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By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By R. W. Freeman, L. L. Tavlarides

The experimental methods used in obtaining kinetic data for solvent extraction systems can affect the validity of the results The method of contacting the two liquids should allow for accurate determination of the surface area, hydrodynamics, and diffusional processes The appropriateness of the Liquid Jet Recycle Reactor is discussed and the modelling of the mass transfer and chelation reaction is presented The LJRR is used to investigate the chelation of copper by LIX65N in toluene from aqueous copper sulfate sulfuric acid solutions The ranges of experimental variables are Copper, 1 8-13.8 g-dm-3, sulfuric acid 0-1.6 g-dm-3, LIX65N, 0 1-1.0 mol-dm-3 Data on the initial rate of copper chelation at the interface is generated Nonlinear regression analysis shows that the following expression adequately describes the data within experimental error.

Jan 1, 1981

By S. Terry, W. Callender, R. J. Cornelius

When a dry ball-mill grinding circuit was in- stalled at the pellet plant of Hamersley Iron Pty. Ltd., it was something of a pioneering venture, since this was one of the first instances where such a circuit had been applied to iron ore on a major scale. The Hamersley pellet plant is located in Dampier on the coast of Western Australia. The feed for it consists of -8mm fines produced as a screened product at the Mt. Tom Price mine 186 miles inland from Dampier. It was these fines that encouraged the choice of a dry grinding facility for the plant. At the outset, tests had shown that the fines could not be filtered satisfactorily with a wet grinding system. At the pelletizing plant, the fines are stockpiled, reclaimed, dry ground in ball mills, formed into pellets on balling discs, hardened on an indurating line, and stockpiled for shipment overseas. These operations are shown in Fig. 1.

Jan 7, 1969

By Arthur C. Spencer

(Glen Summit Meeting, June, 1911.) THREE great deposits of iron-ore, in Camaguey and Oriente Provinces, Cuba, are well known to me through careful field-examinations executed in the years 1901 and 1907. In 1901 I visited the Cubitas iron-ore district, which lies about 12 miles distant from the city of Camaguey in a northerly direction, and the Mayari district, which includes the Sierra Nipe, lying opposite Nipe bay on the north side of Oriente Province. In 1907 I again visited the Cubitas district, and also made a sojourn of several days in the Moa district, where the extensive deposits of iron-ore were observed and studied. The observations of 1901 were made under the auspices of the then Military Governor of Cuba; Gen. Leonard Wood, and my conclusions concerning the value of these deposits were incorporated in a report.1 The examination of certain denouncements of iron-ore in the Moa district in 1907 was made in behalf of iron-masters operating in the United States, to whom I reported the existence of large amounts of easily-workable limonitic iron-ore, properly designated " brown iron-ore " in the terminology now current among iron-ore producers in the United States. In 1908 I published a paper entitled Three Deposits of Iron Ore in Cuba, outlining the occurrence and origin of the surficial ores existing in the Cubitas, Mayari, and Moa districts.2 . 1 A Geological Reconnoissance of Cuba, by C. Willard Hayes, T. Wayland Vaughan and Arthur C. Spencer, printed as a part of the report of the Military Governor of Cuba for the year 1901, vol. i. 2 Bulletin No. 390, U. S. Geological Survey, pp. 318 to 329 (1908).

Mar 1, 1911

By T. F. Bower, M. C. Flemings, H. D. Brody

A series of experiments are reported which show thai reasonable assumptions for analysis of solute redistribution in solidification of castings and ingols illclr(de: negligible undercooling before nuclcation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the Liquid oer distances the order, of dentrite arm spacings, platelike dentrite t/o?$holog?.. Qzmli/ali,e and periment is obtained JOY Al-Cu alloys front measurements of amount of nonequilibrium second phase, minimum solute content at the centers dentrites arms (after solidification), and 3) change in minimum solute content in dentrite arms during solidification. In a previous paper' analyses were given describing solute redistribution in dendritic solidification. The analyses were undertaken primarily to permit prediction of "severity of microsegregation" in a casting or ingot after solidification and cooling to room temperature, but can also be used to predict "local fraction solid' as a function of temperature in the solidifying alloy. Numerical results were given for Al-Cu alloys. The aims of this paper are to examine the validity of some of the assumptions of that analysis, and to compare predictions of the theory with experiments. All experiments reported are on Al-Cu alloys, the bulk on Al-4.5 pct Cu alloy. EXPERIMENTS Experiments conducted were on small ingots, 41/2 in. in diam by about 10 in. high. solidified in a controlled thermal environment (i.e., in a resistance-heated, re-circulating air furnace, whose temperature could be controlled to 1°C). In one series of experiments, the ingots were solidified very slowly (solidification time was varied from 8 to 1000 hr) and at constant rate of heat extraction. In a second series of experiments the ingots were solidified ( 'unidirectionally". Fig. 1 is a sketch of the method of making the two different types of ingots. The unidirectionally solidified ingots were fully columnar, and the slowly solidified ingots had equiaxed structures, Fig. 2. In making the slowly solidified ingots, the mold employed was carbon steel, coated with inert refractory. Typically the mold and its environment were heated to 700°C. The molten alloy was then poured into the mold and the temperature of the system equilibrated above the liquidus. The environment of the mold was next cooled with a controller responding to a differential thermocouple that measured the difference between the temperature of the melt and the temperature of the mold environment. The differential thermocouple consisted of one chromel-alumel junction in the melt connected in opposition with a second junction in the furnace. The potential across the differential thermocouple was input to the controller which acted to keep this potential at a set. constant value; hence the temperature difference between the two junctions was maintained nearly constant. Major resistance to heat flow in the above apparatus was between the metal surface and the furnace atmosphere, not in the metal itself. By maintaining a constant temperature difference between the metal and the furnace atmosphere, the controller maintained an essentially constant rate of heat extraction during solidification, regardless of amount of heat released by the metal per unit temperature change. When the metal temperature dropped just below the eutectic temperature. the ingot was removed from the furnace and water-quenched. The unidirectionally solidified ingots were cast in a similar mold to the foregoing except that provision was made to extract heat through the bottom face of the mold by passing air or water through the mold base, Fig. 1. For these experiments, metal and mold temperature were again equilibrated above the liquidus. Temperature of the mold environment was then held

Jan 1, 1967

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

By P. B. Leavenworth

Twenty-six fields were found in the Texas Gulf Coast in 1940 as compared to 17 fields in 1939. Of these, 14 were oil fields and 12 were gas and distillate. About 150 wells were drilling at the end of the year. Production for the year 1940 amounted to 104,127,247 bbl. as compared to 100,-253,937 bbl. for 1939. Considerable wildcatting for Wilcox production featured the exploration, but discoveries were few and the type of fields found mainly gas and distillate. On the whole, the program was discouraging. New Fields Alta Lomu. Galveston County.—The Alta Loma field was discovered on May 20, 1940, by the Stanolind Oil and Gas Company's No. I John A. Hulen, which blew out at a depth of 9166 it. and ran wild for several days, with an estimated production of 400 bbl. per hour of 36" gravity oil from a sand in the top of the Frio. Water soon appeared but the well produced more than I3o,ooo bbl. of oil between May 20 and June 10, together with a large amount of salt water. Later the well was killed and recompleted on Nov. 23, for 276 bbl. of 34" gravity oil per day. Probably this was the most sensational discovery of the year, although development to the end of the year was disappointing. The discovery was the result of reflection seismograph work of the Stano-End Oil and Gas Co., the principal leaseholders. Bailey's Prairie, Brazoria County.— Glenn H. McCarthy9s No. I W. B. Munson was completed in a lower Frio sand from perforations 11,345 to II,349 ft. for 8 bbl. of fluid (50 per cent black oil, 27" gravity, and 50 per cent B. S. and W.) on Sept. 24, 1940. It was finally recompleted as a gas well from perforations 11,631 to 11,651 ft., on Oct. 9, 1940. The well had been drilled to a total depth of 11,860 ft. This well produced for only a short time and the area is at present inactive. Blessing, Matagorda County.—The Texas Company's No. I A. B. Pierce was completed from a Frio sand from 8265 to 8300 ft. on July 8, 1940, for an initial production of 29 bbl. of distillate, I 1/2 million cu. ft. of gas. One other gas and distillate well was completed in 1940. Borden, Wharlon County.—J. F. Hutch-ins' No. 2 A. P. Borden Estate was completed on Feb. 11, 1940, for 108 bbl. of 35,6° gravity oil, from a Frio sand at 4758 to 4771 ft. This is the second well drilled in the area by Hutchins. Two other wells in 1940 were failures and there was no activity at the end of the year. Dyersdale, Harris County.-The Dyers-dale field was opened by the completion, on Sept. 15, 1940, of H. C. Cockburn's No. I G. Burkitt from a sand in the top of the Frio, through perforations from 4067-4072 ft., for 240 bbl. of low-gravity oil. By the end of the year the field had been fairly well outlined and did not appear to be a major discovery. Duck Bay, Calhoun County.—Coronado Oil Company's No. I Welder, alter having drilled to 10,002 ft., perforated casing from 5654 1/2 to 5659 it. and was completed for 60 bbl. of 36.8° gravity oil On July 27, 1940, from a Miocene sand.

Jan 1, 1941

By P. B. Leavenworth

Twenty-six fields were found in the Texas Gulf Coast in 1940 as compared to 17 fields in 1939. Of these, 14 were oil fields and 12 were gas and distillate. About 150 wells were drilling at the end of the year. Production for the year 1940 amounted to 104,127,247 bbl. as compared to 100,-253,937 bbl. for 1939. Considerable wildcatting for Wilcox production featured the exploration, but discoveries were few and the type of fields found mainly gas and distillate. On the whole, the program was discouraging. New Fields Alta Lomu. Galveston County.—The Alta Loma field was discovered on May 20, 1940, by the Stanolind Oil and Gas Company's No. I John A. Hulen, which blew out at a depth of 9166 it. and ran wild for several days, with an estimated production of 400 bbl. per hour of 36" gravity oil from a sand in the top of the Frio. Water soon appeared but the well produced more than I3o,ooo bbl. of oil between May 20 and June 10, together with a large amount of salt water. Later the well was killed and recompleted on Nov. 23, for 276 bbl. of 34" gravity oil per day. Probably this was the most sensational discovery of the year, although development to the end of the year was disappointing. The discovery was the result of reflection seismograph work of the Stano-End Oil and Gas Co., the principal leaseholders. Bailey's Prairie, Brazoria County.— Glenn H. McCarthy9s No. I W. B. Munson was completed in a lower Frio sand from perforations 11,345 to II,349 ft. for 8 bbl. of fluid (50 per cent black oil, 27" gravity, and 50 per cent B. S. and W.) on Sept. 24, 1940. It was finally recompleted as a gas well from perforations 11,631 to 11,651 ft., on Oct. 9, 1940. The well had been drilled to a total depth of 11,860 ft. This well produced for only a short time and the area is at present inactive. Blessing, Matagorda County.—The Texas Company's No. I A. B. Pierce was completed from a Frio sand from 8265 to 8300 ft. on July 8, 1940, for an initial production of 29 bbl. of distillate, I 1/2 million cu. ft. of gas. One other gas and distillate well was completed in 1940. Borden, Wharlon County.—J. F. Hutch-ins' No. 2 A. P. Borden Estate was completed on Feb. 11, 1940, for 108 bbl. of 35,6° gravity oil, from a Frio sand at 4758 to 4771 ft. This is the second well drilled in the area by Hutchins. Two other wells in 1940 were failures and there was no activity at the end of the year. Dyersdale, Harris County.-The Dyers-dale field was opened by the completion, on Sept. 15, 1940, of H. C. Cockburn's No. I G. Burkitt from a sand in the top of the Frio, through perforations from 4067-4072 ft., for 240 bbl. of low-gravity oil. By the end of the year the field had been fairly well outlined and did not appear to be a major discovery. Duck Bay, Calhoun County.—Coronado Oil Company's No. I Welder, alter having drilled to 10,002 ft., perforated casing from 5654 1/2 to 5659 it. and was completed for 60 bbl. of 36.8° gravity oil On July 27, 1940, from a Miocene sand.

Jan 1, 1941

By D. C. Ganow, N. J. Grant, I. R. Silver, A. R. Chaudhuri

The structural changes that result when a metal is "cold worked" lead to higher values of yield and tensile strength on subsequent deformation at room temperature. Further it has been shown that the beneficial effects of cold work are, to some extent, maintained even at elevated temperatures. The strength improvements from prior cold work decrease as the temperature is raised and are a function of grain size, amount of cold work, and strain rate (or time of test). If recrystallization occurs during test, the cold-worked material may even show weaker stress-rupture properties than the annealed material. A question that arises is whether there is a significant effect on the subsequent creep behavior if the prior deformation is performed under creep conditions at high temperatures not too different than the test temperature, but at significantly different strain rates and for various amounts of strain. An answer to this question was sought in the work described in the present paper. PROCEDURE Two materials were used in this work, high-purity aluminum and a solid-solution A1 2 pct Mg alloy. The compositions are shown in Table I. The grain size in the two materials was 0.2 to 0.3 mm. The deformation for both the prestraining and for the creep tests was at constant stress. The procedure adopted was to prestrain a specimen to the desired elongation, remove the load, and cool to room temperature rapidly by spraying. the test bar with cold water. The specimen was then placed in a creep machine, held at the test temperature for less than 5 min, and loaded. Less than 15 min was required to bring the specimen to temperature. The creep stress was based on the diameter resulting from the prior strain, and values of elongation at fracture listed in the tables do not include the respective elongations resulting from the prestrain. The choice of the stresses for the prestrain and for the creep tests was made so that the tests could be completed in relatively short times to maximize any effect of prestrain. The specimens had a gage length of 1 in., the pure aluminum specimens having a diameter of 0.150 in. and the alloy specimens a diameter of 0.125 in. For pure aluminum, prestrain was at 400' and 600°F with testing at 500°F; for the alloy, prestraining was at 700°F and testing at 600°F. RESULTS The prestrain conditions for the aluminum and the alloy specimens are shown in Tables I1 and IV. In addition to showing the time required to achieve the desired prestrain, the expected rupture Lives are given which would have resulted had the creep prestrain been continued to fracture. The prestrained and the annealed specimens were then tested in creep to fracture; the temperature and stress for the pure aliminum specimens being 500o F and 1800 psi and for the alloy, 600' F and 3400 psi. The creep curves for the prestrained and the annealed specimens of pure aluminum showed all three stages of creep; hence in addition to the effect of prestraining on the rupture life, it was also possible to determine the effect of prestraining on the minimum creep rate, and on the time and elongation at the end of each of the three creep stages. The results are shown in Fig. 1 and Table 111.

Jan 1, 1960

By S. W. MEALS

TWENTY million people in this country and Canada in nearly four million homes can give thanks to our Creator for natural gas, that most wonderful natural fuel with which Dame Nature has so bountifully blessed us. It is a clean, healthy and cheerful fuel, made up almost entirely of carbon and hydrogen. There is no residue, no waste and there are no objectionable constituents; an ideal fuel for the home. It operates like magic, open the valve and it is there for your needs, winter or summer, night or day. You are not required to place your order 30 to 90 days in advance and you do not need to pay for your winter's supply in advance. No ashes to worry about, no flues or chimneys to clean, nor kindling wood to store or bother the housekeeper. We who have been so blessed do not realize what it would mean to be without it. If in place of opening a valve we had to go to the woodshed or coalhouse and then build our fire-carry out the ashes-well, some of us I am afraid would be late reaching our offices and perhaps would miss our hot cakes for breakfast. One cubic foot of gas produced from the White Sand formation contains 1130 B.t.u. and weighs 47/1000 lb.; there are about 24,000 B.t.u. in 1 lb. of gas. Temperatures of over 3400 deg. Fahr. have been obtained with natural gas. Not only is it a superior fuel for the home but it has no equal for use in many large manufacturing industries, especially with the making of glass, pottery and open-hearth steel. In an open-hearth furnace, properly constructed, 5000 cu. ft. will melt one ton of steel. It requires 1/3 ton of bituminous coal gasified in a producer to do the same work, or about 40 gal. of tar or fuel oil, or 11,000 cu. ft. of by-product gas.

Jan 1, 1926

By J. L. Fitch, B. G. Hurd

The presence of gypsum in samples subjected to standard core analysis introduces serious errors in the measurement of water saturation and porosity. The magnitude of these errors, depending upon the type of analysis procedure used, has been evaluated experimentally and theoretically. Water-saturated pore volumes determined by vacuum distillation or retort procedures may be too high by as much as 48 per cent of the volume of gypsum present. The maximum error in this value determined by Dean-Stark extraction with toluene is 36 per cent of the gypsum volume. If pore space is measured by a Boyle's law type porosimeter the maximum erorr due to gypsum is 38 per cent of the original gypsum volume present. The conscientious core analyst may eliminate the errors caused by gypsum by either of two methods. He may apply suitable corrections for the water of crystallization removed from gypsum, or take special precautions to prevent dehydration of gypsum during core cleaning and alzalysis procedures. These alternatives are discussed and methods for obtaining reliable core analysis data are proposed. Gypsum (CaSO4 . 2H2O) occurs as a common mineral in many of the world's sedimentary basins. In addition to its presence as primary bedded evaporitic deposits, it is often found as secondary replacement zones and pore-fillings in host rocks. That it may cause false indications in porosity, both on neutron logs and in standard core analysis, has been generally recognized. False porosity interpretations from neutron logs result because the chemically bound water in gypsum attenuates neutrons as effectively as free water. Errors in core analysis result when gypsum is dehydrated prior to or during the analysis. Vacuum retort procedures used by many laboratories to determine fluid saturation and porosity effect a complete removal of water of crystallization from gypsum. The crystal water, distilled and collected with free water from the sample, is counted as water-sat11rated pore space. Dehydration of gypsum results in a decrease in volume occupied by calcium sulfate and a corresponding increase in pore volume. Thus, if gypsum is dehydrated by sample cleaning and drying procedures, subsequent porosity measurements with gas expansion or compression instruments will be high. The qualitative effect of gypsum on porosity determinations by retort procedures was discussed in a recent article by Bynum and Koepl3. They concluded that since false porosity was interpreted as being water saturated, determinations of oil content were not affected. Others in the industry, however, have pointed out that porosity values are often used with values of water saturation determined independently, e.g., from electric resistivity logs in making reserve estimates. Values of water saturation calculated from the formation resistivity using the Archie equation, S4= are actually low if values of are high due to gypsum. In this case, false porosity values due to gypsum could cause serious errors in calculations of oil-in-place. This investigation was made to determine quantitatively the effect of gypsum on porosity values determined by different core analysis procedures. EXPERIMENTAL PROCEDURES Dehydration of Gypsum The extent and rate of removal of water of crystallization from gypsum under conditions encountered in core analysis procedures were studied. Taken for the experiments were three types of relatively pure, naturally occurring gypsum, viz. selenite, satin spar and massive gypsum. Although all samples probably contained trace chemical impurities, each type lost the theoretical amount of water upon complete dehydration. An automatic recording thermobalance, similar to one described by Mauer2, was used to obtain dehydration rate data for samples heated in dry air. Water

By R. H. Doremus, E. F. Koch

The first carbide phase that precipitates at 120°C from a iron containing about 0.02 wt pct, C was studied with the electron microscope. In both strained and unstrained material the carbide particles appeared to form on the dislocations in the iron, in agreement with the results of the kinetic study in part II. The structure of the carbide was tentatively identified as an expanded a-iron lattice (body-centered tetragonal) with about 0.7 wt pct C. This phase appeared to be metastable and apparently transformed into cementite or epsilon carbide when the iron was over-aged. WhEN a iron containing less than about 0.025 wt pct C is quenched from 700°C to room temperature the carbon is retained in solid solution and precipitates out slowly with time. The morphology and structure of the precipitating phase are still in doubt, two different carbide phases, epsilon carbide and cementite, have been identified, but there is considerable disagreement about the time and temperature at which they appear.1-4 Epsilon carbide seems to form at lower temperatures than cementite, although one group of investigators4 found only the latter phase over a wide range of aging temperatures. Usually these two phases have been identified after aging times much longer than needed to drain the carbon from supersaturated solution, at least for aging temperatures below 200oC. The precipitated carbides have been observed with the electron microscope,'-5 but again most results have come from samples aged much longer than necessary to reduce the carbon concentration in solution to a low value. In this study the carbide phases were observed in earlier stages of precipitation with the electron microscope, in order to learn more about the shape, size, and distribution of the carbide particles. Samples strained small amounts before aging, as well as unstrained samples, were studied, and the structure of the carbide phase was tentatively identified. EXPERIMENTAL "Ferrovac E" vacuum-melted iron, from which the wires for kinetic studies were also made (Refs. 6 and 7 and the following paper) was used for this work. An analysis of this material is given in Table I; it agrees well with the manufacturer's values. The number of inclusions in the iron was very small, as can be seen in the optical micrograph in the following paper. Pieces of iron about 1 mm thick and 5 to 10 mm in diam were used for all the studies except for those in which the sample was strained before aging; then the specimen was a rod 3 to 6 mm in diam and 20 cm long. The samples were held at about 700°C in wet hydrogen for at least an hour to remove residual carbon and nitrogen, after which they were heated to 950" (in the y region) and cooled to room temperature in the furnace. This treatment gave an average grain diam of more than 1 mm, so that the effect of grain boundaries on the precipitation process was negligible. The samples were carburized at 710°C for about 2 hr in hydrogen that had passed over toluene held at -30°C; then they were rapidly quenched into water. From chemical analysis this treatment gave a carbon concentration of from 0.012 to 0.016 wt pct, which is less than the solubility of carbon at this temperature. After quenching, the samples were aged at 120 "C in an oil bath for vari-

Jan 1, 1961

By J. M. Smith, D. Kunii

Effective thermal conductivities of sandstones filled with stagnant fluids were measured using a steady-state technique. Data were obtained for seven sandstone samples, taken from four different locations and ranging in permeability from 18 to 590 md. The measurements with gases (helium, nitrogen, air and carbon dioxide) covered a pressure range from 0.039 psia to 400 psig. Data were taken for four liquids — n-heptane, methyl alcohol, 79.8 weight per cent glycerol-water solution and pure water at atmospheric pressure. The experimental results were used to evaluate the theoretical equations for predicting stagnant conductivities developed earlier 4 The low-pressure measurements permitted evaluation of the consolidation parameter bpDp/ks (necessary to utilize the theory) for the various types of sandstones. Using these characteristic values, the tbeoretical equations correlated well with the experimental conductivity data for the several fluids and rock samples. INTRODUCTION An aspect of heat transfer in solid-fluid systems of considerable current interest is the effective thermal conductivity of porous media. The stimulus for study of the subject arises from the need for sound procedures for designing thermal methods of petroleum production. The general system occurs when there exists a flow of fluid through the pores of the solid material. However, a logical starting point in developing a theory for predicting the effective thermal conductivity in the general system is to attack the special case when the porous solid is filled with stagnant fluid. Since the flow rates anticipated in thermal production processes are very low, such stagnant conductivities k,O are also of practical significance. Kunii and Smith4 recently reviewed the existing data for stagnant conductivities and proposed a theory for heat transfer in porous rocks. This leads to equations for predicting the stagnant conductivity as a function of the properties of the fluid and solid phases. The existing experimental information1-3,5,7,8 covered a range of porosities and agreed well with the theory. However, the available data were insufficient to examine critically the effects of two important properties on koe, — the thermal conductivity of the fluid and the pressure. The objectives of the present study are twofold: (1) to measure the effect on koe of (a) the pressure for gases, and (L) the thermal conductivity of the fluid kg for bloth gases and liquids; and (2) to determine for rocks of different porosities and permeabilities the apparent solid conductivity ks and the consolidation parameter bpDp/ks required in applying the theoletical equations. Measurements extrapolated to zero pressure are helpful in evaluating ks and the consolidation parameter. However, the extrapolations must be based upon data obtained at low pressures because in small pores the molecular conductivity of the fluid may be unusually depressed. This occurs when the mean free path of the molecules is of the same order of magnitude as the pore diameter, that is, in small-diameter pores at low pressures. The phenomenon has been studied recently by Schotte6in beds of unconsolidated fine particles. With particles in the size range of 45 to 200 microns, a significant reduction of kg with pressure was found even at absolute pressures greater than 1 atm. In the sandstones employed in the present investigation, pore diameters lower than those experienced by Schotte are likely, so that the effect would presumably be greater. SCOPE OF MEASUREMENTS Stagnant conductivities were measured for four types of sandstones using a total of seven samples. The characteristics of the samples, including porosity and permeability values, are given in Table

By Harold B. Fell

MANY oil producers are in disagreement with the idea held by some that an increase in the price of crude oil would be unlikely to stimulate much production and that we will be obliged to draw upon foreign sources of petroleum to supplement our domestic production as the years go by. Supporting our con trary opinion are numerous facts and figures. The most recent official estimate of the maximum efficient rate of production from the oil wells of the United States is 5,271,000 bbl per day. The Economics Advisory Committee of the Interstate Oil Compact Commission estimates, assuming certain supplies from imports and from natural gasoline and benzol, that crude oil require-

Jan 1, 1947

By Lawrence H. Van Vlack

The energy of the y-iron grain boundary was determined to be 850 ergs per cm2 at 1105°C. The a/a and the a/y boundaries possess somewhat less energy. The microstructures of several iron alloys are discussed in terms of the interfacial energy relationships. THE dependence of the shape of liquid interfaces upon their energies has been studied for some time.1"3 Recently, Smith' concluded that many of the microstructures observed in metals may be attributed to the energies of the interfaces between the grains and phases. While the energies of liquid surfaces have been measured by numerous different methods: only two attempts have been made to determine experimentally the energy of surfaces involving crystalline solids. Udin, Shaler, and Wulff8 used a procedure introduced by Berggren7 to measure the surface tension of solid copper. It consisted of determining the load required on a thin copper wire so that the surface tension was counteracted, and no net strain resulted. Bailey and Watkins8 sed a different technique and were able to determine both the surface tension of copper and the tension of the copper grain boundary. They measured the contact angle which liquid lead makes against a copper surface. They then calculated the above energies from the surface energy of liquid lead by using the Pb vs. Cu/CuY dihedral angle and the surface groove angle formed during thermal etching. They obtained a value of 1800 dynes per cm for the surface tension of clean copper and approximately 640 dynes per cm for the tension of copper grain boundaries. The former value was somewhat higher than Udin's value of 1500 dynes per cm. This paper includes a determination of the energy of the y-iron grain boundary. In addition, the micro-structural relationships of several other metallic and nonmetallic phases with iron were examined and an attempt was made to interpret the observed structures in terms of interfacial energy relationships. Theoretical Considerations In a three-phase material containing a solid and two liquids, there may be two solid/liquid interfaces, one liquid/liquid interface and one inter- granular interface. Liquid/liquid interfacial energies can be measured directly. Therefore, by determining the energy of such an interface and by measuring the required interfacial angles: the energies of the interfaces involving solids may be obtained.10 They may be shown schematically as in Fig. 1. The above procedure requires the following assumptions: 1—The interfacial energies are, in general, unaffected by boundary orientation, and 2— the shapes of the interfaces are unaltered between annealing and sectioning for microscopic examination. The first assumption is good to a first approximation as shown by Dunn and Lionetti11 except for a few critically orientated boundaries. Two conditions may alter the shape of a boundary upon cooling: 1—Precipitation of dissolved material upon one side of the interface, and 2—a change in volume during the transition from one phase modification to another. The former must be detected by microscopic observation. The latter may become appreciable in systems containing an interface between two liquids which solidify after annealing. However, possible movement of the two-liquid interface may be checked in the system diagrammed in Fig. 1 by measuring 8, for example, and comparing it with its value as calculated from the other interfacial angles by: tan8, C11 05 COS- o- + cos 8, cos- The choice of a suitable pair of liquids is limited by several factors. The relative values of the several

Jan 1, 1952

By C. R. Johnson, R. A. Greenkorn, L. K. Shallenbarger

This paper describes a study, based on core data, of the directional permeability of a sandstone reservoir. Directional air permeabilities are explained and correlated with lithology by the tensor theory of permeability, which is extended to the more general case of heterogeneous anisotzopic porous media. In this case, the permeability tensor is made up of two components: (I) anisotropy (variation around a point) which correlates with bedding, and (21 heterogeneity (variation from point-to-point) which correlates with grain size. INTRODUCTION Previous studies of directional permeabilityl.5-8 have concerned themselves only with anisotropy at a point, rather than with both point-to-point differences and local anisotropies. In this paper, we present the existing tensor theory of permeability for anisotropic porous media and then extend it to the more general case of heterogeneous anisotropic porous media. The laboratory measurements of directional permeability are explained in view of this extended theory and the data are discussed in terms of the lithologic factors that correlate with it. The results show what the heterogeneity and anisotropy of the reservoir element are, and that the directional permeability correlates with lithology. Data used in this paper are measurements of air permeability in eight directions, spaced at 45° intervals, on 142 2-in. vertical plugs from 30 cores. The core data are meaningful in terms of directional permeability because the cores were oriented to within 45O during drilling and coring.3 Although we initially thought that only 60 per cent of the core material was reliable, subsequent study showed that almost all of it was reliably oriented. After determining the air permeabilities, the data were reduced to three independent variables for each plug: the major and minor permeability axes, and the direction of the major axis. These were obtained by converting the permeability data to the reciprocal square root of permeability and fitting the transformed data with ellipses according to the tensor theory of permeability.8 The point-to-point areal variation of the minimum permeability axis is related to grain size. The direction of the permeability axes, where the major axis exceeds the minor axis by at least 5 per cent (measured variation is about 4 per cent), correlates with the bedding. The permeability tensor used in this study must be considered as the sum of a scalar and a tensor, with the scalar being the minor axis permeability as a function of position, and the tensor the directional effect, which is additive permeability over the minor axis. In this case, the point-to-point variation or heterogeneity (minor axis) is substantially larger than the variation at a point or anisotropy. It may be important that this separation of "directional permeabilities" be recognized when considering migration of fluids due to permeability variation. Local migration may be due to anisotropy and point-to-point migration may be due to heterogeneity, but the direction and magnitude of these may not be the same. Furthermore, in truly heterogeneous systems, one would expect that anisotropy would be the smaller of the two effects. THEORY TENSOR THEORY OF PERMEABILITY FOR ANISOTROPIC POROUS MEDIA8 Darcy's law for flow in porous media in its usual form is where qis the flow rate vector, k is the permeability, is the viscosity, is the vector differential operator, and P is the Pressure. Consider flow, q, through a unit area in the direction of the unit vector n from elementary flow tubes parallel

Jan 1, 1965

By D. R. George

Preliminary research has identified several organic and aqueous solutions that are effective absorbents for SO, from simulated smelter gas containing 0.3 to 2% SO2. These SO2 loaded solutions are also compatible to the reaction of H2S and SO2 to precipitate a readily filtered elemental sulfur. The economic removal of SO2 and production of elemental sulfur from stack gases discharged by base- metal smelters is a challenging goal. The magnitude of this task is illustrated by the estimate that about 3.5 million tons of SO2 are discharged to the atmosphere by smelters annually in the U.S. The SO2 concentration of the gases ranges from about 0.5 to more than 3%. As the sulfur content of SO2 is 50% a potential production of 1,750,000 tons of sulfur per year is indicated.

Jan 1, 1970

By William P. Roe, James F. Ellis, W. P. Fishel

This paper reports the distribution of sulphur between iron and titanium in Fe-Ti-S alloys and in Fe-Ti-C-S alloys. The compound TiS was found, which exists as a separate phase at temperatures below 1200°C. Titanium in steels reacts with sulphur in preference to carbon. THE general relationship between sulphides and oxides suggests that titanium should form a sulphide having properties similar to those of titanium oxide. Specifically, titanium should form a sulphide having a high melting point, indicating a stable compound of low solubility in iron. In order for titanium to function as a desulphurizer or sulphur-fixing agent, it must form a stable sulphide. In order for titanium to be useful in steels as a sulphur-fixing agent, it must react with sulphur in preference to carbon; and to prevent red shortness, the sulphide formed must have solubility characteristics such that grain-boundary precipitation of a low melting phase be prevented. The terms desulphurizer and sulphur-fixing agent when used in this paper mean that titanium effectively ties up the sulphur as a stable sulphide of titanium and prevents the formation of FeS. The partition of sulphur between iron and titanium was studied first in a series of Fe-Ti-S alloys with carbon absent, and then in similar alloys with carbon present. It has been established1 a that titanium forms in Fe-Ti-S alloys a sulphide of undetermined composition which can be identified microscopically, and that the titanium-sulphur compound does not respond to sulphur printing. It has been suggested" that titanium acts as a sulphur-fixing agent, although little proof has been given. A report% f The Advisory Committee on Metals and Minerals summarizes the existing knowledge concerning substitutes for manganese in steels. Distribution of Sulphur Between lron and Titanium with Carbon Absent The alloys for this investigation were made by -melting Armco iron, metallic titanium, and iron sulphide in alundum crucibles in an induction furnace. The titanium was added after the other ingredients had melted. In these alloys it is recognized that some TiO, is present, since the melts were made in the air and since no other deoxidizing agent was used; therefore, some of the titanium was not available for union with sulphur. Thirteen ingots were made. Ingots 2 to 8 were cast in baked-sand molds; ingots 12 and 13 were cast in metal molds; and ingot 9 was allowed to cool in the crucible in which it was melted. All ingots were annealed at 900°C for 3 hr and were cooled slowly in the furnace. Subsequent information indicates that this anneal had no effect upon the titanium sulphide particle size, since the sulphide does not go into solution at this temperature. The ingots as-cast were approximately 8 in. long and % in. diam. The compositions of the eight ingots and the results of the partition of sulphur are recorded in Table I. Total titanium and total sulphur were determined by standard gravimetric methods. Sulphur, as iron sulphide, was determined by the evolution method. Boiling HC1 (1:4) liberates the sulphur from iron sulphide, but leaves the titanium sulphide practically undecomposed. A complete separation of titanium sulphide and iron sulphide cannot be made by digesting these compounds in dilute HC1 since titanium sulphide was found to dissolve slowly. The amount of titanium sulphide decomposed will depend upon the time in contact with the acid and upon the particle size of the sulphide. The point

Jan 1, 1952

By K. K. Kershner, W. A. Calhoun, C. W. Funk

Future resources of aluminum may require the utilization of low grade ores to provide a more permanent protection for the nation. Aluminum minerals such as cloy, shale, and high iron laterites may become important sources. An evaluation of reserves is given. New laboratory results are reported on the Vereinigte desilication process. THIS report on future resources of aluminum metal emphasizes the necessity for investigating utilization of low grade potential ores to provide more permanent protection for the nation. Partial or complete interruption of the importation of high grade aluminum ores must be given consideration. Ultimately, aluminum minerals such as clay, shale, and high iron laterites may become the principal sources of aluminum. The development of extractive processes for treating these low grade materials is a step in long-range national preparedness that should receive more attention. In formulating such processes, the application of beneficiation methods for the purpose of classifying the several types of minerals before subjecting each type to the more expensive extractive procedures should be considered, and a careful survey of the basic factors of power sources, transportation facilities, and sources of raw material should be made. Domestic Bauxite Resources Of the domestic supply of current, treatable-grade bauxite, 95 pct comes from Arkansas. The present reserve of Arkansas bauxite suitable for metal production, including abrasive-grade, Bayer-grade, and modified Bayer-grade ores, is 34,000,000 tons. The total reserve of bauxite of all grades is approximately 75,000,000 tons. Reserves are estimated on a mined and dried basis. Data available to the Bureau of Mines in 1948 to 1949 were used in preparing Table I, which shows a breakdown by grades of bauxite for about a half of the reserves of the state. The modified Bayer ore, 10,555,500 long dry tons, is based on a cutoff of 8 to 15 pct silica. The sub- marginal 10,074,700 long dry tons is assumed to contain more than 40 pct gibbsite, more than 15 pct silica, and less than 32 pct available alumina. A considerable amount of this low grade material was consumed in 1949 and 1950. Additional tonnages of bauxitic and kaolinitic clays are indicated by the Bureau of Mines drilling project.' Applying a 50 pct factor to arrive at long tons mined and dried, the results of this project are approximately 31,500,000 tons kaolinitic clay at +35 pct Al²O3 and 11,800,000 tons kaolinitic clay at 20 to 35 pct A1,0,. Total reserves of kaolinitic clays are probably quite extensive—several times the reserves shown in the Bureau's work. Total reserves of bauxitic and high iron clays from the drilling program and previously established figures are 63,980,000 tons. The mineral dressing methods,' the lime-sinter process, he lime-sinter modification of the Pederson process," the lime-soda sinter process,"-' and the Alcoa combination processa. have been described in the literature and will not be elaborated upon here. The less familiar Vereinigte Aluminium-Werke process used by the Germans during World War 11 may require some amplification. It was used to bene-ficiate boehmite ores containing 12 to 18 pct silica for a feed to the European Bayer process. Ore was

Jan 1, 1952