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By C. J. Sparks, J. C. Ogle, E. A. Starke

DEFORMATION of cold-rolled fcc metals and alloys produces one or the other of two types of rolling textures, usually referred to as the copper type or the brass type. The pure fcc metals, with the exception of silver, develop the copper-type texture when rolled at room temperature. Silver, brass, and many other alloys develop the brass-type texture. Transition from one texture type to another can also occur. Solute additions to pure copper cause a transition from the copper-type to the brass-type texture.' Varying the deformation temperature also produces texture transitions. Copper rolled at -196°C developed the brass-type texture2 and silver rolled at elevated temperatures, 200°C, developed the copper-type texture.374 The work of Haessner,' Smallman and Green,6 and Hu and coworkers3'4 seems to have established an apparent correlation between the type of rolling texture (and the texture transition) and the stacking-fault probability. Thus materials with low stacking-fault energies are thought to develop the brass-type texture while high stacking-fault energy materials develop the copper-type texture. Mikkola and cohen7 measured by X-ray diffraction techniques the stacking-fault probability, a, in the ordered and disordered fcc alloy Cu3Au. Unexpectedly, ordered specimens showed about twice the stacking-fault probability as the disordered ones. Marcinkowski and Zwe118 also found stacking faults in ordered Cu,Au, but not in the disordered CusAu. More recently, Camanzi and coworkers9 have shown that the intrinsic stacking-fault energy of Cu3Au undergoes a considerable decrease (approximately 100 ergs per sq cm) when passing from the disordered to the ordered phase. In general, deformation reduces order'' but some of our measurements showed that some long-range order still remains in Cu3Au after cold reduction by rolling 80 pct. From the above considerations Cu3Au offers the possibility of studying the texture transition in fcc alloys without varying either the temperature or the composition. If the stacking-fault energy correlation is correct, an initially ordered alloy should develop the brass-type texture during rolling while a disordered alloy should develop the copper-type texture. The present communication describes some initial results of experiments designed to investigate this possibility. The rolling textures of ordered and disordered Cu3Au samples were determined after various amounts of deformation. The ordered sample had an initial long-range-order parameter of S = 1, determined from X-ray diffraction. The grain size of both the ordered and disordered samples was the same, and the initial textures of both were also identical and approximately random. No obvious differences in the deformation textures of the ordered and disordered materials were detected up to 35 pct reduction and the (111) pole figures of Fig. 1 resemble that of pure copper. However, with reduction larger than 35 pct and less than 50 pct, a marked deviation from the copper texture was noted in the ordered material. The newly developed orientation was close to the (110)[i12] ideal orientations re-

Jan 1, 1970

By W. D. Forgeng, R. E. Grace

The rate of copper corrosion in liquid lead was studied as a function of flow rate and temperature in a closed isothermal loop system between 350" and 500°C. Kinetic data were interpreted with the Nernst-Brunner equation and the Chilton-Colbum mass transfer analogy to heat transfer. Over the range of temperatures and flow rates employed the solution rate constant varied from 2 x 10-3 to 20 x 10-3 cm per sec. The rate constant was found to vary with the 0.76 power of the Reynolds number in the range 7500 < Re < 40,000. The results of this investigation indicate that the Cu-Pb corrosion process is controlled largely by diffusion across a boundary layer. particularly at the higher temperatures. The effective boundary layer for diffusion is found to be approximately three to four times smaller than the momentum boundary layer. CORROSION by liquid metals has long been a problem during melting, static containment, and casting. Recently, considerable emphasis has been placed on the understanding of liquid metal corrosion mechanisms in an effort to prevent mass transfer and eventual failure in liquid metal heat exchangers and in liquid-metal-fueled nuclear reactors. The present investigation was conducted to determine the relationships which exist between corrosion kinetics and hydrodynamic conditions in an isothermal loop containing a simple liquid metal-solid metal corrosion system. The Cu-Pb system was chosen for its simplicity and ease in handling. Previous isothermal Cu-Pb corrosion studies1-3 have been conducted in both static and dynamic systems but not under conditions which allow easy "scale-up" to engineering systems, such as liquid metal heat exchangers. On the other hand, most liquid metal loops which have been used to evaluate mass transfer rates4 have been driven with temperature gradients under conditions of natural convection and unknown flow rates. The primary contributions of this research are twofold: 1) to evaluate the design of a simple isothermal loop corrosion system and 2) to investigate liquid metal corrosion behavior under well-defined hydrodynamic conditions. MATERIALS AND EXPERIMENTAL WORK The apparatus used to measure the Cu-Pb corrosion rates is shown schematically in Fig. 1. The loop system consisted of 1) a reservoir made of Type 316 stainless steel containing a centrifugal pump and 2) stainless-steel tubing containing a removable copper test section. The copper test section was OFHC hard-drawn tubing, 11.0 0.05 cm in length and 0.775 ±0.005 cm ID. A Type 316 stainless-steel venturi meter* was inserted in place of the copper test sec- tion in order to determine the lead velocity as a function of pump speed at each temperature. The Cu-Pb system was chosen for this study because the solubility of copper in liquid lead is large enough to measure accurately but small enough that the diameter of the copper tubing was not changed significantly by corrosion. There are no intermediate phases formed in the system, and the solid solubility of lead in copper is vanishingly small so that back-diffusion cannot occur. Molten lead (corroding grade; 99.94+ pct Pb, 0.0015 max pct Cu) was charged from an auxiliary melting furnace into the system under an argon cover to minimize oxidation. The lead was then maintained at constant temperature by a stirred molten salt bath in which the loop was immersed to a depth just above the lead level in the reservoir, Fig. 1. The total volume of lead in the system was 320 2 cu cm.

Jan 1, 1969

By Arthur T. Allen

THE Kingsport formation, a part of the Knox dolomite of Ordovician age, is composed of 538 ft of dolomitc and limestone. Numerous bands, layers and nodules of chert, arenaceous and shale zones are present. The characteristics displayed by these features have been useful in mapping, prospecting and mining. Perhaps a better understanding of the origin of these zones will increase their usefulness. Introduction The presence of numerous bands, nodules, and irregular bodies of chert within the Kingsport formation in the Mascot locality has long been recognized. Oder and Miller1 mention the general characteristics, but do not deal with the chert occurrences in detail. When the occurrence of chert is studied in fresh exposures underground, a variety of characteristics is noted which has been useful in correlation and in detailing the sub-surface stratigraphy. Although the writer has no desire to enter into a controversy over the origin of chert, many observations have been made of its local characterigtics. A detailed stratigraphic section is included which shows the position of the individual horizons discussed in the following paragraphs. The term "chertification" has been adopted from Fowler and Lyden2 for use here. It refers to the replacement of lime- stone by introduced silicic acid. The writer uses it to refer to the occurrencc of introduced or original chert in limestone and dolomite. In this writing "syngenetic chert" refers to chert which has been deposited contemporaneously with the enclosing limestone or dolomite. Also, it is considered to include interstitial silica shown by chemical analysis and insoluble residues. The term "epigenetic" is applied to all chert which has been introduced after consolidation of the rocks in which it occurs, regardless of the nature of the depositing solutions. Syngenetic Chert It is the belief of the author that a large percentage of the chert found in the Kingsport formation is syngenetic. The widespread occurrence of similar nodules and bands of chert in the same horizon far from one another and far from areas of deformation or alteration of the enclosing rocks is difficult to explain by infiltration of the silica after compaction of the enclosing rocks. When chert of this type does occur near zones of movement it is likely to be involved in faulting and brecciation which indicates that it was deposited prior to deformation. Older Epigenetic Chert There are several occurrences of nodules in the Kingsport which seem to be epigenetic as pointed out in the following examples: A cherty zone occurs 26 ft above the o bed (Fig =). This is not always present but is found in the greater part of mine work-

Jan 1, 1949

By Arthur T. Allen

THE Kingsport formation, a part of the Knox dolomite of Ordovician age, is composed of 538 ft of dolomitc and limestone. Numerous bands, layers and nodules of chert, arenaceous and shale zones are present. The characteristics displayed by these features have been useful in mapping, prospecting and mining. Perhaps a better understanding of the origin of these zones will increase their usefulness. Introduction The presence of numerous bands, nodules, and irregular bodies of chert within the Kingsport formation in the Mascot locality has long been recognized. Oder and Miller1 mention the general characteristics, but do not deal with the chert occurrences in detail. When the occurrence of chert is studied in fresh exposures underground, a variety of characteristics is noted which has been useful in correlation and in detailing the sub-surface stratigraphy. Although the writer has no desire to enter into a controversy over the origin of chert, many observations have been made of its local characterigtics. A detailed stratigraphic section is included which shows the position of the individual horizons discussed in the following paragraphs. The term "chertification" has been adopted from Fowler and Lyden2 for use here. It refers to the replacement of lime- stone by introduced silicic acid. The writer uses it to refer to the occurrencc of introduced or original chert in limestone and dolomite. In this writing "syngenetic chert" refers to chert which has been deposited contemporaneously with the enclosing limestone or dolomite. Also, it is considered to include interstitial silica shown by chemical analysis and insoluble residues. The term "epigenetic" is applied to all chert which has been introduced after consolidation of the rocks in which it occurs, regardless of the nature of the depositing solutions. Syngenetic Chert It is the belief of the author that a large percentage of the chert found in the Kingsport formation is syngenetic. The widespread occurrence of similar nodules and bands of chert in the same horizon far from one another and far from areas of deformation or alteration of the enclosing rocks is difficult to explain by infiltration of the silica after compaction of the enclosing rocks. When chert of this type does occur near zones of movement it is likely to be involved in faulting and brecciation which indicates that it was deposited prior to deformation. Older Epigenetic Chert There are several occurrences of nodules in the Kingsport which seem to be epigenetic as pointed out in the following examples: A cherty zone occurs 26 ft above the o bed (Fig =). This is not always present but is found in the greater part of mine work-

Jan 1, 1949

By W. E. Ruder

IT has been pointed out by Stead 1 that grains of considerable coarseness may be developed in steels containing from 3 to 5 per cent. of silicon, and in a previous paper 2 the present author has shown that under the proper conditions of annealing single grains having an area of 50 sq. cm. may be obtained. It is the purpose of this paper to discuss in more detail the conditions, promoting the growth of these grains, in the hope that the experiments described may throw some additional light upon the general problem of grain growth in metals. These silicon steels lend themselves particularly well to such experiments because of the ease with which the change in structure may be followed and because of the fact that the effect of the carbon present is largely obliterated by the high percentage of silicon. This forms a solid solution with the iron, which acts very much like a pure metal. This alloy has been found to have but one critical point, viz., Are. This point, determined by Roberts-Austen for Hadfield&apos;s 4 per cent. Si alloy, was found to lie at 703° C. Vigouroux3, in working with pure Fe-Si alloys, finds this point to rise from 750° C. for 0.5 per cent. Si to 860° for 6 per cent alloy, with a flat region in the curve from 3 to 4 per cent. Si. No accurate determination of this point has been undertaken by the present author, but it has been roughly determined to lie between 730° and 750°.

Jan 12, 1913

By T. A. Read, M. W. Burkart

The crystal geometry of the cubic-tetragonal interface after partial transformation of an indium-thallium alloy single crystal is described and a general theory is presented. The effects of applied stresses on this transformation are interpreted and the latent heat of transformation is obtained from observations of transformation under stress. A DIFFUSIONLESS phase transformation between face-centered cubic and face-centered tetragonal structures has been reported for the indium-thallium system by Bowles, Barrett, and Guttman1, 2 The transformation takes place at approximately 105 "C at 18 atomic pct Tl and 25°C at 23 pct Tl. In their study, Bowles, Barrett, and Guttman used poly-crystalline samples whereas in the present study single crystals were used to eliminate the transformation constraints imposed by adjoining grains. The use of single crystals made possible a comprehensive study of the effect of stress on the transformation. In the course of the work, it was possible to formulate a new method of analyzing dif-fusionless transformations (presented in this paper) which permits calculation of the geometry of the interphase interface from a knowledge of the crystal structures of the initial and final phases. The specimens were prepared from chemically pure thallium and 99.97 pct In which were weighed out to produce 3 to 4 grams of alloy of the desired concentration. The metal was placed in clean fused silica tubing, then melted, degassed and sealed under vacuum. (To obtain single crystals, it was found that both degassing and extreme cleanliness were essential.) Single-crystal specimens were grown by a modified Bridgman technique.8 pecimens were removed from the tube by dissolving the quartz in concentrated hydrofluoric acid which attacks the specimen very slowly. The specimen then was polished mechanically to produce four flat surfaces, electropolished, and annealed at 140°C for 48 hr. The electropolishing solution used was that described by Bowles, Barrett, and Guttman and the polishing was carried out on both the high and low temperature phases of the alloy. The high temperature polishing was done at 110°C with a stainless steel cathode. Visual Observation of the Transformation in Single Crystals A visual study of the transformation was made on specimens which had been electropolished in the high temperature phase. The specimens were supported on the stage of a metallograph by an electrically heated holder which contained an opening for observing the specimen. Visual evidence of transformation was found in the presence of an interface which separated the two phases. The interface plane defines the boundary of the phase undergoing transformation and manifests itself by the sharp change in angle between the surface of the specimen and the incident light at the juncture of the two phases. On slow cooling, well-annealed specimens transformed from the face-centered cubic structure to the face-centered tetragonal structure by the motion of a single plane interface which traversed the specimen from one end to the other. Upon heating, the interface moved back in the reverse direction. The interface could be started, stopped, or reversed at will. A temperature hysteresis of about 31/2oC was observed in the reversal of the interface. Holding an interface stationary caused it to disappear completely in most cases, whereas in other instances the interface became less distinct depending upon its orientation. The interface could be made to reappear by changing the temperature of the specimen. The low temperature tetragonal structure exhibits only the fine markings or subbands reported by Bowles, Barrett, and Guttman and is illustrated in Fig. 1. These subbands are twin-related. Back-reflection Laue patterns show the breakup of the cubic spots into pairs of spots corresponding to the twin orientations of the tetragonal phase.

Jan 1, 1954

By G. P. Gladis, R. H. Atkinson

PALLADIUM has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items-at least 100 times as rare as gold. Although both visual and spectrophotometric examination demonstrated that the color of palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400° to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By W. A. West

One who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult&apos;s law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener&apos;s paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular. they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion oi the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1947

By W. A. West

One who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult&apos;s law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener&apos;s paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular. they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion oi the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1947

By M. R. J. Wyllie, P. F. Southwick

The importance of the so-called "dirty sand" or "conductive solids" problem in electric log interpretation was first stressed in a paper presented in 1949. Since that time the problem has been generally recognized as a most serious one. Several research papers bearing on the theory of the effects of clay contaminants on reservoir rock resistivities have appeared. These papers, while contributing to the theory of the problem, have not offered any practical solution. In the present paper an experimental investigation has been made of the effects of ion-exchange materials on the electrical properties of natural and synthetic porous media. The method used to make synthetic dirty sands is entirely novel and has proved a valuable guide to a better understanding of the properties of dirty sands generally. The effects of ion-exchange materials on both the resistivity and self potential (S.P.) logs have been examined. From the data obtained it has been possible to formulate a simple, practical method whereby electrical logs of dirty sands can be qualitatively interpreted. The method is in all essentials identical to that presently in use for interpreting clean sands. New light has also been thrown on the significance of the term formation factor when it is applied to dirty sands. In 1949 a paper was presented1 which showed that the presence of so-called "conductive solids" introduced considerable complexities into the analysis of the resistivities of dirty sands, i.e., permeable formations containing clay. The reduction of the self potential (S.P.) resulting from the presence of interlaminated shale or interstitial clay in permeable formations has been discussed by Doll.2,3 Noteworthy papers which dilate further upon the effects of shale and clay on the resistivity of permeable formations are those of deWitte,4,5 Berg,6 Wyllie,7 and most recently, Winsauer and McCardell.8 The last authors have endeavored to elucidate the chemistry of the resistivity phenomena in dirty sands in terms of an adsorption hypothesis. Specifically, they attribute the electrolytic conductivity of shales and clays within a permeable formation to an ionic double-layer effect and, for this reason, regard the term "conductive solids" as a misleading one. Some consideration has been given to the effect of dirty sands on the S.P. by Wyllie7 and by McCardell, Winsauer and Williams." Published work to date has cast light only on certain theoretical aspects of the problems created by the presence of clays and shales within permeable formations. One object of this paper is to describe experiments which serve to elucidate further the theory of the dirty sand problem and particularly the significance of the term "formation factor" as applied to dirty

Jan 1, 1955

By C. R. Claus, G. A. Standish

Since March. 1945, the Magnolia Petroleum CO. has drilled 39 wells in Southwest Coastal Louisiana. All wells were drilled within a comparatively small radius, but the area provides a large variety of problems. The deepest well drilled was 13,518 ft, and the total depth averaged 10,977 ft. Throughout this period drilling mud control and types of mud handled were: (I) phosphate, (2) red lime (late conversion), (3) red lime starch (early conversion), (4) red lime starch oil emulsion, (5) precision controlled low alkalinity-low lime content. and (6) gel muds for completion purposes. Improvement has been obtained in effecting some or all of the following: (I) more rapid penetration, (2) reduction in drilling hazards, (3) better evaluation of cores and logs, and (4) better completions. The geological sequence of zones penetrated range from recent sediments at the grass roots through the Frio section. Anticipation of high-pressure zones and incompetent formations entails precision control of drilling mud weights, and the unconsolidated nature of the various zones requires constant attention to the filtrate, viscosity, and gel strength values. In the Chalkley field, particularly, this combination of problems exists, where the formation pressures and overburden weight density values are in very close proximity. Design of casing and drilling mud programs must be modified to fit each well. INTRODUCTION Field and research work on drilling fluids has made constant progress, enabling operators to prospect progressively deeper horizons. Numerous papers have been written on the theoretical aspects of drilling fluid devel- opment, but in the field engineers have found it difficult to evaluate the role of specific mud constitutents when dealing in terms of thousand barrel mud systems. For that reason field data is somewhat lagging in technical report writing. However, applications of new techniques in the field have usually paralleled, and in numerous instances preceded, research work. The information obtained by Magnolia Petroleum Co. in the course of drilling 39 wells within a comparatively small area in Southwest Coastal Louisiana provides an excellent opportunity of reviewing a specific example of drilling mud evolution. A large variety of problems has been coped with, the most important result being that every well was successfully drilled to its projected total depth. The discussion begins with the advent of deep drilling in this area in March, 1945, and is concluded with a resume of recent drilling operations in the Chalkley field. The primary purpose of this paper is to describe the evolution in types of drilling fluids as it occurred and its application in the solution of various drilling problems. All of this information and experience resulted in the successful drilling of the three wells in the Chalkley field, where a combination of the most sound techniques was necessary in carrying drilling operations to the projected total depths. Other operators along with service company engineers have contributed considerably through the interchange of ideas and information to this paper, but the data and conclusions which are contained are based on first-hand observation of Magnolia Petroleum Company&apos;s drilling operations. The 39 wells drilled by Magnolia Petroleum Co. average in depth 10,977 ft per well, while the maximum depth penetrated was 13,518 ft. The cost of drilling fluids have varied from $8,700 to $165,000, with the over-all drilling costs ranging from $74,000 to $543,000 per well. This wide variance illustrates the unpredictable nature of each well and the effects on over-all cost when high density muds are required to control

Jan 1, 1955

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1&apos; investigated

Jan 1, 1947

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1&apos; investigated

Jan 1, 1947

By E. A. Gulbransen, W. S. Wysong, K. Andrew

The reaction of carbon in solid solution in a metal with the surface oxide fim on many metals may be inferred from thermo-dynamic calculations for high vacua and high temperature conditions. Holm has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. considerable work has been described in the literature on the de-carburization reaction. Several general references may been 2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides on strips of various types Of chrome-nickel alloys. Some of the early experiments On the behavior Of &apos;3 pct chrome-iron in vacua of the order of 5 X lo&apos; mm and at a temperature Of 600°C have been reported.5 These experi-merits showed a &apos;low reaction with the residual Oxygen Or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600&apos; C pure enough to reduce Crz03 formed On the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome- iron and Nichrome V has been investigated in the thin film range by Gulbransenr Phelps and Hickman,&apos; and shown to be "203. It Was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pet nicke1 and 20 pet chromium was heated to 850°C in a high vacuum, the specimen lost weight. The rate Of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. Type Reactions Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type, They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: 1. Metal . (gas) F? metal + gas — degassing of the metal 2. zM(s) + y }i Oi(g) M MIOu(s) -oxidation

Jan 1, 1949

By G. B. Craig, H. E. Rosinger, W. J. Bratina

NUMEROUS studies have been reported on how the mechanical properties of a bcc metal are affected by interstitial solute atoms in the temperature range where appreciable diffusion occurs in finite time. Only recently, though, has work on an "interstitial-free" iron been reported, this by Leslie and sober,&apos; on an Fe-0.15 pct Ti alloy. The data was limited to a maximum temperature of 296°K. This work presents a systematic study of the flow stress and the activation volume of a similar material as a function of plastic deformation over the temperature range 253" to 473°K. The material studied was Ferrovac E iron containing 0.01 wt pct C and 0.0002 wt pct N annealed at 870°C for 1 hr, and the same iron with an addition of 0.15 wt pct Ti annealed at 870°C for 80 hr; cooling rates being 75°C per hr. In the latter alloy depletion of interstitials in the a-iron matrix associated with the second phase formation was expected. The temperature dependence of the flow stress was measured at 6 = 3.33 x 10-5 sec-1 from 253" to 473°K as a function of the deformation in 0.01 intervals from 0.03 to 0.12 strain. Results for two strains, 0.03 and 0.09 are shown in Fig. 1. The flow stress increased and reached a maximum in the Ferrovac E iron with increasing temperature, but showed a consistent gradual decrease in the Ferrovac E-0.15 pct Ti alloy. A yield point and Luders region, observed in Ferrovac E, was absent in the Ferrovac E-0.15 pct Ti alloy. Also, the Ferrovac E exhibited a serrated stress-strain behavior in the temperature range 330" to 400°K; dynamic strain-aging characteristics were absent for the titanium alloy. The activation volume was determined over the same temperature range by the method of stress relaxation at constant strain. Results are shown in Fig. 2. At the temperatures of serrated stress-strain behavior in Ferrovac E the activation volume was found to increase toward infinity and, as the temperature rose, to decrease, to about 100 to 200 v/b3. By contrast, the activation volume for the Ferrovac E-0.15 pct Ti alloy tended to increase continuously from the initial value of approximately 300 at 300°K to more than 800 at 473°K. Above 400°K, then, the corresponding activation volume values of Ferrovac E were less than that of the Ferrovac E-0.15 pct Ti alloy. The activation volumes, Fig. 2, appear to depend on dislocation-interstitial interaction in Ferrovac E and on dislocation-dislocation interaction in Ferrovac E-0.15 pct Ti alloy. The gradual increase in the latter metal is associated with thermally activated motion of dislocation segments.&apos; The decrease of the activation volume in Ferrovac E above 400°K is probably related to the diminishing effect of interstitials on dislocations. Here, the interstitials can be moved along with a dislocation without appreciable drag. As indicated in Fig. 1, removal of interstitials

Jan 1, 1970

By Eric Jette

The nickel-chromium alloys form the base f for many industrial heating alloys, so that this system is of considerable practical importance. The literature on these alloys, however, contains much conflicting evi-dence, not only regarding the solubility limits of the terminal solid solu-tions at different temperatures but even regarding, the number of phases existing in the system. Part of the difficulty undoubtedly arises from the fact that chromium of sufficiently high purity has been available only during the last few years. A second and possibly even more impor-tant difficulty arises from the ease with which chromium reacts with silicon and carbon compounds and the atmosphere to form silicides, carbides, nitrides and oxides. Pilling and kihlgren1 in 1929 reviewed the existing scanty information. They did not consider the diagram by which they summarized the various bits of information to be entirely satisfactory. Matsunaga2 investigated the system by thermal analysis, microscopic examination and other means. Electrolytic nickel of 99.9 per cent purity and thermit chromium containing 0.30 per cent al, 0.40 per cent fe, 0.25 per cent si and 0.04 per cent c were used. A tammann furnace with hydrogen flowing through it was used for melting. Sekito and matsunaga3 reported an x-ray, investigation presumably on these same

Jan 1, 1934

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

The solid solubility of holmium in copper, silver, and gold, determined using metallographic techniques, was found to be a maximum of 0.06, 2.4, and 3.2 wt pct, respectively, nt the eutectic temperatures. The temperatures of these eutectic horizontals, determined by differential thermal analysis, were found to be 868", 787", and 778"C, respectively. The first compound on the silver-rich side of the Ag-Ho system was found to be A&Ho2. In a study by Gold et al.,&apos; on the effect of small amounts of soluble impurities on the electrical resistance and thermoelectrical properties of copper, traces of iron were shown to have drastic effects on the thermoelectric power due to the magnetic scattering of the conduction electrons. Since little is known about the state of the iron ion when dissolved in copper, Gold had hoped to repeat these experiments using certain rare earths as the magnetic scattering centers; because of the tightly bound 4f electrons it is not expected that their spectroscopic state would be affected by alloying. In such an experiment the sole role of the trace rare-earth impurity would be to magnetically scatter the copper conduction electrons without producing appreciable distortions in the otherwise pure copper matrix. Since holmium was chosen for such a study because of its high magnetic moment, it was necessary to establish precisely its solid solubility in copper. The study was extended to include the solvents silver and gold, so that an evaluation of the data using classical solubility parameters could be made. No previously reported work on the systems of holmium with copper, silver, or gold was found in the literature. Information on the solubility of other rare earths in these three metals is also very meager. The solubility limit of yttrium in copper was reported as less than 1 wt pct2 and the solubility of praseodymium in gold as 0.35 wt pct,3 while no references were found on solubility studies of rare earths in silver. EXPERIMENTAL Materials. The materials used in this investigation were distilled holmium prepared in this Laboratory, OFHC* copper, electrorefined silver (99.9 *OFHC = oxygen-free high conductivity. pct), and gold with the analyses given in Table I. Sample Preparation. Samples weighing 1 to 2 g were prepared by arc-melting the components together on a water-cooled copper plate under purified argon atmosphere. The samples, turned and remelted at least five times to ensure homogeneity, showed weight changes of less than 0.1 wt pct after melting. Samples containing less than 0.7 wt pct Ho were prepared by diluting 1 to 2 wt pct Ho alloys with the pure solvent, while samples with concentrations greater than 0.7 wt pct Ho were prepared directly from the metals. The samples were wrapped in tantalum foil, sealed in outgassed Vycor tubing under helium, annealed at the desired temperature for at least 24 hr, and then quenched by shattering the Vycor tube in cold water. Metallographic Methods. Standard mechanical polishing methods were used in preparing the silver and gold alloys for examination, while the copper alloys were electropolished using a 40 pct solution

Jan 1, 1963

By W. C. Winegard, W. J. Bratina

Internal friction characteristics and temperature dependence of the torsion modulus for iodide zirconium containing 2.4 pct Hf were investigated, using a low frequency pendulum technique. The internal friction curve consists of a background which increases as the temperature increases, a maximum at 860°C apparently a background due to the al-lotropic transformation, a maximum due to grain boundary relaxation with an associated heat of activation of 58,000 cal per mol, and an anomaly below 350°C which may be associated with a precipitation perphenomenon, Oxygen in below small amounts reduces the grain boundary maximum substantially. The variation of the torsion modulus at 20°C was found to be 3450 Kg per mm2 for the zirconium used in the present work. IT is well known that small amounts of certain solutes materially affect the ductility of zirconium. Lely and Hamburger,&apos; as early as 1914, found that high purity zirconium exhibited a remarkable ductility, while Fast&apos; has shown that oxygen and nitrogen can cause substantia1 embrittlement. Treco" has recently demonstrated that the ductility decreases sharply with the oxygen content, and that 2 atomic pct O2 embrittles zirconium to such an extent that cold working is impossible. The marked decrease in ductility is difficult to understand in view of the fact that Domagala and McPherson4 report the solid solubility of oxygen in zirconium to be 29 atomic pct at 500 °C. Another metal which behaves much the same as zirconium in this respect is titanium. Pratt et al." investigated the internal friction characteristics of titanium and the effect of oxygen on the internal friction values. It is evident that internal friction measurements are of value for studying grain boundary segregation, as shown by Pratt et al. for oxygen in titanium, by Pearson for oxygen in copper, and by Maringer and Schwope for oxygen in molybdenum. With this in view, the internal friction characteristics of zirconium and the qualitative effect of oxygen on the grain boundary relaxation phenomenon were investigated. Materials and Experimental Procedure The zirconium used in the present work was supplied by the Foote Mineral Co. in the form of wire 0.05 in. diam. The analysis supplied by the manufacturer indicates the amount of hafnium as 2.4 pct, less than 0.01 pct O less than 0.01 pct N,, less than 0.02 pct H,, and less than 0.001 pct C. Additional spectro-graphic analysis indicates the other main impurities as follows: 0.01 pct Fe, 0.05 pct Si, 0.008 pct Cu, <0.005 pct W, <0.001 pct Al, <0.05 pct Mg, <0.001 pct Ni, <0.02 pct Ca, and <0.01 pct Ti. Microscopic examination of the material in the as received condition revealed very fine grains with numerous twins. Specimens were annealed either in situ in the internal friction apparatus or in evacuated silica tubes in an auxiliary furnace. When the specimens were annealed in the auxiliary furnace, they were wrapped in identical zirconium wire to prevent contamination by the container. Metallographic sections were taken in all cases. Some were taken from the specimens used for internal friction measurements after completion of the experiments, while others were taken from control specimens at intermediate stages of the experiments. lnternal friction values were obtained by measuring the free decay of a low frequency torsion pendulum (1 cycle per sec), the suspension of which was

Jan 1, 1957

By Margaret V. Doyle, R. W. Powers

INTERNAL friction measurements, carried out as functions of temperature, have been used extensively to obtain data on the mobility of interstitial impurities in the Group V metals, vanadium, colum-bium, and tantalum. For a given frequency of vibration, the internal friction peaks at a temperature which depends principally on the particular metal and interstitial impurity. Relaxation times and corresponding activation energies are determined from a knowledge of such peak temperatures for various vibration frequencies. These experimentally determined relaxation times are related to the average jump frequencies of the interstitial impurity atoms using the model of Snoek1 and can be related to macroscopic diffusion coefficients as shown by Polder.2 In these Group V elements, the impurity whose diffusion rate has been the hardest to pin down by the internal friction technique has been carbon. The experimental difficulties associated with carbon in these metals were not evident in the earliest investigation carried out by Ke on tantalum.3 The carbon peak was thought to occur near 140°C at 1 cps on the basis of the enhancement of the height of this peak measured on specimens which had been coated with colloidal carbon and heated in vacuo at 1200°C. Presumably on the basis of similar evidence, Wert identified a peak also near 140°C at 1 cps in columbium with the diffusion of carbon in that element." Later, the difficulties of admitting carbon into these metals without simultaneously introducing oxygen were pointed out by Ang and Wert- nd by Marx, Baker, and Sivertsen.6 The latter suggested that the peaks attributed to carbon in tantalum and columbium might arise from the presence of traces of oxygen, adventitiously absorbed during the carburization. Such suspicion was confirmed, at least in tantalum, when it was found possible to prepare C-Ta specimens without contamination by oxygen. Specimens sci prepared, aitnough high in carbon content, gave no evidence of a damping peak near 140°C.7 Recently, the authors were able to Show that carbon diffuses in tantalum at a rate only slightly slower than that for nitrogen.8 At 1 cps, the carbon peak lies at 34g °C, only a few degrees above the nitrogen peak at 341 °C. However, the two could be distinguished by a different stability with respect to aging at 400 °C and by a different dependence of peak height on solute concentration. On the basis of this experience with tantalum, it appeared worthwhile to search also for a carbon peak in columbium in the vicinity of the nitrogen peak." In this report, the location of the carbon peak in columbium is made known and its position relative to the nitrogen peak is compared with the authors&apos; previous findings in tantalum. In addition, a second source of internal friction seen only in specimens of very high purity is discussed. Columbium was obtained from the Fansteel Metallurgical Corp. as either 30 or 40 mil diam stock. The manufacturer gives the following analysis as typical of this material: 99.4 pct minimum Cb, 0.10 pct maximum C, 0.5 pct Ta, 0.04 pct Ti, 0.02 pct maximum Si, and 0.01 pct maximum Fe. Wires 13 in. long were degassed near 2200°C for 4 to 16 hr in an ultimate vacuum better than 2.10" mm Hg in an apparatus described previously.8 This treatment reduced the oxygen and nitrogen damping peaks observed in the as-received material to less than 0.0001 in Q-1 above background. The latter value varied somewhat from specimen to specimen in the range 0.0004 to 0.0008, depending chiefly on the wire diameter and the frequency of vibration. The high temperature evacuation left the specimen in a rather soft condition, the Vhn being reduced to 40 from a value near 121 in the as-received conGi~iur~. The gram size was about the diameter of the specimen. After outgassing, specimens were loaded with carbon by absorption of such hydracarbons as methane or ethylene. Carbon was also added to a few speclrnens by heating them at

Jan 1, 1958

By B. B. A. Luzzat

ALUMINUM is today the most widely used of the nonferrous metals. The technical literature on the aluminum smelting process is, nevertheless, very meager, so that anyone interested in the subject cannot rely on more than a couple of dozen publications.&apos; The patent literature is equally scarce; most patents refer to the production of alumina from aluminum-bearing ores, while not more than a few score significant patents deal with the electrolytic reduction of alumina, which is the real core of the aluminum smelting industry. The "reduction phase" is, from a technical and a scientific point of view, much more interesting than the "alumina phase", which, in effect, is only a combination of such well-known chemical operations as dissolving, precipitating, filtering, drying, and calcining. The electrolytic reduction of alumina, on the other hand, has features which do not appear in any other metal smelting operation. Some of them are of great technical and scientific interest even for those not directly engaged in the production of aluminum. The purpose of this paper is to describe in some detail the basic facts and developments of the reduction phase of aluminum smelting. Two Aspects of the Electrolytic Process The raw material for the reduction process is alumina (Al2O3) . Its purity in general runs as high as 99.50 pct or more. Small differences in the chemical composition generally do not affect the reduction process.* Of more importance are the physical prop- erties of the alumina, since they affect not only its rate of solution in the molten bath but also its heat insulating power.† In the following pages, un- less otherwise stated, it is assumed that a standard "Bayer" alumina is used. The reduction process, by which alumina is broken down into its components, may be roughly defined as its electrolysis in molten cryolite. The oxygen separates at the anode, and the aluminum at the cathode, which forms the bottom of the electrolytic cell. The electrolytic cell (or pot) where the process is carried out is a strongly reinforced steel box. The

Jan 1, 1951