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By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,' in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts' method and a quenching method. In the first method, the Sieverts' technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts' Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,' to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts' apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier's analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964

By Francis Lucas

A microscope objective of given numerical aperture, whew used with light of given wave length, has some fixed limit of resolution. This may be expressed as potential resolving ability-the ability to resolve is inherent in the lens but whether this limit is achieved in practice is quite another matter. Nearly 50 years ago Abbe evolved theoretical considerations which indicated that the ability of a lens to resolve detail is directly proportional to twice the numerical aperture of the objective and inversely proportional to the wave length of the light used. It is true, unquestionably, that as the numerical aperture of the objective is increased the potential resolving ability of the lens is increased and likewise whew the wave length of the light used is decreased, the degree of resolution is increased. Whether Abbe's formula expresses the exact relationship is not a matter of great concern. It suffices to know that to improve resolution, other things being equal, two avenues of approach are available. Either the numerical aperture of the objective may be increased or the wave length of the light decreased. With the apochromatic system it is possible to employ successfully wave lengths from 400 to 500, µµ and still secure reasonably short exposures. The present limit for numerical aperture is 1.40 N. A. although objectives of 1.65 N. A. are wow an experimental possibility for metallurgical work. Thus certain well defined limits are set for those who work within the range of the visible spectrum. In order to take advantage of the increase in resolving power which accompanies a decrease in the wave length of light employed, Dr. A. Köhler and Dr. M. Vow Rohr of the Zeiss Scientific Staff developed the "monochromats." These are quartz objectives corrected for the single wave length 275 µµ which lies in the ultra-violet region of the spectrum. They also developed a series of quartz oculars and a complete photo-micrographic equipment with which to use the quartz optics. Quartz must be used for the optical parts because glass absorbs ultra-violet light almost completely. Thus there was made available about 20 years

Jan 6, 1926

By S. Feuerstein, L. Rice

The effect of low pressures on the flow and fracture behavior of molybdenum is described. For poly crystalline samples, room-temperature tensile tests indicate greater ductility under 10 Torr than under intermediate pressures up to and including atmospheric pressure (760 Torr). In addition, tests conducted at 760 Torr under atmospheres of air, dry nitrogen, and purified argon exhibited no apparent difference in mechanical properties. Critical tests involving baking in situ as well as those involving single-crystal deformation further imply that the ductility effect is a pressure-dependent phenomenon related only to the fracture process. This dependency is discussed in terms of adsorption and diffusion contributions. THE effect of very low pressures on material properties has heretofore been presumed to be important only for substances possessing relatively high vapor pressures at ambient temperatures. Research has therefore been concentrated primarily on organic solids and liquids, and in some instances on metals such as zinc and cadmium. Most vacuum-effect studies' on the mechanical behavior of metals have been performed under conditions of either cyclic loading or creep rupture at elevated temperatures, i.e., over extended time periods. These studies were not restricted to high vapor pressure materials but also encompassed such metals as gold, copper, and nickel. Very little concern, however, was placed upon the importance of a vacuum environment on the mechanical behavior of metals subjected to a simple unidirectional deformation at ambient temperatures. A tension test is generally of short duration as compared to a creep test, and at room temperature vacuum effects if any would be expected to be surface-limited. In early 1963, Kramer and podlaseck2 reported a change in the bulk flow behavior of aluminum single crystals during room-temperature tension tests. The deformations were performed under pressure conditions of 760 to 3.4 X 10-8 Torr and indicated for the first time a vacuum surface effect contributing to the bulk tensile behavior of metal specimens. As a consequence, an experimental program was initiated in this Laboratory to study the effects of ultrahigh-vacuum conditions on the mechanical behavior of metals. The results of a preliminary study on poly-crystalline molybdenum3 revealed, unlike Kramer's observations of changes in the stress-strain behavior, only an increased ductility under ultrahigh vacuum. Flow behaviors were nearly identical for all tests re- gardless of pressure. This paper presents comprehensive results obtained in this area of research. 1) EXPERIMENTAL PROCEDURE Three material categories were used in this study: sintered and are-cast polycrystalline molybdenum of nominal purity 99.93+ pct and single-pass electron-beam zone-refined molybdenum single crystals having a nominal purity level of 99.99+ pct. The interstitial levels (weight percent) as determined by the Materials Testing Laboratories, Division of Magnaflux Corp., were as follows: sintered molybdenum (C— 0.005, H—0.0004, O—0.015, N—0.008); and arc-cast molybdenum (C-0.0038, H-0.0003, O-0.015, N-0.023). Single-crystal molybdenum obtained from Materials Research Corp. had a typical interstitial analysis of C-0.0015, H-0.00007, O—0.00045, and N-0.0001. Tensile specimens having a 5 mm diam by 50.8 mm length were prepared from these materials. An average grain diameter of 0.059 mm was obtained for the sintered specimens following a 4-hr, 1600°C heat treatment. Grain sizes from 0.019 to 0.149 mm were obtained in the arc-cast specimens following heat treatments from 1100° to 1600°C for 1 hr. This series of specimens was used exclusively for the grain-size effect studies. All samples were electrolytically polished in 97 pct sulfuric acid solution prior to testing. Experiments were performed at room temperature in an ion-pumped ultrahigh-vacuum system positioned in an Instron tensile machine, Fig. 1. A constant strain rate of 4.2 x 10-4 sec-1 as derived from crosshead displacement was assumed for the deformations. Starting vacuums ranged from 2 to 0.5 X 10-10 Torr. These pressure measurements were made using corrected values4 of an NRC Redhead gage. Comparative readings were also made against a G.E. triggered dis-

Jan 1, 1967

By Wayne P. Myers

Electricity, as normally thought of by a layman's definition, is a manmade force that has no color, no odor, is not visible, cannot be heard, yet man can control it and make it perform his work for him. A person dare not cheat on it, for it then will master him. It has laws, rules, and regulations that must be strictly adhered to if it is to perform in the safest, most reliable, and economical manner. In the early days of coal mining the power source was man himself. Later man employed steam and compressed air to reduce his muscle power requirements needed in the extraction of coal. By the turn of the 20th century, electricity had become the most common source of power for the coal industry. Steam and compressed air are still found in use in isolated cases today for specific applications; however, they are rapidly being replaced by electricity. Electrical laws and regulations are quite extensive and somewhat complex for the proper generation and use of electricity. Man-made laws, rules, and regulations for the care and handling of electricity, designed for man's safety, are rigidly enforced by the U.S. Bureau of Mines, as well as the various state departments of mines. BACKGROUND Until recent years most underground coal mines used direct current exclusively for all movable and for some stationary equipment. Exceptions were for permanent pumps, tipple, fan, and outside buildings where alternating current was normally employed. However, over 60 years ago there were mines with dual systems. Alternating current was used for cutting machines, drills, and pumps, direct current for locomotives. There were no other machines as these were hand-loading mines. Later, during early mechanization in the 1920s, alternating current was also applied to loading machines at some mines. Use of dual electric systems then declined until fairly recently when

Jan 1, 1973

By George S. Rice

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

Jan 1, 1923

By George S. Rice

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

Jan 1, 1923

By D. W. Frommer

Processing nonmagnetic taconites by selective flocculation-desliming and flotation requires large volumes of water. If impounded without treatment, these off-process waters require excessively large areas for containment. To discharge the waste water into natural waterways would contribute to stream pollution and likely would not be permitted. In U.S. Bureau of Mines experiments conducted in the Twin Cities Metallurgy Research Center's 900-lb per hr pilot plant, approximately 85% of water requirements for the flotation-based treatment of a Michigan nonmagnetic taconite were met by reclaimed water. Water reclamation of the off-process streams from flotation was accomplished by controlled additions of lime, sodium carbonate, and a synthetic flocculant to reduce turbidities to 51000 ppm equivalent SiO*, while maintaining a Ca(II) content of =16 ppm in the finished effluent. Flotation concentrates of good quality were obtained using the reclaimed water. The cost of chemicals used in water reclamation was approximately equal to the savings in flotation reagents attributed to recycling of the water. Water quality is perhaps as important to flotation as are the reagents used. The character of water is extremely variable, depending on whether the source is a well, lake, or stream, upon the season and temperature, upon prior use, and upon the character of the watershed. All of these factors influence the water hardness and the quantity of other dissolved inorganic salts, turbidity, dissolved and suspended organic matter, dissolved gases, and pH. Frequently, the differences in water quality can measurably influence flotation selectivity, often to the point of spelling success or failure. Water hardness is particularly troublesome in flotation systems employing fatty acids, but other unrecognized constituents may also contribute to peculiarities in flotation behavior. Furthermore, a given water source may be entirely satisfactory in one flotation system, but entirely inappropriate in another. In recent years, society has given more attention than formerly to water use, even in areas where water is plentiful. However, both the demands of a growing population, with increased per capita needs, and also those of industry must be met. As a result, riparian rights must be negotiated with the appropriate government agency or agencies so that consumption of water is often allocated or otherwise controlled. Furthermore, the disposal of off-process industrial and domestic water is coming under the increasing scrutiny of these same governmental units. In these respects, the mineral industry is no exception, so that conservation, water reclamation, and reuse may be expected to assume increasing importance. In 1932, it was stated that, "water reclamation is generally more expensive than the economy in water and reagents resulting from its use. It is employed only if it is urgent to save water."' The economic aspects of this statement may still be true, but the unrestricted use of water is becoming less and less an option of the user. The purpose of this paper is to discuss an investigation conducted by the U.S. Bureau of Mines (USBM), in which water reclamation and treatment were undertaken to develop procedures for, and to assess the effects of, water reuse on the flotation treatment of nonmagnetic taconites. This investigation is a logical extension of previous work described by the author and associates at the Twin Cities Metallurgy Research Center employing selective flocculation-desliming and anionic flotation of silica from low-grade, nonmagnetic iron ores2,8 The requirements for the selective flocculation-de-sliming and the anionic flotation of silica processes determined the direction of the investigation. Previous studies had indicated that pH levels of about 11.0 and 11.8 were required for selective flocculation and flota-tlon, respectively. The calcium content of the water was believed to be of importance in both of these operations, and since Minneapolis tap water with a Ca(I1) content of about 16 ppm had been successfully used, an attempt was made to reclaim the process water at an equal level of dissolved calcium. Additionally, the objective was to nullify or effectively limit the effects of dispersants and fatty acid residuals from prior stages of processing. Last but not least, the system of water treatment had to have the capability of reducing turbidities to workable levels. With about half of the effluent being derived from the selective flocculation-desliming step and carrying about 25,000 ppm of highly dispersed, suspended fines, this last objective appeared formidable at the outset. Procedures for water reclamation were derived, in part, from well-known mineral dressing practices, from past observations and investigations, and from concepts contained in various pertinent publications on water treatment."c These procedures involved: 1) flocculation with lime and poly electrolyte-type flocculants, 2) lime-soda-ash softening, 3) chemical precipitation, and 4) mineral surface adsorption. Control was exercised at various stages of water reclamation by frequent measurements of Ca(11), pH, and turbidity.

Jan 1, 1971

By T. Federighi, S. Ceresara, C. Panseri

The results of an exploratory investigation by means of resistivity measurements at -195ºC, on the aging characteristics of a set of Al-Mg alloys with a maximum content of 7 pct Mg, are reported. Whereas for dilute alloys (Mg < 1.5 pct) only a decrease in resistivity is observed at about 100°C (due to the elimination of quenched-in vacancies), for more concentrated alloys such a decrease is preceded by an increase in resistivity in the range between -60ºand +40°C. Following some previous suggestions, this increase is considered as good evidence for clustering of solute atoms @reprecipi-tation process). From the analysis of the results it appears that, although the process is substantially similar to that observed in other Al-rich alloys, it is characterized by a strong interaction between vacancies and zones. THE process of formation of Guinier-Preston zones, i.e., preprecipitation,1&apos;2 which occurs during the aging at about room temperature in many supersaturated aluminum-rich alloys, has been extensively investigated in the past few years by several workers.2,3 owever, a very interesting question arises when the case of Al-Mg alloys is considered: although it is very easy to supersaturate Al-Mg alloys, just in the same way as for many other aluminum alloys showing preprecipitation, only very little experimental evidence was available until a short time ago in the literature supporting the existence of "natural" aging in supersaturated Al-Mg alloys (see, for example, Refs. 4 to 6). On the other hand, as is well known, the X-ray method is not useful in this case because the X-ray scattering factors of magnesium and aluminum atoms are about the same. Recently, however, Cordier and Detert7 have stressed that during the aging at about room temperature of a supersaturated Al-Mg 10 pct alloy it is possible to detect an increase in resistivity; since, as is well known, such an increase is observed also in most alloys showing preprecipitation, the above authors have interpreted their results as evidence for the formation of magnesium-rich clusters (or Guinier-Preston zones) during the aging. In the course of or ientative investigations on preprecipitation in several aluminum-rich alloys, we also could detect a similar phenomenon in more dilute Al-Mg alloys, see Instituto Sperimentale Metalli Leggeri, Annual Report, 1959, and also Ref. 8. Since the details of our observations, although of a preliminary nature, differ from those of Cordier and Detert and allow one to draw a more advanced picture of the preprecipitation process in Al-Mg alloys, we have thought it useful to report our results in this paper and to comment on them briefly.

Jan 1, 1963

By C. M. Loeb, T. E. Norman

The use of ball, rod and tube mills for grinding ore, cement and other materials has grown so rapidly during the past forty years that the world&apos;s annual consumption of ferrous grinding media for these mills is now estimated to be between one half million and one million tons per year. Ferrous grinding balls constitute the major portion of this tonnage. Obviously they represent sufficient value to justify thorough studies of the factors governing their performance. The selection of grinding balls is governed principally by: I. Quality (wear resistance, impact resistance, soundness, and the like). 2. Sources of supply and delivered cost. 3. Grinding characteristics or efficiency in the ball mill. This paper deals principally with the quality of ferrous grinding balls. In the study of these factors certain data relative to the fundamental nature of ball wear in ball mills have been obtained. These data are also presented and discussed briefly. The Development of a Suitable Wear Test A study of the fundamental factors governing the quality of grinding balls has been hampered seriously by the fact that a competent test has, in the past, involved the purchase of several hundred tons of balls of a specific type which were then run in one or more ball mills for a period ranging from several months&apos; to several years&apos; duration. Often, during the period of test, it became necessary to change operating conditions or the character of the ore fed to the test mill with the result that the rate of ball consumption changed and the test figures became of little value. Under such circumstances, progress in the development of better grinding balls, has been necessarily slow. Economic factors and variations in the quality of balls produced by different sources of supply generally make it necessary for each mill operator to determine for himself the most suitable type of balls for his mills. In our own ball mill grinding operations at Climax, Colo., we were faced with this problem. After we had run a few large scale wear tests at considerable expense we decided to investigate the possibilities of a small scale wear test which would be capable of testing numerous types of balls within a relatively short time. The most important requirement of any test is, of course, that it give results which can be used to predict accurately the wear in full scale operations. It was known that Ellis and his associates1,2 had developed a method of testing grinding balls by small scale tests run at the Ontario Research Foundation. Ellis&apos; method of testing was used as a starting point in our investigations. In the course of our tests a number of modifications of the original method were found to be desirable so that, by an evolutionary procedure, a method of small scale

Jan 1, 1949

By I. Cornet

INTRODUCTION WITH the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that the notch sensitivity of magnesium alloy extrusions be further investigated and the influence of various factors upon notch sensitivity be noted. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. The work discussed herein was done under "Restricted" Project NRC-21, reported in Dec. 1943 1; it has been released for publication by the O.S.R.D. SCOPE OF THE INVESTIGATION The notch sensitivity of various magnesium alloy extrusions was determined under axial tension, and also under several conditions of nonaxial tension. Hardness, grain size and other metallographic features were observed; stress-strain data were obtained, and the chemical compositions of the alloys were determined, in order to correlate these quantities with the notch sensitivity. Notch sensitivity under axial tensile load was determined for a few specimens which had been cold worked to various degrees by tensile prestraining. Magnesium alloy extrusions studied included Dowmetal 0, X, J, and M. For comparison, extrusions of aluminum alloy 24S-T, cast bars of aluminum alloy I22-T2, and cast bars of magnesium alloy C were also tested, The specified chemical composition of these alloys is given in Table I. All bars tested were within specification limits of composition. Investigation of the tensile notch sensitivity of various magnesium alloy extrusions, under conditions of axial and eccentric load, showed little or no correlation with stress-strain or other conventional data. Since the many uncontrolled variables present might mask significant relationships, one alloy was selected for intensive study. Magnesium 0 alloy extrusions were subjected to experimental heat treatments, and the changing hardness, tensile strength, microstructure, and notch sensitivity observed. EXPERIMENTAL TECHNIQUES AND PROCEDURES Tensile Testing Bars used for axial loading were machined with 3/8 in.- and with 1/4-in. minimum diam, and included specimens with 6o° V notches (Fig I and 2). Each V-notched specimen was roughed out carefully and then finished with a honed tool. These V-notched bars were sampled frequently, sectioned, polished, and examined at 500 X magnification to control

Jan 1, 1948

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a&apos; phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a&apos; phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.&apos; Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a&apos;, with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a&apos; phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a&apos;. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By Milton Fies

ALTHOUGH pig iron from iron ore and red cedar charcoal preceded the mining of coal by many years, for tradition says that Alabama iron was used to shoe the horses of Andrew Jackson&apos;s soldiers, coal was not produced until 1830. In that year, coal was mined in Tuscaloosa County, in the vicinity of what is now the University of Alabama, and shipped on flat boats (obviously during the wet season, for there were many shoals) down the Warrior River to Mobile. About that time, the first railroad, the Decatur & Tecumseh, was being constructed in northern Alabama to overcome the obstructions to freight traffic caused by the now well-known Muscle Shoals in the Tennessee River. This railroad was patterned after a railroad at Mauch Chunk, Pa., which was used for hauling anthracite from the Panther Creek valley. The Alabama railroad, which required about four years to complete, was 46 miles long and was used solely for the transportation of cotton. Although it was a failure, it demonstrated the practicability of the undertaking, and the succeeding railroads, which were begun in 1834, 1848, 1852, and 1853, added immeasurably to the development of the coal resources of the state. Between the years 1830 and 1860, practically all the coal mined in the state was dug from the outcrop near the river or from the river beds, and shipped by boat to Mobile. Transporting coal down the Warrior River was one of great risk, required much skill, and frequently had heavy losses. It is recorded that this coal was sold to the gas company in Mobile in 1844; it was most likely mined from the Black Creek Seam. In 1914, on the completion of Lock 17, the Warrior River became a navigable stream from 9 miles above Cordova, Ala., to Mobile and offers a great opportunity for the future development of the coal resources of the state.

Jan 9, 1924

By G. M. Yocom

Blowing acid Bessemer converters with oxygen-steam produces steel of below 0.002 pct N2 content. This method of blowing, combined with a dephosphorizing treatment in the steel ladle, results in low-carbon steels of low nitrogen and low phosphorous (under 0.035 pet) contents, which has physical properties equivalent to open-hearth steels of similar analysis. Using a 50-50 mixture of oxygen and steam, the refinitzg rate is increased 25 pct over blowing with natural air, and scrap charge increased from 3 to 10 pet. Bottom life is normal with proper tuyere area and arrangements, fumes are decreased, yields increased, and hydrogen content is normal. THE acid Bessemer plant at the South Works of Wheeling Steel Corp., consists of two 15-ton bottom blown converters with a monthly capacity of 57,000 N.T. The product of the shop is skelp billets for continuous welded pipe and slabs for ordinary drawing and forming quality sheets. Approximately 50 pct of ingot production is regular Bessemer steel of natural Phos content and the remainder is a dephosphorized grade of steel made by a special treatment of the blown metal as it is poured into the steel ladle. The low Phos grade of steel has certain advantages over the higher Phos grade but since both grades were produced by blowing natural air, the N2 content was in the range of 0.015 pct which limited its application. In 1954 it was decided to explore the possibilities of blowing with a steam-oxygen mixture for the production of steel of both low N2 and low Phos contents. The necessary equipment was installed to operate one converter in this manner and early in 1955 an experimental run of 160 heats was made by blowing with a steam-oxygen blast and excluding natural air entirely. During this period the proper operating techniques were established, such as blast pressures, steam-oxygen mixtures, valves and instrumental control equipment, tuyere arrangement in the bottoms, blowing times and production rates, and a thorough study made of the final steel quality. Also during this experimental period the dephosphorizing practice was improved by the use of a tap hole below the lip of the vessel. This provided a clean separation of the acid converter slag and blown metal which made the dephosphorizing treatment more effective. The results of this experimental run dictated further development of this practice and a second run of 720 heats was made in 1957. The quality features and conversion cost results were in line with expectations and accordingly a 400-ton per day oxygen plant is now being installed. The plant is scheduled for completion in September of this year. This will provide sufficient oxygen to operate both vessels on steam-oxygen blast and delete natural air blowing entirely. The steel will then be below 0.002 pct N2 bar content and the dephosphorized grades will be between 0.015 and 0.040 pct Phos. STEAM-OXYGEN BLOWING The steam for the process is fed to the plant at 220 psig pressure through a 6-in. line. The high-purity oxygen is compressed to 200 psig and conducted through an 8-in. line. The oxygen from the main line is valved down to 100 psig and passed through a steam heated heat exchanger. The heat exchanger is regulated to supply oxygen at 300°F to the steam-oxygen mixing station. It is essential that the incoming oxygen be held at this temperature to avoid condensation of the steam with resulting excessive erosion of the clay tuyeres in the vessel bottom. Oxygen is admitted to the mixing chamber by a 6-in. hydraulically operated valve driven by the ratio control regulator on impulse from the flow of steam. Steam is admitted to the steam-oxygen mixture station through a 2 1/2-in. hydraulically driven valve. The ratio control regulator acts to increase or decrease oxygen input as the steam flow increases or decreases with changing positions of the Blower&apos;s control lever. The important point to note here is that steam flow always precedes the oxygen flow as a safety measure. The control valves have sufficient capacity to afford protection should blow pipe trouble develop. A 50-50 mixture for these 15-ton heats demands an oxygen flow of 3800 standard cu ft per min along with 317 lb of steam. The Blower&apos;s stations is provided with an indicating blast pressure gage, and indicating steam and oxygen flow meters. Signal and warning lights indicate the valve positions and line pressures. A control room at the real of the Blower&apos;s pulpit room houses the ratio control and pressure regulators, as well as the various meter bodies. The hand actuated wheels used to change the conditions are mounted on a panel on the front of the meter control house. The recording steam and oxygen meters used for totalizing and accounting purposes are also mounted on this panel.

Jan 1, 1962

By B. L. Landrum, J. Simmons, J. M. Pinson, P. B. Crawford

Patentiometric model data have been obtained to estimate the effect of vertical fractures on the areas swept after breakthrough in water flooding and miscible displacement programs such as gas cycling where the mobility is near one, The data are presented for the case of the fire-spot pattern in which the cemer well is fractured various lengths and orientations, the data indicate that for 10-acre spacing, fractures extetidirrg over 1300 ft in either directior1 from the fractured well may re.srrlt in reductions in sweep efficiencics from 72 to approximately 34 per cent. However. the area swept after break through may be quite largr and only 10 or 12 per cent 1ess than would be obtained if the reservoir were trot fractured. For the specific case when the volume of fluid injected is equivalent to 100 per cent of the pattern vol-unie, the swent area may vary from 80 to 88 per cent, depending on the lenght of the fracture. The former value is that which occurs when the break through or sweep efficiency was orrly 34 per cent and the latter figrrre of 88 per cent is that which is obtained if the reservoir were unfrac-ttm&apos;d. It is pointed out that although the sweep efficiency may he very low in vertically fractured five-spot patterrz.s, the area swept at low water-oil ratios may be only 5 to 10 per cent less than those achieved if the reservoir were unfractured. INTRODUCTION Since the initiation of commercial reservoir fracturing techniques it has been desirable to determine the effect of fractures on the areas swept after breakthrough. Most water flooding or gas cycling projects are continued for substantial periods after the brcakthrough of the injected fluid. Although the sweep efficiency serves as one criterion for rating various flooding patterns. the area swept after breakthrough for various water-oil ratios or percentage wet gas, if cycling. is of perhaps more importance than the sweep efficiency alone. Sweep efficiency data on the vertically fractured five-spot have been presented3. Previous work on the line-drive pattern has shown the effect of vertical fractures on the area swept after breakthrough for the case in which the distance between injection and producing wells divided by the distance between adjacent input wells was equivalent to 1.5 (see lief. 2). The data indicated that for the line-drive pattern it may be desirable to flood or cycle substantially perpendicular to the fractures in order to achieve the greatest recovery for the smallest volume of fluid injected. For this study the center well of a five-spot is assumed as the fractured well. All fractures were assumed to originate at this well and extend into the reservoir for various distances and orientations. All the fractures are straight and are of large permeability compared to the matrix proper. These data are presented to aid the engineer in estimating fractured five-spot pattern performance. ANALOGY The potentiometric model was used in making this study. The model used was 20 20 in. by approximately 1-in. deep. For certain portions of the study one corner of this model was considered to be an injection well and the opposite corner a production well. To simulate vertical fractures a copper sheet was soldered to the wire well and made to conform to the desired length and orientation. In other studies the same model was used except that the four corners of the model might be considered as the corner wells of a five-spot pattern and a fifth well was placed in the center of the model. The well placed in the center of the model was fractured. The total fracture length is L and the well spacing. d. The complimentary fracture angles will be obvious from Figs. 3 and 4. The data obtained on the potentio-metric model assumes the pay to be uniform and homogeneous, the mobility ratio is one, steady-state conditions exist and gravity effects arc neglected. The permeability of the fractures is very great compared to that of the matrix proper. The po-tentiometric model has been used widely both in water flooding and gas cycling projects, and may be used for miscible displacement; how-ever. it is believed that the poten-tiometric model data are more properly applicable to gas cycling than water flooding because the model as-

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.&apos; Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. &apos;9&apos; Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500&apos; and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,&apos; in the a Fe-Fe3C system are those of Bannyh, Modin, and odin&apos; for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.&apos;-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3&apos;C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.&apos; Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By E. T. Turkdogan, P. Grieveson

Molten silver is equilibrated with silicon nitride at 1400°C in nitrogen + hydrogen gas mixtures, and from the solubility data the activity coefficient of silicon is found to be 1.76 at silicon concentrations below 1 pct. Using this value, and that available from the silicon cmbide solubility measurements, together with those derived from the phase equilibrium diagvam, the activities of silver and silicon are estimated for the entire composition range. The main feature of the activity data is that there is a pronounced positive deviation from ideality. The activity of silver in molten silver containing up to 5 pct Si was determined by Schadel, Derge, and Birchenall1 by measuring the vapor pressure of pure silver and of the alloy over a temperature range of 850º to 1050°C. They deduced from their results that there is a positive deviation from Raoult&apos;s law and that the activity coefficient of silver increases with decreasing temperature. However, as pointed out by Kubaschewski and Catterall,2 their activity coefficients are much too high, giving silver activities greater than unity. At a later date McCabe and Birchenal13 showed that the previous vapor pressure data on silver4 were high by a factor of about 1.3; presumably a similar error must have occurred with the vapor pressure measurements on the Ag-Si alloys. The activities of silicon and silver calculated by tager&apos; from the phase diagram and by Gibbs-Duhem integration, respectively, show a positive deviation from Raoult&apos;s law for silicon activity and positive and negative deviations for the silver activity. According to these computations, at infinite dilution of silicon ygi = 1.12 at 1420°C. d&apos;Entremont and chipman6 measured the solubility of silicon carbide in molten silver at unit carbon activity; the equilibrium silicon content is found to be Nsi = 0.017 ± 0.002 atom fraction for 1420°C. Using the data of Grieveson and Alcock7 for the free energy of formation of silicon carbide from pure silicon and graphite, the activity of silicon for unit activity of carbon and of silicon carbide is asi = 0.0308 at 1420°c; therefore for the above solubility data on silver, YSi = 1.81, which is somewhat higher than that given by Hager. Use is often made of silver alloys in the measurements of activities of solutes in metals where silver has a very low solubility; in fact, Ag-Si and Ag-A1 alloys have been used in the past for such purposes. In an attempt to gain more thermodynamic data on molten Ag-Si alloys, measurements have been made in the present study on the solubility of silicon nitride in molten silver; the results on these solubilities are given in this paper together with a detailed discussion of activities of silver and silicon. SOLUBILITY OF SILICON NITRIDE The standard free energy of formation of silicon nitride is known with a reasonably high degree of accuracy. According to the measurements made by Hincke and Brantle8 and by Pehlke and Elliott,&apos; the following are the free energy data for the standard states of solid Si3N4, liquid silicon, and Nz at 1 atm pressure:

Jan 1, 1963

By D. T. Peterson, T. Carnahan

The diffusion coejTicients of carbon, nitrogen, and oxyget were determined in $ thorium over the tempernilcre range 1440" io 1715°C. The diffusion coyfiicir?zls are given by: D = 0.022 exp (-27,000/RT) jor carbo)~, D = 0,0032 exp(-l7,00Q/RTj for nitrogen, and D = u.0013 expt(-11,UOU/RT) for oxygen. Cavl~orz was found to increase the hardness of thoriunz nearly linearly with concentration over the range 100 to 1000Ppm carbon. ThORIUM has a fcc structure up to 1365°C and a bcc structure from this temperature to its melting point at 1740°C. Diffusion of carbon, oxygen, and nitrogen in bcc thorium was of interest in connection with the purification of thorium by electrotransport.&apos; In addition, it was possible to measure the diffusion of all three of these interstitial solutes in the same bcc metal. Only in niobium, tantalum, vanadium, and a iron have all three interstitial diffusion coefficients been measured in a given bcc metal. Diffusion coefficients have been measured for carbon and oxygen in a thorium by Peterson2, 3 and for nitrogen by Gerds and Mallett.4 Activation energies for diffusion are reported by the above authors to be 38 kcal per mole for carbon, 22.5 kcal per mole for nitrogen, and 49 kcal per mole for oxygen. Values of the diffusion coefficients of carbon and nitrogen in 3 thorium have been reported by Peterson et al.&apos; However, these were secondary results of their investigation of electrotransport phenomena in thorium and it was hoped that the present study could provide more precise data. EXPERIMENTAL PROCEDURE The specimens used in this study were the well-known pair of semi-infinite bar type. The couple was formed by resistance butt welding two 0.54-cm-diam by 3.0-cm-long bars of thorium together under pure helium, the concentration of the solute being greater in one cylinder than that in the other. The finished couple then contained a concentration step at the weld interface and diffusion proceeded only along the axis of the rod. The thorium used in this study was prepared by the magnesium intermediate alloy method.5 The total impurity content was less than 400 ppm. The major impurities were: carbon, 100 ppm: nitrogen, 50 ppm; and oxygen. 85 ppm. The total metallic impurity content was less than 150 ppm. The high solute concentration portions of the diffusion couples were prepared by adding the solute to the high-purity thorium in a non-consumable electrode arc melting procedure. Carbon and nitrogen were added in the form of spectroscopic graphite and nitrogen gas while a Tho2 layer was dissolved by arc melting to add oxygen. High-purity thorium formed the low concentration portions in the carbon and nitrogen couples. The low oxygen portions were obtained by deoxidizing high-purity thorium with calcium for 3 weeks at 1000°C according to a method reported by Peterson.3 The high C-Th contained 400 ppm C, the high N-Th contained 400 ppm N, the high 0-Th contained 220 ppm 0, and the low 0-Th contained 25 ppm O. The high O-Th was brine-quenched from 1500°C to retain most of the oxygen in solution at room temperature. These concentration levels were all below the solubility limits in 0 thorium at 1400°C. A resistance-heated high-vacuum furnace was used to heat the couples. The samples were mounted horizontally on a tantalum support which had small grooves near each end. Spacer rods of thorium, 0.4 cm in diam, were placed in these grooves to prevent contact between the sample and the tantalum support. This arrangement should have prevented contamination of the sample by contact with the support. In further effort to reduce contamination, the oxygen diffusion couples were sealed inside evacuated outgassed tantalum cylinders lined with thorium foil. Thorium rings around each end of the samples acted as spacers in this case. Pressure during diffusion runs was about 10-6 torr after an initial outgassing stage. Temperature measurements were made by sighting on black body holes in the sample support adjacent to the samples with a Leeds and Northrup disappearing-filament optical pyrometer. Temperatures were constant during a diffusion anneal to ±5C. The observed temperatures were corrected for sight glass absorption after each diffusion run. The pyrometer was checked against a calibrated electronic optical pyrometer and a calibrated tungsten strip lamp with the electronic pyrometer being taken as the standard. All temperature readings agreed to within ±3C over the temperature range 1450" to 1690°C. Time corrections due to diffusion during heating and cooling were necessary because of the short diffusion times. The diffusion times ranged from 6 min for the oxygen sample run at 1690°C to 90 min for the carbon sample run at 1500°C. A series of temperature vs time plots were made for heating and cooling of the samples to the various diffusion temperatures. This data was then used in a method according to shewmon6 to determine the time corrections. The corrections amounted to

Jan 1, 1970

By J. R. Jargon, H. K. van Poollen

Non-Newtonian fluids may be injected into a reservoir during secondary recovery operations. The non-Newtonian fluid used in this work is a power-law type of fluid that is, the viscosity of the fluid decreases as the flow rate or rate of shear increases. This paper presents equations for steady-state linear and radial flow of such fluids, transient behavior results from a finite difference model of a radial system, and transient behavior results from a field test. The equations that describe the flow of a non-Newtonian fluid are non-linear and are solved numerically. Finite difference solutions are presented as curves of dimensionless pressure drop at the wellbore us dimensionless time for a constant injection rate. Solutions were obtained for 5-percent, 10-percent and 100-percent PV of a non-Newtonian fluid for injection rates of 1, 10, 100 and 1000 cc/sec and for a 5 percent PV of non-Newtonian fluid located at T = Tw&apos; 3, 10, 20, 50 and 100 ft for a flow rate of 1 cc/sec. The buildup curves do not exhibit a stmight-line portion as is the case for Newtonian flow through porous media. Correlations also are shown for the productivity index vs rate for the computer model study and the field tests. INTRODUCTION During various secondary recovery operations non-Newtonian fluids are injected. Such fluids, in general, include thickened water and gelled fluids. The term "non-Newtonian" implies that the viscosity is not only dependent upon temperature and pressure, but also on the rate of shear that is applied to the fluid. For example, water, which is a Newtonian fluid, will have essentially the same viscosity no matter what rate of shear is applied. A pseudo-plastic fluid exhibits a decreasing viscosity when higher rates of shear are applied; a dilated fluid has an increasing viscosity with increasing rates of shear. The objective of studies performed and described in this report is to obtain relationships and mathematical and empirical descriptions of the flow of non-Newtonian fluids through porous media. Simple mathematical relationships, computer studies that include the unsteady-state behavior of such fluids, and field tests are used. PREVIOUS LABORATORY STUDIES Laboratory studies have been performed by several investigators. The fluids used in one investigationl were surfactant-stabilized dispersions of water in hydrocarbons. Its Fig. 6 is reproduced as our Fig. 1. This effective-viscosity vs frontal-velocity diagram shows that this fluid is of the power-law type over a fairly large range of frontal velocities. Gogartyl developed an equation for the effective viscosity as a function of shear rate that reduces to Eq. 2 for frontal velocities greater than about 2 ft/D. The fluid characteristics used in the present study are similar to those reported by Gogarty. Christopher and Middleman2 performed experiments with power-law fluids flowing through pipes packed with glass beads. They used a modified Blake-Koteny

Jan 1, 1970

By D. C. Ganow, N. J. Grant, I. R. Silver, A. R. Chaudhuri

The structural changes that result when a metal is "cold worked" lead to higher values of yield and tensile strength on subsequent deformation at room temperature. Further it has been shown that the beneficial effects of cold work are, to some extent, maintained even at elevated temperatures. The strength improvements from prior cold work decrease as the temperature is raised and are a function of grain size, amount of cold work, and strain rate (or time of test). If recrystallization occurs during test, the cold-worked material may even show weaker stress-rupture properties than the annealed material. A question that arises is whether there is a significant effect on the subsequent creep behavior if the prior deformation is performed under creep conditions at high temperatures not too different than the test temperature, but at significantly different strain rates and for various amounts of strain. An answer to this question was sought in the work described in the present paper. PROCEDURE Two materials were used in this work, high-purity aluminum and a solid-solution A1 2 pct Mg alloy. The compositions are shown in Table I. The grain size in the two materials was 0.2 to 0.3 mm. The deformation for both the prestraining and for the creep tests was at constant stress. The procedure adopted was to prestrain a specimen to the desired elongation, remove the load, and cool to room temperature rapidly by spraying. the test bar with cold water. The specimen was then placed in a creep machine, held at the test temperature for less than 5 min, and loaded. Less than 15 min was required to bring the specimen to temperature. The creep stress was based on the diameter resulting from the prior strain, and values of elongation at fracture listed in the tables do not include the respective elongations resulting from the prestrain. The choice of the stresses for the prestrain and for the creep tests was made so that the tests could be completed in relatively short times to maximize any effect of prestrain. The specimens had a gage length of 1 in., the pure aluminum specimens having a diameter of 0.150 in. and the alloy specimens a diameter of 0.125 in. For pure aluminum, prestrain was at 400&apos; and 600°F with testing at 500°F; for the alloy, prestraining was at 700°F and testing at 600°F. RESULTS The prestrain conditions for the aluminum and the alloy specimens are shown in Tables I1 and IV. In addition to showing the time required to achieve the desired prestrain, the expected rupture Lives are given which would have resulted had the creep prestrain been continued to fracture. The prestrained and the annealed specimens were then tested in creep to fracture; the temperature and stress for the pure aliminum specimens being 500o F and 1800 psi and for the alloy, 600&apos; F and 3400 psi. The creep curves for the prestrained and the annealed specimens of pure aluminum showed all three stages of creep; hence in addition to the effect of prestraining on the rupture life, it was also possible to determine the effect of prestraining on the minimum creep rate, and on the time and elongation at the end of each of the three creep stages. The results are shown in Fig. 1 and Table 111.

Jan 1, 1960