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By S. A. Hovanessian

Analytical solutions are obtained for calculating the pressure distribution in rectangular fields due to injection and/or producing wells located anywhere within the field. The field is assumed to be homogeneous with either constant pressure or no-flow boundaries. These solutions are extended to include the calculation of average reservoir pressure and permeability from pressure build-up curves. Numerical examples are given to illustrate the application of equations to practical problems. INTRODUCTION Pressure distribution analyses are of considerable importance in the field of reservoir mechanics. A number of papers dealing with this subject have appeared in the petroleum literature. perrinel in 1956 presented a summary of the methods available for pressure build-up calculations and discussed the applicability of each in some detail. More recently (1958), Hazebroek, et a1,2 discussed a theoretical method for obtaining pressure distribution in a radial field. Also in 1958, Nisle3 gave a theoretical solution of the pressure distribution in a field extending to infinity with a partially penetrating line source at the origin. Mathews, et a1,4 applied the method of images to existing solutions for pressure distribution in radial fields and obtained expressions for calculating pressures in bounded reservoirs. However, a literature survey revealed that a general analytical solution for the pressure distribution in a rectangular field, with injection and/or production wells located anywhere within the field, was not available. Such a solution could be used to approximate the pressure distribution in a field the shape of which is nearly rectangular. Furthermore, it could be applied to pressure calculations pertaining to a single well taken from a system of wells which were drilled in a rectangular pattern. In this case the boundaries of the well drainage area are considered to be the perpendicular bisectors of the lines joining the well and its nearest neighbors. The basic problem considered in this paper consists of a rectangular field with either constant-pressure 01 no-flow boundaries and with either an injection or production well located anywhere within the field. The physical properties of the rock and fluids present are considered to be constant. Analytical expressions are obtained for the pressure distribution within the field during the production or injection periods. These expressions, which are infinite series, can be used to evaluate pressure at any point within the field as a function of time and position. For fields containing more than one well (production and/or injection), the solutions for each well acting independently are superposed. That is, at any point in the field, the pressures due to each injection 01. production well acting alone can be algebraically added to give the pressure resulting from all wells acting simultaneously. Evaluation of the series solutions given in this paper is readily accomplished by means of an electronic digital computer; and, in most cases, sufficient accuracy is obtained by setting the upper limits of summation at 20. These solutions are extended to include the calculation of average reservoir pressure and permeability from build-up data. A number of numerical examples are given to illustrate application of the solutions to actual field problems. ANALYTICAL SOLUTIONS The partial differential equation representing the pressure distribution in a homogeneous rectangular field (see Fig. I.), having a single source or sink of strength (2, can be written*

By E. P. Miesch, P. B. Crawford

A study was made of the effect of permeable and impermeable lenses in a reservoir on the production capacity of a well. Both steady-state and unsteady-state data were obtained. An electrical resistivity model was used to obtain the steady-state data and thermal models. were constructed to obtain the unsteady-state data. The productivity of a well is affected very greatly only when the lenses are close to the well. The effect of circular lenses on the productivity ratio can be correlated with the distance from the center of the lens to the center of the well divided by the radius of the lens. When this dimensionless distance is equal to six or greater, the effect of the lenses on production capacity will be negligible. The pseudo steady-state productivity of a heterogeneous reservoir can be predicted using steady-state data. INTRODUCTION Many analytical solutions of reservoir behavior assume that reservoir rock is uniform and homogeneous. Although this assumption is used, all of the data from core analyses and well logging indicate that the reservoirs are heterogeneous. Very little work has been done on the performance of heterogeneous reservoirs. The work of Landrum,l et al. showed that transient phenomena in oil reservoirs could be studied with thermal models. Pickering and Cotman2 used thermal models to study flow in stratified reservoirs and investigated the effect of inhomo-geneities in oil reservoirs on transient flow performance. Loucks3 made a mathematical study of the pressure build-up in a system composed of two concentric regions of different permeability. Root, Silberberg and Pirson4 studied the effect of the growth of the flooded region on water influx predictions using a thermal model consisting of three concentric cylindrical regions of different thermal properties which simulated the aquifer, the flooded region and the unflooded portion of the original hydrocarbon region. Tomme, et a1.5 made a mathematical study of vertical fractures. The object of this investigation was to study the effect of highly permeable and impermeable lenses in the vicinity of the wellbore on the pressure depletion history of the well. Steady-state data were obtained for both conductive and nonconductive lenses that completely penetrated the formation. The lenses were symmetrically located at various distances from the wellbore. The unsteady-state data were obtained on seven thermal models. EXPERIMENTAL EQUIPMENT AND PROCEDURE STEADY-STATE DATA The steady-state data were obtained from an electrical resistivity model 30 in. in diameter and approximately 11/2 in. deep. The outside of the model was lined with a 30-in. diameter copper strip, which served as the outer boundary of the reservoir. The bottom was covered with a sheet of plexiglass so that it would be nonconductive. The model was filled with a slightly saline solution. The well size was varied from an 0.064-in. diameter copper wire to a 10-in. diameter copper cylinder. Readings were taken with an impedance bridge using AC current to prevent polarization at the contacts. Copper and wax lenses were used to represent infinitely conductive and nonconductive lenses, respectively. The resistance was first measured for each well diameter with no lenses in the reservoir. Then the conductive and nonconductive lenses were spaced symmetrically at various distances from the well and the resistance read from each lens location. The diameters of the conductive lenses were 3, 1.022 and 0.624 in., and those of the nonconductive lenses were 3, 2.25 and 1.563 in. The ratio of each resistance reading to the resistance reading with no lenses in the reservoir

Jan 1, 1965

By A. P. Young, F. C. Holden

IN many of the early investigations of the aging of titanium alloys, it was observed that the retained beta phase could be aged to a high hardness without an apparent change in microstructure; moreover, in some alloys it was found that even a very rapid quench produced beta having an anomalously high hardness. What appeared to be hard beta phase was designated as "beta prime," to distinguish it from the softer normal retained beta phase. Frost and co-workers'.' demonstrated that the increased hardness is caused by the formation of a metastable phase, omega, which can be identified from its X-ray diffraction pattern. This reaction also has been studied by Brotzen, et a1.,3 and the structure of the omega phase has been published by Silcock, et al.," and by Austin and Doig.3 The X-ray diffraction analysis by Austin and Doig indicated that omega is low in alloy content, approaching the composition of the stable alpha. The aging process proceeds by the path Thus, overaging results in the formation of alpha and the ultimate disappearance of omega. This is accompanied by a decrease in hardness and a recovery of ductility. The present work represents a study of the aging process in a high-purity Ti-6.4 Mn alloy, in which optical and electron microscopy, X-ray diffraction, and hardness data were correlated. The specimens, 1/8-in. sections cut from 1/4-in.-diam rod, were heated in argon to a temperature just into the beta field (810°C), held for 1 hr, and water-quenched. The aging samples were heated in air for 1 hr at 300 to 500°C. The specimens were ground and mechanically polished, finishing with alternate etching and polishing on a slow-speed wheel to remove disturbed metal from the surface. The surface finally was swab-etched, rinsed with tap water, and air-dried. The etchant used was an aqueous solution containing 1 1/2 pct HF and 3 1/2 pct HNO3. This procedure is identical with that used for preparing metallographic specimens, except that the optimum degree of final etching required for electron microscopy may vary from that used for light microscopy. Metal replicas, backed with silica, were prepared from plastic strip-pings for examination with the electron microscope. Complete details of the procedures used for preparing these replicas are available elsewhere." Fig. 1 shows a comparison between the structures revealed by the electron microscope and those obtained by conventional light microscopy. Hardness and X-ray diffraction data are listed in Table I. No evidence of a second phase is apparent in the optical micrographs for the as-quenched sample, or for the specimens aged at 300 or 400°C; fine alpha particles can be seen in the specimen aged at 500°C. In the electron micrographs, visible equiaxed pocks appear in the as-quenched specimen, and, with increasing density, in the samples aged at 300 and 400°C. After aging at 500°C, the structure becomes markedly coarser and develops an oriented appearance of a second phase, coincident with the appearance of visible alpha particles in the light micrographs. These observations are confirmed by X-ray diffraction and hardness data. In these specimens, aged for 1 hr, the intensity of the omega pattern increases to a maximum at the 400°C aging temperature, corresponding to maximum hardness and the maximum density of pocks in the electron micrographs. At this point the beta phase shows a definite enrichment in Mn. At 500°C, little or no omega re-

Jan 1, 1959

By C. M. Wayman, G. R. Srinivasan

A metallographic study of the isothermal products formed between 750° and 285°C was made in an Fe-7.9 wt pct Cr-1.11 wt pct C alloy, and a time-temperature-transformation diagram was determined. The study shows that the austenite decomposes into three different products: pearlite above 540°C, ferrite and carbide between 540° and 300°C, and lenticular bainite below 300°C. No upper bainite forms in this alloy. The results are discussed in terms of carbon diffusion models for upper bainite formation. AUSTENITE transforms into several products depending on the temperature, composition, and rate of cooling, and the various transformation products have been a source of controversy for a long time. Since the classical study of Davenport and ~ain' extensive work has been carried out. The present study concerns the isothermal transformations in an alloy which was used for a detailed investigation of bainite crystallography and provides information supplementary to the work of Lyman and Troiano who studied austenite decomposition in steels containing 1 pct C and varying amounts of chromium. Their work showed that increasing the amount of chromium in high-carbon steels had the effect of depressing the B, temperature and of shifting the TTT curves to longer times and lower temperatures. They further found that if the chromium content is increased in a 1 pct steel to about 9 pct no bainite would form even after a period of 100 days. However, a preliminary investigation by the present authors showed that bainite plates do form in steels containing about 8 pct Cr and 1 pct C. In view of this and some results from a thin-foil electron microscope investigation of the bainite formed in the present alloy: it was considered desirable to investigate the other isothermal products as well. EXPERIMENTAL PROCEDURE The alloy used in the present investigation was obtained from a triply vacuum-melted ingot prepared from high-purity materials. Chemical analysis for the alloy verified the composition to be Fe-7.9 wt pct Cr-1.11 wt pct C. Metallographic observations were made on i by i by « in. specimens which were aus-tenitized at 12 50°C for 50 to 60 hr in evacuated quartz capsules and then water-quenched. Since the M, temperature for this alloy is below room temperature, the homogenizing treatment produced a completely austenitic structure consisting of very coarse austenite grains (ASTM #0-1). Several samples of the austenitized specimens were metallographically prepared and observed for any proeutectoid carbide separation. It was found that all the carbon was in solution. The water-quenched specimens were upquenched and given isothermal treatments at temperatures between 285" and 750°C for varying periods in molten salt or lead baths. The specimens were then water-quenched, and those showing less than 5 pct transformation were used for plotting the beginning of the austenite decomposition. To ensure the removal of the disturbed layer, the mechanically prepared specimens were electropolished in a 1:6 HzS04, CHSOH solution for 10 to 15 sec at 20 v. Final polishing was done with a vibratory polisher using 0.05-p alumina. Various etchants including nital, ferric chloride, and hot ferricyanide (Murakami's reagent) were used to bring out details in the different transformation products. The ferricyanide etch was used whenever the preferential etching of carbides was desired.

Jan 1, 1969

By R. Hastings Keller, Ralph E. Esarey

Oil and gas activities in Indiana during 1943 continued to decline at about the same rate as in 1942. New development, production, and prospecting, all showed the results of Federal regulation, low price for crude oil and shortages of labor and materials. Several local stripper-well operations were shut down, but no large-scale abandonment has occurred as yet. During the year, 277 holes were drilled for oil and/or gas, of which 99 were completed as oil wells, 19 as gas wells and 159 as dry holes. This record was a decline of 21 per cent over last year in the total number of completed tests, 20 per cent in the number of oil wells and 9.5 per cent in the number of gas wells. As in the previous year, most of the drilling (82 per cent) was in the southwestern part of the state, Gibson County ranking first, with 77 completions and 49 oil wells. Posey County was second, with 59 completions and 20 oil wells. The remaining 18 per cent of the drilling was in the old Trenton oil and gas area. The total footage drilled during the year was 482,799 ft., a decline of 18 per cent from the previous year. Of this, 146,559 ft. was wildcat footage. The total initial production of the oil wells completed was 6362 bbl. and of the gas wells was 2,562,000 cu. feet. Three tests in the old Trenton area were drilled into the Cambrian and reported nothing more than tar residue. A Devonian test was to be made in the Griffin field in the Wabash River but owing to the delay caused by Federal restrictions this test did not get started in 1943. It is expected to spud in March 1944. The new discoveries in 1943 were virtually all in the southwestern part of the state, and all, so far, one-well pools, except the North Owensville pool, in Gibson County. The latter was brought in during the month of February and by the end of the year nine wells were producing in the pool, with a reported initial yield of 1260 bbl. per day. By the end of the year it had a daily average production of 401 bbl. and an accumulated production of 39,129 bbl. The average gravity of the oil is reported to be 35.6. On the Ohio-Indiana state line, early in 1943, a new pool was opened up in the old Trenton area. The discovery well was on the Ohio side of the line. An offset well was completed on the Indiana side, with an initial yield of 64 bbl., and settled down to 5 bbl. per day. This well produced 1154 bbl. up to Dec. 31, 1943. There was no further development here, because of the Federal Conservation Order M-68, restricting drilling to one well on 40 acres. The development pattern usually followed in this area is one well to 5 acres. The E. Rogers field was extended by one pool (Table 4). Most of the development in the oil-field pools during the year took place in the Kirksville pool, in Gibson County, and the Caborn pool, in Posey County. The crude-oil production in 1943 was approximately 5,273,000 bbl., a decline of 29 per cent from the previous year. The Griffin field, of Gibson and Posey Counties,

Jan 1, 1944

By J. W. Downey, J. B. Darby, L. J. Norton

THE only previous investigation of the phase equilibria in the Ta-Pd system was reported by Greenfield and Beck.1 Their work (actually a portion of a much broader survey) was limited to the composition range 50 to 75 at. pct Ta and to a single temperature, 1000°C. The results indicated that no intermediate phases were present at this temperature. They pointed out that this was an unexpected result in view of the fact that niobium, which belongs to the same group in the periodic table as tantalum and has essentially the same atomic size, forms a o phase with palladium.' Also, tantalum in combination with rhodium,' iridium,' or platinum' stabilizes the s phase. By analogy, the Ta-Pd system would also be expected to contain a s phase. The present investigation was therefore undertaken to explore more fully the phase relationships in this system. Alloys were prepared by arc melting on a water-cooled copper hearth in an argon-helium atmosphere. The purity of the starting materials was greater than 99.9 pct. The weight losses on melting were less than 1 pct and therefore the alloys were not analyzed chemically. Specimens were wrapped in molybdenum foil, encapsulated in quartz capsules under a vacuum of at least 1 x 10-5 mm of Hg, annealed as indicated in Table I, and water quenched. Optical and X-ray metallography were used for identifying the phases present in the annealed and quenched alloys. The alloys were resistant to attack by several acids; however, a sodium cyanide electroetch and an immersion etch containing 1 part HF, 1 part HNO3, 2 parts H2SO4, and 5 parts H2O by volume were found satisfactory. The X-ray diffraction patterns were taken with a Straumanis-type Debye-Scherrer camera and filtered copper or chromium radiation. A summary of the phases found in this investigation is presented in Table I. No attempt was made to determine the composition limits of the various phases. The present results indicate that this system consists of two terminal solid solutions separated by at least four intermediate phases at the approximate compositions Ta3Pd, -TaPd, TaPd,, and TaPd3. The Ta-rich solid solution, containing less than 10 at. pct Pd at 1150°C, is in equilibrium with a o phase which is stable in the vicinity of 25 at. pct Pd. The latter phase is also in equilibrium with a bct phase at the equiatomic composition. At high temperatures it appears that the Pd-rich solid solution extends to at least 66.6 at. pct Pd and is in equilibrium with the bct phase. When annealed at 900°C, a sample containing 66.6 at. pct Pd transformed to an unidentified phase designated as X. An X-ray diffraction pattern of this phase contained sharp low-angle lines while the high-angle lines were characteristically diffuse. The observed d-spacings and relative intensities for lines in the low-angle region are presented in Table 11. In the vicinity of 70 at. pct Pd an intermediate phase having the TiA13-type structure is formed. It is stable to at least 1100°C, and presumably dissolves congruently into the ter-

Jan 1, 1963

By B. F. Buie

For over 200 years meerschaum has been a significant item of trade between the Near East and countries to the west. Best-known for its use in making smoking pipes and cigar and cigarette holders, it is also used in making a variety of decorative and ornamental items. It is easily carved, and is given an attractive, lustrous finish by rubbing. No published specifications are known, but compact form, purity, uniform whiteness or light color, and uniform, porous texture appear to be requisites. Fig. I a shows the appearance of a piece of crude meerschaum from Turkey; Fig. lb a carved item; and Fig. lc, d, and e show the fibrous and porous texture as revealed by the scanning electron microscope. Neither a major industrial mineral nor a precious stone, meerschaum nevertheless holds a record of long-and continuing-association with art and personal affairs of man. It is also a mineral to which modem methods of exploration and production probably could be profitably applied. An interesting account of the preparation and use of meerschaum in the early part of this century is given by Sterrett (1907). Geology and Mining Mineralogy Meerschaum is recognized now to be the compact variety of sepiolite, the claylike variety of which is one of the minerals included in the chapter on clays. The word meerschaum, from the German meaning "sea foam," was in earlier times used synonymously with sepiolite, a word of Greek origin suggestive of the resemblance of the compact variety-then the only variety known-to cuttlefish bone. At one time meerschaum was used as the commercial name, and sepiolite for the scientific name. However, to think of meerschaum as the name by which sepiolite is known commercially is no longer valid, in view of the recent emergence of the earthy variety as a competitor of bentonite and other clay materials. Present tendency is to restrict the term meerschaum to the compact variety, and to use the term sepiolite as a more general name to include both the compact and earthy varieties. This is the terminology followed in this publication. Meerschaum typically is white to light gray, has a hardness of 2 to 2 ½ , conchoidal to irregular fracture, and specific gravity varying with porosity from about 2 to less than 1. The composition is somewhat variable,- but is near that determined by Schaller (1936) for sepiolite as 2MgO.3SiO2.4H2O. A more modern for mula based on X-ray determination of the crystal structure is given by Caillére and Henin (1961) as (Site) (Mg9)030(OH)6(0H2)46H20. The reason for the firm, compact nature of meerschaum, in contrast with the earthy variety of sepiolite, is not fully understood. It may be due to the presence of a very minor amount of some bonding material such as silica. Scanning electron microscope (SEM) photographs of a specimen from Turkey (Figs. lc-le) indicate that the meerschaum is composed predominantly, if not entirely, of crystalline fibers which merge into sheetlike forms in a complex, intertwined mass. Detailed X-ray and crystal structure data, as well as some data on thermal stability range, are given by Caillère and Hénin (1961) for the sepiolite family of minerals. Mode of Occurrence and Origin Most authors have attributed the origin of meerschaum to alteration of serpentine or other magnesian minerals. The occurrence in alluvium and other surficial deposits does not necessarily indicate that the alteration was supergene. In fact, hydrothermal origin appears more likely for some deposits, though not for all.

Jan 1, 1983

By W. E. Showalter

This paper discusses some of the results of combstion-drive tests which were made in a test cell using a sand bed 10 in. in diameter x 10-ft long. The test method is illustrated and described. The relationship between the API gravity of the in situ oil and the amount of air required for combustion drive is discussed in detail. Other things constant, the air requirement for combustion drive increases as the APl gravity of the in situ oil decreases. If the test results apply to actual reservoirs, the lowest-priced oils may cost the most to recover by this method. Information is shown which indicates that the effect of pressure on the amount of hydrocarbon burned is not large. A method of predicting air requirements from the API gravity of the in situ oil is presented. INTRODUCTION Combustion drive is the term used to identify the process of interstitial or in situ burning as an oil recovery method. Part of the in situ oil is burned to generate the energy needed to produce the remainder of the oil. Combustion drive as an oil recovery mechanism remains an economic uncertainty in spite of all the work that has been done by the industry in both laboratory and field?-6 This paper will show some of the results of tests which were made in a test cell for the purpose of studying the nature of the combustion-drive process. It will present data which indicate that the API gravity of the in situ oil is a significant indicator of the amount of air required to drive a burning front through oil sand. Air requirement varies inversely as the API gravity of the in situ oil. EXPERIMENTAL The tests were performed in a cell which utilized a cylindrical sand section 10 in. in diameter x 10-ft long. The thin-walled metal pipe which held the sand was wound with twenty external electrical resistance heaters which, by means of an automatic controller, maintained adjacent sections of the wall of the pipe at temperatures equal to the temperatures of the contained sand. Each heater covered 6 linear in. of the pipe. By this means lateral heat loss from the sand section was minimized, thereby causing the sand section to simulate more closely a horizontal increment of a combustion-drive reservoir. Fig. 1 shows a schematic diagram of the test assembly. Thermocouples to measure the temperature in the sand were located every 6 in. along the length of the sand section. The pipe containing the sand was enclosed in a cell designed for an operating pressure of 500 psig. The inlet air pressure was controlled at the inlet, and the gas flow rate was controlled and measured at the outlet of the cell. The oil sand used for the tests was prepared by mixing first water and then oil with the noncon-solidated sand using a closed mixer similar to a cement mixer. Table 1 shows a screen analysis of the sand. Ninety percent of the sand was 100 mesh or finer. This sand was a mixture of 80 per cent No. 120 Nevada White Sand and 20 per cent Tennessee Hi-Fusion Moulding Sand No. 3. The Nevada sand was a clean silica sand. The Tennessee sand con-

By B. S. Lement

No appreciable stabilization of the austenite-martensite reaction occurs in a 15 pct Cr-0.7 pct C steel unless some martensite is initially present. Stabilization is induced by interrupting the subcool below M,; however, disappearance of the stabilization effect as manifest by burst formation of martensite may occur on continued holding at the final subzero reaction temperature. The higher the temperature of intermediate cycling after the initial subcool, the more permanent is the stabilization effect at the final reaction temperature. Appreciable conditioning of retained austenite occurs on reheating to about 500°C. These phenomena are explainable on the basis of the reaction-path theory. A RECENT investigation' carried out by the authors has shown that isothermal transformation of austenite to martensite definitely takes place in a 15 pct Cr-0.7 pct C steel and that appreciable amounts of martensite can form in this fashion. Investigations2-" arried out on other steels and iron alloys make it seem probable that isothermal formation of martensite is a phenomenon of fairly general occurrence. The reaction-path theory of Cohen, Machlin, and Paranjpe5,7 explains isothermal transformation on the basis of thermal activation of strain embryos which generate martensite plates with a velocity approaching that of sound. On the other hand, the nucleation and growth theory of Fisher, Hollo-mon, and Turnbull8 egards isothermal transformation as due to growth of athermally formed martensite nuclei. The experimental evidence obtained thus far favors the reaction-path theory in that the martensite reaction seems to be nu-cleation-controlled rather than growth-controlled. Stabilization is another phenomenon of importance with respect to the austenite-martensite reaction. According to the reaction-path theory, stabilization is a result of relaxation of strain embryos. It is postulated that strain embryos are present at the austenitizing temperature in the form of dislocations or lattice imperfections in the austenite which vary in the extent to which the lattice is displaced along the strain reaction path leading to martensite. On quenching from the austenitizing temperature, athermal martensite starts to form as soon as the M. is reached, because the activation energy of the transformation which decreases with decreasing temperature is lowered to below the level of the highest energy strain embryos. Martensite plates are generated during the cooling below M, from embryos possessing energies above the activation energy corresponding to the temperature at which the cooling is stopped. The distribution of lower energy embryos is changed because of the elastic and plastic strains produced in the remaining austenite as a result of the transformation. This effectively increases the number of strain embryos at all levels of energy below the activation energy and tends to stimulate further martensite formation either iso-thermally or on subsequent cooling. However, if the temperature at which the cooling is stopped is high enough for relaxation of strain embryos to occur, some degree of stabilization against further transformation may be induced. Whether stabilization will be observed on subsequent cooling will depend on the extent of decrease of activation energy with temperature. If the activation energy decreases sharply with temperature, it is possible that transformation will appear to continue with decrease in temperature in spite of the loss of embryos by relaxation. However, with a more gradual decrease in activation energy, stabilization will be manifest by no further transformation on cooling over a measurable temperature range until the

Jan 1, 1954

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.'-' The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,' were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.' The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953

By David Cornell, Yusuf K. Sukkar

The fundamental differential equation for fluid flow has been rearranged, integrated numerically for natural gases, and the results presented in tabular and graphical form suitable for the direct calculation of vertical gas flow problems. The integration is rigorous except for the use of a constant average temperature. Both static and flowing bottom-hole pressures may be calculated by (his method without resort to trial and error procedures. INTRODUCTION Bottom-hole pressures can be determined either by direct measurement with a bottom-hole pressure gauge or by calculation. Since measurement with a bottom-hole pressure gauge is costly, calculation of bottom-hole pressures is to be preferred when possible. Calculation involves knowledge of the wellhead pressure, the properties of the gas, the depth of the well, the flow rate, the temperature of the gas, and the size of the flow line. These quantities must be combined in a suitable equation for vertical flow. Several equations have been developed for the purpose of calculating gas flow through both horizontal and vertical pipes1,2,4,5,6,7,8,9 These equations all have the basic differential equation for flow as their starting point. They differ only in the assumptions which are made in order to simplify the integration step. The bottom-hole pressures calculated using any of the better known equations are in good agreement with bottom-hole pressures calculated by a more rigorous but considerably more tedious stepwise integration method. All of these methods, however. require a trial and error solution for the calculation of flowing bottom-hole pressures. The purpose of this paper is to present a method which provides a direct solution of static and flowing bottom-hole pressures without use of a trial and error solution. At the same time the method involves fewer simplifying assumptions than any of the previous methods used, except lor the lengthy stepwise method. The derivation of any practical flow equation begins with the basic differential equation which is rigorous for almost all flow problems. The five terms in Equation 1 represent the potential energy, the potential energy of position, the kinetic energy, the shaft work done, and the energy losses due to motion of the fluid respectively. Equation 1 reduces to Bernoulli's theorem for the case of horizontal flow of an incompressible fluid, no work done, and no energy losses due to friction. In the present case, the term (v) (dv)/(g,.) can be shown to be quite negligible compared to the other terms, and is therefore neglected in the derivation. The term — dws includes work done by a pump or turbine in the system and is zero in this case. The frictional losses in the pipe are included in the term — d(lw) which is expressed in terms of the Moody friction factor as in Equation 2. (f) (v2) (dL) d(lW) = (f)(V2) (dl)/(2) (g) (d) The specific volume of a gas can be expressed in terms of the temperature, pressure, molecular weight, and compressibility factor. The velocity of the gas can be expressed in terms of the weight rate of flow, the specific volume, and the dimensions of the pipe.The reduced pressure Pr is to be used because z can be expressed as a function of Pr and Tr alone for most natural gases:

Jan 1, 1956

By C. L. Sollenberger, Will Mitchell, Ford F. Miskell

Heat treatment of ore prior to comminution reduces power requirements for grinding, reduces grinding media wear, and improves recovery of iron values from a typical Minnesota magnetic taconite. Test data demonstrating this, as well as an analysis of the economics of commercial application of the technique, are presented. THE taconites in general are hard, tough ores, difficult to grind. Liberation of iron mineral constituents usually is accomplished by grinding the ore through at least 100 mesh, and often it has been found necessary to grind substantially through 325 mesh to achieve satisfactory recovery and grade in the concentration process. Because of the fineness of grind required and the enormous tonnages of material contemplated for treatment in the future, costs resulting from grinding media wear and power consumption, together with capital investment required for comminution, approach astronomical figures. Economy in any one of these elements per ton of material ground could very well reflect a considerable saving to the ferrous industry in yearly costs. With this in mind, the Research Laboratories of Allis-Chalmers Manufacturing Co. have launched a program to discover means of effecting this economy. The initial phase of the work as described here deals with a heat treatment of crushed raw ore, followed by thermal shock in cooling, for the preparation of rod mill feed. Several investigators1-" ave noted an improvement in the grindabilities of ores treated in this manner. One investigator2 subjected low grade iron ores to heat treatment in an electric furnace. Basing his conclusions on screen analyses of crushed products, he observed that treated ore was more easily crushed than the untreated. He reported that observation of the treated and untreated ore through a microscope revealed cracks following the grain boundaries in treated ore, whereas no cracks were present in untreated ore. However, few if any have quantified the improvement in terms of total hp hours saved, reduction of wear of grinding media, or reduction of capital costs of grinding equipment involved. By means of Bond rod mill and ball mill grindabilitiesh nd by comparative wear tests, the conditions maintained during this investigation have been definitely evaluated. Heat treatment experiments have been made on a batch scale in a muffle furnace, followed by continuous scale experiments in a rotary kiln under various conditions of temperature, atmosphere, retention time, and quenching to determine the combination that would give the greatest improvement in the grindability of a taconite without affecting adversely the magnetic susceptibility of the magnetite. From these data, relative costs have been calculated for grinding both untreated and heat- treated ore on a basis of plant capacity of 120 tons per hour. Heat requirements for a rotary kiln, as well as the kiln capacity required for the treatment, have been estimated. For these tests 50 tons of ore were obtained from the Aurora mine of the Erie Mining Co., Hibbing, Minn. The ore was reported7 to have been selected from the magnetic portion of the lower chert horizons. An average chemical analysis of' this portion is shown in Table I and an approximate mineralogi-cal analysis is shown in Table 11. No attempt was made to differentiate between the various silicates because the compositions vary widely on the different horizons and depend on the degree of oxidation. Minnesotite, however, is the predominant silicate. The siderite grains were dispersed throughout the ore but were essentially associated with the rock-forming minerals. In a series of preliminary tests in which batches of —6 mesh ore were heat-treated in a muffle fur-

Jan 1, 1953

By M. S. Burton, G. V. Smith, A. Rosen

The kinetics of re crystallization and the effect of recovery on recrystallization of pure iron were investigated within the temperature range of 517" to 632 OC. Grain growth and activation energies were also studied. Two stages can be distinguished during recrystallization; the first is gvowth-controlled and the second is nucleation-controlled. The extent to which the first stage succeeds before the second stage begins depends on both temperature of recrystallization and temperature of recovery. The softening of cold-worked metals and alloys due to transformation of the deformed crystals to strain-free equiaxed grains during annealing is well-known, and early inestiators established that recrystallization kinetics is strongly influenced by minute quantities of impurities. Generally, it is believed that impurities decrease the rate of recrystallization and the rate of grain growth. To understand the basic phenomena of recrystallization, investigations should be on pure materials. Most of the research on high-purity materials has been on metals having the fee Bcc materials, and especially high-purity iron, have been studied only in recent years. It is known that recovery may influence recrystalliation;" however, no general description of the influence, applicable to all materials, has been presented. This paper presents results of a study of the recrystallization kinetics of high-purity iron, after 60 pct cold deformation by drawing, with particular reference to the influence of recovery on the rates of recrystallization and grain growth. From observations of these rates, conclusions are drawn concerning nucleation. MATERIAL AND EXPERIMENTAL PROCEDURE Preparation of Material. High-purity iron, prepared by zone refining of vacuum-melted electroiytic iron at Battelle Memorial Institute under sponsorship of the American Iron and Steel Institute, was used in this study. Table I gives the reported chemical analysis of the material, taken at a point near the last molten zone and thereby rep- resenting the maximum impurity level for the entire bar. Prismatic specimens, approximately 10 x 10 X 50 mm, were sawed from the 50-mm-diam bar, perpendicular to the zone-refining direction, and turned to cylindrical shape. These specimens were sealed in quartz capsules under vacuum, approximately 10"e mm Hg, austenitized at 930° C for 15 min, slowly cooled, removed from the capsules, and cold-worked in air by swaging to approximately 20-pct reduction of area. The encapsulating, austenitizing, and swaging operations were repeated two additional times, after which the samples were encapsulated, austenitized, and cold-drawn to 60-pct reduction of area. A further vacuum anneal at 630°C for 120 min and cold drawing to 60-pct reduction of area produced wire 2.8 mm in diameter. The drawn wire was electropolished to remove deformed material on the surface, after which it was sawed into 4-mm-long specimens for the recrystallization study. Microscopical examination before the final cold reduction revealed equiaxed grain structure with very fine grains in a thin layer near the surfaces of the specimen and nearly uniform ASTM 3-4 grain size in the center. Recrystallization Heat Treatment. a) Direct Recrystallization of Cold-Worked The 60 pct cold drawn iron specimens were recrystallized at five temperatures, 517, 556, 590°, 612, and 632C, in a lead bath covered with graphite (the temperature was controlled to 1°C). Specimens were treated for twelve different times at each temperature, and all were water-quenched after heat &eatment. b) Recrystallization Following Preliminary Recovery Heat Treatment. After cold working, specimens were sealed into quartz capsules under vacuum, 105 mm Hg, and recovery-annealed at 362", 400", and 440°C for 20 hr prior to recrystallization. No evidence of recrystallization was found

Jan 1, 1964

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By R. D. Reiswig, J. M. Dickinson

The 0s-Ir equilibrium diagram was determined. The diagram is of the simple peritectic type, with a peritectic temperature of about 2660°C. The solid miscibility gap is narrower than previously reported, the nearly vertical solvus lines occurring at about 42 and 63 wt pct 0s. Widmanstaetten figures resembling martensite in some of the two-phase alloys account for a previously suspected transformation. In view of the long history of use of such alloys, it is surprising that the 0s-Ir equilibrium diagram has not yet been completely determined. The boundaries of the miscibility gap in this system have been estimated to be between 24 and 39 wt pct 0s and 79 and 100 wt pct OS. It has been predicted3 that alloys of ruthenium, osmium, and rhenium with the fcc platinum metals should solidify peritectically in their two-phase regions. The metallographic examination of natural osmiridium alloys has been said4 to indicate, by the presence of a martensitic structure, the existence of a transformation or a phase separation. On the basis of superconducting transition temperature measurements, a 70 at. pct 0s alloy was found5 to be two-phase prior to annealing. EXPERIMENTAL The elemental components used in this work were obtained from several suppliers as sponge. The purities, stated by each supplier to be in excess of 99.8 pct, were confirmed in each case by a semiquantitative spectrographic analysis. The pure components were premelted in an inert-gas tungsten arc furnace with the evolution of some fume, crushed, and pickled for use as alloy melting stock. Upon arc melting to the final compositions, no fume evolution was observed. Because weight losses of the order of 15 mg or less were observed in preparing alloy buttons weighing 15 g, "synthetic analyses" were used in determining the compositions of the alloys. Alloys used in this investigation contained 15, 20, 33, 40, 42, 43, 45, 50, 55, 60, 63, 64, 66, 70, 79, and 80 wt pct 0s. Heat treatments of the alloy buttons and pieces thereof were performed in a previously described6 tungsten tube furnace under pressures of 105 torr or less. It was found that homogenization treatments on the specimens were essential to remove the severe coring which was present, a 3-hr treatment above 2300°C removing all the metallographi-cally visible evidence of coring. Following the various heat treatments, the specimens were "vacuum-quenched" by melting a tungsten fuse wire and allowing them to drop onto a water-cooled copper plate. In a few instances, specimens were quenched into molten tin for comparison, but no difference was apparent. Vacuum-quenched specimens cooled from 2400°C to below a red heat in less than 60 sec. Typical equilibration times varied from 3 hr above 2300°C to 88 hr near 1100°C. The utilization of successively longer equilibration times and the approach to equilibrium from both directions indicated that the times used were sufficient to give a close approach to true equilibrium. Heat-treatment temperatures were measured with a calibrated Leeds and Northrup optical pyrometer through a 0.120-in. lateral sight hole in the tungsten heater tube. It was known that the assumption of black-body conditions inside the 1-in.-diam by 10-in.-long tube was unwarranted. The empirical results of work with thermocouples and melting

Jan 1, 1964

By Edward B. Walker, Michel Grosmangin

The geological and economic conditions peculiar to the Greater Oficina area are presented to demonstrate the necessity of a low-cost, well-site method of distinguishing gas-bearing formations. The method of gas detection with the neutron log is briefly discussed and its limitations are explained. A new method is described which consists in running a second neutron log with a larger source-to-detector spacing. Field data indicate that under favorable conditions the larger spacing response is proportionately more influenced by the virgin gas zone than is the shorter spacing response. One important condition is that the gas sands be invaded, with a diameter of invasion equal to about two to three times the hole diameter. The calibration of the longer spacing log is made so that the two logs read the same deflection in shale and in a known water or oil sand. Under such conditions, gas is indicated by a positive separation, i.e., the curve for the longer device is displaced to the right of the curve for the shorter device. Because of the non-linearity of the long spacing response, low porosity formations also show positive separations. In sands with large porosity variations, the gas sands can no longer he located visually. They can be detected on a plot of shorter spacing vs longer spac-ing deflections. INTRODUCTION In the Greater Oficina area of Eastern Venezuela, the rapid and accurate detection of gas from well logs is of primary importance because of a combination of economic, geologic, and operational conditions. Briefly, these conditions are: economic—there is no market for gas at the present time; geologic—a single well may contain as many as 30 or more oil or gas sands for which intervals -to be tested must be selected; opera-tional—first, once opened to the casing through perforations, gas sands are extremely difficult and expensive to squeeze off, and second, gas detection must be rapid because the geologist must decide immediately, at the well, which sand to perforate. During the early period of exploitation in Greater Ofi-cina, when clay base muds were used, sidewall samples, together with electric logs, gave fairly good distinction between oil and gas sands. When exploitation became concentrated on deep fields of poorer sidewall sample recovery, and after the advent of oil emulsion muds, now the standard drilling fluid in Greater Oficina, the regular neutron log became the most reliable indicator of gas. In 1953, R. Norelius devised the dual-spacing neutron technique for gas detection. The dual-spacing neutron log has proved to be highly successful in detecting gas and has been adopted as a regular survey by all of the oil companies of the area. Several hundred dual-spacing neutron logs have been run in Eastern Venezuela and several tests per well are available for positive evaluation of the logs. The findings outlined below are based upon this extensive field experience. GEOLOGICAL CONDITIONS OF THE GREATER OFICINA AREA The Greater Oficina area lies on the south flank of the Eastern Venezuela Basin (Fig. 1). Nearly all accumulations of oil and gas in the area are trapped, in whole or in part, against normal faults. All known oil and gas reservoirs in Greater Oficina occur in the Ofi-cina formation (Miocene-Oligocene) or in the "U" sands. The U sands are the lithologic equivalent of the Merecure group (Otigocene-Eocene), which contains oil in many fields north of Greater Oficina. Most of the petroleum produced in Eastern Venezuela is from the Oficina formation.

Jan 1, 1958

By Ralph V. Higgins

This paper concerns the magnitude of the amount of supersaturation that occurs in an underground reservoir during the flow of oil and gas to wells and to the amount of undersaturation that occurs during repres-suring of an oil reservoir where some effective permeability to gas exists. The study is based on earlier laboratory findings of other investigators on the rate of diffusion of gas in oil as a function of the depth of oil. Utilizing these relationships and the principles of reservoir mechanics, a quantitative estimate of undersaturation and super-saturation was calculated. The results showed that the diffusion of the gas is rapid enough that for all practical purposes no supersaturation exists during the flow of oil to wells or undersaturation during repressuring in reservoir sands having some effective permeability to gas. The reason diffusion of the gas virtually keeps the oil saturated is the long time required in radial flow for oil to reach the well and the slow rate at which pressure in reservoirs is increased during repressuring. INTRODUCTION Knowledge of the phase relationships during flow of gas and oil in an underground reservoir is essential to operating the reservoir in the most efficient manner. In material-balance calculations and in fluid-flow studies, the oil is assumed to contain all the gas that it will dissolve at given temperature and pressure. Pressure-volume-temperature relationships are normally obtained in the laboratory using "bottom-hole" or combined samples of the reservoir fluids. In such laboratory determinations equilibrium is obtained between the oil and gas in the pressure cells by mechanical agitation. During the flow of oil and gas in reservoirs, however, no comparable agitation occurs to mix thoroughly these fluids to aid in effecting equilibrium between the two phases. During repressuring of a partly depleted underground reservoir, the gas is usually injected into the reservoir faster than the oil can absorb it; consequently, the oil is undersaturated. On the other hand, as the oil flows through the reservoir to the wells during producing operations the pressure decreases faster than the gas in solution can diffuse through the oil to the gas phase. The oil therefore is supersaturated with gas. Where the oil is undersaturated, gas diffuses away from the gas-oil interface, and where it is supersaturated the gas diffuses toward the interface. In either case the gas moves from a higher to a lower saturation. This report contains the results of a study of the factors influencing the degree of nonequilibrium of the phase relations of oil and gas in porous mediums during the flow of oil through reservoirs to wells and also during the injection of gas into partially depleted sands. Data from an underground reservoir are presented and the degree of supersaturation during the flow of the oil through the reservoir to the well is approximated. Also data from another reservoir are used and the degree of undersaturation during the repressuring operation is calculated. In addition, the flow rates of oil in laboratory experiments and in underground reservoirs are compared, as data from the laboratory are often used to interpret events in the reservoir, and the rates of flow influence appreciably the degree of nonequilibrium. Much of the contents of this report was prepared in 1943; but, because of other activities during and since the war, the manuscript was left untouched until 1952, when it was decided to include an estimate of the amount of undersaturation during repressuring as well as supersaturation during flow.

Jan 1, 1955

By S. L. Couling, D. J-P. Adenis

i2) twinning in poly crystalline magnesium does not usually occur homogeneously but is concentrated in localized regions or bands inclined at about 45 deg to the stress axis. These bands of twinning are in many ways similar to the Luders bands seen in mild steel alzd Al-Mg alloys. Within a hand the percentage of the volume twinned may approach 100 with no twinning outside the band. Bands are not produced in specimens of grain size a3 x 10-= in. or in samples deformed at temperatures 300°F. Annealing of heavily twinned regions leads to re crystallization textures markedly different from those found in the starting material. The exact preferred orientation appears to depend on the starting grain size, the amount of compres-sive strain and the manner in which it is introduced. MAGNESIUM, with its hexagonal crystal structure, deforms plastically at room temperature by a variety of deformation mechanisms, one of the most important of which is (1012) twinning. In single crystals such twinning occurs on compression parallel to the basal plane or tension perpendicular to it. In wrought polycrystalline magnesium, such as rolled sheet, the preferred orientation is such that almost all the grains have their basal planes nearly parallel to the sheet surface. Therefore, if sheet material is deformed by cold rolling or by tension in the plane of the sheet, deformation of the grains by (1012) twinning is not favored. On the other hand, twins form readily on compression parallel to the plane of the sheet as in a compression test, on the compression side of a bent sample, or at the outer rim of a drawn cup. The first part of this paper deals with the morphology of (1012) twinning in polycrystalline magnesium. Some aspects of this subject were covered by Barrett and ~aller.' Of direct bearing on the work to be reported here are the comments of Jetter' in discussion to Ref. 1. He shows that Mg + 1.5 pct Mn alloy sheet when bent about a transverse axis develops a pattern of transverse bands on the surface of compression. A longitudinal section through the sheet shows that the bands are wedge-shaped and inclined to the rolling direction. The bands were identified as "outcrops of regions in which deformation is localized as the result of the reorientation brought about by (1012) twinning". The second part of the paper treats the recrys-tallization texture of the specimens twinned by compression. Magnesium deformed and then annealed generally recrystallizes with no change in orientation.1'3'4 This statement is true provided that the amount of (1012) twinning occurring during deformation is small. In an isolated observation, Anse15 has shown that, when deformation produces much (1072) twinning, annealing causes new maxima to appear in the pole figure. The second part of the paper elaborates on this point. I) MATERIALS AND PROCEDURES All of the experimental work to be reported was done using the commercial sheet and plate alloy AZ31B (nominal composition: 3 pct Al, 1 pct Zn, 0.4 pct Mn, balance magnesium). This alloy is available commercially in two tempers, -0 (fully annealed) and -H24 (partially annealed), and specimens of both tempers were used in various experiments. The average grain. diameter (AGD) for -0 temper 0.125-in. sheet is about 0.5 x 10- in.; where material of larger grain size was desired, anneals at elevated temperature were used to grow the grains. compression tests were made on a screw-driven "hard" machine. The specimens were clamped in a

Jan 1, 1964

By Frederick V. Lawrence

Broadly speaking, fluxes are substances which promote wetting and spreading or enhance the fluidity and manipulative properties of materials in joining, fusion, and smelting operations. The term most strictly applies to substances used to facilitate soldering and brazing; but in the discussion which follows, the definition will be broadened to include materials used to promote fusion in arc welding and which aid in the smelting of metals. In each of the mentioned applications, the role of flux and its composition differs considerably; consequently in the discussion which follows, fluxes for soldering, brazing, arc welding, and smelting applications will be considered separately. Soldering and Brazing Fluxes Soldering and brazing are metallurgical joining processes in which a joint is formed using a filler metal of composition dissimilar to that of the joined pieces (base metal). The filler metal, solder or braze, is always of lower melting point than the base metal. Consequently with these processes there is no melting of the base metal. The successful creation of the joint depends upon the wetting and spreading of the solder or braze around or throughout the joint. The obstacles to successful soldering and brazing are contaminants and tenacious oxide films on the metal surfaces. In soldering and brazing applications, fluxes act to remove and exclude oxides and other impurities from the joint. There is no fundamental difference between soldering and brazing. The distinction between them is made on the basis of temperature. Join¬ing operations carried out at temperatures above 500° C are termed brazing. The higher temperatures used in brazing enable higher melting point filler metals to be used which generally provide stronger joints. The higher temperatures of brazing processes also require fluxes which are substantially different from those used in soldering and which will remain effective at high temperatures. Consequently the distinction between soldering and brazing can also be made on the basis of the fluxes used. Soldering Fluxes Even thoroughly cleaned and degreased, metal surfaces still possess tenacious oxide films which inhibit the soldering of the joint. The reactions which form these films increase with increasing temperature. The rate of oxide formation and the tenacity of the film varies with each base metal. Aluminum, magnesium, stainless and high alloy steels, aluminum and silicon bronzes when exposed to air form hard, adherent oxide films. These metals require highly active and corrosive fluxes to remove and prevent the reformation of oxide films during soldering. Metals such as copper and silver, on the contrary, form less tenacious films at a lower rate, so that mild fluxes are sufficient. Soldering fluxes must dissolve or remove oxides and promote rapid wetting and spreading of the solder. The flux removes the oxide film by loosening and floating it off into the main body of the flux. The oxide removal is often aided by the alloying of the solder with the base metal, undermining small areas of the oxide and detaching them (Anon., 1959). The flux coagulates and suspends the oxide particles which have been loosened. The flux forms a protective cover preventing the reformation of the oxides, permitting the spreading of the solder and the formation of a metallic bond between the solder and the base metal. Constituents of Soldering Fluxes: Soldering fluxes are commonly grouped into three categories: highly corrosive, intermediate, and noncorrosive. One normally would choose to use the least corrosive flux which will give satisfactory performance.

Jan 1, 1983

By P. Shahinian, R. L. Stegman, M. R. Achter

Creep strength has been determined as a function of oxygen pressure for nickel at 510" and 600°C. Creep-rupture life drops from its highest value at the ultimate vacuum of 10-7 torr to a high pressure plateau of nearly constant life which, at 600°C, commences at torr. This behavior is described in terms of a model that relates surface gas adsorption and the generation of fresh crack surfaces. In a calculation based a this model the predicted pressure beyond which the creep strength should not decrease further has been found to agree well with the observed value. The introduction of oxygen during creep in vacuum was found to cause a prompt rise of the creep rate. The magnitude of the environmental effect was much less than generally observed in fatigue and this is attributed to the diffarent crack morphologies in creep and fatigue. GASEOUS environments are known to affect creep resistance adversely1-5 but the effects have received less attention than the much larger ones in fatigue. At low temperatures it has been shown for nickel that the creep rates are faster and the rupture lives are shorter in air than in vacuum and that these environmental effects can be correlated with faster crack growth rates in the reactive environment.' In support of a mechanism of gas adsorption at the crack tip to explain the above effects, a calculation based on kinetic gas theory showed that surface coverage by gas was not as rapid as the exposure of fresh metal at the crack tip in the ultimate vacuum but was in air.7 In fatigue a number of investigations have demonstrated that the reduction of life with gas pressure usually follows a step curve with most of the reduction occurring in a transition range at intermediate pressures and little or no change at high and low pressure.8 There have been no studies, however, in which creep strength has been determined as a function of reactive gas pressure to see whether similar effects would be found. This investigation was undertaken to study the kinetics of the environmental effect in the creep of nickel. EXPERIMENTAL PROCEDURES The environmental creep apparatus was constructed to minimize many of the experimental conditions which can cause scatter in data. Dead weight loading is employed and weights are contained within the environmental chamber to eliminate bellows and the necessity for compensation for gas pressure changes. Elongation over the specimen gage length is recorded from a Riehle Model DV Controlled Environment Extensometer which provides readout to 2.5 x 10- in. Temperature is monitored and controlled from a thermocouple at- tached to the specimen gage length to +0.5oC or better. The freon trapped oil diffusion pump vacuum system included an auxiliary liquid nitrogen trap and, with a wide range variable conductance leak valve, pressures from the ultimate vacuum of 10"7 to l03 torr of any desired gas are obtainable. Pressure is measured by means of a hot filament ionization gage below 10"3 torr and a NRC Model 530 Alphatron Vacuum Gauge above 10-3 torr. The oxygen, which was leaked into the environmental chamber, was an Aviator's Grade of 99.5 pct purity with a dew point of -80°F. Analysis of the nominal 99.8 pct Ni showed the following percentages of major impurities: 0.02 C, 4.01 Mn, 0.005 Si, 0.01 Cu, 0.02 Fe, and 0.034 Mg. Cylindrical specimens were machined with a 0.180

Jan 1, 1970