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By D. J. Pye

Certain high molecular weight synthetic polymers in very dilute solutions decrease water mobility in porous media 5 to 20 times more than would be expected from the solution viscosity. This indicates that increasing water viscosity to reduce adverse mobility ratios in water floods is economically feasible in many situations. Laboratory results are consistent with accepted theory with respect to improved areal sweep, permeability distribution and displacement efficiencies as would be predicted from the solution mobility measured in the core. The laboratory results have been confirmed by field pilot floods which recovered 80 per cent and 100 per cent more oil than comparative water-flood pilots in fields containing 16 cp and 130 cp oil respectively. Economic analyses based on pilot data indicate the method to be profitable. INTRODUCTION The desirability of improving the water-oil mobility ratio in waterflood-ing operations has long been appreciated, especially for high viscosity crudes. Methods of reducing the oil viscosity by application of heat, gas resaturation and miscible drives have met with some success. Conversely, it has been generally conceded that increasing the water viscosity would also be effective, but the amount of thickening agent required to effect an appreciable increase in viscosity is discouragingly high. The use of such materials as glycerin, sugar, or glycols is completely out of the question economically, so that considerable attention has been given to the use of the much more efficient synthetic water-soluble polymers as viscosity improvers; but even these materials are not economically attractive. If increased water viscosity could be economically realized, marked improvements in areal sweep efficiency, as discussed by Caudle and Wittel and others, would be realized in field operations. Similarly, the improved mobility ratio would bring about increased recoveries by correcting permeability distribution problems as discussed by Stiles2 and Dykstra and Parsons,' and improvements in displacement efficiency would be obtained as recognized by Buckley and Leverett4 and Welge.5 LABORATORY STUDIES THE RESISTANCE EFFECT In the course of research to develop a more efficient water-soluble polymer viscosity builder, we discovered that a very few types of water-soluble polymers exhibited a most unusual and very interesting property not previously observed. Among the earliest materials showing such activity were polymers containing acry-lamide. Fig. 1 shows a typical plot of the solution viscosity vs concentration for one of these polymer solutions as determined in an Ostwald viscometer. As usual, such a plot is an approximate straight line on semi-logarithmic paper. Now, an inspection of Darcy's law, shows that a viscosity value can also be determined in a formation sample if the pressure, flow rate and permeability are known. If the core permeability is previously determined with wa- ter or brine, then the viscosity of another aqueous fluid may be determined from the equation. The viscosities so determined for glycerin (glycol or polyvinyl alcohol solutions, for example) agree with the viscometer determinations. However, in the case of the water-soluble polymer solutions in which we are interested, the viscosities measured in the formation sample depart very markedly from the viscometer values. A typical relationship for a polymer solution is also shown in Fig. 1. This unusual departure from the expected response is referred to as a resistance property of the polymer and is quantified as "resistance factor". Since the resistance factor R can best be determined in a core under study, the term has been defined on the basis of the ratio of the brine mobility to the polymer solution mobility at residual oil saturation so that:

Jan 1, 1965

By K. P. Gupta

The Cb-rich boundary of the (Cb,Al) a phase field at 1250OC is near 41 pct Al. The Al atoms tend to occupy the C. N. 12 sites in this structure. A homologous (Ta,Al)a phase was identified. No a phase was found in the Mo-Al system at 1200°C. The first binary o-phase with a non-transition element as a major component was found1,2 in the Cb-Al system. The composition of this phase was reported2 as approximately 34 at. pct Al, based on X-ray diffraction patterns taken of alloys in the as-cast condition. Further study of the composition of this o-phase, therefore, appeared desirable. Since Si was previously found3,4 to occupy preferentially the lowest C.N. sites (I and IV) in the a phase, and preliminary resultsa indicated that Al may show similar ordering, one of the aims of the present work was to obtain more complete information on ordering in (Cb, Al) o. Among the binary systems of Al with Ti-, V-, and Cr-group elements, the Ti-Al, Zr-Al, V-Al, and Cr-Al systems are known to comprise no o-phase. In the present work a Ta-Al and a Mo-Al alloy were studied in an effort to find additional o phases with Al as a major component. EXPERIMENTAL PROCEDURES AND RESULTS An alloy with the intended composition of Ta + 40 at. pct Al was prepared by arc melting in He atmosphere. In both the as-cast condition and after annealing for 10 days at 1250°C and quenching in cold water this alloy consisted of two phases, as seen in the X-ray pattern and the microstructure. One of these phases was identified as the o-phase; the observed and calculated d-spacings are shown in Table I. The lattice parameters of this o-phase are a = 9.972 A, c = 5.214 A and c/a =0.5228, as determined from a Debye-Scherrer pattern using Fe K a radiation. The d-spacings for the unknown second phase are given in Table 11. The alloy contained approximately 25 pct of the unknown phase after annealing, as estimated on the basis of microscopic examination. A Mo-Al alloy was prepared by arc melting, with an intended Al-content of 35 at. pct. The alloy button was annealed for 7 days at 1200°C and water quenched. The X-ray pattern of the alloy in both the as-cast and the annealed state showed the reflections of Mo3Al (Cr30 type structure) and an unknown phase different from a. Six Cb-Al alloys were prepared in the composition range 30 to 50 pct Al. All alloys were arc melted in He atmosphere. After annealing for three days at 1175oC in evacuated silica capsules and quenching in water, the alloys with 30 to 40 pct Al contained three phases, namely the o-phase, Cb3Al (Cr3O-type structure) and an unknown phase. The alloys with more than 40 pct Al contained two phases, namely, what appeared metallographically, the o-phase and the same unknown phase. In the alloys containing less that 38 pct Al, the unknown phase was not present after annealing for 4 days at 1250°c,

Jan 1, 1962

By H. D. Yoo, M. R. Tek, D. L. Katz

The behavior of gas-storage reservoirs subject to water drive is investigated through analog simulation on an electronic differential analyzer. The simulation technique developed on an LM-10 computer permits the prediction of reservoir volume or pressure resulting from the movement of water in the surrounding aquifer. The method developed on the analog computer consists of setting up an appropriate transfer-function circuit and feeding the arbitrary time-varying boundary conditions as an input signal. The input may be specified as gas reservoir pressure, pore volume or the water flux. Several cases studied include an isolated gas reservoir on a limited aquifer, interference among three reservoirs adjacent to a common aquifer and the growth of gas-storage volume on an aquifer. It is concluded that the method developed on an electronic differential analyzer provides an excellent technique to simulate and investigate the behavior of gas reservoirs subject to water drive. The agreement between the reservoir performance as predicted from the simulation technique and as measured from actual field data is found to be better than the range usually encountered in predicting water-drive behavior. INTRODUCTION It is generally known that some gas-storage reservoirs are located on top of blanket sands of large extent, saturated with brine called aquifers. Because the volume of the body of water associated with aquifers is usually very large and water is compressible, the cyclic pressure variations encountered in normal storage service inevitably cause unsteady, compressible flow conditions in the adjacent aquifers. The solution to radial diffusivity equation for a limited aquifer for constant terminal conditions has been know111 since the early 1930's. The solution for the constant terminal conditions for an infinite aquifer was puhlished in 1949.2 The proldem of handling the unsteady flow of water through a porous medium with time-varying boundary conditions has been studied by many investigators through the use of graphical,3 digital4 computing techniques or on an R-C type of electrical analog called a reservoir analyzer.5 The digital computer performs a series of arithmetic calculations to superimpose the solutions of constant terminal conditions, while the R-C type of analyzer permits the simulation of the continuous medium by means of "lumped-cell" electrical resistance and capacitance elements based on finite-difference approximations. The graphical method is based on the convolution integral solution of the partial differential equalion. The purpose of the present study was to simulate the behavior of an aquifer on a general-purpose, electronic differential analyzer to obtain the influx of water or the change in pressure at the reservoir continuous1r and quickly. The use of the electronic differential analyzer was based on well known solutions for the constant terminal conditions already available in the literature.2,6-8 THEORETICAL DEVELOPMENT MODEL. The gas reservoir (R) is described in relation to an aquifer in Fig. 1. The permeability and porosity of an aquifer sand, the viscosity of the brine, and the compressibility of the brine and the formation are assumed to be constant. It further is assumed that the blanket sand is not thick enough to give appreciable vertical pressure distribution. The model in consideration is circular with radial geometry. The aquifer radius can be of limited or infinite extent. The gas-water interface is assumed to be fully segregated, and the displacement of the gas by

By B. L. Averbach, M. Cohen, C. H. Shih

The isothermal formation of martensite is studied in Fe-Ni-Mn and Fe-Mn-C alloys under conditions where the athermal transformation is completely avoided, there being no martensite present at the beginning of the isothermal reaction. The initial rate of martensite formation is extremely low under these conditions, but it increases greatly as soon as some martensite is formed. It appears that true initial characteristics of the isothermal reaction can be studied only in samples wherein the formation of martensite on cooling is completely eliminated. THE phenomenon of isothermal martensite formation is well established1 -" but the observations have been made in the presence of varying quantities of athermal martensite. Complete avoidance of athermal martensite and the formation of martensite under pure isothermal conditions have been reported by Kurdjumov and Maksimova2 in an Fe-Ni-Mn alloy (23 pct Ni, 3.4 pct Mn, and the balance Fe) and have been confirmed by recent experiments of Cech and Hollomon in a similar alloy. In each case, the isothermal transformation rate was a maximum at the beginning of the transformation and decreased as the reaction proceeded. These initial transformation rates were used by Fisher7 for the confirmation of calculated nucleation rates based on classical nucleation theory extended to include the effect of elastic strain energy. Cech and Hollomon have admitted, however, that up to 3 pct martensite formed on cooling in their samples and thus was present at the initiation of their isothermal runs. In this paper, experiments on similar alloys are described, except that care was taken to remove the incidental martensite developed at the surface prior to the isothermal reaction. It is shown here that the reaction rate at the beginning of the strictly isothermal reaction is very low. As soon as some detectable amount of martensite is produced, the transformation rate increases rapidly but ultimately decreases as the reaction proceeds. When martensite is allowed to form isothermally in the presence of about 2 pct of prior martensite, the apparent initial reaction rate is a maximum and corresponds to the observations of Kurdjumov and Maksimova and Cech and Hollomon. It is evident that the cooperative nature of the martensitic reaction results in a significant stimulating or autocatalytic effect on the isothermal reaction rate. Experimental Procedure The chemical compositions of the alloys used in this investigation are listed in Table I. The Fe-Ni-Mn alloys A and B were melted in an induction furnace, cast into ingots 2 in. diam by 4 in. long, and forged into % in. diam rods. The manganese steel (alloy C) was melted in an arc furnace and cast into ceramic molds 1/4 in. diam by 5 in. long. The rods were sealed in evacuated Vycor tubes and homogenized at 1175" to 1200°C for 50 hr. The long homogenization resulted in some manganese loss from the surface, producing a thin layer of transformed material. This surface layer was removed by grinding and the specimens were then swaged to 0.050 in. diam wire. Measurements of electrical resistance were made with a Kelvin double bridge to follow the course of the martensitic transformation. A small permanent magnet was also useful in scanning an entire specimen for small localized quantities of martensite. This test is almost as sensitive as the electrical resistance method in detecting the presence of martensite (which is ferromagnetic in these alloys) and it was especially useful in deciding whether a specimen was completely free of martensite. The wire specimens (0.050 in. diam by 2.5 in. long) were sealed in evacuated tubes and austenitized for 5 min at 1150°C. The specimens were quenched into water and, unless otherwise stated, stress-relieved for 1 hr at 650 °C in order to induce greater uniformity in the subsequent martensitic transformation. As dem-

Jan 1, 1956

By C. van der Poel

When oil is displaced from a horizontal formation by another fluid of lower density, the latter tends to override the former in the shape of a tongue owing to gravity segregation. This gravity tongue has an adverse influence on the oil recovery. If the fluids are miscible, diffusion (mixing) takes place at the interfacial boundary of the gravity tongue. This mixing should have a favorable effect on oil recovery. The report describes a laboratory study of the magnitude of the mixing zone under various conditions, so as to assess the effect of diffusion on oil recovery both in laboratory experiments and under actual field conditions. The technique used enables visual observation and measurement of the size of the mixing zone in transparent glass-powder packs. The results show that in experiments in small models and cores the width of the mixing zone may well be of the same order of magnitude as the height of the model. In such cases oil recovery is favorably affected by mixing. It can further be concluded that, under conditions prevailing in the field, mixing of the injected fluid with reservoir oil is equal to that caused by molecular diffusion alone, eddy-mixing not taking place to any appreciable extent. A simple calculation, then, shows that molecular diffusion is too small for a beneficial effect to be expected from the injection of miscible fluids in horizontal or nearly horizontal reservoirs unless pay zones are thin. INTRODUCTION This paper gives results of experiments made on the mixing which occurs when a miscible displacement is carried out in a horizontal reservoir. This mixing takes place at the interfacial boundary of the gravity tongue formed when the lighter injected fluid overrides the oil present in the reservoir. The object of the experiments was to simulate the field case where, for example, propane with a viscosity of 0.075 cp under reservoir conditions displaces an oil of viscosity 0.6 cp. In the experiments the lighter fluid had a viscosity of about 1 cp and the heavier one a viscosity of about 8 cp, so as to obtain the same viscosity ratio. In order to enable the results to be compared with those published in the literature, a set of experiments with viscosity ratio equal to one was also performed. EXPERIMENTAL TECHNIQUE The technique developed for the purpose enables the width of the mixing zone to be studied as a function of time and place. A glass-powder pack is saturated with a water-glycerine mixture of suitable viscosity, which represents the reservoir fluid. The pack is then rendered transparent by dissolving sufficient ammonium thiocyanate in the mixture to obtain a solution with a refractive index matching that of the glass powder. Alkaline water to which phenol-phthalein has been added is used as the lighter and less-viscous displacing fluid. In those places where mixing or diffusion of the two liquids occurs, the slightly acidic ammonium-thiocyanate solution neutralizes the alkali in the water, and the glass pack shows up white against the red-colored invading water. If a black cloth is hung over the back of the apparatus, the transparent part of the glass pack appears black. In this way the position of the two phases and the transition zone between them is clearly visible, as shown in Fig. 1 (where the red-colored invading water is the grey-shaded zone lying uppermost). In all experiments the amount of alkali in the water was chosen such that the upper contour corresponded to a concentration of 5 per cent of the dense liquid. The lower contour is determined by the size of the glass grains and the thickness of the pack and, consequently, varies from experiment to experiment. Corresponding concentrations of the dense liquid range from about 97 per cent for packs of small grain size (permeability = 1 darcy) to about 95 per cent for those with large grains

By C. H. Li, J. A. Sarteli, W. Bonfield

The stress to cause a permanent micros train of 2 x 10-6 in. per in. (defined as the microscopic yield stress) in beryllium is found to be very sensitive to surface condition. The initiation of plastic flow in as-machined specimens, which contain a high density of twins and large residual compressive stresses to a depth of about 0.010 in. from the surface, occurs by the nucleation of slip from high stress fields around twin tips in the surface layers. Removal of the damaged surface layers by chemical polishing results in an appreciable increase in the microscopic yield stress, which is attributed to the remoual of stress raising twins rather than to the release of residual stresses. IT is well known that the macroscopic mechanical properties of beryllium are very sensitive to the nature of its surface finish. Matthews and coworkers1 have shown that the tensile strength of rolled beryllium sheet can be considerably enhanced by chemical polishing, presumably due to the removal of the high concentration of notches, twins, and large residual compressive stresses normally found in the surface layers of ground specimens. There was no similar effect of surface condition on the macroscopic yield stress (the stress to produce 0.2 pct strain), a point to which we shall return. To date there have been no extensive studies on the effect of surface condition on the microstrain region of beryllium. Recent measurements2 of the stress to cause a permanent microstrain of the order of 10-6 in. per in. on machined hot pressed QMV beryllium, gave values ranging from about 600 to 3500 psi. Reasons for the considerable scatter in the results were not discussed. In this paper, we wish to show that the microstrain region of polycrystalline beryllium is, in fact, very sensitive to surface condition. The stress to cause a permanent strain of 2 x 10-6 in. per in. which for convenience we will refer to as the microscopic yield stress, can be increased by almost a factor of 2 by minimizing the amount of surface damage. The variation of microscopic yield stress is attributed to the presence of twins in the surface layers, rather than to residual compressive stresses. EXPERIMENTAL PROCEDURE The starting material for this investigation was commercial purity hot pressed QMV beryllium, with an average grain size of about 20 . The effects of surface treatment were assessed by comparing the microstructure with residual stress measurements and microstrain properties. Specimens were prepared for metallographic examination by wet grinding with 240, 400, and 600 papers, followed by polishing with a suspension of fine alumina in warm 20 pct oxalic acid. After this treatment, the surface could be examined, either in the unetched condition with polarized light, or after etching in 2 pct hydrofluoric or boiling 20 pct oxalic acid with normal light. Thin films of beryllium suitable for electron transmission study were prepared from bulk specimens by chemical polishing with hydrofluoric and phosphoric acids, and were examined in an RCA-EMU-3 electron microscope. Residual stress measurements were made by a procedure similar to that of Treuting and Read.3 Specimens 4.0 in. by 0.625 in. by 0.080 in. were prepared by three different machining procedures, namely: turning, grinding, and sawing, in order to introduce different levels of residual stresses. An electrical resistance strain gage was attached to one side of the specimen, and that surface was then protected by an acid-resistant enamel, while the opposite surface was removed by etching approximately one thousandth of an inch at a time. The change in specimen curvature in the longitudinal direction was noted and the residual stress was calculated by the following formula:

Jan 1, 1963

By M. C. Flemings, A. A. Tzavaras

Analytical and experimental procedures are descrihed for quantitative determination of volume-fraction microporosity in metals by mimorarlio-graphg. The analysis assumes spherical pores but allows for the observed fact that pores or portions of pores smaller than a given thickness do not project an image on the film. Volume-fraction microporosity was measuured in cast low-alloy steel and shown to vary from 0.6 x 10-4 to 10 x 10 depending on mode of solidification and on whether the material was air- or vacuum-cast. The aim of work described herein was to develop a method of quantitative measurement of the volume fraction of microporosity in cast metals. Microporosity, present in nearly all castings and ingots, is always interdendritic in nature and may be large enough to be seen on a polished surface with the naked eye. More generally, it is smaller in size, and its detection more difficult. Three techniques might be considered for measurement of microporosity: 1) lineal analysis of a polished metallographic surface, 2) density measurement, or 3) quantitative microradiography. As will be shown later, volume fractions of porosity in directionally solidified castings may be the order of 10-4 to 10-3; such small amounts of porosity are difficult to identify and measure on a polished surface. Density measurement is also not a suitable technique (for alloys) when the volume fraction of porosity is low. This is because the density of the base metal is often not known within the necessary accuracy, due to microsegregation or partial phase transformations. In general, it is not possible to completely eliminate microsegregation without also altering the porosity. Because of the limitations of the foregoing techniques, quantitative microradiography was employed to determine amount of porosity. In recent work, microradiography has been found to be useful for qualitative measurement of porosity, including determination of size and shape of individual pores;&apos;)&apos; however, quantitative determination of amount of porosity has not been attempted. I) CALCULATION OF VOLUME-FRACTION POROSITY The following analysis employs procedures similar to those of Cahn and Nutting3 and Hilliard.4 Major simplifications are that pores are assumed to be spherical and to be present in sufficiently small quantities that no overlapping occurs. A basic difference from the previous treatments is that the limited "sensitivity" of microradiography is considered. Assume first 1) cavities are spherical and of uniform diameter, 2) cavities are randomly distributed, 3) volume-fraction porosity and specimen thickness to pore radius ratio are sufficiently small that overlapping of the projected images of cavities is negligible, 4) sensitivity is limited (i.e., holes or portions of holes of less than a given thickness do not project an image on the film). The sensitivity, is defined as: where 5 = minimum thickness of void from which an image will be projected on the film and t = specimen thickness. Now, from Fig. 1, it is possible to distinguish between two different types of holes. These are 1) holes whose centers lie within the region t/2 > X > 6/2, where X is distance from one surface of the specimen (positive into the specimen), and 2) holes whose centers lie within the region (6 — r) < X < 6/2, Holes whose centers lie outside X = (6 -r) project no image on the film. These two types of pores are considered separately below. Type 1 Pores. When 6 is greater than 0, the image of a spherical cavity of radius r appears on the film as a circle of radius a which is smaller than r. From geometry, Fig. 1: a2=r2-52/4 [2] where a = radius of image of pore on film and r = radius of pore. Since the pores are randomly distributed and spherical V =4/3pr2Nv [3] where V = volume fraction of voids and Nv = number of pores per unit volume and the number of images of Type 1 pores per unit area of film, N&apos;A, is

Jan 1, 1965

By R. S. Wagner, H. Brown

Criteria for nucleation with the aid of twin planes during crystal growth from the melt are discussed. It is shown experimentally that bismuth crystals can grow from a subercooled melt in a twinned bismdtic form. A mechanism of growth based on the presence of at least me twin plane is proposed. It is well known that faceted growth can be observed in crystals grown from the vapor phase, dilute solutions, or from the melt. Faceted growth, in which the crystal is bounded by its slowest growing faces, will occur if the growth rate is strongly orientation dependent. The addition of atom layers on a facet plane can only occur by two-dimensional surface nucleation or with the aid of an imperfection. Nucleation with the aid of dislocations was proposed by rank&apos; and observed to be of particular importance in crystal growth from the vapor phase. Nucleation with the aid of two-dimensional imperfections, notably twin planes, was suggested by stranski2,3 and Frank.4 A twin plane, terminating at the growth interface, can form a reentrant step at which nucleation can occur at a much smaller super-saturation (or supercooling) than required for two-dimensional surface nucleation. Nucleation by a twin plane usually results in a fast growth rate along a crystallographic direction parallel to the twin plane. Such a nucleation mechanism, based on the presence of a twin plane, has been used by Dawson5 to explain the growth and morphology of sheet-like crystals of paraffin n-hectane. In recent years more evidence was found that nucleation by twin planes occurs frequently in crystal growth from the vapor phase and from dilute solutions, for example, in cadmium,&apos; barium titanate,7 silver,8 silicon9 and gallium arsenide.10 In crystal growth from a supercooled melt, however, nucleation by twin planes has so far only been observed in materials with the diamond or zinc blende structure. Bennett and Longini11 were the first to recognize the important role a single twin plane plays in the growth of germanium dendrites. Subsequently, it was found that a prerequisite for continued propagation of germanium dendrites is the presence of two parallel twin planes which form a self-perpetuating system of nucleation sites.12 Sili- con and some III-V compounds such as InSb also grow dendritically by twin plane nucleation. It appears that the following criteria must be satisfied in order that nucleation with the aid of twin planes can occur: A) The growth form of the material must be faceted." B) The formation of twin boundaries, by a fault in layer sequence during growth, by plastic deformation, or by an accidental meeting of properly oriented crystals, must be possible. C) Twinning must form a reentrant step where the twin boundary terminates at the faceted growth interface. D) These three conditions are necessary, but in certain cases not sufficient for continued crystal growth with the aid of a twin plane. Depending on interface morphology, a combination of more twin planes is sometimes required to form a self-perpetuating system of nucleation sites. This investigation was carried out with the idea in mind that nucleation with the aid of twin planes is a more general phenomenon and should occur in those materials, grown from a supercooled melt, which satisfy the criteria outlined above. It has been found that crystals of high-purity bismuth grown from a supercooled melt can grow by the aid of a twin plane. In the first two sections the faceted growth form and the twinning elements of bismuth are discussed. In the last section prismatic crystals of bismuth, which appear to grow with the aid of a deformation twin are discussed.

Jan 1, 1962

By D. C. Seidel, E. F. Fitzhugh

The cementation of nickel from acidic solutions by metallic iron is discussed. The cementation is carried out in pressure vessels at temperatures above 100°C. The results from bench scale studies on variables such as retention time, temperature, and solution pH are presented. A continuous processing flowsheet is proposed. Cementation is one of the oldest known hydrometal-lurgical reactions. The cementation of copper on iron was recorded by &apos;Paracelsus the Great&apos; in about 1500,1 and by 1600 the technique was being used to recover copper at the Rio Tinto operations in Spain.2 At least one early author felt that cementation may have been one of the primary reasons for the alchemists&apos; belief in the transmutation of metals.&apos; The early writings state that when iron was placed in the clear waters from some mountain springs, the iron disappears and copper is found in its place. To the alchemists this may well have been one of the most convincing proofs that transmutation could and did occur. Since these early times the recovery of copper from acidic solutions by cementation has been practiced in plants throughout the world. Probably the cementation technique in some form has been common to more copper mining and milling operations than any other single recovery process. During current hydrometallurgical extraction studies, which were sponsored by the Republic Steel Corp. at the Colorado School of Mines Research Foundation, Inc., it was found that under the proper conditions, metallic nickel could be cemented from acidic solutions by powdered iron. The reactions are apparently similar to those that occur during the cementation of copper, but the nickel cementation had not been anticipated because iron and nickel are nearly adjacent in the electromotive series. The potential difference between iron and copper is approximately 0.78 v, while the potential difference between iron and nickel is less than 0.21 v. The cementation of nickel with iron at room temperature is almost negligible, but when the reaction is carried out in a closed vessel at temperatures in excess of 100°C, the nickel can be cemented almost quantitatively. The part played by this discovery in a practical method of nickel recovery is set forth in a separate paper.3 The following paragraphs are a discussion of experimental studies that were made to investigate this cementation reaction. The technique has been designated the HTC or High Temperature Cementation procedure. The cementation work was part of a study on hydrometallurgical techniques for the extraction of nickel from the garnierite or silicate type nickel ores. A hydrothermal extraction procedure had been developed, and this technique produced an acidic pulp or solution that contained both nickel and appreciable amounts of magnesium.3 Small quantities of ferric and ferrous iron were also present along with cobalt, manganese, and chromium. The potential for recovering the nickel from these acidic solutions by ion exchange or solvent extraction did not appear to be promising because of the relatively high magnesium content. The Ni ++ and Mg++ have nearly identical ionic dimensions and tend to be co-absorbed or extracted during ion exchange or solvent extraction treatments. Preliminary tests indicated that the nickel could be precipitated as a sulfide when using the high pressure H2S precipitation technique developed for the Moa Bay operations of the Freeport Nickel CO.4 This technique gave good recoveries, but the nickel sulfide product requires considerable additional processing before a marketable form of nickel is realized. The process also requires clarified feed solutions, and the solids-liquid separations on the garnierite residues are difficult. A program was initiated to investigate alternate procedures that might shorten the route to a marketable nickel product, and hopefully also permit bypassing the difficult solids-liquid separation steps required for the H2S precipitation technique. It was during these studies that the nickel cementation reaction with iron was encountered. EXPERIMENTAL EQUIPMENT AND PROCEDURES The bench scale precipitation tests which were conducted during this experimental program were made in 2-liter stirred autoclaves.* A photograph showing the form and arrangement of the autoclave

Jan 1, 1968

By J. Murray Riddell

The method of treating hazards wherein value is decreased, is cited by R. D. Parks. Quite properly, the theory of probabilities is made use of when multiple hazards are under consideration. E. F. Fitzhugh, Jr. deals with the enhancement phase graphically and uses percentage of expectancy as derived by a study of conditions and the selection of a chance factor. It is believed that both of the authors referred to fully recognize the part which human judgment plays, and as coupled with experience, training, and the application of the theory of probabilities; in that respect the composer of this paper is in accord. Within the past year, the task of arriving at a mathematical method for handling the enhancement phase, and, additionally, coupling the negative and positive phases, was explored. In citing the hazard, or negative phase, reference is made to the text by Parks.

Jan 1, 1949

By J. Washburn

Two simple types of dislocation distribution were introduced into zinc crystal specimens and the effect of each on the stress-strain curve was investigated. Quantitative results were obtained for simple edge dislocation arrays and for an array of screw dislocations lying in the slip plane. A CCORDING to present knowledge, the disloca-tions present in large annealed metal crystals can be divided into two somewhat arbitrary groups: 1—single dislocation lines distributed more or less at random or forming elements of a three-dimensional network in which the distance between adjacent dislocations is of the order of 10 2 to lo-&apos; cm and 2— widely separated planar arrays of edge dislocations forming dislocation walls or small angle boundaries within which adjacent dislocation lines are spaced at much smaller distances (lo-&apos; to 10- hm). The former can be considered as a dislocation interpretation of the mosaic crystal proposed by Darwin and Ewaldl, &apos; 40 years ago to account for anomalously high integrated intensities of X-ray diffraction maxima. Small angle boundaries, although now known to be present in most single crystals used for mechanical testing, were not generally recognized by the early workers. This was partly due to the fact that only recently have improved X-ray and metal-lographic techniques been available for checking the macroscopic perfection of crystals."" It has long been known that changes in growth conditions and in annealing procedure, which might logically be expected to cause variations in the structural details of both the dislocation network and of dislocation boundaries, produce marked variations in some mechanical properties such as yield strength." However, no quantitative experimental correlations between changes in dislocation distribution and changes in mechanical properties have yet been made. Such a correlation has been difficult to obtain because, even when great care is exercised to keep the histories of a number of single crystal specimens identical, it usually has not been possible to avoid considerable variation in macroscopic per- fection.&apos; The number and orientation of dislocation boundaries vary from specimen to specimen. This has probably been an important contributing factor to the large scatter in the results of most mechanical measurements on pure single crystals. Some recent experiments"% ith single crystals of zinc have shown that the presence of dislocation boundaries in a specimen can increase its resistance to deformation by slip. With polycrystalline aluminum and nickel, there is also evidence that dislocation boundaries within the individual grains of the aggregate can increase the resistance of the material to plastic deformation, either as measured by tension tests at room temperature or by creep tests at higher temperatures.&apos;" " Although the foregoing observations seem to have established the fact that substructure can have a strengthening effect, the test conditions were too complex to give much information concerning the mechanism. In the foregoing cases, a network of intersecting boundaries having various orientations and boundary angles were present. Before their apparent strengthening effect can be understood, it will be necessary to isolate and study separately the effect of a number of variables: 1—boundary angle, 2—boundary orientation with respect to the active slip direction, 3—number of boundaries, 4—intersections of boundaries, 5—detailed structure of the boundaries, and 6—interaction of impurity atoms with dislocations in boundaries. The object of the present work was to study the effect of dislocation boundaries on flow stress under the following simple experimental conditions: 1— substantially pure shear deformation and 2—boundaries of controlled angle, orientation, and number. In this way, it might be possible to distinguish the important variables from the relatively unimportant ones. Experimental Procedure Stress-strain curves of hexagonal metals are generally nearly linear even out to very large strains."

Jan 1, 1956

By M. R. Geer, H. F. Yancey

John Grifien (Pittsburgh)—I wish to congratulate the authors on this paper, which, I am sure, will promote a clearer conception of the various criteria which have been advanced as measures of coal-cleaning performance. Their clear descriptions of the more important criteria that have been advanced and explanations of their meaning and application have been sorely needed and, if widely promulgated and followed, should remove much of the confusion which, heretofore, has been evident. I suggest that much of this confusion has also arisen from lack of common agreement as to the exact meaning of the words and terms used in our discussions of this subject. I am sure I have been equally guilty in this respect and suggest it is time that we select a committee to study vocabulary as well as criteria, so that common understanding and agreement can be had. Thus, I suggest, that the title of this paper should have used the words "coal-cleaning performance" and not "coal-washery performance." My understanding is that "washery" refers to a complete plant and it has additional functions to that of coal-cleaning, such as control of size, moisture, etc. Also, I do not agree with the authors that the formulas given in their paper, the Fraser and Yancey formulas, are necessarily the only ones that can be called efficiency formulas. When a dictionary is consulted one realizes that the words "efficiency" and "efficient" have not precise meanings but only very general ones and must be further defined for each particular use, if they are to have any precise meaning. To my mind, the first of the Fraser and Yancey formulas given should never be used as expressing "efficiency" alone but only by the fuller phrase which truly expresses the kind of efficiency it states, which is "coal recovery efficiency." For complete clarity we then need only define "coal" for the particular circumstances under which the formula is used. This would recognize the fact, fully explained by the authors, that the limits in coal qualities imposed by the market have imposed a factor—and a variable factor—which has influenced any answer obtained by this formula. Such a procedure makes it entirely practical and logical to use the values of any of the qualities of coal—ash, sulphur, phosphorus, specific gravity—or a combination of them to define what is coal for that particular use of the formula. Further, it is clear to me that the criteria to be used must be dictated by the objective in view and the use for which the data are obtained. The authors clearly point out that the Fraser and Yancey coal-recovery efficiency formula is influenced by three factors, "one is determined by the coal, one is dictated by market or use conditions, and one is an inherent characteristic of the cleaning unit itself." The formula which uses the inverse of misplaced material as a measure of efficiency is also a coal recovery efficiency formula and is influenced in like manner by these three factors. As the authors point out, both are useless in obtaining data which enables a direct and valid comparison of the performance of a given cleaning unit on two coals where the other two factors vary or of the performance of two or more cleaning units of different types unless the values of the other two factors are identical. Much of the confusion in our discussions of and literature on coal cleaning has come from failure to understand clearly this fact. Many such comparisons have been made from which erroneous conclusions have been drawn. I am, therefore, particularly glad to see the authors&apos; emphasis on 4?-1e criteria which indicate the "sharpness of separation. I feel that these are the essential criteria

Jan 1, 1952

By W. O. Philbrook, K. M. Goldman, G. Derge

THIS is the third in a series of papers from the Metals Research Laboratory dealing with the transfer of sulphur across the iron-slag interface in a carbon-saturated system. The first paper&apos; showed that the transfer obeyed first-order kinetics. The second&apos; presented detailed evidence in support of the three-stage mechanism: FeS(Fe) FeS(slag) FeS(slag) + CaO(sing) ? CaS(slag) + FeO(slag) FeO(slag) + C ? Fe + CO. This emphasized the role of an iron-sulphur complex as the transfer agent across the interface and as an essential intermediate in the overall process. The present paper shows the influence on the process of the individual elements, carbon, silicon, manganese, and phosphorus, the alloying elements normally present and of interest in commercial blast furnace operations, aluminum, which has a pronounced accelerating influence, and nickel and copper, which are common minor impurities in the raw materials. The experimental methods and procedures for interpretation of data are the same as described earlier.1,2 Induction heated, graphite crucibles were used, and sulphur-free slag was added to the molten iron containing sulphur and the selected alloy. Slag samples were taken at regular time intervals and analyzed for sulphur and other components of interest. The authors wish to state specifically that these experiments were not intended to simulate industrial blast furnace operations. However, they do represent a study of the kinetics and mechanism of sulphur transfer at the slag-metal interface under specified laboratory control of the major variables in the system. It is believed that the results can be usefully applied to the blast furnace if consideration is given to the differences which are known to exist between the two conditions. A rigorous evaluation of the accuracy of rate studies is difficult. Recognized sources of error include sampling and analysis of both slag and metal, temperature measurement and control, selection of zero time, composition of the gaseous atmosphere over the reaction system, and extraneous sources of sulphur from the graphite crucible and reagent materials. In this study carefully standardized procedures were followed consistently in order to minimize the errors. It is believed that the reproducibil-ity of duplicate runs indicates that errors have been rendered negligible relative to the observed effects from intentional variables. For example, original experimental points for duplicate runs are shown in Figs. 1, 2, 7, etc. In most cases in this paper the drawn curves represent an average of at least two heats. The spread in sulphur values at a given time ranges from 0.02 to 0.08 pct, which is a small frac-tioi of the total values ranging up to 2 pct S in slag. In the systematic study of the influence of alloy additions, each element was added over a range of concentrations. The two slags used in this study were designated as "acid" or 1530 and "basic" or 1545. They had the nominal compositions given in Table I. Rates were measured in the temperature range 1500" to 1650°C. Data will now be presented to illustrate the various features of the study. Silicon The first alloying element examined was silicon, because its presence is unavoidable in any silicate slag system through the reaction y/2SiO2(slag) + xM?y/2Si(liq.Fe) + MxOy where M is any reducing agent such as iron or carbon. It is known that the attainment of equilibrium by this reaction is extremely slow and probably not reached in the blast furnace." The influence of silicon on the final stages of the sulphur reaction has also been studied.&apos; It has been shown5 hat silicon increases the activity of sulphur in iron. For such reasons silicon may also be expected to influence the kinetics of the reaction. The observed effects will now be described. The general procedure was to melt 530 grams of ingot iron in a graphite crucible, 3 in. OD, 2 1/4 in.

Jan 1, 1955

By Lawrence H. Van Vlack, Otto K. Riegger, Gerald I. Madden

The microstructural variations of periclase (MgO) in the presence of oxide liquids are examined under the steelmaking variables of: 1) temperature, 2) liquid composition, and 3) FeO additions under different oxidation levels. Attention is given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. Silicate liquids penetrate more extensively between individual periclase grains than do liquids containing high percentages of Fe2O3 Higher MgO solubilities in the liquid and lower MgO contents of the solid favor more rapid grain growth. The presence of a second solid phase reduces the periclase grain growth rate and increases the amount of the solid-to-solid contact within the oxide microstructures at high temperatures. The service suitability of a refractory depends on many factors. Two are of major importance and include 1) the thermal resistance to melting, and 2) the mechanical resistance to loads at service temperatures. Neither is a simple consequence of the service temperatures because service conditions will alter compositions, produce partial melting, and induee phase changes. Consequently, the equilibrium phase relationships have been rather thoroughly studied and give a knowledge of the thermal resistance to melting, but do not give full information about the mechanical properties because two refractories with the same types and quantities of phase may have different microstructures. Although variations of microstructures with time, temperature, and composition have been subjects for extensive investigation in metals, only a limited amount of comparable microstructural work has been performed for refractory materials.&apos; This study was an attempt to evaluate some of the consequences of service parameters upon the microstructures of refractories so that bases may be established for the analyzing of high temperature mechanical properties. Periclase (MgO) was chosen as the refractory oxide; variables included those which are encountered under steelmaking conditions such as 1) temperature, 2) liquid composition, and 3) FeO additions under various oxidation levels. Specific attention was given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. The most closely related work on microstructures of polyphase materials is that of Van Vlack and Rieg-ger2 on the microstructure of magnesiowüstite [(Mg,Fe)O] in the presence of silica. In that work which pertained to solid solutions with less than 40 pct MgO, most of the quantitative work was performed on FeO microstructures. The chief conclusions concerning these relatively low-melting oxide solids were as follows: 1) the rate of crystalline grain growth is inversely proportional to the grain diameter, 2) grain growth proceeds more rapidly at higher temperatures but is slightly retarded by additional liquid content, and 3) a Silicate-containing liquid penetrates as a film between the individual magnesiowüstite grains independent of time, temperature, amount of liquid, or the MgO/ FeO ratio. The above observations are in contrast to prior work3 on the microstructure of silica in the presence of iron oxide-containing liquids where the liquid does not penetrate as a complete film between solid grains. The phase relationships for the compositions of the present work are shown in Fig. 1 which is a summary of the work of several investigators.4 Of importance is the fact that CaO forms a more stable structure with SiO2 and Al2O3 than do either MgO or FeO. The oxygen potential has little effect on periclase unless iron oxide is also present. The iron oxide is ferrous at moderately low oxygen levels, changing to ferric as the Oxygen potential is increased so the spinels, magnetite, and magesioferrite are formed.5 These two phases are relatively stable in air at steelmaking temperatures. I) EXPERIMENTAL PROCEDURE ractory were made with reagent grade Oxides. The magnesium oxide used was 99 pct MgO after ignition, and the iron oxide raw material had a minimum content of 99 pet Fe2O3. The CaO, SiO2, and A12O3 were also reagent grade raw materials. After mixing, the required compositions were pressed into pellets at a minimum pressure of 5000 psi to insure compaction of the raw materials and prevent excess void content. A silicon carbide element tube furnace was used with thermocouple control for sin-

Jan 1, 1963

By G. Venturello, C. Antonione, G. Della Gatta

Results from work on the effect of inferstitials on recovery and recrystallization of&apos; very pure iron (99.995 pet) doped with nilrogen up to 400 ppm are reported. Nitrided specimens were obtained by heating the iron in a static atmosphere of NH3 + H2. The samples were cold-rolled 80 pet, subjected to a series of isochronal and isothermal anneals, and submitted to examination by X-rays, micrographs, and hardness tests. Small additions of nitrogen show a strong effect in reducing recovery of&apos; the mechanical properties of high-purity iron. At the temperatures of. the experiments, this effect proved greater than in the case of carbon. At 400°C pure iron recovers more than 50 pet of the total hardness increase, carburized iron vecovers 25 pet, and nitrided iron only 10 pet. On the other hand. the addition of nitrogen has, similarly to carbon, a very small effect on recrystallization; the effect is, however, slightly higher than that of carbon. When the concentration Of nitrogen is above the solubility limit in a iron at the temperattue of the experiments, an increase in the frequency of nu -cleation is also observed. THE object of the present work is to improve knowledge on the effect of interstitials both on recovery and on primary recrystallization of pure iron. In fact. at present there are no available data on the effect of nitrogen on high-purity iron. The only work which at present can be somewhat related to this problem is a work of Leak et al.1 in which grain boundary internal friction at high temperature in the presence of increasing amounts of nitrogen is studied by a torsion pendulum. The present work is a continuation of a previous one2 on the effects of carbon. EXPERIMENTAL PART Preparation of the Material. Pure iron was prepared following the same methods used in the pre- vious work2 and was nitrided using controlled quantities of ammonia in an apparatus similar to that used for carburizing. The apparatus consists essentially of a gas-tight quartz tube containing the specimens. The tube, maintained at constant pressure by means of a mercury seal, is placed in a resistance furnace. For nitriding, the NH3 + H2 atmosphere with a suitable concentration of NH3 was introduced into the tube, which had been previously carefully evacuated and degassed by heating at 600°C. The hydrogen used was carefully purified by passing it through a palladium filter. The ammonia required was prepared with the following reaction: CaO + 2NH4CI —CaCl2 + H2O + 2NH3 by heating the mixture of CaO and NH4C1 in a glass flask and then collecting the ammonia in a graduated Hempel burette. For each nitriding program a given amount of NH3 prepared by this method was introduced together with the H2 into the tube previously evacuated. Nitriding of the sample was then performed at 570°C for 48 hr. After this, to ensure a homogeneous distribution of nitrogen, the samples were further heated for 72 hr at 800°C. With this method which uses a static nitriding atmosphere, carefully controlled conditions of purity are obtained. Contrarily, with the conventional continuous-flow methods, using large quantities of circulating gas, there is a greater risk of introducing impurities into the samples. Furthermore, the required nitrogen concentration in the specimen is easily predetermined and obtained. A plot of the relation observed between the initial concentration of NH3 in the gas and the quantity of nitrogen introduced into the iron samples is given in Fig. 1. The data refer to samples of 1.2-mm thickness and to the nitriding conditions previously described. Furthermore, as a comparison, the data relative to two 0.5-mm-thick samples are reported. The presence of a reservoir in the cold zone of the reaction bulb made possible the gradual dissociation of ammonia on the sample in the hot zone. Internal-friction methods were used to determine the content of nitrogen dissolved in the iron samples. Some analyses were also carried out with chemical methods. The following table, Table I, shows a comparison of data obtained with chemical and internal-friction methods. The correspondence between chemical methods and internal-friction

Jan 1, 1964

By Don M. Jackson, Robert W. Howard

Techniques for the epilaxial growth of single -crystal silicon carbide films on silicon were developed. The vapor-phase decomposition and bydrogen reduction of silicon tetrachloride (SiC14) and Propane (C3H8) resulted in clear films of silicon carbide, lip to seveval microns in thickness. The growth took place in a horizontal . silicon epilaxial reactor at 1100°C (pyrometer) at a rate of- 3000Å per minute. Electron diffraction and X-ray diffraction studies demonstrated that the films were single-cyrstal, ß -phase, or cubic silicon carbide. SiO2 film were used to mask areas of the silicon sur-lace in order that the silicon carbide might be grown in controlled geometries. Both n- and p-type films were grown on p-type silicon waters.. Heavily doped silicon films of the same conductivity type as the silicon carbide films were deposited over the silicon carbide in order to affect better probe contact to the structures. when n-type silicon carbide mesas were grown on p-type silicon substrates the de vollage-current relationships between films and substrates were that of junction diodes. These diodes showed a sensitivity to while light ill that the incident light increased forward- and reverse-satro,ation currents, P-type silicon carbide mesas grown on p-type silicon were ohmic rather than rectifying in their voltage -current relationship. No conclusions could he reached concerning heterojunc-tiou rectification in the structure. SILICON carbide is a semiconductor with many interesting properties. It decomposes at temperatures above 2200°C.1 It occurs in two general crys-tallographic forms—hexagonal (a Sic) and cubic (ß Sic)—with the cubic form having a forbidden-gap energy of 2.32 ev and the hexagonal form (specifically the 6H polytype) a gap energy of 2.86 ev.3 It behaves as an extrinsic semiconductor at temperatures approaching 5003C. It has been shown to have a high resistance to radiation damage4 and p-n junctions formed in Sic have been shown to radiate visible light under forward- or reverse-bias conditions. Epitaxial silicon carbide on silicon carbide has been successfully grown through the use of a variety of techniques, such as gaseous cracking of SiCL4 and CC4, nearly all of which require a deposition temperature above 1500°C.6 This paper will cover very recent work on the gas-phase deposition of highly ordered films of silicon carbide on high-quality silicon single-crystal substrates. The films have been shown to ex- hibit junction-rectification properties when geometrically isolated regions are electrically biased with reference to the silicon substrate. There will be no discussion of the mechanism of heterojunction rectification, but the methods of film fabrication, geometry control, and structural evaluations will be covered in detail. Electron diffraction, X-ray diffraction, and diode electrical properties were used to characterize the films and the junctions. GAS-PHASE DEPOSITION OF Sic The techniques for the deposition of silicon carbide films were a logical outgrowth of the standard silicon epitaxial process. The major premise followed was that, for any film to nucleate in an ordered fashion where there is considerable mismatch in lattice parameters (in this case 22 pct), an extremely clean, damage-free substrate surface must be presented to the gas stream. Thus a standard gas-phase HCl etching step was used to prepare the substrates for growth. A minimum of 5 µ of substrate-surface material was removed prior to the deposition of Sic overgrowth films. The techniques used for growing silicon carbide films were those of growing silicon alone, with the added injection of a hydrocarbon gas into the hydrogen and silicon tetrachloride gas stream. The hydrocarbon gases used thus far have been research-grade (99.99 pct) methane (CH4) and propane (C3H8). Propane ultimately gave the best results. The gas flows were controlled through a panel shown schematically in Fig. 1. A hydrogen main stream of 30 liters per min passed through the horizontal quartz-tube epitaxial reactor, while SiC14, C3H8, HC1, and doping gases were injected as side streams. The

Jan 1, 1965

By F. F. Skiba, J. E. Warren

An idealized miscible displacement process in a three-dimensional, heterogeneous porous medium has been studied via experimental computation based on a "Monte Carlo"&apos; model. The macroscopic dispersion which results solely from variations in the permeability of the porous system is related to the scale of the heterogeneity as well as the distribution function for the permeabilities. The interpretation of laboratory data is often subjective and may bt? misleading since ambiguities are not always recognized. Furthermore, an experiment performed on a conventional oil-field core does not yield a valid measure of Macroscopic dispersion for reservoir engineering purposes since the scale of heterogeneity that is significant in the laboratory is not significant in the reservoir. The analysis of field-performance data is discussed and it is shown that a unique characterization of the reservoir can not be obtained from this information alone. A possible method based on a minimum of data, for estimating the spatial distribution of permeabilities in a reservoir is postulated INTRODUCTION Many studies concerned with diffusion and dispersion in porous media have been undertaken because of the potential importance of miscible displacement processes for increasing the recovery of oil. The results from a large number of these studies have been published; in a recent paper Perkins and Johnstonl presented a comprehensive survey of the pertinent literature and excellent appraisal of the "state of the art". In this investigation, dispersion resulting from macroscopic variations in the properties of the porous medium is of primary interest. Dispersion, in this sense, is caused by fluctuations in the velocities of the individual fluid elements as they move through the porous system. This phenomenon is the result of inhomogeneities in the permeability and/or porosity, but it can be amplified by differences in the characteristics of the fluids involved. The objectives of this study are the following: (1) to determine the qualitative manner in which macroscopic rock properties affect the observed dispersion coefficient; (2) to evaluate the possible influence of macroscopic dispersion on laboratory experiments; and (3) to appraise the significance of macroscopic dispersion with regard to reservoir performance. Investigations of this type are essential since many miscible displacement processes, while seemingly understood from a mechanistic point of view, do not behave in a predictable manner under field conditions. Although a plausible explanation is that the process is dominated by the environment, little serious effort has been devoted either to describing the reservoir itself or to determining the probable effect of the reservoir properties on the process. This study is intended to be exploratory in nature; however, it is hoped that it will provide additional insight into the physical problem and that it will suggest areas suitable for further investigation. EXPERIMENTAL COMPUTATION MODEL To limit the observed dispersion to that which results solely from variations in the properties of the porous medium, an idealized process in which one incompressible fluid displaces another identical fluid is simulated. This simulation is achieved by means of a modified Monte Carlo method — by tracking a number of mathematical particles (tracer) through the system according to the steady-state, single-phase velocity distribution. Then the system is characterized by the distribution of the residence times of the particles. Since any number of particles can be injected simultaneously (a true delta-function distribution) and only pressure conditions are imposed on the boundaries, the model is completely determinate. Furthermore molecular diffusion, microscopic dispersion, adsorption and/or reaction are automatically precluded from the model. The heterogeneous medium is represented by a rectangular, three-dimensional array of uniform, homogeneous porous blocks which are randomly arranged; it is assumed that any two opposing faces of the system are held at fixed potentials

Jan 1, 1965

By R. E. Cook

This work presents the development and application of equations of the form developed by Martin1 to describe gravity segregation performance during natural depletion. One-dimensional depletion analyses are applied to several hypothetical reservoirs. Considerable attention is given to the changes in saturation distribution in the dip direction resulting from depletion at various rates. Vertical gas saturation distribution within a sand having vertical permeability is studied to illustrate conditions which provide For low gus-oil ratio production from wells selectively completed away from sand tops, as observed from well performance. Results of performance calculations are shown graphically and illustrate the rate sensitivity of the gravity segregation mechanism and the influence of reservoir geometry and withdrawal distribution. It is shown that for sufficiently high depletion rates gas saturation distribution in the dip direction is characterized by the formation of two discontinuities, or saturation "fronts"; the updip front being the gas-oil contact of the secondary gas cap and the downdip front occurring at a position dependent upon the reservoir depletion rate, withdrawal distribution and reservoir geometry. The gas saturation in the region between fronts is shown to continually increase with time, while that downdip from the lower front remains very low and relatively stable. The effect of increased depletion rate is to reduce the region of stable gas saturation and thus enlarge the portion of the reservoir producing with continually increasing gas saturation. Special attention is given to the performance of reservoirs having sufficient vertical permeability to permit liberated gas to segregate vertically within the sand section before proceeding in the updip direction. It is shown that reservoirs of this type are far less sensitive to depletion rate due to the mechanical control of producing gas-oil ratios afforded by selective well completions away from sand tops. It is shown that gravity segregation performance is adversely af- fected by decreasing reservoir cross-section area in the updip direction. It is also shown that down-dip withdrawal concentrations can restrict gas segregation rates in the dip direction. INTRODUCTION The natural depletion performance of several large producing reservoirs in Western Venezuela has unmistakably shown the significant role that gravity forces play in governing the gas-oil ratio behavior of individual wells and the over - all pressure-production performance of the reservoirs. Analysis and prediction of the natural depletion performance of these reservoirs is of great importance in determining the economics of pressure maintenance operations. In 1957, a method for the analysis of pressure maintenance performance was presented by Martin1 which, in the original and more general form of the equations involved, provides a physically sound basis for the analysis of one-dimensional gravity segregation performance during natural depletion. The work reported herein is an application and extension of Martin&apos;s outstanding developments to a series of hypothetical reservoirs in an attempt to explain the general behavior of the gravity segregation mechanism and the influence of such parameters as depletion rate, reservoir geometry and withdrawal distribution. The study considers two types of flow: "distributed flow", where vertical permeability in the reservoir is zero and fluids flow only in the dip direction while uniformly distributed over the sand thickness; and "segregated flow", where vertical permeability is sufficient to permit gas to segregate against the sand top before proceeding updip. This latter type of flow has been recognized as an important mechanism active in the massive sand reservoirs of Western Venezuela. ANALYSIS OF ONE-DIMENSIONAL DISTRIBUTED FLOW SYSTEMS For an inclined reservoir having zero vertical permeability, the velocities of oil and gas flow at any point in the reservoir can be derived from Darcy&apos;s equations as

By D. W. Lillie

Property changes produced by irradiation of Al-0.4 wt pet Li alloys at 270°C to a burnup of 0.155 pct of all atoms are described. Metallographic evidence of the formation of internal pores and the concentration of gases at grain boundaries is shown. Some conclusions are drawn concerning desirable property characteristics for resistance to radiation swelling. RADIATION induced gases are of great practical significance in nuclear engineering since they affect the behavior of fissionable fuels and control rod materials. In fuels the gases xenon and krypton are the major offenders, producing serious em-brittlement at low irradiation temperatures and gross swelling at high irradiation temperatures. In control rod materials containing boron, the production of helium from the B 10 (n, 0) Li7 reaction produces similar reactions. Since the trend in reactor design is for operation at increasingly high temperatures, the phenomenon of high-temperature swelling by these induced gases has been the subject of considerable recent study. The objectives of such work have been to obtain engineering information and quantitative data on the effects in specific fuels and control rods and to obtain further understanding of the mechanism of gas damage so that more intelligent corrective steps can be made. Analogue systems are often useful for the latter objective and in this case alloys containing Li are suitable in view of the reaction Li6 + n - He4 + He 4. Both products are gases and no serious radiation problem is produced to complicate post irradiation handling. Considerable caution is, of course, necessary in any operations in which tritium release is possible. The present program was initiated to provide a detailed study of the effects of He + H3 generated by irradiation in Li-bearing alloys. The results on Mg-Li solid solution alloys have been reported elsewhere.&apos; This paper presents information on irradiation of an A1-0.4 pct Li alloy in which the lithium was present as highly enriched Li6 in order to maximize the radiation burnup. PROCEDURE The original intent in the selection of the alloy content was to have Li in solid solution at all temperatures. It became apparent, however, that the solubility of Li in A1 was substantially lower than that reported in the original reference consulted.&apos; This was substantiated by the work of Nowak3 who reported solubility of less than 0.01 pct Li at 100°C. The alloy used (0.4 pct Li) was therefore two phase at room temperature. The irradiation temperature was estimated to be about 270° C, and at that temperature all or almost all of the Li would be soluble under equilibrium conditions. The precise state of the alloy under irradiation is not known. Aluminum used was 99.996 pct purity (max. impurities Si 0.002 pct, Mg 0.001 pct, Fe 0.0005 pct, and Cu 0.0005 pct). The lithium was obtained from Oak Ridge National Laboratory; 96.1 + 0.1 pct of the lithium was ~i~, but chemical impurities were 0.25 pct Ca, 0.05 pct Fe, 0.02 pct Na, 0.02 pct Cu, 0.01 pct Sr, and 0.01 pct Ba. The two metals were melted in an alumina crucible in a resistance heated furnace in an atmosphere of helium. A l-in. ingot was cast in an iron mold, machined to %-in. round, hot swaged (350°C) to 0.080-in. round, cold swaged to 0.060-in. round, and finally cold drawn to 0.040-in. round. Four-inch wire lengths were then cut and annealed at 250°C for 4 hr in helium. Irradiations were carried out in a VT hole in the Argonne CP-5 reactor. The wires were held in an aluminum jig, sixteen wires per capsule, and were maintained in a helium atmosphere for maximum heat transfer. Eight wires of pure aluminum and eight of Al-Li alloy were placed in each capsule. Argome Laboratory statements were accepted as establishing flux and exposure levels. These were based on previous experience and flux map-

Jan 1, 1961

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&apos; 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,&apos; 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&apos; 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