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By C. E. Coleman, D. Hardie, A. E. Wraith

A photoguaplric method of measuring crack velocities has been applied to an examilzation of- the effect of hydrogen on the impact properties of zirconium. Results indicate that the crack in hydrided zirconit travels at about 26 m per sec whereas that in the uacuum -annealed is dependent on the speed of the hammer. RECENT work on the effect of hydrogen on zirconium reveals that when hydrided zirconium is tested in slow bending the crack producing failure can be unstable. The mode of fracture seems to involve the crack linking up broken hydrides by a ductile mechanism in the zirconium matrix.2" In order to compare the fracture of zirconium with that of other metals which show unstable crack propagation, notably steel, the rate of the crack spread must be known. As the methods previously used for measuring crack growth are either unsuitable for the present work5-'' or very costly," a simple technique has been devised in which the maximum crack velocity is derived from a series of crack position-time measurements. EXPERIMENTAL PROCEDURE The experimental arrangement is shown schematically in Fig. 1. The flash unit12 was triggered when the Charpy hammer touched the specimen and the 6-psec flash of the lamp delayed by a preselected time interval in the range 100psec to 10 msec. The camera was left on open shutter during the test. From direct measurement on a calibrated photographic print, Fig. 2, the position of the crack and the specimen was found at a known time after impact and, from a series of such tests using an appropriate range of flash-delay times, the crack velocity was estimated. Preliminary experiments were carried out on mild steel above and below its transition temperature. Vacuum-annealed zirconium, and zirconium hydrided to 100 ppm H were then tested at 20" and 150°C. For comparison, Zr-2.6 pct Nb alloy (in the 0 + transformed /3 condition), vacuum-annealed or hydrided to 100 ppm H, was tested at 20 C. The chemical analyses of these materials are given in Table I. For the high-temperature tests a fine chromel-alumel thermocouple was spot-welded onto each specimen close to the notch. The test piece was heated up to 200°C to allow enough time for preparing the apparatus while the specimen cooled to the testing tem- perature. It was assumed that the specimen cooled uniformly. The accuracy of the flash-delay time was better than i2 pct i 5 psec. The crack length was taken as its maximum distance traveled normal to the length axis of the specimen. Errors in these measurements arise as a result of the uncertainty in the location of the crack tip and the difficulty in defining the exact position of the crack starting point. The latter was due to the bonding and large amounts of deformation at the hammer contact point, especially in the vacuum-annealed specimens tested at 150°C. The maximum error in the measurements was however estimated to be about 5 pct. DISCUSSION OF RESULTS From the trial experiments using mild steel above its transition temperature it can be seen from the plot of crack length against time after impact, Fig. 3. that a reasonable estimate of the maximum crack velocity at the surface of the specimen may be made. Other features of note are the initiation time before the crack is first seen and the slowing down period

Jan 1, 1967

By W. C. Maurer

Although millions of feet of rock are drilled annually, the basic drilling mechanisms involved are not well understood. The primary reason for this lack of knowledge is because the basic principles of rock failure are not well understood and rock failure is the primary mechanism in drilling. A better understanding of the drilling mechanisms would enable a more scientific approach to the design and use of drills and bits. The paper reviews several models which have been proposed to explain various aspects of the different drilling methods. These models are described and their limitations and areas of application are discussed. Drilling rate relationships are developed and related to the basic rock failure mechanisms. TYPES OF MECHANICAL DRILLS There are three basic methods of mechanically attacking rock: 1) percussive action, 2) rotary action, and 3) combined rotary-percussive action. A percussion drill applies a force perpendicular to the rock surface and the bit moves into the rock perpendicular to the surface, forming a crater beneath it (Fig. 1). A rotary drill applies a constant thrust to the bit while a torsional force moves the bit parallel to the rock surface, breaking the rock ahead of it. A rotary-percussive drill applies both a rotary force and a percussive force to the bit which moves into the rock at an angle to the surface. The commonly used drills can be classified as: rotary-drag, diamond; percussive-hammer, piston, churn; and combination-rotary-percussive, roller.

Jan 1, 1967

By H. Bartholomew, L. Bernstein

Experirmental bonds of Ag-In SLID to gold, copper, nickel, Kovar, Dumet, nickel-plated molybdenum, ALL-Pt vrzetallizing on ceramic, and nickel-plated Mo-Ti metallizing on Al2O3 ceramic have been made and exalnined. Metallographic taper sections were made of all bonds for Phase identification. In addition, failuve temperatltres were determined for bonds heated undev shear load. Sowe bonds were subjected to electvon-probe microanalysis. The ternary SLID system Ag-In-Sn was similarly evaluated. Plwtonticrogaphs and electron-probe data are discussed and related to over-all phase diagrams , diffusion effects, and wetting properties of the liquid. The rates of diffusion andor compound formation of gold, silver, and copper in indium and In-Sn liquids are found to descend in that order, as measured by the relatzve thickness of phase layers in the interfaces of bonds made at 200to 400°C. It is concluded that the SLID process enables one to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures, and meet most requirements for application in interconnection, silicon bonding, or hermetic sealing of electronic devices. In a previous publication by one of the authors, the theory and principle of SLID bonding in simple binary systems was discussed. SLID bonding can be defined as a joining process using a preform with a laminated structure: a low-melting material clad on a high-melting core. During the bonding cycle a metallurgical transformation occurs such that the resultant structure can withstand, without reliquefying, temperatures higher than those at which the bond was made. The phases present in the joint interface region are high-melting compounds or, if equilibrium is reached, solid solution. Properties will depend on the phases present, ultimately approaching those of the solid substrate core of the SLID preform. The high-temperature strength of bonds made in these systems was correlated to phase identification in the interfacial bond regions from metallographic cross sections and electron-probe X-ray microanalysis data. When complex electronic components are assembled, multiphase systems result at the interfaces of bond regions. In these ternary and higher-order systems very little diffusion and phase-diagram data is available with which to predict the nature of the interfacia1 region that will result from conventional fabrication processes and subsequent field use of the component. Clarke and Rhines did early work in the field using the Al-Mg-Zn system as a vehicle. Guy and co-workers studied a portion of the Cu-Zn-Ni system and some mathematical4 and general5 aspects of multiphase diffusion. irkald' and coworkerse recently studied diffusion in the Cu-Zn-Sn system. No diffusion studies have been made on ternary systems directly applicable to this investigation but some phase diagrams are available: g-u-n, u-i-n, and CU-i-n. I) DESCRIPTION AND EXPERIMENTAL PROCEDURE The elements Au, Ag, Cu, Ni, In, and Sn are found in alloy systems commonly used in fabricating and assembling electronic components. Reference to the appropriate phase diagrams9 and the previous publication will indicate that the binary systems of any of the two low-melting elements, indium and tin, with any one of the other four higher-melting elements are capable of producing SLID bonds. It is not unreasonable to assume that any ternary or higher-order alloy system containing at least one of the elements gold, silver, copper, or nickel and one or both of the elements indium and tin could be used to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures. Indeed, the liquidus contours and isothermal sections of those phase diagrams available7 do so indicate. The parameters affecting the bond and the equipment used in evaluating the bond were described in an earlier paper.' The current investigation used the

Jan 1, 1967

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar' in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.' Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,' be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,'' however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

By A. T. Chatas

A description of the geometrical characteristics of spherical reservoir systems, a discussion of unsteady-state flow of such systems and examples of engineering applications are presented as backgmund material. The fundamental differential equation, a description of average spherical permeability and the introduction of the Laplace transformation serve as theoretical foundations. Engineering concepts are investigated to indicate particular solutions of interest, which are analytically obtained with the aid of the Laplace transform. These are numerically evaluated by computer, and presented in tabular form. INTRODUCTION A tractable mathematical analysis of unsteady fluid flow through porous media generally requires incorporation of a geometrical symmetry. The simplest forms include the linear, cylindrical (radial) and spherical. Most analytical endeavors have concentrated on cylindrical symmetry because it occurs more often in petroleum reservoirs. Nevertheless, some reservoir systems do exist that are better approximated by spherical geometry. Review of technical literature revealed but a single reference to unsteady spherical flow in petroleum reservoirs.l The motive and purpose of the present work was to remove this gap in technical information, and to provide the practicing engineer with some useful analytical tools. The mathematical details associated with the particular solutions of interest involved use of the Laplace transformation. Hurst and van Everdingen previously demonstrated the efficacy of this operational technique, and in many respects the present treatment was patterned after their earlier work.2 PRELIMINARY CONSIDERATIONS GEOMETRICAL CHARACTERISTICS Geometrically, a spherical reservoir system is defined at any instant of time by two concentric hemispheres whose physical properties of interest vary only with the radial distance. Every physical property is thus restricted to be a space function of only one variable: the distance along a radius vector emanating from the center. Such a system is composed of an outer region and an inner region, separated by a defined internal boundary. The inner region simply extends inward from this boundary, whereas the outer region extends outward from it to an external boundary. The position of the internal boundary is presumed fixed, so that the size of the inner region remains constant. On the other hand, the position of the external boundary at any given instant of time is determined by the distance into the system that a sensible pressure reaction has occurred, Thus, the external boundary may change position with time. It initially emerges from the inner region and advances outward to its ultimate position. When this ultimate position coincides with a geometric limit, the reservoir system is said to be limited. When it coincides with points subject to pressure gradients furthest removed from the internal boundary, yet short of a geometric limit, the system is said to be unlimited. In this investigation two different boundary conditions are imposed at the ultimate boundaries of limited systems. The first requires that no fluid flow occur across this boundary; the second that the pressure remain fixed at this boundary.3-5 UNSTEADY-STATE FLOW In a strict sense virtually all flow phenomena associated with a reservoir system are unsteady-state. The transient behavior of these phenomena requires accounting, however, only when time must be introduced as an explicit variable. Otherwise, steady-state mechanics may be used. Analytically, steady-state conditions prevail in a reservoir system only over that portion of its history when this relation is satisfied:

Jan 1, 1967

By R. R. Goddard

By use of the frequency response method with a radioactive tracer, it was possible to determine fluid dispersion and distribution in a natural consolidated and an unconsolidated medium. Measurements were made in a linear flow system at oleic saturations of 69 per cent in the consolidated medium, and 100 per cent in both media. Dispersion and distribution were obtained by measuring the amplitude attenuation and the phase velocity of sinusoidal waves with a dual monitor apparatus. The gamma ray emissions permitted in situ measurements at any distance along the porous samples. One result of importance was that the effective diffusivity increased as the wave length increased. As a consequence, a dispersion coefficient appropriate for the injection of large slugs might exceed the value measured by use of small slugs. Since flow models based solely on fluid velocity and an effective diffusivity coefficient imply that the diffusivity should be independent of frequency, such representations were not adequate for the data of this study. A comparison was made with a capacitance model of porous media with deadend PVs, but even this model was not completely adequate. By using attenuation and phase velocity data, fluid dispersion can be predicted without postulating a differential equation satisfied by the tracer concentration, thereby eliminating the need of a complicated model to represent dispersion. INTRODUCTION The flow of similar miscible fluids through a porous medium can be fairly adequately described by two parameters: the average fluid velocity and the effective diffusivity.1-3 It has been pointed out recently, however, that significant discrepancies exist between this representation and the experimental data.4-7 An improved agreement can be obtained by introducing additional parameters based on the concept of dead-end pores. The purpose of the present investigation was to find out whether the frequency response method could be used to measure the relevant parameters. The method was used in the following form. A stream of fluid was flowed at a constant rate through a sample of porous material and the concentration of a radioactive tracer in the fluid was varied sinusoidally at a fixed frequency. The effects of flow through a porous medium are a decrease in the amplitude of the concentration wave and an increase in the velocity of the peaks of the waves above the average velocity. Attenuation and phase veIocity of the waves were measured as a function of frequency and fluid velocity. The simple two-parameter model implies that the diffusivity should be independent of frequency. Data reported in this paper show that the diffusivity decreases as the frequency increases. Hence, as shown also by many others, the two-parameter model is not completely adequate. Coats and Smith 5 used two additional parameters in their model: the volume of the dead-end pores and the rate of mass transfer between dead-end pores and the flowing stream. Their capacitance model of a porous medium containing some stagnant fluid, to which transfer occurs by molecular diffusion, did not explain the dispersion results of either the present study or of theirs. Instead, the capacitance effect can be better described as the result of extreme velocity variations within the pores of the medium, with transfer between the velocity zones by convection. EXPERIMENTAL PREPARATION OF POROUS MEDIA Data reported here were obtained with a natural Berea sandstone, and with two packings of 20/25 mesh sand. Pertinent information about these media is listed in Table 1. The sandstone core was first sealed with a non-

Jan 1, 1967

By R. W. Smith, R. W. M. Lai

Although several recent papers have shown that equilibrium contact angle in dodecylamine solution-quartz systems can often be directly correlated with flotation behavior, it appears that under conditions of relatively high amine strength and pH such a correlation can't be made. Under these conditions, when there are precipitated amine dipoles present, it appears that a dynamic contact angle formed immediately after introduction of fresh gas bubbles into the system is also of importance. The dynamic angle decreases in magnitude as a function of time. Apparently the decrease is the result of changes in interfacial tensions (liquid-gas and solid-gas) as a function of time. Dynamic angles of the type described can't be observed in trimethyldodecylammonium chloride solution-quartz systems. Several recent papers1-3 have shown quite conclusively that contact angle data can often be correlated directly with flotation behavior in cationic surfactant solution-quartz systems. At the same time, Iwasaki, Cooke, and Colombo4 have shown data for a dodecylammonium chloride solution-goethite system where, in the vicinity of pH 12 and a collector concentration of 10" M, 100% flotation occurs when equilibrium contact angle appears to be zero. A clue to this discrepancy can be found in the work by smith2 who reported the occurrence of dynamic, time dependent, contact angles in a quartz-dodecyl-amine solution system at relatively high pH values and at surfactant concentrations greater than or equal to 10-4 M. It was found that under these conditions, if a fresh bubble was brought into contact with a properly conditioned and polished quartz surface, a large angle was obtained. The large angle, however, instantly started to diminish in magnitude, sometimes to a smaller stable angle and sometimes to its complete disappearance. Also, if the bubble was preconditioned for some minutes (or sometimes even seconds) in the same amine solution, the smaller or sometimes zero stable angle was obtained when the bubble was brought in contact with the quartz surface. One is immediately led to the thought that perhaps it is these dynamic angles when they exist, not stable angles, that are of primary importance in flotation. The present investigation attempts to further study the relationship between contact angle and flotation

Jan 1, 1967

By V. Patarini, D. Kuehl, F. Galasso, M. Salkind

In recent years, a great deal of research has been directed toward the production of continuous low-density, high-strength, high-modulus boron fibers for aerospace applications. A technique which has proven to be quite successful for forming these fibers involves the reaction of boron trichloride and hydrogen on a hot tungsten wire. In this process, a boron fiber is produced which consists of a tungsten boride core covered with amorphous or crystalline boron depending on the temperature of the preparation.2,3 The purpose of this paper is to present the properties which have been obtained to date from measurements and observations on these fibers. Selected samples of boron filament produced by reacting boron trichloride and hydrogen on a 0.5 by 10-3 in. diam tungsten wire substrate using different reacting temperatures were cross-sectioned, polished, and photomicrographed with cross-polarized light. The temperature of the wire was measured using a two-color optical pyrometer. Photomicrographs of these samples are shown in Fig. 1. Three general types of boron, in addition to the tungsten borides, have been identified by means of X-ray powder diffraction techniques: a) at low temperatures (below 1400°C) the boron is deposited in the amorphous form; b) at temperatures between 1400° and 1500°C the boron is deposited in the ß tetragonal form; and, c) above 1500°C the boron is deposited in the B rhom-bohedral form. In the depositing range of 1400" to 1500°C the boron initially deposits as amorphous and becomes crystalline as evidenced by the large equi-axed grains which then merge into columnar grains in later stages of boron deposition. This can be seen in Fig. 1 and has been observed in the X-ray patterns of these fibers, which contain both halos from the amorphous boron and lines from the ß tetragonal form. Above 1500°C the only boron reflections observed in the X-ray patterns were those of the ß rhombohedral form and only columnar grains are seen in the photomicrographs. Photomicrographs of the surface in Fig. 2 show the smooth-surface kernal-type deposition which corresponds to the amorphous form and the rougher surfaces which correspond to the crystalline form. Mechanical measurements were made on amorphous boron produced at 1300°C rather than the crystalline boron because the strengths of these filaments were greater and were more consistent. A tensile tester consisting of a fixed crosshead containing a double

Jan 1, 1967

By J. Skrove, C. R. Boardman

In situ permeability of the rock outside the Hardhat chimney was determined by pressurization of long holes with air. Experimental data indicated a remarkable difference between fracture permeability of the rock near the chimney and that at a considerable distance. Although permeable fault zones were known to exist in the granite stock, the measurements of background permeability were quite low, on the order of tenths to several millidarcies. The observed difference is about two or three orders of magnitude above this background in the region 125 to 215 ft radially from the shot point, or 80 to 165 ft radially from the vertical axis of the chimney. The presence of a collapsed drift immediately beyond this region precluded measurements which could have defined the maximum extent of the zone of high permeabilily. INTRODUCTION Previous exploration has revealed that contained nu-clear explosions create cavities which generally collapse, resulting in rubble-filled chimneys and annular fractured zones. These geometries have been shown to result in complex flow regimes which should increase the production rate from hydrocarbon reservoirs.' Empirical scaling equations have been developed for estimatina chimney radii and heights for a variet; of rock media.' The exten; of the annular fractured zone has been documented and associated permeability changes have been observed qualitatively for several explosions. This study was begun to establish the nature and magnitude of the permeability of the latter region. It is anticipated that results will be useful in estimating permeability changes and consequent production stimulation which might ensue from a contained explosion in a hydrocarbon reservoir. The post-shot environment of the Hardhat event (a 5-kt contained nuclear explosion in granitic rock) was c'hosen for the experimental measurements. The Hardhat device was detonated at a depth of 939 ft, and subsequent exploration revealed a chimney of broken rock with a radius of 65 to 70 ft and a height above shot point of 281 ft.' BeFore the explosion, the Hardhat medium was highly jointed and fractured (Fig. I). Jt was expected that differential rock motion along these and other weaknesses induced during cavity growth and collapse would significantly alter the permeability of the rock mass. EXPERIMENTAL METHOD Initially, three 2-in. diameter holes (Nos. 10, 12 and 19) were drilled about 25 ft outward through the walls of the 500-ft level drift (elevation 4,253 ft, Fig. 2). One was drilled near the chimney and two holes, one vertical and the other horizontal, were drilled near the shaft. Order-of-magnitude differences in permeability obtained by pressurization measurements indicated further: investigation was warranted. A series of 3-in. diameter holes was then drilled with water as a coolant into the walls and roof of the drift (Fig. 2). An 11-in. long packer was set from 1 to 8 Et inside each hole and air was injected at measured Row rates. Hole pressures were monitored at the collar. Permeability was low enough in the holes near the access shaft that pressure could be maintained long enough to obtain good pressure decay rates. In the vicinity of the chimney, however, permeability was so high that this was not possible and air was injected under steady-state conditions. About one year later, these same holes were retested to

Jan 1, 1967

By R. Al-Hussainy, H. J. Ramey

Previous gas well test analyses have been based mainly upon linearizations of ideal gas flow results, although a method for drawdown analysis based upon real gas flow results has been proposed. Linearizations based upon ideal gas flow require estimation of gas physical properties at Tome sort of average pressure, and implicitly involve the assumption that pressure gradients are small everywhere in the reservoir. A new real gas flow equation has been developed by means of a substitution which couples presTure, viscosity and gas law deviation factor. This sub-stitution has been called the real gas pseudo-pressure. Use of the real gas pseudo-pressure leads to simple equations describing real gas flow which do not contain pressure-dependent gas properties, and which do not require the assumption of small pressure gradients everywhere in the flow system. Equations required to determine flow capacity, well condition and static formation pressure from pressure drawdown and build-up tests with the real gas pseudo-pressure concept are presented. Also shown are applications of the real gas pseudo-pressure to back-pressure testing, the gas materials balance and rigorous determination of average gas properties for previous gas flow equations. Included are sample calculations for well test analyses. INTRODUCTION A recent study' of the flow of the transient flow of real gases in ideal radial systems showed that it is possible to consider gas physical property dependence upon pressure by means of a substitution called the real gas pseudo-pressure. The substitution has the advantage that it enables engineering solutions for steady and transient flow of real gases that are more accurate and general than those previously available. The solutions are particularly important for the case of gas flow in tight, high-pressure formations under large drawdowns. Even for more ideal flow conditions, the real gas pseudo-pressure concept leads to important rules for finding average gas physical properties pertinent for older well test analyses. Ref. I provides a detailed study of the theory behind the real gas flow correlations to be used in this paper. The purpose of this paper is to provide necessary engineering forms for use of the real gas flow results, and to illustrate applications. The following considers flow of real gases in an ideal radial flow system. It is assumed that: (1) formation thickness, porosity, water saturation, absolute permeability, temperature and gas composition are constant; (2) gas compressibility and density are functions of pressure as described by the gas law pv = znRT; (3) gas viscosrty is a function of pressure; (4) effective permeability to gas may be a function of pressure to account for liquid condensation; (5) condensate is immobile; and (6) the formation has no dip.

Jan 1, 1967

By Y. Wang, M. M. Singh, H. L. Hartman

Knowledge of the state of stress at the bottom of a drillhole is of practical importance in rock drilling, since the induced stresses must exceed the strength of the rock in order to cause fracture. This note reports on a numerical method to determine the stress distribution at the bottom of a borehole induced by a static bit load and overburden and fluid pressures. The procedure adopted is similar to that for the plane-strain, discrete model employed by Harper and Ang.1,2 The rock medium is considered to be homogeneous, isotropic, and elastic-perfectly-plastic. METHOD OF ANALYSIS AND PROGRAMMING The discrete model adopted consists of two types of points: mass points and stress points. The configuration and numbering notation are depicted in

Jan 1, 1967

By J. G. Bouwkamp

This paper presents three general approaches towards the solution of the stress distribution and the behavior of tubular connections as used in offshore well drilling structures. First, the possibilities of using plastic models and photoelasticity techniques in evaluating the stress distribution in gusset plate connections are analyzed. The results of photoelastic studies on the stress distribution in the in-plane gusset plate of two-dimensional joints are presented. The influence of the configuration of the gusset plate (with and without cut-outs) is discussed. Second, the paper deals with recent developments and applications of computer programs to analyze connections with directly inter-welded tubes and with gusset plates. The possibilities and limitations of these programs are discussed. Stress patterns analyzed with these programs are presented for different joint configurations. Finally, the basic test procedures and results of a test on a tubular joint under static and alternating loads are discussed. INTRODUCTION The effective design of tubular connections as encountered in offshore well drilling towers or floating platforms has been complicated basically by the radial flexibility of the tube walls. This flexibility is a source of severe stress concentrations which can initiate an early failure of these joints. In an attempt to reduce the influence of the wall flexibility of the column tube, certain joints are presently designed by inter-welding the incoming branch members. In those designs, the force acting normal to the chord tube can be reduced considerably. A second group of joints incorporate gusset plates or stiffening rings to stiffen the column wall and to distribute the incoming branch member forces over a larger part of this wall. A third approach to improve the stress distribution in a tubular joint is to increase the wall thickness of the column member. This can be achieved by simply applying a thicker wall section in the vicinity of the joint. A fourth possibility to restrain the radial flexibility of the tube wall is to fill the column member with concrete. Also, a single, cast steel seat welded to the column tube can be used to improve the stress distribution in this wall. Although all these designs improve, in general, the state of stress in the column wall, the altered stiffness often causes the development of critically stressed areas in the web members. At the same time the actual design in most instances is decisively influenced by the site which governs the depth and controls the forces produced by waves, earthquakes and ice flow. Also, the towing, erection and foundation requirements of offshore structures can affect the actual design selection. Because of the complexity of the structural configuration of tubular joints, the stress analysis of these connections has necessarily been based on simplified and often crude assumptions. For the earlier and smaller type of connections with about 4-ft diameter column sections, the primary problem was to evaluate the relative stiffness of the column wall section and the load transfer between joint members. Due to the recent developments of offshore drilling structures with increasingly larger connections (e.g., column diameter. 32 ft; web members, 8.5 ft) this problem has become even more critical. One design philosophy for such large joints follows a member-to-member connection with radially heavy reinforced column sections. This radial stiffness can be attained by closely spaced and intensively stiffened horizontal diaphrams together with vertical stiffeners. A second solution incorporates a concrete-filled section between the outer and inner walls of the column tube. Another philosophy considers large gusset-plated joints. The problem in these joints is to develop an effective load transfer between the branch tubes and the gusset plate and to minimize the stress concentrations in the member walls as effectively as possible. Several concepts are followed to achieve this gradual transfer between web-member walls and gusset plates. Because the number of joints in these huge platforms is limited compared to the over-all size, a proper design of these joints is even more important than was the case for the many joints in the smaller, but multi-legged towers. A failure of one of those ultra-large joints could well cause the complete collapse of such a structure. Under these circumstances an accurate analysis of the large joints is of the greatest importance, together with information regarding the expected behavior of such joints under critical alternating load conditions. Recent applications of photoelastic model techniques have proved to be quite effective in evaluating the elastic behavior of such joints. Although a complete study of such connections is quite well possible with present-day photoelastic techniques, it might often be feasible and necessary to limit the objectives and to restrict these investigations to the study of a specific aspect of the joint. Another very promising avenue of approach to solve the complex stress pattern in these connections seems to be the recent development of digital computer programs. In this category, cylindrical shell programs and finite element methods for more complex configurations have

Jan 1, 1967

By J. A. Lund, A. M. Lawson

THE structures of quenched eutectoid and hypereu-tectoid Fe-Cu alloys have been examined by X-ray diffraction and by optical and electron microscopy. The relevant portion of the Fe-Cu phase diagram is given in Fig. 1. Several values have been reported for the solubility of copper in a Fe at the eutectoid temperature, including 1.4 wt pct by orton' and 2.13 wt pct by Wreidt and Darken.2 Alloys containing 4.8 and 7.5 wt pct Cu have been prepared from two batches of Ferrovac E iron (0.005C and 0.013C) and electrolytic tough pitch copper (99.90 Cu). Specimens of dimensions 0.8 by 0.8 by 0.1 in. were cut from hot-rolled material, austenitized, and quenched into brine at 25°C. Similar specimens were also cooled in the furnace, after a short soaking treatment at 1100°C, at a rate estimated to be 10°C per min in the temperature range of 900" to 500°C. X-ray diffractometry was performed on quenched and on furnace-cooled bulk specimens using iron radiation. Only a bcc phase could be detected in all samples. Lattice parameters were calculated from measurements on four lines, made up of two resolved high-angle doublets. Comparisons were made against a silicon standard. Results are shown in Table I. Based on X-ray diffraction studies of a series of alloys of lower copper concentrations, orton' estimated that the tattice constant of a Fe at 25°C increases 0.0014A per wt pct Cu in solution. Extrapolating Norton's data, it may be concluded that all copper was retained in solution in the brine-quenched 4.8 pct Cu alloy, and that approximately 5 pct Cu was also held in solution on quenching the 7.5 pct Cu alloy. Typical microstructures of brine-quenched specimens, as observed by optical microscopy, are shown in Figs. 2 and 3. Precipitation of the E phase (copper-rich) occurred along the y grain boundaries on quenching the 7.5 pct Cu alloy, rendering them readily detectable in the microstructure, Fig. 3. The original boundaries in the 4.8 pct Cu specimens were gener- ally not discernible, however. This indicates that the z phase which was seen in the higher-copper alloy was probably of proeutectoid origin. Thin foils for transmission electron microscopy were obtained from bulk specimens by spark machining to 0.006 in. thickness, followed by electrolytic polishing. Typical transmission electron micrographs

Jan 1, 1967

By P. G. Shewmon, H. E. Collins

A study has been made to determine the sites at which sulfur adsorption occurs on copper surfaces. measurements were made of the relative torques, Ys, at the intersection of twin boundaries with surfaces near the three low-index orientations, i.e., (100), @lo), and 011), over a range of H2S/H2 ratios. HZS concerztvations j'ro~n 3 to 1500pp)n between 830" and 1050°C were used. It is concluded that sulfur adsorption occurved preferentially though not exclusively at edge sites near the (100) and (110) surfaces in the HzS range — 700 Ppm giving rise to negative torques near these orientations. Beyond this HzS range, adsorption occurred at all sites. Near the (111) surface, 7/y little with HzS concentration up to approxiwzately 75pptn. Above this range, the results indicate adsorption is occurring OH both terrace and edge sites. SCIENTIFIC interest in surfaces and their interactions with a gaseous environment dates back to the beginning of the 19th century. The scientific luminaries of that period—Faraday, Maxwell, Rayleigh, Dewar, and Gibbs—were already concerned about such processes. However, it has only been within the past several decades that adsorption on metal surfaces has been actively studied. This increased interest in adsorption has been brought about by the advent of new and improved experimental techniques and apparatus, e.g., ultrahigh vacuum, and field-emission and ion microscopes. However, most of the work done using these techniques has been carried out at low temperatures. When adsorption studies have been made at either low or high temperatures, they usually gave no indication of the particular surface orientations or type of sites on which adsorption was occurring. In the last few years, there have been a series of studies in which the surface tension, y,, and/or its derivative with respect to orientation, 7, have been studied as a function of orientation and atmosphere.'-7 Nearly all of the work on the relative torque,* ~/y, silver annealed in hydrogen and air.6 Recently Winterbottom and Gjostein" have used a modified and more accurate Mykurian method to determine the y plot of gold in hydrogen The only work in which T/~, has been measured over a range of chemical potentials for a given solute, p2, is that of Robertson and shewmon7 on the Cu-0 system. They measured T/Y, vs Po, (10"" to 10- l3 atm) at 1000°C in various mixtures of Hz0 and HZ. From this work they estimated the value of p2 at which one half of the surface sites are occupied with oxygen, pg, as being in the range 10- l6 to 10- l5 atm of oxygen. They also found that increasing Pa increased the magnitude of ~/y, near the (111) and (100) orientations. This indicates that oxygen is not adsorbed preferentially at step edges, but uniformly over all surface sites. In addition, they did one experiment on sulfur adsorption on copper surfaces, which indicated that sulfur adsorption decreases ~/y, near the (100) orientation, while not affecting ~/y, near the (111). This could be interpreted as indicating that sulfur adsorbs preferentially at step edges near the (100). In this paper the primary objective of the work has been to carry out a study of sulfur adsorption on copper surfaces over a range of temperatures and p,. In conjunction with this work, thermal grooving at grain boundaries has been examined as a method of determining the effect of sulfur adsorption on y,. METHODS Ideally, one would like to have information on the quantity of solute adsorbed on a surface and the types of sites at which it is absorbed as a function of p2. The total quantity adsorbed or the surface excess is given by the thermodynamic equation Thus data on the variation of y, with pz indicates the value of p2 at which adsorption becomes appreciable and the quantity adsorbed. The type of adsorption site is more difficult to deduce but information on this can be obtained from the variation of rz with 8, the angular deviation of the surface orientation. This is obtained from the thermodynamic equationlg Data on t and ys as functions of p2 have been obtained by the following methods. 1) Twin Boundary Grooving—By determining the effect of adsorption on the torque, 7, where T is the variation of surface energy, y,, with orientation, it is possible to obtain some indication as to the preferred sites of adsorption. Experimentally, the torque value measured is the relative torque, 7/ys The twin boundary grooving technique suggested by Mykura'' was used in this study to determine near the three low-index orientations— (loo), (110), and (111). Mykura's equation relates 7 /yS to measurements of the di-

Jan 1, 1967

By T. C. Boberg, R. B. Lantz

This paper presents a method for calculating the producing rate of a well as a function of time following steam stimulation. The calculations have proved valuable in both selecting wells for stimulation and in determining optimum treatment sizes. The heat transfer model accounts for cooling of the oil sand by both vertical and radial conduction. Heat losses for any number of productive sands separated by unproductive rock are calculated for the injection. shut-in and production phases of the cycle. The oil rate increase caused by viscosity reduction due to heating is calculated by steady-state radial flow equations. The response of successive cycles of steam injection can also be calculated with this method. Excellent agreement is shown between calculated and actual field results. Also included are the results of several reservoir and process variable studies. The method is best suited for wells producing from a multiplicity of thin sands where the bulk of the stimulated production comes from the unheated reservoir. The flow equations used neglect gravity drainage and saturation changes within the heated region. INTRODUCTION This paper presents a calculation method which can be used to predict the field performance of the cyclic steam stimulation process. The calculation method enables the engineer to select reservoirs that have favorable characteristics for steam stimulation and permits him to determine how much steam must be injected to achieve favorable stimulation. While the calculation represents a considerable simplification of physical reality and the results are subject to numerous assumptions which must be made about the reservoir, it has been found that realistic calculations can be made of individual well performance following steam injection. The duration of the stimulation effect will depend primarily on the rate at which the heated oil sand cools which, in turn, is determined by the rate at which energy is removed from the formation with the produced fluids and conducted from the heated oil sand to unproductive rock. A complete mathematical solution to this problem is a formidable task, and finite difference techniques would undoubtedly have to be used. The calculation method pre- sented here utilizes analytic solutions of simple related heat transfer and fluid flow problems. The method is sufficiently simplified that it can be used as a hand calculation, although the calculations are somewhat lengthy and laborious. For that reason, the analysis was programmed for an IBM 7044 digital computer. Well responses observed at the Quiriquire field in eastern Venezuela&apos; have been matched using this program after making suitable approximations for reservoir and wellbore conditions. One of the most valuable uses of this calculation method is to assess the effect of reservoir and proc-cess variables on the stimulation response. This paper contains results of several studies made of key reservoir and process parameters. Among the most important of these is the influence of prior wellbore permeability damage. If a well is severely damaged prior to stimulation, a higher stimulation response will be observed than if it is undamaged. If a portion of this damage is removed, a permanent rate improvement will occur. THEORY I)ES(:KJJ&apos;TION OF CALCULATION METHOD The process of cyclic steam stimulation is essentially one of reducing oil viscosity around the wellbore by heating for a limited distance out into the formation through the injection of steam. Suitable modifications of the calculation technique presented here can be made so that stimulation of wells by hot gas injection or in situ combustion can also be calculated. A schematic drawing of the heat transfer and fluid flow considerations included in the calculation method is shown in Fig. 1. In brief, the calculation assumes that the oil sand is uniformly and radially invaded by injected steam. For wells producing from several sands, each sand is assumed to be invaded to the same distance radially. In calculating the radius heated rn energy losses from the wellbore and conduction to impermeable rock adjacent to the producing sands are taken into account. After steam injection is stopped, heat conduction continues and oil sands with r < ra cool as previously unheated shale and oil sand at r > r, begin to warm. The effect of warming of oil sand out beyond r, has little effect on the oil production rate compared to the effect of cooling of the oil sand nearer the wellbore than ra. Thus, in computing the oil production rate, an idealized step function temperature distribution in the reservoir is assumed where the original temperature exists for r > rn and where an average elevated temperature exists for r < rn. The average temperature in the oil sand for the region r < rn is computed as a function of

Jan 1, 1967

By Charles L. Mantell, George Ferment

This investigation determined the jeasibility of current-potential curves as an analytical tool for monitoving manganese electroicinning solutions for metallic impurities. Nine metallic impurities were studied: trickel, cobalt, silver, copper, zinc, molybdenum, catlmiun magnesium, and sodium. The individual effect of each metallic irzplrl,iLy on the standard point-izatiorr was determined for a range of &apos;concentration. Not all of Ihe impurities affected the polarization curve; correlation between transition current and cotrcetztration of impurity. Molybdenum had an uncorrelated effect on the polarization curie. The effects of binary mixtures of impurities were studied to see if the transition current of the mixture could be predicted. Interactions occurred between impurities which prei&apos;etzted the pvecliction the transition current of tile rrlisLitr.e by additive laws. The polarization curve was shown to be sensitive to metallic impurities which affect the current efficiency of a manganese cell. THE application of current-potential curves in manganese electrowinning is not new but played an important part in the conversion of an inoperative large-scale pilot plant into a continuous comnercial operation.1"" The effects of trace metallic impurities in manganese electrowinning solutions on cathode current-potential curves,5-19 specifically nine impurities (nickel, cobalt, silver, copper, zinc, molybdenum, cadmium, magnesium, and sodium) were studied for a range of concentrations. Cadmium, magnesium, and sodium had no effect. Nickel, cobalt, silver, copper, and zinc yielded a correlation between transition current and concentration of impurity: molybdenum had an uncorrelated effect. Binary mixtures of impurities were studied to de-termine if the transition current could be predicted from the values for the individual constituents. Interactions between impurities prevented the prediction of the transition current of the mixtures by an additive law. The polarization curve was shown to be sensitive to metallic impurities which affected the rurrent efficiency of a manganese cell. The electrowinning of manganese relies upon maintaining a high-purity electrolyte. Purification schemes were developed to remove all of the heavy metals, the magnesium and calcium. Concentration limits have been established for single impurities. With high-purity electrolytes, favorable cell efficiencies are consistently obtained; but with impure solutions there is a reduction in efficiency. With the rapid rise to commercial prominence of electrochemical processes, there has been a lag in developing rapid methods for determining whether an electrolyte is sufficiently pure for efficient electrolysis. The most sensitive test for impurities is the behavior of the electrochemical cell. Impure electrolytes will cause a serious reduction in cell efficiency, and in many cases metal deposition will be prevented or reversed. The effects of impurities are not usually evident until after long periods of electrolysis, resulting in a disruption of the process. A method which could predict the behavior of an electrolyte in terms of cell efficiency prior to reaching the commercial cell is needed. Van Arsdale and Maier," Allmand and Campbell,a1&apos;22 and others attempted to develop an electrochemical process for manganese,"3"29 but all met with some degree of difficulty. Jacobs et a studied the effects of metallic impurities in manganese electrowinning. Plant methods were based on a 2-hr plating in a small electrolytic cell. The final method was based on a 24-hr plating run, performed in a relatively large test cell. Here, current efficiencies were calculated with and without impurities in the electrolyte, and the critical concentration was established as the maximum amount of impurity that the electrolyte could tolerate before there was a serious loss in efficiency. The amount of impurity that could be tolerated decreased as the plating time increased, indicating deposition of the impurity. This test duplicated the conditions of commercial practire, and was sensitive to impurities. Small amounts of impurities significantly affect the hydrogen overvoltage at a metal surface, increasing or decreasing it depending upon the nature of the impurity. ockris established the limit for the onset of poisoning at 10-l moles per liter. The effects of impurities were studied by potential-time curves at a constant current density. The technique did not lend itself to rapid analysis in that several hours were needed to establish stable potential-time curves. Serfass and coworkers3&apos; developed calorimetric and spectrophotometric techniques for analyzing for trace impurities. Our method4&apos;" is based on current-cathode potential curves produced by continuously changing the cell voltage at a programmed rate. Starting with a clean stainless-steel cathode, the cell voltage was initially adjusted to yield zero current: the program was then started and the current was plotted as a function of the cathode potential. Fig. 1 is a typical current-potential curve. In initial region A the hydrogen-evolution reaction predominates and the polarization curve

Jan 1, 1967

By D. T. Peterson, F. A. Schmidt, J. D. Verhoeven

The velocity of mig-ration of these solutes in thorium metal due to a high amperage dc current was measured at several temperatures. All three solutes migrated in the same direction as the electron flow. Diffusion coefficients were combined with the migration velocities to predict the steady-state concentration profile. Electrotransport was shown to be an effective method of removing carbon, oxygen, and nitrogen from thorium and resistance ratios several times larger than for crystal bar thorium were achieved. However, the maxirnum attained purification was well below the predicted values, apparently due to some form of contamination. THE migration of solutes in metals when a high current density dc current is passed has been known for many years. This phenomenon has been the subject of a number of reviews published in recent years.l~* Many of the earlier investigators of electromigration of interstitial solutes interpreted the direction and velocity of migration on the basis of a charge on the solute particle. This interpretation is unclear because, in a given experiment, one cannot separate the contributions to the force moving the solute which arise from the charge on the solute in an electric field gradient and the momentum transfer from the scattering of the electrons or holes. There have been only a few quantitative measurements of interstitial migration velocities and some of these have been characterized by poor accuracy or by errors in the analysis of the experiment. The electrotransport mobilities of carbon, nitrogen, and oxygen in thorium were determined by observing the rate of movement of a discontinuity in the concentration profile. This method was used by Carlson el a~.~ to determine the mobilities of interstitial solutes in yttrium and its advantages are discussed in that paper. The specimen is essentially a pair of semi-infinite, bar-type diffusion couples. The electro-transport velocity was measured by observing the displacement of the mean concentration point in a measured length of time. The diffusion coefficients were calculated by the Grube method from the concentration profile. The transport mobilities and diffusion coefficients can be used to predict the concentration profile in an electrotransport experiment of a given time, current density, and specimen length. At long times a steady state will be reached such that the natural logarithm of the concentration of each solute varies linearly along the bar with a slope which is equal to the velocity of the migrating solute divided by its diffusion coefficient. The estimation of the purification potential of electrotransport is discussed by ~erhoeven.&apos; A comparison of the concentration profile and the purification which should be expected from known solute velocities and diffusion coefficients with that which is obtained in an experiment can be very useful in indicating whether the maximum possible purification has been achieved. EXPERIMENTAL METHOD The apparatus used in this study consisted of a sample chamber which was equipped with two electrodes, a sight glass, and a flange for mounting to a high-vacuum system capable of obtaining pressure of 2 x lo-? Torr. The chamber was made of stainless steel and was 4 in. in diam and 6 in. long. The seal between the electrodes and the chamber was made with "0" rings and compression bushings. The thorium specimens were threaded and screwed into tantalum "U"-shaped adapters attached to the ends of the electrodes. This arrangement is shown in Fig. 1

Jan 1, 1967

By M. R. Tek, F. F. Craig, J. O. Wilkes, C. S. Goddin

The waterflood performance of a water-wet, stratified system with crossflow is computed by a finite difference procedure. The effects of five dimensionless parameters on tile oil displacement efficiency, water saturation con-tour.7 and crossflow rates are evaluated in the absence of gravity forces. Crossflow due to viscous and capillary forces is shown to exert a significant effect on oil recovery in a field-scale model of a two-layered. water-wet sandstone reservoir. The crossflow is at a maximum in the vicinity of the front advancing in the more permeable layer. Under favorable mobility ratio conditions, the comparted oil recovery with crossflow always is interrnerliate between that predicted for a uniform reservoir and that for a layered reservoir with no crossflow. INTRODUCTION The important erects of reservoir heterogeneity on waterflood performance are commanding increased attention in the technical literature. Much of this attention is centered on two categories of layered reservoirs: those in which layers are non-communicating and those in which crossflow of fluids occurs between the layers. In the first category, the reservoir is assumed to consist of discrete layers, each uniform within itself and differing from the others only in such properties as thickness, porosity and absolute permeability. The performance within each layer is calculated by one-dimensional flow theory, and the performance of the total reservoir is obtained by summing individual layer performances. Capillary and gravity effects usually are not considered. Representative publications dealing with thi5 type of reservoir are those of Stiles,&apos; Dykstra and Parsons,&apos; Hiatt,3 Warren and Cosgrove&apos; and Higgins and Leighton." Prediction of performance for reservoirs in the second category is considerably more difficult since viscous, capillary and gravitational forces all play important roles in causing crossflow between layers. A number of authors have investigated the simpler problem of two-dimensional displacement flow in a stratified system with a mobility ratio of unity and negligible capillary and gravity effects.&apos;; Others have considered two-dimensional, non-steady-state flow of a single, slightly compressible fluid in a stratified reservoir. A limited number of laboratory oil displacement tests in layered models with crossflow have been reported. Miscible floods (with resultant zero capillary forces) in layered five-spot models were conducted by Dyes and Braun," who studied the effect of mobility ratio with zero gravity forces, and by Craig et al. 12 who studied the effect of gravity forces at constant mobility ratio. Waterfloods in layered five-spot models (with cross-tlow due to capillary, viscous and gravity forces) were conducted by Gaucher and Lindley,"&apos; who showed the effect of gravity forces in causing underrunning of the injected water and by Carpenter, Bail and Bobek, 14 who demonstrated the reliability of Rapoport&apos;s" dimension-less parameters for scaling layered systems. Waterfloods in rectangular layered models were conducted by Richardson and Perkins."&apos; who investigated the effect of velocity at constant mobility ratio and with zero gravity forces, and by Hutchinson," who studied the effects of varying mobility, layer permeability and layer thickness ratios. The differential equations which rigorously describe waterflooding in a heterogenous porous medium are non-linear and do not facilitate analytical solution. By using finite difference approximations it is possible to obtain a solution to any desired degree of accuracy. Such a solution, using an alternating direction implicit procedure (ADJP), is described by Douglas, Peaceman and Rachford.18 In the present study, a computer program using ADJP explores systematically the effects of important parameters on waterflood performance of a two-dimensional, two-layered, field-scale model of a water-wet sandstone system. Particular attention is given to evaluation of the water saturation contours and crossflow rates at the interface between layers to gain improved understanding of the crossflow mechanism. PROCEDURE BASIC: FLOW EQUATIONS The basic flow equations for two-dimensional, two-phase, immiscible, incon~pressible flow in a porous medium are:

Jan 1, 1967

By Ronald K. Linde

Metastable Ag-Cu solid solutions at two compositions beyond the maximum limits of solubility obtainable by quenching from the solid state were obtained by rapid quenching from the liquid state. The process of transformation of the metastable solid solutions into the equilibrium phases was studied by means of X-ray diffraction intensity measurements and electrical-resistance measurements; metallographic examination was also performed. Results are compared with those for an alloy quenched from the solid state at a composition which exists as a solid solution at elevated temperatures. Activation energies for the trans-formation were computed to be 33,600 * 2500 and 33,100 * 2000 cal per g mole for the 60.1 and 75.0 at. pct Ag;Cu compositions, respectively THE kinetics of precipitation in supersaturated solid solutions obtained by quenching from high temperature has been thoroughly studied in many alloys, and detailed investigations of the early stages of nucleation and subsequent growth of the equilibrium phases have been carried out. All of these studies have been made on alloys quenched from the solid state, however, and it is the purpose of this paper to present some of the results on the kinetics of transformation of metastable solid solutions in Ag-Cu binary alloys whose compositions lie outside of the solid-state limits of solubility. Limits of solubility in the solid state can be increased by rapid quenching from the liquid state. This was first demonstrated by Falkenhagen and Hofmann, who obtained appreciable increases in solubility limits of the elements of the first transition series in aluminum by rapid cooling of liquid alloys through contact with a copper mold maintained at liquid nitrogen temperature.&apos; The same basic idea of cooling a liquid alloy by conduction onto a substrate rather than by convection of a gas or liquid (conventional quenching) has been recently revived and extended to very high rates of cooling by Duwez and his collaborators. The new technique was first applied to Ag-Cu alloys because the existence of a eutectic in this system is not predicted by the Hume-Rothery rules of alloy phase formation. Rapid quenching from the liquid state resulted in metastable solid solutions at all concentrations. The kinetics of decomposition of these metastable solid solutions containing 60.1 at. pct Ag;Cu (eutectic composition) and 75.0 at. pct Ag;Cu is the subject of the present paper. EXPERIMENTAL TECHNIQUES Alloys were made in 10- to 20-g heats using silver of purity 99.99 pet and copper of purity >99.999 pct. Components were weighed accurately to 0.1 mg and melted by induction heating in an alumina crucible under an atmosphere of hydrogen. Weight losses amounted to less than 0.02 ~ct in all cases. Rapid cooling from the liquid state was achieved in an apparatus of the type described by Pietrokowsky. 3 In this technique a freely falling drop of molten alloy is caught between a stationary anvil and a fast moving piston, both anvil and piston being lined with copper. The resulting foils were approximately circular (about 2 cm in diam) and from about 50 to 150 u in thickness, depending on the pressure driving the piston. Metallographic samples were prepared for polishing by edge-mounting foils in Quickmount. The mostef-fective etching procedure was found to be: 10 parts NH4OH (concentrated), 1 part H2O2 (30 pct), 5 parts H2O, swab for 5 to 10 sec. The transformation of the metastable alloys to equilibrium was followed by X-ray diffraction and electrical-resistivity measurements. The peak intensity and the integrated intensity of suitable Bragg reflections of the metastable and stable solid solutions were studied with a Norelco dif-fractometer, using nickel-filtered copper KO radiation. The peaks were step-scanned at intervals of 0.05 deg. Using either a Kelvin bridge or a null circuit with a Leeds and Northrup K-2 potentiometer, the changes in electrical resistance due to phase transformation were measured for specimens cut into strips about 20 mm long and 4 mm wide. All resistivity measurements were carried out at liquid-nitrogen temperature. The isothermal heat treatment was accomplished by sealing the samples in argon-filled aluminum containers with stainless-steel O-rings. Containers were then suspended in wax baths with temperatures in the

Jan 1, 1967

Jan 1, 1967