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By B. E. Terkelsen, B. J. Piearcey

A study has been made of the effect of unidirectional solidification on the creep behavior, stress-rupture properties, and thermal shock resistance of four nickel-base superalloys. The alloys Mar-MZOO, B-1900, IN 100, and TRW 1900 show improved rupture ductility and thermal shock resistance when tested with the columnar grains parallel to the major stress axis during test. The relative improvement in creep-rupture properties depends on the intrinsic strength of the alloy, a property which depends on composition, heat-treatnient, and crystallographic orientation. The data clarifies some of the factors affecting the properlies of the cast nickel-base superalloy. COMPONENTS designed for high-temperature use have, in recent years, been fabricated by precision casting techniques using nickel-base alloys developed specifically for use in the conventionally cast condition. This development was a result of both the increasing complexity of the component and the recognition that high-temperature strength was incompatible with workability. The use of castings can be economically favorable, but, more important, the recent complex designs of air-cooled gas turbine blades and vanes in alloys which possess the necessary high-temperature strength cannot be forged. Common modes of failure of high-temperature components are excessive creep, creep rupture, and thermal fatigue. If rupture occurs then the mechanism is usually by inter crystalline cracking along those grain boundaries oriented transverse to the major stress axis. In the stronger alloys, rapid propagation of intercrystalline cracks result in apparent premature failure demonstrated by the absence of third stage creep in a creep-rupture test and low rupture ductility. Tensile ductility shows a similar trend, that is, decreasing ductility with increase in strength. It is not surprising, therefore, that increases in creep strength have only been obtained with a loss in resistance to thermal shock, a property which shows a dependence on tensile ductility. VerSnyder and ~uard' showed that the application of unidirectional solidification to a brittle Ni-Cr-A1 alloy both improved the rupture life of the alloy and increased rupture ductility. Since this casting method results in columnar grains, it appeared that the solution to the lack of ductility in nickel-base alloy components was the elimination of the source of failure, namely the transverse grain boundaries. This concept was recently developed2 to produce cast-to-size gas-turbine blades and vanes consisting entirely of columnar grains oriented parallel to the major stress axis of the component. Not only did the process impart increased rupture life and ductility to the components, but it also increased their resistance to thermal shock. During this development, the effect of unidirectional solidification on the properties of several alloys was investigated. The resulting data allows certain conclusions to be drawn regarding the factors affecting the creep and stress-rupture properties of the cast nickel-base superalloy and also its resistance to thermal shock. Detailed information was obtained on the alloys Mar-MZOO, B-1900, In 100, and TRW 1900. The composition of the alloys studied are shown in Table I. MATERIAL PREPARATION AND TESTING The conventionally cast alloys are cast as +-in.-diam bars in innoculated shell molds under conditions designed to maintain control of grain size. Unidirec-tionally solidified casting were produced in the form of 3-in.-diam ingots. Specimens from the latter were machined such that the axes of the columnar grains were parallel with the axis of the test bar, except in certain cases where the transverse properties of the material were being evaluated. The specimens were tested in an axial loading creep machine.' Temperatures were measured with thermocouples, attached just outside each end of the gage length, to assure uniform temperature along the entire specimen. Chromel/alumel thermocouples were used up to 1800"F and Pt/Pt-10 pct Rh thermocouples above 1800"F. The specimen temperature was recorded and maintained within i2"F throughout the test. Creep extensions were measured automatically with extenso-meters attached to ridges on the specimen and recorded continuously using linear variable differential transformers and multipoint recording equipment. MICROSTRUCTURE The microstructures of transverse sections of the four alloys studied are shown in Figs. 1 and 2. Fig. 1 shows optical micrographs of the alloys, both in the conventionally cast and unidirectionally solidified conditions. Each alloy displays a cored dendritic structure, a distribution of MC carbide, and the presence of the y — y' eutectic constituent.~ In the case of IN 100 and B-1900, Fig. 1 indicates that in these specimens the eutectic is degenerate. That is, it consists only of y' pools indicating that the y constituent has been solutioned during the cooling period after solidification. The major effect of unidirectional solidification on the microstructures of the alloys is a tendency to promote a more dendritic form of MC carbide and an increase in dendrite arm spacing, both effects being a result of the slower solidification rate in the unidirectional solidification technique. V, lec tron micrographs of transverse sections of the four alloys in the two cast conditions are shown in

Jan 1, 1968

By J. Kent Smith

THE object of this investigation was to ascertain the effect of varying percentages of beryllium upon pure copper and the properties of the resultant alloys in their softest condition, the effect of heat hardening on them, and the extents to which these properties could be augmented by different combinations of heat hardening and cold rolling. The data compiled in this paper represent partial results of continuing work done by the writer during the years 1930 and 1931, which was a continuation of the unpublished ground work incepted in the laboratory of the Beryllium Corporation of America by H. B. Pulsifer in the year 1926. A short bibliography on beryllium alloys is appended to this paper. It has, of course, long been known that copper subjected to cold work is hardened and strengthened to a considerable extent, furthermore it had been qualitatively noted in previous experiments that copper-beryllium alloys seemed to take on hardness and strength as the result of cold work at a greater rate even than does plain copper. It was decided therefore to endeavor quantitatively to determine such rate of increase, as also the relative increases by combinations of cold working and heat hardening. The results are summarized in Tables 3, 4 and 5. A preliminary series of experiments had indicated that by an exposure to the heat of 575° F. for 2 1/2 hr. age-hardening of a 2.50 per cent beryllium-copper alloy took place. Slab ingots of nine different beryllium-copper alloys were prepared under identical conditions by means of the addition of a previously prepared 12.5 per cent beryllium-copper alloy to well melted and deoxidized pure copper. The ingots were then reduced by hot rolling to 12 gage (about 0.080 in.). These strips were heated to 1450° F. and quenched in cold water, and thus brought to their softest condition. (See Table 1.) Strips were next "precipitation-hardened" by reheating to a definite temperature. Similar strips to those itemized in Table 1 (which had been quenched from 1450° F.) were reheated for varying periods of time at 575° F. The hardness figures show that a metastable condition, of which the range of stability is dependent entirely upon time at the given temperature, begins to be noted in copper samples containing as little as 0.85 per cent beryllium. It is extremely noticeable in samples containing

Jan 1, 1932

By R. F. Miller, R. F. Campbell

Sixteen steels containing different combinations of chromium and molybdenum, in amounts up to 5 per cent of each element, were examined for microstructure and hardness after air cooling and after furnace cooling from suitable austenitizing temper- atures. Diagrams summarizing the structnres and hadness resulting from these two cooling rates are presented (Figs. 3, 4, 7).t Data were also obtained on the influence of these two elements, individually and in combination, on the depth of decarburiza-tion observed after furnace cooling (Fig. 8). Composition of Material The chemical composition of the steels investigated is given in Table I. The plain carbon steel was made in a 2 5-ton Heroult electric-are furnace, while the alloy steels were made in a 4.5-ton Ajax-Northrup elec- tric induction furnace. The cast ingots were hot-rolled to 1.75-in. bars. Air-cooled Series The I.75-in. bars were forged to flat plates, 0.25 in. thick, from which specimens 0.5 in. wide by 2 in. long were cut. The specimens were pretreated to improve their homogeneity by heating to 1830°F. (I000°C.) for 20 min. and oil-quenching. They were then reheated to 1740°F. (950°C.) for one hour and air-cooled, after

Jan 1, 1942

By R. F. Campbell, R. F. Miller

Sixteen steels containing different combinations of chromium and molybdenum, in amounts up to 5 per cent of each element, were examined for microstructure and hardness after air cooling and after furnace cooling from suitable austenitizing temper- atures. Diagrams summarizing the structnres and hadness resulting from these two cooling rates are presented (Figs. 3, 4, 7).t Data were also obtained on the influence of these two elements, individually and in combination, on the depth of decarburiza-tion observed after furnace cooling (Fig. 8). Composition of Material The chemical composition of the steels investigated is given in Table I. The plain carbon steel was made in a 2 5-ton Heroult electric-are furnace, while the alloy steels were made in a 4.5-ton Ajax-Northrup elec- tric induction furnace. The cast ingots were hot-rolled to 1.75-in. bars. Air-cooled Series The I.75-in. bars were forged to flat plates, 0.25 in. thick, from which specimens 0.5 in. wide by 2 in. long were cut. The specimens were pretreated to improve their homogeneity by heating to 1830°F. (I000°C.) for 20 min. and oil-quenching. They were then reheated to 1740°F. (950°C.) for one hour and air-cooled, after

Jan 1, 1942

By R. J. Hafsten, E. S. Davenport, R. A. Grange

THE influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,1 and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely retarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths, Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745°F. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245°F. (675°C.), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarse-grained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite-that is, at temperature levels above about 1000°F. (540°C.)-but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to be presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000°F. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. MATERIAL AND EXPERIMENTAL PROCEDURE The material investigated was a commercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent M0. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By N. Tiner

THE mechanical properties of magnesium-alloy castings are greatly improved by grain refinement, and at present considerable attention is being paid to methods of obtaining fine-grained castings. One method of achieving this end is the use of proper melting and superheating techniques. These have been employed commercially to a great extent, but no comprehensive study of the subject appears to have been published at present. Numerous investigations found in the literature include some reference to superheating techniques, 1-4 and Achenbach, Nipper and Piwowarsky,5 based principally on thermal analysis, ascribe the grain-refining action of superheating to the influence of solid foreign particles or dissolved gases present in the melt upon the course of crystallization. The primary purpose of this paper is to present the principal facts concerning the effect of superheating on grain size of magnesium alloys. Attempts are also made to explain the experimental results in terms of a general hypothesis. The investigations are limited chiefly to common commercial casting alloys. In order to carry on this work, it was necessary to determine the factors influencing grain size and to develop a proper technique for the preparation of samples. The preliminary tests made by the author indicated that the grain size of magnesium alloys resulting from the solidification of a melt is determined by alloy composition, presence of impurities, rate of cooling during solidification, thermal history of the melt and to some extent the structure of the charge used. The rate of cooling is in turn dependent upon the mass of the melt, pouring temperature, and dimensions, properties and temperature of the mold into which the melt is poured. The final grain size of the alloys is still further modified by heat-treatment subsequent to casting. It is not within the scope of the present paper to discuss all of these factors, and it would suffice to note here that when equal amounts of magnesium alloys are prepared from the same alloying materials, melted in graphite crucibles under the same thermal conditions, then cast into graphite molds at a constant temperature, the .resultant solids have the same grain size. By maintaining all other factors constant, it is thus possible to vary thermal conditions of a melt and to examine the grain size of resultant castings. PREPARATION OF SAMPLES AND GRAIN-SIZE TESTING The alloys investigated in this paper were taken from ingots made by Permanente Metals Corporation or prepared by the author with pure carbothermic magnesium and necessary alloying elements. Melting was carried out under a flux in a graphite crucible heated uniformly by an

Jan 1, 1945

By J. J. Kanter

There has been much research and commercial development in recent years in the use of chromium and nickel in steels of various types, including those intended for high-temperature service. By "high-temperature steels" are meant those specifically designed for service at elevated temperatures in steam plants, oil refineries and other industries where high-temperature operations are conducted. This paper is devoted to some preliminary data on the effect of silicon on certain of the most popular chromium-molybdenum steels now being used in quantity by the refining industry and includes a short statement on the influence of copper in steels intended for high-temperature service. Uses of Silicon Next to oxygen, silicon is the most widely distributed and abundant of the earth's substances. Although classed as a nonmetal, it is highly important in the metallurgy of all steels, having been used for years as an efficient and economical degasifier and deoxidizer. Silicon is added to various steels in the form of ferrosilicon, generally at the end of the heat so as to avoid oxidation losses. With acid steels it is added in the furnace (also in the ladle) and generally with basic steels is added in the ladle, so as to avoid reaction with the basic lining through high-temperature acidic reaction with silica, which may be formed by oxidation of the silicon alloy. Several grades of ferrosilicon are available, containing, respectively, 15, 50, 75 and 90 per cent Si. By far the largest tonnage produced is the 50 per cent grade although the 75 and 90 per cent ferro-silicons are used as ladle and furnace additions in the manufacture of steels of high silicon content. The introduction of silicon into steel as an alloying element is well known in connection with high-yield-strength constructional steel for bridges, ships, car construction, etc., and it is also well known as an alloy-

Jan 1, 1938

By J. J. Kanter

There has been much research and commercial development in recent years in the use of chromium and nickel in steels of various types, including those intended for high-temperature service. By "high-temperature steels" are meant those specifically designed for service at elevated temperatures in steam plants, oil refineries and other industries where high-temperature operations are conducted. This paper is devoted to some preliminary data on the effect of silicon on certain of the most popular chromium-molybdenum steels now being used in quantity by the refining industry and includes a short statement on the influence of copper in steels intended for high-temperature service. Uses of Silicon Next to oxygen, silicon is the most widely distributed and abundant of the earth's substances. Although classed as a nonmetal, it is highly important in the metallurgy of all steels, having been used for years as an efficient and economical degasifier and deoxidizer. Silicon is added to various steels in the form of ferrosilicon, generally at the end of the heat so as to avoid oxidation losses. With acid steels it is added in the furnace (also in the ladle) and generally with basic steels is added in the ladle, so as to avoid reaction with the basic lining through high-temperature acidic reaction with silica, which may be formed by oxidation of the silicon alloy. Several grades of ferrosilicon are available, containing, respectively, 15, 50, 75 and 90 per cent Si. By far the largest tonnage produced is the 50 per cent grade although the 75 and 90 per cent ferro-silicons are used as ladle and furnace additions in the manufacture of steels of high silicon content. The introduction of silicon into steel as an alloying element is well known in connection with high-yield-strength constructional steel for bridges, ships, car construction, etc., and it is also well known as an alloy-

Jan 1, 1938

By P. F. Gnirk, J. B. Cheatham

Single bit-tooth penetration experiments under static load were conducted on six rocks at confining pressures of O to 5,000 psi using sharp wedge-shaped teeth with included angles ranging from 30 to 120° In general, the force-displacement curves for all rocks exhibit an increasingly nonlinear and discontinuous behavior with decreasing confining pressure. The confining pressure at which a rock exhibits a macroscopic transition from predominantly ductile to predominantly brittle behavior during penetration vmies from about 500 to 1,000 psi for the limestones to greater than 5,000 psi for dolomite. The correlation between calculated values of force per unit penetration based on plasticity theory and experimental values is quite encouraging, even at confining pressures as low as 1,000 psi A qualitative correlation between volume of fragmented rock per unit energy input for a single bit-tooth and drilling rate for microbits appears to exist over a confining pressure range of 0 to 5,000 psi. INTRODUCTION Laboratory experiments utilizing a small-scale drilling apparatus have demonstrated that penetration rates are reduced considerably as a result of increasing the confining pressure from atmospheric to a few thousand psi?-3 This undesirable situation can, in general, be attributed to a combination of decreased efficiency of chip removal at the bottom of the borehole, increased rock-failure strength, and a possible change in the mechanism of chip generation and rock fragmentation with increasing confining pressure. To more fully understand the principles underlying the last circumstance, it is the purpose of this investigation to experimentally study the mechanism of single bit-tooth penetration into dry rock at low confining pressures and, in particular, to establish the confining pressure at which the penetration mechanism may undergo a brittle to ductile transition for various rock types commonly encountered in drilling. Confining pressure as used here refers to the differential pressure between the borehole fluid pressure and the formation-pore fluid pressure. EXPERIMENTAL PROCEDURE Using an experimental apparatus previously described: a single, sharp wedge-shaped tool was forced under a "statically" applied load into an effectively semi-in finite dry rock sample subjected to a prescribed confining pressure. To prevent the invasion of the con fining-pressure fluid into the pores of the rock sample during penetration, the exposed surface of the rock was jacketed with a layer of silicon putty.* Electrical instrumentation incorporated into the apparatus yielded a graphical plot of force on the tool as a function of penetration or displacement of the tool into the rock during an experiment. During the course of the experimentation the following conditions were maintained constant: (1) pore pressure — atmospheric (i.e., the rock was dry); (2) temperature — 75F; (3) rate of loading — essentially static (approximately 0.002 in./sec); (4) bit tooth — a sharp wedge-shaped tool loaded normal to the rock surface; (5) rock surface — smooth and flat; (6) drilling fluid — hydraulic oil; and (7) maximum depth of penetration — approximateiy 0.1 in. In addition, each experiment was performed on a different rock sample so the rock surface is free of a layer of cuttings and of any previous indentation craters. The influence of the corners of a borehole was neglected, since each rock sample was cemented inta a section of aLuminum tubing to simulate a semi-infinite body. Indentation experiments were made on a sandstone, two limestones, a marble, a dolomite and a schist with a 60' bit-tooth over a range of confining pressures from atmospheric to 5,000 psi and at a constant confining pressure of 1,000 psi for a variety of bit-teeth with angles ranging from 30 to

Jan 1, 1966

By William E. Harris

Time and experience have demonstrated that by means of the Waelz process zinc, lead, cadmium, arsenic, antimony, bismuth and tin can be volatilized satisfactorily. In this way difficult gold ores are being treated to allow for the recovery of the precious metal. Iron ore containing zinc is being treated to remove the zinc and recover the iron. In Germany, thallium is being recovered in commercial quantities from the zinc oxide fume; indium, germanium and gallium are also concentrated to a degree warranting recovery, even though these rare metals are only recognizable in the ore by means of the spectroscope. The physical, chemical or mineralogical condition of the raw material affects very little the applicability of the process. The name Waelz is derived from the German word Waelzen, meaning a "trundling motion," which very aptly describes the movement of the charge through the slowly rotating kiln. The recovery of zinc and lead by volatilization in a rotary kiln has its origin in a process patented in 1910 by Edward Dedolph, of British Columbia. The Dedolph patent was taken over by the Metallgesell-schaft of Frankfurt-on-Main, Germany, which in cooperation with the Griesheim-Elektron, now a part of a large industrial combine, introduced certain improvements (Ohlmer, Specketer patents), but without bringing the process to a state suitable for large-scale operations. The war temporarily stopped all work on the process, and it was not until after the war that the Krupp Grusonwerk, of Magdeburg-Buckau, Germany, quite independently of the Metallgesellschaft, instituted research work in this field of metallurgy, which in 1923 led to the Waelz process proper. The Krupp Grusonwerk and the Metallgesellschaft A.G. later on collaborated, and by their joint efforts further developed and perfected the Waelz process, which they are marketing together as "Waelz-Gemeinschaft." The process is capable of treating a varied type of material; for instance, oxidized and sulphide zinc ores, calamine (zinc carbonate ore) waste dumps, jig tailings, jig slimes, table concentrate slimes, brass ashes, zinc-bearing iron ores (where the iron sinter is the real objective and the zinc oxide a by-product), electrolytic-zinc leach residues, zinc muffle residues and works sweepings, lead-furnace slags, tin ores and slags, anti-

Jan 1, 1937

INCREASING realization that pouring and ingot-mold practices involve many factors of fundamental importance to ingot quality and general steel-mill operations has caused these phases of steelmaking to become major concerns of operators and metallurgists engaged in control of quality and costs. Methods of pouring steel from the ladle into the ingot molds have some direct effects on ingot quality. The mold itself governs solidification and dimensions of the ingot and in so doing exerts some very tangible influences not only on ingot quality but also on product yields and general steel-mill processing. In addition, practices are employed' in the handling of molds during daily open-hearth operations that are important to quality and production costs. Therefore, pouring and mold practices must be considered highly specialized and important steps in steel-mill operations. MOLD DESIGN Mold design is difficult to discuss in a precise manner because it varies greatly throughout the industry, both in theoretical concepts and practical application, and few well developed data are available. Most ingot molds are designed to meet conditions peculiar to a given plant wherein quality standards are dictated by end-use requirements, which may differ considerably, even for the same grade of steel. The mold designer must also consider the equipment available to process ingots and the product obtained from them. Such equipment, used for stripping, heating, blooming and finishing operations, is seldom, if ever, exactly the same in any two steel plants. Thus, pronounced contrasts in mold designs can be expected to continue, even among plants making strictly comparable types of product, particularly because some producers are just beginning to realize the benefits possible from specialized designs. Certain fundamentals are used in mold design but even these

Jan 1, 1951

By O. D. Sherby, J. L. Lytton, C. R. Barrett

Randomly oriented polycryslalline copper of 99.995 pcl was tested in tension at temperatures of 626o, 496o, and 406o. The gvain-size mnge investigated was from 0.03 to 0.7 mm. Grain sizes were produced by two techniques: 1) varying the amount of prior cold work and the amealing time at constant annealing temperature so as to obtain various vecrystallized grain sizes with minimum grain growth, and 4 holding the prior cold work constant while varying the annealing time or temperature so as to obtain varying grain sizes by grain growth. Polycrystalline samples (grain size of 0.03 mm) with a strong. [001](100) texture were also studied. The relationship between the steady-state creep rate, Es, and pain size was found to be the same indepentent of the technique used to prepare the various grain sizes. For specimens with grain diameters above about 0.1 mm ea zuas esse)ztiallj~ independent of grain size, while for smaller grain diameters Cs increased slightly with decreasing grain size. Strongly textured polycrystalline copper, which contained low-angle grain boundaries, exhibited steady-state creep rates that were slightly lower than those observed in randomly oriented copper, of the same gain size. The results are explained by conside?%ng- the contribution of grain boundary shearing to the total strain and the effect of grain size on the resulting creep substructure. EXPERIMENTAL observations concerning the influence of grain size on steady-state creep rates are varied and oftentimes conflicting. Numerous early investigators found that an increase in the grain size resulted in a decrease in the high-temperature steady-state creep rate, i,.'-" Other workers have foundthat ef decreases with increasing grain size up to some optimum grain size and then increases with a further increase in grain size.'- '' It has been suggested that es, decreases with an increase in grain size only because the range of grain sizes studied normally lies to the left of the grain size for optimum creep resistance. However, sherbyl2 and Feltham and his co-worker13, 14 have found that even for small grain sizes 2, does not always decrease with an increase in grain diameter but may be proportional to the square of the grain diameter. A possible explanation for the different creep rate-grain size relationships which have been observed is that in most experimental studies different grain sizes have been prepared by annealing at various temperatures. For metals in which the impurity concentration is high (greater than about 0.1 at. pct) this type of

Jan 1, 1968

By C. S. Matthews, M. Prats, R. I. Jewett, J. D. Baker

By mathematical analysis it was found that injectivity history of a uniform five-spot pattern can be calculated by rather simple formulas. These calculated injectivities were found to agree rather well with injec-tivities measured in a potentiometric analog. With this as a basis, a simple method was finally developed which allows prediction not only of rate of injection but also of rate and kind of production at the production well, for a uniform five-spot. Using this method formulas for the eflective injectivity and production behavior of a waterflooded reservoir having a wide range in permeability can be calculated by considering that the reservoir consists of several layers, each having a uniform but different permeability. Rather good agreement is shown by a comparison of the observed production history of a field in the Illinois basin and that calculated by the methods just described. INTRODUCTION The importance of being able to predict the injection rates for a water flood is well known, for upon injection rate depends the life of the flood, the size of pumping and treating facilities, and the rate of oil recovery. One method of determining rates of injection is through a pilot flood. However, it appears that even if a pilot flood is resorted to, a theoretical method for calculating injection rate will be valuable in extending field results to times after inter- ference and to locations of other five-spots. It is also important to be able to predict the production history of a flood. Such prediction must generally be done by theoretical means, since in general a small pilot flood will not furnish much quantitative information in this regard because of the distortion after oil-bank interference. Methods for predicting the behavior of five-spot water floods have been proposed by Yuster and Cal-houn' and by Hurst.? However, these methods do not consider the effect of the mobility of the different fluids in the reservoir. Other investigators3,4,5,6 have determined the effect of the water-to-oil mobility ratio on the production history by means of different experimental techniques. Most of the published work applies to homogeneous sand bodies, does not provide information for determining the injection requirements of a flood, and seldom considers the rate of build-up of the oil bank as it fills up the partially depleted reservoir.* The present work was undertaken because of the lack of predictive method which takes into account mobility ratio and the rate of buildup of oil bank resulting from the void space in a partially depleted reservoir. As water is injected into the reservoir, which contains oil, water, and gas in macroscopically homogeneous saturation, it forms several banks ahead of the injection well. In each bank or region there is assumed to be only one mobile phase—water in the water bank, oil in the oil bank and gas in the gas region. The saturation in each region and a plan view of the banks are shown in Figs. 1 and 4, respectively. FACTORS AFFECTING INJECTION AND PRODUCTION RATES Results in this report are determined as functions of the three parameters, F, M, and M, , and of a fourth parameter, r,/L** which relates the size of the well to the flood spacing. The parameter F is the displacement factor defined by Hurst in Ref. 2. It determines the rate of build-up of oil bank as it fills up the partially depleted reservoir. When gravity effects are neglected, the four parameters just given are sufficient to describe the waterflood behavior for horizontal and homogeneous reservoirs having incompressible liquids. Definition of InjectIvity The dinlensionless injectivity (or injection rate) used in this report is defined by

By C. R. Whitney, G. N. Maniar, D. R. Muzyka

Previous results have shown that Pyromet 860, an Fe-Ni-base heat-resistant alloy, is stable at temperatures as high as 1500°F for aging times as long as 100 hr. This Paper describes the results of long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Times as long as 37,660 hr were employed. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffraction, and microprobe techniques. phase, containing cobalt, nickel, and molybdenum, was detected after extended exposures from 1200" to 1400°F and careful study was performed to describe the kinetics of its formation in this alloy. µ phase formation apparently has little effect on the elevated-tem-perature properties of Pyromet 860. For times as long as 500 hr at 1300°F and below, with µ phase present, m significant effects on ambient temperature properties were noted. For longer times at 1300°F and after 1400°F exposure, the effects of u phase on ambient temperature tensile strength properties are not clear due to y' effects and grain boundary reactions. Electron-vacancy, N,, numbers were calculated using different methods described in literature and correlated with the present findings. In the selection of alloys for use in gas turbine applications, structural stability ranks as a primary criterion. High-temperature strength and cost are also of major concern. With these factors in mind, Pyromet 860 alloy, an Fe-Ni-base superalloy was designed. This alloy combines the cost advantages of Fe-Ni-base alloys such as A-286, 901, and V-57 with improved strength and structural stability'1,2 and no tendency to form the embrittling cellular 77 phase. A previous study3 reported on the stability of Pyro-met 860 at temperatures from 1375" to 157 5°F and times up to 100 hr. That study showed that the y' precipitates increased in size and separation and decreased in number with an increase in time or aging temperature. No deleterious phases were found to occur. In the present work, samples from four production heats were subjected to long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Various heat treatments were used on the starting samples and tests were run up to 37,660 hr. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffrac- tion, and microprobe techniques. Electron vacancy numbers, Nv , calculations were made by TRW.4 Experimental results are correlated with the Nv data used to predict occurrence of intermetallic phases such as a phase. EXPERIMENTAL PROCEDURE Mechanical Tests. Material for the present study came from four production size heats of Pyromet 860 alloy, weighing from about 3000 to about 10,000 lb. All of these heats were made by vacuum induction melting plus consumable electrode vacuum remelting. The nominal analysis for this alloy is compared with the actual analysis of the four heats in Table I. Sections of these heats were forged to 9/16-in. round bar,3/4-in. square bar, 3-in. round bar, 4-in. square bar, and a gas turbine blade forging about 16 in, long, about 6 in. wide, and weighing about 20 lb. In general, all forging of this alloy is done from a 2050°F furnace temperature. Longitudinal test blanks were cut from the centers of the smaller bars, from mid-radius positions for the 3- and 4-in. bars, and from the air foil of the gas turbine blade and heat-treated according to the procedures outlined in Table 11. Heat treatment A is the "standard treatment" recommended for this alloy for best all-around strength and ductility. Heat treatment B is a modification of treatment A for improved tensile strength at moderate temperatures. The treatment coded C was designed for treating large sections according to a procedure previously described.' Heat treatment D was developed to yield optimum stress relaxation characteristics at 1050°F for a steam turbine bolting application. After heat treatment, the test blanks were machined either to plain bar creep specimens with a gage diameter of 0.252 in., to combination smooth-notched stress-rupture bars with a plain bar diameter of 0.178 in. and a concentration factor of Kt 3.8' at the notched section, or to notch-only specimens. All specimens conformed to ASTM requirements. Metallography. Most of the creep-rupture tests were continued to failure. A few bars were fractured as smooth or notch tensiles after creep-rupture exposures. After fracturing, ordinary metallographic sections were made primarily in gage areas adjacent to fractures to represent a "high-stress" region and through specimen threads to represent a "low-stress" region. All metallographic sections were made in a longitudinal direction with respect to the test specimen axes. For optical microscopy, the samples were etched in glyceregia (15 ml HC1, 5 ml HNO,, 10 ml glycerol). For XRD analysis, the phases were extracted electrolytically in two media: 20 pct &Po4 in H20 for selective extraction of y' and 10 pct HC1 in methanol for carbides and other phases.

Jan 1, 1970

By A. U. Seybol

Eight binary iron alloys were examined after ion nitriding experiments to determine the behavior of the following elements: Al, Mo, Mn, Si, Ti, V,Cr, and C. Only Al, Cr, Ti, and V additions caused hardening in binary iron alloys. A few steels were examined to see the effect of Cr, Cr + Al, Cr + Ti, and Cr + V. It is suggested that a useful new class of ni-triding grade steels might be those containing about I pct V. The nitriding of steel, first described by Fry1 about 45 years ago, rapidly attained commercial application with very little knowledge of the fundamentals involved. While Fry,' in describing the status of nitriding in 1932, apparently correctly postulated hardening by precipitated nitrides, the details of the nitriding process were not understood, nor has the situation changed much since that time. It is also interesting to note that the compositions of some typical nitriding steels given by Fry at that time have changed little in the intervening years. Currently used nitriding steels owe their surface hardening to either chromium (as in 4340 steel) or aluminum plus chromium as in the Nitralloy grades, where both CrN and AlN appear to contribute to harden ing. Titanium additions have been studied experimentally, but thus far titanium steels have not won wide commercial acceptance. This subject will be expanded later. The orthodox ammonia nitriding process has been reviewed very adequately many times as in Jenkins3 and Case and VanHorn,4 and their is no need to outline the process here. Ion nitriding is not as well-known, although there have been several descriptions5-9 of the process given, sometimes with comparisons with the ammonia process. Most of these papers are primarily concerned with a description of the equipment, or of the physics or electrical engineering aspects of ion nitriding, but Noren and Kindbom9 gave the results of a metallurgical investigation using both processes. In brief, ion nitriding is carried out in a vacuum chamber from which the air is exhausted and replaced by a N2-H2 mixture, typically containing 10 to 20 pct N2, at about 5 to 10 torr pressure. While ammonia gas has also been used in ion nitriding, there is no evidence that ammonia makes any improvement in the ion nitriding process. A few hundred volts dc is applied between the grounded container wall (positive) and an insulated center post supporting the work (negative) to be nitrided. A glow discharge is created in the ionized gas, accelerating positive nitrogen ions to the work. These ions contain enough energy to form the normally unstable Fe4N "white layer", thus establish- ing surface nitrogen solubility characteristic of the a Fe/Fe4N equilibrium. This creates a substantial concentration gradient, driving dissolved nitrogen into the steel. The temperature employed is in the same range (around 500" to 550°C) as in ammonia nitriding, but because of factors which are not understood at present the nitriding time is ordinarily considerably reduced in ion nitriding. Other advantages have been cited,9 but it is not the purpose of the present work to contrast the two processes. The present objective was to examine the behavior of binary iron alloys during ion nitriding with respect to the microstructure, hardness level, and depth, and to examine some of these factors in steels as well. In this way it was hoped to be able to find out something about the individual role of these elements in steels. While all the work was done by ion nitriding, there seems to be no reason why any conclusions reached would not equally apply to ammonia nitriding, excepting only the kinetic aspects of the process. Another objective was an exploration of the critical-ity of the ion nitriding variables: gas composition, pressure, temperature, and time. EQUIPMENT AND MATERIALS The equipment used was substantially as described by Jones and Martin.8 The vacuum tank was about 12 in. in diam by about 18 in. high, and consisted of water-cooled stainless steel, with a single small window at the top for viewing inside. This sat on a heavy mild steel base equipped with the main pumping port, pressure control port, and vacuum gaging. A series of variable resistances was interposed between the glow discharge and a large-capacity -40 amp variable primary transformer feeding a 1000-v transformer, but 600 v were about the maximum ordinarily used. With the small l-in.-round, 4-in.-thick discs used for nitriding, the electrical load was usually about 500 v at 0.8 amp. The specimen temperature was controlled by a stainless-steel sheathed chromel-alumel couple, whose junction was in the steel stool upon which the flat discs were placed. These were ground through 400 Sic paper. Cycling of the temperature controller caused -0.2 amp variation in ion current, providing an ample control band. The binary iron alloys were made from vacuum-melted hydrogen-deoxidized electrolytic iron and alloys of 99.9 pct purity. Cast ll-lb-square tapered ingots were forged and hot-rolled to about 11/4-in.-diam rounds. Discs of 1/4 in. thickness by about 1 in. diam were machined from the rods for nitriding specimens. The following alloys were prepared: 1 pct each of Mn, Mo, Cr, Ti, Al, V, Si, and an Fe-0.8 pct C alloy. EXPERIMENTAL VARIABLES Of the variables total gas pressure, nitrogen partial pressure, temperature, and time, only nitrogen partial pressure was found to be critical to the operation. A critical nitrogen partial pressure was found corre-

Jan 1, 1970

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By Thomas M. Price

Sand production for use in hydraulic concrete is probably the most important element affecting the physical characteristics of the resulting concrete in the opinion of most engineers, aggregate producers and contractors of today, who are engaged in the effort to produce stronger concrete per unit of cement used. Their opinion is based on both laboratory and field results. In the past, proper cement production has been the object of most of the study given this subject and while it is still studied by the extensive and well equipped laboratories that are a part of every cement mill, as well as by all governmental laboratories, at the present time the object of most of these studies has been in the field of low heat and quick setting qualities rather than the effect on the strength of the concrete. It is recognized that concrete must have two important qualities; namely, workability with the least water possible, and uniformity. These qualities have been accepted as axiomatic and possible to obtain if the foreman in charge knew his business. Now, however, with concrete produced by plants that mechanically weigh and chart all the ingredients, including water, of a batch of concrete, the foreman cannot cut and fit his aggregates, cement and water to fit his own desires and the secret of the important qualities of workability and uniformity are found to lie largely in the sand, hence the attention given its production at the present time. With this condition in mind the engineers of the United States Bureau of Reclamation and the Six Companies Incorporated in designing the plant for producing the aggregates for the Boulder Canyon Project included every possible means for the production of a sand of a constant and acceptable fineness modulus as well as a constant moisture content, and for attaining these results with as few detrimental ingredients, like silt and vegetable matter, as possible. This aggregate plant (Figs. 1 and 2) is in Hemenway Wash, 7 miles north of Boulder City. It is 4 miles upstream from the low-level mixing plant. At this screening plant 8,234,000 tons of raw aggregate are being

Jan 1, 1934

By G. S. Brooks

WITH the gradual depletion of the natural-gas pools of the Kansas district, together with the uncertainty of further cheap fuel developments, some. of the western zinc companies turned to the coal fields, attracted by their permanency and the 'success of the Matthiessen & Hegeler Co. and the Illinois Zinc Co. Being then confronted with the problem of using a relatively high-priced fuel, although the ultimate' supply was very great, the fuel economies of the kilns and furnaces became of far more importance, and the more modern equipments, as a result, embodied distinct gads in this phase of the business. In addition, there have been some pronounced advances in the actual making of gas from these coals. Increased efficiency in gas making has contributed its share to lowering costs and those plants located in the higher priced fuel districts have probably been obliged to study these economies somewhat more closely. Naturally, many beneficial changes have resulted in both practice and apparatus in these sections. On, certain western coals, for instance, the actual saving in fuel consumption has been 50 per cent. By this is meant that, where about 1.75 tons were burned to smelt 1 ton of oxidized ore, 0.7 to 0.9 ton is now required. While comparisons by W. R. Ingalls1 of fuel economies in smelting in this country and Germany before the war may, in general, be correct, they do not appear to-do justice to the more progressive. American practice. It is doubtful whether German plants were substantially bettering these fuel ratios. Data furnished by Bender and Frams do not afford records averaging less than 0.9 ton coal per ton ore on materials from 40 per cent. to 50 per cent. zinc.

Jan 9, 1919

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells' effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer's Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding' showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,' the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966

By Harrison, Henry Fay

The study of an entirely new series of alloys may be undertaken from a desire to obtain knowledge applicable to the perfection of industrial alloys, or merely to test certain theoretical considerations. In the case of antimony-tellurium alloys, the theoretical side only is at present important; but it is hoped that the results of this investigation may have some industrial value, at least indirectly, by furnishing one more example for comparison when studying commercial alloys. The statement is found in various places that antimony is isomorphous with arsenic, bismuth and tellurium; but very little experimental evidence has been offered in support of this assumption. All four metals crystallize in rhombohedra, and the ratio of the axes a: c is approximately the same—which seems to indicate, but does not prove, their isomorphism. The close association of these metals in minerals also seems to indicate that they are isomorphous. There are, however, certain differences in their properties which render this coriclusion somewhat doubtful, and it is therefore desirable that inde-

Jan 1, 1902