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By E. P. Mathewson

THE experiments described in this paper were made at the Washoe Reduction Works, Anaconda, Mont., for the purpose of determining the relative speed of elimination of the iron, sulphur and arsenic during the process of bessemerizing copper-mattes. The samples were taken from a horizontal "barrel" converter, 8 ft. in diameter and 12 ft. 6 in. long, having an average charge of 9 tons of matte, and blown with a 16-1b. air-pressure. All samples were taken with the blast on, turning the converter from its normal blowing-position to nearly verti¬cal, so that a conical mold, with a long handle attached to a horizontal rod, could be introduced from a platform above the converter into the mouth of the converter and a sample taken. The difficulties of taking a sample with the blast on are appar¬ent, and the irregularities of the lines in Figs. 1, 2 and 3 can be readily accounted for by the amount of slag in the samples. On the whole, the plotting of the results gives comparatively uniform lines, considering the conditions. The samples were taken by the regular sampling-force of the works at 10-min. intervals, as shown in Tables I., II and III, which also give the chemical analysis of the samples so taken. The test shown in Table I. was made with a new converter; that of Table II with a converter that had made three charges and had been cleaned out; that of Table III with a converter that bad blown one charge to white metal, and had then been " washed " out and used for the test. In plotting these results, it was necessary to take, as a basis, the percentage of copper in the samples. This basis does not exactly represent the true condition, since the volume is constantly decreasing and a certain quantity of copper passes into the slag, but it is as near as can be obtained in practice. Take, for instance, in Table I., the sample No. 5, which shows : Cu, 59.9;

Jan 1, 1907

By M. V. Nevitt

THE Cr,O-type, or P-tungsten, structure having the space group (Oh2— Pm,n) is one of the most widely occurring structures found among the intermediate phases involving transition metals. Including the phases reported here for the first time, the total number of these A,B phases now known is 39. Greenfield and Beck' have correlated the lattice parameters of these phases with the Goldschmidt radius of the close-packed chains of A atoms. Laves' discussed the apparent size of the A and B atoms in this structure. Gel1er" proposed a scheme for reproducing the lattice constants of the phases by the use of a list of effective C.N. 12 radii for the component elements. Reported here is a survey of the A,B combinations which appeared favorable for the stability of the Cr,O-type phase but which, at the time the investigation was begun, either had not been reported upon or had conflicting reports as to the existence of the structure. Seventy systems were investigated, and 8 Cr,,O-type structures were found. Six of these also were reported by other investigators in the interval between the start of this investigation and its completion. This survey yielded information as to the influence of the relative sizes of the A and B atoms on the stability of the phase and, for the various families of Cr,O-type phases, the effects of the sizes of the A and B atoms on the lattice constant. Likewise, a somewhat clearer picture of the connection between the position of the A and B elements in the Periodic Table and their Cr,O-type phase-forming tendencies has become apparent. Experimental Procedure Alloys were prepared in the form of arc-melted 3-gram buttons in all cases where the vapor pressure of neither component was high enough to cause

Jan 1, 1959

By J. W. Mitchell

Season cracking of 70-30 cartridge brass cases of small arms and artillery ammunition has been under investigation at the Frankford Arsenal for many years. The nature of this stress-corrosion failure has been found to be intergranular. Much of this work, however, has been directed toward improvements in method of manufacturing the cases so as to reduce the tendency to season crack and little progress had been made toward finding the source of the chemical agent producing the inter- granular corrosion. Ammonia has been shown to produce season cracking in brass and is known to be present in certain atmospheres, particularly industrial, in sufficient concentration to cause cracking. However, in the case of small arms ammunition, the hypothesis that atmospheric ammonia is the cause will not hold, since small arms ammunition is hermetically sealed during storage and yet occasional lots are found to have cracked after 3 to 5 yr. storage. Much of the early study of season cracking in small arms ammunition was done by Nicholas H. Murdza of the Frank- ford Arsenal. In 1936, he suggested that the corrosive agent might be one of the decomposition products of smokeless powder and mentioned nitrogen oxides specifically. Then in 1937, Murdza suggested that the breakdown of smokeless powder in storage resulted in the formation not only of nitrogen oxides but also ammonia

Jan 1, 1945

By J. J. Pye, J. B. Drew

Mzasurements of the surface diffusion coefficients of metals have been made. Diffusion profiles for the Ag-Ag system were obtained by means of a radioactive point source and a precision auto-radiographic technique. The activation energy for silver self diffusion (=8.1 kcal per mole) is lower than that previously reported (-10 kcal per mole) on poly crystalline wire by Nickerson and Parker. The bresent data indicate an effect due to parasitic volume diffusion at temperatures above 500°C. RELATIVELY few measurements have been made of the surface self-diffusion coefficients of metals. Nickerson and arker' measured the diffusion of silver over the surface of poly crystalline wires and estimated that the activation energy was 10.3 kcal per mole. Winegard and chalmers2 carried out measurements on both polycrystalline and single crystal surfaces but did not report a value of the activation energy. They found, however, that at temperatures between 250" and 400°C the diffusion coefficients were on the order of lo-' sq cm per sec and that there was an acceleration of the migration of silver on the polycrystalline sample when a change of surface shape occurred. Winegard and Chalmers used an autoradiographic technique, hereafter designated ARG, and Nickerson and Parker used a surface scanning geiger counter in order to determine the diffusion profiles. More recently, Hackerman and simpson3 measured the surface self-diffusion coefficient of copper at a single temperature (750°C), and the value of the diffusivity (- 10-5 sq cm per sec) is in agreement with that given by jostein from his thermal grooving measurements. This paper reports the results of an investigation of the surface self-diffusion coefficients of silver over a large temperature range and describes the adaptation of autoradiographic (ARG) techniques for the determination of diffusion profiles obtained from a radioactive point source. EXPERIMENTAL PROCEDURE The experimental procedure is a modification of the method employed by Hackerman and simpson3 in their measurements on copper. A brief description of their technique is as follows: A radioactive needle which sinters to the surface during the diffusion an- neal serves as the source of diffusing atoms. After the diffusion run the needle is removed and the surface is scanned with a shielded counting arrangement. The diffusion profiles reported in this paper were obtained by a modification of the above procedure which employs a precision ARG technique. Previous investigations in this laboratory and elsewhere51B have shown that under carefully controlled developing conditions and by the use of calibration sources a linear relation exists between the concentration of the isotope and the photographic density for values below unity. The use of ARG under these conditions has advantages over the counter scanning method in that cumbersome shielding and requirements for great mechanical precision of the scanner are eliminated. Also the ARG gives a complete picture of the surface which is advantageous in studies of anisotropic diffusion. A recording microdensitometer having a 0.1 p wide slit was employed. At low temperatures the disturbing effects of subsurface radiations are negligible. The diffusion anneals are carried out in the cell shown in Fig. 1. The needle is formed by grinding down a 1.0 mm rod of high-purity silver until a tip of 0.2 mm radius or smaller is formed. This tip is plated withA"' which becomes the source of the diffusing atoms that are detected by ARG. The needle carrier and the crystal holder, Fig. 1 are constructed of quartz and ports are provided in the holder pedestal which allow free vapor circulation ((2.0 oz) and the carrier apron fits snugly over the crystal holder cap, insuring that the needle does not move and scratch the surface. Temperatures are provided by a stabilized tubular furnace which can be quickly positioned around the cell, thus bringing the crystal up to temperature in a time that is short compared to the diffusing times. The diffusion anneals range from 2 hr for the high-temperature samples to about 25 hr for those at the lowest temperature. The possibility of vapor transport of the radioactive metal as a contributing factor in the diffusion profile was investigated in two ways. One method was to suspend the needle directly over a dummy sample, raise the temperature, for periods of time equal to the diffusion times, and then take an auto-radiograph of the surface. Negligible radioactivity appeared. In the second method a thin slot in the crystal face on one side of the source provided a "cong path" for surface diffusion. If evaporation was the primary source of surface atoms the region of radioactivity around the source would be symmetrical. This was not the case. The profile dipped abruptly at the edge of the slot but on the other side of the source the usual diffusion profile appeared.

Jan 1, 1963

By John R. Green

Rotary kilns, varying in construction, are used in a variety of processes. Products differ and operating conditions vary accorcling to economic requirements. All of these variables influence the degree of instrumentation and type of control necessary or profitable to install. Products fired in rotary kilns are the results of combined temperature and time treatment and the interrelation of these two factors should be kept constantly in mind in the perusal of this paper. Measurements of Kiln Temperature The securing of proper temperatures within the rotary kiln, either of the charge or of the kiln lining in the high fire zone, are basic objectives of kiln operation; therefore the measurement of these high-temperature conditions merits first consideration. For these measurements, radiation pyrometers, properly designed and protected, have proved adequate, particularly where records ox automatic control are desired, while Optica1 pyometers may serve as portable indicators. Light-sensitive devices or photoelectric cells in this service are capable of producing records as well as certain forms of automatic control. High-temperature measuring devices for rotary-kiln work should have the measuring unit protected from dust, as a continued accumulation of deposit would lower the readings. Fig. 1 shows a typical application of radiation equipment to a rotary kiln, mounted far enough away from the sighting hole through the kiln hood to be protected From puffs or stingouts and with a sighting tube having a series of settling chambers, to prevent dust from reaching the lens. Although dust conditions inside the kiln itself usually fluctuate considerably and have their effect upon the readings at that moment, such effects are not cumulative and show as a continuous fluctuation in the temperature indicated, provided the radiation unit and recorder are responsive to such slight and rapid temperature fluctuations. The ambient temperature to which a measuring unit is subjected fluctuates from possibly 0" to over zoo°F., therefore these changes should have no effect upon the final reading or upon the life of the measuring unit. A very narrow sighting angle is desirable, so that measurement of temperature may be made as far as possible into the high fire zone without effect of the flame temperature. There should some sighting means on the measuring unit, so that the proper field may be viewed. Measurement of wall temperature taken at a point where the charge has just left the wall is less affected by dusting conditions than when taken elsewhere. Factors influencing Temperature Table I gives an outline of the factors that produce kiln temperatures and comments on the possibility of measurement and control. Of greater number and of varied influence are the factors that control when, where and how the heat is delivered to the kiln, the type of flame and the rate of

Jan 1, 1942

By John R. Green

Rotary kilns, varying in construction, are used in a variety of processes. Products differ and operating conditions vary accorcling to economic requirements. All of these variables influence the degree of instrumentation and type of control necessary or profitable to install. Products fired in rotary kilns are the results of combined temperature and time treatment and the interrelation of these two factors should be kept constantly in mind in the perusal of this paper. Measurements of Kiln Temperature The securing of proper temperatures within the rotary kiln, either of the charge or of the kiln lining in the high fire zone, are basic objectives of kiln operation; therefore the measurement of these high-temperature conditions merits first consideration. For these measurements, radiation pyrometers, properly designed and protected, have proved adequate, particularly where records ox automatic control are desired, while Optica1 pyometers may serve as portable indicators. Light-sensitive devices or photoelectric cells in this service are capable of producing records as well as certain forms of automatic control. High-temperature measuring devices for rotary-kiln work should have the measuring unit protected from dust, as a continued accumulation of deposit would lower the readings. Fig. 1 shows a typical application of radiation equipment to a rotary kiln, mounted far enough away from the sighting hole through the kiln hood to be protected From puffs or stingouts and with a sighting tube having a series of settling chambers, to prevent dust from reaching the lens. Although dust conditions inside the kiln itself usually fluctuate considerably and have their effect upon the readings at that moment, such effects are not cumulative and show as a continuous fluctuation in the temperature indicated, provided the radiation unit and recorder are responsive to such slight and rapid temperature fluctuations. The ambient temperature to which a measuring unit is subjected fluctuates from possibly 0" to over zoo°F., therefore these changes should have no effect upon the final reading or upon the life of the measuring unit. A very narrow sighting angle is desirable, so that measurement of temperature may be made as far as possible into the high fire zone without effect of the flame temperature. There should some sighting means on the measuring unit, so that the proper field may be viewed. Measurement of wall temperature taken at a point where the charge has just left the wall is less affected by dusting conditions than when taken elsewhere. Factors influencing Temperature Table I gives an outline of the factors that produce kiln temperatures and comments on the possibility of measurement and control. Of greater number and of varied influence are the factors that control when, where and how the heat is delivered to the kiln, the type of flame and the rate of

Jan 1, 1942

By Willard P. Ward

HAVING been engaged during the past year in the manufacture of ferro-manganese in a blast furnace, I have imagined that some further information on this subject might be of interest to that large number of members of the Institute who are engaged in the iron and steel industries. The great question of the economical production of good steel, ingot metal, or homogeneous iron (we scarcely know now what to call it) from good materials, and at reasonable prices, has, thanks to the intelligence and energy of a few American engineers, been successfully solved in this country. Nearly all first-class railroads, and many that would riot rank so high, have adopted the Bessemer rail. Martin boiler-plates are rapidly gaining ground, in competition with

Jan 1, 1877

By Willard P. Ward

Having been engaged during the past year in the manufacture of ferro-manganese in a blast furnace, I have imagined that some further information on this subject might be of interest to that large number of members of the Institute who are engaged in the iron and steel industries. The great question of the economical production of good steel, ingot metal, or homogeneous iron (we scarcely know now what to call it) from good materials, and at reasonable prices, has, thanks to the intelligence and energy of a few American engineers, been successfully solved in this country. Nearly all first-class railroads, and many that would not rank so high, have adopted the Bessemer rail. Martin boiler-plates are rapidly gaining ground, in competition with

By R. F. Hehemann, D. J. Cometto, G. L. Houze

The w transformation in the Zr-Nb system was studied using X-ray diffraction, dilatometric, re-sistornetric, hardness, and metallographic techniques. w forms in a diffusionless, completely reaersible manner on quenching and in a diffusion-controlled manner- on aging. The temperature at which w begins to form on quenching was determined as a Junction of composition and was found to decrease with increasing solute content. w formed bv aging establishes a metastable equilibrium with an enriched ß phase. The ß/w + ß transus has been determined for this metastable equilibrium and employed to rationalize retrogression and reversion phenomena observed in these alloys. The decomposition mechanism is discussed in terms of a gradual or continuous transformation from ß to the w state. BETA- stabilizing alloying elements lower the MS temperature of the martensitic bcc (ß) to hcp (a') transformation in zirconium and titanium alloys. In certain titanium alloys, a lower symmetry modification of the martensitic structure, termed (a"), also has been reported.1,2 These martensitic transformations are suppressed when the amount of the ß-stabilizing element exceeds a critical level. However, the high-temperature ß phase cannot be quenched to room temperature without change. At alloy contents just above the critical level, |ß trans-forms to the w phase when cooled rapidly.3-6 The amount of w in quenched alloys is reduced by increasing alloy content, and this phase virtually disappears above a critical composition.5 In addition to the transformation during cooling, w also can be formed by aging ß at temperatures below approximately 500°C, and significant alloy enrichment of retained 13 accompanies the isothermal transformation.1-8 The structure of LC is closely related to that of the ß from which it forms.9-15 The bcc (ß) lattice can be generated using a hexagonal cell with three atoms located at (000) and ±(2/3, 1/3, 1/3). This cell has an axial ratio of 0.612 and is oriented with respect to the cubic cell such that (0001)H (111)C and [1120]H [101]C. Consequently, there are four possible orientations of the hexagonal cell, associated with the four (111) planes of the bee lattice. Formally w can be obtained from 0 by allowing the two atoms at the ±(2/3, 1/3, 1/3) positions to approach the coordinates ±(2/3, 1/3, 1/2) and there are four equally probable orientations of w for each 0 grain. In titanium alloys w retains the cubic axial ratio of 0.612" and hence also can be indexed as triply cubic, but this is not the case for aged Zr-Nb alloys where w is clearly hexagonal with an axial ratio of 0.622." The lattice parameters and atomic positions of w depend on thermal history and alloy content. The atomic positions (000), ±(2/3, 1/3, 1/2) provide reasonable agreement between calculated and observed diffracted intensities for w in the fully aged condition.10,14 In the quenched condition, on the other hand, the atoms appear to be displaced from the central plane12,13,15 and assume positions ±(2/3, 1/3, Z = 0.42-0.48) rather than ±(2/3, 1/3, 1/2). This results in a structure with trigonal rather than hexagonal symmetry. The readily detectable parameter and axial-ratio changes of w in Zr-Nb alloys make this system especially attractive for studying the structural changes that occur in the formation and aging of w. Particular attention in this investigation has been directed to the relationship between the structure of w in the quenched and aged conditions, and to certain aspects of the reaction kinetics. MATERIALS AND PROCEDURE Zr-5, 12, 17.5, and 25 pct Nb alloys were prepared by a double arc-melting practice, encased in stainless-steel cans and hot-rolled to 1/8-in.-thick sheet.* Charged weights have been employed for the niobium contents and interstitial analyses are reported in Table I. Dilatometric, X-ray diffraction (filtered CuK, and MoK, radiation), metallographic, and hardness techniques have been employed to follow the transformations during isothermal and quench-aging heat treatments. In quenched specimens, the electrical resistivity also was studied. Betatizing was conducted for 1 hr at 900°C. With the exception of the isothermal dilatometric studies, samples were

Jan 1, 1965

By Howard A. Meyerhoff

AS a source of mineral wealth, the larger islands of the West Indies have never had an enviable reputation. The Spaniards took possession of them in the sixteenth century hopeful that they would yield gold; but it was not long before they knew the rather rigid limitations of Antillean gold production and were seeking-and finding ---richer deposits of the precious metals in Mexico and on the west coast of South America. Although a great deal of wealth changed hands in the West Indian islands in subsequent years, the fact may be laid to the abundance of pirates and privateers and not to the richness of local ore bodies.

Jan 1, 1941

By S. G. Cupschalk, F. A. Dahlman, J. J. Wert

Studies have been undertaken to determine the indicidual effects of particle size, degree of long-range ovder, antiphase domain size, and root mean square stran on the microhardness and yield strength of ordered alloys. Dnta have been analyzed for Cu3Pt initzally ordered to a value of 0.82 and after deformations of 1 and 6 pct. It was observed that deformation fleatly reduced the degree of long-range order. Furtherrnore, wztkin this range of relatively small deforntntlons, the average particle size changed very little while the antiphase domain size was greatly reduced. Smultaneosly, the mcrohardness changed by a factor of two durzng the deforrtation process. PREVIOUS studies have reported some of the effects of cold work on the broadening of X-ray diffraction peaks. These investigations were performed on powder and wire samples representing both ordered and disordered states; i.e., the specimens were initially studied in a severly cold-worked condition. By comparing the difference in line shape between the annealed and cold-worked peaks, fundamental information was obtained concerning particle size, strain distribution in different crystallographic directions, degree of long-range order, and change in antiphase domain size. Considerable theoretical work has been done concerning the analysis of diffraction data obtained from cold-worked metals. Stokes' expressed the change in diffraction profiles in terms of Fourier coefficients. Much of the work in this area has been summarized by warren2 in an extensive review article concerning the analysis of plastic deformation by X-ray diffraction. Cohen and Bever3 applied these techniques in studying the effects of cold work on alloy systems exhibiting long-range order. They utilized the Fourier coefficients of fundamental peaks in conjunction with those of the superlattice peaks to determine the change in antiphase domain size. Little work of this nature has been reported for ordered systems that have undergone small degrees of plastic deformation. The purpose of this investiga-tion was to determine the effects of small deformations in such a material with respect to particle size, strain distribution in various crystallographic directions, antiphase domain size, degree of long-range order, and hardness. EXPERIMENTAL PROCEDURE CusPt was used for the initial investigation since the order-disorder transformation takes place with- out a change in crystal structure. The transformation is readily detectable via X-ray diffraction techniques due to the large difference in the scattering factors of copper and platinum. Additionally, the alloy is relatively low melting (approximately 1300°C) and is easily deformable in both the ordered and disordered states. 1) Specimen Preparation and Cold Working. A 100-g, 12-in. diam., cylindrical specimen of Cu3Pt was prepared by melting and casting 99.99 pct pure Cu and Pt i.n vacuo. Prior to any mechanical working, the material was homogenized in a vacuum for 60 hr at 100O0C, and surface defects were removed by machining to a depth of approximately 116 of an in. The material was then cold-rolled, with an intermediate anneal, into a strip approximately 12 in. wide by 14 in. thick. Straightening and flattening removed another 0.025 in. from the thickness. After a recrystallization treatment at 750°C for 30 min, the specimen was slow-cooled from 55OoC, at the rate of 6°C per hr, down to 150°C to induce superlattice formation. This treatment yielded an ASTM grain size of 7 and a degree of long-range order equal to 0.83 0.06. After obtaining X-ray and Knoop hardness data, the sample was cold-rolled approximately 0.75 pct in one pass through a hand-operated jewelers' mill. X-ray and hardness data were again obtained and the specimen was reduced an additional 5.41 pct in a single pass through the mill. 2) X-Ray Measurements. The specimen was examined in the ordered condition and after the two degrees of cold working previously mentioned using a General Electric XRD-5 unit equipped with a spectrometer and scintillation counter. Using Mo-Ka radiation with a zirconium filter, six orders of the 100 reflection were obtained. It was anticipated that point counting would be necessary for an accurate determination of the low-intensity peaks and tails: however, it was demonstrated that, by using a scanning speed of 0.2 deg per min and the appropriate time constant, the recorded data were sufficiently accurate. Thus, for ease of experimental procedure, all peaks were recorded on chart paper. Specimen position in the holder was considered to be insignificant after making a series of measurements of the same peak area in different positions with respect to the beam. Since peak overlapping did occur at high values of 20, it was necessary to separate the peaks graphically prior to analyzing the data in order to minimize this source of error. The peak tails were also carefully drawn to obtain the best possible data. Fourier coefficients of the line profiles were calculated on an IBM 7072 computer, and graphical meth-ods2j3 were employed in analyzing the results. For this type of calculation, in which the line profile is represented by intensities taken at set intervals, the intervals selected must be sufficiently small to give an accurate representation of the line profile. It was decided that for 20 = 0.02 deg the line profiles were

Jan 1, 1967

By E. W. Engle

For several years the Fansteel Products Co. has been engaged in e production and development of various of the rarer metals. It is at present engaged in the commercial production of tantalum, tungsten, and molybdenum in a very high state of purity. The information contained in this paper is partly a general compilation from various sources and partly information obtained as a result of recent years of work in the laboratory of this company. Tantalum, tungsten, and molybdenum form a group peculiar to themselves among the commercially available metals. Their very high melting points (tantalum 2770' C., tungsten 3350' C., and molybdenum 2550" C.) set them apart so far as the metallurgical processes for their production are concerned. Further, when properly prepared and treated they will stand a somewhat unusual degree of cold work, that is work below the temperature at which marked crystal growth takes place. Such cold-worked metal may show a high tensile strength; tantalum to 130,000 lb. per sq. in., tungsten to 490,000 lb., and molybdenum to 260,000 lb., in the form of fine wire. In physical appearance, these metals are not unlike some steels; they may be better described by saying that polished tantalum somewhat resembles lead; polished tungsten, iron; and polished molybdenum, nickel. The polished surfaces of all three remain untarnished in ordinary air. Air containing corrosion-producing impurities will, in general, show molybdenum the least resistant to corrosion and tantalum the most resistant. Molybdenum has, however, a high degree of resistance to corrosion by hydrochloric acid, a property that should render it of commercial interest. On the other hand, it is markedly attacked by some of the weaker organic acids. The three metals oxidize rapidly when heated at or above a dull red in air. This feature limits their use in many applications where their high melting point and strength make them appear usable. Tungsten and molybdenum, at red heat, are quite inert to hydrogen and nitrogen; while tantalum has a rather remarkable affinity for all the ordinary gases, which results in its becoming embrittled in their presence. This

Jan 1, 1925

By Robert Maes, Robert de Strycker

The Cu-Sn-As systeM was studied in the region near the Cu-42 and (214-As binary diagrams, where reactions in the solid state appear, resulting from the decomposition of the y(Cu-Sn) phase and from the formation of the 7 phase (Cu,As). The techniques used were microscopic observation, thermal analysis by dilatometry, and X-vay diffraction. The formation of the 7 phase gives rise to a ternavy pevitectoid veaction; the decomposition of the y phase gives rise to five transitional reactions. The temperatures of almost all these reactions could be determined; in the most favorable cases , the accuracy of this determination was of 11.5-C. The 7 phase is stabilized by tin additions, the arsenic atoms being replaced by tin atoms up to 35 pct; this has allowed the preparation of pure j) phase and the confirmation, by extrapolation, of the conrposition of this compound in the Cu-As diagram. In the first part of this work, the solidification reactions in the Cu-Sn-As phase diagram were studied. In the copper corner, the structure of the alloys presented the evidence of reactions in the solid state: on the one hand, all the alloys containing the y phase of the Cu-Sn diagram showed, under the microscope, that this phase had formed different decomposition products after complete solidification; on the other hand, the appearance of the 7 phase of the Cu-As diagram necessitated the introduction of a peritectoid formation reaction. The study of the decomposition of the y phase has been done by preparing about forty alloys that were homogeneous y at high temperature. The formation of the 7 phase has been studied by means of a few alloys with a composition near the homogeneity field of this phase at room temperature. The part of the Cu-Sn phase diagram of interest for this study is represented by Fig. 1, with the phase designation which will be used in the remainder of this paper; it is drawn after Hansen and Anderko.' The Cu-As diagram has already been presented in Part I of this work; the significant features of this study are the existence of the arsenides CusAs and Cu5Asz, and the formation of a compound CUEAS, designated as the 7 phase, by a peritectoid reaction at about 325°C. EXPERIMENTAL METHODS The fundamental technique for the investigation of this part of the Cu-Sn-As constitution diagram was microscopic observation; the greatest part of the observed alloys has also been subjected to thermal analysis by dilatometry; a few selected alloys have then undergone an X-ray analysis by powder diffraction. Alloy Preparation. The alloys were prepared from the same products as in Part I of this study: cathode copper, arsenic with a purity better than 99.5, and tin with a purity of 99.98. The fusion of the ternary alloys was realized from

Jan 1, 1967

By J. W. Wolfe

The Benedict-Webb-Rmbin equation of state was used in digital computer programs to make rapid determinations of natural gas equilibrium phase compositions. Mixture components were the nine hydrocarbons, methane through heptane. Comparative tests were made with data from field separators, plant exchangers and literature sources. For most tests made, the B-W-R equations predrcted component K-vallles, mixture enthalpies and phase aensities within tile accuracy of available correlations for rune-component mixtures: significant deviations were noted when mixtures contained components heavier than heptune. INTRODUCTION Rapid, accurate methods for calculating the properties of hydrocarbon mixtures are needed for predicting the behavior of natural gas processes. For example, because of the common use of two-phase separation methods in gas proccssing, calculations must be made for the density and composition of equilibrium vapor and liquid phases. In addition, predictions must often be made for the temperature and pressure changes associated with the flow of single- and two-phase natural gas fluids through heat exchangers, chokes and turbines. The complex nature of non-ideal mixtures makes rigorous calculations for these natural gas properties difficult and time-consuming. Natural gas properties have conventionally been determined with generalized data correlations. These correlations, such as the K-values presented in the NGAA Equilibrium Ratio Data Book, are usually based on some average property of the mixture and have proven to give satisfactory estimates for the properties of most oil and gas systems. Digital computers, however, have not only increased the utility of these correlations, but also have made practical the use of equations of state for calculating the properties of natural gases. Potentially, if basic pure component data are available, all the desired thermodynamic properties of mixtures can be derived from a single equation of state describing the mixture. Currently. the best equation of state for describing the behavior of pure, light hydrocarbons over single-and two-phase regions, both below and above critical pressure, is that of Benedict. Webb and Rubin.' The equation contains eight constants which are determined by empirically fitting the equation to pure-component PVT data. Benedict and his co-workers presented the clevelopment of their equation as early as 1940.2 The B-W-R equation is a modification of the Beattie-Bridgeman equation of state and gives better PVT predictions than the Beattie equation at densities above the critical density. Benedict et al. made the equation applicable to mixtures by relating the mixture constants to composition and the constants for pure compounds. These authors, in a serics of articles in 1951,' showed the accuracy of the B-W-R equation when applied to light hydrocarbons and their simple mixtures, and demonstrated the equation's utility for making vapor-liquid equilibria calculations. Since its inception, the B-W-R equation has been the subject of many papers. Numerous additions and modifications have been proposed,'-',"'-':' the purpose of most being to improve the equation's ability to predict PVT properties of specific mixture systems. In 1959, Opfell, Pings and Sage summarized much of the work on the B-W-R equation in their book on equations of state." Since natural gases are primarily mixtures of light hydrocarbons, the B-W-R equation is a natural choice for an equation of state to compute both phase equilibria and thermodynamic properties of natural gases. Consequent-

Jan 1, 1967

By J. A. Pusateri, M. A. Orehoski, N. R. Arant

Plant studies on commercial-size ingots and laboratory experiments with induction furnace heats have demonstrated that the major source of ingot cracks is associated with two conditions arising during top-pouring practice: 1—solidification during pouring, and 2—turbulence created by the impact of the stream. Methods of controlling the two factors were effective in eliminating or significantly reducing ingot cracks. BECAUSE the process of removing surface defects from hot-rolled product is so costly, the steel industry is striving constantly to develop methods of preventing, or at least decreasing, the occurrence of surface defects. Investigations have revealed steel-making and processing variables related to major surface defects, and controlling these variables has led to improvements in surface quality. However, the fundamental causes of major surface defects, such as ingot cracks, have not been determined; consequently such defects persist. At the Research and Development Laboratory of the United States Steel Corp. in Pittsburgh, a seam research program was initiated to determine the fundamental causes of certain major defects. As a part of the program, ingot cracks in killed, finegrained C1020 steel were selected for study. A cost survey indicated that, of the steels produced in sizable tonnages, carbon steels in the range of 0.18 to 0.23 pct C content require the most conditioning. Since this is particularly true of C1020, any im-provement of surface quality that might be effected from the study would be beneficial. Also, since the frequency of ingot cracks is exceedingly high for this grade, the steel would provide an excellent opportunity for a thorough study of the ingot-crack-ing problem. Why steels in this carbon range tend to exhibit more ingot cracks than do other steels was not considered in the investigation; the mechanism of ingot-crack formation was of paramount importance. Also, only the top-pouring practice was considered in the investigation, because this pouring procedure is used more extensively than others. In this study, ingot cracks are defined. as deep surface defects that sometimes are observed in an ingot prior to rolling but usually are observed during the initial stages of rolling on the primary mills. These defects may occur at any angle to the rolling direction but are most prominent in the transverse or nearly transverse direction. The appearance of ingot cracks on the rolled product varies with respect to their angle of formation and with the extent of rolling after their first occurrence. Ingot cracks are also termed "deep seams," "arrowheads," "irregular cracks," and "transverse cracks." Fig. 1 shows ingot cracks in a rolled bloom. This report summarizes: l—the exploratory investigation of commercial-size ingots; 2—the labor-atory investigations related to determining the source of ingot cracks and developing corrective methods; and 3—the plant evaluations of laboratory methods of decreasing ingot cracks. Exploration of lngot Cracks in Commercial Ingots Materials and Experimental Work: At the Du-quesne Works of the United States Steel Corp., five heats of killed, fine-grained C1020 steel were selected for the exploratory phase of the seam-research program. The heats were made by open-hearth practices that are considered most conducive to good surface quality. They were top-poured into 22x25 in. big-end-up hot-topped molds. One as-cast ingot and four other ingots rolled to the following cross-sectional sizes were set aside from each heat: 16x20 in.; 9 1/2x10 in.; 5x5 in.; and 2x2 in. The processing of the heats, from the time of charging in the open hearth furnaces to the end of the rolling operation on the primary mill, was observed carefully and recorded. The cast ingot and the four rolled ingots from each heat were examined for surface defects. The cast ingots were split longitudinally near the vertical center plane to expose the ingot structure beneath badly cracked regions. Also, a series of transverse sections was cut at about 1 in. intervals in a badly cracked area of one ingot. All sections were ground, polished, examined by sulphur printing and deep etching, and photographed. The rolled ingots

Jan 1, 1955

By John C. Martin

The discovery of a new gas reservoir demands that the planning of a sottnd well-spacing program be initiated early in the development stage. It is the purpose of this discussion to illustrate by actual field examples the application of basic well-spacing principles, previously developed for oil reservoirs, to the problem of well spacing in natural gas fields. These studies are presented for the field use of geologists and engineers who are concerned with the initial planning of the proper development of the newly discovered gas reservoir. INTRODUCTION The phenomenal growth of a vigorous natural gas industry emphasizes the increasing importance of natural gas as a source of energy, fuel, and raw materials to our nation's economy. Since 1945 marketed production of natural gas for the U. S. has increased 21/2 times to a record high of 10.6 trillion cu ft during 1957. As major participants in the gas industry, we share an added interest to develop and produce our natural gas reserves with constantly improved efficiency. The subject of well spacing is vitally important to the gas industry, for the well itself plays a significant role in the development of the natural gas reservoir and in control of the recovery process. Maximum utilization of wells is an integral part of sound conservation practices. The discovery of a new gas reservoir demands that careful choice of well location and well spacing be made and that the planning of a sound well spacing program be initiated early an the development stage. With the drilling of the first development well, efforts of the geologist and engineer must be directed toward acquisition of adequate technical evidence upon which a firm recommendation for a spacing program may be based. With this technical appraisal as a foundation, operators and state regulatory agencies jointly can go far in providing a framework for sound development of gas fields to achieve a program of conservation that avoids the unnecessary well. WELL-SPACING CONCEPTS Through laboratory and field investigations of the mechanism of the recovery of oil and gas, of fluid behavior, and of effective control of reservoir and well, a crystallization of ideas regarding reservoir behavior has emerged as a well-developed technology. Associated with a better understanding of the fundamental principles underlying reservoir and well behavior has been the growth of concepts concerning the role of wells and their spacing in the development and operation of an oil or gas reservoir. In addition to serving as outlets for the withdrawal of fluids from the reservoir, wells are recognized as having two other important functions: (1) providing access to the reservoir to obtain information concerning the characteristics of the reservoir and its fluids, and (2) serving as a means by which the natural or induced recovery mechanism may be effectively controlled. Beyond a minimum number of wells required to fulfill these two functions, additional wells will not increase recovery. With particular emphasis upon well spacing in oil reservoirs, many studies of the well spacing-recovery relationship have evolved the concept that the ultimate oil recovery is essentially independent of the well spacing.' These fundamental concepts are no different when regarding the role of wells and their spacing in the natural gas reservoir. They are equally applicable to the consideration of well spacing in gas reservoirs. For the gas reservoir, the problem of well spacing then revolves around the question of drainage and the degree or extent to which a well may drain gas from its surrounding reservoir environment. Theoretical and Experimental Work During the past 30 years, theoretical and experimental work carried on to study the physical principles involved in the flow of fluids through porous media has shed light upon the matter of drainage. Fundamental mathematical equations have been derived to describe the mechanism of flow of oil and gas through porous rocks. With the recent advent of high-speed digital computers, attempts have been made with mounting success to develop solutions, employing numerical techniques, to mathematical expressions that describe more rigorously the physical behavior and mechanism involved in the unsteady-state flow of compressible fluids, such as a gas, through porous rock. In 1953, Bruce, Peace-man, Rachford and Ricez published a stable numerical procedure for solving the equation for production of gas at constant rate. The results of these calculations are significant with respect to this matter of drainage, for they indicated (1) that depletion of the gas reservoir resulted in a drop in pressure at the extremity of the

By J. W. Bolton

PRODUCTION of sound bronze castings is a matter of great practical interest to users and manufacturers of high-grade non-ferrous engineering specialties. Although there has been much excellent research in this field, there still remains some confusion regarding the fundamental principles underlying production of really sound bronze. The literature of the past 20 years on this subject indicates that the prevailing opinion of metallurgists and foundrymen has been that unsoundness in bronze is due generally to oxidation. The following references are typical.

Jan 1, 1929

By Sir Lowthian Bell

WITH the exception of air and water, it is open to question whether there is any form of matter which the human race could less easily spare than iron. Short of going the length of asserting that, without this metal for an anchor or steel for the compass, the adventurous navigator could never have crossed the wide Atlantic, we may credit the locomotive' and the steamer, and hence iron, for that sequence of events which has peopled North America with the

Jan 1, 1891

By J. H. M. Thomeer

A method is presented that provides a mathematical description of capillary pressure curves and, probably, of differences in pore geometry of samples. The technique is based on the observation that the location and shape of a capillary pressure curve reflect characteristics of the pore structure of the sample. INTRODUCTION It has been noted1-5 that the observed differences in shape and location of capillary pressure curves reflect some basic properties regarding the pore geometry of the samples. For example, according to basic concepts of capillarity, the following statements can be made regarding the location and shape of a capillary pressure curve.* The location of the curve with respect to the (Vb)pc and PC axes is a measure of the interconnected pore volume and of the cross-sectional area of the pore first entered by mercury, respectively. The shape of the curve depends on the interconnection of the pores and the sorting of the pore sizes. It has been the object of this study to use this information as a starting point in an attempt to find a unique mathematical description of the PC — (Vv)p, relations of different samples. It may be expected that parameters in such a relation can then be used to describe differences in pore geometry of these samples. For a practical description of the PC — (Vb)p, relation, however, it appears desirable to describe each curve (i.e., each sample) by a limited number of parameters so that the curves taken from all samples form a family, each member of which is uniquely determined by one single combination of values of all parameters.

Discussion of the paper of John H. Hall, presented at the New York. Meeting, October, 1913, and printed in Bulletin No. 79, July, 1913, pp. 1247 to 1256. WILLIAM 'R. WEBSTER, Philadelphia, Pa.:-I would like to call ,attention to the fact that the results of the ordinary tension and bend tests do not always give us the information we want even if we figure out the amount of work done. You want a bending test of sufficient width and full thickness. In the case of eyebars, for instance, I have had experience with a 10- by 1-in. eyebar which gave perfectly good results in a full-size test of the finished bar. The 10- by 1.5-in. and 10- by 1.75-in. eyebars from the same heats-of steel were absolutely worthless in full-size tests. The narrow bending tests from all these bars gave good results. Bat after going into the matter fully, we found that if pieces about 3 in. wide and full thickness were used for the. cold bending tests, the heavier material would not stand this test, but failed. That is, in order to check the quality of the rolled bar you should have a wide piece of full thickness for cold bending, as the narrow pieces give misleading results. J. E. JOHNSON, JR., New York, N. Y. :-I would like to ask if there have been any tests made to compare the results of Charpy tests with the true dynamic test similar .to the Wohler test, except that the piece is subjected to a tensile or compressive stress and to alternating stresses in addition, at the same time. This seems to me to approach more nearly than any other test to the conditions of actual service. where the piece is under a fixed initial stress plus a highly variable and often alternating stress. Some tests were made on this plan in England within a year or two. The test piece was Subjected to either a tensile or compressive stress of known amount and simultaneously to alternating stresses in addition. Such a. test as this gives information which we cannot get by a tensile test or even from the tensile strength multiplied by an. elongation. Such tests, however, are exceedingly tedious and require long periods of time in order to obtain valuable results. If material could be subjected to these dynamic tests and the same material to the. Charpy shock test, and if some reasonable qualitative relation could be established between the results of the two tests, then we could assume that the shock test, which is so simple and easy to make, was a measurably accurate test of the dynamic qualities of the material. At present it does not seem

Jan 12, 1913