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By E. F. Johnson, F. H. Brinkman, H. J. Welge, S. P. Ewing

This paper presents a method for predicting the manrler in which oil will be displaced from a porous body by enriched gas. The calculations apply to a gas rich enough to give a partially, but not a completely, misci-ble displacement. The method — a three-component, two-phase analysis — takes into account condensation of some of the intermediate hydrocarbons from the injected gas into the oil, as well as enhanced volatility of heavier hydrocarbons at elevated pressures and temperatures. The condensation swells the oil and decreases its viscosity, thus aiding in its recovery. The calculations have been extended to apply to actual crude oil-natural gas systems by arranging the components into three groups according to their volatility. As an approximation, each group is then treated as a single component in the analysis. The influence of an angle of dip for an inclined displacement is also taken into account. The recovery predictions are corroborated by experiments which used both consolidated sand cores and un-consolidated glass beads. In some of these tests, actual live crude oil was displaced by a multicomponent gas typical of enriched gases used in oil fields. INTRODUCTION This paper presents a method for predicting the amount of oil that can be displaced from a homogeneous, linear, porous body at various stages during the injection of enriched, or "wet", gas. The porous body can be in either a horizontal or an inclined position. 'This type of displacement is sometimes known as condensing gas drive The method is developed especially for the case in which the injected gas is enriched enough to be partially, but not completely, miscible with the reservoir oil. The need for a calcula-tive procedure for this type of operation is emphasized by the number of field projects where completely miscible drives are not practical, but where near-miscible conditions are feasible. The factors taken into account in the predictive calculations include: (1) the condensation of gas components into the oil, with a resulting increase in oil volume; (2) the lowering of oil viscosity by the addition of lighter ends from the gas; (3) the increase in oil volatility at high temperatures and pressures; and (4) the physical displacement of the oil by the gas. The techniques developed in the paper can be extended to other nonequilibrium displacement processes. Other such processes that we have analyzed include a displacement by lean gas which stripped intermediates from the oil, and a water flood in which the water con. tained in solution a substance somewhat soluble in the oil. ANALYSIS OF ENRICHED-GAS DRIVE GENERAL PRINCIPLES Our method for predicting the amount of oil that can be displaced by an enriched gas uses an analogy between a three-component and a multicomponent system.' The predictive method is based on these assumptions: (1) constant, or nearly constant, pressure; (2) complete equilibrium by diffusion perpendicular to the main direction of flow, but no significant mixing along the direction of flow; (3) constant injection velocity; and (4) flow in a linear porous body. The composition of a liquid or a vapor with respect to three components can be plotted on a three-component, or ternary, diagram like that in Fig. 1. Let Point A represent the composition of the oil originally in place. In this case, Oil A is undersaturated with gas. If Point A lay on the equilibrium Curve BF, the oil would be saturated. In the extreme case where the original oil contained no intermediates or dissolved gas, Point A would lie at the lower left-hand corner of the ternary diagram. In a displacement of Oil A by Gas D, there will be a progressive change in the composition of the oil phase as more and more gas is brought into equilibrium with the oil. The end result of this progressive change is an oil having the composition represented by Point F. This oil is richer in intermediate hydrocarbon and methane than the original oil and, therefore, has a greater forma-

By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß'-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,' alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0' phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967

By Claude P. Heiner

W-hile the litle of this paper embraces the entire West Coast, the author, in the interest of simplification, has confined the discussion to California—particularly the central section. California's population has risen 45 pct since 1940. Its electric requirements have also increased, not only because of the growth in industry and population but also because of the widespread tendency of all types of electric consumers to use more electricity than ever before. The growth of California's electric utilities is shown by published data covering operations of three of its large systems and is given in Table 1. New Capacity Steam Driven In meeting these additional electric loads there has been a substantial increase in generation from fuel burning plants as shown by the published energy statistics given in Table 2. Increased Fuel Oil Consumption A study of construction plans of the three electric utility systems named in Table 2 clearly shows that expected new electric loads are to be met, to a large extent, by new steam generating capacity as shown by Table 3. D. D. Smalley, Vice President of the Pacific Gas and Electric Co., in an address before the Pacific Coast Electrical Association in June 1948, stated that California utilities plan to meet new electric loads through greater use of steal11 plank and that in 1951 approximately 45 pct of the area's electric production would be by steam as compared to 33.6 pct in 1946. He stated that if load growth develops as expected and if the year 1952 is dry, thereby requiring high load factor steam operation, the Pacific Gas and Electric Co. would need the equivalent of nearly 25 million barrels of fuel oil. Federal Power Commission reports show that the energy input to the Pacific Gas and Electric Co. system was approximately one billion kilowatt-hours greater in 1947 than in 1946. They also show that the steam plant operating capacity factor in 1946 was approximately 35 pct; in 1947 it, was 72 pct due, probably, to the extreme drought. able 3 shows that Pacific Gas and Electric Co. now has under construction 327,000 kw of hydro capacity which, by 1950, will bring its total hydro generating capacity to 1,313,899 kw. In addition to hydro capacity under construction that company also has 975,000 kw of steam generating capacity under construction, which by 1951 will bring its total steam capacity to 1,560,834 kw. If it is assumed that this total steam electric capacity is operated at a capacity factor of 45 pct, in 1951, over 6 billion kilowatt-hours would be generated. If the load growth on the Pacific Gas and Electric system continues at the current rate of approximately one billion kilowatt-hours per year and if it is assumed that 70 pct of this increase would be generated by steam (30 pct assumed to be generated by hydro facilities with average water conditions), the steam electric production in 1960 would amount to 12 billion kilowatt-hours, which would require fuel the equivalent of 24 million barrels of oil or 6 million tons of coal. Government Projects Inadequate Much has been written with respecl to the plans of the Department of Interior in regard to the installation of hydroelectric plants as a part of multipurpose dams relating to reclamation. flood control, and power generation. An examination of the effect of such plans on the power supply for central and northern California is of interest. The Depart,ment of Interior now has five 73,000 kw units at its Shasta hydro plant on the Sacramento River. It now appears that its three 25,000 kw unit Keswick hydro plant on the same river will be available during the winter of 1949 to 1950. Its estimates show that in a dry year there is sufficient water for operation of Shasta units at an average load factor of 36 pct and Keswick units at a load factor of 41 pct. It is also giving consideration to the development of the Pine Flat and Haas hydroelectric plants on Kings River for generating capacities of 45,000 kw each. The total installation of Government, units in Central Valley and Kings River in California is relat.ively small when compared with t.he

Jan 1, 1950

By Paul G. Shewmon

The migration of slightly solzrhle spherical particles through a solid under the infllrence of a temperature gradient is analylzed for the cases of various transport mechanisms. It is shown that the variation of the velocity of the particles with radius, r, depends on the dominant mechanism of matter transport around or through the inclusion. Thus the velocity varies as r-1 jor surface-dijf1~sion controlled migratzon. is independent of r for volume diffusion in either phase, and varies as if the rate is determined by an interfacial reaction (n is the order of the interfacia1 reaction). These same results hold tor the migration of a cvlinder of length much greater than its radius. and .for other types of potential gradients, e.g., an electrical field. These equations are combined with recent electron-microscopic ohservations to show that the rate of migratzolz of small helium-silled bubbles through copper is determined by surface diffusion of the metal atoms. With these equations and the temperature gradients attainahle in an electron-microscope joil, the dominant transpar/ mechanism (or any migrating pnrtzclos can he determined. AS a result of fission, rare-gas atoms are created in the hot fuel element of a nuclear reactor. These insoluble atoms precipitate to form bubbles of the gas in the fuel. The subsequent migration and coalescence of these bubbles is thought to play a dominant role in the swelling of fuel elements which in turn can limit the fuel-element life. As a result of this practical problem and because of the relative simplicity of the system, workers in several laboratories have imbedded rare-gas atoms in metals with the aid of an accelerator and studied the formation and behavior of the bubbles that form on annealing. Recently Barnes and Mazey have studied the migration of such helium-filled bubbles in copper foils using the electron microscope and the temperature gradient that can be induced in the foil by the electron beam. They found that the smaller bubbles moved faster than the larger ones. It is shown below that, if this is true, the rate-controlling step in their migration is surface diffusion of metal atoms instead of volume diffusion, vapor transport, or an interfacial reaction. The analysis given is in no way limited to gaseous inclusions so the variation of velocity with particle size for any relatively insoluble precipitate particles could be used to obtain information about the relative importance of surface diffusion, volume diffusion, and interfacial reaction in such two-phase systems. VOID MIGRATION IN A TEMPERATURE-GRADIENT ANALYSIS Barnes' studies indicate that helium does not dissolve or diffuse in metals to a measurable extent, so that when the voids move they must do so through the movement of metal atoms from the leading to the trailing sides of the void.' Thus voids might move by surface diffusion, diffusion of vacancies in the surrounding lattice, or vapor transport. We consider first the case of flow by surface diffusion alone. We assume that there is a force, in the sense of irreversible thermodynamics, tending to move the atoms around the bubble in a given direction. We designate this direction as the x axis and the force per atom as Fa. The net rate of flow of atoms from one side of the bubble to the other, under the influence of this force, is the surface flux, Js, times the cross-sectional area available for flow, A,. A, is taken as the circumference times the thickness of the high-diffusivity surface layer 6. Thus where 51 is the atomic volume. For bubbles to advance a distance dx, a volume equal to nr : dx must flow around the void so that The minus sign enters because the bubble moves in the direction opposite to that of the force on the atoms. Equations for volume diffusion and diffusion through the vapor can be obtained in the same manner. For vapor transport we have Ag = and the ratio of the densities of metal atoms in the gas and the solid (pg/pl) enters so that

Jan 1, 1964

By W. V. Swarzenski

In its effort to combat waterlogging and soil salinity, the Water and Soils Investigation Division of WAPDA (West Pakistan's Water and Power Development Authority) has carried out an extensive program of test drilling andwater sampling since 1954. Data collected during the past ten years have permitted the delineation of fresh and saline groundwater zones in the Punjab Plain. Fresh groundwater containing generally less than 500 ppm of total dissolved solids is found in wide belts paralleling the major rivers and in other areas of fresh-water recharge. Locally, fresh groundwater extends to depths of 1500 ft and more. Saline groundwater occurs down gradient from sources of recharge, particularly in the lower central parts of the interfluvial areas, and presumably underlies most of the Punjab Plain. The groundwaters of the Punjab are characterized by their evolution from calcium, magnesium bicarbonate waters near sources of recharge to waters containing a dominant proportion of sodium. The highly mineralized waters of the Punjab are generally of the sodium chloride type, whereas in the Dera Ismail Khan District, sodium sulfate waters predominate. The pattern of distribution of saline groundwater zones and the observed gradual increase in mineral content, down gradient from sources of recharge, can be explained best by a hypothesis stressing the process of evaporation from the water table and solution of minerals within the alluvial aquifer. In 1954, detailed groundwater surveys in the Punjab Plain were initiated by WASID, the Water and Soils Investigation Division of West Pakistan's Water and Power Development Authority. The investigations, undertaken under a cooperative agreement between the governments of Pakistan and the United States, were aimed at the formulation of reclamation measures to improve waterlogged and saline soils, and to assess the groundwater potential of the Punjab and other areas of West Pakistan. The nature and urgency of WASID's primary task limited the exploration of the alluvial aquifer generally to its uppermost part. About 1030 test holes drilled in 47,000 sq miles of the Punjab defined the nature of the alluvium to depths of about 600 ft and yielded data on water quality to 400 or 500 ft. A report on the hydrology of the Punjab, based on the results of these investigations was published by WASID in 1963.' The present report incorporates data obtained by WASID since 1962 in a program of deep test drilling in the Punjab and the adjacent areas of Bahawalpur and Dera Ismail Khan District, permitting the definition of fresh and saline groundwater zones to depths of 1500 ft in some areas. Groundwater in the Punjab Plain is contained in alluvial deposits, predominantly sand and silt, which extend almost everywhere to depths of 1000 ft and more. The alluvium has been deposited by the Indus River and its tributaries since late Tertiary time and is contiguous with similar deposits in India. The Indo-Gangetic Plain extends from the foothills of the Himalayas to the ancient rocks of the Peninsular Shield in central India and to the ocean. Gradients are generally very low and range from about 1% ft per mile in the upper part of the plain to less than 1 ft per mile in the south and southwest. The monotony of the alluvial plain is broken by scattered bedrock outcrops in two of the interfluvial areas, Chaj Doab and Rechna Doab. The bedrock hills are projections of the northwest-trending Delhi-Shahpur Ridge that is largely buried by alluvium. The rocks of the buried ridge, presumably of Precambrian age, are essentially impermeable and define the lower limit of the alluvial aquifer in parts of Chaj, Rechna, and Bari doabs. Elsewhere in the Punjab, there are no outcrops of other consolidated rocks and their presence below the alluvium is conjectural. The principal areas of bedrock outcrops, near Kirana and Sangla, are shown diagrammatically in Fig. 1. The movement of groundwater through the alluvial aquifer of the Punjab has been described by Green-man and others.' In most of the area, the pre-irriga-tion water table sloped from the rivers downstream and toward the central axes of the doabs, indicating that the rivers were sources of groundwater recharge. As a result of seepage from irrigation canals, water levels have risen as much as 90 ft. In 1960 they were within 5 to 15 ft of the land surface and above the

Jan 1, 1970

By G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of' each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring' and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman' for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By R. J. Charles, G. Agar

Experiments on single particles show that the amount of material created during impact that is finer than any chosen size is proportional to the energy of the impact. As the underlying principle of comminution, it might be stated that each unit of energy input to a given comminution system tends to add to the system an identical assembly of new particles and subtract an equivalent volume of larger particles. Thus, two of the consequences of the fact that each unit of energy tends to add identical assemblies of new particles to the system are: 1) on continued application of energy the total charge in any batch comminution system tends to assume the characteristics of this assembly, and 2) the process of comminution may be described by a relationship such as E = Ak-a. Recently Schuhmannl presented a theory of comminution which puts rational perspective on the extensive controversy surrounding most of the existent theories of comminution. With hindsight the origin of controversy can be ascribed to a relatively simple circumstance. In general, a progressive shift of a size distribution curve towards finer sizes is observed as energy is added to a comminution system. It is also observed that, with continued grinding, the size distribution curves usually change and appear to approach some constant shape. Inves-tigators generally felt that an appropriate method of relating and generalizing such data would be to consider the hypothetical case where particles in the system were uniformly subjected to comminution such that each of these particles, receiving its proportion of input energy, was transformed into a number of smaller particles of uniform size. Since the changes in shape of the size distribution curves during size reduction were clearly associated with the coarse particles in the system, it was also assumed that these changes accounted for little of the input energy and one could deal solely with the equilibrium shape towards which the size distribution curves tended. Although the unrealistic nature of the foregoing points of view was realized some justification was felt for such treatments since, in most cases, the resulting mathematical formulae could, by the adjustment of at most two parameters, satisfactorily describe experimental observation. Difficulties arose, however, in that the formulae required a specific influence of the feed size on the comminution process. In actual fact, the application of a feed size term in fitting experimental data was often found to be unnecessary or contrary to the above formulae. Secondarily, much discussion arose concerning the appropriate energy number that would relate the size change of one particle to the amount of comminution energy it received. As has been previously shown3 all the above theories that treat comminution as a continuous process of size reduction may be related to a proposition of the following form: dE = -Cfn [1] where dE is the increment of energy, dx is the size change, x is the particle size, and C and n are constants. It is now clear, as pointed out by Schuhmann, that Eq. 1 is inapplicable to comminution processes, since comminution cannot be considered other than as a discontinuous mixing process in which the overall size distribution of the product results from mixing, in various proportions, finished material with unfinished, and sometimes untouched, material. A striking illustration of this mixing phenomena may be obtained by comparing the size distributions of grinds in a typical batch ball mill with size distributions calculated on the basis of mixing various proportions of feed material with a ground material which obeys a power law size distribution relationship. Figs. la and lb illustrate such a comparison and the similarity of these figures indicates that mixing plays an important role in determining the overall shape of the product size distributions. Figs. la and lb illustrate, additionally, the underlying basis of the comminution theory presented by Schuhmann.' In the preliminary grinding of relatively close sized feed particles in a batch ball mill, one may visualize that, when a successful encounter of a ball with a feed particle occurs, then the particle undergoes severe size reduction and the size range in which the resultant particles reside is far removed from the size of the feed particles. After a number of feed particles are reduced by independent but similar impacts and one examines the size dis-

Jan 1, 1961

By Reynold Q. Shotts

CHEMICAL methods, based on the relative rates of oxidation of fusain, bright coal, and dull coal by nitric acid, have been devised to determine these coal components.1-4 Results obtained by oxidation methods for fusain have been checked against results obtained from microscopic methods5, 6on duplicate samples of the same coals, but to the author's knowledge this has not been done for bright and dull coal components. For this reason it is not certain that the two methods of analysis identify essentially the same chemical or physical units. It would be highly desirable to see results of the application of both methods to duplicate samples, but in the absence of any such data the author has attacked the problem indirectly. From the U. S. Bureau of Mines samples were obtained of three Alabama coals which the USBM had analyzed optically and reported on over the past 30 years. These samples were subjected to analyses by oxidation rate methods. Results of this work, and comparisons with the USBM analyses, have been published." This was the first indirect approach to the problem. The present report attempts a second indirect approach by way of internal validation. By nitric oxidation samples of two whole coals were carefully analyzed for fusain, bright coal, and dull coal. One coal was analyzed in duplicate. Duplicate portions of each of the coals were divided into three density fractions by means of heavy liquids. A duplicate portion of one of the coals was divided by sieving into three size fractions. Each fraction was analyzed by oxidation and its percentage composition calculated in terms of fusain, bright coal, and dull coal. Because the weight percent of each fraction was known, a material balance calculation for the whole coal was also made. The resulting reconstituted analysis of the whole coal could be compared to that determined by direct analysis. In addition, specific reaction rate constants were determined for each component and for each whole coal or fraction. Arbitrary reactivity indexes were calculated by dividing by 100 the sum of the products of the percent of each component in the coal and its specific reaction rate constant. The resulting figure was an average reactivity index for each coal or fraction. Weighting the reactivity indexes for each fraction by the percent of the fraction in the coal gave a reactivity index for each whole coal which could be compared to that calculated directly from the whole coal analysis. If oxidation analyses really delineate definite physical entities within the coal, or even definite groups of similar entities, reconstituted analyses calculated from fraction analyses should check closely those made of the whole coal. It probably is true that optical methods identify and describe a greater variety of components than do chemical methods and that variations are wide in the appearance and quantity of those components identified optically. Chemical methods based upon differences in oxidation reaction rates would of necessity be less discriminating, as between similar components, than would optical methods. The procedures followed for oxidizing the samples, analyzing the residues, plotting and calculating the percentage of each component, and calculating its specific reaction rate constant have been fully described.'-' In brief the method originally proposed by Fuchs et al.1 for the determination of fusain consists of the oxidation of small samples of coal in boiling 8N nitric acid in a condenser-fitted flask. After boiling for periods of 1/2 to 4 hr, the unoxidized residue is filtered and washed. The washed residue is treated with normal sodium hydroxide, diluted, and allowed to stand for several hours. The resulting brown liquor is removed, and the filtered residue dried, weighed, ignited, and weighed again. The ash-free residue is expressed as a percent of original dry, ash-free coal. The percent residue is plotted against time, and the extrapolation of this line to zero time gives the percentage of dry ash-free fusain present in the original sample. The shape of the resulting time plots has been explained' by the assumption that they are the result of two different types of reaction, the first part representing a first order reaction with rate a func-

Jan 1, 1956

By H. E. Swanson

A description of the field apparatus has been published by D. G. Brubaker. Data from laboratory model studies of the in-line and broadside methods of operation are detailed. The conductor models include a single sheet conductor at several strike and dip angles and a schistose-type conductor. In addition, data on the effects of the strike length and of the depth of the conductor are presented for the broadside method of operation. All of the data show that the inclintion reverses direction over the top edge of dipping single sheet conductors. Differences between anomalies over conductors dipping between 90" and 30" are subtle,but flat-lying sheets can be readily distinguished from steeply dipping sheets. Schistose conductors are easily distinguished from single sheet conductors, and a procedure is given for determing the direction of schistosity. The depth of penetration under ideal conditions is 0.7 of the coil separation. In 1950, The New Jersey Zinc Co. (of Pa.) developed a lightweight apparatus for electromagnetic prospecting. A description of this apparatus has been published by D. G. Brubaker.1 It consists of a small, battery-powered vertical source coil and a direction-finding receiving coil. Source and receiver are kept a fixed distance apart and move as a unit along the survey lines. At each receiver station the inclination of the magnetic field created by the source is measured. Two methods of operation are used, in each of which measurements are taken with a constant source-to-receiver distance and with the plane of the source oriented to pass through the receiver station. In one procedure, called the in-line method, source and receiver travel in tandem along the same line. In the other procedure, called the broadside method, source and receiver move along adjacent lines, with the source-to-receiver direction oriented parallel to the assumed strike direction. The data recorded in either case are the inclinations, measured in degrees from the horizontal, of the magnetic field created by the source. These data are plotted at the receiver stations on a map. Scale-model studies of both methods of operation have been conducted in the laboratory and are reported in this paper. APPARATUS Small source and receiving coils wound with many turns of fine copper wire were used to produce and measure an alternating magnetic field in the same manner as the field apparatus. The model source coil was mounted in a vertical position and oriented so that the receiving coil was in the plane of the source. The receiving coil was mounted in a frame so it could be rotated to obtain the inclination measurements. The source coil was excited by a 100-kc signal generator. A tuned amplifier and a voltmeter were used to detect the null position of the receiving coil. The coils used in the field apparatus are usually spaced about 400 ft. The coils used in the model work were spaced from 4 in. to 4 ft apart. Thus the scale of the model work ranges between 1/1200 to 1/100 natural size. The model conductors were aluminum-coated building paper supported on wooden frames. The conductivity-thickness product was measured using a four-electrode system and was found to be about 300 ohms-'. CONDUCTIVITY CONSIDERATIONS The electromagnetic response from a thin sheet conductor is a function of the product of the conductivity of the sheet times the thickness of the sheet times the frequency of the alternating electromagnetic field times some linear dimension of the system such as the coil separation which indicates scale. The secondary electromagnetic field produced by the conductor increases in amplitude from zero at zero conductivity to a maximum value for infinite conductivity, while the phase of the secondary field with respect to the primary field shifts from 90" at zero conductivity to 0" at infinite conductivity. Several authors2-' have shown that most of both the increase in amplitude and the change in phase of the secondary field takes place over a three-decade range of the conductivity-thickness-frequency product. Only small changes in the amplitude and

Jan 1, 1961

By J. S. Aronofsky

The first step in a quantitative analysis ot the mechanism of oil displacement by water in a fractured reservoir is usually conceded to be the solution of the differential equation describing the saturation distribution of two immiscible fluids flowing in a porous medium, where the capillary pressure is taken into account. In such a system the production mechanism may consist of displacement of oil both by the flow of water due to natural or artificially imposed pressure gradients and by imbibition, which implies a flow of water not due to external pressure gradients. Owing to the presence of the two oil displacement mechanisms, the mathematical model given by the differential equation intended to describe the system may not properly represent the behavior of the physical system. In fact, in the reservoir the rate of water advance may be very slow, and in the case of a fractured reservoir with a great number of large fractures, the pressure difference determining the flow of water through the matrix may be much less than 1 lb/'psi over lengths of a few feet. In such a case, imbi-bition (the exchange between oil in the matrix and water in the fractures resulting from capillary forces) may become, with time. a significant element of the production mechanism. It occurred Lo the authors, however, that without going into a physical analysis of the process of production, it might be possible by means of simple abstract reasoning to throw some light on the variation of recovery with time under conditions occurring in a highly fractured oil reservoir with rising water table. The object of this paper is to present both the reasoning and its application to a reservoir of the highly fractured type. Specifically, the analysis given here was undertaken to try to explain the increase of recovery (as defined later) with time as observed in this reservoir, without having to assume unlikely variations in the reservoir parameters with depth. This attempt has been successful as will become clear upon comparison of the computed recoveries with the actual field data. ABSTRACT MODEL Let us consider a small volume. of porous matrix saturated with oil at time, t = 0. Let the process of oil displacement by water start at time, t = t,,. At some time, t, the process will have terminated. Then a volume of oil equal to or smaller than the original oil contained in the matrix will have been produced. The first basic assumption that describes the model and guides the forthcoming reasoning is that the oil production from the small volume. dv, is a continuous monotonic function of time and that it converges to a finite limit. Such an assumption is not inconsistent with the results of laboratory waterflood tests as well as with results of imbibition tests where this is, in fact, observed. The second basic assumption is that none of the properties which determine the rate of convergence change sufficiently during the process to affect this rate or the limit. Let it be assumed that the form of the function of time relative to production from the matrix volume. dv, is given by where V,(t) is the volume of oil produced up to that time t. R is the limit toward which the recovery converges, A is a constant giving the rate of convergence, and V,(t) is the volume of oil originally in place in the volume, dv. It should be noted that recovery at time I will be understood here to he It follows that r. tends to R as t tends to infinity. CONSTRUCTION OF RESERVOIR FROM ABSTRACT MODEL Let the reservoir consist of a series of identical blocks of porous matrix stacked vertically and separated by fractures. Let each of these blocks satisfy the conditions of our abstract model. These conditions are: (1) that recovery is a continuous mono-tonic function of time converging to finite limit, and (2) none of the properties that determine the rate of convergence change sufficiently to affect the rate or the limit. Let water be rising in fractures so that oil production from any part of the block starts when the water comes in conLact with it. TOTAL RECOVERY FROM THE RESERVOIR COMPARED TO RECOVERY FROM A SINGLE MODEL ELEMENT As stipulated in Eq. 1, in the case of the abstract model,

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By J. B. Cohen, B. W. Howlett, M. B. Bever

The partial molar heats of solution at infinite dilution in tin of aluminum at 300° and 350°C and of gallium, indium, and thallium at 240°, 300°, and 350°C have been measured by tin solution calori-metry. Aluminum, gallium, and thallium are endo-thermic on solution; indium is exothermic. Any temperature dependence of the heats of solution lies within the experimental scatter. Over the dilute ranges investigated, only aluminum has a measurable change in its heat of solution with composition. HEATS of solution of one element in another reflect the interaction between them. The investigation of partial molar heats of solution in dilute alloys is of particular interest as the properties of the solvent are altered to only a limited extent by the presence of the solute and also as the interaction between solute atoms is small. When the heats of solution of a related series of elements in a solvent are known, a systematic comparison may be made. In the investigation reported here, the partial molar heats of solution of the Group III elements aluminum, gallium, indium, and thallium in dilute solution in tin were measured. This work follows an investigation of the heats of solution in tin of the Group IB elements.' EXPERIMENTAL PROCEDURES Materials. Samples of gallium, indium, and thallium were obtained from Johnson, Mathey and Co., Ltd. Indium and thallium were supplied as wire, 1.6 mm in diam; gallium was in the form of irregular pieces. The supplier reported the following minimum purities: gallium—99.95 pct; indium—99.99 pct; thallium—99.99 pct. The aluminum, obtained from Alcoa Research Laboratories, was reported to be 99.995 pct pure. The tin was supplied by Baker and Co., Inc.; the reported analysis indicated a tin content of at least 99.96 pct with lead as principal impurity. Calorimeter. this description will cover only the essential features of the calorimeter with special attention to modifications made since an earlier description was published.' A Dewar flask containing the tin bath was held in a constant-temperature bath of a near-eutectic mixture of lithium, sodium, and potassium nitrates. This bath, which was stirred vigorously, was heated by a primary resistance winding in the container wall and by a secondary winding immersed in the salt. The voltage supplied to both windings was stabilized. The temperature of the salt bath was controlled by means of a platinum resistance thermometer in one arm of a Wheatstone bridge. The light from a mirror galvanometer in the bridge circuit fell on a photocell which controlled the current in a saturable reactor in series with the secondary winding. In this manner, the temperature of the salt bath was controlled to ±0.003°C and that of the tin bath to at least ±0.002°C. Each of these temperatures was measured by two iron-constantan thermocouples in series, coiled in a helix to minimize heat loss and immersed in the salt and tin baths in protective sheaths. The temperature of the laboratory was kept constant to ± 1°C during a run. Specimens were dropped into the tin bath from an addition arm held at O°C which was part of the cal-orimetric system. The system was evacuated to about 0.02 1 to minimize oxidation and to reduce transfer of heat. The bath was stirred by a glass stirrer introduced through a double Wilson seal. The samples were scraped clean before weighing, which was carried out as rapidly as possible. Each sample was immediately placed in the evacuated addition arm to minimize contamination. These precautions were especially necessary with aluminum. After the runs with gallium and thallium at all temperatures and with indium at 240° and 350°C (Series I) were completed and before the runs with indium at 300°C and aluminum at 300° and 350°C (Series 11) were begun the following changes were made. The shape of the Dewar flask was changed so as to result in a lower surface to volume ratio of the bath and at the same time the amount of tin was reduced from 500 to 400 g. The paddle type stirrer was replaced by a helical screw and the rate of stirring was increased to about 150 to 200 rpm.

Jan 1, 1962

By W. Rostoker

Single isothermal sections were constructed for the titonium-rich corners of the systems Ti-Fe-O, Ti-Cr-O, and Ti-Ni-0 with a view to locating the shape and disposition of the ternary intermediate-phase fields for the compounds isomorphous with Fe3W3C. IN a previous note,' it was reported that a group of ternary intermediate phases existed which occurred in the general composition range Ti,X,O-Ti&O where X was one of the following elements: copper, nickel, cobalt, iron, or manganese. In two instances, binary intermediate phases occurred (Ti²Cu and Ti²Ni) which appeared to be isomorphous. The X-ray diffraction patterns of the phases could be indexed on a cubic lattice whose cell edge was of the order of 11 kX. Karlsson2 stated that the line extinctions and line intensities indicated that these phases were isomorphous with Fe³W³C and therefore belonged to the space group Oh. This author also noted that no unique phase of this type occurred at the composition Ti,Cr,O. This latter statement was accepted as true at the time the previous technical note was written.' However, work continued along these lines and that reported here has shown that a phase isomorphous with Fe³W³C does exist in the vicinity of the composition Ti³Cr³O but not at or near Ti4 Cr²O. The lattice parameter of this phase was found to be 13.01 kX. Metallographic examination of both as-cast and annealed specimens of these supposed ternary oxide phases disclosed structures which were far from single phase in many instances. It was considered a point of some interest to locate more positively the composition coordinates of the single-phase fields. To this end, single isothermal sections for the systems Ti-Fe-O (1000°C), Ti-Cr-0 (1000°C), and Ti-Ni-0 (900"C) were constructed. Phase relationships were studied by both X-ray diffraction and metallotrra~hic methods. Allovs were prepared as 10 g buttons by melting in a noncon-sumable electrode, water-cooled copper crucible arc-melting furnace using a helium atmosphere. Oxygen was introduced quantitatively by the use of weighed amounts of TiO² or TiO. Iodide titanium and the purest available alloying metals were used. All results are discussed in terms of the nominal composition of the melts. Previous experience with making oxygen-rich alloys had shown that oxygen losses were not significant if a homogeneous melt was produced. Weight-loss measurements were used to check loss in metallics during melting. Anneals were conducted in evacuated Vycor bulbs, and annealing times ranged from 24 hr at 1000 °C to 48 hr at 900°C. To achieve equilibrium in certain sluggish alloys, seven-day anneals were used. Debye-Scherrer powder patterns were taken in a 14 cm diam camera using filtered CuK radiation (K² = 1.541232 kX; K., = 1.53739 kX). Specimens were prepared by crushing and screening previously annealed buttons. In general, the X-ray diffraction results were used to identify the major phases, while the metallographic examinations were more useful in indicating the number of phases present. By the use of the combined results and general fundamental rules governing ternary equilibrium, it was possible to construct isothermal sections in good detail. In some instances where auxiliary lattice-parameter data were available, it was possible to lay down tie lines and to locate more positively corners of three-phase fields. Isothermal Section of the System Ti-Fe-O at 1000°C The binary systems Ti-O³ and Ti-Fe4 have been published. Binary phases, TiO, TiFe, and TiFe2, are likely to be encountered in the titanium-rich corner of the system. The structures are NaCl (Bl), CsCl (B2), and MgZn, (C14) types, respectively. Although preliminary X-ray diffraction studies indicated the presence of a ternary phase in the composition range Ti,Fe,O-TiJ?e,O, metallographic examination of two specimens at these compositions revealed the presence of other phases. Thirty-eight alloys were used to delineate the phase boundaries of the isothermal section illustrated in Fig. 1. The five almost single-phase ter-

Jan 1, 1956

By R. L. Mauger, P. E. Damon, B. J. Giletti

This report includes the lead isotopic dating of a suite of galenas from Arizona and an application of the K-Ar method to the dating of a Laramide porphyry copper deposit, the Silver Bell Mining District. The lead isotopic data supports prior age assignments based upon geologic inference. The Silver Bell study illustrates the necessity of correlative geologic and petrographic investigations for the interpretation of the results of potassium-argon dating. LEAD ISOTOPIC DATING OF GALENAS FROM ARIZONA ORE DEPOSITS A group of galenas from Arizona ore deposits have been analyzed for lead isotope ratios. The results were used to calculate model ages by the. method of Russell, Stanton and Farquhar,l6 in which the age is calculated directly from the Pb206/Pb207 ratio. The use of Pb206/Pb207 ratios eliminates the errors inherent in measuring the abundance of Pb204. The Holmes-Houtermanns model is the other model commonly used for calculating model ages. Both models assume that any lead sample is composed of primeval and radiogenic components and the calculated age is the time at which the lead was extracted from its source area. Using the Holmes-Houtermanns model, a lead is ordinary if its isotopic ratios lie on an isochron. The growth curve that passes through the experimental point determines the U/Pb ratio in the source area. The RSF model assumes the source area for conformable leads is the mantle, that this has a uniform U/Pb ratio, and thus all ordinary leads must lie on a single growth curve, having a mantle U/Pb ratio. The definition of an ordinary lead differs between the models, and differences in age arise mainly from the assumptions made to evaluate parameters in the model equations. These assumptions depend on the hypothesis chosen to explain ore genesis. In the RSF Model, the Pb206/Pb207 ratio is derived as a function of time. The equation contains three undetermined parameters which are evaluated by assuming three known points lie on the curve. These are the following: 1) Primeval lead from the Canyon Diablo and Henbury meteorites, 2) Modern conformable leads which lie on Patterson's zero isochron, 3) Lead from the Bathurst, New Brunswick base metal deposits. The Bathurst deposits are postulated to be examples of "conformable base metal deposits", as proposed by Stanton.l9 A conformable deposit has a particular genetic history and, as a result, the orebody conforms to stratigraphic layering in the host rock. The metals are brought to the surface in volcanic rocks which originated in the mantle. Weathering products of these rocks, including sulfur and metals, accumulate in areas undergoing sedimentation. The formation of sulfide ion in the sediments by the action of sulfate reducing bacteria causes fixation of iron as pyrite. If the pyrite becomes concentrated in favorable stratigraphic horizons, any base metal deposit eventually formed by replacement of pyrite will have a strata bound character. Compaction and expulsion of pore water from the sediments at depth result in upward mobility of solutions containing soluble base metal chlorides. The strata with high pyrite content act as chemical traps for the base metal ions and replacement occurs. An important result of this general evolutionary model is that, if complete separation of lead and parent isotopes occurred during accumulation of the sediments, any ore deposit formed solely of metals derived from those sedimentary rocks will contain "conformable" lead. This would be true even if the actual ore deposit were formed at a later date by some epigenetic process. In this case, mineralization would be controlled by local conditions, and need not conform to stratigraphic layering. Also, any ore deposit containing lead derived from a mantle or mantle-like source, even though not conformable in Stanton's sense, will fall on the curve for conformable ores and thus give a meaningful model age. Model ages for Arizona galena deposits are listed in Table 1. Fig. 1 is a location map. Jerome-Humbolt District: Galenas from the United Verde mine at Jerome and the Iron King mine at Humbolt give model ages of 1750 m.y. and 1640 m.y. respectively. Both deposits are massive sulfide bodies in a host rock of older Precambrian

Jan 1, 1965

By R. C. Davis, R. F. Berry, G. W. White, B. T. O’Connell, L. A. Stacha

The formation density logging tool provides a radioactivity measurement that yields formation densities in situ. The relationship between bulk density and porosity is well understood. With knowledge of grain and fluid densities, porosity may be computed from the indicated formation bulk densities in shale-free formations. The porosities thus determined may be used with a resistivity log for water-saturation determinations. One technique utilizes a density vs resistivity plut. A plot of density vs Sonic-log transit time is used for porosity determinations in shaly sands. This method is particularly suited to wells drilled with oil-base or salt muds. In shale-free formations, comparisons of density values nnd neutron-log readings are used to identify lithologr and, thus, to select appropriate values of grain density for porosity computations. Through the use of Formation Density, Sonic and neutron logs, the interpretation problems caused by complex matrix lithologies are simplified. Other applications of the Formation Density log are found in the identification of minerals in evaporite deposits and in yield determinations of "oil shales". INTRODUCTION Widespread field application has demonstrated that the measurement of formation density is a useful and revealing technique for well logging. Responding to the bulk density variations of the formation, the Formation Density log affords valuable data on the porosity, lithology and fluid content of the formations. Although not without its own limitations, the Formation Density tool may provide effective interpretation under conditions that hamper or preclude the use of other porosity devices. When used in conjunction with other devices, such as the Sonic or neutron, complex matrix conditions may be better understood, defined and evaluated. A previous paper' described the valuable contribution of the Formation Density tool in the logging of empty, or gas-filled, holes. The purpose of the present paper is to describe applications of the device in liquid-filled holes. THE FORMATION DENSITY TOOL The Formation Density tool was devised to measure the bulk densities of formations in situ. Actually, the device responds to electron density, but in the overwhelming majority of cases of interest, the electron density is very closely proportional to the bulk density. In other cases appropriate corrections can be made if necessary. Comparisons of log-derived densities with true densities for the more common matrix minerals are shown in Table 1. The tool consists of a gamma-ray source and detector mounted in a skid which, during the logging operation, is in contact with the borehole wall (see Ref. 1 for schematic). Gamma rays are emitted by the source and diffused through the formation. The number of diffused gamma rays reaching the detector at a fixed spacing from the source are counted. An increase in counting rate by the detector indicates a decrease in bulk density in front of the skid. Conversely, a decreased counting rate signifies an increase in bulk density. A measurement of hole diameter, between the face of the skid and that of the eccentering arm, is recorded simultaneously with the measurement of diffused gamma rays. Since the tool is a wall-contact device, the size of the borehole has little influence, provided good contact is maintained with the wall of the hole. Only in extremely large or small boreholes does the actual diameter become significant. However, for most accurate measurements the borehole size should be taken into account. Fig. 1 presents the departure curves for the conversion of counting rate to bulk density for liquid-filled holes of various sizes. It is of utmost importance that the skid maintain good contact with the wall of the hole. If, due to roughness or caving, there is mud between the skid and the formation, the tool will include in its response the relatively low-density mud, and the apparent density reading will be too low. Normally, permeable beds do not cave appreciably, so that reliable readings are usually available for zones of interest. Nevertheless, the caliper reading over the zone of interest should be examined for any wall roughness. When mud cake exists between the skid and the formation, the Formation Density log sees it as part of the formation. When thick mud cakes exist, a correction is required. For best results in wells having thick mud cakes,

By V. F. Hollister

The Queen Charlotte gold deposit (also known as the Specogna, Babe, or Cinola) was discovered in late 1970 by Efrem Specogna and Johnny Trico. They were prospecting along the trace of the Sandspit fault, and they sampled jarositic material that included veins from the fault zone. Their assays included some good gold values. They located the Babe Claims in 1971 and optioned them to Kennco Explorations Ltd. Kennco conducted stream sediment and soil geochem studies, geological mapping and drilling of 55.2 m (181 ft) in two drill holes. Kennco withdrew from the property, and by 1977, Cominco, Placer Development, Silver Standard, and Quintana Minerals had each successively worked on the deposit. Consolidated Cinola Mines bought the claims in 1977 and completed exploration of the deposit ultimately in a joint venture arrangement with Energy Reserves. Energy Reserves entered in late 1979, and by 1983, a total of 200 surface and 12 underground drill holes had been completed, totaling 28 600 m (93,832 ft). In addition, a 461.9 m (1515 ft) adit was driven in the ore body. Reserves published by Cinola aggregate 34 Mt (37 million st) of 1.7 g (0.060 oz) Au per tonne. All industry geologists working in the area agree that the Queen Charlotte gold is an epithermal gold deposit in porous volcaniclastic and clastic rocks that is genetically related to a Miocene-Pliocene rhyolite plug. The geologic description here follows the oral presentation made by G. G. Richards, J. S. Christie, and M. R. Wolfhard at a 1976 CIM meeting. Additional comments by the late C. S. Ney of Kennco Explorations are included with the Richards, Christie, and Wolfhard data to complete the geologic set- ting. The attached reprint by Champigny and Sinclair (1 980) provides additional data on the deposit. The Queen Charlotte (Babe, Specogna, or Cinola) gold deposit is located on Graham Island in the northern Charlotte Islands, at the fault boundary of the Skidegate plateau and the Charlotte lowlands. The Sandspit fault marks the physiographic boundary, and it is intruded by rhyolite porphyry at the deposit. Because displaced geochem anomalies, drain- age patterns, and topography suggest dextral and east side down movement for the fault, exposed east block rocks are younger than rocks west of the fault. The east block, which included the ore deposit, is a lowland largely masked by unconsolidated Pleistocene and Recent clastic rocks. Rocks west of the rhyolite plug, on the Skidegate plateau, are Cretaceous carbonaceous and calcareous shale unconformably overlain by a thin veneer of rhyolite tuff. The deposit is about 100 m (328 ft) above sea level. GEOLOGIC SETTING At the ore deposit, the Sandspit fault is a complex structure. However, lithologies on either side of the fault-controlled rhyolite porphyry plug are distinct. West of the rhyolite, the upper member of the Cretaceous Haida formation shale is the most common rock type. The member is composed of dark grey to black, poorly consolidated, and thinly bedded carbonaceous and calcareous shale. The sequence is silicified to an argillite or a hornfels near the rhyolite. West of the rhyolite porphyry plug, but not importantly involved in the mineralization, is a thin masking cover of rhyolite tuff. The tuff unconformably succeeds the cretaceous shale, but it is largely eroded in the mine area. East of the fault-controlled rhyolite porphyry plug is a thick section of conglomerate and sandstone of the Miocene- Pliocene Skonun formation. The ore body occurs within the coarse clastics, the rhyolite intrusive as the western boundary. Ore is entirely contained within the clastics. Original permeability of the clastic rocks was a major control for ore deposition and alteration, and for that reason, the Skonun formation is described in greater detail. The Skonun formation clastics unconformably overlie Haida shale. The Skonun is at least 300 m (984 ft) thick in the mine area, where it trends northerly and dips easterly 15º to 25º. The sequence is about 62 percent conglomerate, 3 1 percent coarse arkosic sandstone, and 7 percent interbedded siltstone and sandstone. Contacts between adjacent beds are generally sharp. Stratigraphic correlations between drill

Jan 1, 1985

By C. G. Dunn, P. K. Koh

THE primary recrystallization texture in cold-rolled silicon iron, which is the matrix texture for developing the Goss texture or the cube-on-edge texture by secondary recrystallization at temperatures near 900°C,1-5,21 has not been adequately described. Thus from the present available information, it is not possible to explain satisfactorily both the grain-growth selectivity of the matrix and the often observed magnetic torque curve, which itself provides some information on the texture. Also lacking is information on the special annealing texture that develops in this material when the annealing temperature is 1200°C or higher and the rate of rise to temperature is extremely rapid. From the work of May and Turnbull5 and from unpublished work, it was known that isothermal annealing near 1200°C tends to reduce the extent of secondary recrystallization and that a much weaker cube-on-edge texture results if appreciable normal grain growth replaces secondary recrystallization. Koh and Dunn6,7 have obtained additional information on complex primary recrystallization textures from further studies made after normal grain growth. In these instances the initial textures were retained during normal grain growth. A similar result reasonably could be expected in the present study except for the presence of a grain growth ihibitor1-5,8,9.21 and its tendency to allow only a few grains to grow. However, any information on the orientations of grains in the special annealing texture, even if far from representative of the initial matrix texture, would provide useful information on the nature of the matrix texture. In the present texture study the method of Newkirk and Bruce,10 which is based on the methods of Geisler" and Schwartz, 12 is used to obtain a complete (110) pole figure of the primary recrystallization texture. The high-temperature annealing texture is determined simply from the orientations of a large number of selected grains. The kinetic nature of the process that produces the annealing texture is treated elsewhere13 and it is shown that a form of secondary recrystallization with a very high rate of nucleation occurs during rapid annealing at high temperatures. EXPERIMENTAL PROCEDURE Commercial 0.014-in. cold-rolled silicon iron strip (3.16 wt pct Si), prepared by two stages of cold rolling with an intermediate short anneal, was given a decarburizing 3-min anneal at 800°C. Me-tallographic studies indicated complete recrystallization. Short-time anneals at 900° C and at higher temperatures proved that secondary recrystallization had not begun at 800°C, in fact, the short additional anneals were still in the induction period of secondary recrystallization. A rapid rise to an annealing temperature of 1260°C (2300°F) was obtained in a BaC12and NaCl fused salt bath. The structures that resulted from anneals in the range 12- to 1000-sec duration were relatively finegrained, even though the growth was a form of exaggerated grain growth13 or secondary recrystallization with a high nucleation frequency.= Many of the grains were large enough for an X-ray study using a 5-mil X-ray beam. A transmission Laue Camera and an optical-mechanical stage for moving the grains into the X-ray beam were used. A total of 325 grains were X-rayed in this manner and the grain orientations determined. Complete (110) pole figures were obtained for the primary recrystallization texture using CoKa radiation at 30 kv in the back-reflection range, such as (220) for (110) poles, as described recently by Newkirk and Bruce.10 The low voltage serves to reduce the spurious white radiation to a minimum. A filter of 0.001-inch iron foil was located in front of the detector slit for transmission and in front of the beam slit for back reflection. A new and improved specimen holder extended the useful tilting angle range for transmission to 70 deg instead of 60 deg as previously reported.' A torque magnetometer was used to obtain the magnetic torque curves for a number of l-in. diam disk specimens. RESULTS The (110) pole figure of the material after recrystallization at 800°C is shown in Fig. 1. The positions of the pole concentrations are found to be

Jan 1, 1961

By J. O. Edstrom, G. Bitsianes

Parabolic rate constants were determined for the formation of wiistite by the solid state reaction between magnetite and iron. The reaction was diffusion controlled and inert marker studies indicated that the mass transport through the wiistite layer was accomplished by means of iron migration. Relationships between rate constants and self-diffusivities are discussed. The transport capacity for iron through dense wustite layers was found to be sufficient to carry on reduction, even in gaseous reduction processes. REDUCTION of iron oxides has been the subject of many investigations. Most of the work, however, has been done on rather crude material and there have been difficulties in correlating the data on a quantitative basis. The reverse process of the oxidation of iron has been studied more thoroughly and usually by starting from the pure metal. As a result, the mechanisms of oxidation are now fairly well known.It has generally been found that the oxidation of metals follows the so-called parabolic 1aw;Q hat is, when the oxides are formed as dense layers, their thicknesses are proportional to the square root of the reaction time. This parabolic law follows directly from Fick's first law of diffusion The flux, J, is defined as the quantity of diffusing substance passing per unit time through unit area of a plane at right angles to the direction of diffusion. This flux is proportional to the concentration gradient of the diffusing substance, and the factor D, known as the diffusion coefficient, is introduced as the proportionality factor with dimensions of (length)'/time. If the flux is measured as the increase of thickness of the oxide layer (Ax) per unit time (t) and the assumption is made that the concentrations of the reactants at the phase boundaries of the layer are independent of time, Eq. 1 reduces to Integration of this expression yields the parabolic function ax = k . t. [31 The product of the diffusion coefficient and the concentration difference across the oxide layer is included in the constant k. When iron is exposed to a highly oxidizing atmosphere, the oxide phases are formed normally in a topochemical fashion, i.e., the interfaces between the phases maintain parallel positions to the original surface of the specimen. Above 570°C, the phases are orientated usually in the order of iron, wiistite, magnetite, and hematite, a condition in conformance with the requirements of the Fe-0 system. Below 570°C, the wiistite phase is unstable and has not been found as a normal constituent in the oxidation products of iron. There is a strong probability that continuous layers of the solid oxides are formed as the specific volumes of the phases increase in direct order from iron to hematite.' , ' Regarding mass transport through dense solid oxide layers, Wagner' has postulated that diffusion in oxides generally may be interpreted as migration processes of ions and electrons. There must be normally a concentration gradient across the growing oxide layer for diffusion to occur. This condition requires that there be deviations from the ideal stoi-chiometric composition of the oxide and accordingly deviations from the strict order of an ideal lattice. Such "lattice defects" include interstitial ions, cation and anion vacancies, quasi-free electrons, and electron holes and are decisive for all migration processes.' Cations, anions, and electrons all may have some mobility in the oxides but the movement of one of the particles generally far exceeds that of the others. Previous work', 1,2,7 has shown that during the oxidation of iron the migration through the wiistite layer, and probably also the magnetite layer, is confined to the movement of iron ions. Migration through hematite, however, has been found to take place by oxide ion movement. These behaviors are in direct agreement with the type of vacancies present in the respective oxides. Reduction of Iron Oxides The gaseous reduction of iron oxides, like the oxidation of iron, takes place in a topochemical fashion at distinct interfaces between the appearing phases."-'" Porosities might be expected in these reaction products, since their specific volumes are less than that of the starting material. Frank and van Der Merwe" have shown, however, that it is theoretically possible for nonporous layers to form if the degree of misfit in specific volume is less than about 15 pct. These aspects on porosity formation

Jan 1, 1956

By D. P. Kedzie, R. A. Dodd

The fatigue strength, fatigue hardening, and effect of fatigue deformation on subsequent age hardening of supersaturated Al(Cu) solid solutions have been determined as functions of alloy composition and temperature. The fatigue strength/tensile strength ratios, determined at 150°, 25°, and -195°C, decreased with increase in alloy content for all temperatures, but the F.S./U.T.S. ratios at -195°C decreased much more rapidly than did the ratios for 150" and 25°C. This suggested that strain aging and/or age hardening occurred during tests at higher temperatures. Additionally, the F.S./U.T.S. ratios at 150°C exceeded those at 25°C for all compositions, indicating greater strengthening during fatigue at 150°C. The effect of fatigue or tensile deformation at 150°, 25°, and -195°C on subsequent age hardening showed that the deformatzon increased the rate of precipitation and indicated that mechanically produced vacancies were probably formed during deformation. Fatigue hardening was studied at 150°, 25°, and -195°C, and the effect of room-temperature rests after 10 and 100 cycles was examined. The results confirmed that strain aging occurred at the higher temperatures . DURING the last 15 years various mechanisms of fatigue crack nucleation and growth based on dislocation and vacancy interactions, operating singly or collectively, have been proposed. The probable consensus of present opinion is that the fatigue process in pure metals essentially involves dislocation interactions, and that vacancies formed by such interactions play a minor or inconsequential role. However, there is some evidence that age-hardened alloys tend to overage during fatigue, probably by local vacancy-enhanced diffusion, and strain aging also might be important in selected cases. Furthermore, it has been established that the behavior of quenched-in vacancies in Al(Cu) and other solid solutions is composition-sensitive. Therefore, it seemed worthwhile to investigate various aspects of the fatigue behavior of supersaturated Al(Cu) alloys and to examine the results in terms of vacancy-enhanced effects. EXPERIMENTAL The alloys used in this investigation were prepared from 99.994 wt pet A1 and OFHC copper, the latter containing 0.04 pet 0 as the principal impurity. Six alloys were made, containing, by actual analysis, 0.58, 0.96, 1.96, 2.85, 4.45, and 5.51 wt pet Cu. They were induction-melted in air in graphite crucibles, cast as 7-in. by 7/8-in.-diam rods in graphite molds, and hot-rolled to 5/8 in. diam. The experimental work was a three-part program involving the determination of a) 10' cycle fatigue stresses as a function of alloy composition and temperature; b) the effect of fatigue deformation on subsequent aging of the supersaturated alloys; and c) fatigue hardening as a function of alloy composition and temperature. For determining the 105 cycle fatigue stresses, a portion of the 5/8-in. stock was machined into Krouse rotating cantilever beam fatigue specimens, 2 in. in length by 1/4 in. minimum diameter. These were tested at +150°, 25°, and -195°C (liquid nitrogen) on a Krouse high-speed machine, with special weights to provide lower -than-normal loading ranges, this being necessitated by the small load requirements of those alloys of lower copper content. For the high-temperature tests a small resistance heater was designed to clear the collets and fit in between the chucks, while for the low-temperature tests a hollow nylon cylinder was used, having closed ends drilled to pass a fatigue specimen, and positioned similarly to the heater. A plexiglass container completely enclosed the fatigue machine; rubber gloves fixed to ports in the walls enabled the machine to be operated from outside the box. A tray of magnesium perchlorate dried the air in the container and prevented both atmospheric corrosion fatigue at room and elevated temperatures and troublesome ice build-up at low temperatures. A total of ten to fifteen specimens was used for each combination of alloy composition and temperature. The result of each test was plotted on a standard S-N diagram, and the next stress was selected on the basis of the trends indicated by previous specimens. In this manner a small portion of the S-N diagram was constructed, and the 105 cycle fatigue stress obtained. Small Krouse fatigue specimens were also used to study the effect of cyclic prestrain on subsequent

Jan 1, 1964

By S. J. M. van Leeuwen, R. Feenstra

The effect of jets on bit penetration has been investigated by means of a 50-ton drilling machine and 8½-in. commercial jet bits, drilling under representative bottom-hole conditions. The conclusions apply to the drilling of impermeable rock only. Penetration rate is in all cases primarily hampered by a differential pressure effect, known as dynamic hold-down. Jet action can reduce this slightly. Major gain in penetration rate, up to 25 or 50 per cent, is already ohtained at medium-high jet power. At high bit load, penetration by soft to medium-hard-formation bits is further hampered by bit-balling. Its alleviation requires intensive tooth scavenging, which is best performed by slanted nozzles with trailing, high-velocity, high-volume jets, hitting bottom in front of the teeth. Penetration may then improve by a 100 per cent. At high bit load, bottom-balling limits the penetration of insert-type bits. In this case bottom scavenging is required, which is most effectively performed with high velocity jets from nozzles extended close to bottom. As a result of this measure, penetration may improve 70 per cent in non-friable rock, and less in friable rock. This will make the insert-type bit more versatile. Toothed hard-formation hits suffer at high bit load from both bit- and bottom-balling. Slanted nozzles, possibly much extended, with high-velocity, high-volume jets then have best prospects. INTRODUCTION For years the use of jet bits in oil well drilling has been increasing, in conjunction with ever greater hydraulic horsepower. To the same extent, the need for efficient use of the horsepower has grown.' This paper, it is hoped, will contribute to an understanding of how effective jet action may be obtained. It deals with the effect of jets on phenomena that are known' " to hamper bit penetration. To study this effect, laboratory drilling tests were performed with 8½-in. commercial bits under bottom-hole pressures representative of deep wells. The investigation has been restricted to the drilling of practically impermeable rock. In the following sections, the increase in bit penetration rates due to jetting is discussed for conditions which made the troublesome phenomena stand out one at a time. A brief definition and interpretation of these phenomena is given in Appendix A. Appendix B gives the results of measurements of fluid velocities along the hole bottom, performed in stationary flow tests. Descriptions of equipment, bits, rocks and mud are collected in Appendix C. Unless otherwise mentioned, drilling conditions were kept standard as given in Table 1. CUTTING TRANSPORT TO THE ANNULUS Jet action was for some time believed to merely improve the transport of cuttings from bottom to annulus, resulting in a clean hole bottom. Flow tests performed in 1954 at the Battelle Memorial Institute6 showed, however, that jet velocities of the order of 40 ft/sec sufficed to clear even large (0.4-in.) chips from bottom in the time between two successive tooth actions. In the field, optimum jet velocities are appreciably higher, indicating that other effects must be involved. This much is confirmed by the results of our drilling experiments in soft rocks performed under atmospheric pressure, i.e., in absence of pressure-differential effects. Fig. 1 shows that variation in the nozzle velocity from 40 to 330 ft/sec had no effect on penetration rate, unless the bit penetrated more than 7 mm per revolution, which is about half the tooth height. At such high rates—150 ft/hr at 100 rpm—cuttings would be caught in the tooth cavities, leading to bit-balling, which was noticed on inspection of the bit. The jets thus assisted in keeping the tooth cavities clean. This is just perceptibly reflected in the penetration-rate curves of Fig. 1: Much the same results were obtained in hard rocks with hard-formation three-cone bits. The conclusion is that transport of loose cuttings towards the annulus does not require a powerful jet action. In the following sections we shall see that in deep-well drilling other phenomena are of greater importance. DYNAMIC HOLD-DOWN It is generally accepted that, in deep-well drilling, bit penetration is hampered primarily by the existence of a difference in pressure between the fluid in the hole and that in the rock at the depth of cutting.2-5 In the drilling

Jan 1, 1965