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By J. C. Melrose, W. B. Lilienthal

The application of Bingham's law to the behavior of drilling fluids in a rotational viscometer permits the expression of viscometric data in terms of plastic viscosity and yield value, the flow properties of a plastic fluid. A commercially available rotational viscometer is described, and when modified to a multispeed type viscometer, is shown to provide a simple and convenient instrument for the measurement of these properties both in the laboratory and in the field. The data obtained are shown to be useful in defining and understanding mud control problems relating to chemical treatment and to the hydro-dynamic behavior of muds. INTRODUCTION The highly complex drilling fluids which are required for deep drilling often give rise to new and unusual mud control problems. Rapid and economic solutions to these problems may require, on the one hand, better understanding of the changes which contaminants and chemical treating agents produce in the colloidal and inert solids of the mud, or, on the other hand, closer control of the hydrodynamic behavior of the mud. The latter objective obviously can be achieved only if a correct rheological analysis of the flow behavior of drilling muds is available and if this is accompanied by the appropriate rheological measurements. The purpose of this paper is to describe such measurements in the field, and to show how the resulting data can be of value in solving difficult mud control problems. It is now generally recognized that Bingham's law of plastic flow can be utilized in describing the hydrodynamic behavior of drilling fluids in the non-turbulent flow range. Beck, Nuss, and Dunn' have recently applied this law to the flow of mud in small pipes, and Rogers2 has reviewed the rather extensive literature on this subject. So far, however, the use of Bingham's law has been restricted to the analysis of mud flow in pipes or capillary tubes, and it has not been directly applied to the flow in rotational viscometers. In the work to be reprted, the Reiner-Riwlin3 equation for the flow of a plastic fluid in a rotational viscometer has been utilized to permit the expression of multispeed viscometric data in terms of plastic viscosity and yield value. the two absolute flow properties of a plastic fluid. With regard to the application of these measurements, the calculation of the relationship between pumping rate and pressure drop, both in the drill pipe and annular space, has long been a subject of interest. Beck, Nuss, and Dunn,' following Caldwell and Babbitt: base their calculations for non-turbulent flow on Buckingham's integration of Bingham's law for pipe flow and measurements of the plastic viscosity (rigidity in their terminology) and yield value. In the case of turbulent flow, Fanning's equation is employed, and the pressure drop is relatively insensitive to the flow properties of the mud. Since flow in the drill pipe is likely to be turbulent at usual circulation rates, the plastic flow properties will chiefly influence the pressure drop in the annular space. As pointed out by Beck,' the control of this component of the total pressure drop may be of special importance where lost circulation problems are encountered. Other hydrodynamic problems to which it should be possible to apply measurements of the plastic flow properties include predictions of the velocity distribution in non-turbulent flow and the critical velocity for transition to turbulence. Plastic viscosity and yield value. as abmlute flow propertie.;, will reflect the colloidal or surface-active behavior of the solids present in drilling fluids. Measurements of these properties should therefore find application in developing a better understanding of such behavior and in characterizing the type and condition of these solids. Garrison and ten Brink have utilized multispeed viscometric data in this manner. although their measurements were not expressed in terms of the absolute flow properties. In connection with the application of these measurements, it should be recognized that the presently used one-point viscosity measurements are relative in nature. The API Stormer 600-rpm measurement, for example. is a function of both plastic viscosity and yield value, as well as mud weight, and will often be misleading when its application to mud control problems is attempted. NOMENCLATURE, UNITS, AND DEFINITIONS In Fig. 1 an idealized plot is given of the flow variables involved in any viscometric measurement. It is seen that the flow behavior of plastic fluids is characterized by two constants — plastic viscosity, µp, and yield value, F. Other workers hate used the term rigidity for plastic viscosity or the term mobility for its reciprocal. The term plastic viscosity, however, emphasizes the close relation this property bears to the viscosity of a true fluid and is expressed in the familiar viscosity units of centipoises. The yield value is expressed in lbs/100 sq ft, the units adopted for gel strength measurements with the APT shearometer. Definitions of these properties based on rheological or macrc)scopic flow considerations follow from Fig. 1. The plastic viscosity of a substance obeying Bingham's equation is defined

Jan 1, 1951

By H. A. Jr. Koch, C. A. Hutchinson

Miscible phase displacement of oil from reservoirs has been emphasized in the past few years. The reason for this emphasis lies in the high oil recovery attainable by this process. Removal of capillary effects in the reservoir leads to recoveries approaching 100 per cent in the area contacted by the miscible phase. The miscible slug process is one means of obtaining a miscible displacement. Here a band or slug of I,PG is injected into the reservoir prior to gas injection. The idea is to maintain the band of LPG "wedged" between the gas and oil phases and thus achieve a miscible phase displacement. A second method lor achieving miscibility is through the injection of a gas which is not miscible with the reservoir fluid but which develops a zone of miscibility in [he reservoir through mass trans-ier with the reservoir oil.' This mass transfer results in either an enrichment of the lean injected gas by intermediates from the oil or an enrichment of the oil by intermediates from a rich injection gas or one that has been enriched on the surface by LPG addition. We are interested here in discussing the process in which miscibility is developed at the displacement front by the evaporation of interrnediatcs from the oil phase into the gas phase. This process "builds up" its own slug of miscible material at the displacement front and therefore does not require the injection of LPG to obtain miscibil-ily. Each process has its own area of applicability. Generally, the high pressure gas process is applicable only with reservoir fluids which con-!ain a high concentration of inter- mediates. If the high pressure gas process is technically feasible at pressures less than 4,500 psi, it is probably more desirable economically than the slug process. The slug process has broad applicability in the shallower reservoirs and with reservoir fluids which contain a relatively low concentration of LPG and natural gasoline constituents. This paper deals with some new concepts of the high pressure gas injection process where it is proposed that flue gas can be substituted for hydrocarbon gas without sacrificing our goal of miscibility. MECHANISM Introduction Considerable effort has been devoted to study of the mechanics ot the high pressure gas injection proc-one generalization result-ing from some of these studies was that the composition of the injected gas is relatively unimportant in establishing the miscibility pressure* for a given reservoir fluid. This generalization is correct for the composition range of gases typically encountered in the field. Two such gases are a gasoline plant tail gas containing 85 per cent methane and 15 per cent ethane, and a field separator gas containing 70 per cent methane and 30 per cent heavier components. The most important factor which sets the miscibility pressure in the operation is the reservoir fluid composition, particularly the concentration of LPG-natural gasoline constituents. The injected gas is the agent by which the LPG-natural gasoline constituents are concentrated at the displacing front to create a miscible displacement. Based on these results, it appeared feasible that some inexpensive gas, such as flue gas, might be substituted for hydrocarbon gas for use in the high pressure gas process. A re-examination of the phase relations of the high pressure gas injection process should clarify the principle behind using flue gas (essentially nitrogen) as an injection gas. Three Component Diagram The phase relations of the high pressure gas injection process have been illustrated by the use of the three component diagrams.'," In Fig. 1 we have arbitrarily represented the multi-component reservoir system by three components; methane, ethane through hexane, and heptanes plus. The solid curve ABC is the phase boundary curve. It represents the locus of compositions which have fixed saturation pressure at a fixed temperature; the lower branch AB shows bubble point compositions, the upper branch BC, the dew point compositions. Point B is the coniposition of the critical mixture at this temperature and pressure. The dashed lines (tie lines) connect vapor and liquid compositions which are in equilibrium. Let us consider Reservoir Fluid D which we wish to displace in 21 miscible manner by gas injection. Let us further restrict the discussion to the case where miscibility between an injection gas and the reservoir fluid at the displacement front is developed by gas enrichment in the reservoir. For this case, any gas whose composition lies between Points C and E on the right side of the three component diagram can be used to give a miscible displacement of Reservoir Fluid D. This is true because the more mobile injected gas moves faster than the displaced oil and is in continuous contact with virgin oil at the displacement front. This leads to a continuing enrichment 01' the gas at the displacement front by evaporation of the C, - C,

By Jerry L. Straalsund, D. Bruce Masson

A dew-point technique was used to determine the thermodynamic activity of zinc at 430°C in a series of e phase Ag-Zn alloys. The composition of the alloys ranged from 72 to 88 at. pct Zn. This range included the composition at which Massalski and King3 found a reversal in the composition variation of the crystallo-graphic c/a ratio, which they attributed to an overlap of the Fermi surface across the (002) faces of the Brillouin zone. The data is presented in a graph in which RT In yz,, where yz, is the activity coefficient of zinc, is shown as a function of atomic percent zinc. This curve has an unmistakable change in slope at the same composition that Massalski and King observed the beginning of the reversal in the c/a ratio. This change in slope of the thermodynamic data is also attributed to a Brillouin zone overlap. Equations are presented to demonstrate that the thermodynamic activity can be related to the density of states of the conduction electrons, and that the observed phenomena are consistent with this model. It is also demonstrated that the contribution of the density of states can be related to the excess stability, a phenomenological parameter recently shown by Darkeen" to be significant in the interpretation of thermodynamic data of metallic phases. The data seem to indicate that zone overlap has caused a spinodal point, and the resulting misci-bility gap, in the phase diagram. THE problem of developing an adequate thermodynamic model of solid solutions has proven to be difficult, and is still only partially solved. The main approach has been to develop a statistical model, such as that of an ideal solution, regular solution, and so forth, to which can be attached corrections for electronic, vibrational, magnetic, ordering, or other contributions. Such corrective terms are usually derived on an ad hoc basis, and it is difficult to predict in advance what their relative importance will be. This problem has been discussed in general terms by Oriani and Alcock,' who have reviewed several thermodynamic models and a few empirical correlations. The measurements described in the present paper were made to demonstrate in a special case the importance of one such corrective term, the contribu- tion of the energy of the conduction electrons of an alloy. It was our premise that the contribution of the energy of the conduction electrons to the thermodynamic activity of the alloy components could be detected; further, that such an effect would be observed at alloy compositions where other phenomena, also ascribed to the energy and density of states of the conduction electrons, are observed. The idea of the importance of the conduction electrons is hardly new. Hume-Rothery and his adherents have developed the well-known theory of alloy phases in which the sequence of phase fields in binary equilibrium diagrams, especially those involving the noble metals with the IIB, IIIB, and IVB subgroups, can be correlated by replacing the composition variable with the ratio of conduction electrons to atoms, e/a. Jones and others have developed a physical explanation for this correlation, in which they consider the solubility limits of phase fields to be restricted by an intersection between the Fermi surface and a Brillouin zone. The general features of the model are also quite well-known—presumably zone intersection causes the density of states to decrease at critical alloy compositions. The attendant increase in energy of conduction electrons in the original crystal structure allows an alternate structure to become more stable as the concentration of polyvalent solute is increased. In spite of the wide acceptance of these ideas on phase stability, there is only indirect* evidence, such as the variations in lattice parameter recorded extensively by Massalskizy3 and others, that Brillouin zone interactions occur. There are few experimental measurements, other than the correlations of the phase sequence, that substantiate the premise that the energy of conduction electrons affects the solubility limits of alloy phases. Much thermodynamic data of alloys has been found to be consistent with the theory; yet there is a lack of detailed data at compositions where zone intersection and overlap are thought to occur. One would expect that the energy of the conduction electrons would make a measurable contribution to the thermodynamic properties of alloys at compositions near zone intersection and overlap if the theory of Hume-Rothery and Jones is correct. This conclusion cannot be avoided, because the phase boundaries are determined by the requirement that the chemical potential of the components be equal in both phases at equilibrium. An electronic effect large enough to alter the stability of a phase should also affect the thermodynamic activity by a measurable amount.

Jan 1, 1969

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,' Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.' In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,' employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,' i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,'' was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

By V.F. Marsters

Seepages of oil in Ecuador have been known for many years. The locality first to receive attention, and still worked in a modest way, lies on the north shore of the Santa Elena peninsula, between La Puntilla and Salinas. Operations mere first conducted largely by local cdpital. Later, foreign companies acquired large blocks of land, where they have done considerable drilling. For details concerning present drilling activities in Ecuador, we are indebted to Leon Price, an Ame~ican resident engineer of Ecuador. The information solicited came to the author through the office of the American Consulatell with permission to use it. The coastal plain bordering the Province of Tumbes, Peru, continues to the northeast, but narrow on passing the Zarumilla River. From this point northward it widens toward Santa Rosa. In fact, the pampas, as shown on the official Wolf map, correspond fairly well to the areal extent of tbe coastal plain as far as Guayaquil. This is shown in a general way on the accompanying map. The author understands that the Guayaquil enlbayment is bordered on all sides by the coastal plain, as recognized at Tumbes and farther southwest, and that it can be followed without a break as far north as Palmar. This view is supported by the mapped area regarded by Mr. Price as favorable or possible oil territory. Moreover the islands in the Gulf of Guayaquil are the same geologically as the coastal edge, being composed of Tertiary sediments. The author understands also that Tertiary formations occur north of Palmar. According to a report by Mr. Cardon, of Guayaquil, Tertiary sediments are exposed in the region of San Francisco and extend to and beyond Pta. Calera. There is also reason to believe that at least the lower part of the valley of the Santiago River is occupied by Tertiary sediments, ~~hich probably border the const line and extend into the River Mini l)nsin, and into Colombia. On the south coast there are many seepages, most of them near the inner edge of the coastal plain, between Zarumilla and Santa Rosa and also between Santa Rosa and Machala. I11 the latter region are

Jan 1, 1923

By V. F. Marsters

Seepages of oil in Ecuador have been known for many years. The locality first to receive attention, and still worked in a modest way, lies on the north shore of the Santa Elena peninsula, between La Puntilla and Salinas. Operations mere first conducted largely by local cdpital. Later, foreign companies acquired large blocks of land, where they have done considerable drilling. For details concerning present drilling activities in Ecuador, we are indebted to Leon Price, an Ame~ican resident engineer of Ecuador. The information solicited came to the author through the office of the American Consulatell with permission to use it. The coastal plain bordering the Province of Tumbes, Peru, continues to the northeast, but narrow on passing the Zarumilla River. From this point northward it widens toward Santa Rosa. In fact, the pampas, as shown on the official Wolf map, correspond fairly well to the areal extent of tbe coastal plain as far as Guayaquil. This is shown in a general way on the accompanying map. The author understands that the Guayaquil enlbayment is bordered on all sides by the coastal plain, as recognized at Tumbes and farther southwest, and that it can be followed without a break as far north as Palmar. This view is supported by the mapped area regarded by Mr. Price as favorable or possible oil territory. Moreover the islands in the Gulf of Guayaquil are the same geologically as the coastal edge, being composed of Tertiary sediments. The author understands also that Tertiary formations occur north of Palmar. According to a report by Mr. Cardon, of Guayaquil, Tertiary sediments are exposed in the region of San Francisco and extend to and beyond Pta. Calera. There is also reason to believe that at least the lower part of the valley of the Santiago River is occupied by Tertiary sediments, ~~hich probably border the const line and extend into the River Mini l)nsin, and into Colombia. On the south coast there are many seepages, most of them near the inner edge of the coastal plain, between Zarumilla and Santa Rosa and also between Santa Rosa and Machala. I11 the latter region are

Jan 1, 1923

Papers presented at two joint meetings of the Mineral Industry Education Division, Geophysics Committee, the American Geophysical Union and the Committee on College Curricula of the American Association of Petroleum Geologists, at the A I M E meeting in New York on Feb 17 and 18, 1941 At the first meeting, the Musing Geology Committee, the Society of Economic Geologists and the Committee on Applications of Geology of the American Association of Petroleum Geologists also took part [ ]

Jan 1, 1941

Papers presented at two joint meetings of the Mineral Industry Education Division, Geophysics Committee, the American Geophysical Union and the Committee on College Curricula of the American Association of Petroleum Geologists, at the A I M E meeting in New York on Feb 17 and 18, 1941 At the first meeting, the Musing Geology Committee, the Society of Economic Geologists and the Committee on Applications of Geology of the American Association of Petroleum Geologists also took part [ ]

Jan 1, 1941

R. W. Raymond, New York City: From a study of Mr. Johnson's paper, I conclude that his apparatus is simple in construction and operation, and imitates in a revolving machine the movements of hand-shoveling. It does what a man would do in removing sand from the waste-water with a perforated shovel. I am sorry to say that I fear the present condition of the brown-ore mining industry in the East, as long as

Jan 1, 1899

The presentation of the John Fritz Medal to Professor Henry M. Hone will take place in the auditorium of the Engineering Societies? Building, 29 West 39t,h Street, New York, at 8:30 o'clock on the evening, of May 10. It is hoped that many members of the Institute will be able to attend this ceremony, and the committee desires to make special mention of the fact that ladies are cordially invited to be present.

Jan 5, 1917

E. G. SPILSBURY, New York, N. Y.-I would like to ask Mr. Wemple what is the total loss in redistillation; not merely the weight of the lead removed, but also the loss clue to rehandling of a large amount of blue powder, and that clue to the final remelting in the tank furnace? LELAND E. WEMPLE.-The loss of zinc by redistillation, on the first operation, is approximately 5 per cent. This loss does not cover the lead

Jan 4, 1918

E. H. Dix, JR., Chairman L. W. M. PEIRCE, Past-chairman R. F. MEHL, Vice-chairman ALBERT J. PHILLIPS, Vice-chairman E. M. WISE, Secretary International Nickel Co., Bayonne, N. J. W. M. CORSE, Treasurer LOUIS JORDAN, Executive Secretary 29 West 39th St., New York, N. Y. Executive Committee W. H. BASSETT, JR. R. H. LEACH' W. H. FINKELDEY W. E. REMMERS2 J. A. GANN H. J. ROAST G. O. HIERS C. S. SMITHS L ZICKRICK

Jan 1, 1936

By James Gayley

The occurrence of obstructions in furnace-hearths is nothing new to blast-furnace managers. The removal of them is becoming more and more simplified every day. The appliances that can be readily obtained at any works, are so simple in construction and effective in operation that they can overcome the most obstinate condition of affairs that can exist in a furnace-hearth. The old method of opening up tuyeres and notches with sledges and chipping-bass,. Was

Jan 1, 1886

By G. R. Leverant, M. Gell

The high- and low-cycle fatigue poperties of MAR-M200 directionally -solidified into columnar-grained and single crystal forms were determined at 1400" and 1700°F. These results were compared with the corresponding properties of conventionally -cast MAR-M200. The low-cycle fatigue lives of the columnar-grained and single crystal materials were similar at both temperatures and were one to two orders of magnitude greater than those of conventionally-cast material. The variations in the fatigue lives among the three forms of MAR-M200 were related to the more rapid rate of intergranular muck propagation compared to that of transgranular propagation. In conventionally-cast MAR-M200, cracks were initiated in grain boundaries and crack popagation occurred rapidly along an almost continuous grain boundary path. In the columnar-grained material, crack initiation occurred on short transverse segments of grain boundaries, but crack propagation was transgranular. The fatigue lives of columnar-grained and single crystal materials were approximately the same because most of the life in both materials was spent in trans-granular propagation. For the directionally -solidified materials, the number of cycles to failure, Nf, can be related to the total strain range, , by: heT = K where n and K are 0.16 and 0.044 at 1400'F and 0.29and 0.098 at 1700, respectively. In addition to intergranular crack initiation in the columnar-grained material, initiation also occurred at we-cracked MC carbides and micropores in both directionally-solidified materials. At 1400°F, fatigue life was reduced with increasing MC carbide size, but at 1700 there was no effect of carbide size. THE creep and stress-rupture properties of conventionally-cast nickel-base superalloys can be greatly improved by directional solidification into either single crystal or columnar-grained forms. The improvement in properties results from a reduction in intergranular cavitation and crack growth in the columnar-grained materials and the complete absence of this fracture mode in the single crystals. This paper describes the effect of grain boundaries on the elevated temperature fatigue properties of the nickel-base superalloy MAR-M200. The effect of cycling frequency on cracking arid fatigue life and the role of MC carbides and micropores on crack initiation are also emphasized. The fatigue properties of columnar-grained and single crystal MAR-M200 at room tem- perature,4,5 and the change in the mode of fatigue crack propagation with temperature6 have recently been described. I) EXPERIMENTAL PROCEDURE The material used in this study was the nickel-base superalloy MAR-M200, directionally-solidified into columnar-grained and single crystal forms. The columnar grains were approximately 0.5 mm in diam. The nominal composition of these materials in wt pct was 0.15C, 9Cr, 12.5W, loco, 5A1. 2Ti, lCb, 0.05Zr. 0.015B, bal Ni. They were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr. which resulted in 0.2 pct offset yield stresses of 150,000? 144,000, and 95,000 psi at room temperature? 1400°, and 1700°F, respectively. The corresponding elastic moduli parallel to the testing direction were 19.2. 15.0, and 12.5 x 106 psi, respectively. Specimen design, testing procedures and alloy mi-crostructure have been described previously and will only be summarized here. Following the 1600°F aging treatment. MAR-M200 contains an ordered, cuboidal, y' precipitate 0.3 1 on edge, which is coherent with the 1 matrix. The y' precipitate is quite stable; even after testing at 1700°F. the precipitate is only slightly enlarged and its corners somewhat rounded. The alloy also contains a small volume fraction of micropores, and MC carbides. some of which contain preexisting cracks5 formed during casting. These cracks are always parallel to the long dimension of the carbide. Measurement of MC carbide size has been described previously.5 Axial fatigue tests were conducted in air over a wide range of strain amplitudes in both the high - and low-cycle fatigue regions, with specimen lives varying from about 10' to 10' cycles. Low-cycle fatigue (LCF) tests were strain-controlled with strain varied between zero and a maximum tensile value at a frequency of about 2 cpm. High-cycle fatigue (HCF) tests were stress-controlled with the stress varied between 5000 psi and a maximum tensile value less than the yield stress at a frequency of either 10 cps or 0.033 cps (2 cpm). The temperature in the gage section was controlled to 52°F. Specimen axes were within 5 deg of the [001] growth axis of the single crystals and the common [001 ] growth axis of the columnar-grained material. Specimen gage sections were electro polished prior to testing. After the standard heat treatment, three specimens were coated with a typical aluminide coating applied as a slurry. An additional specimen was given the coating heat treatment without actually being coated. In all cases: specimens were reaged at 1600°F for 32 hr after receiving the coating heat treatment at 1975'F for 4 hr.

Jan 1, 1970

By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

By Richard B. Greenwalt

INTRODUCTION Direct reduction of iron ores has unquestionably become established as an important step in the worldwide steelmaking industry. The history of this development has been long and fraught with difficulty. In 1800, Champlain suggested the direct reduction concept using carbon and a shallow hearth vessel. Roughly 100 years later, Jones attempted a commercial process using carbon and producer gas in a rotary kiln. During the early years of this century, numerous attempts were made to start commercial direct reduction plants using such processes as Hoganas, Wiberg, Krupp-Renn, and others. Most of these were short lived, being abandoned due to a variety of technical and economical factors. Today, however, a new generation of direct reduction processes has emerged. We enter 1977 with at least 40 commercial plants in operation using 15 processes in 14 countries. These plants have combined total annual capacity of roughly 10 million tonnes of direct reduced product. Many articles have been written, and projections made, concerning the future growth potential for direct reduction. As is al- ways the case with projections, the numbers vary, but the outlook does not. Anyone who participated in the years of effort that have gone into this field of endeavor should be excited and justly rewarded by noting the shape of the curve in Figure 1.

Jan 1, 1977

By Jack Fox

It is some time since these columns have contained a report to the members on just what is doing in the Society of Mining Engineers. Accordingly, even though it is now a month and a half after the Annual Meeting in Denver, it seems that a report on what transpired at the SME Board Meeting there is in order. First off, I'd like to say that the Members of the Society of Mining Engineers can be justly proud of their representatives on the SME Board of Directors. Of 21 members and officers on the "Old" Board of Directors, 19 were present. President Brower Dellinger chaired the "Old" Board Meeting. Of the 21 members on the "New" Board of Directors, every single one was present. James Boyd, the outgoing AIME President, attended and expressed his appreciation of the support that the Society of Mining Engineers had given him during his year as President of AIME. Members Multiply Robert S. Shoemaker, Chairman of the SME Membership Committee, pointed out that based on figures available, the Society of Mining Engineers had a net gain of 523 members during 1969 while SPE had a 490 net gain and The Metallurgical Society a net loss of 159. This is probably the first time in the last 20 years that anyone has exceeded the SPE net gain in membership. While SME still has a way to go to surpass the Society of Petroleum Engineers in number of members, we did have, on December 1, 1969, 16,369 members. However, 419 were dropped at the end of that month leaving us with a net for the year of 15,950.

Jan 1, 1970

By Richard Moldenke

One of the gravest problems of the iron foundry today is the accumulation of sulfur in commercial scrap and its effect on the castings made therewith. The ordinary jobbing castings today show a sulfur content of 0.18 per cent;, and occasionally as high as 0.22 per cent. The product of the foundry during the war is undoubtedly to blame for this rapid increase and conditions will become worse as the millions of tons of gray-iron castings of the war period return to the foundry in the form of commercial scrap. In the ordinary cupola remelting of pig and scrap, at least 0.02 per cent. sulfur is taken up; often double that amount. The high cost and difficulty of obtaining pig iron during the war period compelled the use of considerable scrap in the mixtures; frequently charges containing 90 per cent. of bought scrap were melted. Naturally the sulfur content of the castings increased. Until the advent of the basic-hearth electric furnace, the only method of holding the sulfur within reasonable limits was to use high percentages of pig in the foundry mixtures. Pig iron seldom contains over 0.05 per cent. sulfur, if well made. With pig iron forming 60 per cent. of the charge and the gates, runners, rejections, and bought scrap the other 40 per cent., the sulfur content of the castings can easily be held down to 0.10 per cent. Pig iron, however, costs more than scrap even when melting loss differences are considered, hence as small a percentage as possible will be used. The recent advance in knowledge of rational melting and the consequent reduction in losses directly due to oxidation of the metal and cold iron, has permitted the acceptance of castings with a much higher sulfur content than formerly. The steel industry also is seeking to determine how high sulfur may go with safety. In the iron foundry, however, there is the danger of a low cupola bed or an unduly retarded air-furnace heat, with the consequent raising of the freezing point of the metal and segregation effects resulting from high sulfur with insufficient manganese. The iron foundryman must, therefore, have a means of correcting his

Jan 1, 1922

By Richard Moldenke

One of the gravest problems of the iron foundry today is the accumulation of sulfur in commercial scrap and its effect on the castings made therewith. The ordinary jobbing castings today show a sulfur content of 0.18 per cent;, and occasionally as high as 0.22 per cent. The product of the foundry during the war is undoubtedly to blame for this rapid increase and conditions will become worse as the millions of tons of gray-iron castings of the war period return to the foundry in the form of commercial scrap. In the ordinary cupola remelting of pig and scrap, at least 0.02 per cent. sulfur is taken up; often double that amount. The high cost and difficulty of obtaining pig iron during the war period compelled the use of considerable scrap in the mixtures; frequently charges containing 90 per cent. of bought scrap were melted. Naturally the sulfur content of the castings increased. Until the advent of the basic-hearth electric furnace, the only method of holding the sulfur within reasonable limits was to use high percentages of pig in the foundry mixtures. Pig iron seldom contains over 0.05 per cent. sulfur, if well made. With pig iron forming 60 per cent. of the charge and the gates, runners, rejections, and bought scrap the other 40 per cent., the sulfur content of the castings can easily be held down to 0.10 per cent. Pig iron, however, costs more than scrap even when melting loss differences are considered, hence as small a percentage as possible will be used. The recent advance in knowledge of rational melting and the consequent reduction in losses directly due to oxidation of the metal and cold iron, has permitted the acceptance of castings with a much higher sulfur content than formerly. The steel industry also is seeking to determine how high sulfur may go with safety. In the iron foundry, however, there is the danger of a low cupola bed or an unduly retarded air-furnace heat, with the consequent raising of the freezing point of the metal and segregation effects resulting from high sulfur with insufficient manganese. The iron foundryman must, therefore, have a means of correcting his

Jan 1, 1922

By J. B. Rather

The use of sulfuric acid in refining illuminating oils antedates the beginning of the petroleum industry in America by many years. It was used as early as 1792 by Tower in refining "coal oil" in the British Isles, and by 1860 there were 53 refineries in the United States manufacturing "coal oil," most of them using sulfuric acid as a refining agent. Following the completion of the Drake well in 1859, many of the "coal oil" refiners began to use petroleum for manufacturing illuminating oil, and their methods and equipment were adapted so far as possible to this new raw material. The value of sulfuric acid in refining L'coal oil" having been established, this reagent was immediately tried and found to be satisfactory in refining petroleum. Notwithstanding the tremendous advances in petroleum technology since that time, sulfuric acid remains today the most valuable and most widely used means for refining petroleum products. Early Methods of Disposal of Acid Sludge With the almost immediate expansion of the petrolrum industry came the problem of disposing of the acid sludge produced in the refining operations. While in 1859, the year of the discovery of the Drake well, a patent was granted for sludge separation and separated acid concrntration, most of the earlier refiners, and rnany of their successors, felt that separation and recovery of spent acid was uneconomical. Accordingly, many of then) disposed of the sludge in any way that seemed expedient nt the time. It was huricd in the refinery grounds, harged and tlurnped at sea, run into neighboring streams, or dumped into sewers. Some optimists carted it to open pits in the hope that it would eithcr sink into the ground or evaporate. Not so many years ago, the superintendent of nn eastern refinery, who was using the open-pit method of disposal, lost, a sludge cart, with horse attached, in such a pit. The horse was recovred almost immediately, but its availability for further use was reduced to zero by the loss of its hair.

Jan 1, 1928