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ECONOMICS In the preceding pages you will find an attempt to judge the direction of one phase of the mining industry in Drift, and following that a quick round up of what happened to production in 1958 in Trends. Next, Charles Merrill presents a comprehensive price history for the mineral products of greatest importance, complete with figures for the past 50 years. On the following pages Nathaniel Arbiter and Charles Will Wright take a look at price trend prospects and the cold war in mining, respectively. MINERALS BENEFICIATION Fifty years progress is reviewed as a springboard for a look ahead. In the past decade the art has moved forward, but the author fears that the science is not progressing as promisingly.

Jan 2, 1959

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By C. Gatlin, N. E. Garner

Results of impulsive wedge penetration tests on two synthetic, plastically deforming rocks are presented. Basic data obtained were force-time, displacement-time, and force-displacement curves for the impacts, plus the crater geometry. Wedge geometry and blow frequency were varied over a considerable range. The synthetic rocks consisted of wax-sand mixtures; two waxes of diflerent ductilities were used to provide variable "rock" characteristics. Conventional triaxial tests showed that these synthetic rocks exhibited force-deformation curves and Mohr envelopes quite similar to real rocks, except that strengths were much lower. Measured forces from static penetration tests agreed closely with theoretical values; however, dynamic force values were much higher than the static. These latter disparities are attributed to the viscous nature of the waxes. Thus the utility of these or similar rock models must depend on the scaling of rock viscosity, which is as yet unknown for impulsive loadings at elevated stress states. It appears, however, that some macroscopic, static phenomena may be studied with wax-sand rock models. INTRODUCTION The resistance of solid materials to indentation or perforation by projectiles or other penetrators has been studied by workers in many areas. Despite these efforts no universally accepted laws or formulas are available for describing experimental observations. In the metals field the force-deformation behavior of impacting bodies is often analyzed by the Hertz law for elastic collisions, the Meyer law if plastic deformations occur, or some combination of both.' The similarities of these expressions to empirical drilling formulas of the oil industry are apparent. Beginning with the basic contributions of Simon and co-workers at Battelle,' a number of experimental papers concerning the reaction of rocks to vertical impact have appeared in the U. S. mining and petroleum literature.'-' Most published data have, to date, been obtained at atmospheric pressure, although some early high pressure information was reported by Payne and Chippendale.8 Maurer" has recently utilized available brittle impact data to develop a drilling rate equation based on the experimentally observed proportionality between crater volume and blow energy. His result agreed with earlier efforts by both Somerton, who used dimensional analysis, and Outmans, who used plasticity theory. It has long been known that rocks exhibit different modes of failure depending on the state of stress. The literature in this area is considerable; however, papers by Bredthauer, Handin and Hager,13 nd Robinson", are adequate to illustrate the point. Since rocks flow plastically at certain triaxial stress conditions, the mathematical theory of plasticity has been used to analyze the rock drilling problem. Cheatham'" has altered the wedge identation solution of Randtl to rocks, and has developed useful equations for penetrator forces under a variety of conditions. Outmans" has utilized Hill's solution in a similar manner to develop a drilling rate equation. Both Cheatham and Outmans used the linear Mohr-Coulomb rule to relate rock strength and confining pressure. The actual stress at the hole bottom is not easily ascertained, although photoelastic studies by Galle and Wil-hoit," plus the analytical treatment of Cheatham and wilhoiti8 provide some insight. Consequently it is not clear to what extent the highly idealized rheological model of a perfectly plastic solid can be realistically applied to the rock drilling problem. This paper is the first report on a long range experimental study of crater formation in rocks at elevated stress states. The data presented here are from the first phase of the project. Data obtained from impulsive wedge impacts on two synthetic, plastically deforming rocks are presented. MODEL ROCKS Geologists have long been faced with modelling the behavior of the earth and, as a consequence, have studied scaling problems in some detail.' In general, their main problem is handling the wide disparity between laboratory and geologic time. In our studies the time effects (blow velocity or rate of loading, blow duration, etc.) were essentiafly the same for both. model and prototype, as were were geometry and tooth penetration. Thus application of available scaling laws suggests that Similarity is obtained if the stress-strain curves of model and prototype are similar." For this reason Hubbert and Willis''

By Elmer Weber, W. M. Baldwin

Solid lead obeys a single parabolic weight increase vs. time law. In contrast, liquid lead undergoes three successive parabolic weight increases vs. time laws, the first of which has a low constant relative to the latter two. The conversion times for the change from one parabola to the next decrease with increasing temperature. IN recent reports on the subject,1,2 it was noted that zirconium and titanium scale in air by a complex mechanism. The scale first forming on the metal is protective to the extent that it gives a low constant, K, for Tammann's, and Pilling and Bedworth's parabolic equation: w² = Kt [1] relating weight increase, w, due to chemical reaction of the metal with the air, and time, t. After hundreds of hours of apparent stability in some cases the first scale yields to another that offers little protection to the metal. This transition from one scale to another, from a slow parabolic oxidation reaction to a fast one, was not due to impurities in the atmosphere or incidental effects (changing environment, etc.) but was a specific behavior of the metal itself, the transition occurring at definite times (dependent on temperature) and showing other reproducible traits. In view of this behavior how can long-time service behavior be predicted from short-time laboratory tests, not only in the case of these metals, but in any case? Certainly a systematic study of the type of scaling behavior described above—wherever it is found—would help to answer this question. The present paper is a report on the behavior as it is found in lead—the only metal to the authors' knowledge for which the behavior has been described at all, if inadequately, for our present purpose.* At least four oxides of lead are known, of which one occurs in two allotropic forms. They are ß (red) tetragonal PbO stable up to 486°C;8 a (yellow) orthorhombic PbO stable from 486°C up to its dissociation temperature in air at about 2300°C;9 minium or Pb3O4 which from the dissociation pressure data given in Fig. 1 decomposes to PbO at 540°C in air; lead sesquioxide or Pb2O3,; and lead dioxide or PbO2 which, according to Fig. 1, decomposes in air at 400°C to minium. In view of the high dissociation temperature of PbO, lead will scale up to at least its boiling point. Further, it is known that oxygen is almost insoluble in liquid lead.'V his implies a fair probability that an oxide scale would not dissolve in the molten metal and would afford the same protection to lead in the liquid state as in the solid. All of the oxides of lead for which specific gravity data are available are more voluminous than an equivalent weight of metal or a lower oxide from which they might form, hence the scales will be in compression. Lead oxides are known to be ductile, so it would be anticipated that they would form coherent nonporous scales. It is not surprising to learn, then, that both solid and liquid lead scale according to the Tammann, and Pilling and Bed-worth law.14,15 (Gruhl states that at 600°C and above lead oxidizes linearly with time because of "spitting" of the scale.) The parabolic constants K reported by various investigators3,14-16 are badly scattered, however, as shown in Fig. 2. The oxides formed on solid lead were described as being reddish-brown but were not chemically identified by Pilling and Bedworth.15 Gruhl's descripdin³ of the appearance of the scales On his liquid samples indicates that a (yellow orthorhombic) PbO is formed initially on the specimens but gives Way eventually—at least at temperatures below 486 °C— to .ß (red tetraunal) PbO, and that below 540°C minium—Pb3O4 :is firmed at an even later time as an overlay on either the red or yellow PbO. Fig. 3 is a graphical interpretation of Gruhl's description. Gruhl does not indicate any change in the parabolic scaling rate as yellow PbO converts to red. He does indicate that minium reduces the scaling rate, al-

Jan 1, 1953

By John Brownson

Ge-Si N-N heterodiodes hare been built recently which show promise as high-speed logic devices. Low-resistivity germanium is deposited on silicon substrates held at temperatures above the germanium melting point and an alloyed heterojunction formed. The diodes are fabricated from this material using conventional mesa techniques. Over-all device qualify has been greatly improved by the use of epitaxial silicon substrates, that is, a subsirale consisting of a film of thin, high -resistivity silicon on a thicker Piece of low-resistirily silicon crystal. A semimpirical device design equation has been devised which predicts switching performance fairly well within the range of resistivitics and geometries employed. Switching times 01 0.9 ns and PIV 's of —20 v are typical of the better 10-ma diodes. Switching times as low as 0.5 ns have been observed for 10-ma diodes and as low as 2.8 ns for 200-ma diodes. With further development it should be possible to improve switching speed by a factor of four. IN our laboratory, Ge-Si heterodiodes have been built recently which show promise as high-speed logic devices. The diodes have been built using a process reported in some detail in an earlier publication.' The process in short involves alloying a thin film of low-resistivity germanium into a silicon substrate. the germanium having been transported and deposited by the well-known Theuerer halide reduction process.2 This process contrasts with that reported earlier by Oldham who used an essentially conventional direct epitaxial deposition technique.3 Oldham's process, unlike ours, requires cleavage of the silicon sample inside the reactor furnace the instant prior to deposition. Our process has the advantage of yielding large-area macro-scopically plane heterojunctions. Heterodiodes in general have several interesting properties. Without attempting to summarize the theory of heterojunctions.4 two of these properties which have direct relevance should be mentioned. First, N-.V and P-P heterojunction diodes rectify alternating current. Provided that either the band gap or the electron affinity of the two materials is different (which in general is the case), electronic barriers will exist in the junction band structure. When the device is sufficiently forward-biased, the barriers shift so as to permit current flow, and when it is reverse-biased. the barriers block current flow. Second, for N-N and P-P heterodiodes. the foward-conduction process involves majority carriers only. Consequently. when such a device is turned off. there is no minority-carrier storage and hence the diodes switch on and off quite rapidly. As we have reported earlier. N-P and N-N Ge-Si heterodiodes have been built in this laboratory. As one would predict from theory, the N-P heterodiodes were rather slow in turning off while the N-N's were quite fast. Similarly, the turn-off time of the N-P's increased rapidly with forward current while that of the N-N's was independent of forward current. Both N-N's and N-P's were moderately photosensitive. Photocurrents resulting from normal room illumination were as high as 1 µa at 1 v for small-area devices. The most disappointing parameter of the early N-N devices was reverse leakage.' The reverse characteristic was invariably "soft" and leakage at only several volts reverse bias was intolerable. The reverse characteristic was greatly improved by using higher-resistivity silicon substrates. Leakage becomes large at voltages about one third of the avalanche voltage one would expect of a P-N homo-junction formed on silicon of the same resistivity. Thus leakage could be reduced to reasonable limits by using unconventionally high-resistivity silicon. Medium-power diodes formed on 30 ohm-cm substrates leaked typically 15 to 50 µa at 100 v reverse bias. The use of high-resistivity silicon substrate material, however, created a new problem. In order to have an acceptable forward-conductance characteristic. the area of the diodes had to be increased. With this increase in area, the capacitance increased. Switching time for N-N heterodiodes is essentially a linear function of capacitance. Thus when the resistivity was raised. so was the switching time. A SEMIEMPIRICAL HETERODIODE DESIGN EQUATION As a result of our experiments with a limited range of diode geometries and resistivities. a semi-

Jan 1, 1965

By E. Wainer, K. D. Burnham

A wet beneficiation technique for producing wollas-tonite from its ore in high yield and purity has been evaluated in a pilot plant operation at the rate of 75 tons per month. Finely crushed, unsized wollastonite ore mixed with water is passed through a high in tensity oscillating wet magnetic separator of unique design and in a single pass over 90% of the wolla-stonite exhibiting a crystal purity of 99.8% is obtained irrespective of size of feed fraction. Thereafter, the material is processed by closed cycle standard wet milling and classification techniques to yield a 1µ size product, though any mesh size up to and including 50 mesh may be obtained, if desired. Costs appear to be significantly lower than those available from dry processed techniques. Wollas tonite made by this unusual wet process appears to have potential utility in the following fields: ceramics, paints, plastics, paper, organic finishes, reinforcement of portland cement items, controlled porosity refractory ceramic foams, cinder and concrete block paint, and the like. The 1µ and certain chemically processed varieties of wollastonite may have unusual utility in the paper industry both as a filler and as a coating material and in the organic finish industry. Extensive deposits of wollastonite ore equivalent to an average tenor of 50% to 60% of this latter mineral in easily separable form exists in and around Essex County in northern New York State in reserves of the order of several tens of millions of tons. While important portions of these deposits are susceptible to open pit mining techniques, one operation near Wills-boro, N.Y., involves tunnel mining and dry milling and beneficiation techniques. This mill and tunnel mine is presently being operated by The Cabot Corp. and a variety of particle sizes are now sold into markets in the ceramic, paint, plastic finish, floor tile and in similar fields in substantial tonnages on a repetitive basis. Serious investigation and study over the past several years has indicated that, outside of the obvious economies of open pit techniques for mining purposes, wet beneficiation and milling procedures applied to the ore not only represent a potential for greater economies in the production of a superfine finished product but yields products of improved properties exhibiting increased market potential which may not be available from the dry ground product. The Lewis and Deerhead deposits, controlled by the Adirondack Development Corp., appear to be identical to the Wilisboro deposit. Utilizing ore taken from the Lewis and Deerhead deposits, a pilot plant process for the wet beneficiation, milling and classifying of wollastonite ore has been operated for several months. After scalping a marketable garnet product from a minus 16 mesh dry crushed feed on a high intensity roll magnet the balance of the material is then roll crushed in a closed cycle until it will pass a 50 mesh screen. The product constitutes the feed of the wet magnetic separator. The heart of the new beneficiation process is a cyclically operated wet magnetic separator which exhibits the unique feature that unsized feed is easily handled. Product yields of higher purity are equal to that obtained with dry magnetic separations which use closely sized dry ore and multiple passes, but only produce wollastonite of about 98% mineral purity as determined by sink float techniques. It was anticipated that the wet processing through the grinding, milling and classification stage would yield a low cost 1µ ground product which should make available greatly increased applications for the mineral beyond those presently enjoyed. The improved purity was also expected to provide coarser sizes which might be utilized as a raw material for chemical modification which again would expand the uses of wollastonite. The evidence thus far collected appears to indicate that this premise may be expected to be fulfilled. There are on the surface of wollastonite particle sites at which cheinical reactions may occur1. It is believed that wet ground material provides a better base which will allow wollastonite a deeper entree into the field of chemical raw materials. Wet ground at 20µ and finer permits with certainty a number of chemical reactions, some of which are mentioned later in this article. While well crystallized wollastonite makes up the majority of the ore, the balance consists mainly of very weakly magnetic diopside of the hedenbergite-

Jan 1, 1965

By L. S. Allen, R. L. Caldwell, W. R. Mills

Borehole models used in the study of nuclear well logging are reviewed and the merit of heterogeneous us homogeneous formation simulation is discussed. .A heterogeneous model for simulating sandstone formations of variable porosity is described. Simulation adequacy was checked by steady-state and pulsed-neutron measurements. INTRODUCTION In the course of developing new methods of nuclear well logging, the problem of testing new logging instruments under controlled conditions always arises. This testing is usually done in wells of known lithology, porosity and fluid saturation, or in laboratory test facilities which simulate the borehole environment. Although the former approach is possibly more satisfying, it is frequently difficult or inconvenient to find wells with enough variation in the cited parameters for a truly comprehensive study, On the other hand. laboratow- test facilities can simulate a wide variety of formation and borehole conditions if care is exercised to maintain adequate simulation under all conditions. Workers concerned with the development of nuclear well logging methods have reported several types of research facilities in the past. Tittle, et a1 used cubical tanks filled with Ottawa silica sand to study the steady-state behavior of thermal and epithemal neutrons in simulated sandstone logging environments.1 In addition to the effects of fresh vs salt water, a wide variety of casing sizes and compositions were investigated. Tittman also used a large tank of Ottawa sand to measure the slowing down length of sio2;2 for making the same measurement in CaCO3, however, an assembly of solid Vermont marble blocks was used. More recently a very useful and carefully planned test pit for nuclear logs was constructed under the auspices of the API.3 This facility consists of three massive limestone sections, each 6-ft thick and more than 5 ft in diameter. The blocks are buried, one on top of the other, in a concrete- lined pit having a total depth of 24 ft. Each section is made of a different limestone to achieve porosity variation, the selection being Carthage (2 per cent), Indiana (19 per cent) and Austin (26 per cent). The blocks are traversed by a 7 7/8-in. diameter borehole and are saturated with fresh water. Great care was taken to insure total saturation of the stone. Homogeneous mixtures and materials have not been used exclusively for simulating earth formations. Tittle, et a1 4 showed that a heterogeneous lattice of water and graphite could be used to simulate Liquid furfural with very little effecton measured thermal and epi thermal neutron distributions. Subsequently, a lattice-type model for simulating limestone earth formations was designed and built by Berry This limestone model was constructed of 7/8- x 11/4- x 36411. marble rods glued together with a plastic resin to form a 36-x 42- x 42in. cube. The cube was honeycombed vertically with 7/8- x 7/8- x 3641-1. holes for porosity and had a 111/2-in. diameter hole in the center to serve as the borehole. Lower porosities were simulated by placing marble rods in the square holes. The finished cube was used with the borehole vertical and set in a tank to hold liquid for filling the holes in the rock matrix. A second type of heterogeneous borehole model has been proposed by Kukharenko, et a1.6= In this concept the model is composed entirely of solid material. The hydrogen equivalent of formation fluids is simulated by making the model of alternating layers of dense rock and celluloid. Additional hydrogen is included by drilling vertical holes in the rock sections and filling them with solid forms of hydrogeneous material. The volume of the holes is equal to the volume of the celluloid layers, so an axial and radial dispersion of the hydrogeneous material is thus obtained. One such model was composed of alternate 50 mm-thick sand layers and 2 mm-thick celluloid sheets. Approximately 200 appropriately spaced plastic tubes were used in each sand section. The plastic tubes were filled with paraffin for additional hydrogen concentration. This arrangement yielded a model with a water-equivalent hydrogen concentration of 10 per cent. Experimental data taken in this model and in a model consisting of the same material but homogeneously dispersed showed that the heterogeneous system adequately

Jan 1, 1966

By R. Simon, D. J. Graue

This paper presents correlations for predicting the solu-lility, swelling and viscosity behavior of CO2-crude oil sys8i.m~. The correlations were developed from experimental data obtained by the authors. These data are also presented. The data were determined by measuring the properties of mixtures of CO, and nine different oils. Experiinental conditions covered a range of 100 to 250°F and pressures up to 2,300 psia. Properties predicted by the correlations have average deviations, expressed as per cent of experimental value, of 2 per cent for solubility, 0.5 per cent for swelling and 12 per cent for viscosity. INTRODUCTION Interest in CO2 injection as an oil recovery process has led to the development of performance prediction methods which can be applied to specific reservoirs.1 iS To use these performance prediction methods, it is necessary to know the solubility, swelling and viscosity properties of CO2-crude oil mixtures at reservoir conditions. Some information on these properties has appeared in the literature; however, this information did not cover the range of different oils and conditions needed to prepare generalized correlations for reservoir engineering purposes. Consequently, an experimental program was undertaken to collect the data needed. The data obtained and the correlations developed from the data are described in the following sections of this paper. SOLUBILITY OF CO2 IN CRUDE OILS CO2 solubility data in the literature come from six principal sources. The solubility prediction method of Welker and Dunlop3 is limited to 80F. The information in Ref. 4 is of two types: the first includes binary and ternary mixtures of CO, and light hydrocarbons (C1 to C6), and the second gives data for CO1 and heavy hydrocarbons for a temperature range of 40 to 90F. Ref. 5 contains a KCO2 chart for systems whose convergence pressure is 4,000 psia. The KCO2's are based mainly on CO2-natural gas mixtures. Poettmann's work covered CO2 solubility in one condensate and one crude oil6,7 Ja-coby and Rzasa measured CO? solubilities as a function of pressure and temperature for two natural gas-absorber oil mixtures and two natural gas-crude oil mixtures.'8 CO, concentration in these four systems was fixed at 5 mol per cent. The work reported in this paper extends CO, solubility data to a variety of different crude oil types in a temperature range from 110 to 250F and pressures up to 2,300 psia. The experimental procedure used by the authors to obtain the solubility data consisted of combining known amounts of pure CO, and crude oil in a visual cell at a fixed temperature and measuring the bubble point of the mixture. Measurements were made for a total of 40 different CO2-oil mixtures and the results are shown in Table 2. The mixtures included nine different oils (seven crude oils and two refined oils) whose properties are listed in Table 1. All nine oils had vapor pressures less than 1 atm at the experimental temperatures. Consequently, analysis of the bubble-point vapor showed a CO, concentration over 99 mol per cent. At no time during these experiments was a second, more dense, liquid phase observed. The solubility correlation which was developed from the data in Table 2 is presented in Figs. 1, 2 and 3. In these figures, solubility is expressed as xco2 the mol fraction of CO, in the CO2-oil mixture. Fig. 1 shows solubility as a function of CO2 fugacity6 and temperature. Fig. 2 shows the same solubility data expressed as a function of saturation pressure and temperature. The solubility shown in Figs. 1 and 2 is for an oil whose UOP characterization factor is 11.7. UOP characterization factors of crude oils can be determined from Ref. 10 if the viscosity and APT gravity of the oil are known. Fig. 3 gives the solubility correction factor for oils whose UOP characterization factors differ from 11.7. The solubility correlation in Figs. 1, 2 and 3 predicted

Jan 1, 1966

By C. E. Kemp, A. B. Dyes

Results of a field research project on the thermal recovery of oil by movement of a combustion front are presented. This field test was conducted in the South Belridge field, This The war paitern was a Southsing1e 2.5-acre five-spot pattern in the 700-ft deep Tulare sand. Results of this project indicate the technical feasibility of producing high viscosity, low-grallity crude oils by thermal means. It was demonstrated that heavy oils could be moved rapidly over considerable distances by thermal drive, and that high percentage recoveries of oil could be effected. The bulk of the oil recovery came after arrival of the burning front at a production well. However, rapid corrosion and high-temperature failure of conventional pipe and equipment both below and above surface occurred. Stainless steels gave more satisfectory performance under these conditions than did conventional steels. Oxygen was seldom observed in gas from wells ahead of the burning front, and it appears that the front was continuous throughout the life of the experiment. INTRODUCTION During late 1953 and early 1954, industry-wide attention was focused on the thermal recovery of oil by movement of a combustion front through an oil zone. Two separate Oklahoma field tests were described in publications by Kuhn and Koch, and Grant and Szasz. To obtain basic information needed for making engineering and economic appraisals of commercial recovery of heavy oil by this thermal recovery method, a new field research projecta3,4 was started May 31, 1955. Twelve oil companies contributed to this project with General Petroleum Corp. as operator. Since combustion recovery experiments* with heavy oils in other areas had been conducted in small patterns,"' an important purpose of this test was to determine whether the process could be operated in a pattern of near-commercial well spacing. The south Belridge field, located 30 miles north of Taft, Calif., was chosen because its oil sands are similar to many heavy oil sands which typically have low primary recovery and leave a large amount of oil in place. such fields are not particularly suited for common secondary recovery methods. DESCRIPTION OF TEST SITE The test interval was a Tulare sand at a depth of about 700 ft. Nine test wells were drilled, cored and completed from Oct., 1955, through Jan., 1956. The initial pattern shown on the map, Fig. 1, consisted of an injection well (II)', four producing wells (1P-4P), and four observation wells (IT-4T). An old well (81) was also recompleted for use as an observation well. The area enclosed by the original four production wells was 2.5 acres; the distance from the injection well to each production well was 233 ft. During the combustion period, Well 5P was drilled to replace Well 2P, and Well 6P was drilled to replace Well 3P. The new wells were 25 ft beyond the old production wells along a diagonal from the injection well, and resulted in an increase in pattern area to 2.75 acres. Isopachs are shown in Fig. 1. The average thickness of the oil sand in the test pattern was 30 ft. Fig. 2 presents two cross sections through the test pattern. Oil sand is represented by white and claystone by gray. The dashed lines indicate layers of conglomerate grading to claystone. The sand thickness was fairly uniform throughout the test pattern except in the 1P area. The sand body dips gently from the northwest to southeast, about 3 degrees from horizontal. The sand is unconsoli-dated, and grades from very fine material to pebbles as large as 2 in. in diameter. Table 1 presents the average initial properties of the formation. The in-place porosity of 37 per cent was estimated from the porosity of coke-consolidated cores taken after combustion. Original core analyses data were adjusted to 37 per cent, giving pore volume saturations of 60 per cent oil, 37 per cent water, and 3 per

By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.' At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By W. F. Domis, F. von Gemmingen, R. W. Whitmore, F. Garofalo

Constant-load creep-rupture tests at 1100°, 1300° and 1500°F were made on a Type-316, 18 Cr-8 Ni-ZMo, austenitic stainless steel to determine the relationship between ruptzire life and other aspects of creep behavior, The test program was designed on a statistical basis to check the variability of various creep properties and to determine emprically the dependence of minimutn creep rate and ruptzire life on initial stress, The dependence of the rupture life, tn, on the initial stress, a,, is found to be related to the stress dependence of the wrinimum creep rate, i,, and secondary creep strain, The instabilities or breaks found in the conventionual log - logt, plots can be traced to either a change in the linear dependence of log i, on log a, or to a change in secondary creep strain. In the alloy tested, rupture is found to be predowmanantly of the inter crystalline type, For this material, the secondary creep strain is -found to depend on the nature of the grain boundary precipitate, which affects grain boundary migration. It has been shown for a variety of metals and al tested at elevated temperatures under creep conditions that the empirical relationship exists between rupture life, tr, and minimum creep rate, i,. This relationship, in which C and a are in some cases independent of stress or temperature, shows in a general way that creep rupture depends on creep behavior prior to tertiary creep stage. To determine more fully the factors which control creep rupture requires, therefore, more knowledge of the relationship between rupture and creep behavior. To obtain such information, constant-load creep-rupture tests have been made on a Type-316, 18 Cr-8 Ni-2 Mo, austenitic stainless steel at 11000, 1300°, and 1500°F. These tests were designed on a statistical basis to determine the variability of the various creep properties measured and to determine empirically the stress dependence of minimum creep rate and rupture life. As a result of this work, various empirical relations have been established defining more closely the factor, C, in the relation between rupture life and minimum creep rate. This factor is found to be proportional to the amount of strain during secondary creep. The variation of secondary creep strain with rupture life and temperature is determined and its effect on rupture behavior discussed. The variability in minimum creep rate and rupture life is also dis- cussed and the dependence of these quantities on initial stress is interpreted. TEST MATERIAL AND TEST PROCEDURES The material tested is an austenitic stainless steel, AISI Type 316, of the following composition: C, 0.07 pct; Mn, 1.94 pct; P, 0.01 pct; S, 0.021 pct; Si, 0.38 pct; Cr, 18 pct; Ni, 11.4 pct; Mo, 2.15 pct; All 0.003 pct and N, 0.043 pct. The material was received as a hot-rolled 0.5-in. diam bar which was sectioned into 3.25 in. long blanks. Each blank was heat treated by holding 1/2 hr at 2000° F followed by water quenching. A 3/8-in. coupon was removed from each heat-treated blank and the microstructure was examined, the grain size determined, and the hardness measured. The microstructure was found to be uniform from blank to blank and the grain size was found to range from 4 to 6 ASTM numbers. Hardness, measured using a 20-kg load, varied between 127 and 148 Vpn. Tensile creep-rupture specimens having a 0.25 in. diam within a 1.5-in. reduced section were machined from the heat-treated blanks. Constant-load tests were made on these specimens at 1100°, 1300°, and 1500 F. Six specimens were tested at each stress level. Three creep-rupture machines were employed for tests at each temperature, two specimens being tested in each machine for each stress level. To minimize any effect due to local inhomogeneities along the length of the as-received bar the specimens were randomized before test. Each specimen was tested to rupture and in most cases an autographic extension-time curve was obtained. For very low stress levels at 1500°F no auto-

Jan 1, 1962

By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.

By M. A. Childers

Recent work with controlled laboratory tests.' field experience and a new analytical approach indicate that casing centralization, pipe movement and relative rheological properties between the mud and cement (yield point and density) are the three controlling factors in successfu1 primary cementing of dual casing. Turbulent flow has been demonstrated to be unnecessary under the severe displace ment conditions of parallel dual strings of casing. Simultaneous reciprocation of dual casing in directionally drilled boreholes is highly dependent on centralization and on the rapid initiation of pipe movement once the casing has been run to total depth. Successful cementing of 30 out of 32 dual, 3%-in casing wells substantiated these conclusions. A review of 15 dual, 3 1/2-in. casing wells completed prior to the adoption of these principles disclosed only one success. Mathematical and graphical techniques permit the engineer to analyze and anticipate the success or failure of a cementing operation. Standoff, mud displacement and reciprocation can be analyzed mathematically and planned in deep, directional or straight boreholes by review of annular geometry, relative rheological properties between the mud and cement, and forces caused by caring weight, functional drag and differential sticking. Introduction The objective in primary cementing is to displace the drilling fluid with cement that will bond to the formation and casing to prevent communication through the annulus. The predominant cause of failure appears to be channels of gelled mud that remain in the annulus after cementing.1 '* Past investigations have noted many procedures that could improve the displacement process.2-' These procedures include centralization, chemical preflushes, mechanical mud cake removers, controlled flow rates in certain regimes, pipe movement an1 control of mud and cement properties. Not until recently have the effects of many of these procedures been isolated so that their individual importance could be determined. In a recent paper,' a comprehensive and analytical laboratory study of various factors controlling the displacement process concluded that there are three major factors in obtaining complete mud displacement by the cement slurry. 1. Good relative rheological properties between the mud and cement. The cement should be heavier and have a yield point and plastic viscosity higher than the mud being displaced. Buoyancy forces often can dominate the displacement process. 2. High degree of standoff or centralization. The more centered the casing, the greater the likelihood of complete mud displacement and removal. 3. Pipe movement obtained by rotation or reciprocation. Often unfavorable rheological properties between the mud and cement, and poor standoff can be compensated by pipe movement. This work demonstrates the compatibility of the latter concepts with field results extended to the more severe dual casing displacement process. Early Experience With Dual 3'/t-In. Primary Cementing Early slim casing completions in the West Delta Block 73 field, offshore Louisiana, included 17 dual 3%-in., 3 single 3% -in. and 1 dual 2% -in. casing installations. Table I provides data on these earlier wells. Usually, common Class A cement was placed across the pay zone and 12 percent gel cement was placed to a height of 500 ft above the highest productive sand. Centralizers (6%-in. OD maximum expansion) were placed two or three per joint on both casing strings from total depth through the completion intervals and at least one per joint for the remainder of the cement sheath. A number of techniques and procedures were attempted to improve cementing success. Casing was run simultaneously or separately with a number of mud conditioning and circulating techniques. Mechanical aids such as cement bonders, slmiding sleeves, turbulizers and various sizes and strengths of centralizers were used. Common and gel cements were mixed with fresh or sea water with a number of different additives to control retardation and dispersion. Cements were thinned and mixed at high rates to try to induce turbulent flow in the annulus. On one well the "slow flow" method was used." Perforating was accomplished with a jet orienting gun. Unsuccessful cement jobs were indicated by production of extraneous fluids or by pressure communication between zones. On test, five wells flowed water, four flowed sand and six had pressure communication with the other string or the 10%-in. casing. A total of 25 remedial squeeze ce-

Jan 1, 1969

By R. G. Davies

The activation energy for steady state creep above -500°C is observed to be independent of the applied stress although it varies from -67 kcal per mole at 2 at. pct Si to -100 kcal per mole at 11 at. pct Si due to changes in crystallographic order. The magnitude of the activation energy, by comparison with Fe-A1 alloys, indicates FeSi type of order in certain alloys. X-ray results confirmed the presence of FeSi type of order. It is proposed that dislocation climb is the rate controlling mechanism for all the alloys. It has been demonstrated that when a diffusion mechanism is the rate controlling process, the formation of a superlattice in brass,1 Fe3A1,2 Ni3Fe,3-5 and Feco6 1) increases the creep resistance, and 2) increases the activation energy for steady state creep. Furthermore, a study of creep in Fe-15 to 20 at. pct A1 alloys7 has revealed that as the alloy composition approaches the long-range order field, there is an increase in the activation energy for steady state creep which is thought to be due to an increase in short range order. Fe-A1 and Fe-Si alloys are similar in that they both form the DO3 superlattice in which aluminum or silicon atoms have only iron atoms as first and second nearest neighbors. There are, however, two important differences between the alloy systems: 1) The superlattice formation at -350°C commences at -10 at. pct si8 as compared to -20 at. pct Al,9 and 2) Fe-A1 alloys form a FeAl (B2 type) super-lattice where aluminum atoms have all iron first nearest neighbors even at 22 at. pct Al, but so far no similar FeSi superlattice has been observed. With the similarity between Fe-A1 and Fe-Si alloys in mind, alloys of iron with 2 to 11 at. pct Si were examined for variations with composition of the activation energy for steady state creep and of creep strength. The temperature range of greatest interest was above 1/2 TM (TM is the absolute melting temperature) where it is usually observed that diffusion is the rate controlling process. A subsidiary X-ray investigation of the Fe-Si system was undertaken in an attempt to define the position of the order-disorder boundary as a function of cooling rate. EXPERIMENTAL DETAILS a) Creep. Specimens whose gage length was 1.5 in. and with a cross-section 0.04 by 0.08 in. were strained in tension by a lever-arm arrangement, and the load was adjusted between each creep test to maintain constant stress. The apparatus and mode of operation have been fully described in a previous publication.7 As each test produced a creep strain of 0.25 pct, the variation in stress during the test was negligible. Creep strain was measured at the end of one of the alloy steel grips by a displacement transducer with the out-of-balance potential being recorded on a variable speed recorder. The full-scale deflection of the recorder could be varied in steps to give limits of sensitivity of between 0.1 and 0.001 pct creep strain. The alloys, Table I, were made available by the Metallurgical Department, National Physical Laboratory (N.P.L.), england,10 and by the Research Department, General Electric Co. (G.E.), Schenectady, N.Y. They were hot worked at -850°C, warm worked at 550° to 650°C, and recrystallized in vacuum at -750°C to give a grain diameter of -0.1 mm. All the alloys had a very low impurity content; those from the N.P.L., for which a complete analysis is available,&apos;&apos; show carbon less than 0.026 pct, manganese less than 0.006 pct, and oxygen plus nitrogen less than 0.0024 pct. b) X-ray Procedure. A General Electric XRD-5 X-ray set with a focussing lithium fluoride mono-chromator in the diffracted beam, and a pulse height analyzer to eliminate harmonic wavelengths of the cobalt radiation, was used to investigate the structure of several very fine grained (grain diameter <.01 mm) Fe-Si alloys after the following heat treatments: 1) Quenched from 700°C, 2) slow cooled from 650°C (-40°C per hr), and 3) very slowly cooled from 400° to 100°C (10°C per hr with a 24 hr anneal every 100°C). The method of obtaining the diffraction pattern over the range of 20 from 15 to 45 deg was to count for at least 100 sec every l/3 deg with a slit subtending 1 deg in 20 at the focus; the probable counting error was less than 2 pct.

Jan 1, 1963

By E. Lifshin, R. E. Hanneman

QUANTITATIVE applications of the electron micro-beam probe frequently involve the evaluation of complex mathematical expressions and/or the analysis of large amounts of experimental data. The purpose of this communication is to describe briefly a versatile and useful computer program system that is applicable to analyze rapidly a wide variety of practical microprobe problems. This system consists of a group of ten FORTRAN programs that can be stored on tape, cards, or in the memory disc of the computer. These programs, or links, can be run individually or in any prespecified sequence without interrupting the operation of the computer or without destroying information which is being transfered from one link to another. For the program system described here a GE-235 computer with disc storage was used, so that the DCHAIN method of program linking was employed. Included in the library are programs to: 1) initiate analysis of a new set of data and transfer control between all other programs in any predetermined manner; 2) generate theoretical calibration curves of composition vs relative intensity; 3) generate empirical deviation parameters from least-square fits of experimental calibration data from standards of known composition; 4) convert raw X-ray data to corrected composition; 5) determine inter diffusion coefficients by Matano analysis of con centrat ion -distance data on a uniaxial diffusion couple; 6) determine activation energies and frequency factors of temperature-activated processes such as diffusion; and 7) generate calibration curves for determination of the thickness of thin films using microanalysis. A detailed description of these computer programs and their underlying principles is available on request from the authors."&apos; The first program to generate theoretical calibration curves of corrected relative intensities vs composition uses the Poole and Thomas atomic number correction&apos; and the Philibert absorption factor&apos; with a voltage-dependent mass absorption coefficient for electrons in the alloy. A modified Castaing fluores- cence correction is also used which includes the effects of both Ka and KO radiation and over voltage.&apos; Once the theoretical curves have been calculated in 1 wt pct intervals, these results are least-squares fit to obtain Ziebold deviation parameters&apos; which are stored in COMMON in the computer memory. The net discrepancies between the original theoretical calibration curve and the regenerated curve using the Ziebold parameter are computed. Although this link is explicitly written for K-K fluorescent interactions, it can be applied to K-L, L-K, and L-L interactions as previously disc~ssed."~ Similar programs have also been written to utilize the Wittry fluorescence correction, Birks combined corrections, and various other corrections.&apos; These modified programs have proved to be quite useful for quantitative comparisons of the results of the various theories. The program for conversion of raw X-ray data to corrected composition includes corrections for drift, backround, and instrumental dead time. The corrected intensities are converted to composition by use of the Ziebold equation"2 and parameter obtained from the program system. The results can be obtained for either atom or weight fractions. In addition to accurately computing interdiffusion coefficients the Matano analysis program calculates least-square smoothed values of concentration, concentration gradient, and curvature for each point on the raw input concentration profile. In order to obtain high accuracies a unique method of performing a least-square polynomial fit to incrementally advancing profile segments which overlap is used.&apos; This program has been successfully modified for use in ternary diffusion problems3 and can readily be modified to handle analysis of diffusion profiles which include phase boundary discontinuities. This link is generally applicable to analysis of interdiffusion data obtained by other techniques as well as by the microprobe. The primary function of the next program is to least-squares fit experimental diffusion data to the normal Arrhenius function: D = Doexp(-Q/RT), to obtain values of Do and Q. In addition the probable error and one, two, and three u statistical confidence limits of DO, Q, and log D are evaluated. This program is also directly useful for analysis of any other simple temperature-activated processes including conductivity, and certain deformation and chemical processes. The program to generate calibration curves for film-thickness determination using the microprobe is based on a numerical integration of the equation derived by Cockett and ~avis.&apos; Values of film thickness obtained by this program for copper on various substrates are in good agreement with measurements made by other techniques. Versions of the above program system have been prepared for use with or without a remote teletype connection to the computer for processing on either a real-time or time-share basis. The instrumentation coupling a microprobe to a teletype for automatic data collection and analysis by the presently described program system has been reported elsewhere by the authors.&apos; If teletype equipment is not used to communicate with the computer, standard methods of card reading and tape reading can be used. In either

Jan 1, 1967

By E. Douglas Sethness

The uranium industry is booming. In Texas alone, there are about 22 different companies with active exploration programs. Twelve solution mines have been permitted; three surface mines have been authorized; and two mills are currently in operation. However, the industry also has a problem, and that is the disposal of radioactive wastes. Over the past several years, stories concerning nuclear wastes have appeared frequently in the news. One of the most frequently cited cases occurred in Grand Junction, Colorado. In 1966, after ten years of investigations, the U. S. Public Health Service (PHS) discovered that tailings from a uranium mill were being used as fill material and aggregate for local construction purposes. It was estimated that between 150,000 and 200,000 tons of material had been removed and used under streets, driveways, swimming pools, and sewer lines. In addition, tailings had been used under concrete slabs and around foundations of occupiable structures. Further studies prompted the Surgeon General to warn that the risk of leukemia and lung cancer could be doubled at the measured radiation levels. More recently, the L. B. Foster Company discovered that its building site in Washington, West Virginia, was radioactive. While digging a foundation, the ground erupted and a ball of fire 30 feet high shot out. Evidently, the dirt was laced with radioactive thorium and zirconium, a potentially explosive mixture contained in a Nigerian sand which had been used by the previous site owners in the manufacture of nuclear fuel rods. Just this month we have read about legal suits to stop exploration for a nuclear waste disposal site in Randall County, Texas. The U. S. Department of Energy is trying to locate a deep underground nuclear waste depository for final burial of over 76 million gallons of high-level wastes. The problem is acute, the wastes are accumulating at a rate of about 300,000 gallons per year. Nor do these numbers include the spent fuel elements from nuclear power plants that are in temporary storage facilities. Fortunately, public awareness of these and other related issues is high. Unfortunately, the differences in the waste products from the nuclear fuel cycle are not always apparent to the general public. There are two distinct types of radioactive wastes: "high-level", which consist of spent fuel or wastes from the reprocessing of spent fuel; and "low-level", which, in general, are by-product wastes. There are numerous non-technical definitions that can be applied to help the layman differentiate between high-level and low-level wastes. For this latter purpose, it is best to think of them in terms of what we can see and feel. In general, high-level wastes are physically hot and can cause acute radiation sickness in a short period of time. Low-level wastes are not hot, but may cause chronic health effects after long exposure. The wastes which we are concerned with in the uranium mining and milling industry are low-level wastes. As recently as ten years ago, there were very few controls or regulations governing tailings disposal methods. At the same time, mine reclamation was not enforced through either state or Federal laws and the long-term viability of abandoned tailings ponds was not assured. The regulatory climate has changed significantly in the last decade, however. The low-level radioactive wastes generated by uranium mining and milling are generally contained in a tailings pond. Approximately 85-97% of the total radioactivity contained in uranium ore is present in the mill waste that goes to such tailings ponds. The isotope Radium-226 is probably the most potentially harmful radioactive parameter in the ponds. Radium emits gamma radiation and is also an alpha particle emitter. Because gamma radiation is very penetrating, it presents a potential health problem when a source is located external to the body. Gamma radiation will go through the body, causing damage to each cell encountered on the way. Although alpha particles have very little penetration capability, they can cause extensive cell damage. For this reason, alpha particles are a problem after inhalation or ingestion. Radium creates a health hazard by both of these mechanisms. Radium decays to radon gas which can be inhaled and serve as an alpha particle emitter. Additionally, radium is very soluble and readily enters the natural hydrologic cycle if allowed to leach from a tailings pond. With a half-life of 1620 years, radium has plenty of time to be taken into the food chain and end up in our bodies, emitting alpha particles. Because the potential health problems are better understood today than ten years ago, and because the Nuclear Regulatory Commission (NRC) has developed increasingly stringent government regulations, the uranium mining industry applies a high level of technology to the disposal of nuclear wastes. In most cases, low-level radioactive wastes are disposed of at or near the site where they are produced. There are six commercial burial grounds for low-level wastes, but it would not be economical to ship all mine or milling wastes to these sites. The on-site disposal methods most often used are ponding

Jan 1, 1979

By E. Miller, K. Komarek, W. Johnson

The activity of aluminum in solid Cr-A1 alloys has been measured by an isopiestic technique between Cr-A1890&apos; and 1126" and 13 and 80 at. pct Al. The integral free energy of mixing has a minimum value of —5600 cal per g-atom at 59 at. pct Al. The maximum solid solubility of aluminum in chromium was determined to be 43 at. pct Al, and the composition limits of the compounds CrA14, Cr4A19, and Cr5Al, at 1000"~ were found to be 79 to 80, 66 to 70, and 59 to 63 at. pct Al, respectively. The thermodynamic properties of the Cr-A1 system have been investigated as part of a thermodynamic study of aluminum-transition metal systems.172 Little information is available on the equilibrium properties of the Cr-A1 system. The heats of formation of solid Cr-A1 alloys have been determined by Kubaschewski and Haymer at 600" and low-temperature specific heat data have also been obtained.~ More extensive work has been performed on the phase diagram, and a compilation has been provided by Hansen and Anderko,~ their phase diagram at elevated temperatures being essentially based on the work of Bradley and LU.~ The high-temperature portion of the phase diagram shows an intermediate phase CrA14 decomposing peritectically at 1018°C and existing at 82 at. pct A1 at 1000°C. They also identified the compounds with solubility limits of 72 to 75 at. pct A1 at 1000°C, and Cr5A1,, existing at 61 at. pct A1 at 1000°C. The maximum solid solubility of aluminum in chromium at 1000°C was found to be 46 at. pct Al. These elevated-temperature data were obtained by examination of quenched samples and were considered as less precise than the lower-temperature data. Koester, Wachtel, and Grube7 have revised the phase diagram as a result of their magnetic susceptibility and X-ray study. The results of this work differ appreciably from those of Bradley and Lu at temperatures above 800°C. The CrA1, compound is given as existing between 79 and 81 at. pct A1 at 1000°C, and they do not indicate the presence of a CrA13 phase reported by Bradley and Lu. They also report the compound Cr4Alg as having solubility limits of 66 to 70 at. pct A1 at 1000°C, while Bradley and Lu show this compound stable only up to 870°C. Koester et al. state that the high-temperature modification of the compound Cr5A18 is stable down to 1125"C, and not 980°C as stated by Bradley and Lu, and that the low-temperature modification of Cr5Al, has a range of homogeneity of 58 to 63 at. pct A1 at 1000°C. They also report that the maximum solid solubility of aluminum in chromium is 43 at. pct A1 at 1000°C. APPARATUS AND EXPERIMENTAL PROCEDURE An isopiestic method was employed which has been successfully applied to the determination of aluminum activities in solid ~e-All and Ni-Al alloys. Alloy specimens were held at different positions in a temperature gradient and were equilibrated with aluminum vapor from an aluminum reservoir kept at the temperature minimum of an impressed thermal gradient in a closed alumina system. Diffusion of aluminum into the specimens occurred until equilibrium was reached, at which the partial pressure of aluminum in each of the specimens was given by the vapor pressure of the pure aluminum reservoir. The activity of aluminum referred to liquid aluminum as the standard state in a given equilibrated sample at temperature T could therefore be expressed by: vapor pressure of pure aluminum at _ the temperature of the reservoir Vapor pressure of pure liquid aluminum, at specimen temperature T Since both the temperature of the aluminum reservoir and the specimen temperatures were determined experimentally, and the vapor pressure of pure aluminum is known as a function of temperature,&apos; the activity of aluminum in a given aluminum alloy of known composition could be calculated. Initial runs were made with samples consisting of pure chromium chips placed in alumina crucibles. These runs exhibited large inconsistencies, indicating that equilibrium was not attained. High aluminum content Cr-A1 alloy powders were therefore substituted for the pure chromium specimens. The starting composition of the alloys was adjusted through experimentation until the concentration change necessary to attain equilibrium was small. In this manner, consistent results were obtained in reasonable times. SPECIMEN PREPARATION Alloy specimens were prepared from chromium of 99.997 pct minimum metallic purity: with 0.028 to 0.038 pct H, 0.0002 pct N, and 0.27 to 0.46 pct 0 (Aviquipo, Inc.). The aluminum had a purity of 99.99+ pct and the following impurities: 0.003 pct Cu; 0.002 pct S; 0.002 pct Fe; 0.001 pct Pb; 0.001 pct Ga (Aluminum Corp. of America). Alloy powders were prepared from weighed mixtures of chromium and aluminum by double-arc melt-

Jan 1, 1969

By Thomas P. Forbath

THE sudden realization that known sulphur reserves amenable to mining by the Frasch hot water process are nearing exhaustion focused attention on widely scattered surface deposits throughout the world. These deposits are not necessarily of lower sulphur content than ores located underneath Louisiana or Texas salt domes which usually average about 30 pct sulphur disseminated in limestone matrix. Their near surface occurrence, however, renders exploitation by the Frasch process impossible. As is well known, the Frasch process depends on the presence of 500 to 1000 ft of overburden and cap rock above the sulphur deposits to permit melting underground sulphur in place by diffusing hot water under pressures of 200 to 600 psig in the formation and raising the molten sulphur to surface by air lift. This process renders possible the production of pure sulphur which is 99.5 pct pure without any subsequent treatment. Surface deposits contain sulphur in the same range of concentrations as the salt dome deposits, i.e., from 10 to 50 pct sulphur, associated with various gangue materials such as silica, limestone, and gypsum. The pirincipal distinction, then, does not lie in the percentage of sulphur contained in the ore, but in the geological nature of the deposit. A recent study&apos; of the world sulphur supply situation estimated 1950 sulphur production in the free world countries at 5.6 million long tons, of which the United States produced 5.2 million tons, or 93 pct of the total. While America&apos;s domestic needs alone would have been covered by national production, about 1.4 million tons were exported during the same year. Despite all the steps which are being taken to restrict use of elemental sulphur and to force the fullest possible development of alternate sulphur sources here and abroad, the deficit in elemental sulphur production will probably increase with time. As a result of intensive prospecting for oil throughout the Gulf Coast area discovery of significant new salt domes is held unlikely. With the growing scarcity of sulphur and what appears to be an inevitable rise in price, recovery from deposits not amenable to Frasch-process mining assumes greater economic importance. Untapped Reserves The most important deposits in this category are located in Sicily, where elemental sulphur occurs in Miocene limestone and gypsum formation. Sulphur content of these ores ranges from 12 to 50 pct with an estimated average of 26 pct. Although quantitative estimate of these reserves is not available it is held that they exceed 50 million tons of sulphur. Similar deposits occur also on the mainland which contribute about one-third of Italy&apos;s total current annual production of 230,000 tons, but these are known to be nearing exhaustion. Significant surface deposits of volcanic origin are located in South America, Japan and western United States, silica being characteristic gangue con-stituent. The largest of these deposits are in South America. More than 100 extend over a zone 3000 miles long, paralleling the west coast of South America. &apos;Total sulphur content of these deposits has been estimated to be as high as 100 million tons. The main islands of Japan also possess at least 40 known volcanic sulphur deposits with probable reserves of 25 to 50 million tons.&apos; Prospected reserves in western United States might amount to 2 million long tons, principal deposits being located in the northwestern part of Wyoming, southern Utah, and eastern California. Volcanic deposits of lesser importance are found around the Mediterranean, in Turkey and Greece, and in Africa, Egypt, Abyssinia, and Somaliland. Beneficiation Methods Different methods of beneficiation have been used in these various locations. In Italy the Calcarone kiln and Gill regenerative furnaces are used exclusively. Both utilize heat liberated by burning part of the sulphur in the ore to liquify or vaporize the remaining sulphur, which is recovered by solidification or condensation. The Calcarone kiln is of conical shape, generally 35 ft in diam at base and 18 ft high. A kiln of 25,000 cu ft capacity burns for about two months and yields about 200 tons of sulphur. The Gill furnace consists of a series of chambers with domed roofs. Sulphur is burned and melted in one chamber at a time and the hot combustion gases are used to preheat the ore charge in the subsequent cell. These furnaces operate on a cycle of 4 to 8 days. The recovery yield of both systems is about 65 pct. Sulphur losses amount to 25 pct through the combustion to sulphur dioxide; about 10 pct is retained in discarded calcines. Ores containing less than 20 pct are not considered suitable as furnace feed. These methods are not only wasteful because of the low recovery obtained, but represent a serious atmospheric pollution problem. Sulphur produced ranges from 96 to 99 pct purity and thus does not match Texas or Louisiana sulphur. Owing to the present shortage, sulphur in the Middle East sells

Jan 1, 1954

By C. C. Templeton, J. C. Rodgers

A key step in feed water treatment for generating wet steam for thermal oil recovery is the removal of calcium and magnesiunt hardness by cation-exchange series softening. Knowing the solubility of any scale forming salts in brines at elevated temperatures is necessary for fixing the level to which the feed water must be softened. Such calcium sulfate solubility data, previously not available above 392F, were determined by the authors in a flow equilibrium apparatus mud will be reported elsewhere. These data were used to develop a method for predicting the solubility of anhydrite in hot water or steam droplets for saturated steam pressures as high as 2,000 psig (637F). (The calcium sulfate solubility product is represented by a combination of two factors, one reflecting the effects of ionic strength and the other accounting for the effects of complex ion formation in either calcium-magnesium-rich or sulfate-rich brines.) The method is applied to a calcium-magnesium-rich brine If moderately high salinity from a pilot hot-water flood, I nd to several sulfate-rich, low-salinity feed waters and l lowdown (cooled steam droplets) samples from steam s ak operations. The predicted calcium hardness levels corresponding to the calcium sulfate solubilities agreed reasonably well with the results of laboratory solubility determinations run on the field samples. Further testing of the method is needed for brines of other composition classes. Existing field cation exchange softeners in the cases tested are performing adequately since all the samples were found to be undersaturated with respect to calcium sulfate at their operating temperatures. Introduction Prevention of scaling caused by precipitation of calcium sulfate (anhydrite) is of considerable concern in connection with thermal recovery processes using wet steam or hot water. To avoid anhydrite precipitation in a heated system, an engineer must keep the product of the calcium and sulfate concentrations in the water or steam droplets below the value of the solubility product of anhydrite for the temperature and brine composition in question. Usually it is most practical to keep the concentration product lower than the solubility product by keeping calcium low in the presence of high sulfate, or by keeping sulfate low in the presence of high calcium. This can be done by a choice of combinations of natural waters and water treatment processes (such as series cation exchange softening to remove calcium). Until recently, few anhydrite solubility data, particularly for solutions containing other salts, were available for temperatures above 392F (211 psig steam); Marshall, Slusher and Jones&apos; studied the CaS0,-NaCI-H,O system up to 392F and surveyed the work of previous investigators. To model natural brines, one needs to study the solubility of anhydrite in aqueous solutions of sodium chloride, sodium sulfate, calcium chloride, magnesium chloride and their mixtures. Since steam pressures as high as 2,000 psig (637F) may be involved in thermal oil recovery projects, a solubility study was conducted between 482 and 617F.&apos; Discussed in this paper is the application of these data to the prediction of anhydrite precipitation in some practical steam soak and hot-water injection projects. Any simple method for predicting the solubility of an inorganic compound over a wide range of temperatures and solution compositions must be based on some assumptions, and therefore must yield approximate results. On the one hand, natural brines contain too many ionic species for all to be included in a simple scheme; on the other hand, there is no adequate theoretical basis for the exact prediction of solubility in even simple solutions of mixed electrolytes. However, it is possible at a given temperature to base a reasonable prediction scheme on two phenomena:&apos;-&apos; the increase in solubility with increasing total concentrations of all ions (as measured by the ionic strength; see the Appendix), and an increase due to formation of cornplexes between calcium ions and sulfate ions and between sulfate and magnesium ions. Stiff and Davis&apos; developed such a scheme for predicting the solubility of gypsum (CaSO, ¦ 2H,O) in brines at temperatures u~ to 212F. However, for the higher temperaturei of present interest, the stable solid phase is anhydrite (CaSO,). This study involves a two-part method for predicting anhydrite solubility products. First, one predicts a value K, for a given ionic strength I and a given temperature T corresponding to mo./msr, = 1 from data of the CaS0,-NaCI-H,O system. Second, one determines a group of factors F .= F(Ca) • F(Mg) • F(SO,), where the individual factors account for increases in the solubility product due to complex formation by high concentrations, respectively, of calcium, magnesium and sulfate. Combining the two parts, one obtains the solubility product in molalities as

Jan 1, 1969

By L. W. Holm

Laboratory flooding experiments on linear flow systerns indicated that high oil displacement, approaching that obtained from completely miscible solvents, can be attained by injecting a small slug of carbon dioxide into a reservoir and driving it with plain or carbonated water. Data are presented in this paper which show the results of laboratory work designed to evaluate this oil recovery process, particularly at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi. Under these conditions CO2 exists as a dense single-phase fluid. It was found that a bank, rich in light hydrocarbons, was formed at the leading edge of the CO? slug during floods on long cores. Formation of this bank is probably due to a selective extraction by the C02 and, it is believed, partially accounts for the attractively high oil recoveries. In crddition to the efficient displacernerlt of oil from the pores of the rock by this process, the favorable rnobility ratio related to a C0 2-water flood also contributes to high oil recovery. A further advantage of this process is noted on limestone and dolomite rock, in that the CO1 reacts with the porous medium increasing its permeability. Flooding experiments were conducted on sandstone and vugular dolomite models. The results of this experimental work show the effect on oil recovery of type of porous medium, pore geometry, flooding length, and flooding pressure. The porosity of the cores and rilodels varied from 16 to 21 per cent and their pern~eabilities ranged from 100 to 200 md. A reconstituted West Texas reservoir oil, a West Texas stock tank oil, an East Texas stock tank oil and Soltrol were used to represent reservoir oils in this study. Oil recoveries ranging from 60 to 80 per cent of the original oil in place in these cores were obtained by CO2,-carbonated water floods at pressures between 900 and 1,800 psi, compared with conventional solution gas drive and water-flood recoveries of 30 to 45 per cent on the same cores. Oil recoveries greater than 80 per cent resulted frorn f1oods at pressures above about 1.800 psi. There high recoveries were noted from both the sandstone and the irregular Porosity carbonate cores. In all floods, additional oil was recovered by a solutiorr gas drive resulting from blowdown following the flood. Oil recoveries of 6 to 15 per cent of the original oil in place were obtained during this blowdown period. This additional recovery was found to be a function of oil remaining after the flood, decreasing with decreasing oil saturation. It was also noted that highest oil recoveries by blowdown were obtained when carborlated water rather than plain water followed the CO, slug. INTRODUCTION Miscible phase or solvent flooding processes, which are designed to increase oil recovery -from petroleum reservoirs, involve the injection of small quantities of a petroleum solvent into the reservoir, followed by an inexpensive scavenging fluid which is miscible with the solvent. Essentially complete displacement of oil from the pores of reservoir rock has been obtained by this technique. CO,, although not completely miscible with most reservoir oils at moderate pressures, is highly soluble in these oils at pressures above about 700 psi; there is appreciable swelling and reduction in the viscosity of oil when CO, is dissolved in it. Therefore, CO, could be expected to perform similarly to other oil solvents as a displacing agent. CO, is also highly soluble in water at elevated pressures, so water should be a satisfactory material to drive a slug of CO, through an oil-bearing reservoir. A favorable mobility ratio would be obtained through the reduction in viscosity of the oil and the use of water as a final displacing agent. A number of investigations of the use of CO, to improve oil recovery have been reported in the literature.2,3,4,5,6 These studies, however, have been conducted on uniform porosity sandstone at relatively low temperatures and pressures. The behavior of CO1 as a flooding agent at temperatures above its critical temperature could not be predicted adequately from these studies, particularly for the case of non-homogeneous rock. The purpose of this work was to evaluate the oil recovery efficiency of a process involving the injection of a CO2 slug followed by carbonated water, at reservoir temperatures above 100°F and in the pressure range of 600 to 2,600 psi, and to compare this process with conventional water flooding. The investigations were primarily designed to provide information on the efficiency of the process in irregular porosity carbonate rock. The effects of flooding path length, the presence of free gas, the type of oil to be recovered, and the amount of solvent required were also determined. The essential results of static phase behavior studies and experimen-