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By R. R. Harvey

Recent evidence has indicated that the films forming at crude oil-water interfaces are the result of naturally occurring su,rface-active components in the crude oil rather than oxidation products resulting from exposure of the oil to air. Since the presence of such films may strongly affect the displacement of oil from porous media, a knowledge of their composition and formatiorz is of fundamental importance. In this study, without the assumption of a specific mechanism, film formation is considered to involve the transfer of a weakly surface-active species in solution in the oil to the oil-water interface. The film gas law and the Gibbs adsorption equation may thus he applied to the system. The rigid films which form upon decrease of the oil-water interfacial area are considered a result of the very slow rate of re-solution of the film material into the oil. When the shrinkage of the interface is very rapid, the amount of film material leaving the interface is negligible, and the system may then be treated in the same manner as an insoluble film. The combination of these treatments leads to a new concept of the film factor in which it may he quantitatively related to the concentration of film-forming material at the interface. Suitable experiments can then yield the following information. 1. Original concentration of surface-active species in the oil. 2. The change of concentration with time. 3. Concentration of surface active species at the interface. 4. The change of this concentration with time. 5. Interfacial tension of the system at any time and its variation with time. 6. Equilibriunz concentrations for a given set of conditions. 7. Concentration requirements for solid film formation. 8. Molecular diameter of the adrorbed species. These calculations may be made solely from data taken from measurements on the original oil. While using the pendant drop method of interfacial tension measurement of crude oil-water systems, Bartell and Niederhauser' remarked on the thin, transparent, pliable, solid films or membranes which were often formed at the interface between crude oil and water. As a result of their observations of these films, Bar-tell and Niederhauser concluded: 1. The films are formed by material from the oil adsorbed at the interface rather than by a reaction at the interface. 2. The adsorption of the film-forming material is a rather slow process. 3. There are good indications that the process is reversible; i.e., the film constituents may re-dissolve into the oil. 4. The film will spontaneously spread over any new surface formed. 5. The process of adsorption at the interface is accompanied by a decrease in the interfacial tension of the system. Although they had proved that film formation was not due to a reaction at the interface, Bartell and Niederhauser were unable to demonstrate conclusively whether these film-forming constituents were present in the original reservoir oil or whether they were formed as oxidation products after exposure of the oil to air. Recent evidence seems to point to their presence in the original oil. Although the true nature of the film-forming constituents is still uncertain, these conditions would be fulfilled by the assumption of the presence of a slightly soluble surface-active component in the original oil. This component would migrate to a freshly formed interface because it would thereby lower the free energy of the system. The component at the surface constitutes an expanded monolayer which would become compressed, upon retraction of drop, due to the slow rate of re-solution of the film components into the bulk of the oil. It is possible, by involved extraction processes, to separate or at least concentrate this film-forming fraction. However, using the assumptions made above, the technique of monolayer film study may be applied to reveal much of the nature of the adsorbing material without resorting to an actual separation of the film-forming constituents.

By H. Bartholomew, L. Bernstein

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

Jan 1, 1967

By A. Weiss, W. A. Coster

The search for ore is characterized by a great variety of uncertainties, each of which can be resolved by obtaining information at a cost. Three exploration stages may be distinguished in which information can be obtained, based on inherently different cost structure: 1) the reconnaissance or scanning stage, 2) the examination or screening stage and 3) the project stage. This exploration sequence would roughly coincide with replies to questions as to: where, how, why and how much. As complete information in each stage is too costly to acquire, we must assess the probability that adequate information will be furnished by a limited amount of effort and attempt to maximize the expected value of ore to be found for a given exploration expenditure. Several problems are discussed relative to the mathematical formulation and possible computer procedures for determining the optimum allocation of a total exploration effort. Based on the available literature possible solutions to this problem are indicated. When scanning through published literature on mineral exploration, it seems at first that there is little room for substantial and systematic improvements in the efficiency with which the problem of discovery of new ore deposits is presently being handled by large organizations active in exploration. It appears equally difficult to offer something relevantly new which could generate a break-through in exploration thinking and cause a marked improvement in the ratio of successful undertakings to the total exploration projects started. On the other hand, a number of experts in recent years have urged that the problems in prospecting be analyzed in a more skillful and sophisticated manner than in the past. Their thesis is based mainly on the premise that the cost of finding mineral deposits will increase with increasing technical difficulties. In present large-scale exploration ventures, especially in those regions where outcrops and immediately visible geologic evidence are scarce, older methods of prospecting are increasingly being replaced by more indirect and systematic geophysical and geochemical methods with more emphasis on correct statistical design of exploration patterns. It is perhaps the oil industry which has made the greatest strides in developing statistically, well justified patterns in its search for oil; possibly because oil seepages, as indicators of the presence of oil, left off at an earlier point in time than did outcrops as indicators of base metals. Among the pioneers in the field of statistics and operations research, as applied to mineral exploration, the excellent works of Allais, Slichter, Koop-man, Mickey, de Guhnin, Krumbein, Griffith, Sichel, Krige, de Wijs, and Matheron may be mentioned. It should, however, be pointed out that three subjects of basic importance to the allocation of exploration efforts have so far received only scant attention in published literature, even by the aforementioned authors. In the first place, a more precise definition of the object of the search, i.e., a minimum-size orebody, seems to be outstanding. Secondly, a decision model is not a widely-discussed subject. Thirdly, no concentrated attempt so far seems to have been made to establish probabilities of the occurrence of economic deposits on a regional scale and to arrive at a slightly more accurate knowledge of the probability laws governing the deposition of ore. It is not the purpose of this paper to create new order in the complexity of uncertainties in which our decision processes in exploration necessarily have to be conducted. Rather, we intend to highlight some of the outstanding, hitherto unmapped territory, where diligent compilation and a utilization of present and historic data may statistically improve our chances of success. We hope that the contribution of this paper will lie in bringing allocation problems into better focus and in increasing the mineral industry's realization of the magnitude of the factors involved. THE MINIMUM-SIZE OREBODY The concept of target specifications for what constitute a minimum-size orebody in exploration is a rather variable one and depends to some extent on

Jan 1, 1963

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By Brian E. Davies, Bobby G. Wixson

INTRODUCTION The mining, extraction and refining of metals into useful materials is an honorable profession with an ancient and productive history. Civilizations have long depended upon metals for their implements, structures and machinery necessary for survival, growth, and development. Today, as in the future, metals and minerals are essential to the progress of mankind as we approach the 21st century with technologies and concepts that will require new concepts and production from the metal mining and processing industries. Today is the tomorrow we talked about yesterday and the implementation of new ideas is essential if we are to achieve "Frontier Technology in Mineral Processing". Unfortunately, the state-of-the-art mining, processing, smelting and refining methods historically employed were less than desirable environmentally, which has caused todays public to view the metal mining and processing industry with concern. Presently the ancient rock and chat tips connected with old Roman lead-zinc mines which were worked in Wales are causing stream contamination problems that must be corrected at considerable expense to the local governmental agencies (Firth, J.N.M., et al., 1981). However, improved progress has been made and the environmental control and clean-up procedures utilized by modern lead-zinc operations in the "Viburnum Trend" or "New Lead Belt" of South East Missouri may serve as a model to illustrate how alternative technologies, environmental concerns and cooperative efforts contribute to efficient mineral production within the confines of a U.S. National Forest region without significant environmental impacts. This area received international attention when it was opened within the boundaries of the Clark National Forest in the mid 1960's. By 1970 it ranked first in the world by producing 432,576 short tons of lead ore and has since continued in this position producing 451,153 short tons of lead ore in 1983 representing 91% of the total United States lead production (U.S. Bureau of idines, 1983). This production comes from a mining area approximately 40 miles long by 10 miles wide extending in a north-south direction. Geologically the lead is disseminated throughout the Cambrain age Bonneterre Formation, mostly a dolomite, at depths ranging from 700 to 1200 ft. (213.4 to 365.8 m). Galena (lead) is the principal ore mined with lesser quantities of sphalerite (zinc), chaleopyrite (copper) and silver being recovered as economic co-products. This new mining development in one of Missouri is most scenic areas could have led to a classic confrontation between industries and environmentalists. Instead, through the cooperation of industries, governmental agencies and university researchers, the Ozark environment has been protected, and may serve as a model for future coexistence of the mineral industry with the environment. Cooperative Program Development As early as 1965 five new mines and two lead smelters were being prepared for production and environmental concern was an essential part of that planning. All the mining companies became acquainted with representatives of the various federal and state agencies and scientists from the University of Missouri-Rolla (UMR). During the next six years, St. Joe Minerals Corporation, American Metal Climax, Inc., Cominco American Incorporated, Ozark Lead Company (Kennecott) and American Smelting and Refining Company participated in cooperative research efforts. The companies also participated in information exchange meetings, the development of improved analytical methods and the utilization of research findings in the modification or construction of pollution-abatement facilities. Early on research was carried out to determine background values and to establish natural baselines of trace metals in the surrounding environment. The unusual topography and drainage pattern of the mining area were helpful since it was possible to establish control sites and test sites below individual mine-mill operations to study waste-water effects on the receiving streams. The location of the ‘New Lead Belt', mines, mills,

Jan 1, 1985

By I. S. Levy, J. L. Brimhall, B. Mastel

Specimens of' Hastelloy X-280, a low-cobalt version of the solid-solution- hardened nickel-base alloy Hastelloy X, were given a series of thermomechanical treatttzents. They were then Lensile-tested at room temperature and 1350°F. The Microstructures of the specimens tested at 1350°F were studied by electron Microscopy. Microscopy showed that dislocation tangling, caused by the cold working, mas still in evidence after aging-for 24 hr to temperatures as high as 1550oF. (Cr, Mo)23 C6, (Fe, Mo)6 C'. as well us an unidentifiable phase precipitale due to the combination of the thermomechanical treatments and subsequent tensile strain. The room -temperature and 1350°F tensile properties show a general increase ill strength and decreccse in ductility with increusing cold-work level. This is due to the dislocation taangling-. PerLurbatiot~s to this general trend occur- due to solid-solution weakening at the higher cold-work levels as a direct result of the preciplitation reactions. THE requirements for corrosion resistance and high-temperature strength place nickel-base alloys among the more promising materials for advanced nuclear reactor applications. However, when these alloys are irradiated at service temperatures, they generally suffer severe embrittlement'" and reduction in rupture life.3 Certain experimental treatments resulted in improvements in the tensile and stress-rupture properties of Hastelloy X-280, a solution-hardened nickel-base alloy.' To provide a basis for understanding these improvements, unirradiated tensile specimens were examined by electron microscopy. The results are reported in this paper. EXPERIMENTAL DETAILS Material. Hastelloy X-280, a low-cobalt version of Hastelloy X, is a member of the solution-hardened class of nickel-base alloys. The Hastelloy X-280 was obtained from 4- and 1-in: thick plates in the mill -annealed condition. Table I gives the chemical composition of the material as reported by the National Spectrographic Laboratories. ~x~erimental Treatments. Plates of suitable size, 12 by 3 by 1 in., or by + in., were cut under a water jet from the stock material and examined ultrasonic -ally for homogeneity of grain size and absence of voids. The acceptable plates were solution-treated at 2150°Ffor 1 hr and air-cooled. These plates were then reduced in thickness by cold rolling 0, 10, 15: or 20 pct along the original rolling direction. The plates were machined into buttonhead tensile specimens with a gage diameter of 0.125 in., with a gage length of 1.125 in., and with their tensile axes parallel to the rolling direction. The specimens were examined for quality of finish with a penetrant dye, ultra son ically checked for voids, and finally given a dimensional tolerance check with an optical comparator. The acceptable specimens were aged for 24 hr at either 1000" or 1500 F and air-cooled. These specimens were then held at 540°F in a water loop for approximately 18 days to qualify as controls for similar specimens irradiated under the same conditions of time, temperature, water chemistry, and flow rate. Table U summarizes the treatments. These treatments were investigated to establish whether prior precipitation and stabilization of carbide phases at strain sites within the matrix could reduce the amount of carbides available for precipitation at grain boundaries during service. Tensile-Test Conditions. Specimens were tested to fracture at room temperature or 1350 F in air on an Instron tensile-testing machine at a crosshead speed of 0.05 in. per min. The time for the furnace to reach equilibrium at 1350°F was approximately 30 min; soak time prior to testing was 15 min; and test duration was approximately 5 min.

Jan 1, 1968

By L. H. Robinson

A proposed method of drilling utilizes sequential detonation of two types of explosive charges delivered to the hole by a conventional drilling fluid through pipe. A shaped charge first produces a long thin hole. A second charge, called a gauging charge, is pumped into the thin hole, explodes, and enlarges it to full gauge. In one suggested configuration, the explosives are contained in cylindrical capsules 4- to 5-ft long. A drilling head is positioned 2- to 3-ft off bottom. When a capsule is pumped to the bottom of the hole and stops, pressure inside the drill pipe increases and differential pressure detonates the explosive. Primacord along the length of the capsule disintegrates the capsule. The debris circulates out of the hole with the drilling fluid. The gauging-charge action was examined using 2-ft cubes of Berea sandstone. The sandstone (18 per cent porosity) was vacuum-saturated with water and surrounded by concrete. To prevent reflected tensile pulses, the acoustical impedance of the concrete matched that of the sandstone. A 750-psig pressure was applied to a drilling fluid within a shaped-charge-formed hole before detonating the gauging charge. In these tests, 190 gm of rock were removed for each gram of explosive detonated. A similar series of experiments on low-porosity (0.40 per cent) metamorphic limestone provided a more rigorous test. Extensive fracturing from the gauging-charge action prevented an estimate of the volume of the expanded hole. The diameter of the hole was irregular, ranging from about 2 to 4 in, or about fivefold larger than the hole created by the shaped charge. INTRODUCTION In the past, explosives have found a varied but somewhat limited use in the oil field. An early well stimulation technique, still in use today, in vo lves shooting ni troglycerin to en large the borehole and to increase matrix permeability near the wellbore. Bullets and jets are now the conventional method of perforating casing and tubing. Detonations are frequently used to "back off" or "shoot off" stuck pipe and, of course, seismo-graphic work has long depended on explosive-generated pulses to find attractive earth structures. Efforts to use explosives in drilling operations have received limited examinations1-3 which, in one respect, is surprising because explosives offer one way to transmit large amounts of energy directly to the bottom of the hole. Recently, Ostrovskii l described a Russian method of drilling with explosives that utilizes small capsules containing explosives which are pumped into the mud stream to the bottom of a borehole. As the capsules leave the end of the drill pipe, a detonation mechanism is armed. Impact detonates the explosive. In another configuration, two liquids (an oxidizing agent and fuel) in the capsule are separated by a frangible membrane. Separately, the liquids are nonexplosive. Near the bottom of the drill pipe, the capsule passes through a narrow constriction which ruptures the membrane. The mixing of the liquids produces an explosive. Impact is again used to detonate the explosive. About the time Ostrovskii was developing his method, Humble Oil & Refining Co. was independently doing research on another explosive drilling concept based on the sequential detonation of two types -of explosive charges. The proposed technique consisted of alternately pumping a shaped charge and then a "gauging charge" down a well. The shaped charge should drill a long, tapered hole, and the gauging charge should expand it to full gauge. This paper presents the visualized drilling concept and gives results of laboratory work which showed that sequential firing of charges can form hole at an attractive charge-to-rock removal ratio. An important finding was that increased environmental pressure, which is to be expected in wells, increases rock removal efficiency of the gauging charge.

Jan 1, 1966

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By Milton Williams

A comparison is made between the amount of interstitial water found by analysis in cores and that estimated from the resistivity curve of the electric log for the corresponding strata of producing reservoirs. It is shown that while the determined and the estimated water saturations are in good agreement in some cases, this agreement may be due to a fortuitous compensation of errors. Estimates of water saturations made from the electric 1og by use of existing relations should, therefore, be employed with caution. Also presented are data on the variation of salinity of interstitial waters in reservoir sands, and on the effect of variation of salinity and porosity on the validity of estimates of water content made from the electric log. INTRODUCTION Throughout the history of electric logging there have been recurrent cycles of optimism and pessimism as to the value of the electric log in the quantitative estimation of reservoir fluid content. The very early days of electric logging were an optimistic period, in which there was widespread faith in the ability of the resistivity curve to reflect fluid content, and in the ability of the potential curve to indicate textural characteristics. In time the accumulation of exceptions to this idealistic behavior brought about a general disillusionment, and caused the more pessimistic of those dealing with electric logs to believe that the sole importance of the log lay in stratigraphic correlation. Within the last several years optimism as to the quantitative use of the electric log has been revived, primarily as the result of the stimulating work of C. E. Archie' on the estimation of interstitial water in sands from resistivity data. Even though the general trend of thought on the quantitative value of the electric log reflects optimism, it is inevitable that there are some widely divergent opinions of the validity of quantitative estimates based on the electric log. A valid method of estimation of fluid content by means of the electric log and a general knowledge of the textural character of the reservoir rock would be of signal importance, not only in that it would save time and money in securing information on reservoirs now being drilled, but also because it would permit the evaluation of reserves in many fields drilled without adequate core data subsequent to the advent of electric logging. Because of this importance, Humble's Production Research Division, in cooperation with various other company divisions, initiated several years ago series of tests designed to evaluate the reliability of estimates of fluid content made from the electric log. The investigation was limited at the outset to sand reservoirs, since it was felt that the inclusion of limestone reservoirs would entail needless complications. In devising these tests it was immediately apparent that the chief difficulty in evaluating the worth of any method of estimation lay in establishing the true value of fluid content. The results of direct analyses of cores cut with ordinary mud were not sufficient, because of the probability of contamination of the fluids by filtrate from the drilling mud; the results of restored state tests on cores were deemed unsuitable because these results can hardly be said to furnish a primary standard. The method adopted was the direct analysis of cores cut with an oil-base drilling fluid. Such cores, when properly handled, are believed to afford the most precise determination of water content available at the present, and, in addition, lend themselves readily to the determination of various other properties which are pertinent to the estimation of fluid content from the electric log. Since it was desired to compare the fluid contents estimated from the electric log run in ordinary mud with cores cut in the same hole, the use of oil-base fluid necessitated the changing over, after all cores were cut, to a conventional mud. This procedure presented several advantages, one of which was that the use of oil-base fluid permitted

Jan 1, 1950

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By F. W. Jessen, N. Lamont

The effect of an existing fracture or joint plane, which may exist in a rock, on the extension of a hydraulically induced fracture through the rock has been investigated in the laboratory. By use of a series of models made from various outcrop rocks, the width and orientation of existing fractures do not alter the extension or direction of the hydraulic fracture. The results, which conform quite well with the Grifith theory of failure, are illustrated by a series of photographs of the various models. INTRODUCTION The process of hydraulic fracturing has been widely used in the oil industry since its introduction in 1948 and has made possible the production of many reservoirs which would have been uneconomical prior to this process. Numerous studies of the mechanics of the process2-h nd of the effects of oriented fractures on recovery'.' have appeared in the literature. The increased recoveries led to attempts to predict the orientation of hydraulic fractures at the wellbore and to the development of methods to control this orientation. Field tests have been devised"." which indicate the validity of theoretical predictions of fracture orientation at the borehole. The direction of extension of hydraulic fractures from the borehole has not received much attention since most studies have predicted, at least implicitly, that a fracture will continue in the same plane unless a change of state of stress in the rock occurs. Since such predictions are based on the assumption of rock homogeneity, the effects of rock heterogeneities are left unknown. Most sedimentary rocks are composed of layers which reflect the changing depositional conditions of geological time. In addition, the more competent rocks frequently are fractured and jointed as the result of structural deformations or tectonic movements. Evidence of such joint systems exists in many surface outcrops, and it can be assumed that similar systems occur in many subsurface rocks, although the individual joints may be rather tightly closed due to overburden forces. This paper investigates the effect that an existing fracture in a rock would have on the direction or orientation of an extending or advancing hydraulic fracture when it intersects the existing fracture. The study was conducted on small rock models under triaxial stress conditions. The results indicate that an existing fracture will have little effect on the hydraulic fracture. THE MODEL STUDY The rock model represents an elemental portion of the earth containing an existing fracture which is located at some distance from a borehole from which hydraulic fracture is being extended. A generalized view of a model is presented in Fig. 1. The models were constructed from cement blocks and natural rocks. The various materials tested and some of the physical properties are listed in Table 1. The rocks were cut into rectangular blocks with dimensions of 11/2 X3Y2 X4 to 8 in. An initial slot was cut into the end face of each block along the longitudinal axis normal to the top face. The slot was filled with plastic aluminum along its outer edge to a depth of 1/16 in. A hole of 3/8-in. diameter was drilled into the sealed slot at the center of the end face to serve as an entry port for the fracturing fluid. Existing fractures of various types were simulated in the models. A "hairline" fracture with essentially zero width was created by cutting the model into two parts with a diamond saw and replacing the two parts together along the cut. A finite-width fracture was created by placing a layer of sand grains between the two faces of the cut just described (see Fig. 12). A large open fracture (similar, perhaps, to a vug) was created by cutting the model in two parts and removing a portion of the downstream block to a depth of % in. See Fig. 13. For a fourth

By K. H. Ribe

Water often enters an oil reservoir during completion or workover operations on a well and forms a partial "water block" to oil production. A mathematical study of radial two-phase flow, neglecting capillary effects, has been employed to study the formation of such a water block and subsequent re-moval by production from the well. The effects of reduced oil permeability about the well on the well productivity were studied. The fluid saturation distributions about the well during formation and removal of the water block have also been computed. Several relative permeability relations and viscosity ratios were employed. If water has invaded the formation, its influence through relative permeability effects alone can cause the following. 1. Oil productivity will be depressed for extended periods after production is resumed and will build up only gradually as the water is removed. 2. Oil injected for treatment of water blocking will delay rather than promote restoration of full well productivity by enlarging the region invaded by water. Thus, unless the specific action of chemicals contained in the oil is needed, oil injection appears undesirable. INTRODUCTION During oilwell workover operations, water may enter the oil-bearing formation from the wellbore. When production is resumed, oil must flow through the region invaded by this water. The presence of this region can cause both well productivity and oil production rate to be low and oil to be produced with high water-oil ratio for some time after production is initiated. This situation is sometimes described as a water block. The introduction of water into the formation may result in other actions which also lead to reduction in well productivity and which are also usually included in the connotation of the broad term, water block. Often considered, for example, are the possibilities of clay swelling by contact with fresh water and the formation of emulsions with the formation oil. If it is suspected that such specific actions have taken place, remedial treatments are undertaken which usually involve the injection of chemicals in oil. Since the introduction of water, even in the absence of specific interactions with the formation or oil, will cause a temporary water block (which might be misinterpreted as evidence of a more severe situation), it is of importance to evaluate the magnitude and duration of this blocking which results purely from the reduction in relative permeability to oil in the vicinity of the wellbore. It is also of interest to evaluate the effect of oil injection on the productivity of a well blocked by water in this manner. Inasmuch as this unfavorable condition may persist for some time, it may lead to premature condemnation of a workover or premature abandonment of a potentially productive pay zone. A quantitative evaluation of the influence of water entry on the oil productivity through changes in relative permeability was made by solving a radial form of the Buckley-Leverett equation. The distribution of water saturation around the wellbore during the entry of water was calculated and was followed by a similar calculation of the saturation distribution during the period of resuming production. At any stage in the removal of the invading water, knowledge of the distribution of its saturation permitted calculating the attendant loss in oil productivity. The influence of the shape of the relative permeability relationships was also evaluated by carrying out the calculations for two hypothetical cases. Further, the effect of the oil-water viscosity ratio was examined by repeating the calculations, for several ratios of unity and greater, with the same relative permeabilities. Fi-nally, results are presented to show how the length of time a well must be swabbed to resume production depends on the length of time it has been subjected to invasion by water. STATEMENT OF THEORY Differential Equations Water is assumed to enter a producing formation which is initially at the connate-water saturation and contains no gas. The water and oil are treated as in-

By J. M. W. Mackenzie, M. H. Buckenam

Flotation experiments using stearic, oleic, linoleic, linolenic, and ricinoleic acids and naturally occuring products rich in these acids as collectors for calcite are described. The results confirm the validity of the rule of Hukki and Vartiainen relating the collecting power and unsaturation of the C18 acids. Reasons for this relationship are discussed and a close relationship between mineral depression and critical micelle concentration is reported. It has long been recognized that the unsaturated fatty acids are in general superior flotation collectors to their saturated homologues. Whereas earlier workers concentrated on saturated and monoethe-noid acids, recent investigations have centered on oleic, linoleic, linolenic, and the substituted mono-ethenoid acid: ricinoleic. From studies of the collecting properties of palmitic, oleic, linoleic, and linolenic acids on ilmenite, rutile, hematite, and magnetite, Hukki and Vartiai-nenl concluded that the collecting power of fatty acids increased with unsaturation of the hydrocarbon chain. Sun, Snow, and Purcel12 investigated the collecting properties of unsaturated fatty acids as collectors for phosphate ores and concluded that the collecting power increased with increasing unsaturation of the hydrocarbon chain up to two double bonds and that further unsaturation decreased the collecting power. More recently Sun3 studied the collecting power of the C18 fatty acids stearic, oleic, linoleic, and linolenic on 37 minerals. The results of these experiments with a few exceptions showed that the collecting power of the acids increased in the order stearic, oleic, linoleic, and linolenic. The relative collecting powers of linoleic and linolenic acids were in many cases altered by the cleanliness of the mineral surface prior to flotation. Sun concluded that linolenic acid may become oxidized by atmospheric oxygen during flotation, a reaction which would reduce its effectiveness as a collector. This deduction is supported by Gaudin and Cole4 who concluded that oleic and linoleic acids do not undergo appreciable oxidation of the double bonds during flotation but that the linolenic acid double bonds are measurably affected. The most complete investigation on the influence of hydrocarbon chain unsaturation on the collecting properties of fatty acids is that of Kivalo and Lehm~svaara.~ These workers using linolenic acid of a higher purity than Hukki and Vartiainen showed that this acid was superior to oleic and linoleic acids as a collector for magnetite. They also found that ricinoleic acid was a more effective collector for this mineral than the other acids investigated, an observation particularly apparent at high collector concentrations. Seeking to explain the superiority of the unsaturated acids these authors considered the effects of critical micelle concentration, surface activity, hydrolysis, and cross sectional area of the hydrocarbon chain in relation to unsaturation. Using what, according to the results of Caviere are erroneous surface tensions of the soap solutions of these acids, they concluded that the surface activity decreases and the critical micelle concentration increases with increasing unsaturation. In view of the data of Cavier, whose results show that surface activity of these soaps increases with unsaturation, the deductions of Kivalo and Lehmusvaara are open to criticism. The degree of hydrolysis of the soap solutions as measured by Kivalo and Lehmusvaara decreases as the unsaturation of the fatty acid increases, a result which helps to explain the superiority of unsaturated acids as collectors. In view of the superiority of unsaturated acids as collectors for many minerals, attention has been directed towards the utilization of fatty acid raw materials such as tall oils and linseed oils which contain considerable quantities of these acids. This paper describes test work to determine the effect of unsaturation of the hydrocarbon chain on the collecting properties of fatty acids on calcite, and includes comparable test work using natural products rich in unsaturated acids. TEST WORK Reagents: The pure fatty acids used were oleic, linoleic, and linolenic. Of these, oleic was supplied by British Drug Houses Ltd. and the others were produced by the Hormel Inst. When not in use these

Jan 1, 1961

By T. K. Perkins, O. C. Johnston

Because of the influence of dispersion on miscible-displacement processes, diffusion and dispersion phenomena in parous rocks are of current interest in the oil industry. This paper reviews and summarizes a great deal of pertinent information from the literature. Porous media (both unconsolidated packs and consolidated rocks) can be visualized as a network of flow chambers, having random size and flow conductivity, connected together by openings of smaller size. In such a porous medium, the apparent diffusion coefficient D is less than the molecular diffusion coefficient Do, as measured in the absence of a porous medium. For packs of unconsolidated granular material the ratio D/D, is about 0.6 to 0.7. For all porous rocks, both cemented and unconsolidated, the ratio of diffusion coefficients can also be represented as D/Do = 1/FF where F is the for- mation electrical resistivity' factor and 4 is the porosity. If fluids are flowing through the porous medium, dispersion may be greater than that due to diffusion alone. At moderate flow rates the porous medium will create a slightly asymmetrical mix zone (trailing edge stretched out), with the longitudinal dispersion coefficient approximately proportional to the first power of average fluid velocity (if composition is nearly equalized in pore spaces by diffusion). If the velocity in interstices is large enough, there will be insufficient time for diffusion to equalize concentration within pore spaces. In this region, longitudinal dispersion increases more rapidly than fluid velocity. At low velocities in interstices, transverse dispersion is characterized by a region in which transverse diffusion dominates. If the fluid velocity gets high enough, there will be a transition into a region where there is stream splitting with mass transfer but with insufficient residence time to completely damp-out concentration variations within pore spaces. There are several variables that must be con- trolled to get consistent longitudinal and transverse dispersion results, viz., (1) edge effect in packed tubes, (2) particle size distribution, (3) particle shape, (4) packing or permeability heterogeneities, (5) viscosity ratios, (6) gravity forces, (7) amount of turbulence, and (8) effect of an immobile phase. INTRODUCTION Diffusion and dispersion in porous rocks are of current interest to the oil industry. This interest arises because of the influence of dispersion on miscible-displacement processes. In a recovery process utilizing a zone of miscible fluid, there is the possibility of losing miscibility by dissipating the miscible fluid or by channeling or "fingering" through the miscible zone. Diffusion and dispersion are two of the mechanisms that may lead to mixing and dissipation of the slug. On the other hand, dispersion may tend to damp-out viscous fingers which may be channeling through the miscible slug. 58 Hence, dispersion may be detrimental or beneficial (if it prevents fingering through the miscible zone). Therefore, it is doubly important that we understand these processes. In this paper we review, summarize and interpret a great deal of information from the literature. In particular, we will briefly discuss molecular diffusion in miscible fluids. Then we will discuss what differences to expect for diffusion in a porous rock. If there is movement of the fluid through the rock, then there may be an additional mixing or "dispersion". Furthermore, the dispersion longitudinally (in the direction of gross fluid movement) and transverse to the direction of fluid movement will not be equal. We will discuss both types of dispersion as well as several variables which can affect dispersion (viscosity differences, density differences, turbulence, heterogeneity of media, etc.). This group of variables has sometimes led to difficulty when comparing literature data. DIFFUSION OF MISCIBLE FLUIDS If two miscible fluids are in contact, with an initially sharp interface, they will slowly diffuse into one another. As time passes, the sharp interface between the two fluids will become a diffuse

By J. A. Musselman, P. F. Gnirk

A study was made of indexed penetrations by a single dull bit tooth under statically applied loads into rock subjected to confining pressures from atmospheric to 5,000 p.si and atmospheric pore pressure. Experimental results obtained with a 45" wedge tooth over the above range of pressures are presented for two limestones and a sandstone, a variely of indexing distances and two degrees of tooth dullness. The optimum distance between successive bit-tooth penetrations required for maximum rock damage and chip formation decreases substantially with increa.sing confining pressure above the brittle-to-ductile transition pressure of a particular rock. However, the distance remains approximately constant for a variation in confining pressure below the transition pressure. At a given confining pressure, the bit-tooth force required lor chip formation is constant for indexing distances greater than optimum, but generally decreases linearly with decreasing indexing distance for distances less than optimum. The chip-formation force data obtained at confining pressures for which the chip-generation mechanism is macroscopic-ally of a pseudoplastic nature compare favorably with previous theoretical results for indexed dull hit-tooth penetrntion into an idealized, rigid, perfectly plastic rock. INTRODUCTION To study the cutting action of a roller-cone bit, the interaction of a penetrating bit tooth with craters formed in a rock surfacc by the passage of previous bit teeth must be considered. Current knowledge of the basic mechanics of bit tooth-rock intcract:on under simulated borehole environmental conditions has been extensively reviewed.',' Particularly of current interest are the effects of bit-tooth shape, distance between successive penetrations and differential pressure at the rock surface on the extent of the interaction. Pertinent to this paper are results of an experimental investigationb f the interaction between successive penetrations by sharp, wedge-shaped bit teeth. It was demonstrated that both bit-tooth angle and differential pressure influence the extent of rock damage between successive bit-tooth penetrations. Specifically, the optimum or minimum distance between successive penetrations required for maximum interact'on or chip generation tends to decrease with decreasing bit-tooth angle and increasing differential pressure. In addition, at differential pressures on the order of 2,000 psi for four va- rieties of limestones and sandstones, the macroscopic mechanism of chip formation exhibits a transition from brittle to ductile. In this paper, experimental consideration is given to successive or indexed penetrat ons by wedge-shaped bit teeth. Since pore pressure in a rock sample is maintained at atmospheric pressure, the differential pressure at the fluid-rock interface is equal to the confining pressure. The degrees of bit-tooth dullness include teeth with flat and round apexes (Fig. 1). Of primary concern in this paper are the bit-tooth forces required for chip formation, the macroscopic mechanism of chip formation and the minimum distance between successive penetrations, i.e., optimum indexing distance required for maximum rock damage, as functions of differential pressure. Of further interest is a comparison of actual bit-tooth chip formation forces at elevated differential pressures with calculated forces from previous theoretical results4 for indexed dull bit tooth penetration into a rigid-plastic rock. EXPERIMENTAL APPARATUS AND PROCEDURE The experimental apparatus consists of a pressure vessel equipped with a piston through the side of the vessel (Fig. 2). A single bit tooth inserted in the lower end of the piston is forced at a desired rate into the rock when the ram pressure chamber is pressurized. Electrical instrumentation incorporated into the apparatus yields a graphical plot of force on the piston as a function of bit-tooth penetration or displacement into the rock. Since the piston and ram assembly are in force equilibrium for a constant confining pressure in the main vessel, the fluid volume in the vessel remains constant during bit-tooth penetration. Hence, the force resisting penetration of the tooth is independent of the force exerted on either end of the as-

By A. D. McMaster, M. L. Gimpl, N. Fuschillo

There is interest in the use of rhenium metal films as resistive elements in thin-film circcits, and already some zvork has been done using er)aporated rhenium films. It has been found that rheniim films protected from the atmosphere by an evaporated layer of silicon monoxide show excellent electrical stability. Unprotected films, however, are subject to aging- effects, notably the increase in electrical resistivity as a function of time. This phenomenon can be understood as primarily one of oxidation of the thin films. This paper is concerned with the study of the oxidation and crystallization behavior of such unprotected films. It has been found that the oxidation rates are a function of the substrate temperatures used during the deposition of Lhe metal films. The strictures observed in the films are correlated with the film resistivities and some data are presented to establish the existence of the various types of oxides of rhenium. ThERE is some interest in the use of thin films of rhenium metal as resistive elements in monolithic, thin-film integrated circuits. Some work has been done using evaporated films and it has been found that such films, if protected from the atmosphere by an evaporated layer of silicon monoxide, show excellent electrical stability up to temperatures of 500"." Rhenium films unprotected from the atmosphere tend to age and the electrical resistivity of the films increases as a function of time. Rhenium films, of the order of <100A thick, prepared by electron-beam evaporation techniques are found to oxidize very readily when exposed to dry air at room temperature. It would seem, therefore, that this aging phenomenon could be attributed to the oxidation of the metal films. In this investigation, the oxidation and crystallization behavior of thin films of rhenium evaporated onto silicon monoxide substrates were studied as a function of the substrate temperatures used during the evaporation. The films were examined using electron-microscopy and electron-diffraction techniques. EXPERIMENTAL RESULTS Rhenium metal was evaporated onto suitable prepared substrates which were heated to various temperatures. The evaporations were performed in a vacuum of approximately 5 x 1CT5 torr. The evaporation was carried out at a rate of approximately 10A per omin. The final film thickness was approximately lOOA and the resistance ranged from 5000 to 10,000 ohms per square. The substrates used for supporting the metal films were made by evaporating 75A of silicon monoxide onto freshly cleaved mica. The silicon monoxide film was then floated off the mica by immersing the composite in water. The film could then be picked up on a clean nickel grid. Silicon monoxide substrates were chosen because of their similarity to quartz and glass substrates commonly used for making thin-film resistors. Fuschillo, Gimpl, and McMas-ter have also shown that silicon monoxide films have only minor structural changes at temperatures up to 800°C. This fact simplified the interpretation of any changes observed in the electron micrographs or electron-diffraction patterns obtained from the deposited rhenium films. After the evaporations were completed, the substrates were cooled to room temperature, except where noted differently, before the coated substrates were removed from the vacuum system. All aging of the deposited films was done in a desiccator. The evaporated films were examined in an electron microscope equipped with a hot stage that would permit continuous observations of the samples up to temperatures of 1000°C. RESULTS A series of electron micrographs of the rhenium films deposited on the silicon monoxide substrates are shown to Figs. 1 to 3. In all cases, the metal films are approximately 100A thick and the micrographs were taken 1 hr after the deposition was completed. here was no apparent structure in the films deposited on the substrates held at the higher temperatures. The

Jan 1, 1967

By Wayne E. Glenn

The San Miguelito Field of Ventura County, California, lies along the coast approximately five miles northwest of the city of Ventura. The structure is one of several in the Ventura anticline, a series of anticlinal folds trending northwest-southeast through the San Miguelito Field. The Ventura Avenue Field lies to the southeast along the anticline, and Padre Canyon and Rin-con Fields lie to the northwest; the series then extends beneath the Pacific Ocean. Production is obtained from the Lower Pico and Repetto formations of Pliocene age, and oil accumulation is controlled by faulting, lithology and structure. The first well in the First Grubb Pool was completed in November, 1931, and to date 48 producing wells have been drilled on the 276 productive acres. Approximately 685 ft of net pay are contained in the eight sand bodies grossing 1,220 ft of section. Production of oil to date has been 15,-600,000 bbl. A gas injection project was instigated in April, 1940, but was discontinued in September, 1949. This paper is confined to a discussion of the development and performance history of the First Grubb Pool of the San Miguelito Field. LOCATION AND GEOLOGY The San Miguelito Oil Field is located in Ventura County about five miles northwest of the city of Ventura along the coastal highway to Santa Barbara. It is located within sections 23, 24, 25, and 30 of Township 3 North, Range 24 West, San Bernardino Base and Meridian. Surface elevation in the field ranges from sea level to plus 1,200 ft, and the terrain is extremely rugged. The structure is well defined on the surface and on the wall of the Amphitheatre Canyon where appears a so-called "text book" anticlinal section. The San Miguelito structure is an asymmetrical, elongated anticline about two miles long and three-fourths of a mile wide. The trend of the axis of the anticline is northwest-southeast. Fig. 9 illustrates the contours and major faults of this structure. Dips on the southwesterly flank average about 40 degrees, whereas the northeasterly flank ranges from 60 to 75 degrees. There are several faults striking generally east and west. These faults do not appear to affect materially the area of accumulation or performance behavior. It is believed that accumulation was affected by steeply dipping beds and extremely low permeability of the northeast flank of the structure. As shown by the typical log, Fig. 1. the San Miguelito Field is divided into two stratigraphic producing intervals. The First Grubb Pool comprises the interval from the "G" to "L" markers; the Second Grubb Pool from the "L" to "M" markers. The First Grubb Pool, ranging in thickness from 1,105 to 1,680 ft, with an average of 1,220 ft, includes approximately 685 ft of oil-bearing sands. The First Grubb zone consists of eight sand intervals separated by shales. The shale bodies separating the eight sand intervals within the First Grubb Pool are continuous throughout the major part of the structure and serve as an effective barrier. Many of the thin, irregular shale or siltstone streaks within these sand bodies are discontinuous and do not affect well performance appreciably. The productive horizons in the First Grubb Pool are siltstones and sandstones of the Lower Pico and Repetto formations of Pliocene age. It is apparent from inspection of the typical log that the "G" to "L" interval might have been separated into at least six producing zones and selectively pro. duced. Unfortunately the electric log and some of our modern tools were not available or were in their infancy dur. ing the period 1931 through 1937. Not until 1937 when eight wells had been completed were there sufficient geological data to permit definition of the sand bodies. Then the problem of reservoir control in this multiple-sand field, where all sands are open to a common

Jan 1, 1950

By W. Hodge, A. F. Haskins, R. M. Evans

Refractory boron compounds are shown to resist corrosion by molten zinc. Coatings were made from ferroboron and manganese boron by several methods: welding, hard facing, and pack diffusion; and techniques of coatings are very important. Mechanical failure of the diffusion coatings can be partially eliminated by applying them to type 416 chromium steels rather than carbon steels. Welded coatings made with a tungsten arc are better than those made by other welding methods. Sintered compacts of mixtures of iron and chromium borides developed strengths of about 30,000 psi. They resisted corrosion of zinc at 600°C and oxidation at higher temperatures. MOLTEN zinc rapidly attacks common metals of construction. The rate of attack is greatly amplified at temperatures over 500°C. However, there are many applications where it is necessary, or at least advantageous, to use metal construction, such as for galvanizing pots and zinc smelter equipment. Condensers and agitator linings used in continuous zinc smelting processes are eroded and corroded by violently agitated molten zinc. Pumps, tubing, and other parts to permit transfer of molten zinc would be desirable in many zinc handling operations. The development of metallic materials which are resistant to molten zinc also might permit its use as a heat-transfer medium in modern high efficiency power plants. In reviewing previous work on zinc-resistant metals, it was evident that most of the available data refer to corrosion at temperatures just above the melting point. Tungsten and high Mo-Fe alloys containing more than 80 pct Mo resist corrosion by molten zinc.&apos;, &apos; Imhoff states that because chromium is not attacked by zinc, chromium plating improves galvanizing pot life." Nitrided cast iron has been used in die-casting machines&apos; where the molten alloy is 96 pct Zn and 4 pct Al. Other metals that have been suggested as of possible value for zinc resistance are columbium, tantalum, and titanium.V he corrosion of steel by zinc has been discussed by many authors,z, "2 None of these materials resisted corrosion by molten zinc at the temperatures used in this investigation, i.e., 600" to 700°C. I. Exploratory and Resistant-Coating Tests To make a study of zinc-resistant metals, exploratory tests were conducted to sort out roughly those materials which seemed most worthy of further development. This preliminary study included both solid metals and surface coatings. Exploratory Corrosion Tests in Molten Zinc—In initiating a study of this problem, numerous samples of metals and alloys were evaluated by dynamic corrosion tests made at 440 °C. Each metal was tested in its most readily available form, which, because of shape and size, was often unsuited for standard corrosion testing. The equipment used for dynamic corrosion testing of all materials, except in a few initial experiments, is shown in Fig. 1. Samples were tied to tungsten rods with tungsten wire, immersed in the zinc, and revolved at 12 rpm about the circumference of a 4 in. diam circle. Speed of travel was about 12.5 fpm. The molten zinc was protected from oxidation by an atmosphere of carbon monoxide, or, at a later period in the program, by a 9:1 mixture of nitrogen and hydrogen. When the effect of both molten metal and atmosphere was desired, the zinc level was lowered. Special high grade zinc was used in all of the corrosion tests. Corrosion losses for materials tested are shown in Tables I and 11. Whenever the materials were available in suitable form, the losses are reported in mils per year. It was recognized that weight losses on irregularly shaped specimens did not show the corrosion rate but the important consideration—poor resistance to corrosion—could be determined readily.

Jan 1, 1956

By C. N. J. Wagner, E. N. Aqua

Dilute Fe-Si alloys (0 to 5 wt pet Si) were cold-worked by making filings at room temperatuve. The analysis of the broadening of the X-vay powdev pattern peaks yields anisotropic particle sizes normal to the (110), (100), and (112) planes which are a consequence of deformation faults (probability a) and twin faults (probability p). The combined fault probability (1.5a +ß) increases from 0.01 in pure iron to 0.02 in Fe-5 pct Si. The root mean square stvains vary with crystallographic ovientation due to elastic anisotropy of the alloys, and increase from about 0.0035 in pure iron to 0.005 in Fe-5 pct Si measured in the [100] direction. Assuming that deformation and twin faults occur with equal probability, the X-ray data would imply that the stacking-fault energy does not change upon alloying. THE crystallographic aspects of the plastic deformation of dilute Fe-Si alloys has been studied many times since the observation of glide band structures by Barrett et a1.l These glide bands were much straighter than the wavy bands observed by Gough2 in unalloyed iron nearly 40 years ago. This difference in the morphology of the slip band structure has been verified many times, most recently by replication electron microscopy3 and dislocation etch-pitting methods.4,5 These observed differences in deformation behavior have been considered to result from the degree of cross slip that occurs in pure iron and in the Si-Fe alloys. The lowered tendency for cross slip would result from a lowering of the stacking-fault energy of iron by the silicon alloying addition. Experimental evidence for this lowered stacking-fault energy in the Si-Fe alloys, obtained with transmission electron microscopy, is the observation of dissociated dislocations in Fe-6 pct si6 and Fe-3 pct Si alloys,7 and the observation of sharply defined cellular substructures in Fe-3 pct si6,7 compared to the more diffuse substructure in zone-refined iron.&apos; The activation energy for recovery of cold work is greater in the Si-Fe alloys than it is in pure iron, indicating that cross slip has become a more difficult process.9 The purpose of this investigation is to determine the change in stacking-fault probability from the broadening of powder pattern peaks in dilute silicon-in-iron solid solutions, when cold-worked at room temperature. The knowledge of the stacking-fault probability and the dislocation density, both of which can be deduced from line-broadening analysis of two orders of reflections from (110), (200), and (112) planes, will permit us to calculate the change in stacking-fault energy upon alloying silicon into iron. Previous X-ray investigation of cold-rolled Fe-5 wt pct Si (100)[001 ] single crystals did not reveal any line broadening, whereas cold-rolled Fe-3.1 wt pct Si (001) [110] and (001)[100] single crystals10 showed line bro2dening as a consequence of small particle sizes (-200A) and root mean square strains (-0.25 pct), which are comparable to those found in cold-worked iron filings.11 EXPERIMENTAL PROCEDURE A series of five Fe-Si alloys containing nominally 1 to 5 wt pct Si and pure iron were cold-worked by making filings at room temperature. The actual silicon content deviated at the most by +0.1 pct which is of no significance in the present study. The carbon contents of these materials were less than 0.02 pct. The X-ray diffraction patterns were measured with molybdenum, cobalt, and iron radiation using a GE and a Philips diffractometer. The (110)-(220), (200)-(400), and (112)-(224) pairs of reflections were

Jan 1, 1968