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By J. R. Long, T. R. Graham

THIS report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. PRELIMINARY WORK In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, 0 to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening, effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By J. B. Newkirk, A. H. Geisler

Certain of the permanent magnet alloys provide ideal systems for the study of the kinetics of the precipitation reaction and the correlation of structure with properties. One such system, Cu-Ni-Fe, was found by Bradley1,2 to exhibit a coherent transition state in the precipitation process analogous to that reported for Al-Cu alloys somewhat earlier.3 The attractiveness of some perrnanent magnet alloys for study lies in the fact that vertical sections of the ternary phase diagram in certain regions of composition (Fig I) have as their prototype the binary Ni-Au diagram. Alloys of this type decompose into products that have the same crystal lattice type but only slightly different lattice parameters. The advantages that such alloy systems oA&apos;er for study over the usual in which an intermetallic compound is formed are many: 1. Since the precipitate has the same crystal strutture as the matrix, complex atomic movements are not required to form the new lattice. 2. Similarly, complex orientation relationships are not involved for both the matrix and the precipitate would be ex. petted to have the same orientation. 3, Small &,registry of the decomposition products at equilibrium (in contrast with Cu-Ag alloys) is conducive to extensive coherent growth in the transient state and thus the transition lattice can be detected by the usual X ray diffraction methods. 4. Finally, the relative quantities of precipitate and depleted matrix can be varied from 0 to 100 pet* thus permitting wide freedom for the study of the effect of cornposition on coherent growth and properties. In the Cu-Ni-Fe alloys of appropriate composition, the face-centered cubic precipitate and also the depleted matrix when first formed are coherent with the parent matrix.1&apos;2 The two have the same <Jo parameter as the original matrix but they are both tetragonal; the precipitate has an axial ratio c/a < I while that of the depleted matrix is c/a > I. When coherency is lost they assume the normal face-centered cubic structure with the depleted matrix having a lattice parameter greater than the original matrix and that of the precipitate less. Such a mechanism would also be expected for CU-Ni-CO alloys because of the similarity in constitution but this had not been demonstrated. The Present investigation was conducted on a CU-Ni-CO alloy. The constitution diagram and magnetic properties of these alloys have been fairly well established, however, no previous determinations of mechanism of precipitation and no correlation of structure with properties had been made. Thus, an alloy of this system Was chosen for a comprehensive investiga-

Jan 1, 1949

By d&apos, L. Berenbaum, F. Heurle, R. Rosenberg

The structure of aluminum films obtained by evaporation was studied by electron microscopy, mostly by replica techniques and X-ray diffraction. The resistivities and stress conditions of the films were also determined. Film properties were studied as a function of source selection, substrate type, residual pressures of oxygen and water vapor, substrate temperature, and rate of growth. The formation of abnormal localized growths and whiskers resulting from annealing treatment subsequent to deposition was investigated. Films deposited onto single-crystal substrates were found to be epitaxially 0riented; for such films, relative orientations between films and substrates were determined. ALTHOUGH wide use has been made of evaporated aluminum films for the formation of conducting lines on semiconductor devices, relatively little has been reported concerning the structural characteristics of such films.1"9 The purpose of this study was to obtain an overall view of the dependence of these characteristics on film deposition and subsequent annealing conditions, which were similar to those used in silicon planar technology. Accordingly, most of this study was carried out using oxidized and bare silicon wafers as substrates, although some work was also done using alkali halide, magnesium oxide, and mica substrates. However, the main concern remained pragmatic. Emphasis was given to the study of the effects of deposition and annealing conditions on film characteristics such as structure, resistivity, and stress. I) EXPERIMENTAL PROCEDURES The films which were investigated in this study were deposited in 18-in.-diam glass chambers which were connected to the usual type of trapped diffusion pumps filled with silicon oil. Through the use of liquid-nitrogen-cooled Meisner traps and titanium sublimation pumps placed inside the deposition chambers, the pressure could be lowered to the lower portion of the 10- I Torr range and little increase in pressure would occur during the deposition cycle. Unless described otherwise, the substrates were 1-in.-diam p-type silicon wafers having a resistivity of 10 ohm-cm. The wafers were oxidized in wet oxygen at 975°C followed by a short dry-oxygen exposure at the same tempertture to a total oxide thickness of approximately 6000A. The wafers, backed by a layer of gallium, were mounted onto molybdenum discs brazed to a copper block.10 The latter was heated by imbedded commercial cartridge heaters. The substrate temperature could be maintained to within +10°C of a prescribed temperature during film deposition. The search for a satisfactory source for the controlled evaporation of aluminum has led to the use of 1-in.-diam crucibles" machined from rods of a commercially available, refractory composite* of Bn and

Jan 1, 1969

By G. Sachs, E. J. Ripling, S. I. Liu, J. J. Lynch

INTRODUCTION IT is a generally recognized fact that by repeated straining the fracture stress of any metal is reduced to a fraction of its value for static loading. The value of this fatigue strength depends upon numerous factors, such as the states of strain and stress, the limits of straining, and the number of repeated loadings or cycles.1.2,3 The large volume of previous investigations on fatigue is concerned entirely with large numbers of cycles, say exceeding 10,000 and up to 500,000,000. However, the changes in fracture stress and fracture strain occurring after a small number of repeated loadings have attracted little attention. Apparently the only investigations of this type are those byLudwik4,5 who subjected steel, copper, and aluminum wire to repeated torsion. In each test the torque was varied between identical values in the two directions of twisting. Depending upon the magnitude of the moment, fracturing occurred after a number of cycles, up to 10,000. The results of Ludwik&apos;s tests will be discussed later. Such torsion does not readily yield actual stress and strain values. Therefore a preliminary study was made of the effects of repeated direct stresses, i.e., tension and compression stresses. Because such tests are considerably more tedious than torsion tests, only high stresses were used in the preliminary work, yielding definite changes in metal properties after a few cycles. It was found in these tests that strains could be controlled more readily than stresses in the investigated range of high stresses. This paper, consequently, deals with the effects of strains of equal magnitude but different signs. The metal was first prestrained in static tension by a certain amount then subjected to compression to yield the same amount of strain after unloading. This loading cycle was repeated up to a maximum of seven times. After various cycles, the stress-strain curves in tension were determined, up to fracturing. As material for these tests, the aluminum alloy 24ST was selected because it exhibits a comparatively small amount of necking in the tension test. This alloy permitted, therefore, rather accurate control at the high strains necessary to produce fatigue failures at less than seven cycles. The results of this investigation appear sufficiently interesting to extend the method of attack in various directions. It is intended to study (I) the effects of cycles up to a few thousands and (2) the effects of strains of different magnitude in tension and compression, respectively. The latter variable also includes as a special case the effects of compressive strains.

Jan 1, 1948

By W. Crafts, J. L. Lamont

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,&apos; as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By J. L. Lamont, W. Crafts

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,&apos; as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,&apos; who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C&apos;. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,&apos; who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C&apos;. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By R. M. Brick

SEGREGATION can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming. steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-12 per cent Si alloys. The phasial condition implicitly described above-solidification over a range of temperatures with a compositional difference between solid. and liquid-is found in nearly all solid solutions or combinations of solid solutions and eutectics. Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually determinable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be. described first because it is an essential part of the picture. CORING Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus 1, 3, 7 and solidus 2, 5, 8, and where the vertical 1, 4, 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. 1b) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1944

By J. Rogers. K. L. Sutherland, E. E. Wark, I. W. Wark

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts &apos;he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By E. E. Wark, I. W. Wark, J. Rogers. K. L. Sutherland

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts &apos;he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By Enid C. Plante

THIS paper deals with the flotation of the mineral fluorite (calcium fluoride) and of two associated gangue minerals, calcite and quartz. The aim of the investigation was to produce "acid-grade" fluorite, which must contain less than one per cent of silica. Several reagents are used successfully in practice for floating fluorite from its ores. Oleic acid is the most widely used collector, usually at temperatures above 60°C, with sodium silicate as a dispersant for quartz and quebracho or tannin to depress calcite. Sulphides (e.g., galena) are often removed first by xanthate flotation. Many investigators23 report results in which more than 80 pct of the fluorite is recovered in a concentrate assaying 96 pct or more of fluorite and less than I pct of silica. This investigation was undertaken with the intention of floating the gangue, which is the minor constituent of the ore, from the fluorite. Hence emphasis was first placed on the cationic compounds that float quartz. No satisfactory separations were obtained in this way, and other reagents were investigated to discover whether these were more effective than oleic acid in floating fluorite from quartz in the usual way. The first part of the paper describes experiments with several long-chain collectors available commercially. Most of this work has been by captive-bubble and cylinder flotation tests, with some batch tests in a flotation machine. The second part describes the use of sodium cetyl sulphate as a collector for fluorite and includes laboratory tests and extension of the work to batch tests in the flotation machine. A method for determining the adsorption of sodium cetyl sulphate on fluorite has been developed and is described. Theory of Collection by Paraffin-chain Salts It may be assumed that these compounds are adsorbed at the mineral surface in one or more of three ways outlined by Kolthoff :12 I. Exchange adsorption between lattice ions in the mineral surface and collector ions in solution. Closely related is adsorption by the collecting mechanism postulated by Taggart,17 in which there is metathesis between the collector and the mineral cation or anion. 2. Exchange adsorption between adsorbed gegen ions (p. 67, ref. 19) and collector ions in solution. 3. Adsorption of nonelectrolytes (polarnonpolar) without displacement of adsorbed ions. With cationic collectors, inorganic cations in the solution (e.g., hydrogen ion) compete with the collector ions and therefore act as depressants, while inorganic anions have the same effect with anionic collectors. From this follows the general conclusion that ions of the same charge as

Jan 1, 1947

By C. R. Taylor, John Chipman

THE study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8: I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. EXPERIMENTAL METHOD Furnace The furnace used in this investigation differed from previous designs and may be considered a fourth modification of the original rotating furnace. Its essential features are shown in Fig. I. The outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base C are alberene stone. The coil supports D are of "Formica," a material formed from phe-

Jan 1, 1942

By D. L. Martin, E. R. Parker

IN a previous paper, one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with, and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a strengthening, so that a longer life at a given stress and temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver .2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. EXPERIMENTAL PROCEDURE Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1943

By E. P. Klier

The work of Klier and Lyman1 on the bainite reaction has led to the full description of this reaction for medium-carbon low-alloy steels. Certain experimental data reported by Klier and Lyman appear, however, to be improbable of obtaining in very high-carbon steels. The study herein reported consists of an analysis of the transformation characteristics of a 3 per cent chromium, I per cent carbon steel by means of X-ray and metallographic methods. From the results obtained it is concluded that the bainite reaction in this steel is more complicated than that reported by Klier and Lyman for the low-carbon low-alloy steels. Henever, the mechanism of bainite formation in this steel appears to be essentially the same as proposed for the low-carbon low-alloy steels with the modification that the first volumes to transform are carbon-rich rather than carbon-poor. Experimental Procedure The analysis of the steel studied was: Cr, 2.89; C, 1.02; Mn, 0.33; Si, o.35; S, 0.012; P, 0.020. The stock was received from the Carpenter Steel Co. in rolled bars. Specimen Preparation Specimens were austenitized at 1200°C. (2192°F.) for 25 min. in purified nitrogen. The resultant A.S.T.M. austenite grain size was 0-1. Isothermal transformation was allowed by quenching the specimens into liquid metal baths controlled to 5°C. at 540°C. (1004°F.) and above, and to 2°C. at 490°C. (914°f.) and below. Following the desired degree of transformation all specimens were water quenched. Metallographic Examination Specimens 1/4 in. round by 1/4 in. were used for nietallographic examination. Etch-ants used were Vilella&apos;s reagent (I gram picric acid, 10 ml. hydrochloric acid to make 100 ml. ethyl alcohol solution) and alkalinc sodium picratc (electrolytic). Vilella&apos;s reagent was effective in revealing all microconstitucnts, while the alkaline sodium picrate developed the carbon-rich structures or carbides only. X-ray Examination Two X-ray techniques were used—the Debye-Scherrer method and a back-reflection method. &apos;The small specimens necessary for the Debye-Scherrer method were austenitized and then allowed to transform, or were cut from the larger metallographic specimens. The metallographic specimens were used for the back-reflection X-ray analysis. When it was desirable to determine the structure of the carbide present, sliver specimens were electrolytically etched to develop a carbide coating, then were exposed in the cameras. This technique was frequently necessary to allow positive identification of the carbide.

Jan 1, 1945

By Lester L. Hirst, Arno C. Fieldner, Henry H. Storch

EXPERIMENTAL work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogenation of bituminous coal and tar by the Bergius-.I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 lb. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydrogenation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. EQUIPMENT AND GENERAL PROCEDURE OF RESEARCH The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By N. A. D. Parlee

THE gas-liquid metal diffusion cell technique1-3 has been used to study the diffusion of nitrogen in Fe-C alloys. The actual apparatus and technique were the same as employed by the authors to study the diffusion of hydrogen in liquid iron.&apos; The diffusion cell&apos; was formed by immersing an alumina tube in a stagnant melt contained in an alumina crucible. The tube (hereafter called absorption tube) contained nitrogen gas at 1 atm and was connected to a sensitive gas-measuring system. The change in the average concentration of nitrogen in the melt in the absorption tube was determined by measuring the rate of absorption of nitrogen in the diffusion cell. Eq. [I], 1-3 derived from the appropriate solution of Fick&apos;s second law, was used to examine the data and to calculate chemical diffusion coefficients (D) in situations where the absorption appeared to be controlled by diffusion in the liquid: where V is the stp volume in cu cm, d is the diffusion cell diameter in cm, p, is the density of the melt in g per cu cm, pg is the stp density of nitrogen in g per cu cm, C, is expressed in wt pct, D is in sq cm per sec, and t is in min. According to Eq. [I], a plot of v vs vt should yield a straight line passing through the origin if absorption is controlled by diffusion in the liquid. The slope of this line could be used to determine the value of D under appropriate conditions. As discussed in earlier reports,1,2 the initial thermal expansion of the gas upon immersing the absorption tube distorts the line in the initial stages of a diffusion experiment. However, this is not a serious problem since the slope of V vs 6 plots can be determined from the data points obtained after the initial expansion ceases. The volumes reported on the data plot presented here represent absorption after this thermal expansion ceased. Several preliminary diffusion experiments were attempted with melts of pure iron and with Fe-C alloys containing up to 0.6 pct C. In these cases, no or very little absorption was observed. The only data obtained were for an Fe-C melt which was in addition thoroughly deoxidized by successive hydrogen and vacuum-degassing treatments. These treatments introduced an appreciable amount of aluminum into the melt and reduced its omgen content. The original charge material for this melt contained 0.23 pct s and approximately 0.001 pct &. After repeated hydrogen and vacuum-degassing treatments two diffusion experiments were performed. The analysis of the melt

Jan 1, 1968

By Alexander Bowie

In many places throughout the Western mountain plateau regions of the United States coal beds in place have been burned over very extensive areas, the fire evidently originating on the nakedly exposed outcrop of the coal bed and gradually burning its way into the bed for considerable distances under very heavy cover. The surface evidences of the burned-out coal beds are seen in the calcined and discolored rocks overlying the places of the outcrops. The greater the mass of the burned coal the higher the results of its combustion can be seen in the overlying strata. I have noted many instances of this condition in the States of South Dakota, Wyoming, Colorado, New Mexipo, and Arizona. In the lignite fields of Dakota and Wyoming I noted stretches of level country many square miles in extent where the surface rooks were roasted and vitrified by the burning of a great bed of lignite lying nearly level and with a light cover; this is probably the most favorable natural condition for the burning out of a coal bed. The less the depth of the rock covering overlying the coal bed, the better the chance for a continuous supply of air to the fire; but when the coal bed dips heavily into the ground, or even if level, if it passes under a hill or mountain which gives the bed a heavy covering of strata, the fire has more chances of being extinguished from natural causes than in the first condition described. The distance which a crop fire may extend into a coal field is very much influenced by the dip, the thickness of the coal bed, and the nature of the rock covering immediately overlying it. In reasoning on this subject, it would seem logical to assume in the case of a coal-bed cropping at the base of a hill and dipping into it, with an extensive drainage surface above the crop line, that a crop fire would be promptly extinguished by the caving in of the overlying strata and the precipitation of the rainfall from the drainage surface above the outcrop through the breaks formed in the caving strata. This consideration would be more or less effective according to the climate of the location and the nature of the overlying strata. In a humid climate where the rainfall was heavy the water from the natural precipitation alone would probably extinguish a crop fire before it could work its way very far under cover, but in an arid climate this preventive does not seem to be effective.

Jan 1, 1915

By Paul A. Schafer

BALATOC mine, the principal gold-producing mine in the Philippines, is 10 miles southeast of Baguio, in the Cordillera Central of northern Luzon.1 The region is a deeply dissected plateau, ranging in altitude from 3000 t0 5000 ft. above sea level. The rocks consist chiefly of granodiorite, diorite, and remnants of metamorphosed sediments, cut by dikes of andesite porphyry and quartz-diorite porphyry. All are intruded by a volcanic breccia plug, oval in horizontal section, about 3200 ft. long and 2300 ft. wide, which is the north central part of the mineralized area. Three main vein systems have been developed (Fig. 1): q6, 231 and 364, which strike about N.70°E. and dip 5o to 90°S. Each system is a braided zone consisting of many individual components. They are disturbed by a series of premineral faults or shear zones striking about N.45°E. Twelve of these produce important effects on the persistence, character, and quality of veins. From west to east the faults are named (after claims): Hog, Big Gun, Bull, Pine, Lolita, Bar No. I, Bar No. 2, Curt, Sun, Helen, Itoe, and Frog. They are early breaks formed prior to the N.70°E. vein fractures. Mineralization occurs on them but, with several prominent exceptions, they are too low grade to mine. A number of northwesterly striking faults complete the structural pattern. Although they are relatively abundant, the effect on the veins is so small that they do not present any problems in mining or development. All of these faults that have been observed are later than the N.70°E. veins and offset them to the left. NORTHEAST FAULTS The early northeast faults* are notably continuous in spite of their small displacements, 20 to 100 ft. Frequently they appear so weak that their importance is masked and their identity clouded. The gouge along any of these faults may vary from exceedingly weak at one point to very strong at another point only a short distance away. In other words, the amount of gouge depends on the changes of attitude of the fault plane, and is no indication of the extent of the movement. Places where walls are spread apart are filled with gouge squeezed from tight places. Also, mineralization sometimes obscures fault gouges by replacement. The mineralization of northeast faults has produced several important ore bodies; namely, 231 west on Pine fault and q6 vein on the same fault. To a smaller extent, Lolita, Curt, Bull, Bar No. I, and Sun

Jan 1, 1942

By Charles A. Ashburner

VERY little is known of the economical value of the coal-betas of. the State of Texas. The first authentic statement in regard to their occurrence is that contained in the reports of the United States Explorations for the Pacific Railroad, near the 32d parallel of latitude, published in 1853-55. Professor William P. Blake reports, "that a number of seams of bituminous coal, varying, in thickness from two to four feet, have been opened along the Brazos River, in Young County, about one hundred and fifty miles west of Fort North." Dr: Shumard also states, "that the characteristic fossil forms of the Carboniferous Era have been found with this coal, and considers the ago of the formation established. Fossils obtained from the carboniferous limestone remove all doubt of the age of these deposits."† In the spring of 1879, I was called upon by. some Eastern capitalists to make an examination of the Brazos coal-field, in order to obtain the thickness, extent, and value of the coal which could be mined and be- made merchantable for steam, heating, and metallurgical purposes. The demand for coal in this section of the country is great, and a fuel. which in our Eastern markets might be considered of inferior quality, would here find a ready sale. It must be remembered that the market value of a coal does not depend upon its absolute purity, but upon its actual value in heat units which it is capable of producing. A poor coal which can be cheaply mined near the: consumer, is infinitely more remunerative to a mining company than a superior coal whose cost to the consumer is greatly increased by high mining charges and railroad freights. The value of the Texan coals does not depend upon their purity but upon their low first cost and nearness to a market. A glance at a geological map of the United States, will show that the Brazos coal-field is the extreme southwestern extension of what may be called the Missourian, Fourth or Western, bituminous coal * I am permitted by the gentlemen for whom the examination was made to publish the general statements contained in this paper. † Macfarlane&apos;s Coal Regions of America. More recently brief mention has been made of the coal-field in the pamphlets of the State geological survey. These reports are, however, too general, too indefinite, and too impracticable to permit of any conclusions as to the value of the coal as an economical, merchantable fuel.

Jan 1, 1881