Search Documents

By H. A. Wilhelm, P. Chiotti, G. A. Tracy

A summary of analytical, X-ray, thermal, and metallographic data obtained in the study of the Mg-U system is presented. No intermetallic compounds are formed by these two elements, and their mutual solubility is limited at temperatures up to 1255°C. The compositions of the liquids which coexist at 1135°C under a pressure of 3 atm are 0.14*0.05 wt pet U in magnesium, and 0.004 wt pet Mg in uranium. The solubility of uranium in magnesium decreases to 0.0510.03 wt pet at 675OC, and to about 0.0005 wt pet at 650°C. Due to the reactivity of both uranium and magnesium toward crucible materials, the choice of a suitable crucible presented a problem. Crucibles made from high purity magnesia to which 10 wt pet MgF2 was added to reduce porosity proved to be satisfactory. Some observations made with the use of other crucibles are given. THIS investigation was made to establish the phase diagram for the Mg-U system. Ahmann,' formerly of the Ames Laboratory, did some work on the system. He used several methods in an attempt to prepare Mg-U alloys. One of the methods involved the reduction of UF, with a large excess of magnesium. In these experiments, the magnesium wet the surface of the uranium, but there was no evidence for compound formation. The maximum solubility of magnesium in uranium was indicated to be 0.01 wt pet. In another set of experiments, uranium chips as well as uranium powder were heated in contact with molten magnesium in a graphite crucible for periods of time up to 48 hr. A reaction layer was found at the Mg-U interface in several instances. X-ray analysis of the layer material showed the presence of UC and some additional unidentified lines which were interpreted as indicating the possibility of an intermetallic compound of uranium and magnesium. These studies indicated the maximum content of magnesium in uranium to be 0.043 wt pet. One sample of magnesium which had been heated at 1025°C in contact with excess uranium was found by chemical analysis to contain 0.275 wt pet U. Rules, based on empirical or semi theoretical considerations, which attempt to predict the alloying behavior of metals have been presented in the literature. Although these rules are not infallible, they nevertheless serve as useful guides. Using them, several generalizations can be made concerning the Mg-U system. According to Hume-Rothery's' atomic

Jan 1, 1957

By F. L. Ruhlman, Max C. Eastman

The termination of the recent war marked a major changc in the oil-field operations at. Elk Hills. Production was greatly curtailed, various experimental production projects were started, and a long-range exploratory program was inaugurated. Production was reduced from the wartime peak of 65,000 bbl per day to the current rate of about 8ooo bbl per day in order to maintain an available source of crude that can be drawn upon during a national emergency. The existing production rate is deemed essential to carry on the experimental production projects. These projects are being conducted to determine the best methods and means of maintaining the Reserve, shut in, but in a state of readiness to produce the maximum quantity of oil in the most expeditious manner. Projects now being investigated include: (I) protection of surface equipmerit; (2) repair of wells that might damage the reservoir; (3) gas injection; (4) water eneroachment, (5) gravity drainage. An exploratory program is being carried on to determine the amount of recoverable oil in the unexplored portions of the Reserve. The Shallow-zone exploration is practically completed, but owing to the complexity of the Stevens structure and the magnitude of the oil discoveries in the Stevens, exploration will probably continue in that zone for another two years. Introduction Summary of Development History of Elk Hills Although a detailed history of Elk Hills oil field is presented in various publications,1,2 a summary of its unusual development and production history will be given in order that the present problems may be more readily understood. The first development that resulted in commercial production was in the central part of the Reserve. The first well, Hay No. I, in sec 36-R,* was completed in January I9I9, and was soon followed by 37 Others in the same general area. It is commonly referred to as the Hay-Carman area and was shut in in stages from 1925 to 1934 as a result of litigation regarding the title to the land. Not being highly producti,, only about 6½ million barrels of oil with a large volume of gas was produced from the area prior to the shutdown. Shortly after the start of the development of the Hay-Carman area, drilling was started 6 miles east in sec 36-S' Tupman NO. I came in for 5000 bbl per day early in I92o, It was followed by more than 200 others in the next few years, and the field became one of major importance. Produc-

Jan 1, 1949

By S. R. B. Cooke, S. W. Clark

Adsorption of calcium and magnesium by quartz was determined over a wide pH range using flame photometry for solution analysis. A parallelism was noted between calcium adsorption at alkaline pH and flotation of activated quartz by means of various fatty acid collectors. Abstraction of calcium from 100 ppm solutions increased above pH 10.5 until all of the calcium was removed at pH values between 12 and 12.5. Calcium was desorbed from the quartz over the pH range 12.5 to 13.0 and returned to the solution. Precipitation of magnesium hydroxide prevented measurement of magnesium adsorption above a pH of 9.9. A calcium adsorption isotherm determined at pH 9 matched measurements of barium adsorption by other investigators over the range where adsorption corresponded to the equation of a Freundlich adsorption isotherm. In accordance with the Gouy-Chapman theory for adsorption in the diffuse layer, adsorption of the divalent cations under these conditions was four times the adsorption of monovalent sodium. Activation of quartz by multivalent metal cations in flotation using anionic collectors has been studied by many investigators. The occurrence of activator cations in the water of flotation mills makes depression of silaceous gangue very difficult. Alternatively, in some flotation systems it is practical to cause activation of quartz so that it is floated from the desirable mineral values. The present study was initiated to investigate the activation of quartz by measuring adsorption of calcium and magnesium ions as a function of solution pH. Early empirical tests showed that quartz would be activated to flotation using anionic collectors if any of a number of divalent or trivalent metallic cations were present in the pulp.1*2 Subsequent studies by Clemmer,3 Cooke and Digre,4 Cooke,5 Schuhmann and Prakash,6 and Cooke, Iwasaki, and Choi,7-8 showed that flotation depended strongly upon the alkalinity of the flotation pulp, the concentration of the activating cations, and the chain length and structure of the organic collectors used. The concept of the electrical double layer has been applied to the case of the quartz-aqueous solution interface by Gaudin and Fuerstenau,9-10 and by de Bruyn 11 to explain the activation of quartz by multivalent metal cations. Studies of the surface of quartz by Gaudin and Fuerstenau9,10,12 and by Li " using the streaming potential technique contributed much information on the electro kinetic condition of the surface of quartz in the presence of various organic and inorganic ions. Measurement of adsorption of ac-

Jan 1, 1969

By J. P. Matoney, E. J. Sandy, D. A. Dahlstorm

INTRODUCTION Before an understandable discussion concerning coal-dewatering processes can be initiated, it is necessary to define some terms of usage. The many different meanings and interpretations of terms preclude development of standard definitions so that the terms which are defined in this chapter should be regarded mainly as working terms intended to facilitate communication. A coal slurry ' might be defined as a watery suspension carrying particles of fine coal and other assorted material ranging upward in size from the finest clay particles. Some particles may be in the colloidal sue range and exhibit characteristics of suspended colloids. The dilution of the system generally is such that it is in a condition of independent particle subsidence. In some coal mining areas a slurry is regarded as a suspension of fine coal and other materials having a dilution that cannot be economically dewatered by filtration. A coal slime may be regarded as a slurry containing particles of such size range that 50 per cent or more (by weight) will pass a 200-mesh sieve. Slime suspensions generally are difficult to handle without special treatment in conventional sedimentation equipment. A coal sludge is defined as a slurry that has been partly dewatered by sedimentation usually to a thick or viscous consistency where further dewatering can be most readily facilitated by filtration. Culm and silt are terms characteristic of coal-preparation practice which should be defined. In anthracite terminology, culm is the generally coarse residue or waste accumulation of coal, bone and rock from preparation plants most of which are no longer functional. Culm has a wide range of sizes, some rather coarse, and except to differentiate it from silt, the term is of limited interest in this discussion. In anthracite terminology, silt is the accumulation of waste fine coal, bone and slate settled out from preparation plant water in excavated basins. Silt is generally made up of particles ranging in size from 3/32-in. round-opening screen to the very finest sues. Silt is also referred to at times as sludge, fines, slush, and mud and is the partly dewatered derivative of what has been previously defined as slurry. In the terminology of the bituminous coal producing areas, the word culm commonly corresponds to slurry or slime, depending upon the size distribution of the suspended solids. Editor's Note: Because of the numerous and varied contributions of the associate authors of this chapter, the text does not differentiate between sections authored by each individual as is the case in most chapters of this book.

Jan 1, 1968

By M. Cohen, B. L. Averbach

Many hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or sub-atmospheric coo1ing.l,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained . steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1949

By R. I. Parsons, M. B. Standing, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By B. L. Averbach, M. Cohen

Many hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or sub-atmospheric coo1ing.l,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained . steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1949

By M. B. Standing, R. I. Parsons, E. N. Lindblad

The recovery of the heavier components from a gas cap or retrograde pool is shown to be the greatest when the sand is cycled with a dry gas at a low pressure. This conclusion is in direct opposition to the belief that the most efficient production program is pressure maintenance and cycling at or near the dew point. The results are calculated from: (I) constant volume, variable composition pressure-volume-temperature tests on a mixture of trap gas and liquid from a producing well; (2) published equilibrium constant data and the measured composition of the dew-point material; and (3) the fact that in a sand section of homogeneous permeability, injected gas displaces reservoir gas nearly, quantitatively. The results are based on the simplifying assumption that variable permeability systems may be defined by the ratio of two statistical parameters, and that gas injected into an actual sand will behave as though the sand were composed of many layers, each of constant permeability. Introduction Pressure decline in gas-condensate type reservoirs is accompanied by the formation of a liquid phase throughout the reservoir. Over the past ten years the processing of the material from these types of reservoirs for the heavier hydrocarbon components and the return of the light fractions to the reservoir ("cycling") has become increasingly popular. It has often been stated that the purpose of such a program is to prevent the loss of the retrograde liquid phase formed in the reservoir. The purpose of this paper is to present the results of laboratory tests and computations concerned with several possible methods of producing a gas cap or condensate type of reservoir. The results show that the recovery of heavier hydrocarbons for this type of reservoir is not a maximum under conditions of cycling at or near the dew-point pressure. Instead, variations in permeability and the ability of the dry injected gas to revaporize condensate, point to cycling at a considerably reduced pressure as the optimum production-method. In addition the paper suggests a way of evaluating sands for their permeability variation. The calculations presented in the following sections of the paper are in terms of the production of the butanes and heavier fraction from the gas cap of a field which had an original pressure of approximately 3000 psi. Specifically, the calculations show: 1. To what extent the condensate formed in the reservoir after pressure decline can be recovered by the cycling of a dry absorber-plant gas through the sands. 2. Whether there would be greater recovery of hydrocarbons if cycling were instigated at the original reservoir pressure.

Jan 1, 1948

By R. M. Brick

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

Jan 1, 1944

By Helmut Thielsch

METALLOGRAPHIC specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production " requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and photography in electron microscope and (5) interpretation. PREPARATION OF METAL SURFACES Usual metallographic polishing is generally satisfactory. It is important though that the final polish be applied very care- fully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside from superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the same for 20 min. in a solution containing 8 grams cupricsulphate in 40 C.C. of concentrated HCl and 40 C.C. of H20 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by 10 min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

By C. R. St. John, R. W. Lindsay, Charles R. Austin

MANY of the factors influencing the creep behavior of ferrous alloys have been investigated and reported upon in the literature, including such variables as grain size, steelmaking practice, nature and stability of the microstructure, and the effect of alloying elements in steels. However, with respect to the latter, the microstructures involved are usually heterogeneous and as a result the effect of the addition is related to its effects on the various phases present in the microstructure. In the instances where this structure consists of ferrite and carbide, the behavior of the alloy addition will be related to its action in strengthening ferrite and in opposing temperature softening of ferrite as well as coalescence of carbide. The present paper is the third in a series comprising a comprehensive review of investigations on the properties of iron binary alloys. 1.2 Its purpose is to describe the results of isolating one microstructural phase, namely ferrite, and studying its creep characteristics in both the unalloyed and alloyed conditions. This should aid in establishing to a large degree the importance of ferrite in the creep behavior of steels consisting of the previously mentioned ferrite-carbide aggregate. REVIEW OF PREVIOUS WORK In view of the fact that the present investigation deals only with the effects of silicon, manganese, chromium, molybdenum, nickel, and cobalt, and to a certain extent with the effects of carbon, the review of previous literature will be confined to these elements. Practically no references were encountered dealing with the influence of these elements on the creep characteristics of the isolated phase. However, various contributions have dealt with the creep behavior of low-carbon steels alloyed with the elements under consideration. A particularly concise review in this respect is given by Bullens (Battelle)3 and much of this material has been drawn upon. The definite improvement in creep resistance and high-temperature strength conferred by molybdenum is well known. Published suggestions by the A.S.M.E.4 permit of an increase of some 2000 to 5000 lb. per sq. in. in permissible design loads over a temperature range from 650° to 1000°F. as a consequence of additions of 0.40 to o.60 per cent of this element in carbon steels of the order of o.25 to o.35 per cent carbon content. Babcock and Wilcox Tube Co.5 has published data showing the pronounced increase in stress necessary to cause one per cent creep per 10,000 hr. when additions of 0.5 or 1 per cent molybdenum are made to a plain carbon steel. These data apply to temperatures over a range from 800° to 1000°F.

Jan 1, 1945

By Norman Brown

It is suggested that the difference in ease of cross-slip among the fcc metals determines the relative amounts of [111] and [100] wire texture which occur in each metal. Since the ease of cross-slip is controlled by the stacking fault energy, it turns out that the amount of [111] texture should increase as the stacking fault energy increases. Arguments and existing data are presented to support the above suggestion. THE fcc metals generally have a dual texture, [11 and [loo], after wire drawing. As yet no fundament explanation exists concerning the variation of the amounts of each texture among the metals. Barrett&apos; has compiled data which show how the relative amounts of each texture vary from 100 pct [Ill] in the case of aluminum to 25 pct [l1] for silver. In this paper it is suggested that the value of stacking fault energy plays a major part in determining the amount of each type of texture. The double texture has its origin in the classical rotation of a single crystal under tension. An equilibrium position of the crystal is one in which three or more equivalent slip systems are operating simu taneously. Most crystals, initially, tend to rotate toward the [1ll] or the [l00] pole depending upon its initial orientation. This single-crystal behavior is essentially the same as the rotational behavior of the polycrystalline metal as worked out by Taylor.2 The next point to consider is whether the [Ill] or [100] orientation is more stable. There have been many discussions of this question3&apos;" which, in general, have lead to the conclusion that 11111 is most stable. For example, Pickus and Mathewson 4 suggested that a [Ill] texture produces more effective flow becake the [ 110] slip direction makes a smaller angle with the [111] than with the [loo]. A crude statistical argument will be presented which again favors the (1111 orientation. In order to maintain a pure [loo] wire texure, slip must occur in equal proportions in four of the six possible <110>slip directions. In order to maintain a pure [Ill] texture, slip must occur in equal proportions in only three of the six <110>directions. Since the <110> directions are the only slip directions in a fcc metal and if it is assumed that each of these six directions is equally probable, then the relative probability of a [1ll] texture vs a [l00] texture may be calculated. The statistical weight of a particular texture is the multiplicity of a texture times the probability of obtaining any one. The statistical weight for [Ill] is

Jan 1, 1962

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942

By R. B. Adamson

The fatigue behauior of irradiated copper single crystals is compared to that of unirradiated crystals. Proton or electron irradiation did not substantially change the fatigue-lzj.e, fatigue-hardening-, or slip-line characteristics, while neutron irradiation did appear to alter these parameters. Postfatigue transrrzission electron microscopy did not reveal any marked structural differazces between irradiated and unirradiated specimens. Possible dislocatio~a mechanisnzs to explain the observed behavior are discussed. A LTHOUGH considerable work has been done to ascertain the effects of radiation on the tensile properties of metals (e.g., Refs. 1 and 2), little work of a basic nature has been reported on the effect of radiation on fatigue properties. Since it is known that fatigue properties are sensitive to conditions at the surface of the metal, it was felt that charged particle irradiation, whose penetration into metals is very small, might influence the fatigue behavior. To investigate this surface effect, irradiations with 10 mev protons and 1.5 mev electrons were conducted. The range of 10 mev protons in copper is about 0.236 mm; which is very small compared with the thickness of the specimens used (1.53 mm). The range of 1.5 mev electrons is somewhat larger, on the order of 0.665 mm.4 On the other hand, irradiation with reactor neutrons produces damage throughout the entire specimen, so neutron irradiation can be used to study the effects of bulk damage. The damage introduced by proton and neutron irradiation is expected to con!ist of large interstitial dislocation loops,5 tiny (<25A) vacancy loops," and/or various vacancy-rich regions called depleted zones.&apos; In the case of electron irradiation at about -173°C the damage is expected to consist of isolated Frenkel pairs.&apos; The effect of radiation damage on the fatigue properties of some engineering materials has been reported,g,10 but the results are not clear-cut or consistent. SPECIMEN PREPARATION Zone-refined copper was used to grow single crystals by a modified Bridgeman technique in an inert helium atmosphere. Using a seeding method, single crystals were obtained as bars about 6 in. long with a cross section of 3 by $ in. Immediately upon removal from the split-mold graphite boat in which they were grown, the very soft bars were embedded in a room-temperature setting plastic. They could then be cut into specimen lengths without introducing any long-range damage. Generally, four or five specimens plus one seed were obtained from each bar. The plastic material was dissolved away in acetone and the orientation of each sample was checked by the standard Laue X-ray

Jan 1, 1968

By P. J. Soltis

Direct as well as indirect evidence of a-phase ordering was found in a "near-a" type titanium alloy, Ti-8Al-1Mo-1V. The annealed alloy showed an anomalous decrease in second-stage creep rate at 950°F (510°C) and 47,500 psi. Anomalous increases were noted in initial yield stress after 500 hr creep exposure and in tensile strength after 1100 hr creep exposure. Debye-Scherrer X-ray diffraction patterns obtained on fine-grained polycrystalline speci-ment showed much line broadening and development of superlattice lines after 500 hr at 510° C. Examination with the light and electron microscopes failed to reveal phase changes in thermally exposed material, but detailed metallography is presented illustrating the plastic and fracture characteristics of the alloy. Electron-metallographic evidence is presented, however, which shows the nature of the nucleation and growth of ordered regions from the disordered a in annealed material. In the original phase diagram of the binary Ti-Al system constructed by Ogden et al.1 aluminum was shown to be soluble in a titanium over a wide temperature range at concentrations up to about 30 pct. Subsequently, a number of papers2-7 have appeared which indicate the existence of either intermetallic compounds and/or ordered phases in the a field up to 25 pct Al. In the most recent of these, Goldak and Gordon paw7 have determined unequivocally the ordered hexagonal D019 structure for Ti3Al in a 25 pct Al alloy. No superlattice lines were observed above 1112°F (600°C). Previously, the embrittle-ment encountered by Crossley and Carew4 in low- temperature heat treatments of binary Ti-Al alloys low in aluminum had been attributed to the appearance of a new phase in light micrographs. In the present work, direct as well as indirect evidence is presented showing the existence of a-phase ordering in what is essentially the binary Ti-8A1 alloy containing small percentages of the ß stabilizers molybdenum and vanadium, i.e., the "near-a" Ti-8Al-1Mo-1V alloy. Although Bohanek and Kessler8 have shown that this alloy has good stability at temperatures up to 1100°F (593°C), the present work shows instability at 950°F (510°C) where long exposure times were used. Light and electron microscopy proved very useful in revealing the mechanical behavior of ordered a and led to the conviction that ordered "near-a" alloys may have remarkably good properties and useful engineering applications.

Jan 1, 1965

By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1&apos;2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O&apos;s. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO&apos;s are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.&apos; At 900°C noticeable decomposition takes

Jan 1, 1964

By P. G. Shewmon

If interfacial equilibrium is maintained at the interface between a growing precipitate and the supersaturated matrix, so that solute diffusion alone determines the growth rate, the precipitate shape should evolve toward that characteristic of the dendrites found in solidification. However, this shape is rarely observed in precipitation reactions proceeding at high temperatures where interfacial equilibrium is usually felt to prevail. Thus some other stabilizing factor must enter, to keep the interface smooth. It is shown that a slow interfacial reaction (low interfacial mobility) will stabilize the interface, while transformation stresses have a IN studying the kinetics of phase transformations such as solidification or proeutectoid precipitation at high temperatures, it is customary to assume that equilibrium exists across the interface and that the rate of the reaction is determined by the rate at which heat and solute diffuse to and from the interface. In the case of precipitation, such an assumption predicts an almost infinite rate of initial growth. It is generally stated that the rate cannot be infinite and that during some initial period the rate must be determined not by solute diffusion but by an interfacial reaction, i.e., transferring atoms across the interface. The duration of this much weaker stabilizing eFfect and impurities tend to enhance instability. It is also concluded that a sets an upper limit on the wavelength of the perturbation that can give instability. Thus initially all flat or smoothly curved particle interfaces will be stable even if their growth is diffusion-controlled. Proeutectoid precipitation in the Fe-C system is considered in some detail and it is shown that the experimental results can only be rationalized if the growth rate of ferrite in steel transformations is determined by a slow interfacial reaction for all hut a few orientations between the two phases. initial period has never been clearly established, but it is generally assumed to be too short to affect any measurable results.&apos; Several authors have pointed out that in the case of interfacial equilibrium any bump in the surface will grow out ahead of the planar interface due to the higher gradient in front of it.2j3 Thus the interface will be unstable with respect to an irregular interface with points (plates) propagating rapidly out ahead of the interface into the supersaturated phase. Recently, Mullins and Sekerka have given equations for the stabilizing effect of surface tenion.~ They found that for particles with a radius of curvature of 1 p or greater the stabilizing effect of surface tension will be completely overcome by a supercooling, or supersaturation, of as little as

Jan 1, 1965

By C. S. Barrett, P. Coheur

ANNEALING twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the recrystallization texture,1 and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (111), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3,4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture this is true, for example, with the (113) [211] texture so commonly reported for brass-hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism . MATERIALS AND METHODS The samples investigated were of secondary copper (melted in Belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice has not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip 10 cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a cameral that traversed

Jan 1, 1946

By L. F. Terry, H. K. Ihrig, D. J. Sabin, Ralph E. Davis

This paper presents the results of a study of the comparative values of the several fuels commonly used by industrial plants. It shows that the energy actually recovered from any fuel and turned into useful work is dependent upon several factors: (1) the total energy available in the fuel, (2) energy losses resulting from combustion reactions and (3) energy losses dependent upon the mechanics of the firing operation. The chemistry of combustion and the losses resulting therefrom are discussed. The Advantages and disadvantages of the several mechanical methods of firing and the resulting heat losses in each are developed. Data obtained from several typical fuel operations, where careful records have been maintained, are presented to show that the practical results in the actual operation are in harmony with the theoretical results developed in the earlier part of this paper. Water power and solid, liquid or gaseous fuels are at present the only commercial sources of energy. The economic utilization of any one of them depends, in the final analysis, on the cost of energy per unit of finished product to which the energy is applied. The location of the plant utilizing the particular fuel chosen is a large factor in the original choice. The cost per unit at its original natural source, or even in its delivered form, is not always the final measure of its worth. The use of electricity as a source of energy illustrates this to the extreme. Electric current produced from water power is very cheap in certain localities. In Norway, current is sold as low as ½0# per kw-hr., while in dry cells it costs as much as $10 per kw-hr. Yet the sale of dry cells is a large business. The selling price of gas also varies widely. In some localities natural gas for the manufacture of carbon black sells for as low as $0.02 per million British thermal units, while artificial gas for domestic purposes sells for as high as $6 per million B.t.u. Obviously the cost per unit of energy is not the final determining factor in its purchase. Any discussion of the economic utilization of fuels must include costs in relation to the units of finished material manufactured. In large central power generating stations, this is the over-all cost per kilowatt-hour, and in ceramic firing the cost per unit of finished product of a certain quality is the criterion of economic utilization.

Jan 1, 1931