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By T. R. Cass, M. R. Achter

A technique for measuring the creep and rupture strength of nickel specimens bonded by sintered oxide layers has been developed for the investigation of the role of grain-boundary oxide in the oxidation strengthening of nickel during creep at 817 °C. Prom the inverse dependence of the rate of bonding on the thickness of the starting oxide, it is suggested that the rate of diffusion of Ni++ through NiO is the controlling process at the start of sintering. Cornparisons of the creep and rupture strength and of the microstructure of sintered couples with conventionul creep specimens suggest rupture in nickel is prevented by load-bearikzg, ikltergranular layers of oxide. A number of recent investigations have shown that at high temperature and low stress the creep-rupture strength of nickel and nickel-base alloys may be much greater in air than in an inert gas or vacuum.'-7 For example, at 817°C and 2500 psi, nickep failed in vacuum in 48 hr but not in air after 4000 hr, and a Ni-Cr-A1 alloy5 at 1038°C and 3000 psi failed in vacuum in 4 hr but not in air after 731 hr. Fig. 1 is a typical creep curve in air for materials experiencing this pronounced environmental strengthening. A common feature of these curves is the entry into a third stage of accelerating creep, concurrent with the for-

Jan 1, 1962

By James R. Russell

Rock bolts are commonly used to support and stabilize the rock around excavated openings. The assumption is made that the less competent rock near the surface can be supported by bolting it to more competent rock away from the surface. Naturally, a rock bolt can be no more effective than its anchoring mechanism which induces a stress field into the surrounding rock. Details of various types of bolts have been described e1sewhere.l The purpose of the present investigation is to study the stress distribution around an expansion-type rock bolt anchor, using the theory of elasticity. The elastic stress distribution provides some insight into the behavior of rock bolt anchors which may eventually lead to improved designs. Very little information is available on the induced stress field which is rather complex; consequently, photoelastic techniques have been used to obtain a qualitative picture of the stress ditribution.2 The present work provides quantitative information on the stress field induced by an idealized distribution of surface tractions, provided that the assumptions of the linear theory of elasticity are approximately satisfied. FORMULATION OF THE PROBLEM Consider an elastic region which extends to infinity and contains a circular cylindrical hole as shown in Fig. 1. The hole is assumed to be the bolt hole and the surface tractions shown are assumed to be caused by an idealized rock bolt anchor. The relationship between the idealized

Jan 1, 1972

By A. A. Venghiattis

This paper is discussed not because of its intrinsic value but because it has been related by its authors to the oilwell gun perforators. It is well known that conditions almost ever present in oilwell perforations are the overburden and the presence of the casing. Because of the lack of information in the paper on the dimensions or confinement of the target rocks, one is led to guess that they were not confined at all and, particularly, that no steel front plates were used on the impact face of the rocks to materialize the presence of the cemented casing. This situation, plus the fact that small steel balls have been used as projectiles instead of actual bullets, makes the whole thing unapplicable to oilwell perforation. When shooting is performed against target rocks confined (as shown on Fig. 1) in such a way as to give a fair image of the overburden applied to the formation to be perforated, as well as of the cemented casing, the following are found. 1. There is no cratering worthy of mention, even with bullets having 10 times higher impact energy per unit projected area than the steel balls mentioned in the article. This has been confirmed with sandstone as well as with other rocks (granite, limestone and chalk). See Figs. 2 and 3. 2. Penetrations vary closely as the logarithm of the impact velocity. On this matter I have established the relation

By Jean Howard

THERE are two mechanisms by which secondary crystals can develop in bcc alloys, namely 1) impurity inhibition and 2) strip-thickness inhibition. This paper reports some studies of each mechanism; the alloys were Si-Fe, A1-Fe, Cr-Fe, Mo-Fe, and Ge-Fe, as well as iron itself. All the alloys, which were of interest as part of a program of work on soft magnetic materials, were made by a powder-metallurgy process, using carbonyl iron (Grade MCP) as the starting material. Earlier phases of the work have already been published. Work described previously1 shows how the oxygen content of the sintering. atmosphere can be used to produce silica in the material which acts as a grain-growth inhibitor. Since then it has been found more convenient to make use of the oxide in the iron powder to control the silica content of the material. The compacts are sintered in vacuum which allows a direct reaction to take place between the iron oxide and the silicon. Details are given elsewhere.4 By this method, and by suitable adjustment of the rolling schedule, material with cube-on-edge secondary crystals has been produced in thicknesses from 0.1 to 0.001 in. in iron containing from 2-1/2 to 4-1/2 pct Si. It was also found possible to process 6-1/2 pct Si-Fe to 0.001 in. This was achieved by refinement of the sintered-compact grain size by using fine-particle silicon (i.e., <200 mesh). The brittleness of the material necessitated hot rolling to 0.020 in., from which thickness cold rolling was possible. If the conditions of sintering and the cold-rolling schedule were correct (i.e., as given elsewhere4 for 3-1/4 pct Si-Fe) secondary crystals of (110) [001.] orientation could be developed. The size of the secondary" crvstals" could not be

Jan 1, 1965

By R. S. Archer

The proper representation of equilibria involving graphitic carbon in the constitutional diagram of the iron-carbon system is admittedly an unsolved problem, the complete solution of which will probably require the establishment of more experimental evidence than is at this time available. The object of this paper is to present the author&apos;s observations on some of the phenomena in question and his interpretation of this and other recorded evidence. The chief of the recently disputed questions upon which the author has experimental evidence concerns the occurrence of graphitization at temperatures below the Al point. In a paper1 presented at the September, 1919, meeting of this Institute, the following is found: "the results given would seem to indicate that the graphite eutectoid lies at a smaller value of carbon content than has been previously supposed. At least this is true unless there is either a marked formation of graphite eutectoid at these rates of cooling, or a decomposition of pearlite into graphite, both rather unlikely suppositions, but not impossible ones." In a discussion of this paper, H. A. Schwartz2 takes the position that the possibility of graphitization occurring below the A1 point is an open question, but that complete graphitization (to less than 0.10 per cent, combined carbon) commonly occurs above this temperature. Another opinion from the malleable castings industry is found in a recent paper3 by Touceda: "Also the carbide of iron can be broken up into its two soft constituents at the temperature referred to. This temperature is called the critical temperature, or critical range, and for air-furnace hard-iron castings it is in the vicinity of 1440" F. It is the

Jan 1, 1922

By R. S. Archer

The proper representation of equilibria involving graphitic carbon in the constitutional diagram of the iron-carbon system is admittedly an unsolved problem, the complete solution of which will probably require the establishment of more experimental evidence than is at this time available. The object of this paper is to present the author&apos;s observations on some of the phenomena in question and his interpretation of this and other recorded evidence. The chief of the recently disputed questions upon which the author has experimental evidence concerns the occurrence of graphitization at temperatures below the Al point. In a paper1 presented at the September, 1919, meeting of this Institute, the following is found: "the results given would seem to indicate that the graphite eutectoid lies at a smaller value of carbon content than has been previously supposed. At least this is true unless there is either a marked formation of graphite eutectoid at these rates of cooling, or a decomposition of pearlite into graphite, both rather unlikely suppositions, but not impossible ones." In a discussion of this paper, H. A. Schwartz2 takes the position that the possibility of graphitization occurring below the A1 point is an open question, but that complete graphitization (to less than 0.10 per cent, combined carbon) commonly occurs above this temperature. Another opinion from the malleable castings industry is found in a recent paper3 by Touceda: "Also the carbide of iron can be broken up into its two soft constituents at the temperature referred to. This temperature is called the critical temperature, or critical range, and for air-furnace hard-iron castings it is in the vicinity of 1440" F. It is the

Jan 1, 1922

By J. L. Huitt, B. B. McGlothlin

The introduction of new fracture propping agents that are brittle but much stronger than sand created the problem of what loading strength is required for a propping agent to be effective in a given formation. It is shown that the load at which the propping agent crushes should exceed the load at which total embedment in the fracture faces is possible. Simple laboratory tests to determine loading strength of the propping agent and embedment in the fracture faces, and use of these data in selecting a propping agent for a given formation, are discussed. INTRODUCTION One of the most important factors in the design of hydraulic fracturing treatments is the selection of a propping agent that can effectively provide the fracture flow capacity needed for stimulation of a well. Sand, once generally accepted as being synonymous with propping agent in hydraulic fracturing, is now recognized as having limited effectiveness in many formations because of its low resistance to crushing. Sand particles are brittle and have relatively low strength. Because of this property, sand particles are crushed in rocks that offer high resistance to the penetration of fracture faces by the proppant particles when the fracture attempts to close under the action of the overburden load. For rocks that offer a high resistance to penetration, deform able particles are more effective propping agents than sand. However, for this same type of rock, a propping agent that does not deform, yet does not crush, is often more effective. Thus, a rigid propping agent with sufficient strength to prevent crushing is desirable. A method for determining the strength required for a rigid propping agent to function effectively in given formations is discussed. BEHAVIOR OF RIGID PROPPANTS AND FRACTURE FACES RELATED STUDIES An early qualitative description of the reaction of propping sand in fractures was given by Hassebroek et al.&apos; In discussing fracturing in deep wells, the authors mentioned that even though propping sand entered the fractures, a high flow capacity did not result due to crushing or embedding of the propping sand. Dehlinger et al.2 in discussing the reaction of propping sand surmised that, because of the hardness of sand particles, deformation occurred in the fracture faces contacting the propping sand. In later studies,3,4 methods of determining the embedment of propping sand in fracture faces of soft rock and the critical load at which propping sand is crushed by the fracture faces in hard rock were discussed. In working with de-formable proppants, Kern et al. considered proppant particles to be deformed into cylindrical disks by action of the overburden and then pressed slightly into the fracture faces by further action of the overburden. Rixie et al.&apos;0 reported on embedment pressure and presented a method of selecting a propping agent for use in given formations. The propping agents included sand, walnut shells and aluminum pellets. All these studies have contributed materially to a better understanding of propping agent behavior; however, the strength of brittle proppants (sand, glass and ceramics) required to result in embedment rather than crushing has not been discussed. This topic will be covered in the ensuing discussion. PROPPANT PARTICLE CRUSHING—-EMBEDMENT For this discussion, a rigid propping agent is considered to be one that is brittle and fails under tensile stress when loaded to a critical value. In an earlier study4 it was shown that the Hertzian4 loading theory could be applied to a spherical brittle propping agent if the propping agent and fracture faces behaved elastically. At the failure of the proppant, the ratio of the load to the square of the diameter of the particle should be constant for a given material combination, or: Lc/dp2=C ............(1) A partial derivation of this equation from proppant and formation properties is included in the Appendix. Should a rigid particle not be crushed as a load is applied, it embeds in the fracture faces. A study3 of particle embedment in fracture surfaces has been published. The embedment can be described by an equation based on Meyer&apos;s metal penetration hardness relationships: d1/dp=B 1/2[L/dp2]m/2..........(2) In Eq. 2, B and m are constants that are characteristic of the rock; the significance of the other terms is shown in Fig. 1. A STANDARD DEFINITION FOR PROPPANT LOADING STRENGTH Eq. 1 is useful in appraising propping agent strength," but it is strictly applicable only when the area of contact between a particle and a fracture face (or loading plate)

Jan 1, 1967

By E. R. Brownscombe, Francis Collins

The pressure distribution in a reservoir producing an incompressible fluid by radial flow in a horizontal structure is a simple logarithmic function&apos; used daily by reservoir engineers. The assumption of an incompressible liquid is equivalent to assuming that pressure is maintained constant at the well radius and at some external "radius of drainage," or, in other words, that the entire flow into the well passes across the external radius. In most cases a well is surrounded by other wells draining adjoining areas so that the "radius of drainage" is not a line of constant pressure with flow equal to the flow into the well but rather a contour of zero pressure gradient across which no flow occurs, production being due to the expansion of the liquid within the area. The radial flow steady state pressure distribution for this case does not seem to be extensively used despite the fact that the mathematical analysis has been given in detail&apos; and the results are simple and generally applicable. &apos;The object of this discussion is to develop this result from a physical rather than a mathematical viewpoint, thereby aiding intuition in judging circumstances to which it may be applicable. If the production rate at a well in an unsaturated reservoir is maintained constant while no flow occurs across the outer radius a steady state will soon be reached in which the flow rate or pressure gradient is constant with time at all points in the reservoir. To preserve such a condition it is necessary that the pressure decline at the same rate at all points in the reservoir, that is, the curves of pressure versus radial distance at successive times are all parallel. Then each unit volume of oil is expanding at the same rate and contributing an equal share to the production. The rate of flow q across any circle r is thus proportional to the volume of the reservoir between r and the external radius re, or q = qw (I-r2/r2e) ......(1) where q, is the production from the well and it is assumed that rw is very small compared with re. This equation can be combined with the differential form of Darcy&apos;s law for radial flow, 2phkr dp q =—— ........(2) aµß dr ( where q is not a constant as in the incompressible flow case but is a function of r given by Equation (1). If Equation (1) is substituted in Equation (2) the variables p and r can be separated and the result integrated to obtain the pressure distribution p = pw +--------In------------- 2pkh[ rw 2re2] ......(3) This equation differs from the incompressible case only in the addition of the term proportional to the square of the radius

Jan 1, 1950

By T. E. Leontis, R. S. Busk

WORK was initiated several years ago at The Dow Chemical Company to determine the applicability of powder metallurgy processes to magnesium and its alloys. Although it was found possible to apply the normal techniques of compacting and sintering, it was discovered early that the technique of extrusion offered special promise. This technique and the alloys produced were therefore studied extensively, and the present paper is a partial report of those studies. It is expected that a second paper will discuss more extensively some of the alloy systems simply mentioned here. Although the literature on powder metallurgy is very extensive, there are only two articles dealing with magnesium13,14 and there is no reference to the direct extrusion of the powder of any metal without the preliminary step of compacting. Furthermore, no mention has been made of the possibility of designing alloys by the technique of powder extrusion, particularly alloys that cannot be made in any other way. Sauerwaldl3 discusses the extrusion of magnesium and aluminum powder to produce alloys containing nonequilibrium phases, but again he emphasizes the importance of pre-compacting before extrusion. There seems to be general agreement that some form of hot-pressing is essential to obtain in a compact the full theoretical density of the metal used.&apos;-" The nearest approach to the technique of direct powder extrusion is that of extrusion of pre-sintered compacts,&apos;-" for which the best review through 1944 is that by Kieffer and Hotop.11 Ensign* discussed a specialized technique of "extruding" already compacted and sintered gears for the purpose of sizing. Sauerwa1d13 discussed the compacting and extrusion of magnesium and magnesium-aluminum alloy band-saw chips. The properties of the extruded compacts were found to be comparable with those of extrusions prepared from solid billets. He also extruded a compacted mixture of magnesium and aluminum powder and found the properties to be somewhat different from those obtained on an extrusion made from a cast billet of the same composition. The second reference dealing specifically with the powder metallurgy of magnesium is Stern&apos;s patent," in which is described the extrusion of scrap chips and turnings following a hot-pressing and sintering step. Considerable emphasis in most of these articles is placed on the necessity of atmospheric protection to minimize the danger of oxidation. Experimental Procedure The first experiments were made with the small extrusion press shown in fig. 1. With this press, billets of about 1/2 in. diam are used to produce wire

Jan 1, 1951

By Maxwell Adams

Considerable interest has recently been developed in sage-brush oil because of its possible utilization as a flotation agent in the mining industry. A list of some of its physical properties, together with the method used in its extraction, may prove of interest at this time. Something over a year ago, a study of the essential oils in desert plants was begun in the Chemical Laboratory of the University of Nevada. None of the oils so far studied possess properties of special interest to engineers, except the oil of sage, Artemisia tridentata, which has exceptional power as a flotation agent. This plant, known as common sage brush, also called black sage, is widely distributed over the semi-arid West, being found quite generally on most of the dry plains and mountains west of Missouri. The method of extracting the oil followed in these experiments is very simple. The leaves, twigs and small branches are placed in an airtight drum, having a capacity of about 27 cu. ft. Steam is admitted through a number of ,small openings at the bottom of the retort, and the pressure maintained at 20 to 25 lb. per sq. in. for 3 hr. The escape of the steam from the retort is regulated by allowing it to pass through a stop-cock into a condenser. The water in the receiver is drawn off from time to time and the oil, which is insoluble and floats upon the water, is thus collected. At the end of 2 hr. most of the oil has been driven out, though traces continue to come over for a much longer time. By raising the pressure, the time required could probably be shortened and the yield increased, but the lack of laboratory equipment has prevented the carrying out of this experiment. The stock wood, bark and branches contain no oil, the distribution of the oil being limited to the leaves and young shoots. There is a seasonal variation in the amount of oil contained. Samples collected on different dates gave the following amount of oil: May 1, 0.42 per cent.; May 27, 0.6 per cent.; June 30, 0.72 per cent.; Aug. 1, 0.9 per cent.; Sept. 10, 1.0 per cent. The increase appears fairly constant from early spring, when the leaves first appear, until light frosts occur in the autumn. When the plant is air-dried there is some loss of oil, as the following data will show: Two 100-lb. samples were collected at the same time. One was distilled when green; the other was air dried for

Jan 1, 1917

By Luther Wagoner

Having given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and believing it might be interesting to extend the work to include some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S. steamer Albatross, and marked as follows: Depth in No. station. Locality. Latitude. Longitude. Fathoms. 1. 2103. Off Delaware bay. 38&apos; 47&apos; 20" N., 72o 37&apos; W., 1,091. 2. 2265 to Between Chesapeake 35° 37&apos; N., 74O to 75O W., 49 to 70. 2297. bay and Hatteras. 3. 2420. Off Chesapeake bay. 37&apos; 03&apos; 20" N., 74O 31&apos; 40" W., 104. 4. 2528. East of Georges 41° 47&apos; N., 65o 37&apos; 30" W., 677. bank. 5. 2572. SE. of Georges bank. 40° 29&apos; N., 66O 041 W., 1,769. 6. 2681 South of Nantucket. 39&apos; 43&apos; N., 70&apos; 29&apos; W., 990. The above samples were assayed by the cyanide-method, described in my former paper (p. 807), about 30 g. of sample being used, and the following results were obtained: Value in Milligrams Per Metric Ton. No. Station. Gold. Silver. 1. 2103. 145 1,014 2. 2265 to 2297. 44 304 3. 2420. 15 353 4. 2628. 267 1,963 5. 2572. 125 377 6. 2681. 66 414 No. 4, Station 2528, consisting of red clay and volcanic ash, mas re-assayed ; 35 g. was roasted at a low heat for one hour and weighed 34.05 g. after roasting; the color was changed to a deep brick-red; and when assayed by the cyanide-method

Jan 1, 1908

By W. Seymour

Uranium was cold rolled to a reduction in thickness of 90 pct and the preferred orientation of the grains was determined from X-ray intensity data. Complete pole figures for a large number of atom planes were plotted, and the preferred orientation was found to be duplex (102) [0101 + (012) [021]. These preferred orientations are compared with those reported for many of the hexagonal-close-packed metals. THE preferred orientation of a highly reduced cold-rolled uranium strip was determined in order to obtain additional experimental data which would be useful in further understanding the deformation mechanisms of uranium. The preferred orientations reported herein are not in agreement with those theoretically predicted by Calnan and Clews&apos; for cold-rolled uranium sheets, and differ somewhat from those reported from experiments by Fisher, and Burke and Turkalo. Such variations might be accounted for by differences in the fabrication temperature and the reductions. Experimental Procedure The uranium used in this investigation had been hot rolled to 0.060 in. at 575°C from 0.393 in., and from a 0.060 to 0.020 in. thick sheet at 275°C. From this point the sheet was cold reduced 90 pct to 0.002 in. at room temperature. Three specimens were used to obtain complete pole-figure data. The first was a 1/2 in. square section illuminated by the X-ray beam on the rolling surface. The other two were l/2 in. square longitudinal and transverse sections each made as follows: Approximately 200 1/2 in. square sections of the foil were piled one on top of the other, so that the rolling direction for each piece was kept coincident. A 1/2 in. square by 1/8 in. thick steel section was placed on the top and bottom of a pile and the entire assembly was then bolted tightly together through a 1/8 in. diam hole drilled down through the center. Each pile was then surface-ground from the two proper sides to sections 1/2 in. square by 3/16 in. thick. These specimens were then polished flat and electro-polished to remove 0.005 in. of the surfaces to be examined. It can be shown that uranium is so opaque to a Cu Ka X-ray beam that only a small percentage would be transmitted by one micron of uranium. Therefore, a method of measuring the X-ray intensities diffracted from specimen surfaces was used. The specimens were mounted in a modified Schulz reflection holder&apos; which automatically changed the position of the specimen at a constant rate. The holder, in turn, was mounted on a General Electric XRD-3 Spectro-Goniometer and an automatic record made of the diffracted X-ray intensity vs specimen position. While a specimen moved automatically through 10" inclination, at a rate of l° per min, it simultaneously rotated 360" about a normal to the illuminated surface. (The inclination and rotation angles are referred to as F and a, respectively.) The data were then plotted along the resulting spiral path on a stereographic projection, Fig. 1. Because of defocusing effects on the diffracted beam which occur when diffracting surfaces are in-

Jan 1, 1955

By A. Steiner, E. Miller, K. L. Komarek

Equations have been derived to calculate the chemical potentials of the components of liquid binary alloys from liquidus and enthalpy data. The equations are applicable to systems with intermetal-lic compounds of limited solid solubility. The liquidus curve of the Mg-Sn system was accurately redetermined, and the melting point of the compound Mg2Sn was found to be 770.5° * 0.3°C. The thermo-dynamic properties of the liquid alloys were calcu -lated from the liquidus data. The activity of tin shows both positive and negative deviations from Raoult&apos;s law and the relative integral entropy is positive. THE phase boundaries in an equilibrium phase diagram are functions of the thermodynamic properties of the coexisting phases. Specifically, the shape of the liquidus curve near an intermediate compound is determined by the properties of the compound and the liquid phase. Hauffe and wagnerl have derived an equation for the chemical potential differences (ui) of the liquid alloys near the congruent melting point when the heat of fusion of the compound and the liquidus curve are known. In their derivation the temperature dependence of the ui value was neglected, and liquid of stoichio-metric composition was chosen as the reference state. To obtain chemical potentials over the ntire composition range of the phase diagram with the pure components as the reference state, equations have been derived which incorporate the temperature dependence of the chemical potentials. Such a thermodynamic analysis can be carried out when the liquidus curve and the enthalpy values are known. The equations have been applied to the redetermined liquidus curve of the Mg-Sn system to obtain the thermodynamic properties of liquid Mg-Sn alloys. The Mg-Sn phase diagram has been studied by various investigators and the results have been compiled and critically assessed by Hansen.2 Preliminary thermal analyses showed that the basic features of the diagram were correct. The system has one congruent melting compound, Mg2Sn, two eutectics, and some solid solubility of tin in magnesium. However, the published liquidus temperatures show considerable scatter. In order to perform an accurate thermodynamic analysis, the liquidus curve between the magnesium-rich and tin-rich eutectic compositions was therefore redetermined by careful thermal analysis using highest-purity starting materials. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd, Toronto, Canada) had a purity of 99.99+ pct with the following impurities (in ppm): 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu, <10 Fe; tin (Cominco Products, Spokane, Wash.) contained 99.999+ pct Sn. The graphite crucibles were machined from graphite rods (United Carbon Products Corp., Bay City, Mich.) which had an average total ash content of less than 30 ppm. All the graphite parts were baked out in vacuum at 950" to 1000°C for a minimum of 24 hr to remove volatile organic materials. The graphite crucibles (3 in. long, 1-5/8 in. OD, 1-3/8 in. ID) were tightly closed with a threaded cover (1/2 in. thick) which had a central thermocouple well (2-1/4 in. long, 5/16 in. OD, 3/16 in. ID). Cover and thermocouple well were machined from one piece of graphite. A thin sheath of quartz was inserted in the well to protect the thermocouple

Jan 1, 1964

By E. A. Gulbransen, A. Pebler

Pressure-composition isotherms have been determinedfor the systems ZrMo2 -H2 between 0" and 900°C at hydrogen pressures between 10-4 and 760 Torr. Tkese studies plus X-ray diffraction analyses of selected compositions show that these intermetallic compounds form a complete series of hydrogen solid solutions within this temperature and pressure range. The partial molar enthalpies and entropies of solution of hydrogen in the three intermetallic compounds were calculated. The solubility of hydrogen in these Laves phases can be related to their free electron concentration. ThE reaction of hydrogen with inter metallic compounds of zirconium with Laves phase-type structure has both theoretical and practical interest. The in-termetallic compounds have structures different from any of the pure metals. In addition the electron to atom ratio of the intermetallics varies appreciably. In the nuclear materials field, these materials are of interest since intermetallic compounds may exist as precipitates in commercial zirconium alloys with transition metals. From studies on the hydrogen reaction, one can establish the stability of the intermetallic compounds relative to the hydrides of the component metals. The intermetallic compounds may also be used as getters for hydrogen and as materials for hydrogen storage. This paper will present the results of equilibrium and structural investigations of the ZrCr2-H2, the ZrV2-H2, and the ZrMo2-H2 systems for the temperature range of 0" to 900°C and the pressure range of Torr to 1 atm. A complete thermochemical analysis will be made of the measurements. Some of the results have been referred to in a survey paper&apos; covering the types of hydrogen behavior observed in zirconium alloys. LITERATURE ZrCr2 is the only intermetallic phase in the Zr-Cr system.&apos; It exists in two allotropic modifications. Between 900" and 1000°C the hexagonal MgZa (C14) structure transforms into the cubic MgCu2 (C15) structure. Beck4 has previously shown that the intermetallic ZrCrz takes up hydrogen into solid solution up to a composition H/ZrCr2 = 1.14 at room temperature and 1 atm hydrogen. A ZrCr2 hydride was stated to have a fcc structure. The binary Zr-V system has been investigated by williams5 although Rostoker and Yamamoto 6 had given earlier a partial phase diagram. ZrV2 was the only intermediate phase found in the system. wallbaum7 reported earlier that the compound ZrV2 hp the MgZm (CJ4) type structure with a = 5.288A and c = 8.664A. This was not comfirmed by Elliot8 nor by Matthias, Compton, and corenzwit9 who reported that ZrV2 has a cubic MgCua LC15) type structure. The latter authors gave a = 7.429A. Also, several authors do not agree on the temperature of the peri-tectic horizontal. It appears that ZrV2 may exist in several modifications. A high capacity for occluding hydrogen was reported by Beck4 who found H/ZrV2 = 1.38 at room temperature and 1 atm of hydrogen. ZrMoz is the only intermetallic phase in the Zr-Mo system.10 ZrMoa is formed by a peritectic reaction of the melt with a molybdenum-rich solid solution. ZrMo2 has the C15-type structure with a = 7.59A. MATERIALS High-purity chromium, vanadium, and molybdenum were used together with grade 1 crystal bar zirconium to prepare the alloys. Table I lists the chemical analysis and the sources for the metals. Ten-gram alloy compacts were levitated and melted in an inert argon

Jan 1, 1968

By P. Somasundaran, I. J. Lin

There are several methods described in the literature for the determination of the order and the rate constant for the flotation of minerals. These often involve some type of computational or graphical procedures. A relatively simpler method developed on the basis of a technique used by Chang" in chemical kinetics is described in this paper. Chang&apos;s technique, like most others in chemical kinetics," is based on the law of mass action which states that the rate of a chemical reaction is proportional to the active masses of the reacting substances at any given time. Application of this law to the flotation of minerals would involve the adaptation of the terms "flotation" for "chemical reaction" and "floatable amount of the minerals" for "the active masses of the chemical reactants." There are indeed a large number of physical processes controlling the actual flotation rate. The most inefficient one of these could be considered equivalent to the slowest reaction in a series of chemical reactions. If variables such as aeration rate and agitation are kept at constant levels, the rate of flotation under free flotation conditions (i.e., conditions under which the suspension is dilute) will be given by the following equation: where C is the concentration of the floatable minerals in the pulp at any given time t, K is the rate constant, and n is the order of the reaction. If we represent the floated fraction of the floatable mineral at time t as m (0 m - 1) and C at t = 0 as Ca, integration of Eq. 1 yields

Jan 1, 1974

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,&apos; Mc Quillan,&apos; Van Thyne et dl.,&apos; and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger&apos; discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95&apos; *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By H. C. Fiedler

X HE development of the cube-on edge secondary re-crystallization texture in Si-Fe strip requires that normal grain growth be restrained. It has been shown that the degree of restraint and hence the completeness of secondary recrystallization depends upon the size and number of second-phase particles, which in turn is dependent upon the prior processing history.1y2 The purpose of this note is to show that, for heats in which manganese sulfide particles are providing the restraint to grain growth, the choice of hot rolling temperature depends upon the manganese content. The making and processing of the heats to the final gage of 0.012 in. has been described.3 The compositions are given in Table I. Apparent in Fig. 1 is the decrease in the ability of strips hot-rolled from 1175°C to undergo secondary recrystallization as the manganese content increases. It has been shown that 1175°C is below the solubility temperature of 0.014 pet S in even the 0.038 pct Mn alloy: and the observed behavior is attributed to an increasing fraction of the sulfur forming large manganese sulfide particles at the heating temperature for hot rolling. This fraction of the sulfur is thus unavailable to subsequently form the small, uniformly dispersed particles which are needed to restrain normal grain growth. Since the sulfur is completely in solution at 1325°C,3 strips from all three alloys show strong secondary recrystallization behavior when hot-rolled from that temperature.

Jan 1, 1969

By Charles R. Keyes

PAGE I. Introductory............ 140 II. Location and History...........140 III. Surface-Relief of the District....... 141 IV. General GeoloGic Features........ 142 1. Main Relationships and Map....... 142 2. Résumé of Geologic History..143 V. Geologic Formations Represented...144 1. Broader Considerations......... 144 2. Geologic Section.......... 145 3. Nomenclature.......... 146 4. El Pasan Limestones..146 5. Santa Rita Limestone.... 146 6. Silver Shales........... 147 7. Bella Shales........... 147 8. Berenda Limestone..147 9. Grande Limestone... 148 10. Lake Valley Limestone........ 148 11. Sierra Limestone.......... 149 VI. Unconformities........... 149 VII. Geologic Structure.......... 150 1. Main Characteristics......... 150 2. Folding........... 1.50 3. Faultings........... 150 4. Relations of the Eruptives...153 VIII. Geologic Relations OF the Ore-Bodies...... 154 1. Governing Factom......... 154 2. Position.......... 154 3. Relations to Foldings...155 4. Relations to Lines of Dislocation... 15.5 5. Relations to Present Surface.Relief..156 6. Relations to Eruptive Rocks...157 7. Relations to Lithologic Nature of the Rocks.... 158 IX. MINERALOGIC CHARACTER OF THE ORES...... 158 X. Origin of the Ore.Deposits..159 1. General Statement......... 159 2. Original Source of the 0re.Materials...160 3. Contact-Metamorphism of the Region... 161 4. Process of 0re.Concentration..162 5. Lowering of Ground-Water Level..162 6. Formation of Cerargyritic Ores...163 XI. Recapitulation........... 168

Jan 1, 1909

By L. Yarborough, L. R. Smith

This paper presents results of a laboratory study of retrograde condensate recovery by revaporization into dry injection gas. Flow tests were performed in 10.6-ft long sand packs at 100F and 1,500 psi. In three runs methane revaporized the liquid from a n-pentane-methane mixture in the presence of immobile water. TWO of these tests were water-wet, and the third was totally oil-wet. In the three runs n-pentane recovery was complete after 2.5 hydrocarbon PV of injection. There was no significant performance difference between the two wettability extremes. In a fourth experiment, a methane-hydrogen sulfide mixture revaporized a synthetic light, sour condensate. No water saturation was present. Equilibrium compositions and volumetric data were obtained for the four-component condensate. The heavy component, n-beptane, was removed after 6 PV production. Comparison of the effluent fluid compositions with known equilibrium data shows that the flowing fluid was equilibrium vapor and that the mixing zone between equilibrium vapor and dry injection gas was short. Data indicated that complete recovery of retrograde liquid occurred after it was contacted by a sufficient quantity of dry gas. INTRODUCTION When pressure declines below the fluid dew point in a gas condensate reservoir, a liquid phase forms. In this process, referred to as retrograde condensation, the quantity of liquid formed is frequently small enough that the liquid is not a flowing phase. To prevent loss of valuable retrograde liquids, the process of dry gas cycling has been employed for several years as a more or less standard practice. In this procedure the reservoir pressure is maintained above the fluid dew point so that the liquid components may be produced as vapor and then separated at the surface. Although full pressure maintenance by gas cycling seems ideal in terms of preventing liquids loss, several factors can reduce the atuactiveness of such an operation. From a study of a condensate reservoir in Alberta, Canada, Havlena et a1.1 con-cluded that cycling under conditions of declining pressure leads to economic advantages and to a high recovery of hydrocarbon liquids. This study considered effects of volumetric sweep efficiency, retrograde behavior of the original wet gas and revaporization characteristics of the retrograde liquid when contacted by dry gas. The first major work concerning revaporization of liquid in a gas condensate system is that of Standing et a1.2 Calculations based upon the PVT behavior of a recombined gas condensate fluid indicated that all retrograde liquid can be recovered if it is contacted by a sufficient quantity of dry gas. The paper considered the effect of variable permeability upon the recovery of retrograde liquid. Standing et al. concluded that recovery of heavier components in the retrograde liquid is greatest if reservoir pressure is allowed to decline below the dew point prior to dry gas injection. Since the work of Standing et al., several laboratory studies have been reported which show that recovery of hydrocarbon liquids by vaporization into dry injected gas can contribute to increased recovery above that obtained by ordinary production practices. Vaporization from retrograde condensate,3 conventional oil4-7 and volatile oil8 reservoirs has been considered. There is little work that deals with revaporization recovery from condensate reservoirs. This study demonstrates that vapor-liquid equilibrium exists when a dry gas is injected into a porous medium containing retrograde condensate; investigates the effect of wettability on revaporization of retrograde condensate; and provides an indication of the amount of dry gas necessary to

Jan 1, 1969

By Paul A. Beck, John Towers, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350&apos; to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.&apos; Fig I shows a log D vs. log t plot of French&apos;s data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French&apos;s data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.&apos; Walker&apos;s specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker&apos;s data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949