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By Winthrop P. Haynes

The symposium on production for the year 1944 includes more foreign papers than any one of the past three years, because of a partial relaxation of the censorship in many Western Hemisphere countries. The committee was not successful, however, in securing papers from Europe and the Near and Far East at this time, with the exception of Saudi Arabia and Bahrein. Where possible, these papers include summaries upon production for the missing war years, so that we shall have no permanent gap in the records. At the close of the war, we hope again to publish the usual more complete form of report for all important oil-producing countries. EXCERPTS FROM CIRCULAR TO AUTHORS In order to facilitate interpretation of the data in this chapter, we print the following excerpts from the Circular to Authors. The field is the unit in this tabulation. In cases of fields extending across State boundaries, such as Rodessa, it is suggested that each State author treat the section of the field in his State as a unit, and by a footnote indicate that the field extends into an adjacent State. Each place in the table may represent one of three possibilities; either the proper entry is determinable and can be supplied by the author, or an approximate figure can be supplied which is the author's best guess and should be entered followed by an x, or it does not apply to the particular field and the space is left blank. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. The entry of a zero is a positive declaration, and it is an important declaration where it is in order. It is thought that the nearest whole numbers are sufficiently accurate for our purposes except as to percentage of sulphur in oil. If an author desires to report any other figures to tenths, he may do so. The quantity of gas produced should include, where possible, gas sold or otherwise marketed, and gas blown into the air, burned as flares or otherwise wasted. Segregation of these figures would be interesting if the authors can make such segregation. In any event, the figures should represent as nearly as possible the total quantity of gas removed from the reservoir. . Under the columns on "Depth," the average depth to the top of the productive zones and to the bottom of the productive wells, when subtracted, should give the approximate thickness of the productive zone. For fields where this is not true because of unusually high dip or for some other reasons, it is suggested that the authors indicate in their text the approximate average thickness of the productive zone. The net thickness of the producing formation should be the thickness of the producing zone, less the estimated amount to cover the portions of the zone that do not yield oil, such as dense shales, etc. It is recognized that for some fields the authors can only make rough guesses; in such cases, they should enter their best estimate followed by an x. Average production per acre-foot need not be reported as it can

Jan 1, 1945

This volume summarizes characteristics and the geological setting of porphyry copper deposits of the Western Hemisphere. Grouped by characteristics, porphyry copper deposits are described in six regions: Andean orogen, Appalachian orogen, Alaska, northern Cordilleran orogen, southern Cordilleran orogen, and the Caribbean. Each region has its own peculiarities of geologic setting, and those deposit characteristics that may be projected from one chapter to another will be used in reaching the conclusions from which to draw genetic models for porphyry copper deposits. The term porphyry in this volume denotes a type of ore deposit, rather than a rock classification. The classification of intrusive igneous rocks used in this volume is shown in Figs. 36a and 42 (pp. 103, 130). Some modern classifications suggest mineral-ratio definitions other than those used in this volume; however, most literature references cited are based on the classification shown in Figs. 36a and 42. The reader should be aware, therefore, that quartz monzonite in this volume contains from 35% to 65% potassuim feldspar and at least 10% quartz. A term used in this volume is defined where introduced within the context of a specific chapter. Distensional tectonic conditions are used in the sense of Cady (1972) in the Appalachian orogen, for example. Porphyry copper deposits are defined as large bodies of mineralized rock, usually including a porphyritic intrusive phase, that have copper sulfide minerals disseminated through them. The definition has no commercial connotation and is used strictly in a noneconomic sense to encompass the spectrum of copper mineralization associated with these deposits. Terms commonly accepted in the literature are not defined. Porphyry molybdenum and porphyry copper deposits commonly are distinguished by most economic geologists. The basis for the separation is summarized in one chapter of this volume. To permit the reader to more easily peruse the bibliography for any particular region, references will be found at the end of each chapter. The bibliography is not intended to be complete, but is designed to provide adequate minimum coverage for descriptions of deposits in the chapter concerned. Each entry is properly referenced in the text of that chapter to facilitate the reader's research into any particular topic. This volume is written from the point of view of the exploration geologist whose task it is to evaluate the structural, petrographic, mineralogic, and metallogenic characteristics of a porphyry copper deposit. The goal of the evaluation is to determine if, and where, concentrations of metals may exist in an igneous- hydrothermal system that includes the most complex set of geologic factors found in any of the many types of ore deposits. The successful porphyry copper geologist is simultaneously a petrographer, geochemist, structural geologist, and mineralogist. Some porphyry copper deposits have developed in volcanic arcs underlain by a Benioff seismic zone with a trench paralleling the arc. The most convincing example of a deposit known to have developed in an environment where subduction is an active process is the 3.3 m.y. (million years) old Dry Creek occurrence in the Aleutian arc (this volume). On the other hand, the younger deposits in the Cascades appear to have formed in a volcanic arc lacking both the Benioff zone and the offshore trench. Subduction is not widely accepted as an active mechanism for the period when the younger Cascade deposits formed. Subduction has also been questioned for deposits formed at a great distance from a plate boundary (e.g., Bingham). Regardless of the pros and cons regarding subduction, most deposits are associated with regional faults. Strike-slip

Jan 1, 1978

By R. B. Basham, C. W. Macune

Very small anomalies in oil well temperatures are detected and measured by recording the difference in temperature existing between two thermally sensitive elements which are Spaced several feet apart on a small diameter carrier and lowered into the bore hole. The elements operate in a balanced electrical circuit, sending only a reference signal to the surface as long as normal gradient temperatures are encountered. When either element enters a temperature disturbance, the circuit is unbalanced and produces large recorder deflections for minute anomalies. The system is highly sensitive to small changes in thermal gradients caused by gas or fluid movements and to the boundaries between beds of different thermal conductivities. Typical logs show successful applications of the process to locating gas and water leaks in casing, gas entry. and gas-oil contact. INTRODUCTION Temperature measurements in oil wells have been made for many years in the search for additional sub-surface data. It has been generally agreed that many conditions in the bore hole cause temperature anomalies which, if located and measured, could yield useful information. But it has been recognized also that many of the irregularities, such as those produced by small water and gas leaks in casing, might be very small and therefore difficult to detect with certainty.' Although tem-perature measurements have been made which show anomalies of less than one degree deviation from normal gradient temperatures, the results are usually uncertain and unconvincing. The general practice, therefore. has been to apply temperature surveys only to well conditions known to produce appreciable disturbances, such as large gas movements and cement hydration. The recent demand for additional data has focused attention on the problem of making dependable temperature measurements in the many instances when anomalies are small but none the less significant. It was for the purpose of detecting these minute irregularities in bore hole temperature that the program described in the following text was undertaken. It is emphasized that this presentation is not offered as a complete study, for the process is still partially experimental. But it is believed that the results obtained thus far will be of interest to the industry and will indicate some of the system's potential usefulness. DIFFERENTIAL MEASUREMENT The chief value of differential measurement lies in the fact that a difference between two factors can be measured with a scale of values best suited to that difference, a scale that might be cumbersome or impractical if applied to the factors themselves. When it is known that all factors will be nearly equal in value, and therefore the differences consistently small, it is possible to select a scale which will permit very accurate measurement of the differences. This advantage is in contrast to the difficulty of measuring small increments of a single variable, where the increment must be measured by a large scale which is suitable for measuring the entire factor. Gradient temperatures are usually measured under this latter condition where temperature measuring apparatus must have a scale extending over the range of expected temperatures, say 50' to 25O°F, and it becomes almost impossible to detect small irregularities of less than one degree. The use of large strip chart recorders and divided multiple ranges tend to amplify the small anomaly and make it more pronounced. But the instability of instruments, both

Jan 1, 1952

By D. J. Schmatz

DISCUSSION OF RESULTS The qualitative correlation between low-temperature ductility and prior high-temperature creep strain in nickel obtained in this investigation confirms the result obtained on high-purity brass by Chen and Machlin. However, the quantitative effect is much smaller in nickel. Comparison can be made on the basis of a prior high-temperature strain that is a certain percentage of the total high-temperature elongation to rupture. In the research of Chen and machlin, the prior high-temperature strain of 1/2 pct equaled 8.5 pct of the total high-temperature elongation at rupture. For nickel, in our experiments, 8.5 pct of 21.2 pct equals 1.8 pct. For eh = 1.8 pct, the loss in ductility in percent equals x 100 = b.5 pct. That is, for equivalent bo Formation of Beta Manganese-Type Structure in Iron-Aluminum-Manganese Alloys D. J. Schmatz IRON-aluminum alloys have gained much interest in the past few years for use as a base material for elevated-temperature alloys because of their excel- high-temperature strain the loss in low-temperature ductility is 8.5 pct for nickel as compared to 60 pct for pure a, brass. It is also interesting to note the observation that in nickel the low-temperature fractures, even at the most extreme high-temperature pre-strain, were partly trans crystalline and partly intercrystalline. In the case of a brass, these fractures were completely intercrystalline. According to the data on the percent of the grain boundary area that is cracked, at 22 pct high-temperature elongation, about 12.5 pct of the grain boundary area does not carry load. Thus, the inter-crack areas are carrying a stress that is about 11 pct higher than the nominal stress. A simple model predicts that the overall elongation, which is primarily the elongation in the bulk of the specimen, will correspond to the nominal stress when the stress in the intercrack area equals the tensile strength. Quantitatively this model predicts the equation The form of this equation will agree with that found if the strain-hardening exponent, n, equals unity. Actually this model is too gross an approximation to yield good quantitative results. The question naturally arises as to whether in ordinary hot-working, such as hot-rolling, intercrys-talline cracks are introduced that affect the low-temperature properties. It appears that the answer is that such a possibility cannot be overlooked, if the hot-working induces tensile stresses at temperatures above the equicohesive temperature and if the material tends to be notch sensitive at low temperature. ACKNOWLEDGMENT This research was supported by the Aeronautical Research Laboratory, Directorate of Research, Wright Air Development Center, United States Air Force. REFERENCES lC. Zener: Fracturing of Metals, 1948, Cleveland, ASM. 'H. C. Chang and N. J. Grant: Mechanism of Intercrystalline Fracture. AIME Trans., 1956, voL 8, p. 544; lownal of Metals, May, 1956. 'E. S. Machlin. CreepRupt ure by Vacancy Condensation, AIME Trans., 1956, vol. 8, p. 106; lownd of Metals, February, 1956 'C. Chen and E. S. Machlin: On a Mechanism of High-Temper at ure Inter-crystalline Cracking, lownd of Metals, July. 1957. p. 829. Alloys lent oxidation resistance. Binary alloys of aluminum in iron are ferritic and consequently have poor hot strength. Alloys of iron-aluminum-manganese were made in an attempt to produce an austenitic alloy containing sufficient aluminum to retain the oxidation resistance of binary alloys of iron-alumi-

Jan 1, 1960

By James T. Waber, Allen C. Larson, Karl Gschneidner, Margaret Y. Prince

The original graphical method proposed by Darken and Gurry for predicting which elements are soluble in a given element was slightly modified and was used to predict terminal solubilities in 1455 known binary combinations. it was found that the modified Darken and Gurry method had a reliability of 61.7 pct in predicting extensive solid solubility (greater than 5 at. pct) and of 84.8pct in predicting limited solid solubility (less than 5 at. pct), an over-all reliability percentage of 76.6. Using the same experimental data, it was found that using only the simple Hume-Rothery size-effect criterion was 50.1 pct reliable in predicting extensive solid solubility, only slightly better than a purely random choice. and 90.3 pct reliable for predicting limited solid solubility, an over-all reliability percentage of 67.6. THE first rational rules for determining a priori whether two metals are not freely soluble in the solid state were announced by Hume-Rothery and coworkers.1,2 These well-known rules have been accorded a special place in metallurgical literature. Since the "electronegative" and "relative valence effect" rules of Hume-Rothery were only qualitative in nature it was difficult to use them in a quantitative analysis. The next major step was made by Darken and gurry3 and apparently went unexplored for a number of years. They prepared graphs illustrating the influence of both electronegativity and size difference on the solubility of elements in silver, magnesium, and aluminum, and they drew elliptical figures, whose maximum width was ±15 pct of the solvent radius and the maximum height was ±0.4 electronegativity units. The purpose of the present paper is to assess and compare the effectiveness of using the simple size-factor and the Darken-Gurry criteria to predict which elements will be soluble and insoluble in a given solute. In 1957, waber4 prepared Darken-Gurry plots for determining the solutes that were likely to be soluble in 6 and plutonium and introduced an inner ellipse as an aid to determining which elements should be soluble to a considerable extent. As illustrated in Fig. 1, the major axis of the outer ellipse corresponded to ±0.4 electronegativity units (OD) while the minor axis corresponded to ±15 pct of the radius of the solvent phase (OB). This simultaneous "action" of the two Hume-Rothery criteria was used to indicate which elements would have little or no solubility in the host lattice, namely those elements whose points lay outside this ellipse. An inner ellipse, "centered" over the same point of the solvent was drawn with ±0.2 electronegativity units (OC) and ±8 pct (OA) as the major and minor axes. Solutes with points lying within the inner ellipse were expected to be capable of forming extensive solid solutions with the host element. Use of this method of applying the earlier Hume-Rothery criteria was moderately successful for plutonium. For 6-phase plutonium, only one element out of the eight predicted to be extensively soluble was known to be almost insoluble, and of the sixteen elements predicted to have more restricted solubility, five were known to be essentially insoluble. The success of discerning solubility in the E phase by this method was comparable. One prediction made on the basis of this analysis was that the heavier rare earth metals, such as holmium, erbium, and thulium, should be soluble in the 6 phase, whereas the lighter rare earth elements, such as lanthanum or

Jan 1, 1963

SEC. 1. The membership of the Institute shall comprise seven classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members; 7. Junior Foreign Affiliates. All shall be equally entitled to the privileges of membership, excepting that no member of any class whose residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the class of Member must be at least 27 years of age and must have had at least six years' employ¬ment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members. SEC. 3. Honorary Members: Each candidate for Honorary Membership must be recommended by at least ten Members and must be elected by ballot at a meeting of the Board of Directors by the unanimous vote of the Directors present; provided, how¬ever, that the number of Honorary Members shall at no time exceed twenty. Such election shall automatically act as a transfer of such member from any other class of membership to which he may belong. SEC. 4. -Senior Members: The Directors may in their discretion place on the Honor Roll of Senior Members and transfer from any other class of membership other than Honorary Membership the name of any Member or Associate who has reached the age of seventy years and who has paid dues for thirty years, and for good reasons in special cases may vary the age or number of years. SEC. 5. Junior Members: A person to be eligible for election to the class of Junior Member must be qualified through education or experience to hold a subordinate position in engineering, mining, metallurgical, geological or chemical work. He shall be not more than 33 years of age at the time of election. SEC. 6. Associates: A person eligible for election or transfer into the class of Associate shall be one, who, in the opinion of the Committee on Admissions and the Board of Directors, is suitable for such election or transfer by reason of his interest in or connection with mining, geology, metallurgy, or chemistry. SEC. 7. Rocky Mountain Members: Membership in a special class of life member¬ships without annual or other dues and without right to receive the printed literature distributed to other members or the right and privilege of wearing the official badge of technical members, is given to all members of the Rocky Mountain Club at the time of consolidation. These special Rocky Mountain memberships shall be claimable by any member of the Rocky Mountain Club, not already a member of the Institute, availing himself of the privilege within ninety days after mailing of notice to him, by the Secretary of the Institute. SEC. 8. Junior Foreign Afliate: Upon appropriate action by the Board of Direc¬tors and with its approval, members in good standing of any technical society having its headquarters outside of the United States of America, Canada, or Mexico,

Jan 1, 1937

By C. B. Alcock, R. A. Oriani

Some simple models of solutions are described; these include the regular solution, the subregular solution, and the quasichemical model. The assunzption underlying these models, the physical signzficance thereof, and the experimental manifestations are discussed. Examples are presented from the fields of liquid and solid metallic solutions, liquid slags, mattes, liquid and solid ionic solutions, and mixed carbides to show under what conditions and for which systems these solution models are fair descriptions. The deviations of real solutions from the models are of theoretical interest. Some such deviations, both for dilute and for concentrated solutions, arc pointed out and their Physical sigtzzficance discussed. DURING the past half century there has been a gradual accumulation of thermodynamic data for systems of interest to the metallurgist. There remain many gaps in the data, however, and the metallurgist must often face the problem of estimation of thermodynamic quantities where measured values do not exist. One might hope that the experimental progress would be matched by theoretical advances which would make such estimations possible with a high degree of confidence. However, theoretical progress has been disappointingly slow even for the simplest kinds of solutions, and since the multicomponent systems in which the metallurgist is interested are very complex, one cannot expect theory to be of much help to the metallurgist. In this situation, therefore, it seems worthwhile to examine some simple models of solutions from two points of view: firstly, to see if such crude models represent the thermodynamic facts in as many types of solutions as possible sufficiently well for the needs of the metallurgist, and secondly to see what the deviations from such models show to be important for consideration by theorists. BOND ENERGY MODELS OF SOLUTIONS The simple models that we will examine from these points of view may be termed statistical models, in that they are concerned with the thermodynamic consequences of some simple assumptions about the energy of an assembly of atoms, molecules, or ions, and do not inquire into the physical basis of the interaction. The underlying assumption of these models is that the energy of an assembly of molecules (by which we include also atoms or ions) is given by the sum over all interaction energies of molecules taken two at a time; we will discuss only those models in which the pairwise interactions are restricted to those between nearest neighbors. Thus, in a pure substance of bond energy EAA, the internal energy (with respect to some specific reference state) will be expressed as NAA EAA where NAA is the number of nearest-neighbor pairs. A solution of molecules A and B will be characterized by NAA EAA + NBB EBB + NAB EAB where the Eij represent the bond energies of the nearest-neighbor i-j pairs. If one assumes that the EAA and EBB are the same in the pure components as in the solution, and that the coordination numbers in the two pure substances and in the solution are the same, then the energy of the solution with respect to the pure components (i.e., the energy of solution) is a function of the following linear combination of the bond energies: EAB - 1/2(EAA +EBB) = w. The thermodynamically ideal solution is defined as one in which the activity of each component is equal to the mole fraction of that component at all concentrations and all temperatures. It follows that

Jan 1, 1962

By S. Kado, G. Derge, L. Yang

Self-diffusion coefficients of silver in molten silver have been measured by means of the capillary-reservoir method in the temperature range 1002" to 1105°C. The results can be .represented by the equation D = (7.10 i 0.06) X 10-4 exp [(—8150 ± 1130)/RT]. The heat of activation agrees within the limit of experimental uncertainty with that for the viscous flow. The validity of the Eyring and the Stokes-Einstein equations are examined on the basis of the self-diffusion coefficients obtained and the known viscosity data of molten silver. MEASUREMENT of the self-diffusion coefficient of silver in molten silver was made in the temperature range 1275° to 1378°K, using the capillary-reservoir method and &"' as the radioactive tracer. The experimental arrangement is shown in Fig. 1. Silver of 99.99 pct purity (fine silver), was melted and degassed in vacuum in a graphite crucible situated inside a McDanel vacuum jacket. The crucible (4 in. tall and 1 in. ID) was protected both at the top and at the bottom with graphite shields and contained about 220 g of silver. The sample holder was a piece of graphite rod (1 in. long and 1/2 in. diam) with 4 capillaries drilled longitudinally into it. The holder was screwed onto a long graphite rod (12 in. long and 74 in. diam) which was connected to a steel disk hanging on a nylon string through a glass pulley. The steel disk kept the sample holder at the center of the McDanel tube and was heavy enough to overcome the buoyancy when the holder was lowered into the molten silver. By turning a handle connected to the pulley through a tapered glass joint, it was possible to raise or lower the sample holder without breaking the vacuum. Two such arrangements were constructed, sitting side by side in 2 Kanthal furnaces. One with non-radioactive silver in its crucible was used for the diffusion run and the other with radioactive silver in its crucible was used for filling the capillaries. To fill the capillaries with radioactive silver, the sample holder was degassed first and then lowered into the radioactive molten silver in vacuum. Purified argon gas was then admitted into the system to push the liquid silver into the capillaries. After cooling in argon, the filled capillaries were polished on emery paper to expose the top of the rod and used immediately as samples for the diffusion run which was carried out at the same temperature as that used for filling the capillaries. During the diffusion run, the samples were degassed in vacuum and lowered slowly into the nonradioactive molten silver before purified argon was admitted into the system. After a predetermined period of time, the samples were raised out of the melt and cooled in argon. The temperature of the melt was measured before and after the run with a chromel-alumel thermocouple inside a McDanel protection tube. Another chromel-alumel thermocouple attached to the outside wall of the McDanel vacuum jacket was used to indicate any fluctuation in the temperature of the furnace during the run, which was found to be less than ± 2°C for the longest run made (93 min). The temperature gradient inside the molten silver was found to be negligible. No significant difference was observed in the results obtained whether the melt was stagnant during the run or was stirred by raising and lowering the sample holder slowly a few times a minute for a distance of about 1/4 in. inside the melt.

Jan 1, 1959

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,' and

Jan 1, 1962

By J. F. Radavich

Many heats of steel of low carbon value have been known to produce brittle pieces of steel. The brittleness is believed to be due to the impurities located within the grain boundaries. Such brittle steels have been examined with an optical microscope to ascertain the nature and the amount of the impurities present at the grain boundaries. Due to the relatively low resolving power of the optical microscope, the impurities are not visible in fine detail. The writer obtained some sheet steel and proceeded to determine the location of the impurities and to show the application of the electron microscope to the study of grain boundaries. One sample was known to be capable of becoming embrittled, whereas another sample was believed to be much less susceptible to embrittlement. Treatment of Specimens The specimens were embrittled by annealing above the A3 point under mildly oxidizing conditions. One piece of ingot iron could not withstand a 90" bend, whereas another piece of ingot iron was not affected and could withstand a 90" bend. The brittle piece was then annealed at a high temperature in a hydrogen atmosphere. The annealed ingot iron was termed cured and could withstand a 90" bend very easily. The three specimens examined will be designated as brittle, good. and cured in the discussion that follows. Procedure The sizes of the specimens were as follows: one piece of brittle ingot iron-3/8 by 35 in.; one piece of good ingot iron-96 by 1/8 in.; one piece of cured ingot iron-36 by 54 in. The specimens were too small to be polished by hand and therefore were mounted in bakelite. The polishing procedure was carried out in the conventional manner with the use of 1/0 through 3/0 papers, and the final polish was done with alumina on a billiard cloth. The specimens were then etched in a 4 pct solution of picral in alcohol, and then they were examined through an optical microscope. An area was chosen that showed distinct grain boundaries, and an effort was made to keep near this area when pulling the replicas REPLICA TECHNIQIJE The replica technique used in the preparation of the replicas for examination under the electron microscope is described in Electron Metallography.' It consists essentially of the following steps: 1. Obtaining a suitably etched specimen. 2. Applying a swab of ethylene di-chloride on the surface. 3. Applying a formvar solution on the surface. 4. Placing a screen on any desired spot. 5. Breathing on the fornivar layer. 6. Applying scotch tape on the screen and film. 7. Pulling the film and the screen up with the Scotch tape. 8. Separating the screen from the Scotch tape. This replica technique is very similar to the one described by Harker and Shaefer. However, with the added step, the percentage of replicas removed is very much higher regardless of the length of the time from the etching of the specimen to the actual pulling of the replica. The replicas were then shadow cast with manganese at a filament height to replica distance ratio of 1 1/2:7. This produced a very high contrast replica for use in the electron microscope. One of the dificulties encountered with this study was the restricted area of the specimen. The width of the specimens was the same as that of the 200 mesh nickel supporting screen. In order to increase the effective area, the screens were cut down as shown in Fig 1. The arrow indicates the direction in which the replica was pulled. This operation made it possible to obtain a large percentage of good replicas. Fig 3 shows an electron micrograph of a brittle piece of ingot iron and a grain boundary that was polished mechanically. The surface is very rough probably due to the incomplete removal of the flowed layer by the picral etchant. The grain boundary does show evidence of impurities. It was decided to electropolish the specimens to obtain a much smoother surface than the one obtained by mechanical polishing. ELECTROPOLISHING The specimens were cut in half to expose the metal on the back side. The exposed metal had sufficient area to make good electrical contact and electropolishing was carried out easily. The conditions for electropolishing were 0.9 amp, 35 volts, and 25 sec. in an electrolyte composed of 850 cc of ethyl alcohol, 100 cc distilled water, and 50 cc of perchloric acid. The polished specimens were then etched in the 4 pct picral solution for a shorter time than was necessary for

Jan 1, 1950

By J. L. Huitt, S. R. Darin

The use of a partial monolayer of propping agent to obtain a high flow capacity for a hydraulically induced fracture is discussed. From the results of laboratory work it was shown that a modified form of the Kozeny-Carman relation could be used to describe the flow in the partial monolayer propped fracture. With equations presented in the paper, the density pattern of the propping agent (number of particles per unit of fracture surface) that results in the maximum flow capacity for the fracture can be determined. The maxitnum flow capacity obtained with a partial monolayer is often an order of magnitude greater than the flow capacity obtained in greater width fractures containing multilayers of the propping agent. INTRODUCTION One of the predominant factors controlling the success of a hydraulic fracturing operation is the propping of the fracture. The trend in hydraulic fracturing recently has been an increase in the ratio of propping agent-to-fluid. The primary purpose of this increased ratio is to sustain a propped fracture of greater width. It was shown in a recent study' that for some formations low concentrations of propping agent would result in "closing" or "healing" of the fracture. In some cases, in an effort to insure sufficient propping agent concentration, the fracturing operation is designed to obtain a pack of the propping agent in the fracture. The placing of a pack of propping agent in the fracture provides a fracture of maximum width; however, the width alone does not control the flow capacity of the fracture. The flow capacity is dependent on the permeability of the fracture, as well as the fracture width. Thus, increasing the permeability to obtain larger flow capacities is as important as obtaining a greater width fracture. By increasing the concentration and particle diameter of the propping agent, fractures of sufficient flow capacities are obtainable for effective well stimulation in a number of formations. However, in some of the recovery techniques, the fracture capacity obtained by commonly used practices in fracturing is inadequate. One such recovery technique is gravity drainage via a horizontal fracture placed near the base of the productive zone. For this recovery technique, the fracture capacity desired is usually one to two orders of magnitude greater than the fracture capacity normally obtained in fractures propped with the size of sand commonly used (20-40 mesh). By the use of particles of larger diameter, the permeability of a pack2 is increased; however, even a multilayer pack results in a fracture flow capacity lower than that desired for some formations. For example, a fracture of 1/4-in. width, packed with 8-12 mesh sand of about 2,000 darcies permeability, would result in a fracture flow capacity (permeability X fracture width) of only 40,000 md-ft. If the fracture flow capacity needed is an order of magnitude greater than that cited in the example, an approach different from the formation of a pack in the fracture is needed. One approach is a partial monolayer of large-diameter propping agent. In working with this type of fracture system, it was found that the flow problems were unique to the system; therefore, the study discussed in this paper was made. THEORY AND RELATED STUDIES Previous studies, although related to that described in this paper, have not pertained directly to the flow in a fracture propped with a partial monolayer of propping agent. However, studies such as flow between parallel plates,' flow in packed columns,' fracture flow capacity' and flow in simulated fractures reduce the scope of this flow problem considerably. A fracture propped with a partial monolayer of dropping agent may be considered to be between two extremes — between an open fracture and a bed of particles packed In a conduit of fracture geometry. Thus, it seems appropriate to review the extreme cases.

By S. S. Lisnyak, B. D. Lichter

An important question in the study of the "hot corrosion" phenomenon (i.e., accelerated oxidation of Ni-Cr-base and Co-Cr-base "superalloys" in the presence of sulfur) is the condition of formation and physico-chemical properties of different sulfides in the system Ni-Co-Cr-S. seyboltl has observed the presence of ((chromium-rich" sulfides of compositions M3S4, and M2S3 in the scales of superalloys after hot corrosion; however, as he points out, much confusion exists as to the identity of sulfides found on Ni-Cr and Co-Cr alloys. According to the literature,&apos; ternary sulfides, e.g., NiCr2S4, (monoclinic structure) and CoCr2S4 (spinel structure) exist in these systems. Therefore, it is likely that these compounds are found in the scale of alloys undergoing hot corrosion. At present this possibility has not been discussed in the literature. Accordingly, we have begun investigation on the properties of ternary sulfides and their mutual interaction. The magnetic and electrical properties of pure NiCr2S4 and pure CoCr2S2 have been previously determined."-&apos; In the present work we have studied the interaction between these sulfides at high temperatures by means of X-ray diffraction and magnetic susceptibility. The measurements were carried out at room temperature after appropriate thermai treatment of samples at high temperatures. For alloys containing the three elements nickel, chromium, and cobalt this interaction may be of importance in the study of the hot corrosion phenomenon. The compounds NiCr2S4 and CoCr2S4 were prepared from stoichiometric amounts of the elements and CoS in the case of CoCr2S4. Samples were mixed and sealed in evacuated silica tubes, slowly heated to 900&apos; to 100O°C, and held at temperature for a total of 120 hr (NiCr2S4) or 80 hr (CoCr2S4) with intermediate re-grinding~. X-ray diffraction showed a pure spinel structure for CoCr2S4 and a monoclinic structure for NiCr2S4. Samples of mixtures of the two ternary sulfides were prepared with different compositions, see Table I. Samples were heated for a total of 80 hr at 900&apos;C in evacuated silica tubes, with one intermediate regrind-ing. The capsules were slow-cooled to room temperature in the furnace. Samples for X-ray diffraction were prepared by placing powder on a glass slide with vaseline. Dif- fractometer traces were obtained on a G.E. XRD-5 diffractometer using a chromium tube and vanadium filter (40 kv and 31 ma). The size of the spinel unit cell was determined from the eight highest angle peaks (80 deg < 2b < 160 deg). Calculated lattice parameters were plotted vs cos B . ctn 0 and extrapolated to 6 = 90 deg. Measurements of the magnetic susceptibility were carried out at room temperature using the Faraday method in a magnetic field of 3000 G and using a Cahn RG automatic microbalance. The system was calibrated from the well-established susceptibilities of platinum and palladium: (Xpt = 0.968 x 10-6 g-1 and Xpd 7 5.04 x 10~6 g-1). The weight of samples were approximately 0.200 g. X-ray diffraction patterns for unsintered mixtures showed Bragg peaks from both the spinel (CoCr2S4) and monoclinic (NiCr2S4) structures. After sintering no monoclinic peaks were observed in samples containing up to 40 mol pct NiCr2S4. However, the spinel peaks were displaced to higher angles with increasing

Jan 1, 1970

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.&apos; This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,&apos; a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By H. E. Cline

A criterion for stability of a lamellar structure in two-phase alloys ulas derived froflr perturbation analysis of the steady-state solutions for eutectic growth. Both the mass and thermal diffusion were considered with boundary conditions for coupled lamellar growth. The concept of an effective liquidus slope was introduced. Excellent agreement was found with the experiments of Mollard and Flemings and the theory predicted a range of compositions on one side of the eulectic composition in which stable growth may occur with zero temperature gradient. The lamellar structure was found to be more stable than predicted by simple constitutional supercooling. The effect of impurity additions was also considered. DIRECTIONALLY solidified eutectic alloys may have a structure consisting of parallel plates or rods. It is important to know the range of composition and growth conditions that produce this ideal composite structure. Breakdown of the planar solid-liquid interface during growth may lead to a dendritic or cellular structure as in single-phase alloys. In the case of single-phase alloys, the concept of constitutional supercooling1 may explain breakdown, but in two-phase alloys the concept is no longer valid because the melting point is not given by the liquidus of one phase. Both phases must be considered in the mass and thermal diffusion problem. In the following theory a boundary condition at the solid-liquid interface was determined by using the steady-state equations of Jackson and ~unt&apos; to relate the average temperature and composition of the liquid at the interface. Then a sinusoidal perturbation in the shape of the interface was introduced to test for stability as in the analysis of Mullins and ~ekerka.~ The wavelength of the important perturbation was assumed to be much larger than the lamellar spacing, h, and the perturbation was assumed not to change the lamellar spacing, A. Both the mass and thermal diffusion equation were used with averaged quantities at the boundary to determine whether the perturbation grows or shrinks in time. A stability criterion was determined by considering the case in which the perturbation remains stationary. An example of Pb-Sn alloys was used to illustrate the validity of this theory. I) THEORY A) Temperature at the Interface. The temperature of the interface in coupled two-phase growth is close to the eutectic temperature TE even for alloys off eutectic composition. It is assumed that the interface is in local equilibrium and one expects the temperature at the intersection of the liquid phase and the solid phases a and 0 to be near the eutectic temperature. The interface is undercooled because of curvature and the deviation of the composition in the liquid from the eutectic composition. The average interface temperature Ti for steady-state growth of a lamellar eutectic with a plane interface was determined by Jackson and Hunt&apos; as given in their Eq. [17c]. Instead of using the ratio of the lamellar widths hp/h, as a parameter, the volume fraction of the 0 phase, +, will be used as it simplifies the algebra. The average interface temperature using this notation becomes: The average temperature of the interface depends on the volume fraction of the 0 phase, +, which may be related to the composition of the solid or the bulk composition of the liquid Co by: where C, and Cp are the average compositions of the solid phases. In steady-state growth, the composition of the solid is equal to the composition in the liquid far from the interface. The variation of the average interface temperature with composition is illustrated in Fig. 1 for the case of Pb-Sn alloys with a 10"4 cm lamellar spacing as calculated from Eqs. [I] and [2]. The interface temperature goes through a maximum at a composition near but not exactly at the eutectic composition. There is no reason why the composition corresponding to the maximum temperature should be equal to the eutectic

Jan 1, 1969

By P. M. Blair

This paper presents numerical solutions of the equations describing the imbibition of water and the countercurrent flow of oil in porous rocks. The imbibition process is of practical importance in recovering oil from heterogeneous formations and has been studied principally by experimental means. Calculations were made for imbibition of water into both linear and radial systems. Imbibition in the linear systems was allowed to take place through one open, or permeable, face of the porous medium studied. ln the radial system, water was imbibed inward from the outer radius. The effects on rate of imbibition of varying the capillary pressure and relative permeability curves, oil viscosity and the initial water saturation were computed. For each case studied, the rate of water imbibition and the saturation and pressure profiles were calculated as functions of time. The results of these calculations indicate that, for the porous medium studied, the time required to imbibe a fixed volume of water of a certain viscosity is approximately proportional to the square root of the viscosity of the reservoir oil whenever the oil viscosity is greater than the water viscosity. Results are also presented illustrating the effects on rate of imbibition of the other variables studied. INTRODUCTION The process of imbibition, or spontaneous flow of fluids in porous media under the influence of capillary pressure gradients, occurs wherever there exist in permeable rock capillary pressure gradients which are not exactly balanced by opposing pressure gradients (such as those resulting from the influence of gravity). The importance of such capillary movement in the displacement of oil by water or gas was recognized in early investigations and described by Leverett, Lewis and True in 1942.1 Methods advanced by these authors for studying the process using dynamically scaled models were rendered more general and flexible by the research of later workers.2"4 The influence of capillary forces in laboratory water floods has also been discussed by several authors.6 While imbibition plays a very important role in the recovery of oil from normal reservoirs, Brownscombe and Dyes7 pointed out that imbibition might be the dominant displacement process in water flooding reservoirs characterized by drastic variations in permeability, such as in fractured-matrix reservoirs. In water-wet, fractured-matrix reservoirs, water will be imbibed from fractures into the matrix with a countercurrent expulsion of oil into the fractures. If the imbibition occurs at a sufficiently rapid rate, a very successful water flood can result; if the imbibition proceeds slowly the project might not be economically attractive. Scaled-model studies have demonstrated the vital importance of imbibition in secondary recovery in fractured reservoirs. It is therefore important in the evaluation of waterflooding prospects to develop a thorough understanding of the quantitative relationships of the factors which control the rapidity of capillary imbibition. The imbibition process serves reservoir engineers in still another important way by providing a technique for studying the wettability of reservoir core samples. Such experiments are usually conducted by observing the rate of expulsion of oil or water from core samples submerged in the appropriate fluid. Several papers have been &apos;published on the experimental techniques involved?? Although Handy has recently published a method for calculating capillary pressures from experiments with gas-saturated cores, it has not yet been possible to deduce quantitative information regarding water-oil relative permeability and capillary pressure characteristics of the rock from the experimental results. Thus a technique is needed for studying the quantitative dependence of imbibition rate on oil and water viscosity, initial water saturation, relative permeability-saturation, and capillary pressure-saturation relations. The development of such information, including saturation and pressure profiles by laboratory experiments, would be very difficult. However, recent advances in the applica-

Jan 1, 1965

By A. D. Schwope, L. R. Jackson, K. F. Smith

Burghoff and Blank1 have pointed out that the creep properties of hard-drawn coppers are closely associated with their individual softening characteristics and have further shown that the creep resistance of various types of copper is improved, under certain circumstances, by cold stretching. In the design of certain types of electrical machinery, it is important to have the creep resistance as high as possible; furthermore, short-time creep strength is important since in many cases stresses are large only during warming-up and cooling-down periods. In this paper, data are presented showing the effect of cold work on the short time creep strengths of various types of commercial copper under several conditions. It is shown that trends from short-time creep tests are evident at longer times. Materials Used in the Investigation The coppers used in this investigation were commercial grade and of two basic types, oxygen free high conductivity (OFHC) and tough pitch. Additions of silver in amounts of 15 and 25 oz per ton were added to each of the two coppers. The analyses of these six coppers are given in Table 1. Originally, they started as wire bars 4 X 4 X 54 in. A. square rod was made by hot rolling the wire bars to 9/16-in. rod in 8 passes. This rod was then cold drawn to 0.445-in.-diam rod and annealed for 3 1/2 hr at 1000°F. It was then cold drawn to 0.325-in. rod and again annealed at 1000°F for 3 1/2 hr. Hard square rods were then made by cold rolling to 0.257 X 0.257-in. rod. Soft wire was made from the hard- drawn material by annealing at 650°F for 3 hr. The final rolling was performed using a set of 9-in. grooved rolls revolving at 30 rpm, which produced square wires. Reductions of approximately 5, 20, 30, and 40 pct were obtained using several passes in the same direction for the large reductions. The 5 pct reduction by drawing was accomplished using a steel die having 2 parallel bearing surfaces. The die angle was 7 1/2 degrees and the wires were lubricated with a paste of ceresin wax dissolved in carbon tetrachloride. The speed of drawing was 13 fpm. Since work was done on only two sides of the wire simultaneously, it was necessary to rotate it 90 degrees each pass to insure uniform deformation. The room-temperature tensile properties of the various tempers are given in Table 2. The grain size of the an- nealed 0.257-in. wires was uniform and averaged about 0.035-0.045 mm. Experimental Procedures for Short-time Creep Tests Standard creep-test frames (Fig 1) were used for the testing. Special fixtures were designed to apply axial compressive and tensile loads to the copper wires. The compression specimens were 1 in. long and the ends were ground flat and parallel. The creep in compression was indicated by the movement of reference marks s-ratched on intersliding platinum strips attached to the moving heads of the fixture. The movement was measured with an optical micrometer fitted with a filar eyepiece on which the smallest division was 0.00005 in. The tensile creep specirriens were 4 in. long which provided ample gripping surface for the jaw-type grips. The platinum strips were attached to a one-inch gauge length of the wire and the creep measured as previously described. The single-specimen furnaces were connected to individual power and control sources. The controlling equipment consisted of Foxboro controllers

Jan 1, 1950

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.&apos; These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties&apos;3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By J. Orkiszewski

A method i.s presented which can accurately predict, with a precision of about 10 percent, two-phase pressure drops in flowing and gas-lift production wells over a wide range of well conditions. The method is an extension of the work done by Grifith and Wallis and was found to be superior to five other published methods. The precision of the method was verified when its predicted values were compared against 148 measured pressure drops. The unique features of this method over most others are that liquid holdup is derived from observed physical phenomena, the pressure gradient is related to the geometrical distribution of the liquid and gas phase (flow regimes), and the method provides a good analogy of what happens inside the pipe. It takes less than a second to obtain a prediction on the IBM 7044 computer. INTRODUCTION The problem of accurately predicting pressure drops in flowing or gas-lift wells has given rise to many specialized solutions for limited conditions, but not to any generally accepted one for broad conditions. The reason for these many solutions is that the two-phase flow is complex and difficult to analyze even for the limited conditions studied. Under some conditions, the gas moves at a much higher velocity than the liquid. As a result, the down-hole flowing density of the gas-liquid mixture is greater than the corresponding density, corrected for down-hole temperature and pressure, that would be calculated from the produced gas-liquid ratio. Also, the liquid&apos;s velocity along the pipe wall can vary appreciably over a short distance and result in a variable friction loss. Under other conditions, the liquid is almost completely entrained in the gas and has very little effect on the wall friction loss. The difference in velocity and the geometry of the two phases strongly influence pressure drop. These factors provide the basis for categorizing two-phase flow. The generally accepted categories (flow regimes) of two-phase flow are bubble, slug, (slug-annular) transition and annular-mist They are ideally depicted in Fig. 1 and briefly described as follows. RUBBLE FLOW (FIG. 1A) The pipe is almost completely filled with the liquid and the free-gas phase is small. The gas is present as small bubbles, randomly distributed, whose diameters also vary randomly. The bubbles move at different velocities depending upon their respective diameters. The liquid moves up the pipe at a fairly uniform velocity and, except for its density, the gas phase has little effect on the pressure gradient. SLUG FLOW (FIG. 1R) In this regime, the gas phase is more pronounced. Although the liquid phase is still continuous, the gas bubbler coalesce and form stable bubbles of approximately the rame size and shape which are nearly the diameter of the pipe. They are separated by slugs of liquid. The bubble velocity is greater than that of the liquid and can be predicted in relation to the velocity of the liquid slug." There is a film of liquid around the gas bubble. The liquid velocity is not constant—whereas the liquid slug always moves upward (in the direction of bulk flow); the liquid in the film may move upward but possibly at a lower velocity, or it may move downward. These varying liquid velocities will result not only in varying wall friction losses, but also in a "liquid holdup" which will influence flowing density. At higher flow velocities, liquid can even be entrained in the gas bubbles. Both the gas and liquid phases have significant effects on the pressure gradient. TRANSITION FLOW (FIG. 1C) The change from a continuous liquid phase to a continuous gas phase occurs in this region. The liquid slug between the bubbles virtually disappears, and a significant amount of liquid becomes entrained in the gas phase. Although the effects of the liquid are significant, the gas phase is more predominant.

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 P. F. Gnirk, J. B. Cheatham

Single bit-tooth penetration experiments under static load were conducted on six rocks at confining pressures of O to 5,000 psi using sharp wedge-shaped teeth with included angles ranging from 30 to 120° In general, the force-displacement curves for all rocks exhibit an increasingly nonlinear and discontinuous behavior with decreasing confining pressure. The confining pressure at which a rock exhibits a macroscopic transition from predominantly ductile to predominantly brittle behavior during penetration vmies from about 500 to 1,000 psi for the limestones to greater than 5,000 psi for dolomite. The correlation between calculated values of force per unit penetration based on plasticity theory and experimental values is quite encouraging, even at confining pressures as low as 1,000 psi A qualitative correlation between volume of fragmented rock per unit energy input for a single bit-tooth and drilling rate for microbits appears to exist over a confining pressure range of 0 to 5,000 psi. INTRODUCTION Laboratory experiments utilizing a small-scale drilling apparatus have demonstrated that penetration rates are reduced considerably as a result of increasing the confining pressure from atmospheric to a few thousand psi?-3 This undesirable situation can, in general, be attributed to a combination of decreased efficiency of chip removal at the bottom of the borehole, increased rock-failure strength, and a possible change in the mechanism of chip generation and rock fragmentation with increasing confining pressure. To more fully understand the principles underlying the last circumstance, it is the purpose of this investigation to experimentally study the mechanism of single bit-tooth penetration into dry rock at low confining pressures and, in particular, to establish the confining pressure at which the penetration mechanism may undergo a brittle to ductile transition for various rock types commonly encountered in drilling. Confining pressure as used here refers to the differential pressure between the borehole fluid pressure and the formation-pore fluid pressure. EXPERIMENTAL PROCEDURE Using an experimental apparatus previously described: a single, sharp wedge-shaped tool was forced under a "statically" applied load into an effectively semi-in finite dry rock sample subjected to a prescribed confining pressure. To prevent the invasion of the con fining-pressure fluid into the pores of the rock sample during penetration, the exposed surface of the rock was jacketed with a layer of silicon putty.* Electrical instrumentation incorporated into the apparatus yielded a graphical plot of force on the tool as a function of penetration or displacement of the tool into the rock during an experiment. During the course of the experimentation the following conditions were maintained constant: (1) pore pressure — atmospheric (i.e., the rock was dry); (2) temperature — 75F; (3) rate of loading — essentially static (approximately 0.002 in./sec); (4) bit tooth — a sharp wedge-shaped tool loaded normal to the rock surface; (5) rock surface — smooth and flat; (6) drilling fluid — hydraulic oil; and (7) maximum depth of penetration — approximateiy 0.1 in. In addition, each experiment was performed on a different rock sample so the rock surface is free of a layer of cuttings and of any previous indentation craters. The influence of the corners of a borehole was neglected, since each rock sample was cemented inta a section of aLuminum tubing to simulate a semi-infinite body. Indentation experiments were made on a sandstone, two limestones, a marble, a dolomite and a schist with a 60&apos; bit-tooth over a range of confining pressures from atmospheric to 5,000 psi and at a constant confining pressure of 1,000 psi for a variety of bit-teeth with angles ranging from 30 to

Jan 1, 1966