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By E. T. Turkdogan

This paper deals with an analysis of the conditions leading to the formation of blowholes and surface and subsurface defects in cast low-carbon steels. The theoretical analysis of the problem is based on the concept of the occurrence of deoxidation reactions during cooling of liquid steel and during its solidification. The reaction equilibrium data are given on deoxidation of steel by carbon, silicon, and manganese. The details of the calculations are given on the simultaneous deoxidation of steel by silico-manganese additions to produce a desired level of deoxidation at certain residual concentrations. Based on an idealized model, an attempt is made to calculate the enrichment of solutes in the solidifying liquid entrapped within the interdendritic cells which are known to be less than 200 µ thick. Formulae are derived for the calculation of the change in the residual oxygen content of the enriched liquid steel, controlled by Si/Mn deoxidation. It is shown that for every particular initial silicon, manganese, and oxygen concentration in steel (as residuals in liquid solution at the beginning of solidification) there is a particular carbon concentration below which carbon monoxide, leading to blowholes or pinholes, is not expected to form. There are a number of independent variables which have a decisive influence on the formation of blowholes. For example, it is shown that the position of the curve depicting the critical relation between initial silicon and carbon content for suppression of the evolution of carbon monoxide) can be shifted to lower silicon or higher carbon levels by: increasing manganese content; decreasing oxygen, hydrogen, or nitrogen content; or increasing external pressure on the solidifying mass. FOR the production of sound castings it is essential to prevent the formation of interdendritic worm-holes or pinholes brought about by gas evolution during solidification. Another major problem encountered in solidification of ingots is the formation of surface defects. These problems are thought to be closely associated with the deoxidation reaction occurring in liquid steel during cooling and subsequent solidification. As the liquid becomes richer in impurities during dendritic solidification of steel, a series of reactions may occur in the liquid phase trapped within the branches of growing dendrite platelets. Because of the strong interaction between dissolved oxygen and impurities in liquid steel, the reactions most likely to occur are of the deoxidation type. However, inherent to the extreme complexity of the problem in question, numerous simplifying assump-

Jan 1, 1965

J. H. Lord (Geological Survey of Western Australia): During the last few days in Kalgoorlie here we have heard on various occasions of the great job the mining engineers have done persisting against rising costs and increasing salaries without a rise in the price of gold. I think it has been somewhat overlooked that it has been difficult to find additional ore as well. I consider that geologists also should be commended on their action in persisting to search for more orebodies. This goes on in any mining community, but in Kalgoorlie in particular, I believe, over the last few years that it has been more difficult all the time to find additional orebodies and the Companies are calling for higher grades to offset the economic condition. I feel that this paper by Mr. Finucane shows that the geologists have persevered on an idea and discovered that they can find additional orebodies in the calc schist where previously it was thought that these did not occur. This has added many tons to the ore reserves, and although it is not very significant at the moment, the significance will probably improve as more work is done.The whole thing has shown us the importance of economic geology. Mr Finucane has had many years of experience here and he has given us a very able exposition of the economics of ore finding, and there are not many questions that one could pose to him, because most of the information he presented is obviously fact borne out by drilling, underground development and lining up the ore channels. He did briefly touch on ore shoots-the Oroya shoot and several others. It would be very good if we could, and I feel sure...

Jan 1, 1965

By T. S. Lundy, J. Askill

J. Askill and T. S. Lundy (Oak Ridge National Laboratory)—Moore has proposed a simple correlation between the activation energy for solute diffusion in fee metals and the atomic volume of the diffusing species using both tracer and chemical-diffusion data. The first point we wish to make is that it is wrong to attempt such correlations without separating the two types of data. Activation energies obtained using tracer techniques cannot, in general, be directly compared with those obtained from chemical-diffusion experiments. A knowledge of the variations of chemical potentials with composition is necessary and chemical-diffusion data must be corrected for such variations, even for dilute alloys, before a comparison is possible. Secondly, for nickel, iron, aluminum, and lead, Moore neglected a number of recently published works, e.g., Al26 and Mn54 in aluminum,46 cr51 in nickel,47 and Fe55 in iron.48 These and others should have been used. If one considers only the tracer diffusion data, there is left no simple correlation of the type proposed by Moore. For example, in the case of solute diffusion in aluminum the only reliable tracer data listed by Moore are for zinc and aluminum. The nickel, cobalt, and iron data of Agarwala49 are representative of near-surface diffusion-not bulk diffusion. In conclusion we suggest that for tracer diffusion data in these fee metals there is no justification for proposing any simple correlation of activation energy with atomic volume using the limited data that are presently available. R. H. Moore (author's reply)—The writer has proposed a simple correlation which is useful in estimating the internal consistency of diffusion data. The accuracy of the correlation is, of course, a function of the number of data available. Lundy and Askill take issue with the writer's decision to include data for the systems: nickel, iron, aluminum, and lead, taking the view that the data are insufficient to establish the correlation. The writer agrees that the data are insufficient and has cau- tioned the reader that the correlation is tentative in these instances. Inclusion of these systems is justified by the interesting trends the correlation reveals. For example, the distinction between interstitial and substitutional diffusion may be clearly established, Figs. 4 and 6, and the behavior of transition elements and nontransition elements is indicated to parallel the behavior illustrated by the silver and copper systems. Lundy and Askill have singled out the aluminum system for special criticism. The writer chose to discuss the data for diffusion of iron, nickel, and cobalt in aluminum in the terms used by the original authors9 and has included the comments of Balluffi.l0 The writer did not intend the reader to conclude that data for these elements should correlate with data for the nontransition elements as Lundy and Askill have evidently assumed. Iron, nickel, and cobalt form intermetallic compounds with aluminum, so the activity coefficients of these elements may be expected to deviate markedly from unity. This may account for the low frequency factors observed by Hirano.9 The nontransition elements, on the other hand, yield relatively simple phase diagrams with no evidence for intermetallic compound formation as in the case of iron, nickel, and cobalt. In dilute solution, Henry's law should be closely obeyed, the activity coefficients should not deviate markedly from unity, and the effect on the activation energy should not be large. The accuracy of the correlation applied to these systems will improve as the data is extended. It does not seem unreasonable to conclude that its extension should be encouraged.

Jan 1, 1965

By Desmond De Villiers Oxford, Peter H. Williams

Nchanga Consolidated Copper Mines, Ltd., is one of the four mines operated by the Anglo American Corp. in Northern Rhodesia, now the independent nation of Zambia. Today Nchanga is the second largest single producer of copper in the world, accounting for more than 200,000 long tons of copper annually at a monthly milling rate of 430,000 tons of ore. The average mill-head grade is about 5.20% total copper, of which approximately 60% is copper sulfide. The remainder, referred to as "acid soluble," is copper oxide. Nchanga mines three separate orebodies varying in grade and sulfide-to-oxide ratio. Ore is processed in two separate grinding circuits feeding into three separate flotation circuits. A fourth flotation circuit treats leach plant residue for additional recovery of sulfides.

Jan 1, 1965

By Richard H. Hopkins, R. W. Kraft

A new technique facilitating the rapid determination of the three-dimensional morphology of phases suspended in an opaque matrix is described. The vapidity of the technique is based upon continuous cinephotomicrographic recording of specimen microstructure as the specimen surface is removed under controlled conditions in an electrolytic cell. The advantages of the technique for determining spatial morphologies in opaque materials are illustrated by application of this method to the study of the configuration of faults in a specimen of directionally solidified CuAl2-Al eutectic alloy. A spatial model of the eutectic fault network deduced in this manner has substantiated the facts that faults in this alloy tend to lie parallel to one another in a direction close to that of the specimen growth axis and that the majority of faults tend to bridge lamellae rather than run parallel to them as growth proceeds. For the specimen studied fault density decreased as growth proceeded. ALTHOUGH metallographic observation is a powerful tool for investigating the correlation between structure and properties in metallic alloys, ordinary metallographic methods suffer the fundamental limitation that any conclusions concerning the three-dimensional structure of these opaque materials must rely upon inference from two-dimensional microsections. For this reason it is frequently impossible to make valid judgments regarding the true spatial distribution of the micro-constituents in specimens under investigation. Several techniques have been devised to circumvent the basic limitation of planar microsec-tioning and employed with varying success. These include construction of three-dimensional models of alloy microstructure from sequences of photomicrographs,1-3 quantitative deduction of spatial features based upon statistical studies of data from random and/or selected plane microsections,4-6 and selective dissolution of one phase in a two-phase alloy to reveal the topography of the phase remaining.' However these techniques also have certain obvious disadvantages. Construction of three-dimensional models is a very time-con- suming procedure due to the tedious polish-etch-photograph cycle needed to obtain the necessary photomicrographs to portray the spatial microstructure. Statistical methods by their very nature give only average values of the quantities being studied and cannot therefore give a detailed physical picture of the microstructure to be observed. Finally, the technique of selective dissolution is only applicable in systems where the phases are of vastly different chemical reactivity; it is of little use in the study of single-phase alloys. Since the determination of the three-dimensional structure of opaque materials is hindered by two facts—the materials are opaque to radiation in the visible spectrum and construction of spatial models of microstructure is quite laborious—two solutions to the problem suggest themselves: 1) use radiation of energy great enough to render the alloy transparent, i.e., some microradio-graphic method, or, 2) devise a rapid means to section and record alloy microstructure. Stereomicroradiography has indeed been used to study internal arrangements of phases in several materials8,9 but the method, in general, is limited to very thin specimens (due to X-ray absorption) and simple microstructures. It would seem then that development of a rapid, simple, and generally applicable technique for studying the details of alloy microstructures in three dimensions can best be undertaken by following the second approach above. Using this idea a new technique for rapid evaluation of spatial microstructures was developed based upon cinephotomicrographic recording of the micro-structure of a specimen undergoing controlled electrolytic dissolution. It was further felt that application of this technique to the careful study of the spatial configuration of faults in a CuAl2-Al eutectic alloy would yield information that could be correlated with the extensive data3,6,10-12 already compiled concerning the solidification and crystallography of this eutectic. The practicality and usefulness of similar methods for studying three-dimensional features in alloys has recently been illustrated by the study of dislocation loops in zinc13 and spheroidized structure in steel.14

Jan 1, 1965

By Henry R. Piehler

Continuous seven- and nine teen -filament close-packed silver-steel filamentary composites mere tested in tension. For purposes of comparison, the tensile behavior of the composite was predicted from the measured properties of the individual com-ponents. It was assumed that the axial strain is the same in both components and that the contribution of each component to the composite flow stress is proportional to its volume fraction. Good agreetnent was obtained between the observed and predicted tensile behavior. However, the composite elongation at fracture was about twice that observed when the individual steel wires were tested alone. Composites in which the filaments were widely spaced failed by the consecutive fracture of the filaments. In composites with closely spaced filaments, a composite instability preceded frachcre. These effects are explained in terms of a lateral restraint to the necking of the filaments which develops in the deforming composite. TWO-COMPONENT or composite materials are increasingly being developed and used as structural materials. Of all the composite geometries used, the filamentary configuration has proved to be the most successful. Polymer-bonded fiber-glas, the most common of the filamentary composites, has been investigated most extensively to date. One explanation of the behavior of fiberglas1 suggests that the load transfer between the glass fibers and the polymer matrix occurs primarily through friction. Bond separation between the fibers and the matrix is presumed to occur at very low stresses. Subsequently, only frictional bonding can provide for the transfer of load from the matrix to the fibers. The force normal to the fiber-matrix interface which gives rise to this friction is assumed to arise from the matrix shrinkage which occurs during solidification. The behavior of metallic filamentary-composite materials would be expected to differ from that of fiberglas in several significant aspects. Residual stresses resulting from differences in thermal contraction can be kept to a minimum by proper heat treatment. A strong wetted bond is formed between the two phases. In brazed joints,2 for example, the interphase bond is sufficiently strong that the weaker material will fail before separation occurs at the interface. Most metal filaments can undergo appreciable amounts of plastic deformation before failure. Failure by plastic instability or necking frequently occurs in metallic filaments, but not in glass fibers tested at room temperature. Differences between the behavior of fiberglas-polymer and metallic filamentary composites have indeed been observed in composites containing various types of metallic filaments in a silver matrix.3,4 At strains of the order of 10-2 pct, all the deformation was accommodated by the silver matrix. Hence, the strength of the composite depended only on the fiber concentration and not on the nature of the fiber. At higher strains, the strength of the composite increased when filaments with higher work-hardening rates were used. Surface slip line observations on a silver-mild steel composite that had been stretched 4 pct showed that an appreciable amount of deformation occurred in the filaments. Work on tungsten-copper filamentary composites5 has shown that the ultimate tensile strength for varying filament fractions followed a linear mixture rule. Assuming that the axial strains in both filaments and the matrix are equal, this linear mixture rule can be expressed as: The subscripts c, f, and m refer to the composite, filaments, and matrix, respectively. A and V are the area and volume fractions of each component. sc and of are the ultimate tensile strengths of the composite and the filaments. sm is the flow stress of matrix at a strain equal to the elongation at failure of the filaments. However, the tungsten filaments can undergo only a limited elongation before they fracture without an appreciable reduction in area. A composite containing more ductile filaments might indeed deviate from this linear mixture rule for the ultimate tensile strength, since filament failure by necking might be arrested by the matrix. SPECIMEN PREPARATION Specimens were prepared from 0.8 pct carbon steel piano wires of 0.015 in. initial diameter. The wires were given a thin nickel flash and a silver plate varying in thickness from 0.015 to 0.007 in., depending on the filament fraction desired. In order

Jan 1, 1965

By H. Eklund, R. T. Hukki

This article presents a simple arithmetic derivation for the relationship between sharpness of classification and circulating load, as well as world-wide industrial data which are compatible with the derived equation. It is shown that the sharpness of classification decreases with increasing circulating load. Based on the evidence available a comparison is presented between the performance of the present-day hydraulic classifiers. In a continuously operated closed circuit grinding system the tonnage and the fineness of the components may be indicated as follows: Eq. 8 expresses the relationship between sharpness of classification and circulating load in closed grinding circuits. If CL = 0, E = 100% according to the definition used. This, however, is a purely theoretical case because any apparatus to be called a classifier must produce the conventional two products. Furthermore, if CL = m, E =0%. In order to visualize the meaning of Eq. 8, the effect of factors d (fineness or percentage of under-size of classifier overflow at size x) and b (fineness or percentage of undersize of classifier sands at size x) should be studied. By the most rigid standard, factor d should be given the value of 100%. By so doing the size of classification is defined as that screen size x through which 100% of the classifier

Jan 1, 1965

By J. B. Cheatham, J. G. Yarbrough

Although adequate removal of cuttings from beneath a drill bit is important for efficient drilling operations, very little basic data are available relative to the fundamentals of chip removal by hydraulic jets. A discussion is presented in this paper of an experimental investigation of the jetting action of hydraulic jets in removing loose particles from the bottom of a cylindrical hole. Conditions for which the jet is no longer capable of removing chips from the bottom of the hole are determined. This situation represents equilibrium between the chip removal force and chip Bolddown forces such as gravity and pressure. In most of the tests loose particles were jetted with water or a water-glycerine mixture to determine the dependence of chip removal on hole size, jet size, height of jet off bottom of hole, flow rate, particle density and fluid viscosity. ,A test with a pressurized mud system indicated that relatively low pressures can completely overcome the removal action of a hydraulic jet. Although the system studied herein is not directly applicable to a rotary drill bit, the work with such simplified systems can provide a better understanding of the chip removal action of jets, and with logical extensions it may provide a reasonable basis for the best use of fluid jets in drilling. INTRODUCTION The primary deterrent to maximum drilling rates is the inability of the drilling system to remove rock cuttings efficiently enough to prevent interference with the drilling action.1-2 The objective of chip removal studies is to permit predicting and controlling removal forces under downhole drilling conditions. Conditions at the bottom of a hole during rotary drilling are exceedingly complex and are not likely to be described in a quantitative way by investigations in terms of the total drilling action until a better understanding is developed of the simplified components of the problem.3 The present study is concerned with the elementary condition of removal of chips by a single central jet. Even this relatively simple model provides mathematical difficulties because of the turbulent nature of the flow from the jet and because of the shape of the bottom of the hole beneath the jet. Theoretical and experimental studies have been made of turbulent jets impinging normally on an infinite body and deductions based on analytical solutions to simplified problems can give some insight into the problem of cutting removal by a jet. However, because of the present lack of understanding of the behavior of the interaction between the fluid jet and the chips being removed, an experimental approach was chosen for the present study. Methods have been developed for maximizing hydraulic horsepower, impact force and jet velocity; but whether maximizing these parameters maximizes chip removal with present drilling bits has not been demonstrated. Simplifying the problem of chip removal may make it possible to develop some understanding of the manner in which the jet velocity is dissipated. Better understanding of a simple case should materially assist in extending analysis to more complicated cases. Thus, we are not concerned in the present study with the rock fracturing process itself but only with the removal of the debris from the bottom of the hole. A problem which is quite similar to the chip removal problem is the suspension of solids in stirred vessels. This problem has been studied by the chemical industry and correlations have been obtained by dimensional analysis which permit the design of mixing vats7 An approach similar to that used in the mixing vat problem is used in the analysis of the jetting data in the present paper. EXPERIMENTAL PROCEDURE The test equipment arrangement shown sche-matically in Fig. 1 allows the jetting action to remove particles until an equilibrium height is attained for each combination of hole size, jet size and flow rate.*** Equilibrium conditions require that the removal force is unable to remove additional particles. This balance between holddown and removal forces implies a relationship between the two forces which is constant for the particular system. When the holddown forces are constant,

Jan 1, 1965

By Rex B. McLellan

Studies of the eyuilibrzum between ferrite and austenite with gas mixtures (CO + CO2 and H2 + CHe) have been used as a means of deducing the energy and vibrational entropy of carbon atoms in dilute interstitial Fe-C solutions. A simple model for dilute interstitial solutions is given which enables a solubility equation for the equilibrium between the gas mixtures and the solid to be deduced. This solubility equation is used to estimate the partial In this work measurements of the equilibrium between dilute solid solutions of carbon in iron and gaseous mixtures of CO2 + CO and CH4 + Hp have been analyzed using theoretical solubility equations deduced from a knowledge of the thermodynamic parameters of the gas mixtures and an appropriate model for the solid solution. The solubility equations are deduced by equating the chemical potential of carbon atoms in the gas thermodynamic functions of dilute Fe-C solutions from the measured equilibrium between the solid and the gas mixtures. It is shown that the vibra-tional entropy of a carbon atom in a and y iron is smaller than the corresponding entropy 01. a nitrogen atom in solid solution inferrite or austenite and that there is little difference between the vibrational entropies of both nitrogen and carbon atoms in ferrite and austenite. and solid phases. The chemical potential of carbon in the gas is found from a simple statistical mechanical analysis of the gas mixtures utilizing spec-troscopic data while that for carbon in the interstitial solution is found from a model in which the carbon atoms act as bound oscillators distributed in a random fashion in the solution. The solid solution is dilute enough to enable solute-solute interactions to be ignored. Thus the configurational entropy of the solution is ideal but the mixing entropy contains additional excess terms due mainly to the vibrational changes occurring on solution formation. The partial excess entropies (and the partial energies) do

Jan 1, 1965

By R. A. Vandermeer

It is usually assumed that the rate-determining step in the migration of a grain boundary involves the thermally activated transfer of single atoms across the interface. Chemical reaction rate theory then gives a migration rate which is proportional to the driving force when this is small compared to kT.1 In their recrystallization studies on aluminum, Gordon and vandermeer2 obtained data which was capable of providing the first experimental test of this proportionality. They correlated stored energy (driving force) release measurements determined calorimetrically with fraction recrystal-lized kinetic (growth rate) data acquired metallo-graphically at a temperature where a significant amount of recovery takes place concurrently with recrystallization. Within experimental error, the results of Gordon and Vandermeer confirmed experimentally, at least over a limited range, the linear dependence of boundary migration (growth) rate on driving force in accordance with theory. In obtaining these results, however, an incorrect, implicit assumption was made in relating the average instantaneous growth rate of the recrystallized grains to the measured fraction recrystallized kinetic data. The purpose of this present note is to point out and correct this assumption. An alternate approach, whereby a more proper average growth rate can be calculated from the recrystallization kinetic data, is presented. The earlier data, reevaluated in terms of this new approach, show the same general trend as before so that the original conclusion of Gordon and vandermeer2 is still valid. As was shown in a detailed study3 of the geometrical features of recrystallization in aluminum, the colonies of recrystallized grains can be regarded as uniform cylinders embedded in a three-dimensional matrix, the number of such colonies being constant. Thus during the early stages of recrystallization the volume fraction recrystallized, Xv, can be written as Xv=ynvlr2 [l] where y is a shape factor and i and r are defined as the average length and radius of a recrystallized colony and are spatial averages over the specimen. -nv, is the number of such colonies in a unit of volume. The erroneous assumption made in the earlier paper2 was that r in Eq. [I] could be replaced by

Jan 1, 1965

By A. G. Rozner

TRANSVERSE rupture tests have been commonly used in mechanical investigations of brittle materials. The specimens are simple, easy to prepare, and loading presents no difficulty. Owing to the complexity of stress distribution in bending1 one can determine stresses rigorously only for the elastic range. The bend-test results, however, are at times converted into tensile-strength data, determined as maximum fiber stress. The assumption is made that for small plastic deformations the linear stress-strain relation applies. This problem was experimentally investigated by Bach3 who tested cast iron in bending and in tension and found that the maximum fiber strength obtained in bending exceeded the experimental tensile strength by a factor depending on the geometry of the tested piece. The factor varied from 1.57 for a rectangular cross section to 2.12 for a circular cross section of the tested beam. Since this work was carried out 60 years ago, the cast iron used could be expected to have been highly brittle, thus the extent of plastic deformation prior to fracture very small. We have therefore carried out a number of tests on magnesium-modified cast iron with an average elongation of -5 pct. It was hoped that the data obtained from the tests would serve as a guideline for comparing data obtained in tension and bending for brittle materials. Mechanical properties were measured at room temperature on an Instron tensile machine at a crosshead speed of 0.05 in. per min. The three-point bend test employed cylindrical bars 0.20 in. in diameter with a 1.0-in. span. For the tensile test, cylindrical tensile specimens with a gage length of 0.85 in. and a diameter of 0.160 in. were used. Results are summarized in Table I. From Table I one can see that fracture strength

Jan 1, 1965

By A. S. Grove, C. T. Sah, E. H. Snow, B. E. Deal

A summary of- several recent investigations in to the properties of the metal-oxide-silicon system is presented. A major portion of these studies makes use of the MOS capacitance-z)oltage method of' analysis. The particular areas of investigation which are reported include: 1) a general survey of the electvical properties of thermally oxidized silicon surjbccs; 2) a study of ion migration through silicon dioxide films ; 3) measurements of electron and hole mobilities in surface inversion layers; 4) a study of impurity redistribution due to thermal o.ridatiotz; and 5) measurements of the rates of oxidation oj-heavily doper7. silicon. THE importance of the metal-oxide-semiconductor (MOS) system in the semiconductor industry is well-known. In addition to its importance in the "planar" device technology,' the MOS structure is now also used in the fabrication of active solid-state devices. Consequently, extensive efforts have been made recently to obtain a better understanding of the characteristics of this system. A summary of some studies of the MOS system conducted in our laboratories during the past year is presented. For the most part these studies used silicon as the semiconductor, along with silicon dioxide and aluminum as the other two components of the system. Since the MOS capacitance-voltage method of analysis was used extensively in these studies, we will first briefly describe its nature and consider some of the possible causes of deviation of experimental observations from the simple theory. We will then outline the various related areas of investigation carried out in our laboratories and will briefly indicate some of the results. It should be noted that the purpose of this paper is merely to provide a brief summary of MOS studies. More detailed discussions of the various areas of investigation are given in the references cited. PRINCIPLES OF THE MOS C-V METHOD OF ANALYSIS' A sketch of the MOS structure is shown in the upper portion of Fig. 1. In this case the insulating film is Si02 and the semiconductor p-type silicon. If a large negative bias is applied to the metal field plate, holes are attracted to the silicon surface. The silicon then behaves much like a metal and the capacitance measured is that of the oxide layer alone, Co. If a small positive bias is applied to the aluminum, holes are repelled and a region depleted of majority carriers is formed at the silicon surface. This depletion I-egion adds to the width of the dielectric and the measured capacitance begins to drop. With increasing positive bias, the width of the electrical depletion region increases. At some large positive bias an inzevsion regiotr is formed at the surface and additional charges induced in the silicon appear in the form of electrons in this narrow inversion region. Thus the depletion-region width approaches a maximum value and, consequently, the capacitance reaches a minimum value and then either levels off or rises again depending on the measurement frequency and the rate of equilibration of the minority carriers in the inversion layer.3 Band diagrams, along with the corresponding charge distributions, are shown in Fig. 1 for the above bias conditions. If minority carriers cannot accumulate at the surface to form an inversion region, the depletion-region width continues to increase with increased positive bias and the capacitance drops toward zero as in a reverse biased p-n junction. The effect of a work-function difference $hs between the metal and the silicon, and of surface charges per unit area Qss located at the oxide-silicon interface, is simply to attract charges in the silicon much like the applied bias. It can be shown that this results in a parallel shift of the capacitance-voltage characteristic along the voltage axis by an amount corresponding to AV = -$bIs + Qss/Co. Theoretical curves have been calculated4 giving the capacitance of the MOS structure C normalized to the oxide capacitance Co vs the quantity VG here VG is the voltage applied to the metal field plate. In Fig. 2 such calculations are shown as points for a particular oxide thickness and bulk impurity concentration for a p-type semiconductor. (For an n-type semiconductor the curves would be mirror images of these.) All three cases, i.e., low frequency. high frequency, and depletion, are indicated. Also shown in the figure are recorder tracings of the characteristics of actual devices. These characteristics have been shifted along the voltage axis to compensate the effect of surface charges and work-function difference. It is evident that agreement between experiment and theory is good. The nature of this shift along the voltage axis is

Jan 1, 1965

By George S. Scott

The Bureau of Mines conducted ignition, flammability, and decomposition experiments on gas mixtures containing ethylene to determine its flammability characteristics at elevated pressures and ambient temperatures. Pure ethylene was found to propagate a decomposition reaction at 1,000 psig and ambient temperatures when ignited with 1 gram or more of guncotton in a 2-inch-id bomb. The decomposition products were primarily carbon, methane, and hydrogen.

Jan 1, 1965

By Craig R. Barrett, Oleg D. Sherby

The creep characteristics of four pure metals with widely Varying stacking-fault energies (silver, copper, nickel, and aluminum) were evaluated above 0.5Tm. Creep tests were performed under conditions of constant atomic diffusivity and constant stress over the elaslic modulus. The sleady-state creep rate, Es, was found to he a funclion of the THE most common empirical representation of the steady-state creep rate, Es, at high temperatures and intermediate stresses is of the form where a is the applied stress, E is an elastic constant, A and n are constants (n is typically stacking-fault energ, y, such that Es is proportional to y3,5. In addition, it was uncovered that the primary creep strain and the strain to fracture increased with increasing y, and that the ratio of initial to steady-state creep rate decreased with increasing y. about 5), Q is the activation energy for creep (usually equal to that for self-diffusion), and kT has its usual meaning. sherbyl and McLean and ale' have used this expression to correlate creep data for a number of pure metals. An interesting aspect of Eq. [I] is the absence of any dependence on the stacking-fault energy. While most creep data seem to obey the stress and temperature dependence predicted by Eq. [I], when data for several metals are put on a master plot they do not fall on a common line but form a band. The width of this band corresponds to a variation in Es of 102 to l03. sherbyl attempted to explain this band by assuming that a grain-size effect was present which led to the observed variation. On the other hand, Felt-

Jan 1, 1965

By H. R. Hardy

The study of the mechanical properties of geologic materials was initiated in the Mining Research Section of the Fuels and Mining Practice Division in 1951 as part of a fundamental study of ground stress in Canadian coal mines.1 Early in the investigation of the mechanical properties of geologic materials, however, it was realized that the test results are influenced by the rate and the duration of loading. For this reason, laboratory investigations2,3 were undertaken to study the effect of long-period uniaxial stress on the deformation and failure properties of these materials. A literature survey indicated that work on the time-dependent properties of geologic materials had been very limited in the past.

Jan 1, 1965

By N. E. Truitt, D. G. Russell

The transient pressure behavior of a well which produces a single compressible fluid through a singte-plane wrticat fracture has been investigated mathematically. The fracture is assumed to possess infinite flow capacity, to be of limited mdial extent, and' to penetrate the producing formation completely in the vertical direction. Previous studies of vertically fractured wells have been concerned primarily with production rate performance or semisteady-state pressure behavior. This study was undertaken to ascertain the influence of vertical fractures on transient pressure tests such as pressure build-ups and flow tests. In a vertically fractured system, flow in the region nearest the fracture is practically linear, whereas farther away from the fracture essentially radial flow prevails. Thus, transient pressure analyses based on radial flow theory are somewhat inaccurate. As fracture penetration increases radially, kh values calcutated from pressure build-up and flow test curves become increasingly larger than true values. Failure to consider the effect of fracture penetration also introduces inaccuracies into the catculation of fracture length from the apparent skin factor and into the determination of average reservoir pressure. If the total length of the fracture is 20 per cent, or greater, of the drainage radius of the well, corrections must be made to pressure build-up and flow test results. Methods for correcting such results are discussed in this paper. For wells with prefracturing pressure build-up or flow test data, it is possible to estimate fracture length by comparison with postfracturing build-up or flow test results. In new wells or wells without prefracturing build-up or flow test data, fracture length must be estimated to correct the values obtained from analysis of pressure tests after fracturing. Fracturing efficiency calculations should be made whenever possible to provide an estimate of fracture length. Tables of the dimensionless pressure drop as a function of time and fracture penetration are included in this paper. Using these values should permit analysis of other types of transient pressure behavior in vertically fractured wells. INTRODUCTION Hydraulic fracturing has been used quite successfully for over a decade as a completion and stimulation technique in oil and gas wells completed in low-permeability reservoirs During this period a considerable amount of theory has evolved on the performance of hydraulically fractured reservoirs and on more efficient means of artificial fracturing. Although theory has been developed, no rigorous investigation has been made of pressure build-up and flow test behavior in such wells. Prats et al.1 first discussed the performance of vertically fractured reservoirs for the case of a compressible fluid. Their work was primarily concerned with production performance at constant flowing pressure. These authors also considered large-time (semisteady-state) constant production rate behavior for vertically fractured wells; however, transient pressure behavior at constant rate was not investigated. McGuire and Sikora10 and Dyes, Kemp, and Caudle2 employed an electrical analog to investigate the influence of artificial vertical fractures on well productivity and pressure build-up. They found that fractures which extend beyond 15 per cent of the drainage radius away from the well alter the position and slope of the straight-line portion of the build-up curve. They concluded that these effects must be considered both in the determination of the effective permeability of the formation and in any calculations of final build-up pressure. Although these authors did not undertake an exhaustive study of the influence of vertical fractures on pressure build-up performance, their limited results were quite interesting from the standpoint of the effects they demonstrated. In a more recent paper, Scott- reported the results of an investigation of the effect of vertical fractures on pressure behavior, which was conducted with a heat flow model. Scott's results appear to be consistent with those reported in Refs. 1 and 2. However, the effects of different fracture lengths on performance were not investigated. Pressure build-ups and transient flow tests are among the most diagnostic tools available to the reservoir engineer or production engineer. Since a very high percentage of present-day well completions incorporate the hydraulic fracturing technique, a definite need exists for information on the effect of fractures on transient pressure performance. For these reasons we have undertaken a rigorous study of pressure build-up and flow test behavior in vertically fractured reservoirs. The objectives of this study were (1) to obtain synthetic pressure build-up and flow test

Jan 1, 1965

By R. R. Boucher, O. J. C. Runnalls

A pronounced thermal effect has been observed on heating or cooling a1wninum-rich Al-U and Al-Pu alloys. From microscopic and X-ray diffractionstudies, the effectl has been attributed to trnsfor)nations in the inlemetallic phases UAl, and PuAl , involuing rearrangement or cluslering of vacancies The transformation obsrved in Al-20 wi oct U alloys occurred near the a Al-UAl4 eutectic tem-perature of 646°C making it difjicult to detect from heating curves. When cooling, howeoer, thermal mad X-ray analyses indicnted that the high-temperati~re phase labeled p UAL, precipitated initially during euitectic solidification. As solidification continued and after an induction period o-f 5 lo 20 tnin the nu-cleatiorz and growth of the low- twmperature phase, a UAl4 produced an euolution of energy which raised the observed alloy temperature by 1° to 2°C. in Al-Pu alloys the transformation occurred at 645°C, 5 deg below the eutectic solidification temperccture. The eslimated latent heat of transformation was 25 +5 cnl per g PuAl,. The high-tetnpevcl-ture forms of UAl, and PuAl, were easily 9-etccined by chill casting Al-U and Al-Pu alloys and on reheating the alloys the trcltzsforrnation to the a phase was sluggish even above 600°C. Separated single cryslals o-f UAl4, joy example, showed no evidence Of transformalion after heating for 16 hr at 620°C. The transformation rates increased yapidly enough with increasing temperature, however, that a a spontaneous liberation of energy lens observed on occasion when bealing cast Al-20 wt pet U to neal- the RECENT phase studies on A1-Pu alloys have indicated that earlier reported equilibrium diagrams should be modified to take account of several poly- morphic transformations in the intermetallic compound PuAl,.' During the course of the latter work an unexpected heat evolution was observed while cooling a solid alloy consisting of a mixture of a aluminum and PuA1,. The evolution occurred at 645°C, y below the a A1-Pu A1, eutectic solidification temperature. Subsequent thermal-analysis experiments with A1-U alloys showed that heat was evolved there also at a temperature nearly coincident with the a A1-UA1, eutectic solidification temperature of 646°. A search of the literature revealed that similar thermal effects had been observed before for both A1-U and A1-Pu but had never been fully explained.2,3 The purpose of the present paper is to describe thermal-analysis and X-ray diffraction experiments which have led to the conclusion that the thermal effects are due to transformations which involve the rearrangement of vacancies in the intermetallic compounds UA1, and PuA1,. EXPERIMENTAL PROCEDURE The A1-U alloys were prepared by heating super-pure aluminum (99.99 pct +) obtained from the Aluminum Co. of Canada in a graphite crucible surrounded by an induction coil. At 1000°C high-purity uranium metal produced by the Eldorado Mining and Refining Co., Ltd. was dropped into the liquid aluminum and was dissolved completely within 15 min. The impurities in the uranium were A1—4 ppm, Ca-4, C-70, Cr-3, Cu-6, Fe-30, Mg-2, Mn-10, Ni-25, Si-25, and Zn-2. The A1-Pu alloys were prepared by reacting plutonium dioxide with liquid aluminum under cryolite (3 NaF . AlF,) for 10 min at 1100°C in graphite crucibles exposed to the air. The plutonium was 99.8 pct pure, containing trace impurities of Ca, Cu, Fe, Pb, Si, and Zn. The liquid alloys were usually poured into water-cooled molds to provide castings of uniform composition from which samples could be cut for heat treatment and thermal-analysis experiments.

Jan 1, 1965

By J. L. Brimhall, R. A. Huggins

The structure of deformed internally oxidized alloys of siluer- cotztcrining magnesium and copper-containing aluminum in was studied by thin-film transrrzissiotz electron microscopy. With low to moderate amounts of stvain, the deformation structure in t11e dispersion-hardened alloys was found to consist of a high density of dislocations arranged it a random distribution or in a very fine, but poorly defined, cell stucture, depending on the fitness of the dbsbersion and amount of deformation. 112 contrarst, both pure copper and silver show relative1y Large, distinct cell structures. The particular structures in the alloys are believed to result from particles acting as both dislocaliot~ sources and deflector-s. The Inck of a pvorzolrr~ced deformation texture tr~ regiotzs qf' seoere loctll plastic curvature after heavy deformation can also be traced to the formation of clislocntions on many slip systemes and a lack 01 local concentrations of dislocations of predominantly one sign. THE presence of fine dispersions of a second phase has long been known to have a strong influence upon the mechanical properties of solids. Until recently, the influence of particles on the deformation mechanisms has been assumed to be solely that of barriers to dislocations. This is seen in the classic models of edge dislocations being restrained by the particles.1 4 There is, however, considerable evidence that this is not their primary effect, and that the particles can have a large influence on the defect structure generated by plastic deformation. The presence of particles causes changes in the surface topography observed after deformation. In overaged precipitation-hardened materials containing hard, noncoherent precipitates, fine intersecting slip lines are found after deformation of single crystals. indicating the activation of many slip systems. This has been extensively observed in the A1-Cu systen;, both by optical microscopy and replica electron microscopy.'"13 In some of the observations. the slip lines were seen to extend between the particles. Similar observations of extremely fine slip lines or the apparent absence of normal slip lines have also been found in A~-M~."

Jan 1, 1965

By M. F. Comerford

M. F. Comerford (Smithsonian Astrophysical Observatovy)- The authors' concern about the effects of preferred orientation is justified and emphasizes a phenomenon that can be a source of serious error, but the cogency of their concluding statement bears close examination. They contend that comparison of intensities from parallel planes of the two phases, as proposed by Averbach, Comerford, and Bever,13 leads to incorrect results. The state- ment is based on the fact that, in Fig. 3, intensity measurements at extreme angles of tilt, (2, lead to different values than those given by the average of all the data. The proposed explanation is that unsuspected superpositions of (110), reflections spuriously enhance the martensite intensity. However, it can be shown on appropriate stereographic projections that no superpositions occur which can affect the reflections in question. Hence, the ex-

Jan 1, 1965

By P. A. Tucker, C. R. Hudgens, D. E. Etter, D. L. Roesch, D. B. Martin

The equilibrium phase diagram of the Pu-Cd system is presented based on data obtained by differential thermal analysis, metallography, and electron-microprobe X-ray analysis. Liquidus temperatures range from 320° to 934°C. The system contains one congruently melting compound, PuCd, (945°C), and three incongruently melting compounds, PuCd, (800°C), PuCd, (730°C), and PuCd11 (410°C). A liquid-miscibility gap extends from 2 to 60 at. pet Cd with the monotectic reaction isotherm at 910°C. INTEREST in the potential use of plutonium alloys as reactor-fuel materials has prompted investigation of the phase equilibria in plutonium binary systems. A cursory investigation of the phase equilibria in the Pu-Cd binary system was conducted by differential thermal analysis (DTA), metallography, and electron-microprobe X-ray analysis (EMX). Extensive solid solubility of cadmium in both e and 6 plutonium was predicted1 based on atomic radii and electronegativities. Liquid immiscibility between these two elements was also predicted based on Mott's extension of Hildebrand's method. In the only previous investigation of the Pu-Cd system,2 two intermetallic compounds, PuCd11 (incon-gruent melting point 406°C) and PuCd8, were identified. EXPERIMENTAL The plutonium metal used in this work had a total impurity content of 500 ppm; the major impurities were: carbon (215 pprn), silicon (75 ppm), iron (60 ppm), nickel (40 ppm), and aluminum (25 ppm). The cadmium was reagent grade with a purity of 99.99 pet. The DTA technique for the study of plutonium alloys was previously described in detail.3 The alloys to be studied were prepared in tantalum DTA specimen capsules which were sealed by inert-gas welding. The alloys were homogenized in the liquid state in these sealed capsules which prevented the loss of cadmium by vaporization. Only the thermal arrests in the DTA heating curves were used to define the transformation temperatures of the system since supercooling affected many of the results during cooling. After the alloys were analyzed by DTA, the same alloys were used for the metallographic studies. Metallographic examinations were conducted in the manner described for plutonium alloys., No reaction was detected between the alloys and the tantalum capsules. Alloys for EMX analysis were placed in metallographic mounts together with specimens of unalloyed plutonium and cadmium which served as standards. The samples were highly polished but unetched. No protective coatings were applied to the surfaces of these radioactive specimens. Such coatings are detrimental to the excitation conditions and have been found to be unnecessary for the control of radioactive contamination. RESULTS The results of the DTA studies are presented in Table I. The phase diagram, constructed from these data plus the metallographic and EMX results, is presented in Fig. 1. The congruently melting compound, PuCd2, was identified by the occurrence of a maximum melting point (945°C) at 33.3 at. pet Pu-66.7 at. pet Cd and by the presence of a single phase in this composition.

Jan 1, 1965