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By T. G. Lovering

Nonparametric statistical tests have practical application to many geological problems because, unlike the standard statistical tests, they do not require assumptions regarding the form of the population frequency distribution. Many of them do not even require that the variable be susceptible to numerical measurement. These tests are useful either 1) for geological data representing population distributions of unknown form, or otherwise not meeting the requirements for standard parametric tests; or 2) for sample attributes that cannot be measured but only ranked in order of relative magnitude. The application of two such tests will be illustrated. The Kolmogorov-Smimov test will be used to test for significant differences in copper distribution in samples of two rock types; the Spearman rank-correlation method will be used to determine whether there is a significant association between intensity of rock alteration and copper content of the rock. Nonparametric tests are, in general, quicker and easier to perform than the corresponding parametric tests, and they may be applied to a greater variety of data. They are not as powerful as the standard tests if used on data to which the latter are applicable, and computer programs utilizing them are not generally available. The use of standard or parametric statistical procedures for the interpretation of measured geological data is familiar to most mining engineers and explora- tion geologists. The computation of product moment correlation coefficients on sample assays for more-than one component is already standard procedure in some company operations, as is the use of Student's F test and Snedecor's F test for the comparison of means and variances of sample groups. The application of these three tests is limited by the prerequisites that the samples must be random, independent representatives of normally distributed populations and that the variables involved must be measurable. If such tests are applied to data which fall short of fulfilling these prerequisites, then the probability level attributed to the computed statistic is invalid and the conclusions based thereon may be erroneous. A number of nonparametric, or distribution free, statistical tests have been developed for use with data which are not amenable to standard parametric procedures. These tests have been widely used in the behavioral sciences such as psychology and sociology for some time, but their application to geologic problems is relatively new. Nonparametric tests may be grouped into two main categories: those which test for significant differences in a single variable by comparing either sample values with a standard value or representative values between two or more groups of samples; and those which test for significant association between pairs of variables in a single group of samples. The versatile chi square test, the Kolmogorov-Smirnov one and two sample tests, the Wilcox matched pairs signed ranks test, the median test, the Mann-Whitney U test and the Cochran Q test are examples of nonparametric tests with demonstrated or potential geological applications that belong in the first category. The contingency coefficient, Spearman rank correlation coefficient, Kendall rank correlation coefficient and the

Jan 1, 1963

By F. R. Cattoir, R. W. Kimball, C. T. Anderson

ONE of the principal impurities in all steels is sulphur. Sulphur-bearing, manganese-free steels exhibit hot shortness. Manganese is added to steel to improve the hot-working properties. If no sulphur were present in steel, it is probable that hot shortness would be nonexistent. This paper is the first of a series to be issued by this Laboratory reporting the measurements of hot forgeability tests and the physical properties of Fe-C alloys to which additions of various alloying elements have been made. The present paper describes the results- obtained by the addition of varying amounts of sulphur to Fe-C alloys. To obtain control over residual elements in the various charges melted in the arc furnace, it was considered advantageous to use sponge iron from one source as the melting stock rather than scrap metal having an unknown history. Small amounts of unwanted alloying elements might be introduced into the charge when scrap was used, thereby influencing the results of the various heats. A sponge iron having a high silica-lime ratio was used. Ore from Sunrise, Wyo., had been reduced to sponge iron and briquetted at the Bureau of Mines sponge-iron plant at Laramie, Wyo. The briquettes were 5 in. in diam and 2 to 3 in. in thickness, and weighed about 10 lb each. The chemical analysis of the sponge iron is as follows: C, 0.67 pct; Mn, 0.10; SiO2, 4.75; CaO, 1.4; P, 0.044; S, 0.72; MgO, 0.4; A12O3, 1.1; total Fe, 87.5; Fe metallic, 79.2; and reduction, 90.5 pct. Where a reducing agent was required, crushed graphite electrodes usually were used. The charcoal available contained 0.20 pct S. An analysis of the available coke showed it to contain 0.70 pct S. Where high sulphur heats were required, elemental sulphur additions were made to the ladle. Limestone of good quality was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2, 3.0; and P2O5, 0.014. Melting Procedure Sponge iron was melted to produce metal stock for the experimental alloys in a silica-lined, three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating. Fig. 1 shows this furnace installation. About 25 tons of sponge iron was melted in 75 heats, averaging 927 lb of sponge iron to the heat. An addition of carbon was required to complete the reduction of a portion of the iron oxide remaining in the sponge to prevent high losses of iron oxide in the slag and a low carbon content in the resulting metal. As reducing agents in preparing the melting stock, charcoal, coke, and a carbon product resulting from the thermal decomposition of natural gas were used. The quantity varied from 20 to 60 Ib per furnace charge, with an average of 38 lb. An average analysis of the metal obtained gave 0.52 pct C, about 0.01 pct Mn, 0.070 pct P, and 0.092 pct S. The average yield of metal was 647 lb with 241 1b of slag, the sponge-iron recovery being 70 pct. The metal obtained in melting the sponge iron was cast into pigs weighing about 20 lb each to facilitate recharging into the furnace for further refining. The pouring of the pigs is shown in Fig. 2. The average power consumption for the production of the 24 tons of metal obtained was 1704 kw-hr per ton.

Jan 1, 1954

By L. D. Jaffe

From data found in the literature, a method has been derived for calculating hardenability of titanium alloys from their composition. A single graph gives the contributions of each alloying element. These are simply added to a base hardenability for unalloyed titanium. Results agree satisfactorily with measured harden-abilities. RECENTLY the importance of hardenability of titanium alloys in permitting attainment of high strength and hardness has become apparent. If a titanium-base alloy has adequate hardenability for the section size and quenching practice used, it can generally be heat treated to high strength and hardness either by simple quenching or cooling from temperatures near the ß transus, by quenching and tempering (aging), or perhaps by direct isothermal transformation of ß1,2 If the hardenability is inadequate, high strength cannot be attained. Preliminary charts translating hardenability requirements for shapes quenched in various media into terms of Jominy end quenched hardenability specimens or ideal round sizes are now available for titanium alloys." The method proposed in 1942 by M. A. Grossmann for calculating hardenability of steels from composition has proved to be of great practical value.' It appeared worthwhile to see whether, using information available in the literature, a corresponding method for calculating hardenability of titanium-base alloys could be derived. Data No systematic experimental study of the hardenability of titanium-base alloys has yet been made. There is available, however, a considerable quantity of scattered data bearing on hardenability. Some investigators determined Jominy curves on one or several alloys. Others reported as-quenched hardness for specimens of a few alloys cooled at various rates or in various media. Still others gave the as-quenched hardness for systematically varied composition, using one or several cooling mediums. The measurements utilized in this work were limited to hardness. Strength measurements were not used because a low strength may reflect high hardness combined with brittleness. Since, in general, the hardness of titanium alloys goes through a peak as the cooling rate is varied from extremely fast to extremely slow, the cooling conditions at which peak hardness was found were taken as the measure of hardenability.1,2 When as-quenched hardness was found to drop as the content of an alloying element (believed to increase hardenability) was raised, this was taken as an indication that the cooling rate was faster than that giving peak hardness; otherwise, the hardness should go up because of solid solution hardening. Also, if the hardness increased on tempering at low temperatures, this was again taken to indicate that the cooling rate had been faster than that giving peak hardness. Many of the data did not indicate precisely the cooling conditions for peak hardness but merely set a maximum or a minimum bound, or a bracket. Since the sizes of specimens quenched and the location of the hardness readings were not always given, it was occasionally necessary to estimate reasonable limits for them. Only the nominal compositions were available in some cases. As quenching from below the ß transus is equivalent to starting with a mixture of a and ß phases, whose individual composition would differ from the overall composition of the alloy, only measurements after quenches from above the ß transus were used. Hardness measurements on samples heated during metal-lographic mounting were also discarded. Because of their bulk, the data used will not be reproduced. They have been or will be published elsewhere.5-22 Approach All data were first translated into terms of ideal round size. For conversion from Jominy or quenched round or sheet, the author's graphs were used." For a few furnace cools or helium quenches where cooling rates were given, conversion was made on the basis of equal cooling coefficient.23 Plots of ideal round size for peak hardness against percentage of alloying element were next made for

Jan 1, 1956

By C. J. Ramsburg

The construction and operation of by product coke-oven plants in America are essential to strong national defense and of the greatest importance to many widely diversified undertakings as well as to safety and health. Carbonization Process Coal used under a boiler or in a locomotive is consumed by combustion. Coal used in a by-product oven is distilled or carbonized, meaning that heat is applied to the coal, out of contact with air, causing a distillation that removes the volatile matter in the coal in the form of gas and vapor, leaving coke as a final product. From the gas and vapor distilled from the coal, many valuable substances can be secured, known as by-products. Hence the name "by-product oven." The simplest example of this principle can be shown by means of an ordinary clay pipe. If powdered coal is placed in the bowl of the pipe, the opening of the bowl is plugged with clay, and the bowl placed in a flame, the bowl will become hot, transferring the heat through the wall of the bowl to the coal within. When this coal attains a temperature of about 750°F., gas will begin to pour out of the pipe stem, and this gas may be lighted. A black liquid also will exude from the stem of the pipe, This is tar mixed with certain other products. What remains in the bowl after distillation is coke. A coke oven corresponds to the bowl of the pipe. A modern oven of the latest type is a refractory brick chamber approximately 42 ft. long and 14 ft. high, averaging 18 in. in width. The oven is filled with coal through closable charging holes in the oven top. Each end of the oven consists entirely of a self-sealing door, the removal of which permits the finished coke to be discharged by means of a power-operated pusher machine. The ovens are built in batteries, and the heating is effected by gas burned in vertical flues in the oven walls, each set of flues heating the walls of two adjacent ovens. Such ovens carbonize a charge of approximately 18 tons of coal in 18 hr., or have a daily throughput of 24 tons per oven, producing about 17 tons of coke. In times of need, the output may be increased by raising the temperature of flues, thus shortening the coking time. There is one great essential difference in principle between distillation in a clay pipe and in a coke oven. In the 18-in. oven, the distillation proceeds from two parallel walls held at a high temperature (over zooo°F.) and instead of all the coal being heated at once, the distillation is a progressive one creeping inward. The average travel of this heating is 35 in. per hour from each vertical wall, and as the volatile products are formed progressively they must push away from the interior toward the wall through the previously formed hot coke, then up the walls and Over the top of the coal charge, finally escaping through the outlet pipe. This results in a cracking of the components into many different and valuable substances not formed when the carbonizing temperature is low.

Jan 1, 1942

By Charles E. Nelson

THIS paper will outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as jar as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper and will be discussed briefly.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, this paper will deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. The outline of this discussion will closely follow that of an earlier paper,2 with such changes and additions as seem necessary to bring it up to date. TYPES OF MELTING PRACTICE All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux, which provides protection during melting and a molten pool of flux into which the solid magnesium melts. The flux is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies;, on quiet standing, it separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is desirable. The open-pot method is used generally in the following processes: (I) alloying and remelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drys out or thickens after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to

Jan 1, 1946

By E. C. W. Perryman

The recovery of X-ray line broadening, hardness, and electrical resistivity from cold worked AI-Mg alloys has been investigated. The results, together with those from density measurements, suggest that magnesium atoms freeze in the excess vacancies formed by cold working, and that this affects the climb of dislocations during the recovery process. PREVIOUS work1, " has shown that while 1 pct Mg increases the activation energy for recrystalliza-tion, it decreases the activation energy for the recovery of mechanical properties and decreases the subgrain size both after cold working and annealing. A similar result has been reported by Varley2 for an A1-2 pct Mg alloy. With plastic deformation at high temperatures, McLean and Farmer' and Rachinger have found that magnesium appears to retard the motion of dislocations and, furthermore, they find little or no effect of magnesium on the size of subgrains formed during high temperature deformation. In view of the apparent contradictions as to the effect of magnesium on subgrain size, the recovery process in Al-Mg alloys has been investigated more thoroughly by studying the annealing out of X-ray line broadening, hardness, and electrical resistivity from alloys cold worked at room temperature. Material Used—The chemical analyses of the alloys are given in Table I. Fabrication—The material used was cold rolled 20 pct at room temperature, the grain size prior to the last cold rolling operation being similar to that used in previous work; i.e., 230. The experimental procedure for annealing, determination of X-rav half-veak breadth. hardness measurement, electEica1 resistivity, and density and metallographic examination was exactly the same as previously described." Variation of X-Ray Half-Peak Breadth with Annealing Time—Isothermal annealing curves at 100°, 200°, and 250°C were obtained for material cold worked 20 pct. The half-peak breadth of the (333) Ka, line directly after cold working is shown as a function of magnesium content in Fig. 1. Only with the 2.87 pct Mg alloy was overlapping of the a, and n.. reflections observed to any appreciable extent. To separate these, Rachinger's method' was used. Typical isothermal annealing curves are shown in Figs. 2 and 3 for 100" and 200°C, respectively. These curves are similar to those obtained previously for super-purity aluminum except that the

Jan 1, 1957

By Donald T. Hawkins, Ralph Hultgren

The lorsion effusion method has been used to measure the vapor pressure of lead over pure lead and eight Pb-Sn alloys ranging from 9.1 to 87.9 at. pct Pb in the temperature range 950° to 1125°K. The resulting ?H°y 298 = 46,630 ± 200 cal per g-atow for pure lead is in excellent agreement with previous work. Deriued ?Gph values for the alloys were smoothed and correlated with previous heat of formation data to obtain entropies for the liquid alloys. values for the tin component were calculated by Gibbs-Duhem integmtion. Surfhce depletion of these liquid alloys was found to be absent, as shown by the fact that the measured pressure remained substantially constant with time in contrast with previous measurements on iron-rich solid Fe-Mn alloys. The activities and Gibbs (free) energies of the liquid Pb-Sn system are not well known although the heats of formation have been accurately determined by K1eppa.l Vapor pressure determinations of the activity of lead by Voronin and Evseev2 disagree with those of Predel.3 Elliott and chipman4 measured activities by the electromotive -force technique in the ternary Pb-Sn-Cd system. From the resulting values of the activity of cadmium, they were able to calculate the activities of lead and tin for the binary Pb-Sn system at the compositions xsn = 0.33 and 0.67. Atarashiya, Uta, Shimoji, and Niwa5 determined the activity of tin from Hz-H2O equilibrium measurements, but their results are subject to question due to uncertainty in the final state of their samples. To resolve these differences, measurements of the activity of lead were made using a torsion-effusion apparatus. Among other advantages, this apparatus rapidly detects errors caused by surface depletion, which tends to reduce the apparent vapor pressure of the more volatile component. If the measured torques remain nearly constant with time, only bulk depletion is occurring. This contrasts with the rapid decrease in torque found in solid Fe-Mn alloys at high temperatures and low manganese contents.6 EXPERIMENTAL 99.999+ pct Pb was obtained from the American Smelting and Refining Co. and 99.999 pct Sn from Vulcan Detinning Co. Eight Pb-Sn alloys were prepared by melting together weighed amounts of the pure metals in evacuated Pyrex tubes and quenching the melts in water. Loss of weight in preparation was less than 0.02 pct in all cases. The effusion cells were made from high-purity, nonporous graphite. Graphite was chosen because of its resistance to reaction with lead and tin and because it can be accurately machined with precision orifices. Two cells were used with overall dimensions as shown in Fig. 1. The orifices of cells 1 and 2 were, respectively, 1 and 1.5 mm in diam.

Jan 1, 1968

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium' oxide to form

Jan 1, 1948

By P. C. Upadhyay, J. G. Singh

Reissner's thick plate bending theory has been recast for rocks which exhibit the property of double elasticity: different Young's modulus and Poisson's ratio in compression and tension. The governing differential equation and other relevent expressions have been presented in a form compatible to the applied mechanics results so that they can readily be used. Effect of the ratio of Young's modulii in compression and tension, (Ec/Et), on the maximum plate deflection and the maximum bending moments has been evaluated over a wide range. It has been found that the inclusion of bi-modulus property through a parameter (ß = Ec/Et), changes the sheer deformation of the plate to such an extent that the bi-modular effect of rock cannot be overlooked in the thick plate analysis, especially when ß is expected to be greater than 2.

Jan 1, 1982

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By E. DeGolyer

PROSPECTING for new deposits is a part of the ordinary routine business of the petroleum industry to an extent that is not true for any other mineral industry. The health of the industry depends upon whether we are successful or unsuccessful. How many know what it costs to find oil today and what it has cost in the past? Very few, I will wager. The industry is not well informed upon this extremely important point. We cannot deal in averages for lack of information. Does it cost more or less than previously? Prospect wells are increasingly deeper and, since the introduction of the core drill, prospecting techniques have required increasingly expensive field oper-

Jan 1, 1939

By AIME AIME

BEGINNING Thursday, July 16, the National Broadcasting Co. is broadcasting from 6:30 to 6:45 p.m., over its nationwide network and possibly also by short wave a series of eleven radio programs dealing with the contributions of engineers to the prosecution of the war. The series is being arranged and sponsored by a committee of representatives of the national engineering societies, R. L. Sackett, chairman. The committee began its deliberations before Pearl Harbor and had scripts under way on blackouts, bombs, and damage to structures. The declaration of war emphasized the importance of the proposed radio program. The National Broadcasting Co. and the Office of Civilian Defense enthusiastically endorsed the committee's proposal and have been generous in their help and approval of scripts so far submitted. Controversial matters are included in the broadcasts and changes will be made when requested by O.C.D. up to the minute that a program goes on the air. In this way the latest and authoritative information will be given.

Jan 1, 1942

By N. H. Emmons

THE work of a consulting engineer or manager, when controlling mining-operations, requires that he have all the information concerning the mine in as concise a form as possible, and as the ore-reserves and their depletion and enlargement are the vital points to be studied, it is well to have them kept up to date and in some convenient form. The present paper describes a method adopted by me, which shows in a very clear manner the ore-reserves in a mine. The case illustrated is that of a vein near enough to the vertical for the vertical elevation of the mine to be the main working-map. A flat ore-body would be represented on a similar plat, but instead of the horizontal thickness of the vein being shown in the circles, the vertical thickness would be inserted. Fig. 1 represents an ideal longitudinal elevation of a mine, plotted in the ordinary way, using 100-ft. blocks and section-lines. In a mine where the block-numbers are posted by the engineer underground, the system of keeping the ore-tonnages extracted from the different blocks is easily maintained, and the actual tonnages of ore extracted can be kept so that the surveyor can have a check on his estimate from time to time. The ore-reserve sheet, Fig. 2, should be the same size as the map it is to accompany. Each square is used for the description of the ore-reserve in the block it corresponds to on the elevation. Where the section-lines cross the levels a circle is drawn, in which are written the widths of ore at that point, these widths being used in the calculations of each block cornering in the circle. It has been found convenient to show the figures in black in the lower half of the circle when the actual widths of ore are known, and when it is necessary to make up the figures of probable ore, as at the time of making

Jun 1, 1912

By C. H. Mathewson

THIS paper was prepared upon request as a contribution to a symposium covering the manufacture, properties, and uses of the important non-ferrous metals. In approaching a subject as broad as this, there is a natural desire to build up a comprehensive and finished production which shall constitute a dependable source of information on all questions properly belonging to this branch of metal technology. There are, however, a number of circumstances, apart from the mere routine of labor and thought involved, which operate rather effectively against the possibility of completing such an ambitious program at the present time. First of all, as far as any public record of results is concerned, the commercial rolling, drawing, and forming of zinc with relation to changes of structure and properties-and this we consider to constitute the elements of metal technology-might as well be an unpractised art. We have never seen a published photomicrograph showing the structural characteristics of either hard or soft sheet or strip, although the structure of castings has been frequently described, and other coarse-grained structures resulting from hard-hammering and annealing have been reproduced. Thus, an author in this field must proceed to his task without much assistance from the literature, and the outcome can represent only a personal estimate of principles, facts, or findings, and not a summary

Jan 9, 1919

By Paul A. Beck

While the recrystallization properties of most of the practically important metals are known in considerable detail, those of lead are still relatively little known in spite of some valuable contributions in recent years. This condition probably is due to the difficulties involved in applying the usual methods of investigation. The microscopic method of discriminating between the elongated deformed grains of the familiar lenticular shape and the equiaxed recrys-tallized grains is not successful with fully refined lead: lenticular grains cannot be seen under the microscope with any amount of deformation whatever. The probable cause of this phenomenon was recognized long ago. With large deformation the time of recrystallization at room temperaturc is shorter than the period of preparation of the specimen for microscopic examination; with small deformation the deformed grains arc not noticeably elongated in the first place. However, with small cleformation the migration of the grain boundaries can be observed. The only systematic investigations yet published on the recrystallization of lead, those by R. S. Russell, 1-3 make use of the conditions just described. Russell considered recrystallization completed when no further migration of boundaries could be observed. A serious objection to this method arises from the fact that there is no evidence to support the view that grain-boundary migration results only from recrystallization. If such migration does result from other sources after recrystallization is completed—after the deformed grains have been replaced by new unde-formed grains—the "time of recrystallization" as determined by Russell may be too long. Furthermore, the method is subject to the above.-mentioned limitation because of the unavoidable period of preparation of the sample. According to Russell, even with the fastest technique 5 min. clapsed before the deformed samples were ready for examination, and consequently no reearystallization time shorter than 5 min. could be measured. The lack of success in detecting the recrystallization of lead by the usual hardness or tensile tests is again caused by the time necessary for

Jan 1, 1940

By D. H. Woodard, G. W. Geil, W. D. Jenkins

In a series of papers, the authors and their associates have shown the influence of four important factors on the technical cohesion limit.3-l6 By "technical cohesion limitv is meant the technically determin-able resistance to fracture. The four importarlt factors are the stress system, plastic deformation, temperature, and the strain rate, The influence of any one of these factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. As the term "fracture stress" has come into general use with the same significance as technical cohesion limit, the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. The previously mentioned series of papers contains ample evidence that plastic extension increases the fracture stress of any polycrystalline metal, In a recent paper of the series,l5 moreover, it has been shown that the effect of plastic deformation on the fracture stress cannot be attributed to reorientation of internal flaws but is a work-strengthening effect, similar to the effect on the flow stress, $ Plastic deformation of steels, however, may not only cause work hardening, but may result in additional hardness because of strain aging. Some evidence that strain aging affects not only the flow stress but also the fracture stress, has been presented in a recent paper.14 In that paper, a study is made of the influence Of Plastic deformstion at room temperature on the fracture stress of ferritic steels at -188°C. The study is based on the results Of two-stage tests. In the first stage each specimen was extended a predetermined amount at room temperature; in the second stage the specimen was tested to fracture in liquid air. In most Of these tests the specimen remained in the testing machine during the interval of about one hour between the first and second stages, it was kept under a tensile load of about 500 lb and maintained at liquid air temperature. The effects of various amounts of .plastic deformation on the fracture stress were thus determined and curves were obtained to represent the influence of plastic deformation at room temperature on the stress at brittle fracture in liquid air.14 Two specimens Of ingot iron, however, were removed from the testing machine at the end of the first stage and several days elapsed before the specimens were tested to fracture in liquid air, As shown in Fig 8 of that paper," the points representing fracture of these specimens are far above the curve representing the results of two-stage tests without a rest interval between the stages. The evidence thus indicated that the fracture stresses of these two specimens were increased not

Jan 1, 1949

By R. Fawley, M. A. Quader, R. A. Dodd

Stacking fault energies and annealing twin frequencies have been measured for austenitic stainless steels having a) constant 20 wt pct Cr and varying nickel contents, and b) constant 20 wt pct Ni and varying chromium contents. The effect of nitrogen has also been studied and, to a lesser extent, so has the effect of carbon. All measured stacking fault energies plot linearly against the corresponding annealing twin frequencies, suggesting that, for constant prior deformation and grain size, twinning frequency can be used to estimate stacking fault energy. Compositions low in nickel possess the lowest fault energy, while the maximum fault energy within the investigated composition range occurs mound 20 pct Cr-20 pct Ni. Nitrogen has practically no effect on stacking fault energy when increased from 0.005 to 0.05 wt pct, although Planar dislocation glide is associated with higher nitrogen contents; this may be a short-range order effect. Carbon may raise the stacking fault energy a little, and causes pronounced dislocation tangling in deformed alloys. The basically different dislocation structures promoted by nitrogen and carbon, respectively, are not associated with large variations in stacking fault energy, and the reason for the difference remains unknown. INTEREST in the dislocation configurations developed in plastically deformed alloys arises principally from a desire for an understanding of mechanisms of plastic deformation and fracture. Comparatively little basic work has been concerned with austenitic stainless steels, although considerable interest has developed in the fundamental aspects of deformation of these alloys since the suggestion that those compositions deforming essentially by planar glide are particularly prone to transgranular stress corrosion cracking.' Certain facts are well-established. An 18 Cr-8 Ni steel (type 304) has a low stacking fault energy which is increased by higher nickel contents, and the structure of these steels when moderately plastically deformed changes concomitantly from planar to less planar to distinctly tangled dislocation configurations. These changes are thought to relate to changes in stacking fault energy, and considerable effort has been expended in measuring stacking fault energies of austenitic stainless steels through the determination of node curvatures2"4 even though the method has limitations due to formula approximations,5 an upper limit of measurement of 50 erg cm-2 at the most,5 and the necessity of an extremely meticulous experimental technique. Therefore, it is not surprising that only qualitative agreement between different investigators is generally to be found.'-' At high energies where node radius measurements are inappropriate, some use has been made of annealing twin frequencies to estimate relative stacking fault energies, although a recent critical evaluation of the method suggests that it should be used cautionsly with due regard to effects of grain size and prior deformation.6 Finally, there is a question as to whether the structures of some deformed steels are due to ordering effects. In particular, the role of nitrogen in promoting planar dislocation motion has been suggested to be due to ordering,' but similar suggestions have been made for steels having low interstitial contents.4 EXPERIMENTAL Small ingots of austenitic stainless steels (-50 g) were prepared from components exceeding 99.99 pct purity, the nickel and chromium being Johnson Matthey "Specpure" metals. Carbon was added as pure graphite, and nitrogen as CrN. The components were accurately weighed, and it was assumed that the final composition was the same as the nominal composition

Jan 1, 1969

By John B. Baker, Bernard B. Betty, H. F. Moore

Fox several years there has been in progress in the Materials Testing Laboratory of the University of Illinois an investigation of creep and fracture of lead and lead alloys. In the course of this investigation it has been shown that the phenomenon of creep occurs in part at the grain boundaries of lead and lead alloys. To study the occurrence of creep and the development of fracture within crystalline grains, two series of tests of single crystals of lead have been carried out. The first of these, a preliminary series, by Mr. Betty, has been described.1,2 The second, pursued by Mr. Baker for his doctoral dissertation, was carried out under the direction of Professor Moore, with the assistance of Prof. G. L. Clark in the X-ray work, and the cooperation and advice of Mr. Betty. This paper is based on the test data obtained in this second series. Single crystals of a very pure commercial lead have been prepared, some of them tested to measure creep, others tested to fracture under long-continued steady load, and still others tested under cycles of repeated tension. An interpretation of the test data of these single-crystal tests is offered, which is a combination of parts of several well-known theories. SPECIMENS The single-crystal specimens were made from a piece of very pure commercial lead sheathing. A spectroscopic analysis of one of the single crystals showed the presence of 0.005 per cent Bi, 0.0001 per cent Cu and 0.0003 per cent Ag. Preparation.-The Bridgman method of casting single-crystal speci¬mens was used.3 The specimens were cast to the shape and size shown in Fig. I (dimensions in Fig. 4c) in a duralumin mold. Molten lead does not stick to duralumin. Fig. 1 shows the mold and the blast flames for heating. After the mold had been heated to the temperature of molten

Jan 1, 1938

By G. W. Geil, D. H. Woodard, W. D. Jenkins

In a series of papers, the authors and their associates have shown the influence of four important factors on the technical cohesion limit.3-l6 By "technical cohesion limitv is meant the technically determin-able resistance to fracture. The four importarlt factors are the stress system, plastic deformation, temperature, and the strain rate, The influence of any one of these factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. As the term "fracture stress" has come into general use with the same significance as technical cohesion limit, the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. The previously mentioned series of papers contains ample evidence that plastic extension increases the fracture stress of any polycrystalline metal, In a recent paper of the series,l5 moreover, it has been shown that the effect of plastic deformation on the fracture stress cannot be attributed to reorientation of internal flaws but is a work-strengthening effect, similar to the effect on the flow stress, $ Plastic deformation of steels, however, may not only cause work hardening, but may result in additional hardness because of strain aging. Some evidence that strain aging affects not only the flow stress but also the fracture stress, has been presented in a recent paper.14 In that paper, a study is made of the influence Of Plastic deformstion at room temperature on the fracture stress of ferritic steels at -188°C. The study is based on the results Of two-stage tests. In the first stage each specimen was extended a predetermined amount at room temperature; in the second stage the specimen was tested to fracture in liquid air. In most Of these tests the specimen remained in the testing machine during the interval of about one hour between the first and second stages, it was kept under a tensile load of about 500 lb and maintained at liquid air temperature. The effects of various amounts of .plastic deformation on the fracture stress were thus determined and curves were obtained to represent the influence of plastic deformation at room temperature on the stress at brittle fracture in liquid air.14 Two specimens Of ingot iron, however, were removed from the testing machine at the end of the first stage and several days elapsed before the specimens were tested to fracture in liquid air, As shown in Fig 8 of that paper," the points representing fracture of these specimens are far above the curve representing the results of two-stage tests without a rest interval between the stages. The evidence thus indicated that the fracture stresses of these two specimens were increased not

Jan 1, 1949