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By J. O. Lewis

The operation of gas-condensate fields is comparatively new and involves physical principles with which the industry was not prcviously familiar. It has been necessary to devise methods for testing gas-condensate wells and to correlate laboratory and field data. In this paper new methods are advanced for interpreting well G.P.M.† tests whereby dilution by dry gas can be estimated and information supplied on revaporization of condensates by dry gas. Inaccuracies in well test data are discussed. Changes in flow rates can cause changes in the G.P.M. of the effluent and it may take some time for a well to become stabilized after an important change in flow rate. Retrograde tests as usually conducted cannot be directly compared with field G.P.M. data, because the retrograde tests usually include solution gas in the condensates, which are reported On the cumulative basis whereas field data (G.P.M.) usually report pentaneS PlUS on a rate or instantaneous basis. Introduction Though long known to physicists, the phenomena Of retrograde condensation became known to the oil and gas industry Only in recent years, when deeper drilling disclosed that the behavior of vapors under changing pressures was different in high-pressure reservoirs than under the low-pressure operations with which the industry was familiar. These deep, high-pressure reservoirs in which condensation and vaporization behaved inversely to the accustomed manner became known as "gas-distillate," or preferably "gas-condensate" fields. Partly to prevent precipitation and retention of liquids in the reservoir, but still more to prevent the waste of residue gas, the operation known as "recycling," or preferably "cycling," was instituted, in which the residue gas is reinjected into the reservoir, thus maintaining pressure and driving the wet gas to the producing wells. For lack of field experience to serve as a guide, the industry had to assume that theory and laboratory experiments could accurately forecast retrograde behaviors in operating these gas-condensate fields, but it is obvious that these assumptions should be checked at the first opportunities against actual field experience. To make such checks, it is necessary to accumulate a large quantity of reliable field data, but experience has shown that it is difficult to obtain reliable field data and that the laboratory data as usually presented are not in directly comparable form. The problems of correlation involve the complex phase behavior on the one hand, and a knowledge of field data and a visualization of underground conditions on the other hand. This paper is an approach from field experience, The purposes of this article are to discuss the sources of uncertainty in the data and to present methods of analyzing, interpreting and correlating laboratory and field data. Data mostly from lower Gulf Coast fields are presented, from which some conclusions can be derived, but better data from more sources than those available to the writer will be required before satisfactory answers to many questions can be obtained. This paper is presented to stimulate the analysis and publication of data from other fields, the reexamination of field and laboratory methods, and the taking of more complete and reliable field tests. For these purposes, the writer presents some speculations that otherwise would not be appropriate.

Jan 1, 1947

By Alfred H. Bell, George V. Cohee

In 1941 Illinois produced 134,139,000 bbl. of oil, or 9.5 per cent of the total for the United States, and ranked fourth among the states. The production for 1941 declined 9.2 per cent from the previous year's total of 147,647,000 bbl. Daily average production for 1941 was 366,000 bbl. At the beginning of the year daily production was slightly more than 326,000 bbl. and it remained at appoximately that amount until June, when there was a slight increase. The increase continued until the peak of 431,260 bbl. daily was reached for the week ending Oct. 4. Daily average production at the end of the year was approximately 387,500 barrels. The increased production during the last half of 1941 was largely due to the rapid development of the Johnsonville field, Wayne County, the Rural Hill field, Hamilton County, and the Benton field, Franklin County—new fields discovered in the current year (Fig' 1)—and the Woodlawn pool, discovered in 1940. Discoveries In 19 counties in southern Illinois, 44 new fields were discovered in 1941 (Fig. 2 and Table 2), and extensions to 40 fields were successfully completed (Table 3). At the end of the year there were 10,496 wells in the fields discovered since Jan. I, '937, as compared with 71965 wells at the end Of '940. The area proved for production in the new fields increased from 78,040 acres at the beginning of 1941 to 97,483 acres at the end of the year (Table I)—an increase of 19,433 acres, of which 9,955 acres are in the fields discovered during the current year, and the remainder of 9,478 acres in extensions to pools discovered earlier. Drilling During the past year, 3838 wells were completed in Illinois (Table 4), of which 2912 were oil producers, 13 were gas producers and 913 were dry holes; 76 per cent of the wells drilled were producers. Of the total number drilled, 591 wells are classified as "wildcat" and of these 84 (1 in 7) were successful in obtaining production. The results of an investigation to ascer-tain the reason for the locations of the wildcat wells are set forth in Table 5. Of the 591 wildcat wells, the 292 known to have been located by scientific methods were 21.6 per cent successful. The total footage of wildcat wells drilled in 1941 was 1,341,743 ft., of which a total of 216,995 ft. was drilled in successful wells. Exploration MEthods Subsurface geology and geophysics, largely the reflection seismograph, are still the principal methods used in exploration and development in the state. The number of seismograph parties operating throughout the year was as follows: seven parties on Jan. I, 1941; five on Apr. I; four On July I; eight on Oct. I; fifteen on Jan. 1: 1942.

Jan 1, 1942

By C. L. Meyers, A. V. Levy, G. Y. Onoda, R. J. Kotfila

This paper presents the hypothesis that solid-solution hardening of regions in the order of tens of angstroms thick along grain boundaries is the most important mechanism controlling the ductile -brittle transition behavior of poly crystalline bcc refractory metals. Further, a physical model is developed and a general equation is derived to describe the dependence of the solute concentration at grain boundaries on temperature, nominal impurity concentration, thermal treatments, vain size, and prior plastic deformation. Analytical curves of the solute concentration at grain boundaries us temperature, calculated by means of the derived equation, are found to have the same general form as curves of ductility us temperature plotted from experimental data. Senziquantitative relationships between the transition temperature and metallurgical variables can he determined by using the physical model. The room-temperature brittleness of the poly-crystalline refractory metals (tungsten, molybdenum, and chromium) is a result of their high ductile-brittle transition temperatures. Recently studies on single crystals have revealed that, when sufficiently pure, these crystals have much lower transition temperatures than polycrystalline specimens of similar purity.'-3 For example, the transition temperature (measured by reduction in area in tensile tests) for very high-purity tungsten crystals has been reported to be as low as -50°F whereas polycrystalline specimens of similar purity had a transition temperature near 400" ~.' These results suggest that the ductile-brittle transition behavior of these polycrystalline metals can be attributed principally to the influence of grain boundaries on plastic flow and fracture. This paper contains a discussion of the manner in which grain boundaries influence the ductility of the poly-.crystalline bcc refractory metals and proposes that the segregation of impurities to grain boundaries is the most important mechanism for controlling the ductile-brittle transition behavior of these metals. Further, this paper contains an analysis of the effect of the compositional and structural variables on the grain boundary-ductility relationship, and introduces a semiquantitative model that can provide a foundation for more theoretical treatment to describe the influence of these variables on ductile-brittle transition behavior. PHYSICAL MODEL FOR PREDICTING DUCTILE-BRITTLE TRANSITION BEHAVIOR Grain Boundary Segregation of Impurities. Based on their own observations and on theoretical grounds, numerous investigators have suggested that impurities segregate to the grain boundaries. Such segregation would be expected because regions exist where both large and small foreign atoms fit with less strain than within the undistorted crystal structure. Therefore, the concentration of impurities should be higher at boundaries than within the grain body. TO estimate the degree (i.e., the ratio of grain boundary to nominal bulk concentration) to which an interstitial solute tends to segregate at boundaries within a solvent metal, the solubility rather than the size misfit could be used as a guide because solubility expresses the joint effect of both elastic and electronic factors.5 The solubilities of interstitial elements such as carbon, hydrogen, nitrogen, and oxygen are low in the group V-A metals and very low in the group VI-A metals.6 These low solubilities suggest that segregation to grain boundaries should occur for each of these solutes in both refractory metal groups. The difference between the ductility of single-crystal and polycrystalline bcc refractory metals can be described in terms of two distinct effects.4 The first of these is the general observation that grain boundaries hinder slip within grains and slip transfer between grains, and the second is that deformation is more complex in each grain of a polycrystalline specimen than it is in a single crystal. Mc Lean has pointed out, furthermore, that strong slip-hindrance effects at grain boundaries should occur in metals having strong segregation of impurities to grain boundaries. Therefore, the effect of grain boundaries on the hindrance of slip is expected to be the dominating influence on the ductile-brittle transition behavior of these polycrystalline refractory metals. cahn5 has suggested that temperature and solute mobility should influence solute equilibrium segregation at grain boundaries, and Fig. 1 illustrates

Jan 1, 1965

By H. Biloni, B. Chalmers

Metallographic studies of the segregation of solute in and near the surfaces of chill-cast alloys have shown that, under sufficiently severe conditions, nucleation on the cold mold surface is followed by the formation of a disc of solid of the same composition as the liquid. This disc is surrounded by two concentric rings in which the concentration first decreases and then increases. The discs and rings are surrounded by a region in which arms of low solute concentration separate regions of high concentration. These arms start at the periphery of the outer ring and are initially radial; they make a gradual curved transition from the radial direction to a crystallographic direction. A normal dendritic substrcture is established beyond the position at which the arms have become crystallographically aligned. When the cooling is less severe, the disc becomes less irregular in shape and has a concentration minimum at the center. The term "Predendritic" is proposed for these transitions. A qualitative explanation is outlined for the phenomena observed at the surface and in the equiaxed region of the ingots. It is well-established1-' that the normal mode of solidification for alloys under most conditions is dendritic. A characteristic of dendritic solidification is the growth of rods or plates in specific crys-tallographic directions. The remaining liquid solidifies later, usually with a higher concentration of solute than the original liquid. Very little is known, however, about the transition from a crystal nucleus until the dendritic pattern is established. It is clear that there must be a transition because the nucleus is much smaller than the characteristic spacings found in the "steady-state" structure. And it also seems clear that the initial conditions must be important since the undercooling existing during the nucleation of the grains has a remarkable influence upon the grain size4 and the segregation pattern. The present paper reports a study of the micro-segregation in regions where crystals have nucleated, and the conclusions that can be drawn regarding the early stages of growth, in connection with the details of the solidification process. Aluminum of 99.993 purity, A1-Cu alloys containing 0.5 to 20 wt pct Cu, and Pb-Sn alloys with 5 wt pct Sn were cast and examined metallographically at the as-cast surface, close to the surface, and in the interior after casting. The alloys were cast from controlled temperatures against surfaces at different temperatures ranging from room temperature to approximately the liquidus temperature of the alloy. The surfaces were, in various experiments, graphite, stainless steel, copper, and aluminum. The methods used for metallographic examination were as follows. 1) The Nomarski phase contrast interferometer6 was used to obtain information on the topography of the as-cast surface. 2) The distribution of any solute present in A1 99.993 pct and copper in the A1-Cu alloys was studied by the anodic film technique originated by Lacombe and Mouflard7 and previously applied in the study of the solidification of aluminum by Biloni.8 The electropolished surface of the specimen is anodized under controlled conditions so that the thickness of the oxide film and therefore the interference colors under white light are sensitive to the local composition. This technique was applied to the as-cast surfaces and to metallographically prepared surfaces from the interior. 3) If in Al-Cu alloys, the surface is anodically oxidized for several minutes, instead of seconds as in the color-film technique, the copper segregation is outlined by a different level with respect to the matrix. This method is less sensitive but complementary to that for the color films. 4) The distribution of copper revealed and mapped by the metallographic techniques was confirmed by electron probe. 5) In samples with high concentration of copper, evidence for the copper distribution could be seen optically after electropolishing.

Jan 1, 1965

By H. H. Smith, G. J. Danek, M. R. Achter

Nickel, Type 316 stainless steel, and copper show decreases in reversed bending fatigue strength with increases in air and oxygen pressure. The leveling off of the log N us log p curve for nickel at 300" and 816°C is discussed in terms of a model in which surface saturation gives rise to a critical pressure. A metallographic study indicated that the effect of environment on crack initiation and growth rates is a function of temperature. It is shown that small amounts of impurities in inert gases may substantially reduce the fatigue strength of nickel. 1n a previous investigation1 of high-temperature bending fatigue in air and in vacuum, reversals in the effect of environment with changes in test conditions were atrributed to a mechanism consisting of two processes acting in competition. One of them, oxidation strengthening, has been demonstrated in a straightforward manner by measuring the rupture strength of a sintered nickel-oxide bond.' The detailed operation of the other process, facilitation of crack propagation by surface absorption of oxygen, is uncertain. Thompson et UZ advanced the possibility that the formation of an oxide layer prevented rewelding of cracks during the compressive part of the cycle, while Wads worth and Hutchings4 further proposed that the reaction of oxygen with atoms at the tip of the crack helped the metal to break there, a possibility which has also been advanced to explain crack formation in creep.5 A difficulty in arriving at a mechanism for this lowering of fatigue strength in air is the inconsistency of some of the data. For example, Wadsworth and Hutchings4 found an approximately linear decrease of log cycles-to-fracture (N) with an increase of log pressure-of-air (p) for copper and aluminum at room temperature, while snowden,' although finding a similar linear dependence for aluminum, observed a stepped curve for lead. Between l0-' and 10"1 torr there is a sharp decrease in the fatigue life of lead with increasing air pressure, but plateaus, signifying no dependence on pressure, are found at higher and lower pressures. If, as discussed elsewhere: these environmental effects arise from the adsorption of gas on crack surfaces, it would be expected that as the pressure is increased a saturation point would be observed, beyond which there is no further effect. To gain further information about the form of the log N vs logp curve, it was decided in the present investigation to repeat this type of measurement at elevated temperature on nickel, copper, and Type 316 stainless steel. An additional object of this program was

Jan 1, 1963

By O. J. Huber, P. D. Frost, H. A. Robinson

URANIUM is a (ß-stabilizing, eutectoid-forming element when alloyed with titanium. Udy and Boulger1 have reported that an alloy of 48.6 pet uranium in titanium retains ß-phase when quenched from the ß-region, while compositions of approximately 30 pet uranium transform to martensite during such quenching. Since the eutectoid reaction is rather sluggish, titanium-uranium alloys should be capable of being strengthened by the ß — a trans-

Jan 1, 1959

By Benjamin LeRoy Miller, Joseph T. Singewald

For a number of years Russia, India and Brazil have outranked all other countries as producers of manganese ores. During the 5 years immediately preceding the European war, the average annual production of Russia was 844,000, of India 694,000 and of Brazil 200,000 long tons. Since the outbreak of the war there has been a considerable falling off in the Russian and Indian production, particularly in the former, whereas the production of Brazilian ores has been greatly increased, amounting in 1914 to over 250,000 tons and in 1915 to nearly 350,000, with conditions favorable for a still larger production in 1916. Manganese is one of the few industrially important metals that are not produced in the United States in quantity commensurate with our needs, so that we have been compelled to import annually about 300,000 tons, having a value of over $2,000,000, and these ores have been obtained from the three countries mentioned above. Their rank as contributors to our imports of manganese ores was India, Russia, Brazil; and in 1913, Brazil contributed only one-fifth. During the past 2 years Brazil has furnished rapidly increasing quantities to this country, and, with the falling off of imports from India and Russia, has become our principal foreign source. In 1914, Brazil furnished two-fifths of the imports and more than India or Russia, and in 1915 over nine-tenths. The manganese ores of Brazil are consequently of more than usual interest to us at this time. The Manganese-Ore Distbicts of Brazil , The manganese mining industry of Brazil dates from the year 1894, and since that year the total production has been over 3,000,000 tons. With the exception of a small quantity produced in the State of Bahia from deposits west of the City of Bahia, this output has come from the

Jan 1, 1917

By Burnham E. Field

TAE chemical industry is constantly looking for new materials which either are more resistant to corrosion than those now available or have improved physical properties to meet the requirements of higher temperatures and greater pressures. Attack by acids is-one of the more important forms of corrosion-and in the last few years the development of acid-resistant alloys has been quite rapid. Perhaps the most notable example is that of nitric acid, 'the problem of which has largely been solved by the chromium-iron and chromium-iron-nickel alloys. Sulfuric acid may be handled in lead, iron, or the iron-silicon alloys, depending on conditions. As to hydrochloric acid, no metal or alloy can be called entirely satisfactory for handling. this acid under plant conditions.1 The results of our investigations on the resistance of the nickel-molybdenum alloys to hydrochloric acid have been confirmed by those of Guertler, Rohn, Schulz, Jenge, and others,' but thus far only one such alloy has approached commercial production in Germany; this contains approximately 15 per cent. chromium and 7 per cent. molybdenum with the remainder chiefly nickel. Dr. S. W. Parr, as far back as 1914, developed a complex alloy known as "illium," with a nickel base and containing some molybdenum.3 Dr. Parr was primarily interested in an alloy for lining bomb calorimeters, and while illium does show good resistance to acid it is too expensive for general use. Two United States

Jan 1, 1929

By F. F. Aplan, D. W. Fuerstenau

This chapter presents modern concepts of the flotation of nonmetallic minerals. In particular, it is concerned with such minerals as metal oxides, silicates, sulfates, carbonates, and halides. It is not the purpose to duplicate the two excellent, recent treatises by Gaudin l and by Sutherland and ark,^ but rather to expand their correlations of data, particularly in view of recent, ex- citing new experiments which are shedding new light on the principles of non- metallic flotation. Outstanding success has been achieved over the past 50 years in separating one sulfide from another or from the gangue constituents using a minimal amount of reagents. In contrast to this, selective flotation in nonmetallic systems is often difficult in that one class of compounds alone, the carboxylic acids, may float nearly the entire array of nonmetallic minerals under the appropriate conditions. Moreover, while lime, cyanide, sodium sulfide, and copper sulfate constitute the principal modifiers used to obtain selectivity among the various sulfides, the nonmetallic mineral flotation engineer is con- fronted with a vast array of modifying reagents. In sulfide and native-metal flotation, a strong chemical adsorptive bond is generally formed between the mineral and sulfhydral collector. In fact, re- cent radio-tracer studies show that below monolayer coverage as much as 98% of added mercaptan is adsorbed on the surface of gold.? Contrasted to this, Bloecher's data indicate that for the quartz-amine system only about 60% of the collector is adsorbed.4 This greater residual concentration in the solution results from weaker forces of adsorption in the quartz-amine system. In the flotation of nonmetallic oxide minerals, collector adsorption results from rather weak physical forces, primarily electrostatic attraction and van der Waals attraction between hydrocarbon chains. In the flotation of salt-type minerals, carboxylic acids are adsorbed both by physical and chemical forces. It is a study of the effect of the electrical forces superimposed on the chemical adsorptive forces that contributes most toward understanding nonmetallic mineral flotation. The need for quantification of general rules for the flotation of nonmetallic minerals is so great that Taggart 5 with unmasked sarcasm suggested that after trying anionic and cationic collectors:

Jan 1, 1962

By Frank W. Clinard, Oleg D. Sherby

The effect of multiple an transformations on diffusion in a dilute iron alloy was studied. Inter-penetration between iron and an Fe-Co alloy was evaluated, under thermal-cycling conditions chosen so as to transform only the iron-rich side of the diffusion couple. It is shown that a small but consistent diffusion enhancement by a factor of two results when data from the transforming side of thermally cycled specimens are compared with predicted inter diffusion coefficients based on isothermal data. No enhancement is found when data from the mntransforming side of such couples are compared with predicted diffusivities. It is suggested that short-circuiting by moving pain boundaries is the most likely mechanism contributing to the observed diffusion enhancement from multiple phase transJormations in iron. Transformation-induced Point defects, dislocation-pifie short-circuiting, and point defects generated by dislocation motion are less effective in contributing to enhanced diffusion under the experimental conditions utilized. SO far as is known, no studies have been made of the effect of allotropic transformation on diffusion. previous to this investigation. Studies have been made, however, of the influence of transformation on the diffusion-controlled processes of spheroidization and sintering. Cullen1 has described a method of accelerating spheroidization in an AISI 1030 steel. Partial transformation between a and ? phases was uti-

Jan 1, 1965

By E. S. Machlin, Morris Cohen

GRENINGER and Troiano' were the first to establish the fact that the habit planes of mar-tensitic products are usually planes of high indices. In steels containing 0.55 to 1.4 pct C, the habit plane indices are {225}A.* In steels with more than 1.5 pct C and in Fe-Ni alloys, the indices are {259In. The presence of both habits in certain alloy steels has been reported recently." Several investigators"-" have subsequently attempted to provide an understanding of these complex habit relations. Bowles'6 work is the most recent and the most successful. Like Greninger and Troiano, Bowles concluded that the transformation occurs in two steps, the first, a strain (or displacement) that is homogeneous throughout the volume of the martensitic plate, while the second is a strain that is homogeneous only within relatively small portions of the martensitic plate. The first strain yields the measured tilt of the specimen surface, but does not produce the final martensitic structure. This and the correct lattice orientations are achieved by the second strain. Bowles also reasoned that each strain could be described by the motion of a plane of no rotation and no distortion (hereinafter called the invariant plane) in a direction not necessarily contained in the plane.** In applying these considerations to steels with {225}a habits, Bowles found that the habit plane coincided with the invariant plane of the first strain, a result which signified that the atoms move along certain paths during the transformation. Whether this correlation results from the existence of some sort of a plate nucleus6 lying along the invariant plane of the first strain, or whether the invariant plane primarily defines the preferred directions of propagation of the first strain, will be discussed in a later section. There are two obstacles to the general acceptance of Bowles' treatment: 1—it has not been shown that elements of his double-strain analysis are unique, and 2—it is not known whether his treatment applies to transformations yielding the {2591A habit. Unless these two questions are resolved, the correlation between the habit and invariant planes in the {225}A systems might be regarded as coincidental. Experimental Procedure Using a 70 pct Fe-30 pct Ni alloy as an example of a {2591A habit system, preliminary attempts were made to obtain a double-strain solution based on a Nishiyamax** set of orientation relations and on a Greninger-Troianot set, adopting the stereographic technique described by Bowles" who used the Kurd-jumow-Sachstt set in connection with the {225}A habit. These attempts were unsuccessful because the method is essentially one of trial and error and requires either exceedingly good luck or a prior knowledge of the results being sought. Consequently it was decided to measure independently the strain associated with the formation of a martensitic plate as well as the habit-plane indices of the particular plate. By means of matrix algebra, the measured strain was applied to the austenite lattice, whose orientation with respect to the strain was determined, in order to ascertain whether the resultant structure would have the lattice of martensite. This was not found to be the case, and hence it was assumed that the measured strain was the first of two Bowles-type strains, characterized by the motion of an invariant plane. A solution of this displacement was obtained in terms of the invariant-plane indices and the direction of motion of the atoms. Then the second strain

Jan 1, 1952

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,' Mc Quillan,' Van Thyne et dl.,' and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger' discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95' *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By Robert M. Grogan, Gill Montgomery

Fluorspar, the commercial name for fluorite, is a mineral composed of calcium fluoride, CaF,. Its valuable properties are due to its content of fluorine, and it is the principal commercial source of that element. The name is derived from the Latin word "fluere," to flow, because the mineral has a low melting point and is used in metallurgy as a flux. Cryolite is a sodium aluminum fluoride, Na,AlF,. It is a rare mineral which has been found in commercial quantities in only one place in the world, Greenland. Small amounts of it are shipped from stock in that country, and its place in industry has been taken over almost completely by synthetic cryolite. Because of the relative unimportance of cryolite, discussion of it has been relegated to a short section at the end of this chapter, which is principally concerned with fluorspar. History Fluorspar was used for ornamental purposes by the Greeks and Romans, who fashioned such things as vases, drinking cups, and table tops from it. Various peoples including the Chinese and the American Indians carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola (1564), who wrote about it in 1546. Mining began in England about 1775 and at various places in the United States during the period 1820 to 1840. Production became substantial following the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage were stimulated by growth in the steel, aluminum, chemical, and ceramic industries and were accelerated by World Wars I and II. Fluorocarbons entered the picture in 193 1 and the use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920s, a differential flotation scheme for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low grade ores in the 1940s were outstanding technological contributions that enabled increased production of fluorspar concentrates. In recent years the development of pelletizing and briquetting processes for making flotation concentrates into gravel-size particles for use in steel furnaces and the development of more efficient and selective flotation schemes for treating crude ores containing abundant dolomite and barite have been major improvements in the industry.

Jan 1, 1975

By J. A. Hren, G. Thomas

A high-temperature stage has been used to study precipitation and dissolution in thin foils of Al-20pct Ag alloy directly in the electron microscope. The results show that the aging characteristics are similar to those observed for bulk materials, and in addition, direct evidence is presented for clustering at the solid solution temperature. The limit of solubility of G. P. zones is-350°C. The heterogeneous precipitation, the growth and dissolution of ?&apos;have been studied in detail. Growth of ?&apos; parallel to the basal planes, occurs by continuous motion of inter -facial partial dislocations. Growth stops at intersecting particles due to formation of sessile a/6 <110> interfacial dislocations. Growth normal to the habit plane occurs by the spontaneous nucleation of partial dislocations on alternate (111) planes and the thickening rate is --10-3= times the lengthening rate. The precipitates dissolve in layers and the final product is a whole a/2 <110> dislocation . The nucleation -growth -dissolution processes are thus completely reversible. Kinetic data obtained from the dissolution rates of ?&apos;particles enable the diffusion coefficient to be determined and the activation energy is found to be 37.5(±4) kcal mol-1, which is that expected for dzffusion of silver in aluminum. The velocity of the interfacial dislocations is thus dependent solely on the rate of diffusion of silver atoms. RECENTLY it was demonstrated that a high-temperature stage could be effectively used in the electron microscope to follow directly the processes of precipitation and dissolution in thin foils of A1-4 pct Cu alloy.&apos; These experiments also provided kinetic data which enabled the diffusion coefficient to be estimated. This new development of electron metallography opens up many fruitful areas of research and it was decided to investigate the aging behavior in thin foils of A1-20 pct Ag alloy, particularly the mechanism of heterogeneous precipitation (i.e., precipitation on lattice defects). This system was chosen because the aging characteristics of bulk specimens are now well known,2"7 and because we wished to obtain more details of the role played by partial dislocations and stacking faults in the nucleation growth and dissolution of the hcp ?&apos; phase. This is of interest for the general case of fcc-- hcp transformations. Part of the A1-Ag phase diagram is shown in Fig. 1. The use of a high-temperature stage also enables a study to be made of the clustering process (formation of G. P. zones) and to determine the structure of the solid solution prior to the usual quenching and aging procedures. It is also possible to obtain kinetic data from measurements of the rates of dissolution of precipitate particles. Unlike the results of previous experiments on A1-4 pct CU 1 where much of the initial precipitation occurred on the foil surfaces, the results on the A1-20 pct A1 alloy were identical to those reported for bulk specimens6,7 and no surface precipitation was ever observed. Thus, it was possible to follow the aging sequence: G.P. zones — ?&apos; — ? directly in the thin foils. This paper is concerned with the formation and dissolution of zones and the ?&apos; phase, and no attempt has been made so far to follow the mode of discontinuous precipitation of ?. I) EXPERIMENTAL DETAILS The high-purity A1-20 pct Ag alloy was prepared by the Aluminum Co. of America in the form of 0.001-in.-thick sheets. These were cold rolled with intermediate anneals to a thickness of 0.0004 in.,

Jan 1, 1963

By G. Sachs

THE iron-rich iron-nickel alloys have at-tracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are Atomic per cent nickel FIG. I. FIG. 2. FIG, I.-HONDA&apos;S AND MERICA&apos;s IRON-NICKEL DIAGRAM, FIG. 2.-MARSH&apos;S IRON-NICKEL CONSTITU-TIONAL DIAGRAM. the base of many alloys with various out-standing properties. The iron-nickel alloys, therefore, have been investigated exten-sively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,1 and will be discussed in some detail in the sec-tions of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis,2 which is not dependent upon

Jan 1, 1940

By Albert Zima

ACCORDING to recently published statistics, it is predicted that as much oil must be produced during the next 16 years as has been produced during the past 75, in order to satisfy the high rate of consumption of petroleum products. During 1934, over 17,000 oil wells were completed in the United States, and it is expected that over 20,000 additional wells will be drilled during the current year. Were it not for the remarkable progress made during recent years in the improvement of drilling technique and in the development of equipment used in the production phase of the oil industry, it is doubtful whether sufficient oil could be produced to meet present requirements. A few years ago, wells seldom were deeper than 3500 to 4000 ft., owing to the limitations of the drilling methods and equipment employed. Today, however, through the application of scientific drilling methods and the adaptation of modern equipment and improved materials, many wells range from 6000 to 8000 ft, in depth, and a few recent completions exceed 10,000 feet.

Jan 1, 1935

By D. A. Thomas, M. F. Comerford

Poly crystalline wires of Fe-3.2 wt pct Si were cold-drawn to 31, 66, and 87 pct reductions of area. Mechanical properties and tnicrostructures were studied after recovery and re crystallization. An initial increase in strength during recovery was ascribed to strain aging, and subsequent softening was largely due to polygonization rather than re-crystallization. No unique actioation energies could be determined for the recovery process. Rather, activation energies ranged from 60,600 cal per mole at 10 pct recovery to 83,200 cal per mole when recovery was 50 pct complete. Sites for the nucleation of recrystallization were found to depend on time and temperature. In the early stages of re-crystallization, nucleation occurred in deformation hands. Later, or at high temperatures, recrystal-lized grains were nucleated primarily al grain boundaries. Polygonized structures did not seem to be preferred sites for nucleation. MUCH of the research on deformation, recovery, and recrystallization processes in bcc materials has been performed on single crystals or lightly worked polycrystals. Little study has been devoted to the relation of mechanical properties to micro-structure in polycrystals after severe deformation and subsequent annealing. This paper presents the results of a study of the tensile properties and microstructures of Fe-Si wires drawn varying amounts and annealed at a series of temperatures. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of the following composition: 3.2 wt pct Si, 0.08 Mn, 0.016 C, 0.005 0, 0.0002 N, 0.0001 H, 0.008 P, 0.034 S. The material was received as l-in.-sq bars cut longitudinally from a hot-rolled slab provided by the Armco Steel Corp. The bars were forged to 3/8-in. rounds, centerless-ground to 0.250 in., and swaged to &apos;0.108 in. All subsequent reductions were performed by room-temperature wire drawing at the rate of 2 in. per min. Each preliminary draft gave approximately 30 pct reduction of area and was followed by a l-hr anneal at 1010°C in dry hydrogen. Three lots of wire were made with ultimate cold reductions of 31, 66, and 87 pct reduc-

Jan 1, 1965

By M. R. Tek, R. L. Nielsen

The scaling laws as formulated by Rapoport relate dynamically similar flow systems in porous media each involving two immiscible, incompressible fluids. A two-dimensional numerical technique for solving the differential equations describing systems of this type has been employed to assess the practical value of the scaling laws in light of the virtually unscalable nature of relative permeability and capillary pressure curves and boundary conditions. Two hypothetical systems — a gas reservoir subject to water drive and the laboratory scaled model of that reservoir — were investigated with emphasis placed on water coning near a production well. Comparison of the computed behavior of these par ticular systems shows that water coning in the reservoir would be more severe than one would expect from an experimental study of a laboratory model scaled within practical limits to the reservoir system. This paper also presents modifications of the scaling laws which are available for systems that can be described adequately in two-dimensional Cartesian coordinates. INTRODUCTION Present day digital computing equipment and methods of numerical analysis allow realistic and quantitative studies to be carried out for many two-phase flow systems in porous media. Before these tools became available the anticipated behavior of systems of this type could be inferred only from analytical solutions of simplified mathematical models or from experimental studies performed on laboratory models. To reproduce the behavior of a reservoir system on the laboratory scale, certain relationships must be satisfied between physical and geometric properties of the reservoir and laboratory systems. Where the reservoir fluids may be considered as two immiscible and incompressible phases, the necessary relationships have been formulated by Rapoportl and others.2-5 Rapoport&apos;s scaling laws follow from inspectional analysis of the differential equation describing phase saturation distribution in such systems. It will be recalled that these scaling laws presuppose three conditions: (1) the relative permeability curves must be identical for the model and prototype; (2) the capillary pressure curve (function of phase saturation) for the model must be linearly related to that of the prototype; and (3) boundary conditions imposed on the model must duplicate those existing at the boundaries of the prototype. These three requirements seldom if ever can be satisfied in scaling an actual reservoir to the laboratory system because: (1) The laboratory medium normally will be unconsolidated (glass beads or sand) while the reservoir usually is consolidated. Relative permeability and capillary pressure curves are usually quite different for consolidated and unconsolidated porous media. (2) The reservoir usually will be surrounded by a large aquifer which could be simulated in the laboratory only to a limited extent. (3) Wells present in the reservoir would scale to microscopic dimensions in the laboratory if geometric similarity is to be maintained. In view of these considerations, rigorous scaling of even a totally defined reservoir probably would never be possible. The purpose of this paper is to assess the practical value of the scaling laws in the light of the unscalable variables. This has been done by carrying out numerical solutions in two dimensions to the differential equations describing the flow of two immiscible, incompressible fluids in porous media for a field scale reservoir and a laboratory model of that reservoir. While both the reservoir and the laboratory model were purely fictional, each has been made as realistic and representative as possible. The field problem selected as the basis for the investigation was an inhomogeneous, layered gas reservoir initially at capillary gravitational equilibrium and subsequently produced in the presence of water drive. The laboratory model of this reservoir was designed to utilize oil and water in a glass bead pack. The numerical treatment employed was similar to that of Douglas, Peaceman and Rachford6 and it included both capillary and gravitational forces as

By Edmund S. Davenport

The production of thorium of high purity by the Ca-CaCl2 reduction has been described by Marden and Rentschler,1 who also reported some of the properties of the coherent, ductile metal obtained from this pure thorium powder. The present paper describes the properties of thorium produced by the Ca-CaCl2 process modified in some details to meet commercial conditions. The principal effect of these changes in process has been an unavoidable increase in the oxide content of the thorium. Materials and Methods The thorium employed in this investigation was made from pure thorium oxide (ThO2) by the Ca-CaCl2 reduction. The washed and dried metal powder was pressed into bars approximately 0.160 in. dia. and 10 in. long, at a pressure of 75,000 Ib. per sq. in. The bars were heat-treated in vacuum at 1175&apos; C. for 1 hr. This treatment yielded ingots sufficiently dense and coherent for mechanical working. Thorium has been successfully worked without a protective metallic covering, but for the purposes of this investigation it was more convenient to inclose the ingots in soft iron tubes and swage or roll cold to the desired sizes. The iron sheath was dissolved with nitric acid, leaving the cold-worked thorium exposed. Chemical Analyses Analyses of typical samples of the material used in this work arc given in Table 1. Thorium powder oxidizes in moist air, even at room temperature; no unusual precautions were taken to prevent such oxidation of the material used in this investigation. A certain amount of oxidation probably takes place during pressing; certainly during heat-treating unless a very slow heating schedule is employed. These factors account

Jan 1, 1930

By Robert A. Colten, Frederick C. Hull, Robert F. Mehl

It is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.l,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in I939.3 Two types of process were described: (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. I);2,4 the former, occurring near the knee of the S-curve, has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ael, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenabil-ity; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels." Previous Data on Rate of nucleation and rate of Growth Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Meh1,l and by Dorn, De Garmo and Flanigan.2, It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given. Except for the approximations of Mehl and the work of Dorn, austenite grain size was disregarded, though it is well known

Jan 1, 1942