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By H. H. Podgurski

Above 200°C the observed increase in the apparent solubility of hydrogen in low alloy steels caused by cold work is attributed to the formation of methane in microvoids. This methane can be isolated quantitatively, and furthermore, the amount of methane is in accord with the equilibrium 2H2 + Fe3C = CH4 + 3Fe. The micro-void volume, calculated from the methane content via the equation of state for methane, corresponds approximately to that calculated from the measured density decrement produced by cold work. THIS investigation was undertaken with the intent of employing the hydrogen atom as a probe in detecting specific crystallographic defects in cold worked steel. It was expected that different degrees of chemical interaction of hydrogen with the various types of defects could be utilized. The original aim was to assign concentration values to defect sites. The success of this approach requires that experimental conditions can be attained under which lattice-dissolved hydrogen equilibrates primarily with only one type of defect. A set of experiments which appeared potentially to embody these requirements was described several years ago by Keeler and Davis.1 They noted in the case of a mild steel (low carbon) that the solubility of hydrogen between 200° and 400°C near atmospheric pressure was notably increased by cold working the steel. The observed solubility was an order of magnitude greater than the normal lattice solubility. * Although the Keeler and Davis studies suggested that the density decrement effected by their cold-working operation might be related to the anomalous solubility of hydrogen, they offered no explanation of the relationship between the two effects. Prior to this work, Darken and smith3 had noted a similar effect of cold work upon enhanced sorption of hydrogen by steel when charged by acid pickling. In the light of present-day concepts, interaction between lattice-dissolved hydrogen and dislocations was strongly suggested. More recently, Hill and Johnson,4 working with a

Jan 1, 1962

By V. S. Gupt, W. H. Somerton

Rock may undergo great changes in physical properties when heated to high temperatures and then cooled, The temperature and intensity of reactions causing rock alterntiorl.s can he controlled by introducing certain chemicals during heat treament. Three typical outcrop sandsone samples were saturuted with common salt solutions, then heated to several maximum temperatures. After cooling, it was found that per-rrreuhilities had increased much more for salt-saturated samples than for samples not saturated with salt but heated to the same temperatures. This was only true, however. for samples heated above the melting points of the particrrlar salts. Potassium chloritle was particularly effective with Bandera sandstone. Samples saturated with potassium chlorirlr. solution and heated to 900C showed an 11-fold increa.se in perrrieahility. Samples without potasrirdrn chloritle but heated to the .same temperature. showed only a 2.7-jold incresre in permecahility. In application, it seems possible that injecting chemicalc into the formations from a wellbore followed by applying intensive borehole heating might promote reactions which would greatly improve permeability of the formalions. INTRODUCTION Great changes in the physical properties of rocks which have been heated to temperatures in the range of 600 to 800C have been reported earlier. Permeability increases of 50 per cent, and equivalent decreases in sonic velocity and breaking strength have been observed. Although there might be some suppression of certain reactions responsiblc for these changes when rock samples are heated under simulated reservoir pressure conditions. recent work has shown that these are more than offset by the increased importance of other reactions at high pressures. The reactions considered responsible for alteration of rock properties by heating include differential thermal expansion. dehydration, phase changes and dissociation of mineral constituents. Ceramists have long known that temperatures at which reactions occur can be raised or lowered by the presence of certain impurities in the sys. tcnl. Thus the possibility exists that by saturating rocks with appropriate solutions. desired reactions might be accelerated and unwanted reactions might be suppressec! when the rock is heated. Purpose of the present work was to investigate the effects of several common salts on the thermal alteration of sandstones. Types of reactions which might occur are reviewed and the findings of a number of thernlochemical alteration tests are presented. THEKMOCHEMICAL ALTERATION OF SANDSTONE MINERALS The most abundant constituent of most sandstones is quartz. Quartz can exist in at least eight different forms, but in the temperature range of immediate interest (to 900C) only two forms are of importance—alpha quartz below 573C and beta quartz above this temperature. Although the alpha-beta inversion of quartz is very important in thermal alteration of rocks. it is not particularly important here because the inversion temperature cannot be changed significantly by the presence of impurities or by the application of pressure. The transition temperature of quartz to tridynlite is 867C. but the transition is very sluggish. Tridymite is considered to be a metastable transition phase between two stable phases: quartz?cristobalite. However. the transition temperature for tridymite to cristobalite is 1,470C.4 The quartz-tridymite-cristobalite transition can be accelerated substantially by the presence of fluxing agents. Finely divided calcium, magnesium and titanium oxides accelerate the conversion while A12O may retard it. A Mixture of NaCl and CsCl reduces the temperature for cristobalite formation by as much as 420°C. Feldspars constitute the second most important mineral in sandstones. The melting points of feldspars range between 1,000 and 1,700°C depending upon the variety. No information available indicated any important role of fluxing agents in the thermal alteration of this group of minerals. Carbonate minerals are subject to dissociation at temperatures within the range of the present investigation. The dissociation of magnesite can start at a temperature of 373°C, but the reaction is sluggish and might not occur untll a temperature of 500°C or ,higher is reached. Dolomite dissociates in two stages at 500°C and 890°C, whereas calcite dissociation temperature is about 885C. Because CO2 is released in the dissociation of carbonates, ail such reactions are somewhat dependent upon CO2 partial pressure. In the absence of CO: in the surrounding atmosphere, the dissociation of calcite starts at 500°C.However. when 1 atm of CO surrounds the sample, the dissociation does not start until 900C. The other carbonates are apparently much less sensitive to a change in partial pressure of CO2. The aragonite calcite transformation can occur an!. where within the temperature range of 357 to 488°C. depending upon the presence of impurities such as barium. strontium. lead and perhaps zinc. The differential thermal analysis (DTA) curves of both magnesitc and dolomite vary with the presence of 'impuritics. The presence of iron in particular seems to affect the magnesitc DTA curve

Jan 1, 1966

By Arthur C. Simmons

The area producing Pennsylvania-grade crude oil declined sharply in 1943, with a daily average production in the entire area of 71,056 bbl. as against a daily average in 1942 of 77,786. The total decline in the Pennsylvania-grade area amounted to 2,456,311 bbl., and 1,g81,z71 bbl. of this occurrcd within the state of Pennsylvania. The principal decline occurred in the Bradford field, where it was caused primarily by a drastic reduction in well completions. All of the zones in the Pennsylvania-grade producing area showed a decline except the part of Ohio that produces that grade, where production increased very slightly over 1942. Table I shows the average daily production by months for the several districts of the area. Table z is a comparison of the production in the two districts within the state of Pennsylvania. It is interesting to note that the Bradford field produced approximately half the total quantity of Pennsylvania grade but accounted for nearly three-fourths of the decline in production from the previous year. It is believed that this decline is ocasioned by restrictive price ceilings and a lack of adequate manpower to drill the necessary wells to maintain production. Stocks of Pennsylvania Grade At the beginning of 1942, stocks of Pennsylvania-grade crude totaled 3,196,000 bbl. and at the beginning of 1943 they totaled 2,626,000 bbl. At the end of 1943 the stocks of Pennsylvania-grade crude had declined to 1,95z,000 bbl. The available crude stocks have been almost completely consumed, as nearly all of the present crude stocks are "unavailable" and required for

Jan 1, 1944

By Arthur C. Simmons

The area producing Pennsylvania-grade crude oil declined sharply in 1943, with a daily average production in the entire area of 71,056 bbl. as against a daily average in 1942 of 77,786. The total decline in the Pennsylvania-grade area amounted to 2,456,311 bbl., and 1,g81,z71 bbl. of this occurrcd within the state of Pennsylvania. The principal decline occurred in the Bradford field, where it was caused primarily by a drastic reduction in well completions. All of the zones in the Pennsylvania-grade producing area showed a decline except the part of Ohio that produces that grade, where production increased very slightly over 1942. Table I shows the average daily production by months for the several districts of the area. Table z is a comparison of the production in the two districts within the state of Pennsylvania. It is interesting to note that the Bradford field produced approximately half the total quantity of Pennsylvania grade but accounted for nearly three-fourths of the decline in production from the previous year. It is believed that this decline is ocasioned by restrictive price ceilings and a lack of adequate manpower to drill the necessary wells to maintain production. Stocks of Pennsylvania Grade At the beginning of 1942, stocks of Pennsylvania-grade crude totaled 3,196,000 bbl. and at the beginning of 1943 they totaled 2,626,000 bbl. At the end of 1943 the stocks of Pennsylvania-grade crude had declined to 1,95z,000 bbl. The available crude stocks have been almost completely consumed, as nearly all of the present crude stocks are "unavailable" and required for

Jan 1, 1944

By Chase Palmer, Edson S. Bastin

While the reducing action of organic matter, of ferrous sulphate, and of hydrogen sulphide has frequently been invoked to account for the deposition of native gold and silver from ore-forming solutions, the high efficiency in this respect of certain of the metallic minerals which form the ore itself has not been suffciently recognized. If a little finely powdered chalcocite is placed in a test-tube arid 2 or 3 cc. of a dilute solution of gold chloride are poured over it, two or three shakes of the tube suffice to remove all the gold from the solution. The color of the solution changes from yellow to pale green, showing that copper is dissolved simultaneously with the precipitation of metallic gold. If a piece of chalcocite is hung in a dilute aqueous solution of silver sulphate (1/40 normal), a coating of silver begins immediately to form on the mineral, and within a few moments a beautiful silver tree has developed, similar to that formed when metallic zinc is immersed in a similar solution. When similar experiments are conducted with other sulphides and with certain arsenides and sulph-arsenides, especially those known to be commonly associated with native silver in ore deposits, it is found that these minerals differ greatly in their efficiency as precipitants, especially in their effect on silver solutions. The tests made with most of the minerals were qualitatipe only, but the reactions of a silver sulphate solution on chalcocite and niccolite were submitted to quantitative study to determine the nature of the reactions involved. Quantitative studies of the reactions with other minerals are now in progress

Jan 1, 1914

By Robert C. Beckstorm

Russia produced over one-half of the world's petroleum in 1901. It dropped to a low figure in 1920 during the reorganization of the new government. Since then it has had a remarkable growth under the constant demands from the Central Bureau at Moscow. The five-year plan called for the development of all industries, many of which had permitted their equipment to gat out of repair or become obsolete, so that when the magic wand of authority demanded that they double, triple or quadruple their former production they looked to the oil industry for aid. This plan made necessary the building of new factories, dams and power stations; the developing of mines and agriculture, and in many places the building of cities and railroads. Exports were the solution and petroleum was the logical one to carry the load of development of the more backward industries. It had a ready market and fields located advantageously for transportation, which was cheap, and there was sufficient oil to meet the market demands at that time, as domestic consumption was not great. The building program demanded new and modern machinery and technical aid from abroad. FIG . 1.-PETROLEUM Money was necessary and petroleum was the impor- 1925-1931. PRODUTION IN RUSSIA tant product of exchange. This accounts for the rapid development of the old fields, the search for new ones and the building of refineries and transportation facilities. Fig. 1 shows the advance in production since 1925. There has been a. steady increase since 1920, and with the improved drilling equipment and improved methods it will increase as long as the now proved fields continue to produce new wells. The fields of Baku and Grozny have yielded 95 per cent of this production. The Cara Chukur field, which is being developed at the present time, is an extension of the Surakany at Baku and may be considered a part of the old field. New fields are being

Jan 1, 1932

By L. S. Darken

In the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be represented satisfactorily by the simple equilibrium expression where (P) denotes the concentration of a product and (R) the concentration of a reactant in the reaction r1R1 + r2R2 + • • • D P lP1 + P 2P2 + • • • Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a component is not proportional to its true mol fraction. But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple components and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satisfactorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature— as ionization or the occurrence of polar and nonpolar molecules—are presumably less effective in inetal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By L. S. Darken

In the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be represented satisfactorily by the simple equilibrium expression where (P) denotes the concentration of a product and (R) the concentration of a reactant in the reaction r1R1 + r2R2 + • • • D P lP1 + P 2P2 + • • • Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a component is not proportional to its true mol fraction. But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple components and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satisfactorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature— as ionization or the occurrence of polar and nonpolar molecules—are presumably less effective in inetal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By R. H. Edsal, G. Horvay

The transient one-dimensional heat-conduction equation is solved for two semi-infinite media, at different initial temperatures, brought into (poor) thermal contact. It is shown that the two interface temperatures gradually approach the well-known, instantaneously assumed, common interface temperature of the case of zero contact resistance. The present analysis, with slight modifications, may be used in fair approximation also for the class of problems involving a change of phase. One particular application of the boundary value problem solved in this paper concerns the determination of the temerature distribution in metal castings and molds.P This problem has been treated extensively by analytical methods (see e.g., the literature listed in Refs. 1 to 4) by electrical analogs (see e.g., Refs. 11 to 14) and also by experimental methods (see the literature listed in Refs. 4, 5), but prior to the work of Pellini and Ruddle the experimental results were rather unreliable. Immediate motivation for the work described in this paper was to better understand the results of Pellini,' which are typified by the curves of Fig. 1. Pellini cast 20-in. high, 7-in. sq steel ingots into cast-iron molds of various thicknesses. He measured the temperatures at mid-height, at a number of stations in the casting and the mold, and obtained the cooling curves shown in Fig. 1. The most conspicuous thing about Fig. 1 is the large temperature discontinuity at the interface between casting and mold, due presumably to the shrinking away of the casting from the wall and the attendant creation of an airgap, as the casting cools. Such a contact resistance slows down the anticipated freezing rate; an analytical prediction of this is of much interest in foundry practice. The determination of the effect of contact resistance in the presence of a change of phase will be dealt with, by an approximate method, in a separate paper.' In the present paper the much simpler problem is considered in which there is contact resistance but no change of phase. This problem frequently arises in the analysis of aircraft structures.+ It can initial temperature, and may be regarded as semi-infinite. We suppose the thermal properties in the two media to be time, temperature, and space independent; there are no sources or sinks within the media. In Fig. 2(a) we illustrate, schematically, the case of no contact resistance. The semi-infinite media "0" and "2:' initially at temperatures 8 (- m) and 8(+ -), respectively, are brought into contact at time t =0. A common interface temperature 8,i = is instantaneously established, and thereafter remains constant. Temperature curves are drawn for three instants of time. When there is contact resistance between the two media, the temperature equalization occurs as sketched in Fig. 2(b). Fig. 2(c) illustrates a temperature curve, using the dimension-less notation Barber-Weiner-Boley6 have stated the equations [23a, b] given below, which govern the heat transfer in the two media, and solved them for a rather complicated special case. In their example both media "O" and "2" are finite, are insulated at their far ends, and there is steady heat input into medium 2. In Eq. [27] we give the general solution of the most important special case, where the two media are semi-infinite and there are no sources or sinks. In this case the results may be stated in simple closed form. In Fig. 3, to be discussed in the next section, we illustrate the variation of the interface temperature when steel at 2760" is brought into contact with iron at 100". This example, if we disregard the effect of the heat of fusion, is comparable to Pellini's experimental results, Fig. 1. (Unfortunately, however, experimental determination of the interface temperatures was difficult to carry out, and hence Fig. 1 is not very accurate near the interface.) In Figs. 4 and 5 of the following section, we similarly compare Pellini's sandcasting tests with analytical results for the case where steel at 2760" is brought into contact with sand at 100". It will be pointed out that, insofar as the interface temperatures are concerned, heat of fusion has a minor effect, and so the present approximation, with small modifications, may be

Jan 1, 1961

By E. S. Bardwell, R. J. Lapee

Twenty years ago, W. T. Burns, in his paper presented at the Butte Meeting of the Institute,' discussed the general scheme then in use in the electrolytic copper refinery of the Anaconda Copper Mining Co. at Great Falls, Mont., for removing impurities from tank-room electrolyte and controlling its acid content. Since then marked changes have taken place in copper-refinery practice at Great Falls. The electrolytic copper refinery in use in 1913 has been replaced by a new and entirely modern plant capable of producing up to 27,000,000 Ib. of cathode copper per month. With the building of the new plant in 1916, the treatment of converter anodes was discontinued. At first the substitution of refined anodes for converter anodes resulted in a decrease in the impurity content of the anodes, but as time went on, changes in metallurgical practices at the smelter resulted in substantial increases in the impurity content of the anodes. The leaching of the silver slime to remove copper before shipment to Raritan for treatment further added to the purification problem. The fact that the scheme of purifying electrolyte which Mr. Burns described in his paper has proved adequate for our needs under a wide variation of conditions speaks well for its essential soundness. Method of Purification Briefly, the method adopted for purifying tank-room electrolyte at Great Falls has been as follows: Each day a certain volume of tank-room electrolyte is run off and sent to the purification plant, where it is boiled down to approximately 46' 136. The concentrated electrolyte is then sent to crystallizing tanks where the bulk of the copper is crystallized out as copper sulfate. The mother liquor is then passed through insoluble anode tanks to remove the last of the copper and most of the arsenic and antimony. It is then either returned to the tank room direct or boiled down to 55' Bé, the iron and nickel salts crystallized out and the mother liquor returned to the tank-room circuit as restored acid. Prior to 1930 all of the evaporating was done in lead-lined tanks 13 ft. in diameter by 4.5 ft. deep, provided with lead heating coils through which steam at 30 lb. gage pressure was circulated.

Jan 1, 1934

By Ben E. Lusk

During the past five years, the surface mining industry in Appalachia has launched itself into a technological revolution, which has never been equaled during a similar period of time. Operators have begun to realize that effectively restoring land to a useful purpose, to the satisfaction of all concerned, has to start at the beginning of the operation and be an integrated part of it throughout. In order to insure continued mining in the mountainous areas, with protection of aesthetic beauty, things really have had to change. And so the new steep slope mining theory of "controlled placement" has been developed. Controlled placement is a broad term which means the placement of spoil in steep areas where its condition can be completely stabilized and revegetated. This includes the head of valley fill, mountain top removal, haulback, over the shoulder, block cut, and any other methods where the over-burden is technically delivered, hauled, or compacted, so that there is no adverse after effects when mining has been completed. [(Fig. 1)] Under controlled placement, our whole approach to mining has changed. Before any displacement of soil or uncovering of the coal seam transpires, a complete drainage system

Jan 1, 1977

By George E. Kruger, William F. Butler

The less developed nations maintaining a free enterprise economy (to which this chapter is addressed) have real and substantial opportunities to lay a foundation for general economic progress by using their mineral resources. Most of these nations have mineral resources which could be developed. By seizing these opportunities, nations seeking rapid economic development can secure a source of foreign exchange earnings to finance the imports needed for growth and, at the same time, increase the technical knowledge and well-being of an important part of their population. History clearly shows the manner in which most of the currently industrialized nations have used mineral resources to support their development. Indeed, few nations have managed to achieve a high level of income without a firm base of mineral resource development. The main exceptions appear to be the Netherlands, Switzerland, Denmark, and New Zealand, and the last two have based their prosperity on a highly efficient agriculture. Economic growth in the United States, the United Kingdom, Canada, France, Germany, and Russia was importantly based on the use of indigenous mineral resources. Despite this record of accomplishment through mineral development, many of the currently less developed nations are not taking advantage of the opportunities available in the mineral field. Restrictive laws or practices in many such nations operate effectively to prevent development of mineral resources. This failure to grasp real opportunities for development is based on a series of arguments that the mineral field offers few substantial and attainable advantages. Among these, the following propositions appear the most important:

Jan 1, 1964

By E. H. Jr. Dix

THE consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathews1 and by Tammann.2 Campbell and Mathews described principally the beginning of solidification. They found the curve of beginning of solidification to rise gradually from the melting point of pure aluminum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AlSb. The curve then drops to the melting point of pure antimony. Tammann explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AlSb. The space lattice of the compound AlSb, according to Owen and Preston,3 is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony.

Jan 1, 1930

By FREDERICK C. BROWN

THE practice of fine-grinding is now being so successfully - carried on in some fields, notably in West Australia, and its advisability has been so frequently pointed out' that the matter in this paper is not put forward as being new ; its chief object being to call attention to the importance of fine-grinding in the treatment of comparatively low-grade ores. I have been engaged during the last five years in the cyanide-treatment of ores in the Ohinemuri district (North Island), New Zealand, and I consider that, in the near future, extremely fine-grinding (almost sliming) will become a very important feature of the milling-methods in this field, since it seems absolutely necessary to reduce the most of ores to a very fine state of division if a high extraction is to be obtained; and, in most cases, the extra percentage of saving will leave a good margin above the increased cost of treatment due both to the fine-grinding and to the interest on the capital spent for the grinding-machinery. The average ore of the Ohinemuri field is composed of a quartz-gangue with some calcite, carrying the gold-value in the form of an alloy of gold and silver in about equal proportions, and the silver-value in the form of mixed sulphides of silver, usually associated with a considerable amount of iron pyrites. In the upper levels, the ores are decomposed and carry large quantities of black manganese oxide and some iron oxide, but, as. depth is reached, the decomposed ore gives place to sulphides and, in some mines, rhodonite, manganese silicate, is present in fairly large quantities. The average value of the

Jan 1, 1906

By Willard P. Ward

HAVING been engaged during the past year in the manufacture of ferro-manganese in a blast furnace, I have imagined that some further information on this subject might be of interest to that large number of members of the Institute who are engaged in the iron and steel industries. The great question of the economical production of good steel, ingot metal, or homogeneous iron (we scarcely know now what to call it) from good materials, and at reasonable prices, has, thanks to the intelligence and energy of a few American engineers, been successfully solved in this country. Nearly all first-class railroads, and many that would riot rank so high, have adopted the Bessemer rail. Martin boiler-plates are rapidly gaining ground, in competition with

Jan 1, 1877

By R. D. Nelson, J. C. Shyne

The ß and a ß transformations in plutonium were studied with particular emphasis on the transformation kinetics and microstructure. Significant observations are: 1) The kinetic data show conclusively that the ß — a transformation in high-purity plutonium can proceed isothermally with no athermal component. 2) Plastic deformation of the stable (3 phase retards the subsequent (3 — a transformation. 3) Plastic deformation of the stable a phase accelerates the a — ß transformation; the acceleration is attributed only to residual stresses. 4) The a and a?a volume changes occur anisotroPically in textured plutonium. 5) An apparent crystallogvaphic relationship exists between the parent and the product phases of the and (3 — a transformations. 6) Both applied uniaxial compressive stresses and uniaxial tensile stresses raise the starting temperature for the ß — a transformation. 7) A given uniaxial tensile stress favors the a — ß transformation more than an equivalent applied uniaxial compressive stress opposes the transformation. These observations of the (ß —a and a — ß phase changes in plutonium are consistent with known mar-tensitic transformations. ThIS paper elucidates some of the characteristics of the a— ß and ß —a transformations in plutonium. Because considerable conjecture exists about the mechanisms by which the phase transformations occur in plutonium, experiments have been performed to provide indirect information concerning the mechanisms responsible for the a —ß and ß -a transformations. Indirect information is of particular value in the study of plutonium because of the experimental difficulties presented by the metal. Single crystals have not been produced in any of the allotropes. The large density results in high X-ray and electron-absorption factors and consequently complicating X-ray and electron diffraction. The kinetics of ß — a and a — ß transformations of plutonium and the behavior of the transformations under a variety of conditions have been investigated in detail. Information about the mechanisms of the allo-tropic transformations of plutonium was obtained indirectly from three sources: 1) the effect of plastic deformation of the stable parent phase upon the transformation kinetics; 2) the behavior of the metal transforming under applied stresses; and 3) the microstruc-tural and crystallographic features between parent and product phases. PHASE-TRANSFORMATION CHARACTERISTICS In characterizing solid-state phase transformations in metals and alloys, it is useful to define several types of transformations. An aim of the present work was to identify the low-temperature transformations in plutonium by type, i.e., as martensitic or nonmar-tensitic. Practical definitions for these terms follow. The terms commonly used to categorize phase transformations lack universally accepted definitions. This confusion arises doubtlessly because some terms specify crystallographic or morphological character while other words have a kinetic or a thermodynamic connotation. For example, martensitic specifies certain definite crystallographic restrictions. Unfortunately, martensitic is sometimes used in an ill-defined way to imply kinetic characteristics. Further confusion attends the use of such expressions as nucleation and growth, diffusional, and massive. From time to time new systems of phase-transformation nomenclature are suggested; unfortunately none of these has gained general acceptance.1,2 The authors of the present paper have no intention of entering the controversy. We recognize that some readers may object to the nomencliture used here. For exampie, the terms military and civilian have recently been used in much the same way as martensitic and non-martensitic are used in this paper. This paper is intended to describe several specific details of the low-temperature phase transformations in plutonium. The authors have found it useful to identify these transformations as martensitic; the term was chosen as the best available to describe the experimentally observed features of the transformations studied. A martensitic transformation is one that occurs by the cooperative movement of many atoms; the rearrangement of atoms from parent to product crystal structure occurs by the passage of a mobile semico-herent growth interface. The geometric features characteristic of a martensitic transformation are a specific orientation relationship between the product and parent phase lattices, a specific habit-plane orientation for the growth interface, and a shape change with a specifically oriented shear component. There is no alloy partition between the parent and product phases in a martensitic transformation. Martensitic transformations may display either athermal kinetic behavior or thermally activated isothermal kinetic behavior. Some martensitic transformations occur isothermally, although more commonly martensitic transformations are athermal. Isothermal martensitic transformations are suppressible by rapid cooling. In athermal martensitic transformations, nucleation and growth are not thermally activated and the transformations are essentially time-independent. Nucleation, growth, or both can be thermally activated in isothermal martensitic reactions. Transformation of the parent phase into a marten-

Jan 1, 1967

By Carl Altstetter, Emmanuel deLamotte

The influence of an external stress and plastic deformation on the allotropic transformation of single crystals of a Co-30.5 pct Ni alloy was investigated. Experimental results were obtained from dilatometry, X-ray diffraction, and optical and electron microscopy. The effects of stresses could be conveniently divided into three stress ranges. In range I, from 0 to about 400 g per sq mm, the specimens exhibited a multi-variant phase change on cooling and a considerable amount of retained cubic phase. In range II, from 400 g per sq mm to the elastic limit, hexagonal regions of a given orientation grew in size and the cubic phase disappeared with increasing stress level. In range III, just above the elastic limit, specimens transformed into hexagonal single crystals. It was found that plastic deformation, not applied stress, was the factor which determined whether a single-crystal product was formed. The observed macroscopic shear directions were mainly (112) on cooling, but the behavior was more complicated on heating under stress. To explain these properties of the phase change, a model based on the nucleation of partial dislocations is proposed. IT is well-known1 that, on heating, hcp cobalt transforms into an fcc arrangement by shearing on close-packed planes. The crystallographic orientation relationship of the phases is as follows: the habit plane is (OOO1)hcp ?{lll}fcc and a (1010)hcp direction is parallel to a (112)fcc direction. The temperature at which the transformation occurs in pure cobalt is around 420.C 1,2This temperature decreases with increasing nickel concentration: and at about 30 pct Ni it reaches room temperature. However, many of the transformation characteristics remain essentially the same, particularly the crystallographic features.495 A convenient way of studying the transformation is to alloy cobalt with nickel, thus avoiding the difficulties of doing experiments at the high temperatures needed to transform pure cobalt. Due to the hysteresis of the transformation it is possible to choose a Co-Ni alloy with an Ms temperature below room temperature and an A, temperature above room temperature. Either structure of such an alloy could then be studied at room temperature, depending on whether it had just been heated or cooled to room temperature. The choice of nickel is further favored by the small difference in lattice parameters between cubic cobalt and nickel and the similarity of their physical, chemical, and electronic properties. Co-Ni alloys are reported to have neither long- nor short-range order.6 The main purpose of this work was to investigate the influence of an external stress on the transformation characteristics of Co-Ni single crystals. It may be expected that slip, twinning, and transformation should have many features in common in cobalt, because the (111) planes of the cubic phase operate as slip planes when plastic deformation by slip occurs, they are the twinning planes, and they are the habit planes for the transformation. Many previous investigators7-&apos;6 have concluded that dislocations must play an important role in the nucleation and propagation of the transformation, just as they do for slip and twinning propagation. An external stress will affect their motion, and a study of its influence should yield further information about the atomic mechanism of transformation. The present work extends that of Gaunt and christian17 and Nelson and Altstette18 in both qualitative and quantitative effects of stress. The basic concept underlying all the present theories of the transformation of cobalt and Co-Ni alloys is the motion of a/6<112> partial dislocations over {1ll} planes of the cubic lattice. The ABCABC... stacking of the close-packed planes of the cubic phase can be changed into the hexagonal ABABAB... stacking by the sweeping of an a/6 <112> partial on every second plane. Twinning, on the other hand, requires a shear of a/6 <112> on each close-packed plane. The reverse transformation can be effected in a similar way by a/3 (1010) dislocations moving over every other basal plane of the hexagonal phase. Transformation theories2, 7- 12,14 differ in the details of the nucleation of the transformation and the propagation of the partial dislocations from plane to plane. EXPERIMENTAL PROCEDURE Nickel and cobalt rods supplied as 99.999 pct pure were induct ion-melted together under a vacuum of about 10-5 torr in a 97 pct alumina crucible. An alloy containing 30.5 pct Ni was found to have the desired transformation range, with an Ms near -10°C and an j4s in the vicinity of +10O°C. The ingots were swaged to &--in. rod and electron beam zone-leveled in a 10-6 torr vacuum. This procedure resulted in 12-in.-long single fcc crystal rods (designated I to VII) from each of which several tensile specimens of identical orientation were made. Chemical analysis of the bar ends indicated no contamination or gross segregation and no micro segregation was seen in electron micro-probe scans. Tensile specimens with a 9/32-in.-sq by 1-in.-long gage section were spark-machined from the rods and then electropolished or chemically polished to remove the machining damage and to provide a flat surface

Jan 1, 1970

By P. W. Bridgman

It is a commonplace that experimental physics in the last few decades has discovered manifold complexities in the atomic and subatomic levels, where it was thought for hundreds of years that no structure existed, as is witnessed by the derivation of the word "atom" itself. The field of exploration opened by the discovery of the electrical structure of the atom was so fundamental, rich and stimulating, that it has been almost exclusively cultivated by physicists since they obtained their first intimations as to the nature of the basic facts. Only within the last few years has it begun to dawn on us that we have overshot an enormous domain in which are situated many phenomena of fundamental importance for all the practical uses to which we put matter in our daily lives; the domain, that is, of most of the phenomena of interest to the biologist and the metallurgist. Furthermore, we are beginning to find that this intermediate domain is not entirely simple, but that it contains unsuspected complexities, some of them derived from the complexities of structure on the atomic and subatomic levels, and some of them emergent as matter collects itself into large aggregates, which often offer the key to the explanation of hitherto baffling large-scale properties of matter. Today I want to describe and consider some of these newly discovered complexities in the behavior of matter in bulk. The application to metallurgical problems is not always direct, but I hope to be able to suggest that such general notions as to structure as those here discussed must have important reactions on our attitude toward the problems of metallurgy. Three different sorts of phenomena of this kind to which I shall direct your attention are (1) the so-called structure sensitive phenomena, (2) complexities of such a nature that they are masked by the presence of extraordinarily small amounts of impurities, and (3) complexities depending on internal molecular rearrangements which can be understood only from the point of view of the quantum theory.

Jan 1, 1931

By J. C. Mertz

ACCURATE knowledge of the solid solubilities of the elements that dissolve in the important base metals is needed for guidance in the preparation and heat-treatment of the alloys derived from these compo-nents. While there is still difference of opinion concerning the merits of the X-ray and microscopic methods of determining such solubilities, it is certainly true that the recent extensive use of X-ray diffraction to review the existing constitutional data has revealed many glaring inaccu-racies and has brought about a much improved knowledge of phase-boundary locations, which will inevitably come to include all of the important alloy systems. When the work is done with all necessary precautions it appears that in the majority of cases where the solubilities extend beyond a few tenths of a per cent the X-ray back-reflection technique is capable of furnishing the best of information in this field. For the most prolonged and thorough studies it is obviously advisable to combine the results of several methods, in particular, to obtain an agreement between X-ray and microscopic data. This paper reviews the work previously done on the solubilities of phosphorus, arsenic, antimony and bismuth in copper and, in considera-tion of the uncertainties thus made apparent, presents, new X-ray data obtained with the first three members of this group.

Jan 1, 1936

The development of coal mining in this state has been well described by Goodyear, and much data are also given in the reports of the U. S. Commissioner of Mining Statistics, and the tonnages in Table 69 are from these sources, only a few of them being estimated. [ ]

Jan 1, 1942