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By Cyril Smith

SOMEWHAT over ten years ago the author described studies1,2 on the constitution of the copper-silicon system. The copper-rich portion of this diagram is shown in Fig. 1. The experimental points freely dotted about the diagram seemed to justify an otherwise unconvincing diagram and for several years the curious reverse bend in the alpha-phase bound-ary was accepted as substantially correct, even by later investigators3,4 of the system who introduced changes in the high-silicon phases. The binary diagram has been used as a base for several ternary systems" without any suggested changes. Voce10 suspected the existence of another phase from his study of the cast alloys in the copper-manganese¬silicon system, but evidently hesitated to extrapolate this to the binary diagram, particularly in view of the too ingenious explanation that was advanced" to account for the pools of constituent clearly visible in castings; namely, that they were secondary alpha of twinned orientation deposited from beta. Von Schwarz,12 in 1932, called attention to the fact that this micro-constituent in copper-silicon alloy castings was anisotropic under polar-ized light and asserted that a new phase, not cubic, should be placed in the diagram adjacent to alpha. Sautner,13 on the basis of investigations with the polarizing microscope and with X-rays, introduced this phase into the diagram at about 6 per cent Si. The relevant part of his dia-gram is shown in Fig. 2. Sautner called the new phase beta, renaming the old beta phase zeta. To avoid confusion, in redrawing Fig. 2 the phases have been renamed in accordance with the terminology adopted in the present paper, in which the new phase is called kappa and the other phases retain the designation given them by Arrhenius and Westgren.4

Jan 1, 1939

By Homer Turner

THE nature and comparative features of anthracite and bituminous coals have been discussed by the writer in two previous papers.1 Although this paper is offered as a further contribution to the subject, it seems desirable at the outset to repeat some of the descriptive matter of the early works in order to show the actual connection between various constituents of both coals and the new photomicrographs and other physical and chemical properties.

Jan 1, 1929

By V. Jares

DESPITE the fact that a combination of metals-aluminum-zinc-tin, and sometimes aluminium-zinc-cadmium-is extensively used for aluminum solders, as well as for die-castings, the constitution of these alloys has not yet been made clear. I. BINARY SYSTEMS The system aluminium-zinc is the basis of the ternary alloys under consideration. Their composition was made sufficiently clear by the investigations of Roscnhein and Archbutt,1 Bauer and Vogel,2 Sander .and Meissner,3 Hanson and Gayler4 and Isihara.5 Only the temperature of decomposition of the crystals s seems still to be doubtful, whether it is considered as a compound of Al2Zn3 (according to Bauer and Vogel) or as an intermediate phase of variant composition (according to Hanson and Gayler). This temperature is given by most of the authors, as in the neighborhood of 256° C., only Isihara giving 280° C. As its accurate determination is of special importance in the study of the ternary alloys under consideration it was experimentally controlled in the following manner: An alloy corresponding in composition to the formula Al2Zn3 was made, in which the temperature effect was found to be the greatest. This was drilled and a silver-constantan thermoelement inserted into the cavity so as to be in direct contact with the alloy. The whole was then very slowly heated and the heating and cooling curves determined. The transition temperature from the heating curve was found to be 281° C., whereas-from the cooling curve it was 252° C.

Jan 10, 1926

By V. Jares

DESPITE the fact that a combination of metals-aluminum-zinc-tin, and sometimes aluminum-zinc-cadmium-is extensively used for aluminum solders, as well as for die-castings, the constitution of these alloys has not yet been made clear. I. BINARY SYSTEMS The system aluminum-zinc is the basis of the ternary alloys under consideration. Their composition was made sufficiently clear by the investigations of Rosenhain and Archbutt,1 Bauer and Vogel,2 Sander and Meissner,3 Hanson and Gayler4 and Isihara.5 Only the temperature of decomposition of the crystals 0 seems still to be doubtful, whether it is considered as a compound of Al2Zn3 (according to Bauer and Vogel) or as an intermediate phase of variant composition (according to Hanson and Gayler). This temperature is given by most of the authors as in the neighborhood of 256° C., only Isihara giving 280° C. As its accurate determination is of special importance in the study of the ternary alloys under consideration it was experimentally controlled in the following manner: An alloy corresponding in composition to the formula Al2Zn3 was made, in which the temperature effect was found to be the greatest. This was drilled and a silver-constantan thermoelement inserted into the cavity so as to be in direct contact with the alloy. The whole was then very slowly heated and the heating and cooling curves determined. The transition temperature from the heating curve was found to be 281° C., whereas from the cooling curve it was 252° C.

Jan 1, 1927

By N. C. Fick, R. L. Rickett

DESPITE the large volume of literature on alloys of iron and silicon,1 there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carbon and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in, sheet and strip form, the constitution was determined of a series of commercial silicon steels containing 0.05 to o.08 per cent carbon and 0.20 to 4.31 per cent silicon, over the temperature range 1300° to 2500°F. These alloys were all from regular production heats and of commercial quality. The results of, the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented. MATERIAL AND PROCEDURE All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness-the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. [ ] The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired. range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1946

By K. Tozwa

The electrical conductivity of electrolytes for copper electrorefining and electrowinning processes has been reported by many researchers since 1911. The experimental results show that the conductivity increases with an increase in sulfuric acid concentration and decreascs with an increase in copper concentration. In pure copper sulfate solution, however, the conductivity increases with an increase in the copper concentration. After confirming the conductivity of pure and acidified copper sulfate solutions experimentally, the concentrations of hydrogen ion and free (not hydrated) water in the electrolytes were estimated and it was found that the relation between the conductivity of acidified copper sulfate electrolytes and the products of concentration of hydrogen ion and free water is linear. Accordingly, the conductivity of acidified copper sulfate electrolytes increases with an increase in sulfuric acid concentration and decreases with an increase in copper concentration.

Jan 1, 2003

By William Fink

THE investigation of the phase relations of high-purity aluminum-base alloys is a part of the fundamental research program of the laboratories of the Aluminum Company of America. The results of a number of binary and ternary systems have previously been published in the transactions of this society. The aluminum end of the binary aluminum-titanium system has been studied. This system has received relatively little attention. To the authors' knowledge, there are two previous papers on this subject. E. van Erckelens1 determined the constitutional diagram reproduced in Fig. 1. .According, to this diagram, the liquids represents the separation of TiAl4 (Ti = 30.7 per cent.). He concluded that this is the composition of the compound, because in his work the eutectic horizontal terminated at 30.7 per cent. titanium and the metallographic examination of a sample of this composition revealed only one phase. According to the constitutional diagram developed by W. Manchot and A. Leber,2 reproduced in Fig. 2 from data given in their article, the liquidus represents the separation of the compound TiAl3 (Ti = 37.2 per cent. ). The composition of the compound was derived in a manner similar to that utilized by van Erckelens. Moreover, Manchot and Leber confirmed the composition of the compound by analysis of the constituent left as a residue after dissolving the alloys in weak sodium hydroxide solution. Although these are the only publications describing the constitution of the system, other investigators have studied the composition of the titanium compound. L. Wöhler3 says that there is a compound TiAl3 which was later confirmed by W. Manchot and P. Richter4 and by

Jan 1, 1931

By Robert Mehl

THE purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2° C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsen1 that variations as great as 30° C. exist in the reported data on the A3 temperatures in iron-carbon alloys. For-tunately, the A3 temperature in pure iron is now known to be 910° C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato' on both hypoeutectoid and hyper-eutectoid steels.

Jan 1, 1937

By C. O. Burgess, W. D. Forgeng

DESPITE the increasing interest in and the technical importance of iron-chromium-manganese alloys, very little published information is available regarding their constitution. F. M. Becket's paper1 in 1930 represents the first correlated effort in the field of these alloys. The paper served particularly to draw attention to the commercial possibilities of iron-rich alloys containing chromium and manganese in balanced proportions. The duplex structure of alloys within the commercial range was briefly discussed, but exposition of their structural constitution was necessarily limited because the physical properties and corrosion resistance of the alloys were the main subjects of the paper. Both prior to and following the publication of F. M. Becket's paper, and at his instigation, an extensive investigation of the constitution of iron-chromium-manganese alloys of commercial purity was in progress at the Union Carbide and Carbon Research Laboratories, Inc. The present paper is based on the results of that investigation. In the last few years, investigations covering various portions of this alloy system have also been made in Europe. W. Koester briefly mentioned the effect of annealing on chromium-manganese steel2 and later3 constructed approximate sections of the iron-chromium-manganese equilibrium diagram. M. Schmidt and H. Legat14 even more recently studied this system, and their article and conclusions are of interest as representing an entirely independent study of a number of iron-chromium-manganese alloys. Koester's sections are shown in Fig. 1. The figures summarize the effect of manganese additions to iron alloys containing 5, 10, 15 and 20 per cent Cr as well as the effect of increasing chromium content on iron alloys containing 3, 8, 20 and 30 per cent Mn. These diagrams, within their composition limits, substantiated in some measure the results of our investigation. However, in our work some differences as regards the position of the mixed alpha-gamma fields were found as compared to Koester's work, and we were able to detect the presence of

Jan 1, 1938

By W. S. Pellini, F. N. Rhines

IN many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummer1 have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium 0f experimentation. New values obtained in this way are believed to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by R. S. Dean2 and by E. E. Schumacher and F. C. Nix.3 Their points are represented in Fig. I. In their work the solidus was not located at antimony concentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228°C.; J. E. Stead,7 247°C.; Campbell,8 228°C.; W. Gontermann,9 245° to 252°C.; R. Loebe,10 245°C.; E. Heyn and 0. Bauer,11 245°C.; H. Endo,12 250°C.; R. S. Dean,2 249° to 258°C.; E. Abel, 0. Redlich, and J. Adler,13 245°C.; W. Broniewski and L. Sliwowski,14 250° to 252°C.; H. Seltz and B. De Witt,4 250°C. A temperature of 249°C- appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 249°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1942

By Earl S. Greiner, Eric R. Jette

ALTHOUGH the mechanical and chemical characteristics of certain iron-nickel-silicon alloys have been investigated,1 the available literature shows no results of a systematic investigation of the constitution of this system. This paper describes the results of an X-ray investigation of the constitution of the iron-rich iron-nickel-silicon alloys at 600°C. Data on the constitution of the included binary systems obtained in other investigations have been correlated with the structure of the ternary alloys. Jette and Foote2 have presented a tentative constitutional diagram of the iron-nickel system following X-ray studies on quenched specimens. This diagram shows that the alloys at 600°C. containing from zero to approximately 4 atomic per cent nickel consist of a body-centered cubic (alpha) phase, the alloys containing 4 to 24 atomic per cent nickel consist of body-centered cubic (alpha) and face- centered cubic (gamma) phases, and the alloys containing from 24 to 100 atomic per cent nickel consist of a face-centered cubic (gamma) phase. These investigators recognized that it was not possible to retain the gamma phase in equilibrium by quenching alloys containing less than approximately 25 atomic per cent nickel and that high-temperature X-ray methods were desirable to determine the gamma-phase solubility limit. In a later investigation of the iron-nickel alloys, Owen and Sulley3 determined the alpha-phase solid solubility limit to be 3.5 atomic per cent nickel at 600°C. High-temperature X-ray methods showed the solid solubility limit of the gamma phase to be 14 atomic per cent nickel at 600°C. Since the high-temperature X-ray method should reveal equilibrium conditions in these alloys better than the quench method of other investigators, the results of Owen and Sulley pertaining to the gamma-phase boundary are to be preferred. As the result of an X-ray investigation of quenched iron-silicon alloys, Greiner and Jette4 have shown these materials to consist of a body-centered cubic (alpha) phase containing from o to 26.4 atomic per cent silicon at 600°C. The alloys containing from 26.4 to approximately 50 atomic per cent silicon consist of two phases at 600°C.; namely, alpha and eta. The eta phase corresponds to the stoichiometrical formula FeSi (33.4 wt. per cent Si).* The literature pertaining to the constitution of the nickel-silicon alloys has been reviewed by Ackerman,5 who found disagreements in the results of various investigators on several parts of the system. Subsequent data on the constitution of the nickel-silicon alloys were reported by Osawa and Okamoto.6

Jan 1, 1943

By A. H. Grobe, F. N. Rhines

THE constitution of the indium-zinc alloy series has been investigated by Wilson and Peretti,1 who determined the liquidus and eutectic temperatures by the conventional method of cooling curves and the eutectic composition by analyzing eutectic exudations. Recent developments affecting the availability of indium and consequent increased interest in its applications make a more complete knowledge of the constitution of its alloys desirable. As a part of a program for the reexamination of the constitution of indium alloys by precision methods, the indium-zinc phase diagram [ ] (Figs. I and 2) has been redetermined in its entirety. The eutectic temperature (143.5°C.) reported by Wilson and Peretti has been confirmed exactly, but their value of the zinc concentration at the eutectic, 4 per cent, was found to be high; the new value is 2.8 per cent of zinc. There is also a rather large difference between the forms of the liquidus curves of Wilson and Peretti and those found in the present studies. The solidus curves herein have been located for the first time and the limits of solid solubility have been tenta-

Jan 1, 1944

Some 800 analyses for Cu, Zn, Pb, Ag, Fe, S, CaO, MgO, C02, Si02 and Al203 were used to examine the elemental constitution of the Mount Isa ores, and, for comparison, those of the Northern Leases area.Lead: zinc relations show little order from sample to sample, but means of large zones (Le. individual orebodies) show a highly linear inverse relationship. Lead: silver ratios are fairly constant from sample to sample, and means show a highly linear direct relationship.Sulphide sulphur appears to be related to carbonate and alumina abundance, sulphur decreasing systematically with increase in the ratio CO2:AI203. In all graphs involving members of the group CO2-A203-S the lead-zinc and copper ores conform to the same simple trends, confirming that the two ore types and their host rocks are genetically closely related. The earlier deduction of a volcanic-sedimentary origin for the sulphides of the Black Star orebodies appears compatible with present findings.On the basis of such an origin, the pattern of sulphide occurrence and mineralogy in the Mount Isa district is possibly related to the configuration f the upper surface of the "Eastern Creek Volcanics", the facies patterns of the overlying sedimentary rocks, and to the oldest faults affecting the two.INTRODUCTIONStanton (1962) described and interpreted the chemical constitution of the Black Star No. 2 lead-zinc and the 650750 copper orebodies at Mount Isa. The investigation has now been extended to the other principal orebodies of the area.The earlier study showed that the host rocks of the two adjacent Black Star orebodies were constitutionally closely related, and suggested that this was probably due to their original formation in contiguous zones of sedimentation. On this basis the silica-dolomite of the copper ore appeared to represent the slightly more shoreward, "limey" member, probably a fairly massive algal calcareous sediment laid...

Jan 1, 1963

By J. M. Rotter, R. A. Lohnes, J. Y. Ooi

Reliable prediction of wall pressures in a coal silo demands careful characterization of the stress-strain properties of the coal. This paper describes the results of triaxial compression tests on a typical fine-ground coal used in power generation and describes the fitting of several different constitutive models to the data. The fitted parameters for the constitutive models are well suited to application infinite element analyses. The different models are used to give the reader flexibility in choosing a model and to show the shortcomings of some models. To explore the quality of the fitting process, the fitted results are compared with finite element predictions of the triaxial test itself.

Jan 1, 1998

By S. Feinstein, I. Reznik, Y. H. Hatzor, O. Shitrit, Y. O. Rosenberg, H. J. Vinegar, S. Nguyen

"We report the effects of porosity and total organic carbon (TOC) content on the mechanical behavior of organic-rich chalks, based on laboratory measurements. The organic-rich chalks are from the Senonian Ghareb and Mishash formations. This deposit is an immature oil-prone source rock, about 300 meters thick, situated at shallow depths (several hundreds of meters) in the Shefela basin in central Israel. The study is based on core data collected from the Zoharim borehole.Three main phases comprise the bulk volume of this rock: 1) carbonate mineralogical phase (predominantly calcite); 2) pores (mostly saturated with brine); and 3) solid organic phase (type IIS kerogen). The mechanical effects of porosity (23-45%) and TOC (4-19%) are evaluated based on bulk incompressibilities vs. volumetric fractions analysis. Volumetric fractions of mineralogical and organic phases were obtained by porosity, density and TOC measurements. Saturated rock bulk moduli were measured through ultrasonic velocity measurements. Saturated rock bulk moduli correlate best with the sum of kerogen and pore volume fractions, rather than each of them separately. The volumetric fractions were also used to define the range of bulk modulus of the organic-rich chalk, using the Hashin-Shtrikman upper and lower bounds. Based on Marion's Bounding Average Method (BAM), the normalized stiffness factor of the chalk averaged at w=0.197, indicating a soft pore geometry. Using the average normalized stiffness factor, the BAM predictions showed excellent match with the saturated rock bulk modulus and the sum of kerogen and pore volume fractions. Based on our findings, it is inferred that kerogen grains do not support the solid skeleton but are distributed between the minerals grains. We also propose here a straightforward approach for calculating the Hashin-Shtrikman bounds, based on TOC and porosity measurements. The mechanical effects of porosity and TOC indicated here are very important for the understanding of the influence of immature kerogen presence in highly porous chalks, as the Ghareb and Mishash formations."

Jan 1, 2015

By M. C. Villeneuve

A numerical modelling approach was developed to explicitly simulate geomechanical characteristics of intact rock: mineralogy, grain size and fabric. The approach involved creating a representative constitutive model for each of three common rock-forming minerals: mica, quartz and feldspar. The constitutive models developed are valid within the low confinement realm of excavation boundaries, where tensile fracture processes dominate. The mineral types were assigned to numerical elements, which were associated with each other through an algorithm created in a finite difference model, FLAC 2D (Itasca 2007a), to simulate real crystal geometries and orientations. The numerical models were used in a parametric investigation of the geomechanical characteristics and compared with published observations of the rock yielding process in laboratory testing. This approach has allowed the explicit grain-scale investigation of the impact of geomechanical characteristics on rock yielding at low confinement, leading to an improved mechanistic understanding of excavation-scale rock yielding processes at excavation boundaries.

May 1, 2009

By Ali P. Gordon, James Williams

Joints gasketed with viscoelastic seals often receive an application of a secondary torque, i.e., retorque, in order to ensure joint tightness and proper sealing. The motivation of this study is to characterize and analytically model the load and deflection re-torque response of a single 25% glass-fiber reinforced polytetrafluorethylene (PTFE) gasket-bolted joint with serrated flange detail. The Burger-type viscoelastic modeling constants of the material are obtained through isolating the gasket from the bolt by performing a gasket creep test via a MTS electromechanical test frame. The re-load creep response is also investigated by re-loading the gasket after a period of initial creep to observe the response. The modeling constants obtained from the creep tests are used with a Burger-type viscoelastic model to predict the re-torque response of a single boltgasket test fixture in order to validate the ability of the model to simulate the re-torque response under various loading conditions and flange detail.

Jan 1, 2015

By Carl A Zapffe, George A. Moore

In a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal substructures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the L'disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, unaffected by chemical attack and undis-torted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. Materials Studied In commercial steels, defects caused by hydrogen take various external forms according to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement—-"pickling brittleness "—in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free-machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group 1: Prepared from Armco Ingot Iron As shown in Table 1, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943

By Carl A. Zapffe, George A. Moore

In a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal substructures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the L'disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, unaffected by chemical attack and undis-torted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. Materials Studied In commercial steels, defects caused by hydrogen take various external forms according to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement—-"pickling brittleness "—in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free-machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group 1: Prepared from Armco Ingot Iron As shown in Table 1, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943

By Walter Crafts, C. M. Offenhauer

In a previous study of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is 2 more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about I to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, I per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to I-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudo-martensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously1 that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943