Search Documents

By R. R. Estill

THE rank of the Ruhr coal ranges from a high volatile bituminous coal to an anthracite, depending to some extent on the original depth of the seam. The average Ruhr coal corresponds to a soft bituminous American coal of a coking quality. The average thicknesses of individual coal seams being mined are also comparable (59 in. against 65 in. in the United States). However, consideration of seam conditions and mining conditions other than those just mentioned emphasizes differences rather than similarities with United States soft coal. In general, the Ruhr seams now being mined are much more folded and inclined than American seams. Dips of 20' and 30" are common in seams now being worked, and 30 pct of the coal reserves in the district are in seams dipping more than 35". Only on the tops and bottoms of folds do we find rather flat coal seams. In addition to the folding there is extensive displacement by cross faulting plus a certain amount of strike faulting of an overthrust nature, which results locally in doubling or omission of seams. Because of the long history of mining in the Ruhr, nearly all coal lying near the surface has long since been mined out, and we find that the average depth of mining is at present about 2300 ft below the surface. Deep mining, folding, and faulting result in seam conditions requiring a great deal more roof support than one finds in American soft coal mines. In fact only in the anthracite district and the Rocky Mountain and Pacific coal fields do we find somewhat similar conditions. It is easy to say, therefore, that the problem of mechanization of coal cutting and loading in the German mines is quite different from that which we have so effectively met in America with our mobile cutters and loaders, duck bill loaders, and a room and pillar system of mining our drift and slope mines. Partly because of more limited coal reserves, the traditional German mining system is largely the longwall method, which gives an almost complete coal recovery. Backfilling must be extensively practiced to protect the longwall faces, the over and underlying seams and workings, and especially the surface industrialized areas and barge canals. The German engineers have accordingly concentrated their efforts on the design of cutters, loaders, and conveyors suitable to longwall methods rather than room and pillar methods. Undercutters with cutter bars like American models have been in use in the Ruhr since well before World War 11. In 1941 they accounted for 8.5 pct of the production. This percentage, of course, includes coal which was undercut but nevertheless had to be broken down with air hammers or with explosives. The most common of these cutters is the Eickhoff Standard cutter (see fig. 1). This machine does about 95 pct of the undercutting in the Ruhr today, and is available with either compressed air or electrical power and in at least four different sizes. A variation of the cutter is this one with two cutter bars (fig. 2). At the end of 1947 about 200 of these machines and similar cutters were accounting for 13.2 pct of the total production, a production which was, however, only 60 pct of the 1941 production rate, so that the actual cutter tonnage was only up to a small amount over 1941. In 1941 about 3 pct of the production was accounted for by shearing machines making their cut perpendicular to the longwall face. They were similar to those used in the States. These machines are today considered obsolete and now account for only 0.7 pct of the total production. They are located at only a few mines and at present do not seem to have much of a future in the Ruhr. For the future, the Ruhr miner is looking forward to rather extensive mechanization of face work, with two major types of equipment being developed almost simultaneously. On one hand there is the development of cutter loaders for use in relatively hard coal. They represent the further extension of ideas developed after relatively long experience with the Eickhoff cutter. On the other hand there has been since 1942 an intense interest in the Ruhr in the development of face-stripping methods, particularly by the Kohlenhobel (coal plow) and its modification. At the end of 1947 these cutter loaders, Kohlen-hobels and scrapers together were actually accounting for only about 1.4 pct of total production while air hammers still broke 77.1 pct and as much as 1.2 pct was actually broken by hand picks. However,

Jan 1, 1951

By R. R. Estill

THE rank of the Ruhr coal ranges from a high volatile bituminous coal to an anthracite, depending to some extent on the original depth of the seam. The average Ruhr coal corresponds to a soft bituminous American coal of a coking quality. The average thicknesses of individual coal seams being mined are also comparable (59 in. against 65 in. in the United States). However, consideration of seam conditions and mining conditions other than those just mentioned emphasizes differences rather than similarities with United States soft coal. In general, the Ruhr seams now being mined are much more folded and inclined than American seams. Dips of 20' and 30" are common in seams now being worked, and 30 pct of the coal reserves in the district are in seams dipping more than 35". Only on the tops and bottoms of folds do we find rather flat coal seams. In addition to the folding there is extensive displacement by cross faulting plus a certain amount of strike faulting of an overthrust nature, which results locally in doubling or omission of seams. Because of the long history of mining in the Ruhr, nearly all coal lying near the surface has long since been mined out, and we find that the average depth of mining is at present about 2300 ft below the surface. Deep mining, folding, and faulting result in seam conditions requiring a great deal more roof support than one finds in American soft coal mines. In fact only in the anthracite district and the Rocky Mountain and Pacific coal fields do we find somewhat similar conditions. It is easy to say, therefore, that the problem of mechanization of coal cutting and loading in the German mines is quite different from that which we have so effectively met in America with our mobile cutters and loaders, duck bill loaders, and a room and pillar system of mining our drift and slope mines. Partly because of more limited coal reserves, the traditional German mining system is largely the longwall method, which gives an almost complete coal recovery. Backfilling must be extensively practiced to protect the longwall faces, the over and underlying seams and workings, and especially the surface industrialized areas and barge canals. The German engineers have accordingly concentrated their efforts on the design of cutters, loaders, and conveyors suitable to longwall methods rather than room and pillar methods. Undercutters with cutter bars like American models have been in use in the Ruhr since well before World War 11. In 1941 they accounted for 8.5 pct of the production. This percentage, of course, includes coal which was undercut but nevertheless had to be broken down with air hammers or with explosives. The most common of these cutters is the Eickhoff Standard cutter (see fig. 1). This machine does about 95 pct of the undercutting in the Ruhr today, and is available with either compressed air or electrical power and in at least four different sizes. A variation of the cutter is this one with two cutter bars (fig. 2). At the end of 1947 about 200 of these machines and similar cutters were accounting for 13.2 pct of the total production, a production which was, however, only 60 pct of the 1941 production rate, so that the actual cutter tonnage was only up to a small amount over 1941. In 1941 about 3 pct of the production was accounted for by shearing machines making their cut perpendicular to the longwall face. They were similar to those used in the States. These machines are today considered obsolete and now account for only 0.7 pct of the total production. They are located at only a few mines and at present do not seem to have much of a future in the Ruhr. For the future, the Ruhr miner is looking forward to rather extensive mechanization of face work, with two major types of equipment being developed almost simultaneously. On one hand there is the development of cutter loaders for use in relatively hard coal. They represent the further extension of ideas developed after relatively long experience with the Eickhoff cutter. On the other hand there has been since 1942 an intense interest in the Ruhr in the development of face-stripping methods, particularly by the Kohlenhobel (coal plow) and its modification. At the end of 1947 these cutter loaders, Kohlen-hobels and scrapers together were actually accounting for only about 1.4 pct of total production while air hammers still broke 77.1 pct and as much as 1.2 pct was actually broken by hand picks. However,

Jan 1, 1951

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach's work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,' who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750'F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By C. J. Guntner, R. P. Reed

A commercial 18Cr-8Ni iron alloy (AISI 304L) was examined in tension at 300°, 76°, 20°, and 4°K. Continuous stress-strain recordings were made, X-ray analyses at periodic stress (strain) intervals were obtained, and the magnetic measurements were taken. From this data the percentage of martensitic products [bcc(a) and hcp (E)] was computed as a function of stress (strain). It was found thatup to 15 pct E phase forms at low temperntures. The amount of E formed increases to a maximum at about 5 pct strain, then decreases. This decrease indicates the additional transformation of E to a'. The total amount of E and a' was suppressed at constant stress (strain) at 4°K as compared to 76°K. It is proposed that the suppression of E and a' is associated with the decreased mobility of extended dislocations at very low temperatures. The yield strength decreased as the temperature was depressed below room temperature and then increased rapidly near 4°K. SOME ferrous alloys which are austenitic (fcc ?) at room temperature appear to be unique in that two martensitic products (hcp e and bcc a') may form on cooling to lower temperatures or on application of mechanical stress. The most common room-temperature austenitic ferrous alloys are 18Cr, 8Ni stainless steels. Most aspects of the spontaneous transformations have been previously described for these steels.' Several previous papers have described special aspects of the stress-induced transformations at low temperatures for the stainless steels, such as the existence of the hcp phase (c) after straining at 76oK,2-7 the morphology after straining using electron microscopy,7 and the decrease in E at higher strains at 76oK.4 However, for a complete representation, one must know the stress-strain characteristics and the dependence of both martensitic products on applied stress and temperature. It is the intention of this paper to provide that documentation. To accomplish this, continuous stress vs strain recordings were made at four temperatures: 300°, 76", 20°, and 4°K for annealed AISI 304L (a commercial 18Cr-8Ni alloy). At periodic stress intervals at each temperature the integrated X-ray line intensity of a selected peak for each phase (y, E, and a') was measured. In addition, photomicrographs of the strained surfaces were taken and magnetic measurements were made. The magnetic readings can be directly converted into percent a'.',e With these measurements the percentage of each phase may be plotted as a function of stress (or strain) and test temperature. It was found that up to 15 pct E phase forms upon stressing the AISI 304L alloy at low temperatures. The E percentage increases abruptly after the alloy yields, but then decreases gradually at higher stresses. The rapid increase in e at 76°K is associated with an "easy-glide" portion of the stress-strain curve. The total amount of a' + .G is suppressed below 76°K at a constant stress or strain. The yield strength decreases down to 76°K but increases rapidly below 20°K. EXPERIMENTAL PROCEDURE Tensile test specimens were cut parallel to the rolling direction from 0.1-in.-thick sheet. Continuous stress vs strain recordings were obtained at each test temperature (300°, 76o, 20°, and 4°K) using equipment and methods described elsewhere.' The specimens which were used in the X-ray analysis were stressed to successive increments of strain at each temperature, analyzed at room temperature, then restressed at the test temperature. This procedure was repeated until approximately ten X-ray analyses had been performed with approximately 1.0 pct strain increments. The specimens had a reduced section 1 in. long, 1.2 in. wide, and 0.1 in. thick. They were electro polished prior to testing and after each strain increment. Table I lists the chemical composition, grain size, and hardness for the alloy which was used. This is the same alloy for which extensive mechanical-property tests3 and morphological studies of the spontaneous transformations' have previously been made. For the low-temperature tests (76o and 4°K) below the Ms temperature the specimens were initially cooled to the test temperature, held for 1/2 hr, then warmed and X-rayed at room temperature. The results are listed in Table 11. From earlier work8 it was known that additional transformation on the second cycle would be considerably less (-0.1 pct

Jan 1, 1964

ARTICLE I Name and Object Sec. 1. This Division shall be known as the Institute of Metals Division of the American Institute of Mining and Metallurgical Engineers. Sec. 2. The object of the Division shall be to furnish a medium of cooperation between those interested in the field of physical metallurgy; that is, the nature, structure, alloying, fabrication, heat treatment, properties and uses of metals; to represent the AIME insofar as physical metallurgy is concerned, within the rights given in AIME Bylaw, Article XI, Sec. 2, and not inconsistent with the Constitution and Bylaws of the AIME; to hold meetings for the discussion of physical metallurgy; to stimulate the writing, publication, presentation and discussion of papers of high quality on physical metallurgy; to accept or reject papers for presentation before meetings of the Division. ARTICLE II Members Sec. 1. Any member of the AIME of any class and in good standing may become a member of this Division upon registering in writing a desire to do so, but without additional dues. Sec. 2. Any member not in good standing in the AIME shall forfeit his privileges in the Division. ARTICLE III Funds Sec. 1. The expenditure of the funds received by the Division shall be authorized by the Executive Committee of the Division. ARTICLE IV Meetings Sec. 1. The Division shall meet at the same time and place as the annual meeting of the AIME, and at such other times and places as may be determined by the Executive Committee subject to the approval of the Board of Directors of the AIME. Sec. 2. The annual business meeting shall be held within a few days before or after the annual business meeting of the AIME. Sec. 3. At a meeting of the Division, for which notice has been sent to the members of the Division through the regular mail or by publication in the Journal of Metals at least one month in advance, a business meeting may be convened by order of the Executive Committee and any routine business transacted not inconsistent with these Bylaws or with the Constitution or Bylaws of the AIME. Sec. 4. For the transaction of business, the presence of a quorum of not less than 25 members of the Division shall be necessary. ARTICLE V Officers and Government Sec. 1. The officers of the Division shall consist of a Chairman, a Senior Vice-Chairman, a Vice-Chair -man, a Secretary and a Treasurer. The office of Secretary and Treasurer may be combined in one person, if desired by the Executive Committee. Sec. 2. The government of the affairs of the Division shall rest in an Executive Committee, insofar as is consistent with the Bylaws of the Division and the Constitution and Bylaws of the AIME. Sec. 3. The Executive Committee shall consist of the Chairman, Senior Vice-Chairman, Vice-Chairman, past Chairman, Secretary, and nine members, all of whom shall be nominated and elected as provided hereafter in Article VII. Sec. 4. The Chairman, Senior Vice-Chairman and Vice-Chairman shall serve for one year each, or until their successors are elected. Each member of the Executive Committee shall serve three years. The Chairman shall remain a voting member of the Executive Committee for one year after his term as Chairman. Sec. 5. The Treasurer of the Division shall be invited to meet with the Executive Committee, but without ex-officio right to vote. He shall be appointed annually by the Executive Committee, from the membership of the Executive Committee or otherwise. Sec. 6. The annual term of office for officers of the Division shall start at the close of the Annual Meeting of the Institute and shall terminate at the close of the next Annual Meeting. ARTICLE VI Committees Sec. 1. There shall be standing committees as follows: Programs Committee. Finance Committee, Membership Committee, Annual Lecture Committee, Technical Publications Committee, Mathewson Gold Medal Committee, Nominating Committee, Education Committee and such other Committees as the Executive Committee may authorize. Sec. 2. It shall be the duty of the Programs Committee to secure the presentation of papers of appropriate character at meetings of the Division. Sec. 3. It shall be the duty of the Finance Committee to inquire into and examine the financial condition of the Division and to consider proper means of increasing its revenue and limiting its expenses. The Finance Committee shall audit the accounts of the Division and report to the Executive Committee prior to the Annual Meeting of the Division. It shall render a budget to the Executive Committee estimating receipts and expenses for the ensuing year so that action can be taken on same at the first meeting following the Annual Meeting.

Jan 1, 1953

By W. Rostoker, A. S. Yamamoto, K. Anderko

ALTHOUGH the corrosion resistance of magnesium and its alloys is closely related to iron content, there has been no direct measurement of the solid solubility of iron in magnesium. Bulian and Fahrenhors;1 and Mitchel]2 agree that pure iron or a limited terminal solid solution crystallizes from the Mg-rich liquid. For this reason a magnetic-moment method was selected to estimate that portion of the total iron content which is not in solid solution. Since iron in solid solution in magnesium cannot contribute to ferromagnetism, the difference between chemical and magnetic-iron analyses should yield the solid solubility. By experimentation it was found that the melting of pure sublimed magnesium (99.995 wt pet purity) in Armco-iron crucibles at about 800°C is a convenient way to introduce small amounts of iron. Melts retained 5, 10 and 20 min at 800°C analyzed 0.003,, 0.005,, and 0.018 & 0.001 weight pet Fe, respectively, after being stirred, heated to 850°C, and cast into graphite molds. The as-cast alloys were pickled in acid (dilute HC1 + HNO3), annealed at 600°C for 3 days, scalped on a lathe to remove the pitted surface, pickled again, extruded at about 100°C to 3-mm wire, reannealed 41/2 days at 500°C, and water-quenched. The specimens were again scalped, pickled, and used both for chemical and for magnetic analysis. Most of the precautions described were intended to prevent iron pickup by contact with tools or superficial iron enrichment by volatilization of magnesium during heat-treatment. It is believed that the specimens ultimately used for test were homogeneous and characteristic of phase equilibria at 500°C. Magnetic Analyses A susceptibility apparatus of the Curie type was used for magnetic analyses. Field strengths of up to 10,400 oersteds could be generated. By this method, an analytical balance measures the force of attraction which a calibrated magnetic field exerts on a suspended specimen. The force equation is as follows f/m = M dh/dy where f/m = force per unit mass of sample M = magnetic moment per unit mass dH/dy = magnetic field gradient The dH/dy characteristic of the instrument is determined by the use of a standard palladium sample, and the calibration is made independently for all values of H. Since a large finite field is required to saturate an assembly of ferromagnets, it is necessary to measure the apparent magnetic moment for increasing steps of H until a saturation value is obtained. The percentage of iron in the sample as free ferromagnetic iron may then be computed simply C= 100 (M1/M1) where C = percent content of undissolved iron in sample M1 = saturation magnetic moment of sample per unit mass M1 = saturation magnetic moment of iron per unit mass taken as 217 emu-cm per gm There is no serious difficulty in applying this method except for the unusual magnetic behavior of very fine particles of ferromagnetic substances. It has been found and is the basis for a widely accepted theory that with sufficient subdivision, the magnetic fields required to saturate and the coercive force after saturation rise to exceedingly high values. Recent work on precipitates of Fe and Co from copper solid solutions8 showed that about 5000 oersteds were necessary to approach saturation. The magnetic moments as a function of field strength measured in the present investigation are listed in Table I. Only the 0.018 wt pet Fe alloy yielded a magnetization curve with a fairly well-defined saturation plateau at 3.76x10 -2 emu-cm/ gm. This corresponds to 0.017 & 0.001 wt pet Fe in the alloy. This indicates that the solid solubility must be of the order of 0.001 wt pet Fe. The magnetic-moment data of the other two alloys are badly scattered, indicating that the amount of ferromagnetic iron in these samples is so low that the magnetic forces acting on them cannot be measured accurately by the analytical balance used. Nevertheless, the fact that even the 0.003, wt pet Fe alloy shows ferromagnetism indicates that the solid solubility must be below that value. Acknowledgment This work was sponsored by the Pitman-Dunn Laboratory of Frankford Arsenal, Philadelphia, Pa. The support and permission to publish are gratefully acknowledged. References W. Bulian and E. Fahrenhorst: Zeic. Metallkunde, 1942, vol. 34, pp. 116-170. 2 D. W. Mitchell: AIME Transactions, 1948, vol. 175, pp. 570-578. 3 G. Bate, D. Schofield, and W. Sucksmith: Philosophical Magnsine, 1955, vol. 46, pp. 621-631.

Jan 1, 1959

By Robert E. Green, Wolfgang Sachse

Simullaneous ultrasonic attenuation measurements of both quasishear waves propagating in single cryslals of aluminum indicate that, in the undeformed annealed state, the dislocation density is generally not uniform on all slip systems. Change oof attenuation measurements made during plastic defortnation of crystals , which possessed specific orientations ideal for studying the orientation dependence of dislocation damping, indicate that, for low strain levels, dislocation motion occurs on additional slip systems besides the primary one, even for crystals oriented for plastic deformation by single slip. THE sensitivity of internal friction measurements permits such measurements to be used successfully in studying the deformation characteristics of metal crystals. On the basis of experimental observations, T. A. Read1 was the first to associate internal friction losses with various dislocation mechanisms. Since that time further work2-' has been performed and a dislocation damping theory has been formulated by Granato and Lucke.6 In the amplitude independent region, this theory predicts the attenuation a to be dependent on an orientation factor O, a dislocation density A, and an average loop length L. if is a constant, independent of crystallographic orientation. For a given crystallographic orientation, changes in dislocation density and loop length give rise to the observed attenuation changes accompanying plastic deformation. The Granato-Liicke theory suggests the investigation of the orientation dependence of attenuation measurements in hopes of obtaining information to separate dislocation motion losses from other losses.7 An experimental study of the orientation dependence of attenuation in undeformed annealed single crystals should yield an insight into the uniformity of dislocation distribution throughout the entire specimen. A similar study on crystals plastically deformed in a prescribed fashion should give information about the alterations in the dislocation distribution on the slip systems activated during plastic deformation. The possible modes of elastic waves which can be propagated in aluminum,8 copper,9 zinc,10 and other hexagonal metals" have been calculated. Associated with each mode of wave propagation are dislocation damping orientation factors, which are based on the resolution of the stress field of that particular elastic wave onto the various operative slip systems in the material. These orientation factors have also been calculated as a function of crystallographic orientation in the papers cited above. Einspruch12 obtained agreement between predicted and observed attenuation values of longitudinal and shear waves in (100) and (110) directions of two undeformed aluminum crystal cubes. He ascribed the slight deviations between predicted and observed values to a nonuniform dislocation distribution, or to other loss mechanisms. In shear deformation of zinc crystals, Alers2 found that the attenuation of shear waves having their particle displacements in the slip plane was very sensitive to the deformation, while the longitudinal wave attenuation was affected only when the wave propagation direction was not normal to the slip plane. Using aluminum single crystals oriented for single slip, Hikata3 et al. found that during tensile deformation the change of attenuation of the shear wave (actually quasishear) having particle displacements nearly perpendicular to the primary slip direction exhibited the easy-glide phenomena, while longitudinal waves did not. Similar results were reported by Swanson and Green5 during compressive deformation of aluminum crystals. These results are in qualitative agreement with the calculated orientation factors for specimens of this orientation. In well-annealed, undeformed aluminum crystals, the damping is expected to be due to dislocations vibrating on all twelve slip systems. The orientation factors associated with this initial damping will be designated by O2 and O3, where a, represents the average orientation factor for the slow shear (or quasishear) wave and O3 represents the average orientation factor for the fast shear (or quasishear) wave. The calculation of these values for aluminum crystals by Hinton and Green8 shows that they vary very little as a function of crystallographic orientation—at most, by a factor of 2.47. If the dislocation density and loop length are uniform, then in the initial undeformed state, Here the subscript zero refers to the initial value of the attenuation. Also for aluminum, the calculations8 show that the orientation factors for primary slip only, associated with each shear wave, exhibit a sharp minimum for particular crystallographic orientations. A composite plot of the two shear wave orientation factors for primary slip only is shown in Fig. 1. Since these orientation factors are associated with dislocation motion occurring on the primary slip system only, the proper condition to check these factors might be attained by slightly deforming a single crystal oriented for primary slip. For dislocation motion on the primary slip system only,

Jan 1, 1969

By A. McLean, D. W. Gomersall, R. G. Ward

An experimental study has been made of the solubility of nitrogen in liquid iron and liquid Fe-C alloys using levitation melting and a rapid quenching device. Iron alloy droplets were equilibrated with nitrogen gas at 1 atm pressure, quenched, and analyzed. Previous techniques for studying the Fe-C-N system have produced data which me in marked disagreement. This disagreement is due largely to errors caused by reaction between the molten alloy and the crucible material. With the levitation procedure, errors from this source have been eliminated and precise solubility data obtained for temperatures between 1450° and 1750°C. C-N interactions in molten iron have been expressed in terms of first- and second-order free energy, enthalpy, and entropy parameters. ALTHOUGH the solubility of nitrogen in iron base alloys is in general small, the effects of nitrogen on the properties of steel may be quite profound. For most purposes nitrogen in finished steels is undesirable, particularly in the low-carbon grades, since on cooling to room temperature the solubility limit of nitrogen in the steel may be exceeded and this can lead to embrittlement and loss of ductility on aging. On the other hand, nitrogen can improve the work-hardening properties and machinability of steels while in certain stainless grades nitrogen is important in order to stabilize the austenite phase. It is, therefore, desirable that one should be able to predict the solubility of nitrogen in liquid iron alloys. To do this, information is required concerning the interactions between nitrogen and the various alloying elements which may be present in liquid iron. There have been several investigations of these effects in recent years1"7 and the interactions between nitrogen and many elements dissolved in liquid iron are now known to a high degree of precision at steel-making temperatures. Unfortunately, a number of iron alloy systems which are of interest in steelmaking have been difficult to deal with by the experimental techniques generally used for this type of investigation. Among the most important of these are the Fe-C alloys. In the past, two methods have been widely used for determining nitrogen solubilities: the Sieverts' technique, in which the amount of nitrogen required to saturate a given mass of liquid metal at a particular temperature and pressure is measured volumetrically, and the sampled-bath technique in which liquid metal held in a crucible is equilibrated with a gas phase containing a known partial pressure of nitrogen, and samples drawn from the melt are quenched and analyzed. These two methods have been discussed in detail elsewhere.5,8 With the Sieverts' technique, errors may be introduced from the following sources: i) Gas adsorption on metal films which have condensed on the cooler parts of the reaction chamber. ii) Uncertainty in the determination of "hot volume" calibrations. iii) Crucible-melt interaction, particularly if a gaseous reaction product is formed or if the melt becomes contaminated with material from the crucible walls. The sampled-bath method may also suffer from errors due to reaction between the melt and the crucible material. In addition, there is the possibility that gas may be lost from the sample during solidification and cooling. In the present investigation, the solubility of nitrogen in liquid iron alloys has been studied by means of a new technique based on the use of levitation melting equipment and a rapid quenching device. In addition to the fact that problems of the type outlined above are avoided, this particular approach has the following advantages: i) The high-frequency current induces vigorous stirring within the levitated droplet so that gas-metal equilibration is rapidly attained. ii) The gas phase surrounding the melt can be changed very quickly and is easily controlled. For example, a droplet may be levitated in helium, deoxidized in hydrogen, equilibrated with nitrogen, and quenched, within a period of 15 min. ii) Melts can be readily under cooled or superheated, thus extending the effective temperature range of an investigation and allowing temperature-dependent data to be determined with a high degree of precision. Excellent reviews of levitation melting techniques and their application to physical-chemistry studies at high temperature have been published recently by Jenkins et al.,9 Peifer,10 and Rostron.11 In the present investigation a levitation melting technique has been used to obtain data for the solubility of nitrogen in pure liquid iron and liquid Fe-C alloys at temperatures between 1450° and 1750°C. The solution of nitrogen in liquid iron can be described by the reaction:

Jan 1, 1969

By J. W. Rutter, K. T. Aust

The migration of individual, large-angle grain boundaries has been studied as a function of tempereature and solute concentration in specimens of zone i.e filled lead containig very small additions of silver and of gold. Tile results are compared with various the-ories of grain boundary migration and with observations made prev.iorlsly of grain boundary migration in similar specimens of zone-refined lead containing tin additions. A previous investigation by the authors dealt with [he temperature dependence of grain boundary migration in bicrystals of zone-refined lead containing small additions of tin.' It was shown that tin additions as low as a few parts per million cause a large decrease in the grain boundary migration rate at any given temperature, as well as a marked increase in the temperature dependence of the migration rate. It was found that existing theories of grain boundary migration. based on the motion of dislocations. or upon the concept of atom transfer in groups across the boundary (group process theory). or upon the control of grain boundary motion by volume diffusion of impurity atonls along with the boundary. are incapable of accounting for the observations. The single process theory of grain boundary migration. which is an absolute reaction rate calculation based on the transfer ui atoms singly across the moving boundary, was found to predict the migration rate reasonably well for a number of boundaries whose motion was shown to be very little influenced by impurities, but not for boundaries whose illation was influenced markedly by impurities. It was concluded that the elementary process of grain boundary migration involves the activation of single atoms during transfer across the boundary. and that inadequate knowledge is available to permit the influence of impurities to be properly taken into account. The present study was initiated to check the validity of the above conclusions with other alloy systems, namely high-purity lead with small additions of silver and of gold. Both silver and gold diffuse faster. and with a lower activation energy of volume diffusion. than does tin in lead;' consequently, a study of the effects of silver and gold on grain boundary migration in high-purity lead offered a means of testing theories of boundary migration based on bulk diffusion of the solute (eg. ref. 3). In addition. it was hoped that the present work, in comparison with the results for tin in lead, would provide information concerning which factors are important in determin- ing the interaction between solute atoms and a grain boundary. EXPERIMENTAL PROCEDURE The preparation of bicrystals of zone-refined lead, with various silver or gold additions, was identical to that previously described for the lead-tin alloys.''4 Each bicrystal consisted of a striated crystal which was grown from the melt. and an adjacent striation-free crystal which was introduced by artificial nucleation and growth.''4 The striation or lineage substructure in the melt-grown crystal provided the driving force for grain boundary migration. During the preparation of striated single crystals by growth from the melt, it was found that silver or gold concentrations as low as 2 or 3 ppm by atoms were sufficient to cause formation of the hexagonal cell structure. which is due to the presence of impurity, during freezing. This structure is revealed on the solid-liquid interface by decanting the liquid during freezing. The hexagonal cell structure was observed previously4 in zone-refined lead crystals with tin contents above approximately 200 ppm by atoms. These concentrations of silver, gold, or tin are in agreement with the predicted amounts required for cell formation in lead,5'6 under the present conditions of freezing.4 The absence of cell structure at decanted interfaces, therefore, served as a useful indication that the silver or gold contents were less than 2 or 3 ppm by atoms in the specimens as grown. It was found that grain boundary migration occurred only very slowly when the solute content approached that necessary for cell formation. As a result, the present experiments were conducted with silver or gold additions less than 1 ppm by atoms. This impurity level is well within the solid solubility limits for silver and gold in lead.7 The annealing treatments, measurements of grain boundary velocities, and orientation determinations were carried out as described previously.' However. each bicrystal was also chemically polished in a solution consisting of 8 parts glacial acetic acid and 2

Jan 1, 1961

By C. Richard Tinsley

Like most minerals, coal is inherently a demand-limited commodity. The very sedimentary nature of its occurrence implies greater availability potential than demand. But this situation is overridden by economics among fuels, between coals, and within coal blends. Such considerations make coal forecasting a very hazardous profession indeed. THERMAL COAL If one thought that the lead times involved with a mining project were very long, one has obviously not been exposed to the planning process in the electric generation business - a process seriously confounded by shifts in load growth, environmental pressures, capital intensity, security of fuel sourcing, inter-fuel economics, and so on. But as a general rule, the near-term forecasts for thermal coal can reliably be based on a bottom-up, plant-by-plant analysis. Cement plant conversions can also be reasonably estimated next in order of reliability, although they have a much wider spectrum of coal qualities and fuel sources to choose from with a notably higher tolerance for sulfur and ash. Finally, industrial demand can be assembled from the estimates for conversions by pulp/paper plants, chemical plants, etc. The industrial sector is harder to estimate, since it may involve small boilers or dual-fired units. Assessing demand in the Pacific Rim is relatively a straightforward process in the near term because the major importing countries are all located on the Asian continent with either negligible or very minor (yet stable) indigenous coal production, (itself often operated on a subsidized basis). Furthermore, all imports are seaborne. These major importers are Japan, Korea, Taiwan, and Hong Kong with Thailand, Singapore, and Malaysia up-and-coming consumers. The suppliers to this market all have substantial reserves to back up decades of exports to these countries. Australia, the US, Canada, South Africa, China, and the USSR dominate the supply side. The second oil-shock of 1979/1980 has convinced the importers that reliance on oil can be expensive and eminently interruptible. Thus, they are determined to diversify away from oil' to nuclear and coal for generating electricity and for coal for other purposes where possible. This trend is seen to continue even in the face of the oil glut worldwide and oil-price reductions in early 1982. But the importers are also convinced that reliance on one coal source and, in particular, one infrastructure route for the coal chain from mine to consumer can be equally expensive and interruptible. Strikes in the US and Australia; excessive demurrage at certain ports; relegation of coal to a lower priority on multiple-use railroads in the USSR and China; and concern over escalation on high-infrastructure or high-freight coal chains are among the risks worrying the importers. As a consequence, Pacific Rim thermal coal purchases are being allocated among supplier nations, between ports, and within each country. An example of Japan's shift away from Australia and toward the US and Canada is shown in the estimates in Table 1. But the confidence of the import estimates deteriorates sharply beyond the plant conversion timetables and construction schedules in the near term. If part of the second generation of coal-fired power plants can handle lower-energy coals, the field of suppliers could widen to accept sizeable tonnages from Alaska, Wyoming, Alberta, or New Zealand resources. These supply sources generally have some infrastructure or freight advantage to compensate for their lower quality and to compete on a delivered energy-unit basis. These also offer diversification in sourcing. And the possibility of coal liquefaction in Japan further widens the sourcing network. A great number of Pacific Rim coal forecasts have been generated, especially for Japanese thermal-coal imports which are expected to grow strongly in the 1980's. Since the Japanese themselves have not yet settled their energy policy, the exact numbers are hard to call. Nevertheless, at 50 million tonnes of imports in 1990, Japan would consume 50-60% of the total Asian thermal coal imports as shown on Tables 2 and 6. The next most important consumers are the "island" nations of Korea, Taiwan, and Hong Kong (see Tables 3-5). All three are embarking on power plant developments usually with captive unloading facilities, capable of accepting more than 100,000-dwt vessels. Korea, with no-indigenous bituminous coal, is not especially enamoured with US coals, which are deemed too heavily loaded by freight and infrastructure costs -- up to 70% of the delivered price. Thermal coal contracts are presently split to Australia (70%) and to Canada (30%). Korea Electric Power Co. is already considering second-generation boilers capable of burning lower-quality coals than the present standard. Korea does burn domestic anthracite.

Jan 1, 1982

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio'n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews' on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;' will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment ' consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-

By L. R. Raymond, G. G. Binder

One primary purpose of hydraulic fracturing as a well stimulation technique is to overcome formation damage. The literature provides ways of designing fracture treatments and evaluating their results but not of incorporating formation damage in vertically fractured wells. Results of an investigation of this problem are presented in this paper. Prediction of stimulation ratios in vertically fractured, damaged wells is accomplished with a mathematical model relating stimulation ratio to relative conductivity of fractures whose lengths are not more than about half the drainage radius of the well. Comparison of results from the new model to results in published predictions verify its utility; these results also show that the range of stimulation ratios that can be predicted for undamaged wells is extended to include relative conductivities of less than 300. This extension is important when using fracturing to stimulate wells with high production rates and high native formation permeabilities. For example, large increases in daily oil production rate can be obtained with stimulation ratio increases as low as 1.25. The importance of complete fracture fill-up (uniform proppant packing) is shown through use of the mathematical model. If, at the mouth of a fracture, only a small fraction (1/2 percent) of the total fracture length is not packed with proppant, nearly all the polential stimulation increase is lost. Proppant crushing, compaction and embedment have been shown in laboratory studies to be responsible for low fracture conductivities in wells producing from highly stressed formations. Equipment and methods for testing the effect of stress (overburden) on conductivity of fructures in consolidated and unconsolidated sands are discussed in this paper. Laboratory tests with simlilated fractures in cores from both types of formations showed that crushing, compaction and embedment seriously affect conductivity. Results indicate that similar laboratory tests should be made when accurate knowledge of fracture conductivity is needed to assure good stimulation results for important wells. The chief factor in stimulation ratio reduction was found to be overburden pressure, but the size and type of proppant and the hardness of the formation have significant effects. Fracture conductivity reductions of up to 50 percent were observed with sand propping fractures in consolidated cores; a reduction of 83 percent was measured for an unconsolidated core. The range of effective overburden pressures for which conductivities were measured was from 100 to 5,000 psi. An example fracture design and evaluation problem indicates the usefulness of considering formation damage in planning well stimulation jobs. When damage exists, but its extent and the degree of permeability reduction are not estimated from diagnostic tests, the formation permeability used in planning the job may lead to under-designing. As the example shows, too low a target stimulation ratio can lead to much lower production rates (by half) than could be attained otherwise. Solutions of equations representing several special cases of the mathematical model are presented in graphical form and details of the derivations of the equations are given in the Appendix. INTRODUCTION Since its inception in 1947, hydraulic fracturing has proven to be an effective and widely accepted stimulation technique. In the past 18 years the ability to execute a successful hydraulic fracturing treatment has been substantially increased. The development of design and evaluation procedures1,2 has been one of the major contributions to this increased skill. However, as the art of hydraulic fracturing has moved closer to a science, new problems concerning the design and evaluation of the optimal hydraulic fracturing treatment have arisen. Three questions are pertinent to these problems. I. How is a fracturing job evaluated in a damaged well? 2. What is the effect on the stimulation ratio of not filling the fracture in the vicinity of the wellbore? 3. What is the effect of overburden pressure on fracture conductivity and, consequently, the stimulation ratio? A primary objective of fracturing a well is to stimulate production by overcoming wellbore damage. Presently. however, there is no rational basis for designing or evaluating the optimal fracturing treatment in a damaged well. All present fracture design and evaluation techniques assume that proppants can be uniformly placed in fractures. This assumption may be in serious error, particularly for the portion of a fracture directly adjacent to the wellbore. In this area, turbulence of the injected fluid can cause the proppant to be swept farther into the fracture. Also, loss of fluid from the fracture to the

By A. M. Skov, L. F. Elkins

First response to large-scale water flooding in the fractured very low permeability Spraberry sand has led to a new unique cyclic operation. Capacity water injection is used to restore reservoir pressure. This is followed by marly months production without water irzjection and the cycle repeated. Expansion of the oil, rock and water during pressure decline expels part of the fluids but capillary forces hold much of the injected water in the rock. At least with reservoir pressure restored and with partial water flood development, field performance has proved this cyclic operation is capable of producing oil from the nzatrix rock at least 50 per cent faster and with lower water percentage than is imbibition of water at stable reservoir pressure. INTRODUCTION The Spraberry Field of West Texas presents unusual problems for both primary production and water flooding. Extensive interconnected vertical fractures in the fractional-md sandstone permitted recovery of oil on 160-acre well spacing, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 per cent of oil in place. The concept of displacement of oil from the sand matrix by capillary irnbibition of water has led to field techniques which promise greatly increased oil recovery. Free exchange of laboratory research, reservoir information and results of field pilot tests among the various companies has been very important in development of this technology. Five units covering a total of 170,000 acres have been formed for water flooding, and 10 other areas covering an additional 175,500 acres are in various stages of unitization. Part of the Driver Unit reaching fillup first has demonstrated very unusual waterflood behavior and indicated numerous operating problems that will develop within and among the various units. SPRABERRY ROCK AND PRIMARY PERFORMANCE The Spraberry, discovered in February, 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members: a 10-15 ft sand near the top and a 10-15 ft sand near the base. In part of the field some thinner intermediate sands are oil productive, and others are water bearing. All sands have permeabilities of 1 md or less and porosities of 8-15 per cent. Ordinary core analysis and electric and radiation logs are ineffective in differentiating between oil productive and nonprcductive sands. Sands capable of containing producible oil are best identified by mercury injection capillary pressure measurement and, in some cases, by core water saturation. About 3,500 wells have been drilled in the 500,000-acre trend. Vertical fractures were observed in practically all Spraberry cores. Continuity and interconnection of fractures were confirmed by pressure interference among wells during early development.' Major fractures trend northeast-southwest as indicated by oriented cores and confirmed by five fluid injection tests, by analysis of the pressure transients observed during development,''' and by three interference tests in the Driver Unit Water Flood reported herein. Fracture spac- ing probably averages inches to a few feet. Spraberry wells typically produced 100-400 BOPD initially after hydrauLic fracture treatments. By 1962 oil production had declined to an average of 12 bbl/well/day, near the economic Limits of operation. Reservoir pressure had declined from 2,300 psi initially in the Upper Spraberry and 2,500 psi in the Lower Spraberry to 500-1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low oil production rates at these relatively high reservoir pressures. Cumulative recovery of 208 million bbl of oil is 80 to 90 per cent of that recoverable by primary means. Performance of the entire reservoir is summarized in Fig. 1. IMBIBITION WATER FLOODING By 1952 reservoir performance indicated low primary recoveries. Most engineers, expecting serious channeling of injected fluids through the fractures, held little hope for secondary recovery. With its extensive background of research on the fundamentals of fluid flow within reservoir rocks, Atlantic's Research and Development Division on short notice in 1952 conceived that displacement of oil by capillary imbibition of water into the rock might significantly increase Spraberry recovery. Laboratory data reported by Brownscombe and Dyes scaled to probable reservoir conditions showed potential waterflood recovery equal to or greater than primary recovery with a 10-15 year flood life.= A pilot test using three 40-acre injection wells, one central producing well and 18 surrounding observation wells demonstrated technical feasibility of the process. Injection of 1.5 million bbl of water from November 1952 to August 1955 proved water entered the rock and displaced oil

By P. Pietrokowsky, T. E. Tietz, J. E. Dorn

The amount of solid solution hardening in aluminum alloys was found to be dictated by two factors: the lattice strain, and the change in the mean number of free electrons per atom of the solid solution. To obtain this correlation it was necessary to assume that aluminum contributes two electrons per atom to the metallic bond. WHEN the modern scientific method of analysis was first being formulated, Francis Bacon recorded in his "Essays" (circa 1600) that "an alloy . . . will make the purer but softer metal capable of longer life." During the intervening centuries voluminous data have been reported which demonstrate that the additions of alloying elements do in fact increase the hardness and strength of the pure metals. Nevertheless, the significant details of this problem on the unique effect of each element toward enhancing the mechanical properties of alloys only recently have been subjected to systematic scientific scrutiny. The major objective of this investigation is to determine how minor additions of alloying elements affect the plastic properties of polycrystalline aluminum alloys. By means of such studies it is hoped to provide not only data on the solution strengthening of aluminum alloys, but also a body of facts which will supplement the knowledge already available on the factors responsible for solution hardening in general. A review1"10 and analysis1' of the existing data on the effect of solute elements on the plastic properties of solid solutions reveal that our current knowledge on solid solution hardening is somewhat meager, inconsistent, and inconclusive. Many of the inconsistencies are undoubtedly attributable to the influence of unsuspected factors, such as purity; or uncontrolled factors, such as grain size, on the plastic properties of alloys. Nevertheless the following conclusions might be tentatively accepted: 1. Addition of solute elements invariably increases the yield strength, tensile strength, and hardness of the host element. 2. The rate of strain hardening, in general, increases with the concentration of the alloying element. 3. The strengthening effect in ternary alloys is the sum of the individual strengthening effects of the two solute elements as measured in their binary alloys. 4. The lattice strain is one factor that affects the strengthening of the alloy but it is not the only factor. 5. A second factor might be the difference in valence between the solute and solvent metals. All of the available evidence is in complete agreement with the first conclusion; the remaining conclusions, however, are not in agreement with all of the published data, but, in each case, the major weight of the existing evidence favors these deductions. Additional investigations will be required before most of these tentative conclusions can be accepted without reservation. In the following report an extensive investigation of the plastic properties of binary aluminum alloys is described. This work was undertaken in an attempt to shed more light on the general problem of solid solution hardening. Materials for Test: Aluminum was selected as the solvent metal for the present investigation on the effect of solute elements on the plastic properties of alloys. This choice was made for several reasons: (1) There appears to be little fundamental data in the published literature on the effect of solute elements on the properties of high-purity aluminum alloys. In view of the ever increasing economic importance of aluminum, such data would be of basic interest to the metallurgists concerned with the development of new aluminum alloys. (2) Aluminum is thought to be only partially ionized in the metallic state1' and consequently it might provide more complex relationships of the mechanical properties with the concentrations of the solute elements than more simple fully ionized solvents would reveal. (3) The data on aluminum alloys will provide a broader basis for correlations between the mechanical properties of metals in general and the concentration and atomic properties of the solute elements than is now available. Some complications, however, attend the selection of aluminum: The solubility of the various elements in the alpha aluminum phase are quite restricted, and not always well known. Consequently, only dilute solid solutions are available for study. This, however, may be somewhat advantageous because the dilute solution laws presumably are simpler than those applying to concentrated solutions. In addition, strain-hardened pure aluminum is known to recover at atmospheric temperatures. Very likely its alloys exhibit slower recovery rates. Thus, the secondary factor of effect of alloying elements on recovery might complicate the data. Such compli-

Jan 1, 1951

By Lee Hillard Meltzer, Ralph E. Davis

INTRODUCTION During the past few years emphasis has been placed upon methods of estimating the future expectancy of gas production from natural gas fields. Before technical methods were applied, the production expectancy over future years was based upon the knowledge of gas well behavior, learned through long experience and embedded in the "know-how" of men long in the gas producing business. It is doubtful that a technical study of future expectancy of a gas field or a group of fields was ever prepared for the preliminary planning of a natural gas pipe line system built prior to about five years ago. The decline in well production capacity was naturally recognized by all familiar with the business since its earliest beginnings more than 75 years ago. In 1953, the Bureau of Mines published Monograph Number 7, "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices," which gave to the industry the first technical analysis of the decline in production of individual gas wells. This method affords a means of estimating the future production in relation to decline in reservoir pressure. The demand for technical determination of expectancy of future gas productivity from fields or a group of fields led technical men to the application of the knowledge of well behavior to the problems. The decline in a well's ability to produce as pressures declined could be estimated by the use of the curve known as the "back-pressure potential curve" as developed by the Bureau of Mines. A field containing few, or even numerous, wells could be analyzed on the basis of the sum of potentials of all wells. In most studies of this nature, the problem is to estimate the rate of production that can be expected, not only from present wells but also, from wells that will in the future have to be drilled into the reservoir being studied. The "back-pressure potential" method requires that the following data be known or estimated: (1) Proved gas reserves. (2) Current shut-in pressures and rate at which shut-in pressures change with production. (3) Back pressure potential data on wells in the source of supply. (4) Ultimate number of wells which will supply gas, and their potential. (5) Limitations on productivity such as line pressures against which the wells will produce, friction drop in the producing string, and so forth. It is evident that the resulting estimate of gas available in each year for a future of say, 20 years, contains many uncertainties. While the method may have considerable merit for a field that is fully developed, it cannot be completely dependable in fields that are only partially developed. In such cases, some of the data upon which it is based can only be estimated or assumed. In the study of this problem during the past few years, a method has been developed which we believe has great merit, especially when applied to fields subject to substantial future drilling, and when applied to the study of fields which, on the average, appear to have characteristics similar, in general, to the average of the fields used in the development of the "yardstick" outlined herein. From an analysis of the production history of 49 reservoirs which are depleted, or nearly depleted, a curve has been constructed which shows the average performance of the reservoirs during the declining stages of production. When properly applied, this "average performance curve" can be used to determine the stage of depletion at which a reservoir or group of reservoirs will no longer be able to yield a given percentage of the original reserves. "AVAILABILITY" AND "AVAILABILITY STUDIES" The rate at which. a reservoir will yield its gas depends basically upon physical factors, such as the thickness and permeability of the sand, the effect of water drive, if any, and other conditions, and upon economic factors, such as the number of wells drilled. Within the ranges set by the physical conditions, a rate of delivery tends finally to become established. The rate (or range of rates) represents a balance between the interests of the operator, who desires the maximum return from his property and of the pipe line owner, who desires to maintain a firm supply for his market. This balance, which is influenced by the terms of the contract, determines the capacity which will be developed by the operator, and the time and rate at which the decline in production is permitted to occur. Thus the "availability" of gas

Jan 1, 1953

By A. J. Heckler, J. A. Peterson

A capsule technique was successfully employed to investigate the effect of nickel on the activity of nitrogen in Fe-Ni-N austenite in the temperature range 600" to 1200°C. This technique consisted of equilibrating nitrogen among various Fe-Ni alloys within a sealed silica capsule. Nitrogen transfer among the specimens occurred by N, gas at 900°, lOOO? and 1200?C. Nitrogen gas pressures within the capsules were estimated to be as high as 22 atm. The activity coefficient of nitrogen, fN , in Fe-Ni-N austenite is adequately described by the linear interaction equation: log . wt pct Ni where the standard state is chosen such that fN = I as wt pct Napproaches zero in binary Fe-N. This relationship was determined over the temperature range 873" to 1473°K and for nickel contents of 0 to 35 wt pct. ALTHOUGH chemical thermodynamics of liquid iron alloys have been extensively studied, experimental data for the solid state are needed. These thermody-namic data will provide a basis for understanding phase transformations, precipitation reactions, metal-gas equilibria, and so forth. The interaction of sub-stitutional alloying elements with the interstitial elements is of particular interest. In this investigation the thermodynamic behavior of Fe-Ni-N austenite has been studied. The solubility of nitrogen gas in iron austenite is known to obey Sieverts&apos; law up to about 65 atm.1-6 In addition, the solubility of nitrogen in Fe-Ni austenite has been investigated5"8 using the classical method of equilibrating Fe-Ni alloys with nitrogen gas at 1 atm. A capsule technique similar to that used to study the activity of carbon in alloyed austeniteg&apos;&apos;&apos; was employed in the present work to determine the effect of nickel on the activity of nitrogen in Fe-Ni austenite over the temperature range 600" to 1200°C. EXPERIMENTAL PROCEDURE A series of Fe-Ni alloys up to 35 wt pct Ni was vacuum melted and cast into 1 by 3 by 6 in. ingots. Chemical analyses at the top and bottom of each ingot demonstrated that the ingots were homogeneous with respect to nickel content. The nickel contents are given in Table I. Additional chemical analyses showed that wt pct Si < 0.05, s < 0.01, C < 0.01, Al < 0.006, 0 < 0.004, Mn < 0.002, and P < 0.002. A 2 in. section of each ingot was cold rolled to 0.015 in. The material was then decarburized to a carbon content of less than 0.004 wt pct. A portion of the material of each nickel content was nitrided to various levels in a H2-NH3 gas atmosphere to provide a source of nitrogen during subsequent equilibration. The experimental technique consisted of equilibrating the series of Fe-Ni-N alloys in a partially evacuated sealed silica capsule at the temperature of interest. Both Vycor and quartz capsules were used. In general, the final equilibrium nitrogen content for each Fe-Ni alloy was approached from both higher and lower nitrogen levels. The criterion for establishing that equilibrium was attained was that the final nitrogen content for each Fe-Ni alloy was the same irrespective of the initial level. A schematic drawing of the sample configuration in a capsule is shown in Fig. 1. The samples were arranged so that there was a minimum of physical contact. The samples were also dusted with a fine, high purity alumina powder to help prevent sticking. Several different types of furnaces were used in this study. In each case, a thermocouple was placed immediately adjacent to the capsule during equilibration and the temperature was controlled to within *4?C of that reported. At each equilibration temperature, the following times were found to be more than sufficient to attain equilibrium: 600°C-250 hr, 900°C-150 hr, 1000°C-150 hr, and 1200°C-50 hr. After equilibration the capsules were quenched in water and the nitrogen contents of the specimens determined by a Strohlein analyzer. Analyses of samples after equilibration at 1000" and 1200°C showed no silicon pickup from the silica capsules. RESULTS AND DISCUSSION Transfer Mechanism. The mechanism by which nitrogen was transferred among specimens in an initially hydrogen flushed and partially evacuated capsule equilibrated at 1000°C was investigated. After equilibration the gas in the capsule was collected over water and an estimate of the pressure at temperature

Jan 1, 1970

By E. J. Roberts

Prior to 1916, thickening was an art, and any accurate decision as to what size of machine to install to handle a given tonnage of a specific ore must have been one of those intuitive conclusions, based on both intimate and extensive acquaintance with thick-ners and ore pulps. Then in 1916 "knowledge of acquaintance," became "knowledge about" with the publication of the Coe and Clevenger paper.&apos; The unit operation of thickening had graduated to the status of an engineering science. The fundamental similitude relationships for the two major phases of the operation were defined so clearly that batch tests on models as small as liter cylinders could serve to specify protypes as large as 325 ft in diameter. It is quite apparent from reading the literature that Coe and Clevenger&apos;s contribution is not generally appreciated. In so far as the basic engineering relationships are concerned, the only real advance which has occurred in the 30 odd years which have elapsed since the Coe and Clevenger paper is the recognition of the effect of the rakes on the thickening process. Bull and Darby2 noted this in 1926, and the extensive use of the "gluten type" thickener, in which the effect is magni-fied, bears witness to its importance. Comings3 further verified this effect of the rakes. As a matter of fact, a number of papers show an apparent regression from the Coe paper in that the area determinations are made on the basis of a single test from One concentration of solids. Coe and Clevenger amply demonstrated that this is unsafe, since the controlling zone may be one other than that of the feed dilution. Comings3 neatly demonstrated this without apparently realizing it. Of course there have been significant advances in the application of the operation to industry. Open tray thickeners were introduced to save area; balanced tray thickeners, washing thickeners, and multifeed clarifiers were developed with all of their special hydraulic and mechanical problems. Combinations of all kinds have been introduced, such as combination agitators and thickeners, combination flocculators and clarifiers, combination thickeners and filters. With the establishment of the operation on a firm engineering foundation, installation was facilitated and expansion proceeded. There are still problems, of course, functional as well as mechanical. Sometimes the moisture in the underflow obtained in practice is not as low as is expected on the basis of the test data. Sometimes the underflow is so "thick " that its discharge and subsequent handling requires special attention. Island formation plagues some operators. The use of the thickener as a surge basin and blending tank in the cement industry poses unusual problems. Design of rakes and the drive mechanism must be continually im-proved. Corrosion problems must he overcome. Power requirements for raking the settled solids occasionally is the controlling factor as it was in the case of the all American Canal desilting installation. Other similitude relationships and design problems come into the picture when we enter the field of clarification or nonline settlement. We have an energy dissipation problem in introducing the feed and any models must satisfy the Froude model relationships. Autoflocculation requires detention which involves the same similitude laws that we encounter in the compression zone. Approach to an Exact Science The next step beyond having control of the similitude relationships is to understand the why of these relationships right back up the line to first principles. The ultimate might be that, if given the mineralogical composition of the solids and their size distribution together with an analysis of the suspending liquid, we could calculate the entire thickening behavior of the system. Then we could say we had reduced the operation to an exact science. True it might be more trouble getting this basic analytical data than to make our empirical determinations for area and volume, and we would need an ENIAC to calculate the results, but that does not detract from the desirability of such understanding. Considerable work has been done by the chemical engineers with this end in view. Comings,3 Egolf,4 Work,5 Kam-mermeyer,6 Steinour,7 and others have studied the problem. The writer has no final answer to the thickening story but would like to propose a picture of the mechanics of the two phases of thickening which has been found useful in understanding the subject and which leads to some convenient relationship in treating the compression step and arriving at the compression depth.

Jan 1, 1950

By Vittal S. Bhandary, B. D. Cullity

Swaged iron wire has a cylindrical {001} <110> texture. The texture is also cylindrical after re-crystallization in the absence of a magnetic field, but <111> and <112> components are added to this texture when recrystallization occurs in a field. The mecizanical properties in tension and in torsion are not greatly altered by these changes in texture. AS shown in a previous paper,1 cold-worked wires of the two fcc metals copper and aluminum can be made relatively strong in torsion and weak in tension, or vice versa, by proper control of preferred orientation (texture). The deformation texture can be controlled by selection of the starting texture (texture before deformation), because certain initial orientations are stable during deformation. The present paper reports on similar work performed on bcc iron. In this case it was clear at the outset that there was no hope of controlling the deformation texture, which is one in which <110> directions are aligned parallel to the wire axis. (1t has usually been regarded as a fiber texture, but Leber2 has recently shown that it is a cylindrical texture of the type {001} <110>. In either case, <110> directions are parallel to the wire axis.) There is general agreement on this texture among a large number of investigators, which in itself suggests that the starting texture has no influence on the deformation texture. More direct evidence was produced by Barrett and Levenson,3 who reported that iron single crystals of widely varying initial orientations all had a single <110> texture when cold-worked into wire. Thus <110> is a truly stable end orientation for iron and probably for other bcc metals as well. Under these circumstances attention was directed to the possibility of controlling the recrystallization texture. This texture is normally <110> in iron,4 just like the deformation texture. However, it is conceivable that this texture could be modified by a proper choice of the time, the temperature, and what might loosely be called the "environment" of the recrystallization heat treatment. In the present work the environmental factor studied was a magnetic field. The effect of heating in a magnetic field ("magnetic annealing") on recrystallization texture has been investigated by Smoluchowski and Turner.5 They found that a magnetic field produced certain changes in the recrystallization texture of a cold-rolled Fe-Co alloy. The texture of this material is normally a mixture of three components, and the effect of the field was to increase the amount of one component at the expense of the other two. Smoluchowski and Turner concluded that the effect was due to magnetostriction. With the applied field parallel to the rolling direction, the observed effect was an increase in the amount of the texture component which had <110> parallel to the rolling direction. In the Fe-Co alloy they studied, the magnetostriction is low in the <110> direction and high in the <100> direction. Thus nuclei oriented with <110> parallel to the rolling direction will have less strain energy than those with <100> orientations and will therefore be more likely to grow. In a later paper on the same subject, Sawyer and Smoluchowski6 ascribed the effect to magneto-crystalline anisotropy and made no mention of magnetostriction. In the papers of Smoluchowski et al. the intensity of the magnetic field was not reported but it was presumably large, inasmuch as it was produced by an electromagnet. In the second paper6 it is specifically mentioned that the specimens were magnetically saturated. But if magnetostriction has a selective action on the genesis of stable nuclei during recrystallization, that selectivity must depend only on differences in magneto-strictive strains between different crystal orientations and not on the absolute values of those strains. Thus the saturated state does not necessarily produce the greatest selectivity, because the relative difference in magnetostrictive strains between different crystal directions may be larger for partially magnetized crystals than for fully saturated ones.7 In the present work the specimens were subjected to relatively weak fields (0 to 100 oe) produced by solenoids. MATERIALS AND METHODS Armco ingot iron rod (containing 0.02 pct C and 0.19 pct other impurities) was swaged from 0.25 in. in diam. to 0.05 in., a reduction in area of 96 pct. The mechanical properties in tension and torsion were measured as described previously.&apos; Textures were measured quantitatively with chromium or iron radiation and an X-ray diffractometer,8,1 and

Jan 1, 1962

By F. R. Jones

AT Tahawus, N. Y., National Lead Co. operates the MacIntyre development. Here the world&apos;s largest titanium mine produces 5200 long tons of ore per day and pours 8000 long tons of waste rock over its dumps. Concentrated ilmenite is sent by rail to National Lead Co. pigment plants, and a second product, magnetite, is sold to steel producers in raw form or is agglomerated and shipped as sinter. Several earlier attempts had been made to produce iron from the deposits, which have been known since 1826. These attempts failed, chiefly because of titanium impurity. In 1941 the present owners reestablished the operation for production of war-scarce ilmenite, and the impurity became the main product. The Ore: The MacIntyre ore zone is about 2400 ft long and 800 ft wide in horizontal measurements. Ore outcrops were found on the northwest side of Sanford Hill, 450 ft above Sanford Lake and 2500 ft southeast. The zone dips at about 45" toward the lake and plunges to the southwest. The ore minerals, ilmenite and magnetite, are unevenly distributed in bands roughly parallel to the long axis of the ore zone and are interspersed with bands and horses of waste. Hanging wall ores are fine grained and grade from rich ore to waste rock or gabbro. Footwall ores are coarse grained and are almost entirely ilmenite and magnetite. The foot-wall waste rock, anorthosite, is the common country rock. Several faults cut the ore zone. These faults have no great displacement but do contribute to the great physical variations in ore rock and surrounding waste. The Mine: The MacIntyre mine is an open pit operation, with benches at 35-ft intervals. The lowest bench is now 54 ft below lake level. Loading equipment consists of three electric-powered shovels (a P & H model 1400 with 4-yd dipper and two Bucyrus-Erie models 85-B with 2%-yd dippers) and one diesel-powered shovel (a Northwest model 80D with 2%-yd dipper). Ore and waste are transported to a 48x60-in. jaw crusher in ten 22-ton Euclid trucks with 300-hp diesel engines. Ordinarily the two Bucyrus-Erie 2 % -yd shovels load ore into a fleet of three or four trucks. This combination works two 8-hr shifts per day, moving 5200 long tons of ore to the crusher and removing a small portion of the waste rock. The P & H model 1400 shovel, with a fleet of four trucks, loads waste on three shifts per day. The mine operates on a 5-day week, with a small maintenance crew working Saturday. Oversize rock is broken by a dropball handled by an Osgood model 825 rubber-mounted crane.&apos; Ore and waste are broken by drilling and blasting 9-in. diam vertical holes behind the benches. Bucyrus-Erie 42-T churn drills are used to drill the holes, which are extended 4 ft below the bench level on which the broken rock will fall. Drilling and Blasting History: In its early years the mine was equipped with Bucyrus-Erie 29-T churn drills, which drilled 6-in. holes. To keep up with production requirements the hole diameter was soon increased to 9 in., and by 1950 the three 42-T drills now in use had been acquired. Early blasting experiments with different kinds and grades of explosive led to adoption of 90 pct straight gelatin dynamite as standard. It was recognized that this explosive was expensive, and from the start of operations until 1950 extensive experiments were made using blasting agents of the ammonium nitrate family. Results were recorded as uniformly poor, with great build-up of oversize rock. The expense of these experiments, and the discouraging results, caused the abandonment of any expectation of breaking MacIntyre rock with anything but 90 pct straight gelatin dynamite. Further standardization led to 9-in. well drillhole spacings set at 16 ft in ore and 18 ft in waste, exceptions being permitted only for unusual conditions. The hole burdens were theoretically about 22 ft. Due to the extreme back-slope of bench faces, caused by blasting with heavy charges of dynamite, actual burdens were commonly well over 30 ft. Lack of precise control resulted in many holes having a burden as light as 15 ft. General practice was to stem 6 or 7 ft of hole with magnetite concentrate, the amount of stemming being left to the discretion of the pit foreman. Usually all holes in a row were fired instantaneously with Primacord detonating fuse. Millisecond delays were

Jan 1, 1957