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By Ivor Jenkins

Processes employing 'controlled at-mospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been asso-ciated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and dificult prob-lems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases. Controlled atmospheres such as disso-ciated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,' but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1948

By Ivor Jenkins

Processes employing 'controlled at-mospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been asso-ciated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and dificult prob-lems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases. Controlled atmospheres such as disso-ciated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,' but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1948

By Homer Turner

COALS, other than anthracite, have been so thoroughly studied under the microscope during recent years, that we now know what kinds of plants and what parts of plants form the bulk of lower rank coals from peat to bituminous coal. The microscope has also shown the state of preservation of such vegetation as well as the nature and distribution of products of plant decay. These and further details have been ascertained mainly through the employment of two methods of attack, section cutting and maceration. Anthracite has failed to respond to these methods, so well adapted to the study of lower rank coals and, therefore, has been neglected by investigators to such an extent that there is much doubt as to its microscopical characteristics. The object of this paper is to lift anthracite from its realm of obscurity by demonstrating the wealth of microscopical detail that is revealed when reflected light is used on a properly polished and etched surface and, further, to show the relationship between anthracite and bituminous coal.

Jan 2, 1925

By D. Harker, M. J. Murphy

The mechanism by which age-hardening takes .place is still not completely understood. The principal theories range from the extreme of "precipitaiion-hardening" to that of "order-hardening," with many intermediate gradations. In the hope of obtaining new data on which to base a choice among the many theories, the authors have made electron micrographs of formvar replicas taken from metallic specimens at various stages of age-hardening. The results so obtained on an alloy of 2 per cent beryllium in copper and one of 20 per cent molybdenum in iron will be described in the following pages, as well as the technique used in preparing the replicas. Preparation of Formvae. Replicas of Metallic Specimens This section is concerned with the techniques that have roved successful in preparing formvar replicas for studying the microstructure of metals with the electron microscope. Because of its simplicity and accuracy, the formvar replica1 method developed in the General Electric Research Laboratory has been used exclusively, since it is much simpler than the silica replica method of Heidenreich and Peck2 and produces as good results. The formvar method to be described requires a technique acquired only by practice, and no foolproof set of rules can be given. it is a rapid method and a replica can be obtained in less than five minutes under favorable conditions. This does not mean that perfect replicas can be produced every five minutes, but rather that one can well afford to take several strippings* in order to produce a replica of high quality. The metallographic technique required for replica work—very fine polishing and etching with very dilute solutions—is described here. It can be said, in general, that almost any surface that has been carefully prepared for a photomicrograph at 1000 or more diameters can be used to obtain a replica for the electron microscope. Preparation of Metallographic Specimens The preparation of the metallographic specimens is somewhat more exacting than that usually given to samples to be used for inspection under the light microscope. After much experimentation, it was concluded that the best method consists in polishing the metal through to the coarse cloth, then etching and repolishing on final cloth until the layer of distorted metal is removed. After this procedure has been completed, a dilute etch—to approximately the depth necessary for a micrograph at 1000 diameters—usually produces a sur-

Jan 1, 1945

By George S. Rice

Those who for the first time see, at a mine, a great hole caused by subsidence; or, going underground, see an extensive fall of roof or hanging wall are apt to regard such an occurrence as an accident and not a normal condition of exhaustive mining. Moreover, the public is inclined to believe that a cave or subsidence of the surface is the result of carelcssness in mining or the rapacity of the mine operators in "robbing pillars," a tern too loosely used in descriptions of coal mining. This belief is fostered by the common-law requirement that an owner of the surface or of surface improvements is entitled to full support of the surface. Court decisions have upheld this law even when that owner has sold or leased the underlying mineral, unless a clause in the sale or lease contract exempts the mining company from paying the owner of the surface for damages that may result from mining. Another reason for this belief is the earlier practice (which is still extensively followed in this country) of leaving all coal pillars unmined, except as they have been thinned by so-called robbing; by not extracting the pillars, the surface may be supported by them for years, perhaps for generations. Inasmuch as the practice of leaving permanently in the mines from one-third to one-half of the mineral is wrong, with respect to conservation of a national resource, it behooves the mining engineers to assemble data and disseminate information on the subject, pointing out that subsidence must follow complete extraction, unless expensive methods of back-filling are employed, such as are used in Germany and France. These methods inevitably increase the cost of mining and the price of the mineral produced. It is popular to speak of "waste in mining" without a realization that much so-called wasting is unavoidable unless subsidence is accepted and provision made therefor where the surface is valuable, or else the only present known alternative of hydraulically placing sand or crushed stone filling in the excavations, at an increased cost of the mineral product to the consumer.

Jan 1, 1923

By George S. Rice

Those who for the first time see, at a mine, a great hole caused by subsidence; or, going underground, see an extensive fall of roof or hanging wall are apt to regard such an occurrence as an accident and not a normal condition of exhaustive mining. Moreover, the public is inclined to believe that a cave or subsidence of the surface is the result of carelcssness in mining or the rapacity of the mine operators in "robbing pillars," a tern too loosely used in descriptions of coal mining. This belief is fostered by the common-law requirement that an owner of the surface or of surface improvements is entitled to full support of the surface. Court decisions have upheld this law even when that owner has sold or leased the underlying mineral, unless a clause in the sale or lease contract exempts the mining company from paying the owner of the surface for damages that may result from mining. Another reason for this belief is the earlier practice (which is still extensively followed in this country) of leaving all coal pillars unmined, except as they have been thinned by so-called robbing; by not extracting the pillars, the surface may be supported by them for years, perhaps for generations. Inasmuch as the practice of leaving permanently in the mines from one-third to one-half of the mineral is wrong, with respect to conservation of a national resource, it behooves the mining engineers to assemble data and disseminate information on the subject, pointing out that subsidence must follow complete extraction, unless expensive methods of back-filling are employed, such as are used in Germany and France. These methods inevitably increase the cost of mining and the price of the mineral produced. It is popular to speak of "waste in mining" without a realization that much so-called wasting is unavoidable unless subsidence is accepted and provision made therefor where the surface is valuable, or else the only present known alternative of hydraulically placing sand or crushed stone filling in the excavations, at an increased cost of the mineral product to the consumer.

Jan 1, 1923

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems. A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. INTRODUCTION The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves are needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemical composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. THE PROBLEM At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1941

By O. D. A. Pease, C. D. Young, C. H. Strand

In an effort to employ cast steel of a stronger structure than that found in the annealed steel casting, the possibilities of heat treatment which will increase the strength without materially decreasing the ductulity may be resorted to.

Jan 1, 1915

By Arthur G. Levy, Henry M. How

The purpose of the investigation on which this paper is based is to determine whether the structural change which occurs in the slow cooling of steel below the transformation range has an important effect on its engineering properties. We recognize two distinct things which occur in steel when it is brought from above to below the transformation range, first, the transformation proper, that is, the breaking up of the austenite or solid solution of the cementite in the remainder of the iron, and the liberation of its components as undissolved cementite and as ferrite or alpha iron; and second, a structural change consisting in the gradual coalescence of the ferrite and cementite respectively into larger and larger separate masses. Let us distinguish these from each other by speaking of them as " the transformation " and " the structural change " respectively. If the cooling is at all rapid the unevenness of contraction induces severe stress; so that in a sense a slow cooling has a third influence, the prevention of such stress. This transformation from austenite to ferrite plus cementite can complete itself only below the transformation range; and, because this structural change is a change in the structural arrangement of the products of that transformation, it too can complete itself only at temperatures below that range, say below 725°; and of these temperatures it is only those between 600° and 725° that give the metal sufficient mobility to permit this structural rearrangement to progress with ally rapidity. The transformation is now known to be rapid, but the structural change is relatively slow. The transformation, the liberation of the dissolved cementite from the state of solution in the austenite to a free state, leaves the steel structurally in the

Jan 1, 1913

By Michael Tenenbaum, C. C. Brown

Numerous investigatiolls have been carried out to determine the total oxygen present in the basic open-hearth bath and the results of these studies have clearly defined the factors controlling the bath oxidation during the period prior to deoxidation. On the other hand, very little is known concerning any changes in total oxygen content that may occur during deoxidation, tapping and teeming. The need for such additional data is continually becoming more apparent, since there is no strict technical basis for selecting any particular deoxidation practice. Many steels are made for the same purposes and to the same chemical analyses by widely differing practices. Apparently, each practice is satisfactory. However, it would be desirable to establish more definitely the effects and relative merits of the individual practices. Such information could be used to give a definite foundation for evaluating various types of deoxidation. In order to approach this problem, a study was made of the changes effected in the total oxygen content of several grades of steel by representative open-hearth deoxidation practices. To carry out such studies, it was necessary that a reliable testing procedure for determining the oxygen content of the steel bath and the ingot mold be established. Before entering on any extensive testing program, consideration was given to the available methods of obtaining steel samples and analyzing for oxygen. Testing Procedures It has been shown5-9 that in solidified steel oxygen may ekist in combination with iron, manganese, silicon, aluminum, titanium, chromium and carbon, depending upon the amount of these elements in the sample. In molten steel, however, there has been no direct distinction of the various oxides. Accordingly, the total active oxygen in the molten steel bath is designated by the symbol 0. During deoxidation, various oxides may be present either in solution in the molten steel or as solid or liquid inclusions. Any sample taken from the molten steel for oxygen analysis will include both the dissolved and the mechanically included oxygen. Similarly, samples of the solid steel product will also include the two forms of Oxygen' Methods of Samplirzg the Molten Steel Bath In order to obtain a true oxygen analysis from liquid steel, this element must be completely retained in the solidified sample. Several methods have been proposed whereby this stabilization can be effected. As early as 1915, Kichlinelo proposed a method for testing molten steel, in which the oxygen combined with some added aluminum. The concentration of the resultant aluminum oxide was determined by chemical analysis. This method was

Jan 1, 1945

By Gerald Edmunds

Although the phenomenon of season cracking is still imperfectly understood, there seems to be ample evidence that season cracks are propagated by the combined action of corrosion and a stress of either internal (residual) origin or external origin. The factors that influence season cracking may therefore be grouped according to corrosive media, nature of stress, and character of the material. Thus the important mass of evidence pointing to ammonia as the most frequently active corroding agent causing season - - cracking of brass has naturally led to the development of laboratory tests of a moderately accelerated character based upon ammonia together with auxiliary agents such as air, water vapor, and carbon dioxide as the corroding agent. Similarly, the knowledge that stress must be present has led to the use of externally applied and therefore accurately measurable stresses in laboratory testing. A companion paper(^)^ to the present one discusses the development of these test methods in our laboratories. The present paper discusses data bearing on factors concerning the nature of stress such as its magnitude and direction of application. It also deals extensively with the character of the brass, particularly in regard to the copper-zinc ratio and the structure as developed by mechanical work-

Jan 1, 1945

Jan 1, 1904

By E. P. Polushkin

This work has for its purpose the establishment of a new method for determining the structural composition of alloys. The area occupied by a constituent on a few representative photomicrographs of the alloy is measured, by a planimeter, especially designed for metallographic work, and the volume and proportional weight of the constituent calculated. Experiments have shown that the results are accurate enough to justify the application of the method to many problems in metallographic research instead of chemical analysis. The advantage of the method is the possibility of determining the amount of the constituents without separating them from the alloy; their composition may also be determined if the ultimate chemical analysis of the alloy is known. Suppose Fig. 1 represents a part of a photomicrograph on which the total area of the black figures is to be found. By a system of parallel lines drawn short equal distances apart all figures may be divided into trapezoids. As the area of a trapezoid is equal to its median multiplied by its altitude, the relation between the total areas of the black and the white figures comprised within each strip is equal to the relation between the sums of medians for these figures respectively. This is also true for the whole area of the photomicrograph. Therefore, to determine the total areas of the black and white figures we must first find the proportion between the sums of the medians and then divide the area of the whole photomicrograph in the same proportion.

Jan 1, 1925

By J. H. Fletcher

AIR has been cooled, heated, washed; humidified and dehumidified for many purposes and in many industries. At a number of metal mines air is conditioned to reduce the high humidity and unbearable heat found in deep workings, and at some mines air is washed to allay siliceous dust. Steam is introduced into the intake air at many coal mines, particularly in winter, for the purpose of keeping loose coal dust so moistened that the hazard of an explosion is lessened. This paper will describe a further successful application of air conditioning in a coal mine, where, for over three years, all intake air has been cooled to a constant temperature for the sole purpose of preventing roof falls.

Jan 1, 1931

By Alexander Squire

A BRIEF study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the .properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,1 who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,2 is concerned with the heat-treatment of steels formed by the carburization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decarburization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and i6 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to 1200°C. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By G. R. Gohn, S. M. Arnold

The results of stress-corrosion tests upon several non-ferrous sheet metals are presented in this paper. The metals include tough pitch copper, five binary brasses, two leaded brasses, one copper-silicon alloy, two tin bronzes, and two nickel-silver alloys. The tests indicate that for most of these sheet metals, externally applied bending stresses below the yield point (0.01 per cent offset) do not result in stress-corrosion cracking as determined by the A.S.T.M. Tentative Method of Mercurous Nitrate Test for Copper and Copper Alloys (B 154-41T).~ Only in the cases of low brass, high brass and medium leaded brass, all cold-worked 4 B & S numbers hard, was any corrosion cracking observed below the yield strength, and in all cases such failures occurred at stresses above the proportional limit for these materials. However, when some of the same materials which showed no evidence of stress-corrosion cracking at stresses below the yield strength, are stressed beyond the yield point, stress- corrosion cracking is quite apt to occur. Since experience has shown that some of these materials, particularly the brasses, are susceptible to stress-corrosion cracking under service conditions, these tests would indicate that, besides externally applied stress and corrosion, plastic deformation in addition to that resulting from the original cold working of the material is also required to produce conditions conducive to stress- corrosion cracking.

Jan 1, 1945

By G. R. Love, M. L. Picklesimer

Aboue 950°C the Nb-Zr system consists of a completely miscible bcc solid solution, commonly called the phase. Between 950 and 600°C, and between 20 and 85 pct Nb, the phase deconlposes, after sunciently long times, into two bcc solid solutions. The pct Zr alloys are conveniently descibecl with T-T-T (time-temperature-transformation) curves having a nose at about 2 hr at 700°C. The reaction rate varies only slowly with zirconium content and negligibly with oxygen contanzination; it is speeded up by a factor of 10 to 15 by 90 pct cold ulork and slowed dou by n factor oj 10 to 30 by a two-hundrecljold increase in grain size. Nb-r alloys with compositions between 40 and 85 pct Nb have been the basis for the majority of commercially important superconducting materials. In part because of their commercial promise, more is known about these alloys than about most other high-field superconducting materials. At the same time, there is considerable disputed or incomplete metallurgical information. For example, although Rogers and tkins&apos; indicate a monotectoid reaction at approximately 600°C and a two-phase 01 + 0, field extending between 20 and 85 pct Nb and to a maximum of 95OGC, erhout&apos; has reported that this entire region would be a single homogeneous B were it not for oxygen contamination. Again, although it has been shown that relatively short-time heat treatments in the vicinity of 700CZ significantly improve the ability of short wire samples to carry high currents in high magnetic fields at 4.2K, these observations have never been fully correlated with the structural change or changes occurring during the anneal. We intend to investigate in detail the effect of metallurgical variables, including heat treatment, on the superconducting properties of hard superconductors. To verify that our experimental techniques are valid and to establish a relative standard against which other materials may be measured, we feel it advisable to know the behavior of the Nb-Zr alloys under a variety of processing conditions. As an initial step toward this goal, we have determined in detail the kinetics of the transformations in Nb-Zr alloys. EXPERIMENT A number of problems had to be solved before beginning any fruitful work on the reaction kinetics in this system. While solving some of these problems, either by chance or by design, small amounts of information were obtained about alloys containing 40, 50, 60, 65, 67, 70, and 75 pct Nb, bal. Zr. In addition, a large range of grain sizes and a range of temperatures considerably greater than the range indicated by Rogers and Atkins phase diagram were examined. We will, however, report in detail only the results obtained for the Nb + 33 pct Zr and Nb + 25 pct Zr alloys at three grain sizes, two levels of oxygen contamination, and the temperature range 550 to 950°C. These data are most complete, but the other data are sufficiently complete to indicate the kind and magnitude of the variation of the transformation kinetics outside this range. The first and most difficult problem encountered in this inquiry was one of sample homogeneity. When Nb-Zr alloys are arc- or electron-beam-melted on a cooled copper hearth, solidification is sufficiently slow that there is appreciable coring in the cast structure and a large variation of grain size across the button thickness. Both these factors significantly affect the apparent reaction rate in the system. A two-step solution to the problem was attempted; an arc-melting and drop-casting technique has been developed by conald that greatly reduces the as-cast grain size and virtually eliminates coring segregation. Ingots made in this way exhibited no detectable (3 pct maximum) zirconium segregation. Before it was evident just how good this technique was, we attempted to supplement it with rather long-time, high-temperature annealing of the cast ingots. This annealing was carried out in evacuated and sealed (seal-off pressures < 1.0 x 106 torr) quartz capsules lined with tantalum foil at 1400 to 1450 C for 8 to 72 hr. There were two principal effects of this treatment: the grain size increased to a fairly uniform 150 p, and the surface and all grain boundaries near the surface acquired a film of a second phase, tentatively identified as an oxide (possibly additionally contaminated with silicon). There was no evidence that this 1400 C treatment had affected the zirconium segregation. High-temperature annealing was subsequently used only for grain-size control, but anneals of longer than 4 hr at temperatures greater than 1000°C were performed in dynamic vacuums (pressure no greater than 1.0 x lo torr). Any contamination resulting from these treatments was well below the limits of detection of our techniques. All samples, as cast, were cold-swaged to at least 85 pct reduction in area. The samples called cold-worked were tested as swaged. The minimum re-crystallization anneal for these alloys was about 12 hr at 1050 C; this produced an equiaxed grain diameter of about 4 to 8 P. Annealing for 4 hr at 1450°C produced a grain size of about 80 to 150 p; and annealing for 4 hr at 1650aC, close to the melting point of many of these alloys, produced a grain size of 0.5 to 1.0 mm. At all temperatures, the larger grain size was

Jan 1, 1967

By C. H. Li, R. J. Stokes, T. L. Johnston

Dislocation half-loops, artificially introduced by sprinkling with carborundum, were subjected to stress using three-point loading. The different stages of loop expansion and multiplication were then correlated with the macroscopic stress-deflection curve. Loop expansion started at approximately one-third of the "yield stress," defined here as the motivation stress. Above one-half of the "yield stress" simple multiplication commenced while about two-thirds of the yield stress gross multiplication developed short slip-line segments. These values were not affected by the age of surfaces exposed to both dry and wet air. Slip was not detected on unsprinkled crystals below two-thirds of the "yield stress." Thus the stress to activate intrinsic sources, defined here as the activation stress, was approximately twice the motivation stress. This relationship was independent of the strain rate used. It is concluded that lattice resistance takes the form of a viscous drag rather than a static type of force. THE importance of surface condition and environment as one of the more significant factors controlling the mechanical properties of ionic solids has recently received renewed attention.1-4 In some materials, notably the alkali halides, exposing freshly cleaved specimens to the atmosphere results in a progressive hardening and embrittlement of the crystals. This has been attributed to the surface layer becoming "aged," thereby restricting the motion of dislocations in such a way that pileup and eventually fracture results. It is necessary therefore in studying the mechanical properties of ionic crystals to inquire first into the density and distribution of dislocations in the normal cleaved surface and to understand the role these dislocations play in the onset of plastic flow. Knowledge of the effect of environment on this behavior will then assist in understanding the mechanism of embrittlement on aging. In the work reported here a method is described for studying the initiation of plastic flow from dislocation sources in the surface of magnesium oxide crystals. Preliminary results are described of the influence of surface age on this behavior. EXPERIMENTAL TECHNIQUES The magnesium oxide used in this investigation was obtained from the Norton Co. and had a nominal purity of 99.5.pct. Single-crystal specimens, having dimensions typically 1/4 by 1/8 in. cross section and 1 in. in length, were prepared by cleavage over (100) planes from the parent crystal. They were deformed under three-point loading with 3/4 in. spacing between the two end supports and a constant rate of deflection at the center of 0.001 in. per min. The maximum strain rate therefore was 1.5 X 10-5 sec-1. Reasons for choosing this particular form of loading will become apparent in a later section. In addition, a number of confirmatory type tests have been performed at higher loading rates where the maximum strain rate was increased to 1 x 10-3 sec -1. Following deformation the crystals were etched to reveal the dislocation distribution. In a previous paper5 we described a satisfactory etching solution consisting of 5 parts of saturated ammonium chloride, one part of sulfuric acid, and one part distilled water. Immersion of the crystals for 1/4 hr at room temperature developed reproducible conical etch pits at the points where dislocations emerged through the surface. It should be mentioned that dislocations freshly introduced by room temperature deformation gave sharply pointed etch pits which generally distinguished them from the almost flat-bottomed pits obtained on "grown-in" dislocations. The distinction is obvious in the photomicrograph included in Fig. 5(b). Annealing crystals at 1000°C for 12 hr on the other hand gave sharper etch pits on the grown-in dislocations and the distinction was no lower -possible; a similar observation has been reported for lithium fluoride. We have succeeded furthermore in chemically polishing magnesium-oxide crystals. Boiling in fresh 85 pct ortho-phosphoric acid for only 1 min resulted in a microscopically smooth surface which could again be etched to reexamine the dislocation distribution. This boiling time was sufficient to remove the surface damage introduced by cleavage (see next section). SURFACE DISLOCATION SOURCES There are a number of ways by which dislocations may be introduced into cleaved surfaces to act later

Jan 1, 1960

By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,&apos; but neglected one2&apos; which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970

By Reinhardt Thiessen

UNDER sulfur in coal, is usually understood that form of sulfur which is combined with iron and known as pyrite. It occurs in the form of halls, lenses, nodules, continuous layers, thin sheets, or flakes, both in horizontal planes and vertical cleavage fissures. But pyrites also occur as very fine microscopic particles, or nodules, disseminated through the compact coal. This form has had but very little consideration. Finally, there is sulfur in coal in an amicroscopic form (not visible with an ordinary microscope), probably combined with the organic matter that exists -in tile coal. This form has had considerable attention from a scientific standpoint, but has probably not been recognized enough on the economic side. One or the other, or both, of these two latter forms may comprise the larger part of the sulfur content of coal, especially after it has been washed or otherwise prepared for use.

Jan 9, 1919