper refining, but as the record of a refinery that was among the pioneers in the field and that is to-day, and has been for 17 years, operating under conditions not to be found in any similar plant in the country. I refer to the current density, which is at least 60 per cent. higher than that regularly employed elsewhere, and to the fact that the anodes treated are the direct product of the converter rather than of the reverberatory furnace. The writer has no knowledge of any other refinery treating anodes of this character.

Jan 8, 1913

By C. W. Volek, G. Mandl

Steam-injection tests in the field have shoum that heat transport into the oil/water region, ahead of the steam zone, may have a significant effect on the production process. Earlier theoretical work on reservoir heating by hot-fluid injection can be used to describe the growth of the steam zone, but only if heat transport from steam zone into oil/water region is neglected. It therefore became necessary to re-examine and extend the earlier theory. It was found that this theory ceases to be consistent with the physical model of the process at a certain critical time, tc, which depends on reservoir thickness, temperature, and quality of the steam. The critical time marks an important change in the heat flow across the condensation frovt: the heat flow, which is purely conductive during 0 < t < tc&apos; becomes predominantly convective at t = tc. Accordingly, at t = tc, the equation which governs expansion of the steam zone changes. On the basis of the new equation, an approximate description for the steam-zone growth during t > tc is developed by making use of upper and lower bounds for the exact solution of the problem. The boundary conditions for heat and mass flow inside the oil/water region are established, and a simple method of detennining the saturation at the downstream side of the condensation front is presented. Experimental results show that the theory gives an accurate description of steam-zone expansion before the critical time. At times near critical time, and also after critical time, experimental data show theoretical steam-zone volumes to be high. Even so, the accuracy of the calculated steam-zone volumes is sufficient for practical purposes. THEORY OF STEAM-ZONE GROWTH INTRODUCTION The engineering evaluation of steam-drive processes is based mainly on a mathematical description of reservoir heating by hot fluid injection presented several years ago by Marx and Langenheim.l This theory can be used to determine the growth of the steam zone,2 provided the flow of heat from the steam zone into the liquid zone ahead of the condensation front (Fig. 1) is neglected. Since we must expect, however, that heat transport into and inside the liquid region (the region between condensation front and production wells) will affect both the water/oil flow and the growth of the steam zone, it is necessary to re-examine and to generalize the Marx and Langenheim theory as applied to steam drive, which will hereafter be termed the "old" theory. Observations made in several field tests emphasize the need to study the heat flow across the condensation front (CF). On several occasions it was discovered that heat was transported in the liquid zone far ahead of the advancing CF, resulting in an early breakthrough of warm water. This seems to occur most often when high injection pressures are applied, when "wet" kONINKLIJKE/SHELL EXPLORATIE EN PRODUKTIE LABORATORIUM RIJSWIJK, THE NETHERLANDS SHELL DEVELOPMENT CO. HOUSTON, TEX.

Jan 1, 1970

By William J. Millard

The Island of Trinidad has much the same geological history as the continent of South America. There are present in this area Cretaceous, Tertiary and Quaternary rocks, which were deposited in a basin covering eastern Venezuela and Trinidad, very much as rocks of the same age were deposited in the Maracaibo Basin in western Venezuela. Along the north coast there are metamorphosed and semimetamorphosed Cretaceous rocks which are found as semicrystalline limestone, schists and quartzites, etc. Both the Cretaceous and Tertiary rocks are petroliferous and are responsible for the production of oil in Trinidad and eastern Venezuela. The geological column in the oil-bearing region of Trinidad is shown below.

Jan 1, 1931

By Gerhard Derge

THE chemical and physical properties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use, These processes are carried out at high temperatures and involve such complex chemical systems that fundamental scientific knowledge of the properties and behavior of these slags is inadequate. Various hypotheses have been proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenck1 and the recent papers of Chipman and co-authors.2-5 Another proposal is that these compounds dissociate by completes or partial ionization, the evidence for which has been reviewed by Martin and Derge.7 Whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: I, Studies of solidified slag samples by X-ray diffraction, petrography, and similar methods that can be used at room temperature, The correlation of this information with the high-temperature properties of the molten slag is uncertain, 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature, However, even these data present problems of interpretation because they require a complete knowledge of the metal phase, 3, Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret, Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information, The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems CaO-SiO2 and CaO-A1203-Si02 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1946

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-&apos;; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann&apos;s and Planck&apos;s constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By W. L. Remick

THE hydrotator coal-cleaning process was developed as an economic necessity to meet the ever-increasing demand for an inexpensive method of cleaning coal down to the sizes ordinarily referred to as "dust." As the most urgent demand seemed to be in the anthracite field, all experimental work has been conducted in that territory during the past 2 years, with the exception of a few months during the strike of 1925-26, when some experiments were performed in the Alabama bituminous fields. The first commercial plant was constructed at the Middle Creek Colliery of the Philadelphia & Reading Coal & Iron Co., Pottsville, Pa. This plant is now operating. APPLICATION The field of application of the process is: 1. Cleaning anthracite fines, ordinarily described as "slush" or "silt." Slush contains all sizes from %2 in. down to and including "dust." (Anthracite passing a 32-in. mesh is also referred to as No. 2 Barley and No. 4 Buckwheat.) 2. Cleaning sizes too fine for recovery by other methods. 3. Removal of coal from sand circulated in the Chance sand-flotation process. 4. Cleaning of bituminous sizes. from 3/8 in. down to "dust. 5. As equipment for the performance of the froth flotation process. 6. Other separating, extraction and _washing. processes which may be considered outside the realm of coal cleaning. PRINCIPLE OF OPERATION Fig. 1 shows the method of classification practised under the Hydrotator patent:1 In coal cleaning the machines are operated as "hindered settling" classifiers, the flow of solids and liquids being so controlled that the units may be combined in series.

Jan 1, 1927

By Russell W. Dayton

THE metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concerning the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory - is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chalcography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Königsberger, (1)‡ in 1909, was the first to apply polarized light to the microscopic study of

Jan 1, 1935

Gentlemen.-It is pleasant to be able to report that the year just closed has been a prosperous and successful one for the Institute. As is shown by the reports of the Treasurer and the Finance Committee, the business affairs of this organization are in excellent condition. With property valued at more than three-quarters of a million dollars, and with considerable sums in various funds and endowments, it is possible to spend on each member of whatever class $22.65 each year, more than the maxi- mum amount of dues received from any one, and substantially twice the average amount, $10.94, received from all. To do this has required close management and a strict regard for our limitations. In 1926, when the Budget was made up, the estimated expenditures for the work which it was felt the Institute must do exceeded the estimated receipts by some $14,000. At the close of the year, despite a number of unexpected decreases in receipts, it had proved possible to accomplish substantially all the work laid out and close the books with the usual transfer of initiation fees to the General Reserve, and still only reduce the cash balance $2,074.54. This was made possible by the hearty and loyal cooperation of the whole staff of employees and the extremely large amount of gratuitous service rendered by the officers, the members of the Divisions and technical Committees, and the membership generally. Even so it was impossible, because of limitations of funds, to undertake many things it is highly desirable for the Institute to do, and it was necessary to refuse the publication of important papers and committee studies, because of the lack of funds. PUBLICATIONS In an analysis of the income and expenses of the Institute published in the February issue of our Journal, MINING AND METALLURGY, it was pointed out that the largest item of expenditure is, as it should -be, for publications. Printing, binding, and distributing the various technical papers sent to the members cost in 1926 more than all the money received from dues, including the portion allocated as subscription to the magazine. Within the. year, the following volumes were printed and, with the exception of the second volume of TRANSACTIONS, which was mailed in January, were distributed : TRANSACTIONS, Volume 73, 1241 pages, covering papers on non-ferrous metallurgy, milling and concentration, non-metallic minerals, iron and steel, and the Institute of Metals Division papers read at the

Jan 1, 1928

By W. E. Keck

THERE is a considerable tonnage of iron ore in the Menominee Range Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a rela-tively large quantity of finished concentrate would be obtained (deleteri-ous sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beneficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal min-erals in a nearly puree state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,000&apos;. Of this quantity and value, Michigan produced approxi-mately 19 per cent4. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1937

By W. E. Keck, Paul Jasberg

THERE is a considerable tonnage of iron ore in the Menominee Range of Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a relatively large quantity of finished concentrate would be obtained (deleterious sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beiieficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal minerals in a nearly pure state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,0001. Of this quantity and value, Michigan produced approximately 19 per cent4. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1937

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht&apos;s conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.&apos;, &apos; .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.&apos; Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By J. P. Neumann, Y. A. Chang

Lattice parameter measurements of the hcp phase in the system Ag-A1 near the stoichiometric composition Ag2Al were carried out for specimens quenched from 825°K, annealed for 10 days at 453°K, and annealed for 100 days at 413°K. The three heat treatments resulted in the same lattice parameters at room temperature. None of the specimens showed any superlattice lines. The lattice parameters of this alloy were also measured at temperature from 77° to 750°K. An anomaly in the temperature variation of the lattice paramete.rs occurs in the region near 400°k, which may be associated with local ordering. FROM measurements of the diffuse scattering of X-rays, it is known that the [ phase in the system Ag-A1 near the stoichiometric composition Ag2A1 ex- hibits a considerable degree of short-range order at room temperature.&apos; Moreover, based on the position of the short-range order peaks a superlattice model had been proposed in the same study and it was suggested that lowering the annealing temperature to 420°K might result in long-range order. In the present study, the diffraction patterns and the lattice parameters of three differently heat-treated specimens, i.e., quenched from 825°K, annealed for 10 days at 453°K, and annealed for 100 days at 413°K, were determined from 77" to 750°K. The purpose of these measurements was to investigate 1) whether long-range order could be established by prolonged annealing and 2) whether the lattice parameters at room temperature depended on the heat treatment, since it had been proposed earlier2 that the lattice parameters in this phase are related to the atomic arrangement. 1) EXPERIMENTAL TECHNIQUES Silver and aluminum, both 99.99 pct purity, were melted in a zirconium oxide crucible under helium in

Jan 1, 1969

By L. S. Darken

IT has been known for sometime that in an ionic lattice, such as that of Ag2S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulfide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulfide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall1 support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffusion proposed by several authors, most recently by Birchenall and Mehl.2 This theory has, however, also been questioned3.4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however, Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz,5 who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a similar mechanism, whatever it may be, at a greater or lesser rate, thus giving rise

Jan 1, 1948

By J. W. Downey, M. V. Nevitt

The phase boundaries for the 950" isothermal sections in the ternary systems Zr-Co-0 and `Zr-Ni-0 have been determined for the composition range from 50 to 100 at. pct Zr. The two systems show very similar phase relations, having no extensive solid solution phase fields. Each contains a ternary phase. These phases are apparently isostructural, but their structure has not been determined. Some aspects of the phase relations are discussed in terms of the alloying behavior of transition metals. THE work described in this paper is the outgrowth of a recent study of the occurrence of phases having the Ti2Ni-type structure (structure-type E9,) in certain ternary systems involving Ti, Zr, or Hf with another transition metal and O.", In the Zr-CO-0 and Zr-Ni-0 systems no Ti2Ni-type phases were found to occur. However, there are several interesting aspects of the phase relations in the two systems which have significance from the point of view of the alloying behavior of transition metals. The results of this investigation may also have some importance in studies of the oxidation of Zr-Co and Zr-Ni alloys. In both the Zr-Co-0 and Zr-Ni-0 systems only the 950" isothermal sections were investigated and, as a further restriction, the study was limited to the composition range from 50 to 100 at. pct Zr. A tentative Zr-Co binary diagram has been published by Larsen, Williams, and Pehin. In the composition range pertinent to the present work they report a eutectic at 980°C and 75.9 at. pct Zr, the products of which are the terminal solid solution based on /3 Zr and the compound Zr2Co, and a eutectic at 1080" and 64.8 at. pct Zr whose products are Zr,Co and ZrCo. The solid solution based on /3 Zr is shown to decompose eutectoidally at 826°C into a Zr and Zr2Co. The limits of solubility of Co in a and /3 Zr have not been established. The structure of Zr2Co is not identified in the publication just cited. Dwight has reported that ZrCo has the CsC1-type strcture. The Zr-rich portion of the Zr-Ni diagram has been determined by Hayes, Roberson, and Paasche." The phase relations are very similar to those of the ZrCo system. A eutectic reaction whose products are /3 Zr containing 2.9 at. pct Ni and Zr,Ni occurs at 961°c, and a eutectic between Zr,Ni and ZrNi is found at 985". The solid solution based on /3 Zr decomposes eutectoidally at 808°C. The solubility of Ni in a Zr is not known accurately but is believed to be very small. Smith, Kirkpatrick, Bailey, and Williams7 have found that Zr2Ni has a tetragonal structure of the A1,Cu-type and that ZrNi is orthorhombic. Domagala and McPherson8 have published a constitution diagram for the system Zr-ZrO,. At 950" their diagram indicates that the solid solution of 0 in 0 Zr is stable from 0 to 0.5 at. pct while the phase field of 0 in a Zr extends from 6 to 29 at. pct. These solubility limits were adopted in the present study and no binary Zr-0 alloys were made. No previous data on the phase diagrams of the ternary systems are known to exist. EXPERIMENTAL PROCEDURE The experimental details involved in the preparation of alloys in this laboratory by arc melting have been described in several previous papers"3 and they will not be repeated here. Information concerning the purity of the metals used is given in Table I. Oxygen was added in the form of reagent grade ZrO,. All of the cast specimens in both alloy systems were annealed in air-atmosphere tube furnaces at 950 3&apos; for 72 hr and water quenched. The specimens were protected from oxidation by wrapping them in Mo foil and sealing them in quartz tubes that had been evacuated at room temperature to a pressure of 1 x 10B mm of Hg. The phase boundaries were determined by metallography, and identification of the phases was accomplished primarily by X-ray diffraction methods which employed a powder camera having a diameter of 114.6 mm. The diffraction techniques which are in use in this laboratory have been previously described.&apos; An etchant that proved satisfactory for most of the alloys consisted of 5 pct by vol of AgNO

Jan 1, 1962

By C. E. Birchenall, R. H. Condit, M. J. Brabers

In the oxidation of pure iron above 700°C the overall rate is determined mainly by the rapid growth of wiistite, through which iron ions can diffuse rapidly.&apos; Nickel added to the iron progressively decreases the stable range of composition of wustite.&apos; When enough nickel is added to eliminate wiistite as a stable phase, the spinel is the fast growing phase. This investigation was undertaken to test the hypothesis that nickel substituting for iron in magnetite might decrease the rate of spinel growth by reducing the iron mobility. Nickel ferrite boules grown by the flame fusion process were purchased from the Linde Co. Chemical analysis gave an atomic ratio of iron to nickel of 2.88 and showed no other cations. They were cut into discs and ground to give flat, parallel faces. The experimental procedure employed was like that of Eisen and Birchenall in which the distribution of radioactivity diffused in from a vapor deposited surface layer was determined by counting the residual activity through a series of ground faces. The diffusivities were calculated in a manner consistent with the requirements discussed by Condit and BirchenallP The details will be given in connection with a more extensive spinel diffusion study now in progress. The results of the measurements are shown in the figure in comparison with earlier data on magnetite1 and zinc ferrite. The uncertainties arising from scatter in the activity vs distance relationship and uncertainties in the temperatures are shown by flags. Despite the scatter it is clear that substitution of a considerable part of the iron in magnetite by nickel, in this case about one third decreases the iron mobility substantially. sachs&apos; determination of the distribution of iron and nickel in scales on iron-nickel alloys appears to show that nickel is less mobile than iron in the spinel layer. It is evident, therefore, that nickel plays several roles in reducing the oxidation rate of iron-nickel alloys. 1) It reduces progressively the stability range of wiistite. &apos; 2) It reduces progressively the stability range of the iron-nickel spinel phase in terms of the variation in cation to anion ratio.&apos; 3) As shown in this investigation, it reduces the cation mobility in the spinel phase which is the faster growing phase in the absence of wiistite. The fe was obtained from the Oak Ridge National Laboratory. The research was supported by the Air Force Office of Scientific Research (ARDC) under contract number AF 18(600)-967.

Jan 1, 1961

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.&apos; It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

By F. A. Jerabek, H. L. Hartman

This study presents results of investigations in a small model of segregation in discharged fill slurry, the quantity of solids escaping in the drain liquid, and the relationship of solids to slurry concentration and discharge rate. Compressibilities of fine fill material, in dry and wet states and individual size fractions, are compared. Two terms are frequently used in describing the hydraulic placement of fill material underground: hydraulic stowing is mostly associated with the underground flushing of coarse-sized fill material, such as coal washery refuse; while hydraulic backfilling refers to placement of small-sized fill material, e.g., sand or classified mill tailings, mainly in metal mines. Characteristically, in backfilling, only a few hours may elapse between the time the material is hoisted as ore and redeposited as fill underground. Hydraulic filling was first used about 100 years ago to control subsidence in coal mines. It was subsequently adopted in many mining operations all over the world, but its basic concepts have never been adequately studied and analyzed. This is not surprising, when one considers the number of variables involved in the hydraulic backfilling operation. Recently, much work has been done on the problems of transportation of slurries in pipes. Comparatively less research work has been done concerning the physical properties of fill material (compressibility, cementation, permeability, etc.). Very little work has been done on the problems of fill placing, distribution, and segregation of fill material discharged in the mine void. It is the purpose of this paper to explore two of the basic, lesser known aspects of filling: segregation and compressibility in discharged fill slurry. Difficulties in observing the behavior of hydraulic fill slurry during the pouring operation underground, and insufficient knowledge to conduct any kind of meaningful theoretical analysis, suggest experimental model studies. The tests described in the following sections were conducted in the Rock Mechanics Laboratory of the Department of Mining at Penn State.

Jan 1, 1965

Herewith are transmitted the joint report of the Treasurer and Finance Committee for 1934 and the reports for the same year of the Chairmen of the following Committees: Admissions, Membership, Papers and Publications, Library, and MINING AND METALLURGY. TO these reports you are referred for details of the year&apos;s activities. Finances.-Income for 1934 from all sources totalled $134,967 com- pared with $121,689 in 1933. The increase is accounted for principally by four items: $6000 increase in initiation fees and dues of new members; $1800 in current dues; $4000 in "back" dues; and $2800 in the sale of publications, including TRANSACTIONS volumes and technical papers in the form of "separates." In passing, it may be remarked that income from back dues during 1935 will be less than in 1934, for the obvious reason that the total amount of dues in arrears has shrunk and consequently there is less to draw from. Income from

Jan 1, 1934

By A. J. Opinsky, J. L. Orehotsky, L. L. Seigle

TUNGSTEN incandescent lamp filaments possess a typical structure of elongated crystals generated upon heating the silica-alumina doped wire rapidly to 2200°C or above.&apos; It is known that these very long grains exhibit a preferred orientation, but there is disagreement in the literature about the direction. Rosi,2 and later Rieck; reported that the <135> direction of the large grains in doped wire tends to be parallel to the wire axis, but other investigators have reported that <110> is the preferred direction. Some further investigation of the orientations of large grains in tungsten wire is reported in the following. In the first series of experiments, 6-in. lengths of wire were heated rapidly in a bell jar. Current was passed through the wires and within 15 sec the wires had reached the grain coarsening temperature. 2 min was the annealing time. Wires were heated in hydrogen, nitrogen, and vacuum. Later, wires were heated in an evacuated tube furnace in which the tube was brought from 1000°C to the operating temperature within 25 sec and held 5 min at temperature. Temperatures were measured with an optical pyrometer. After heating, the wires were electro polished and etched, and the orientations of the large grains determined by the Laue back-reflection technique. Most of the experiments were carried out on a single spool of 5-mil silica-alumina doped wire, but a few tests were made with 5-mil thoriated tungsten wire and 10-mil undoped wire. 5-mil silica-alumina doped wires were reduced to smaller diameters by electropolishing for one series of experiments. Orientations of the large grains in silica-alumina doped wire heated in various atmospheres are presented in Figs. 1 and 2 as plots of the direction of the wire axis relative to the cube axes of the crystals. For most of the conditions studied, the preferred orientation cannot be described as a single direction, but the points might be said to group themselves about the arc passing through <110> and <113>. This arc is the trace of the (211) planes and contains the <135> and <124 as well as <011> directions previously observed by other investigators. The preferred orientation of large crystals in silica-alumina doped tungsten wire might be most generally described, therefore, by stating that a (211 ) tends to be parallel to the wire axis. This is true also for wires reduced in diameter by etching and furnace heated, Fig. 2, i.e., the recrystallization texture is apparently unchanged upon removal of the outer layers and substantially independent of the temperature gradient within the wire.

Jan 1, 1962

By F. W. Bloecher, A. M. Gaudin

Using an adsorption-column technique the partition of dodecylamine between quartz and water has been determined at concentrations ranging from 0.5 to 4000 mg per liter. The adsorption varies as the square root of the concentration. Attachment of dodecylamine to quartz is reversible. The amount adsorbed in a flotation operation giving almost complete recovery is under 5 pct of the amount required for a monolayer.

Jan 4, 1950