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By Gordon L. Kinney

The only economically important mineral currently produced in Bangladesh was natural gas. Bangladesh was not a world? ranked producer of any mineral commodity, but the possibility of producing and exporting commercial amounts of liquefied natural gas (LNG) was being examined. Proved reserves of natural gas were sufficient to supply most of the country's industrial and domestic heating and electric needs and still support an export-oriented LNG plant. Other mineral production was of virtually no significance to the economy, although there were a few prospects for nonmetallic mineral development. Bangladesh continued to make economic progress during 1978 and into early 1979. Gross domestic product (GDP) at current prices rose from $6.6 billion in 1976-772 to $8.2 billion in 1977?78 and $9.3 billion in 1978.79.2 In fiscal 1979, the economic conditions were favorable until a severe drought hit most of the country. It W88 reported that conditions were the worst in 40 years, and 88 of July 1979, substantial crop losses were predicted. The agricultural sector accounts for over 53% of the GDP and about 75% of all employment. The poor weather will cause economic problems in the form of slower growth, larger trade deficits, and a higher rate of inflation. The 1978.79 statistics showed that real GDP increased just 4%.

Jan 1, 1981

By Gerald Edmunds

The liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the composition of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. Apparatus By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 13/4-in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 181/2 in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By M. Cohen, R. T. Howard

The purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature transforrnations have been summarized recently by Troiano and Greninger.' Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation (Mg) during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transformation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metal-lographic3 and dilatometric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Stewardi have shown that the Greninger-Troiano metallographic technique8 may be used not only for M, determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below M, in fourteen commercial steels. In the present paper, the Greninger-Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M., thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. Experimental Details Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M. temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1949

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments. and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table I are reported the compositions of the core and cladding alloy for the material used for the experiments. Table i.—Chemical composition of R~OI Used for the Experiments Element Core Cladding Cu........................ . 0.01 Fe......................... . 0.42 Si......................... 0. 0.71 Mg........................ . 0.99 Mn ........................ . 0.54 In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion. Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R~OI varies with the gauge, as shown in Table 2, several gauges were investigated. Material and Procedure he material used was sheet of the following gauges: o.o2~, 0.040, 0.064, 0.102, 0.170 Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: glo°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After zoo min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1946

By Henry Hibbard

Fox the purpose of this paper all steels will be divided into two divisions: effervescing and non-effervescing. This classification must be borne in mind as many statements true of one class are not true of the other. Effervescing steels are those that effervesce in the molds, evolving large volumes of gases, which, in escaping, throw up a spray of molten particles of steel and give the molten metal in the mold a rapid stirring or churning motion until it freezes, or, at least, becomes pasty. This effervescing is intended and proper. The non-effervescing steels, which are more or less completely killed, should not evolve any gas in the molds. Many years ago the writer proposed to call the two classes of steels evolution and solution steels, depending on whether the gases in the molds are evolved or kept in solution, but the present designations seen to be better. In America, at least, effervescing steels are in a class by themselves and include steels made for boiler, tank, and ship plates, steel pipe, soft steel wire, wire nails, soft machinery, and structural steels. These are all low-carbon steels with less than 0.40 per cent. carbon. Low-carbon steels that do not effervesce but are killed are also made; these are put into ingots and castings but they are outside the limits of this paper. Effervescing steel is cast into square or slab molds, either top or bottom poured. Most of the effervescing steel is made in the basic open-hearth furnace, though much is made by the acid Bessemer process and a little is made in the acid open-hearth. It is not made by the crucible or electric-furnace process, in which the volume of gas required cannot be produced in the steel and evolved from it in the mold to give the effervescence desired. Any steel ingot, when teeming is finished, is of a certain size or volume. Leaving out of consideration for the moment the lessening of the over-all dimensions of the ingot through contraction due to loss of heat, the ingot may be placed in one of three classes: It may settle, losing in volume; it may stand, that is, remain constant in volume; it may rise, that is, increase in volume.

Jan 9, 1919

By D. J. McAdam

As shown in three recent papers by the author,6,7,8 in two papers by McAdam and Mebs,9,10 and in a paper by McAdam, Mebs, and Geil,11 the technical cohesive strength of a metal, in any particular state as regards mechanical treatment and heat-treatment, cannot be represented by a single stress value, but must be represented by a diagram with the principal stresses? as coordinates. Each point on the boundary of such a diagram represents a technical cohesion limit. The technical cohesive strength thus comprises an infinite number of technical cohesion limits, each representing fracture under a specific stress combination. Moreover, neither the yield strengths nor the ultimate strength can be represented completely by a single stress value, but must be represented by a diagram with the principal stresses as coordinates. All combinations of the principal stresses may be classified in three groups as illustrated by Fig. I. Fig. Ia shows three typical stress combinations with no two principal stresses equal. The magnitude of each principal stress is indicated qualitatively by the length of the arrow. Arrows pointing away from the cube indicate tensile stresses; arrows pointing toward the cube indicate compressive stresses. Typical stress combinations with two principal stresses equal are illustrated in Figs. Ib and Ic. Such stress combinations would be produced by subjecting a cylinder to combinations of uniform axial and radial stresses. The uniform radial stress may be resolved into two equal principal stresses, with the mutually perpendicular directions rotatable around the axis of the cylinder. Fig. Ib shows stress combinations with S2 equal to Sa. The greatest principal stress is in the axial direction, and the stress combination tends to cause either absolute or relative increase in length.* Fig. Ia shows stress combinations with Ss equal to Sl. The greatest principal stress is in the radial direction, and the combination tends to cause either absolute or relative decrease in length. The complete representation of either technical cohesive strength, yield strength, or ultimate strength generally requires a three-dimensional diagram. When two of the principal stresses are kept equal, however, the strength of a metal may be represented by a two-dimensional diagram with the coordinates representing the axial and radial stresses.6-11 In this paper, attention will be confined almost entirely to stress combinations with two of the prin-

Jan 1, 1944

By Alexander L. Field

The rate of elimination of carbon largely controls the time required to make a heat of steel by the basic open-hearth process and to an important degree determines the cost of refining. Practical experience has led to the generally accepted belief that the use of slags relatively high in iron oxide, such as are required to bring about rapid refining, leads to a certain sacrifice of quality in the product. As a consequence, a compromise must be made between the exceedingly slow rate of carbon drop which would correspond to the ideal case and the rapid rate which would best satisfy the condition of minimum cost. An increase in rate of refining necessarily implies an increase in the concentration of iron oxide dissolved in the metal. However, even for the infinitely slow rate that corresponds to slag-metal equilibrium, the metal would contain a certain definite concentration of dissolved iron oxide. It is a matter of great practical importance, therefore, to determine the quantitative relation between the minimum or equilibrium concentration of iron oxide in the metal and the higher concentrations which must actually obtain in practice. The present paper is devoted to the development of certain equations, derived from the established laws of physical chemistry, which will enable this relation between rate of refining and the degree of oxidation of the metal bath to be computed from operating data. So attempt is made to exhaust the possibilities of this general method of treatment. In considering rate of refining, attention is mainly confined to rate of carbon elimination. However, the equations are of a more general nature and their application may readily be extended. The results of the preliminary calculations given herein indicate that increased rate of refining may have a decided effect in increasing the concentration of iron oxide dissolved in the metal. The uncertainty which attaches to the calculated value for this relationship arises in part from probable errors in experimental data on which the calculations are based, and in part from the lack of complete or favorably disposed information on basic open-hearth practice. When the relation between rate of refining and degree of oxidation of the metal has been more accurately established than has been done in the present paper, it will then become possible to consider what comprises

By M. Cohen, R. T. Howard

The purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature transforrnations have been summarized recently by Troiano and Greninger.' Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation (Mg) during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transformation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metal-lographic3 and dilatometric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Stewardi have shown that the Greninger-Troiano metallographic technique8 may be used not only for M, determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below M, in fourteen commercial steels. In the present paper, the Greninger-Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M., thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. Experimental Details Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M. temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1949

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments. and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table I are reported the compositions of the core and cladding alloy for the material used for the experiments. Table i.—Chemical composition of R~OI Used for the Experiments Element Core Cladding Cu........................ . 0.01 Fe......................... . 0.42 Si......................... 0. 0.71 Mg........................ . 0.99 Mn ........................ . 0.54 In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion. Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R~OI varies with the gauge, as shown in Table 2, several gauges were investigated. Material and Procedure he material used was sheet of the following gauges: o.o2~, 0.040, 0.064, 0.102, 0.170 Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: glo°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After zoo min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1946

By Gerald Edmunds

The liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the composition of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. Apparatus By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 13/4-in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 181/2 in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

By H. Siebel, N. A. D. Parlee

MIZIKAR, Grace, and parlee' studied rates of absorption of oxygen in stagnant liquid silver in a new type of open-ended gas-liquid metal diffusion cell, where the capillary diameters used were 1.5, 2, and 3 mm. They reported that the rates appeared to be controlled by the rate of diffusion of oxygen atoms in liquid silver and they used their data to arrive at the following equation as a reasonably good representation of the diffusivity (D) of oxygen in liquid silver: D = (14.7)10-4 exp (-7100 ± 3200)/RT cm2/sec Since this type of diffusion cell offers a promising method of measuring diffusivities of gas atoms in liquid metals, the senior author of this note and his students are carrying on a critical examination of the method, and are attempting to improve and extend the technique. The research reported briefly here was designed to examine more carefully the earlier conclusion1 that the absorption rate is diffusion-controlled, and to find out whether the diameter of the cell could be greatly increased and thus extend the method to systems where gas solubilities and diffusion rates are much smaller than in the case of oxygen in silver. For the purpose of these experiments, the open-ended capillary cell used by Mizikar, Grace, and Parlee was replaced by a small cylindrical crucible (1 to 1.7 cm in diam) containing pure silver (to a depth of 1.3 to 3 cm) resting in the bottom of a closed-ended vertical quartz tube, with an evacuated quartz filler tube just above the crucible to reduce dead volume. The method of measuring the rate of absorption was otherwise very similar to that of Mizikar, Grace, and Parlee and all the same precautions were taken. A much smaller and shorter tube furnace was used for heating, but simi- lar precautions about temperature gradients were observed. This technique was nothing more than the application of a Sieverts apparatus to the measurement of rates of absorption in small crucibles of stagnant liquid silver. In each run the volume of gas absorbed (V) was plotted against the square root of time (vt) and apparent diffusivities were calculated from the slope of the line, as described by Mizikar, Grace, and parlee.' Care was taken to use only the data obtained during the early part of the total absorption period while the cell functioned as one of infinite depth. The results at 1000°C are summarized in Table I and Fig. 1. The following conclusions may be drawn: 1) Diffusion cells up to 1.7 cm in diam yield, within experimental error, the same values for the diffusivity of oxygen (D) as the capillary cells of 1.5, 2, and 3 mm in diam employed by Mizikar, Grace, and Parlee. Cell diameters as large as 1.7 cm are probably not desirable for the most precise work. Intermediate sizes, perhaps 0.5 cm, will be most practical. 2) All absorptions measured were consistent with a model where the rate is controlled by the diffusion of gas atoms in the metal. The fact that runs at absorption pressures ranging from 0.1 to 1 atm (at any one temperature) give

Jan 1, 1965

By Y. H. Liu, R. Kiessling

The chromium, iron, and tungsten borides have been treated with ammonia at different temperatures. They are attacked, forming metal nitride and boron nitride, and the results are summarized in the tables. In the tungsten-nitrogen system a new phase has been observed, closely related to the known ß phase. THE present investigations were begun to determine whether any ternary phases exist in the transition metal-boron-nitrogen systems for the metals chromium, iron, and tungsten. Attempts to prepare such phases were made by using the borides of the metals as starting materials and ammonia as the nitriding agent. Although no new ternary phases have been found to exist, the results may be of some interest with regard to the technical use of the borides. General Procedure A steady stream of dry ammonia was passed through a silica reaction tube, the central part of which was kept at the reaction temperature while its ends were water-cooled. Weighed amounts of the borides were placed in a silica or porcelain boat and heated at different temperatures for a period of 10 to 24 hr. The boat was then rapidly removed from the reaction zone to the quenching zone, the water-cooled end of the tube, by means of a simple magnetic device. The nitrogen content of the products was determined by the increase in weight of the specimens, and the phase analysis was carried out by X-ray methods. For this analysis a Guinier-type camera, constructed at this Institute, was used with a bent, ground quartz crystal monochromator. The general reaction, which occurred in all the experiments, may be summarized as: metal boride + nitrogen -* boron nitride + metal nitride For the higher temperatures pure metal was formed instead of metal nitride. It is sometimes difficult to Discussi detect boron nitride among the reaction products by X-ray methods. Prolonged exposures of some specimens showed, however, that the strongest reflections of boron nitride were present. Additional evidence for its presence was given by the increase in weight of the specimens after nitriding. This increase was always greater than that corresponding to nitride formation only and was often in close agreement with the formula given above. Finally, a white powder, which was shown by X-ray methods to be boron nitride, was left if the reaction products after nitriding Fe,B at 448°C and FeB at 768°C were dissolved in diluted sulphuric acid. Ch rom iu m - Boron - N itrogen Five phases have been found to exist in the Cr-B system,' , and all were used as starting materials. Investigations on the Cr-N system have shown the existence of two nitrides with ideal composition Cr,N and CrN.".' * The results are summarized in Table I. All the borides are attacked and decomposed into chromium nitride and boron nitride, and the kind of nitride formed depends only on the temperature and not on the boride used as starting material. The lowest reaction temperature, however, is different for the different borides. Thus the 6 phase begins to react at about 735 "C, the r phase at about 800°, the S phase at about 900°, the 7, phase

Jan 1, 1952

By Oscar Weiss

An aerial magnetometer survey was carried out by the author's geophysical organization over the Vrede-fort dome, where Witwatersrand beds are wrapped around a granite plug 25 to 30 miles in diameter. The well-known magnetic shales of the Lower Witwatersrand system (to be referred to as LWW) give strong negative anomalies over the out-cropping portion of the dome. This is unusual as these same shales cause positive anomalies over large areas near Johannesburg and along a strike of 130 miles between the East Rand and Klerksdorp. It is suggested that the negative polarization is caused by heat and stresses connected with the doming. This negative polarization of sedimentary beds, which usually cause positive anomalies, is a good example of how "magnetic lows" can be caused by "structural highs." Significant magnetic anomalies should be tested by gravity and seismic methods irrespective of the sign of the anomalies. South of the line X — Y (see Fig 2 and 5) the gravity anomalies are smaller over the LWW beds and magnetic anomalies suddenly become weaker and even change signs by becoming positive. This peculiar phe- nomenon is explained by faulting which truncated the nearly vertical LWW shales at depth. In this manner the mass of the LWW beds has been reduced together with the weakening of the negative magnetic anomalies by positive poles which occupy the truncated end. Furthermore, by uplifting the beds between f1 and f2 (Fig 2) positive polarization becomes predominant, thus causing positive magnetic anomalies. General The Vredefort dome is one of the internationally known geological structures, which, among others, has attracted the attention of numerous American geologists. It was for this latter reason that our aerial magnetic results over this structure were selected by us for publication in the United States of America. A full description of the exposed geology has been published by Nell and readers are referred to this paper, which is subject to only slight modifications inasmuch as the subdivision of the Witwatersrand system (to be referred to as WW system) is concerned. The Vredefort dome is about 60 miles southwest of Johannesburg. The WW system, after being exposed in the vicinity of Johannesburg, plunges with southerly dips beneath the Vent-ersdorp and Transvaal systems. Along a section southwest from Johannesburg, as shown diagrammatically in Fig 4, we see no outcrops of the WW system until the Vredefort dome, where the Upper and Lower WW system are wrapped around an almost circular arc of a granite mass. Here the whole WW system is overturned around the perimeter of a huge granite plug 25 to 30 miles in diameter. Less than half of the circumference of this dome is exposed; the rest is covered by Karroo dolerites and sediments. The determination of the exact shape of the concealed part of the dome has been a matter of considerable interest and obviously geophysical methods were eminently suited for obtaining this information. A good start was made with a gravimeter survey carried out by the Geological Survey of the Union of South Africa.2 Our own

Jan 1, 1950

By J. W. Hickman

INTRODUCTION RECENT work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of. these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution-type over-the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions.1 In. order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where Cu+ is 0.96Å and Ni-++ is 0.70Å, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with electrons. This composition in the copper-nickel alloys corresponds to 40 at. Pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is filled at 6o at. pct copper or 4o at. pct nickel. Mott and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel -has the-configuration: 3d8 4s2 and copper: 3 d10 4s) then at 60 at. pct copper or 4o at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may' exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. SURVEY OF LITERATURE The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1948

By B. Post, D. Moskowitz, F. W. Glaser

Lattice parameters of various hafnium compounds, two borides, a carbide and a nitride were determined. Some physical properties were measured and comparisons with the properties of the corre-sponing zirconium compounds were drawn. A LTHOUGH borides of transition metals have A been extensively investigated in recent years, there are few references in the literature to borides of hafnium. This is not surprising, in view of the extreme scarcity and great cost of the purified metal. Becker' reported the existence of a boride, carbide, and nitride of hafnium; he listed the formulas as HfB, HfC, and HfN. However, in his work no mention was made of chemical analyses of the reaction products. In this paper results of a study of various hafnium compounds, including borides, carbides, and nitrides, are reported. It was expected, of course, that these compounds would closely resemble their zirconium analogues, which have previously been extensively investigated. Three borides of zirconium are known: ZrB,² ZrB,² and ZrB212.4 In addition, one carbide, ZrC,5 and one nitride, ZrN,5 have been reported. It should be noted that ZrB and ZrB12 are stable phases only in relatively high-temperature regions, unlike ZrB2, which is stable from room temperature to its melting point." It was felt that hafnium would yield corresponding borides, carbides, and nitrides with similar stability ranges. Experimental Procedures and Results A quantity of hafnium metal that was better than 97 pct pure, with zirconium as its major impurity, was furnished by the Argonne National Laboratories. The boron powder used was approximately 96.5 pct pure. In general, the procedure involved mixing the metal and boron powders in the desired proportions, and subsequently hot pressing them. The resulting specimens were analyzed chemically and phases present were identified by X-ray diffraction methods. A Philips Norelco Geiger counter spectrometer was used for identification of components and for measurement of lattice constants. Filtered copper radiation was used for all X-ray work. Electrical resistivity and density measurements were carried out at room temperature. The stable diboride, HfB2, will be described first. Stoichiometric quantities of boron and metal were heated to approximately 2000°C during hot pressing. The reaction product was shown by X-ray diffraction methods to be isomorphous with ZrB2 (space group Dlgh; P6/mm). Values of lattice constants of HfB2 compared with those of ZrB2 are shown in Table I. The calculated density of HfB2 is 11.2 g per cc, compared with a measured (pycnometric) value of 10.5 g per cc. HfB2 specimens prepared under a wide variety of conditions (including variations in initial Hf-B ratios) showed only insignificant variations in lattice constants, indicating a very narrow range of homogeneity. Like ZrB2,7 HfB2 is an excellent electrical conductor. The resistivity at room temperature of hot-pressed samples, approximately 85 pct dense, is 12 microhm-cm. This compares favorably with the electrical resistivity of 10 mi-

Jan 1, 1954

By M. J. Sinnot, J. C. Shyne

Low-frequency mechanical damping measurements were made to investigate internal friction in Fe-A1 alloys. The atomic ordering of the Fe-A1 system strongly influenced the stress-induced ordering internal friction. Magnetoelastic damping was also encounteyed and was shown to be reduced by the application of a static stress. THIS paper describes some damping experiments made on alloys of Fe and Al. Stress-induced ordering internal friction was measured with samples containing from 9.8 to 31.3 at. pct Al. Aluminum is soluble in a-Fe to about 50 at. pct and forms at least two long-range ordered structures, Fe3Al and Feu.' Stress-induced ordering internal friction is known to occur in many substitutional solid solutions, but few measurements of this damping effect have been made with alloy systems that have pronounced ordering tendencies. LeClair and Lomer developed expressions relating the relaxation strength of the damping process to the degree of atomic ordering and predicted that stress-induced ordering internal friction would be zero with complete ordering.' This concept was confirmed experimentally by Lulay and Wert using the system cd-Mg It is also consistent with the weak stress-induced ordering peaks observed in P -brass by Artman and in 16 wt pct Al Fe-Al by bert.' It was expected, therefore that the ordering characteristics of the system Fe-Al would strongly influence the stress-induced ordering internal friction exhibited by the experimental alloys. SAMPLE PREPARATION The alloys used in this investigation were induction melted under vacuum using high-purity melting stock. The iron was electrolytically refined Plastiron 101 which contained 99.85 wt pct Fe. The aluminum was a special 99.95 pct pure grade supplied by Alcoa. The only other raw material was spectrographically pure graphite which was used in small quantities as a deoxidant. The amount of carbon used was slightly in excess of the amount required to completely deoxidize the melt; this resulted in residual carbon contents of 0.01 to 0.02 pct in the finished alloys. The vacuum cast 2 1/2-in. diam ingots were hot rolled to 5/8-in. diam round bars. Portions of these bars were hot swaged and hot drawn to 0.050-in. diam wire. Straight pieces of the hot drawn wire were slowly heated to a temperature of 1300°C in a He atmosphere. After holding for 4 hr, the samples were allowed to cool in the furnace. This annealing treatment resulted in grain growth in the samples, the final grain size being about the same as the wire diameter. The grain boundaries were oriented perpendicularly to the wire axis, giving a bamboo grain structure. The existence of a preferred orientation could not be detected in these coarse grained samples. If the samples had a fiber structure, this probably would have been the same in all samples because of similar processing, thus the influence of crystal orientation on the relaxation strength would have been similar in all samples. The aluminum contents of the alloys are listed in Table I. EQUIPMENT The principle of the torsion pendulum was used for the internal friction measuring device. The

Jan 1, 1961

By E. A. Gulbransen, J. W. Hickman

Recent work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution type over the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions~i In order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where cu+ is o.,,6-,4 and ~i++ is o.,oh;, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with elec-trans. This in in the copper- nickel alloys corresponds to 40 at. pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is flied at 60 at. Pet Or or 4O at. pct nickel. Matt and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel has the configuration: 3ds 4s2 and copper: 3 dl0 4s) then at 60 at. pct copper or 40 at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. Survey OF Literature The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1949

By B. D. Cullity, O. P. Puri

The magnetostrictia of nickel after increasing amounts of plastic elongation was measured at field strengths up to 1500 oe. In addition, the residual stress was measured by means of X-ray line shifts. The observed decrease in magnetostriction following plastic strain is shown to be associated with residual compressive stress. If a metal bar, whose longitudinal axis is taken as the x direction, is plastically elongated in the x direction and then unloaded, X-ray diffraction measurements will indicate the presence of a residual compressive macrostress 0%. However, stress measurement by means of mechanical relaxation does not reveal any macrostress. In a previous paper1 the fictitious macrostress indicated by X-rays was ascribed to a particular distribution of micro-stress, namely, one in which the bulk of the material was stressed more or less uniformly in compression and a very small portion in tension. It was shown that this distribution would account for Neurath's measurements2 of magnetic losses in silicon steel, because of the effect of residual stress on magnetostriction. The present paper is concerned directly with magnetostriction, in nickel, and with the effect on magnetostriction of the residual stress created by plastic elongation. The residual stress was determined by measurements of X-ray line shifts. MATERIAL AND METHODS Commercially pure "A" nickel was investigated. Its nominal composition, in weight percent, is 99.4 Ni + Co, 0.2 Mn, 0.15 Fe, 0.1 Cu, 0.1 C, 0.05 Si, and 0.005 S. Magnetostriction was measured by means of SR-4 electrical-resistance strain gages mounted on specimens 1/4 in. sq and 8 in. long. Magnetic fields up to about 1500 ce were provided by a multilayer, non-cooled solenoid. A considerable amount of heat was developed at the higher field strengths, and, to avoid errors due to changes in the specimen temperature, the following procedure was adopted. Each measurement of the magnetostriction X at a particular field strength H was preceded by demagnetization and an adjustment of the strain indicator to zero; the field H was then quickly switched on and the strain read immediately. Curves of ? vs H were flat for field strengths above about 750 oe for all specimens, and this constant value of X was accordingly taken as the saturation magnetostriction ?s The X-ray measurements of residual stress were made with a Norelco diffractometer on specimens cut from flat bars 1 1/4 in. wide, 1/8 in. thick, and 12 in. long. These measurements were confined to lattice planes parallel to the surface of the specimen. Two reflections were studied: the 311 CrKß line at 28 = 157 deg, and the 420 CuKal line at 28 = 155 deg. The line centers were determined by fitting a parabola to the peak of the line, as suggested by Ogilvie3 and as modified by Koistinen and Marburger.4 The CuKa doublet from the plastically elongated specimens was first resolved by the Rachinger method5. All X-ray measurements were made by counting at fixed angular positions. RESULTS The results of the magnetostriction measurements are shown in Fig. 1 and Table 1. The magnitude of

Jan 1, 1963

By T. D. Tiemann

The extraction of iron oxide from several types of siliceous iron ore by digestion in sulfuric acid solutions was investigated in the temperature range from 80 to 258°F at concentrations from 10-60% H2SO4. Degree and rate of extraction were found to be critical with respect to both temperature and acid concentration, requiring temperatures in excess of 250° F and acid concentrations of 50% to effect 80-90% extraction of iron oxide in 60 min. Rate of extraction is directly related to surface area and apparently controlled by the rate of chemical reaction. The activation energy was found to be approximately 25,000 cal per g mol. Extraction characteristics of the several ores were found to be similar. The Department of Minerals and Metals Engineering at the University of Wisconsin conducts a continuing research program to develop processes for the utilization of low-grade iron ore deposits such as the nonmagnetic taconites of the Wisconsin Gogebic range. Methods under study include high-intensity magnetic and high-tension electrical concentration, flotation, direct reduction and chemical extraction. Concentration of a number of low-grade siliceous iron ores by the extraction of silica in sodium hydroxide solutions has been reported by the writer and others in the literature.1,2,3,4 Residual concentrates containing as much as 65% iron have been obtained from taconites containing less than 30%. Currently an alternative approach is under study, namely the dissolution of iron oxides from siliceous gangue by extraction in acid, with subsequent recovery of the iron from solution. Such a process for extracting iron oxide from the low-grade oclitic deposits of Alberta with hydrochloric acid was investigated and described by Gravenor, Govett and Rigg.5 The current investigation, which is entirely devoted to extraction with sulfuric acid, is the subject of this paper. In part, the objective of this research was to determine the possibility of leaching iron ores in situ with sulfuric acid. The investigation of a recovery method is left to later research. The ores investigated contained hematite (Fe2O3) as the principal iron-bearing mineral and minor amounts of goethite (Fe2O3 .H2O), magnetite (Fe3O4), and iron-bearing silicates. The gangue was essentially quartz occurring as single crystals and microcrystalline aggregates. Detailed description of the ores may be found in the literature.1,2,4,6 A comparison of the specific ores used in this investigation is shown in the partial analyses of Table I. EXPERIMENTAL METHODS All extractions were made at atmospheric pressure using beakers with a mechanical stirrer for those tests run below the boiling point, and Erlenmeyer flasks for those at the boiling point. A thermostatically controlled hot plate was used for heating, and this maintained the mean temperature within the solution to within ±3°F during extraction. The sample of ore for extraction was weighed to + 0.02 g. For tests below the boiling point, the sample was added to the beaker containing the sulfuric acid solution at the desired temperature. For the boiling-point tests, the sample was added to the Erlenmeyer flask followed by distilled water and the

Jan 1, 1968