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By H. B. Smith, B. Egererg

In a previous paper1 the authors dealt with the physical properties of cold-rolled and heat-treated Britannia metal of the approximate composition Sn, 91 per cent., Sb, 7 per cent. and Cu, 2 per cent. It was found that cold rolling to more than 50 per cent. reduction produced a continuous softening of the metal when measured by the Brinell machine, whereas the Shore instrument indicated increased hardness; that the strength of the material followed the Brinell hardness and that the metal therefore became weaker the more it was cold-rolled; and further, it was found that hardness and strength could be largely restored to the cold-rolled metal by "baking" for about one hour at any temperature between 200" and 450" F., the melting point. The higher the baking temperature, the more effective was the heat treatment as far as increased hardness was concerned. It seemed to be of little importance whether the metal was soaked or not at the baking temperature for a great length of time and the rate of cooling seemed to be immaterial. The present paper deals with the same alloy and more particularly with the resistance towards various forms of stress — tensile, bend and deep drawing. The metallography of Britannia metal has in part also been covered and an explanation attempted for the abnormal behavior of this alloy. Tensile and Bend Tests Two ingots 73/4 in. wide, 11 in. long and ¾ in. thick were cast from the same pot. One ingot was cold-rolled in one direction to a strip 0.241 in. thick, which furnished the tensile test specimens; the other ingot was rolled in the same way to 0.253 in. and furnished the specimens for the bend tests. The ingots were cast as described in the previous paper and cold-rolled in six passes.

Jan 1, 1930

By W. R. Kanne, P. R. Strutt, R. A. Dodd

A study has been made of the creep behavior of ß-NiAl of stoichiometric composition in the temperature range 475" to 775°C. Single crystal tensile specimens were deformed under a constant applied load. From slip line studies and tensile axis rotations it was concluded that the crystals deformed by pencil-glide on (100) and (110) planes with a (100) slip direction. Electron microscope thin-film studies showed evidence for profuse cross-slip, and the dislocation Burgers vector was determined to be (100). There was no tendency for the dislocations to lie in definite slip planes, although a strong alignment of segments of edge dislocations was frequently seen. The activation energy for creep in the temperature range 475" and 775°C was judged to be much lower than that for creep at temperatures above 775°C. It is possible that the rate-controlling process is the thermally activated cross-slip of screw dislocations. In recent years considerable interest has developed in the possible use of high-melting-point intermediate phases for high-temperature applications necessitating good creep resistance. Ordered alloys such as Ni3A1, modified by alloying additions, have received particular attention, culminating in the recent development by Pratt and Whitney of single crystal turbine blades.' The intermediate phase NiAl has considerable theoretical interest from a creep standpoint because not only is it ordered up to the melting point (-1650°C at stoichiometry) but it contains a high concentration of structural vacancies on the aluminum-rich side of stoichiometry. These vacancies are known to exert a strengthening effect under some conditions,' but in addition they might be expected to affect high-temperature creep rates through dislocation climb. The present paper deals with the slip line and dislocation structures developed during creep of stoichiometric NiAl between 475" and 775C, and with possible attendant creep mechanisms. MATERIALS AND TEST TECHNIQUES NiAl ingots of stoichiometric composition were prepared by induction melting 99.996 pct A1 and 99.98 pct Ni (kindly provided by the Kaiser Aluminum Co. and the International Nickel Co., respectively) in 100 cc pure alumina crucibles in a helium atmosphere. No chemical melting flux was used in order to avoid con- tamination of the alloy. Each ingot was slowly direc-tionally solidified to avoid porosity and to produce very large grains up to 2 in. in length. In this way, ingots were obtained which were suitable for sectioning into single crystal creep specimens. Chemical analysis indicated that all alloys were within the range 49.6 0.3 at. pct Ni. For the present investigation, identical rectangular single crystal blanks were cut vertically from one particularly large crystal in an ingot using a series of three diamond cut-off wheels with appropriate spacers. Thus, all sliced crystals had the same orientation with the tensile axis parallel to the long side of the rectangle; the initial orientation of the tensile axis is shown as S, in Fig. 1. The blanks were homogenized at 1250 to 1300°C for 48 hr and subsequently cooled slowly to room temperature. A gage length of rectangular cross section and about 0.75 in. in length was prepared on each specimen using an electrolytic lathe and a dilute nitric/phosphoric acid electrolyte. The gage length cross section was 0.250 0.0005 in. by 0.040 ± 0.0005 in. Holes to accommodate tensile grips were electrolytically machined using a rotating acid jet. After creep testing, this same technique was used to cut discs for transmission electron microscopy. Thus, all shaping was done electrolytically, the only exception being that (122) sections were spark-machined from some speci-

Jan 1, 1970

By M. C. Miller, M. R. Tek, D. L. Katz

Previous studies have shown the influence of geometric variations on the drawdown and buildup behavior of a well completed in a homogeneous, porous medium containing a single-phase fluid. Other papers have shown the influence of leakage across caprocks on drawdown tests on water wells and aquifers. This paper presents two additional cases: the influence of an adjacent, expansible source of fluid, and the effect of caprock leakage on the measured in situ permeability and compressibility. Methods are developed for evaluating the influence of these two deviations from a uniform aquifer upon the in situ permeability and compre.ssibility indicated by pump tests. INTRODUCTION In relatively uniform porous media, saturated with a single-phase fluid, the effective reservoir permeability and compressibility of the water porous bed system may be obtained from drawdown and build-up data on wells, such as the initial wells drilled in aquifer storage reservoirs (Homers and Katz et al.7). In considering the drawdown and build-up behavior of wells adjacent to storage reservoirs, or of wells in an aquifer adjacent to an unknown gas field, questions arise as to the quantitative effect of the presence of compressible fluid on the measured permeability and compressibility of the formation. The solution to this problem is presented, using a constant pressure line source at some distance from two wells, one of which is pumped and the other used as the pressure observation well. The solution is presented in terms of the geometry of the wells and their relationship to the constant pressure line. It is known that caprock leakage can interfere with the determination of an aquifer in situ permeability and compressibility (Mantush4, Hantush and Jacob3 and Witherspoon and Muellerll). This paper presents an added case of the effect of leakage through a caprock of known thickness and permeability on well tests starting with a reservoir of constant pressure above the caprock and contributing to the aquifer as a result of the pump test. Again, both a pumping well and an observation well are postulated. These two cases are presented together since both a compressible fluid nearby and. caprock leakage show similar deviations from expected in situ permeability and compressibility results, and the solutions are similar in form. EFFECT OF A NEIGHBORING CONSTANT PRESSURE SOURCE ON IN SITU MEASUREMENTS Bixel, Larkin and van Poollenl presented a paper showing the influence of a discontinuity of the properties of a fluid formation system on drawdown and build-up performance. Their case is related to the present study but may be distinguished from it in that their numerical work and resulting graphs relate only to the performance of the pumping well itself. Incorrect values for in situ reservoir properties may be obtained from pump test data if the skin effect of the well and after-flow are not considered. Analysis of this problem by the authors indicated that the more reliable method of evaluating the influence of an adjacent gas field or expansible source was to use one well for pumping and another well at some distance from it for observing the aquifer pressure performance. An expansible source of hydrocarbon near a pumping well may be approximated by a line of constant pressure for a pump test. Fig. 1 illustrates a pumping well and an observation well near a line of constant pressure. Pressure behavior of an observation well during a drawdown pump test near a line of constant pressure is given by the diffusivity equation:

Jan 1, 1967

By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young's modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu' have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young's modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu' pointed out, calculated variations in Young's modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young's modulus, the shear modulus and Poisson's ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young's modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

By D. R. McCord

Data of a known statistical quality has been successfully used in a system of conventional fluid mechanics equations essentially free of empirical "conformance factors to prediet early detailed field 03 in a reservoir where gravity drainage is important and oil and rock properties vary con. siderably. The system is useful where comparative recovery predictions for one or more cases of natural depletion and gas cap pressure maintenance are needed and the reservoir is not too heterogeneous. INTRODUCTION Many authors, have examined various facet* of the gravity drainage-gas cap pressure maintenance problem over the last several years. Two of them. Burtchaell and Elkins, have published practical studies. In the case described in the present paper the best development and operating plan for one of the important reservoirs of the Bolivar Coastal Field in Western Venezuela was urgently needed. It was requested that sound comparative economics be presented along with an engineering evaluation of no additional drilling, maximum drilling. several cases of gas pressure maintenance, of water flooding and combination cases. A rapid analysis of the effect on recovery of the range of crude and rock properties indicated that none of the published methods using average properties would yield adequate comparative predictions. This paper covers the predictive system developed to deal with natural depletion and gas cap pressure maintenance. The large amount of data available for this field permitted statistically reliable correlations to be made of most rock and oil properties, and the evident smooth areal variations of these properties encouraged the construction of a lineal mathematical model of material balance and fluid flow equations, which could be manipulated by a modified iterative procedure. The manipulation is much more adaptable to computing machines than manually operated calculators and subsequent studies have been prepared for the IBM Card Program Calculator. A matrix as opposed to linear model has been tentatively worked out by other members of our group to deal with more heterogeneous reservoirs. It is more adaptable to computers such as IBM-701 or the Remington-Rand Univac. In 1950, when the system reported below was developed, no rapid computing machines were available to the author. Their existence and promise encouraged an initial approach by hand. Some details of oil and rock Property correlation are included because there are a surprisingly large number of medium-sized reservoirs in the world that show systematic property variations which are significant for a rigorous analycon. All large reservoirs (over half a billion barrels recovery) with which the author is familiar contain at minimum a significant temperature variation. Using the rock and oil property correlations, past pressure and production, the gas-oil ratio history of the reservoir was computed and found to be in close agreement with field measurements. The future performance under cases of natural depletion, gas injection of 100 MMcf/day, and of 130 MMcf/day, was then computed; a 70 MMcf/day case was also carried far enough to provide data for comparative economics. The 130 MMcf/day case proved to be the most attractive. A 50,000 horsepower gas turbine driven centrifugal compressor plant to take this quantity of adjacent field gas from 30 to 1,950 psia and inject it into the reservoir is under construction. The total cost of the project will exceed 20 million dollars.

Jan 1, 1953

By N. J. Grant, H. Brunner

This paber is concerned with the determination of equations relating elongation to the amount of shear taking place both along grain boundaries and in slip planes of poly crystalline aggregates during creep. Certain discrepancies with previously used equations are pointed out. Grain boundaries were observed to become serrated during creep, but it is shown that this does not necessarily prevent further grain boundary sliding. Direct obser-vations of subgrain boundary ingration lead to the conclusion that this migration facilitates sliding along serrated grain boundaries. It is bointed out that the state of stress at triple boints is still unknown. MOST of the mechanisms of deformation contributing to elongation are shear processes, such as slip, kinking, grain boundary sliding, and twinning. For quantitative investigations of individual deformation mechanism it is necessary to know the equation which permits the calculation of speci-tnen elongation from measured amounts of shear. This calculated elongation must then be compared with the observed total elongation. The authors' special interest concerned grain boundary sliding during creep. Although this subject has already been investigated quantitatively by McLean,' Rachinger,' and Fazan, Sherby, and Dorn, calculations indicated that none of the equations used thus far to relate shear with elongation were sufficiently well founded. A basic study of this relationship was thus made and the results of this study (which do not entirely agree with those previously used) are presented. Most of the ideas set forth apply not only to grain boundary sliding but to other mechanisms of shear as well. THE SPEAR-ELONGATION RELATIONSHIP Basic Models—The relationship between shear and elongation is trivial in the simplest case of shear, which is shown in Fig. l(a). The vector A; designates the displacement across the shear interface, and Au, and Aut are its components parallel and normal to the tensile direction, respectively. It is evident that the specimen elongation due to shear is equal to the longitudinal component of the shear vector, and it should be noted that the normal component does not contribute to the elongation of the specimen (there are, of course, two normal components in a three-dimensional model). The model shown in Fig. l(b) may be applied to mechanical twinning and to subgrain boundary tnigration. In this case the width (h) of an already existing shear band increases by the migration of an interface, but the shear angle y (angle of mis-orientation in the case of a subgrain boundary) remains constant. The geometrical relationships indicated in Fig. l(b) permit this case to be reduced to the one shown in Fig. l(a). For the resulting elongation A6 we find: where AV/V = fraction of the volume of the specimen swept by migrating interfaces , and 1 = length of specimen. Thus, assuming for example that the angle of mis-orientation is 1 deg, and that P = 45 deg, we find that the specimen elongates 0.87 pct of its length if the entire volume of the specimen is swept once by such a subgrain boundary. An example of deformation by migration of subgrain boundaries is shown in Fig. 2. The specimen shown was repolished after 9.8 pct creep strain and the test then continued for another \ pct. Since the shear vector has, in general, a component normal to the surface, subgrain boundary migration results in the formation of an inclined band delineating the region swept by the subgrain boundary. These inclined bands become clearly visible when observed with oblique illumina-

Jan 1, 1960

By Wendell S. Williams

Single crystals of TIC doped with boron at high temperat~ires develop second-phase inclusions. The inclusions are in the form of lamellae lying parallel to {l 11 } planes of the Tic matrix and can be vevealed by etching [100] cleavage faces of the boron-doped Tic crystals. measurements of the critical resolved shear stress. t, of TIC crystals containing such inclusions showed that the ropid drop in t wilh increasing temperatu.ve found for pure Tic was greatly reduced. At 1600°C, the inclusion containing crystals had a value of t five limes that of pure Tic. The hardening effect also was found to inhibit hot pressing of TiC powders containing boron impurity. Thermochemical and crys-tallographic arguments suggest that the inclusions are TiB2. The boron content of the hardened carbide is a few tenths of 1 pct. TITANIUM carbide is noted for its high room-temperature hardness. However, measurements of the critical resolved shear stress, T, of single crystals of Tic at high temperatures have shown that t decreases exponentially with increasing temperature.' This temperature dependence of t is attributed to thermally activated dislocation mobility limited by a large Peierls stress.' In turn, this large Peierls stress is believed to be a consequence of strong co-valent and ionic binding in Tic. The rapid drop in 7 with increasing temperature, characteristic of pure Tic, is lessened by the introduction of second-phase inclusions. Exposure of Tic to boron at high temperatures produces such inclusions. A report of the influence of boron on t in Tic is presented, followed by a discussion of the nature and formation of boron-containing inclusions in Tic which are believed to be responsible for the hardening effect. I) CRITICAL RESOLVED SHEAR STRESS OF BORON-DOPED Tic CRYSTALS Tic single crystal boules grown by Union Carbide Corp., Linde Division, were doped with boron by placing them in a carbon crucible packed with boron powder and heating in a vacuum furnace to 2000°C for 1 hr. Samples 1 by 1 by 3 mm were cleaved from these doped boules. High-temperature compression tests' were made on these samples to determine the critical resolved shear stress as a function of temperature . The rapid drop in critical resolved shear stress found for pure Tic crystals' did not occur: tests indicated that the boron-doped crystals at 1600°C had values of T equal to those of pure Tic crystals heated to only 1100°C, Fig. 1. No difference in the shape of the individual stress-strain curves was produced by the boron doping, but the stress scale was multiplied by a large factor. The hardening effect of boron in Tic probably extends to temperatures lower than those used in the present work (1100°C minimum). At room temperature, however, the influence of boron is difficult to determine because the stress required for gross plastic flow in pure Tic is SO high that in practice fracture cccurs first. Microhardness is the only test that can give an indication of the yield stress in Tic at room temperature. such measurements were made5 on boron-doped Tic; the matrix had a hardness value

Jan 1, 1967

By John Wulff, David A. Stevenson

The solubility of iron and cobalt in liquid lead, the solubility of chromium in liquid tin, and nickel in liquid silver were determined up to 1300°C in an atmosphere of hydrogen. Liquid samples were taken at different temperatures and analyzed. The data obtained were plotted to show the relationship between log mole fraction of solute and the inverse of the absolute temperature. Resulting values for the differential heat of solution (AH) and the excesspartial molar entropy (S)are: for the iron-lead system = _24,200 cal per mole and AT = 5.0 e.u. for the a phase, and AH = 18,300 and S = -0.1 e.u. for the y phase; for the cobalt-lead system AH = 16,500 cal per mole and AS =0.7 e.u.; for the chromium-tin system AH = 15,600 cal per mole and AS = 8.5 e.u.; for the nickel-silver system AH =18,000 cal per mole and AS = 4.0 e.u. RECENT developments in coating, brazing, and heat transfer have focused attention on specific cases of solid-liquid interaction in metal systems, particularly those involving dilute liquid solutions. One fundamental quantity of interest in such systems is the equilibrium phase distribution between solid and liquid phases. In any effort to fully understand such interactions, one must be able to describe the equilibrium state precisely. Furthermore, in order to develop genera! relations for such systems, one must know the equilibrium state in a number of different cases. This investigation was devoted to a study of the equilibrium phase distribution in four binary systems: solid iron-liquid lead; solid cobalt-liquid lead; solid chromium-liquid tin; solid nickel-liquid silver. The iron-lead system was previously studied by Shepard and parkman' and later by Fleischer and Elliott2 with differing results. Both investigations were carried out by sampling the saturated liquid, and analyzing it chemically. The cobalt-lead system was previously reported by Pelzel,3 who noticed no discontinuity near the transformation. A limited investigation of the chromium-tin system was made by Wlodek and wulff4 using a weight loss method. This work was done in conjunction with the development of a process for coating molybdenum with chromium from tin solutions. To more fully under- stand the kinetics of the process, a more accurate determination of a solubility was desirable. No significant data were found in the literature on the nickel-silver system. Data on the latter system were, however, relevant to the investigation of the corrosion kinetics of copper-nickel alloys in liquid silver as carried out by Harrison and wagner,5 EXPERIMENTAL APPARATUS AND PROCEDURE Of the techniques available for the study of such systems the most effective appears to be that of liquid sampling,2,6,7 which is the method used in the present investigation. A schematic diagram of the sampling furnace is given in Fig. 1. Large pieces of solute metal, in excess of saturation solubility, were added to 200 g of the solvent metal, and the entire charge placed in an alundum crucible. Analytical reagent or materials of chemically pure grade were used in all investigations. The crucible was contained in a zircon muffle tube positioned vertically in the uniform hot zone of a Globar resistance furnace. The tube was provided with a number of ports which permitted sampling at temperature and in controlled atmospheres or vacuum; the ports were also useful for evacuation and introduction of gases as well as for thermocouple measurements. A chromel-alumel thermocouple Sheated in a porcelain tube was used for temperature measurements. A purified hydrogen atmosphere was employed in all experiments reported in this paper. The hydrogen was purified by passing it first over hot copper gauze to remove oxygen and then through a molecular sieve immersed in

Jan 1, 1962

By C. A. Stout, S. W. Nicksic

The materials that stubilize emulsions of some Southern California crude oils were isolated from the produced crude. These substances were separated into acidic and nonionic fractions by ion exchange chromatography. Each fraction was further broken into groups of homogeneous molecular weight composition by gel permeation chromatography. Both ionic character and molecular weight of the individual fractions are reflected in the properties of the original crude oil emulsion. Specifically, the more acidic and the higher molecular weight fractions appear to be the most effective stabilizers. INTRODUCTION The treatment of oilfield emulsions is a continuing problem for the oil industry. In almost all cases, these are water-in-oil emulsions. Much more is known about the formation and stabilization of oil-in-water (O/W) emulsions than of the water-in-oil (W/O) type. To understand W/O emulsions, more information is needed on the materials responsible for their formation and stabilization. This is especially true in the case of oilfield emulsions where the stabilizing materials are complex mixtures of large asphaltene-like molecules. To study the chemical and physical properties of these emulsion stabilizers, it is necessary first to separate them from crude oil. This separation was achieved in the case of two Southern California crude oils. The materials that were isolated appear at first to be little different from an asphaltene mixture. However, if a mixture of distilled water and mineral oil containing about 1 percent of the natural emulsion stabilizers is passed through a colloid mill, the W/O emulsion formed may be stored in the laboratory for many months without any sign of breaking. This could not be done using undifferentiated asphaltenes from the same wells, indicating that there is a real difference between these materials and ordinary asphaltenes. The colloid mill used to generate the emulsion was required because tile natural emulsion stabilizers had very little effect on oil-water interfacial tension. The one characteristic — complexity of composition — that emulsion stabilizers share with asphaltenes makes virtually impossible the exact structure determination of the components of the mixture. For this reason, it was decided to investigate first the influence of molecular weight on the ability of these materials to stabilize emulsions. The emulsion stabilizers were first separated into acidic and neutral fractions according to whether or not the material was retained on a weakly basic ion exchange column. The extraction procedure was not designed to remove basic components from tile oils, and no attempt to isolate such a fraction was made. Following this separation, selected fractions were analyzed by gel permeation chromatography. Gel permeation separates according to molecular size, largely independently of chemical or polar characteristics. A heterogeneous mixture is separated into a number of fractions having much more homogeneous molecular weight distribution. A number average molecular weight of each fraction is therefore close to the true molecular weight of the principal component of that fraction. The fraction weights, expressed as weight percent of the sample, and the number average molecular weight of a representative selection of the fractions, will be referred to in this paper as the molecular weight profile of the original sample. DESCRIPTION OF GEL PERMEATION ANALYSIS The first reported gel permeation analyses were for separating partially hydrolyzed protein molecules in an aqueous system using expanded starch granules. Most of the theoretical work on gel permeation has been done by biochemists.1 This theoretical treatment is still incomplete, but the

Jan 1, 1969

By H. R. Ogden

The notch sensitivity of titanium alloys is affected by impurity content, microstructure, and heat treatment. Using notch tensile properties to evaluate notch sensitivity, three commercial titanium-base alloys were investigated over the temperature range of -320o to 390°F. The alloys studied were Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo. Six interstitial levels were studied for each alloy in four mi-crostmctural conditions. The ff- 0 alloys were studied in both the annealed and heat-treated condition. All tests were conducted using 1/4-in. diam round tensile samples. The notched samples had a 50 pct notch with a notch sharpness (a/r) of 53, corresponding to Kt 6.3. Notch sensitivity was increased by increased interstitial content, low temperature, and acicular-type microstructures. The heat-treated, high-interstitial content - 13 alloys were more notch sensitive than the same alloys in the annealed condition. In addition, minima in the notch tensile-temperature curves were observed at temperatures near 32°F. These minima became more pronounced with increasing interstitial content. 1 HE increaseduse of titanium alloys in high strength applications at subzero temperatures requires that a better under standing of the low-temperature behavior of the alloys be obtained. At low temperatures, metals generally exhibit increased strength with lowered ductility and tohness. Notch sensitivity and the factors which influence it become more important as the strength level is increased and the temperature is decreased. Some of the factor s which affect notch sensitivity in ti- tanium alloys are composition, interstitial content, microstructure, and heat-treatment condition. In this paper, the results of a study of these variables on the notch sensitivity of three titanium alloys at temperatures from —320o to 390o are reported. The notch geometry selected for this program was chosen to provide a severe test of notch sensitivity. The ability of the metal to flow without initiating fracture under these severe conditions is reflected in the notch-strength values. Since notch strength is, in part, determined by the constraint exerted by the combined tensile stresses, the behavior of notch specimens reflects the properties of the material under combined stresses. For example, a material with a high notch-unnotch strength ratio may be expected to withstand the biaxial stresses encountered in a pressure vessel better than a material with a low ratio of notch-unnotch strengths. This implies that maximum strength alone is not a sufficient criterion for applications of this type. It further may be concluded that the various conditions that promote poor notch behavior also will affect adversely the performance of materials under combined stresses. In the alloys studied, these included low temperatures, high interstitial levels, and hasformed microstructures. EXPERIMENTAL PROCEDURES Three alloys, Ti-5Al-2.5Sn, Ti-6Al-4V, and Ti-2Fe-2Cr-2Mo, were purchased from commercial producers as 2-in.-dam rod stock. Oxygen and nitrogen were added to these alloys by remelting to obtain a variety of interstitial contents as shown in Table I. In order to Compensate for the much more potent strengthening effect of nitrogen compared with oxygen, an oxygen equivalent content is used to describe the total oxygen plus nitrogen contents studied. It has been suggested previously1 thatnitro-gen is approximately twice as effective in strengthening as oxygen, and carbon, to the extent it is in so-

Jan 1, 1962

By Selma Hermann

For the past century, the so-called aluminum bronzes have been assuming a role of ever-increasing importance in the metallurgical field. The last quarter of that century has marked many efforts to find alloying elements that would alleviate some of the undesirable qualities of the aluminum bronzes-for example, the heterogeneity of the alpha solid solution and the extreme hardness of the beta. Much of this work, however, has been rather haphazard-compositions and heat treatment are usually so much at variance as to make comparison impossible. It is the object of this research to study the effect of certain percentages of common alloying elements on aluminum bronzes of analogous compositions and heat treatments. It is hoped that the material gathered here will at least serve as a basis for further systematic study.

Jan 1, 1930

By S. H. Moll, R. E. Ogilvie

The investigation of solid-state diffusion phenomena may lead to much information concerning binary alloys. In particular, a study of the concentration gradients present in multiphase diffusion couples can lead to the determination of the solubility limits of the single-phase fields in the phase diagram. The specific concentration gradient which results from the heat treatment of a diffusion couple depends not only upon the time and temperature of diffusion, but also upon the number of phases existing in equilibrium at the diffusion temperature. Such concentration gradients possess sharp discontinuities whose terminal points correspond to the solubilities existing at the limits of the two-phase field in the phase diagram at the diffusion temperature. In general, there will be a discontinuity in the concentration curve for each two-phase field which exists in the phase diagram between the concentration limits of the couple. A number of investigators have analyzed the gradients present in multiphase diffusion couples. 1-8 The iron-titanium phase diagram exhibits a y loop in the temperature range from 900" to 1400°C, and the limit of the a + y field lies at some composition which is less than 1 wt pct Ti for any temperature. It was felt that a diffusion study could yield values not only for the diffusion coefficients involved, but also for the chemical solubilities in the phase diagram. The concentration gradients were analyzed by an X-ray absorption technique developed by Ogilvie.6 The absorption of a monochromatic X-ray beam is measured in steps parallel to the diffusion direction and the resulting intensity gradients are transformed into concentration gradients by applying the laws of X-ray absorption in a binary system. This technique has been applied by ogilvie6 to the systems Ni-Au, Cu-Au, Fe-Cr, and Ni-Cr; by Gelles7 to the systems Be-Fe, and Be-Ni and by Hilliarde to the system Al-Zn. Linear X-Ray Absorption Analysis—The use of X-ray absorption analysis as a tool for determining concentration gradients arises from the fact that the beam is absorbed according to the quantity and species of elements present in the sample and not according to their state of aggregation. This method is more advantageous than the chemical analysis of machined layers since it is less time consuming and less expensive and can analyze a very small area. IF a homogeneous binary alloy (A + B) is analyzed with two different monochromatic X-ray beams I0(2) and lo(2) the following relation between the transmitted intensities, the intrinsic absorption coefficients of A and B for the two different radiations and the weight fraction of each element may be derived.' In (I/Io) (a+b) xa(u/p)a(2) + xb(u/p)8(2) Eq. [1] is independent of specimen thickness and density, but requires that either element A or B possess an absorption edge between the wavelength limits of the two monochromatic beams. I, is evaluated for each radiation by measuring the transmitted intensity through a varying number of foils of a suitable absorber. A plot of the natural logarithm of the transmitted intensity as a function of the number of foils, when extrapolated to zero foils, yields the value of I,. If a plot of the ratio in Eq. [ I] is calculated as a function of xA, then a master curve results. From

Jan 1, 1960

By W. Ivanick, Frank W. Glaser

ORDERING reactions of Fe-Si compositions in the a region have been mentioned in a number of review articles.7-8 However, little is known in regard to the critical temperature, T at which this transformation takes place. Greiner and Stoughton,' in a study of the constitution of iron-rich Fe-Si alloys below 800°C, placed the onset of order at a composition of about 4 to 5 wt pct (7.5 to 9.5 atomic pct) Si. They observed that at this composition the ductility and strength begin to decrease sharply and brittleness develops. During X-ray studies they observed only the appearance of superlattice lines for compositions containing 12.5 atomic pct Si. More recent X-ray diffraction studies- etected the appearance of superstructure lines (corresponding to the calculated positions of [Ill] and [ZOO] reflections) for alloys containing 9.5 atomic pct. This fact confirms Greiner and Stoughton's original hypothesis in regard to the onset of order at compositions containing about 7.5 to 9.5 atomic pct Si. The physical properties.of Fe-Si alloys containing more than 10 atomic pct Si have been studied only to a limited extent. Their extreme brittleness and difficulties of sample preparation render them of little industrial use in comparison with alloys in the 0 to 10 atomic pct Si range. The properties of Fe-Si alloys reported to date are mostly properties measured at room temperature on ordered compositions It appears that because of experimental difficulties fully disordered alloys could not be produced in the critical composition ranges and their properties could therefore not be reported. In Figs. la, lb, and lc, a summary of physical properties of Fe-Si alloys, measured during recent investigations of the influence of silicon additions to iron, is presented. No mention of determination of the critical temperature, T for disorder could be found in the literature. The following is an account of work done in an attempt to: 1) produce the disordered state of various Fe-Si alloys and establish the critical temperature, T for disordering, and 2) compare the electrical and thermal conductivity characteristics of the ordered and disordered phases as functions of composition. Materials, Preparation of Test Samples, and Testing Methods Fe-Si alloys with high silicon contents (about 10 atomic pct) are usually prepared using powder metallurgy techniques. This method insures accurate compositions and high purity through the use of protective atmospheres during solid state diffusion alloying of the mixed powders."" Iron and silicon powders were mixed in the desired proportions, cold or hot pressed, and then homogenized at 1150°C for periods ranging from 6 to 12 hr under a protective getter and in a hydrogen atmosphere. Fully homogenized samples were quenched in water from various and successively higher temperatures to establish the critical temperature for disorder. Temperatures were determined using Pt—Pt-Rh thermocouples in contact with the test samples. Test bars were approximately 0.6x1.25x7.5 cm. Electrical measurements were made at room temperature by determining the potential drop over a 1.5 cm span for a current of 10 amp. Densities of the samples were determined by immersion. High temperature electrical resistivities were measured using previously described techniques.'" Specific heat conductivity up to 200°C was measured by heating one end of the test bar and water-cooling the other; heat conductivity was then obtained by subtracting the rate at which heat entered the water from the

Jan 1, 1957

By Carroll C. Bailey, William F. Boericke

Mine financing, or providing adequate capital for developing and bringing a mining property into production, is an essential requirement for a successful operation. Today it presents a different picture than even twenty-five years ago. The day appears to be gone when a mining property could pay its own way from grass roots to production. The country has been quite thoroughly combed for surface showings from which sufficient initial profit could be immediately garnered to pay for further development and production facilities. The four M's for success in mining-mineral, market, management, and money-are still essential, but doubled or tripled wage costs and steep advances in cost of equipment and supplies throw increased emphasis on adequate capital funds for converting a prospect into a producer. Consequently, the old picturesque, although seldom rewarding, grub- staking procedure where a single venturesome citizen might advance funds to a prospector on a fifty-fifty basis for whatever discovery he might find, has largely disappeared. Its place, to some degree, has been taken by the small syndicate of venturesome members who band together for furnishing funds to a group of prospectors for the same general purposes. Such a syndicate has a definite organization and is usually assured of sufficient initial funds, or flow of funds, to carry on work for several years. It is usually headed by an engineer-promoter or an entrepreneur trader who has had considerable field experience as well as personal knowledge of his prospecting crews. For the owner of a potential mining property who has ample capital, the problem is to determine (1) justification for the necessary investment in exploration and development, and (2) the economics of the enterprise as to size and degree of integration of the ha1 operating entity. If the owner of such a property has little or no capital, he also faces these same basic problems but, in addition, must be able to present the findings of fact and persuade the prospective investor that the enterprise will produce

Jan 1, 1964

By A. H. Cottrel

SINCE metallurgy exists to provide strong, tough, engineering materials it must inevitably be perpetually concerned with the problem of brittle-ness. The steel-making industry was created because chemically unrefined iron is brittle. The steel-working and alloy-steel industries exist partly because hardness and ductility are mutually exclusive qualities in structurally unrefined steel. Yet, in spite of these immense industries, the brittle failure of steel ships hulls, bridges, pressure vessels, and pipelines, is still a contemporary problem. In fact, brittleness is a normal property of most solids, including metals and alloys, at low temperatures. Only face-centred cubic metals are commonly ductile at the lowest temperatures, and even here exceptions are known.'," Expensive are-melting processes. under inert gases or vacuum, have been developed to overcome brittleness in titanium, zirconium, columbium. and molybdenum. Polycrystal-line zinc, magnesium, and uranium have little ductility at room temperature. Beryllium, chromium, and tungsten have even less; similarly for antimony, bismuth, germanium, silicon, intermetallic compounds, and metallic carbides, nitrides, silicides, and borides. Oxides and other ceramics would be ideal creep-resistant materials but for their extreme brittleness when cold, and great efforts have been made to overcome this problem by mixing ceramics with metals. In fact, the traditional use of the name metallurgy for what is really the science of engineering materials is a recognition that most non-metallic solids have so far been precluded, by their extreme brittleness, from use as major structural materials in mechanical engineering. Most of what we know about brittleness in metals has come from studies of structural steel, and it is this material that shall mainly be considered. The things we have learned from it have a wider application, at least to other body-centred cubic transition metals, although the extent to which similar ideas can be applied to hexagonal metals and other materials is not yet clear. Fracture and Plastic Deformation The theoretical breaking strength of an ideal solid, about E/10 where E is Young's modulus, has been approached reasonably closely in experiments on fibres. But large specimens break at much lower stresses. For example, brittle cracks in large structural steel assemblies have been observed to spread catastrophically at speeds of 6000 ft per sec under stresses of about 10,000 psi, i.e. about E/3000. There are two sources of weakness; stress concentrations, and chemical agents in grain boundaries or on crack faces that lower the surface energy y of the material. Although we shall deal mainly only with the first of these, much of the discussion is also applicable to the second when different values of y are used. Griffith's well-known formula p = [ 2Ey/p(1 - v2)c]1/2 [1] gives the smallest tensile stress p able to propagate an atomically sharp surface crack of length c or interior crack of length 2c through a thick plate (compared with c) of elastically isotropic material of

Jan 1, 1959

By A. Lubinski, J. E. Hansford

Rotating drill pipe passing through dog-legs suffers fatigue damage due to cyclic bending stresses. Curves of the cumulative fatigue damage incurred in either steel or aluminum drill pipe going through Such dog-legs are presented. These curves provide means for properly planning the rate of angle build-up in directionally drilled wells and allow discarding of drill pipe which has been fatigue-damaged in dog-legs. INTRODUCTION Drill pipe which is subjected to bending as it rotates, experiences a cyclically varying bending stress. If this bending stress is sufficiently large, the drill pipe is fatigue-damaged by each revolution, and ages as fatigue damage accumulates. Drill pipe can be bent intentionally, as in the case of directionally drilled holes, or unintentionally due to unde-sired changes in hole direction caused by variations in formation properties, weight on bit, etc. These changes in hole direction, whether intentional or unintentional, are called dog-legs. The theoretical limits of dog-legs which are permissible before the drill pipe begins to fatigue can be calculated.' However, in wells where the maximum permissible dogleg is exceeded, the concept of cumulative fatigue damage can be used to estimate damage suffered by the drill pipe. This concept has already been used to estimate the cumulative fatigue damage of drill pipe due to drilling vessel roll.' The purpose of this paper is to extend the usage of the cumulative fatigue damage concept to drill pipe in doglegs, and to draw conclusions which may be beneficial in preventing numerous frustrating and expensive drill pipe failures. FATIGUE OF STEEL DRILL PIPE IN IDEALIZED GRADUAL AND LONG DOG-LEGS It is taken for granted that, if necessary, the reader will become familiar with the definitions and concepts which follow by examining the reference cited in each case. For Ref. 1, it will suffce to read only through the section Abrupt Dog-Legs. 1. Concept of the two extreme kinds of idealized doglegs: gradual and long dog-legs and abrupt dog-legs,' 2. Concept of why the bending moment in drill pipe un- der tension is the largest in the vicinity of the tool joint,' 3. Concept of why dog-leg severity which drill pipe can withstand decreases with an increase in tension,' and 4. Definition of the rate of change of over-all hole angle (dog-leg severity)." Figs. 1 and 2 indicate the aging (fraction of life expended) of steel drill pipe passing through a gradual and long dog-leg. Both figures have a left-hand ordinate scale labled Length of Drill Pipe Below Dog-Legs. This scale can be used for cases in which the drill collar weight is applied to the bit and does not contribute to the tension in the drill pipe. It can be used for either 3 1/2-, 4 1/2- or 5-in. drill pipe. This is due to the fact that, if the drill collars do not contribute to the drill pipe tension, then the effect of pipe tension on bending due to a change in pipe size is nearly compensated for by a corresponding change in pipe rigidity. On the other hand, if drill pipe is rotated off bottom, then drill collars contribute to the tension in the drill pipe and this increase in tension is not compensated for. In this case, one of the three right-hand ordinates must be used (the one which corresponds to the correct drill pipe size). In the right-hand ordinates, tension should be understood as the weight in mud of the portion of the drilling string below the dog-leg, minus the weight on bit.

Jan 1, 1967

By Harmon D. Nine

DISCONTINUITIES in the strain vs cycles to failure (S-N) fatigue curves have been reported for polycrystalline materials by Porter and Levy for copper,&apos; by Benham and Ford for mild steel,&apos; and by Williams and Stevens for 18/5 stainless steel.3 However, the considerable scatter of the points for polycrystalline materials have made a statistical analysis of the data necessary to confirm the discontinuities. By using oriented single crystals of high-purity material and low grown-in dislocation content, the reproducibility has been improved to a degree which makes statistical analysis unnecessary and clearly shows discontinuities in the S-N curves. A recent publication4 reports an abrupt change of slope in the S-N curve for ( 100) axially oriented copper single crystals fatigued in torsion. The reported discontinuities in the S-N curve, along with a different mode of failure in the two branches of the curve, have been interpreted as being due to two different amplitude-dependent mechanisms. Further work on copper single crystals of (111) axial orientation has now been completed which supports the existence of an amplitude-dependent change in the mechanism of fatigue. In the present study torsional-fatigue experiments were performed at room temperature in air on (111) axially oriented single crystals. The crystals were grown and prepared as reported in Ref. 4. Two different methods of growing the crystals also discussed in Ref. 4 produced crystals of two different perfections: Type I with dislocation density of >l06 per sq cm and Type I1 with dislocation density of <l05 per sq cm. In accordance with the accepted hypothesis that crystal flaws are primarily responsible for the scatter of fatigue lifetimes, particularly at low amplitudes, the values for the three lowest amplitudes for Type I crystal are believed to be uncertain. They are marked in braces in Fig. 1. On the other hand, at amplitudes above a surface shear strain (SSS) of *0.003, the data for both types of crystals are in agreement. Most remarkably the S-N curve for torsional fatigue of (111)-oriented single crystals is composed of three segments separated by rather large discontinuities, Fig. 1. Metallographic and X-ray measurements indicate that the lower branch corresponds to the low-amplitude (F) region of the (100) copper single-crystal results as discussed in Ref. 4, and the two upper branches correspond to the high-amplitude (H) region. The lower discontinuity in the (111) S-N curve and metallographic evidence give further support to the hypothesis that different mechanisms of failure operate for high and low strain amplitudes. Reference to the resolved shear stress diagram, Fig. 2, shows that the highest stressed systems in

Jan 1, 1965

By E. J. Efsic, C. M. Wayman

The fcc to bcc y to a transformation in an Fe-24.5 at. pct Pt alloy was studied and found to be martensitic. Large martensite plates are formed in this alloy which are ideal for crystallographic studies; the Ms temperature is about -5°C. Ordering of the parent phase prior to transformation to martensite causes a pronounced lowering of the Ms temperature. For the first time in the case of alloys of iron, measurements of the habit plune, orientation relationship, and magnitude and direction of the shape stvain have been obtained on preselected martensite plates. It is shown that by measuring the initial and displaced (as a result of the shape strain) positions of three or more non-parallel fiducial scratches on one reference surfice the maguitude and direction of the shape strain and the state of distovtion at the parent-mavtensite interface can be determined with a reasonable degree of accuvacy. The agreement between the phenomenolog-cal crystallographic theory of martensitic transformations and the experimental results habit plune, orientation relationship, and nlagnitude and direction of the shape strain) is essentially perfect, and is thought to be the best reported to date for iron alloys. THE comparatively few investigations on binary Fe-Pt alloys have been concerned with magnetic properties, ordered phases, and the equilibrium diagram itself. Various investigations have shown that the equilibrium diagram is of the open y field type; in addition there is a peritectic transformation, a minimum melting point, and three ordered phases: Fe3Pt, FePt, and FePt3. The results of a number of investigators1-6 have shown that the temperature dependence of the y to a (and reverse) transformation in iron-rich alloys is reasonably well-established. The Fe3Pt phase was first noted by Kussman and Rittberg,7 and its existence was later confirmed by Franklin et al,8 Steijn and Donahoe,9 and Berkowitz et al.10 The FePt phase was reported by Isaac and amman&apos; and later confirmed by a host of others.3,6,7,12,13 Kussman and Rittberg7 noted the existence of the superlattice FePt3. Prior to 1956, the 1 to a transformation in iron-rich Fe-Pt alloys was termed "irreversible". In 1957 Klokholm and Donahoe" termed this transformation martensitic, presumably because of its occurrence at temperatures well below those where diffusion normally takes place. This observation served as a point of departure for the present investigation, and in the very early stages of the work to be discussed it was readily verified that the y to a transformation in iron-rich Fe-Pt alloys is indeed martensitic. Quite large martensite plates exhibiting the well-known surface tilt were observed. These plates are ideal in the sense that the boundaries between the parent and product phases were usually very straight. It thus appeared that Fe-Pt martensites would be ideal for crystallographic studies, and this was the purpose of the present investigation. Details of the crystallography of martensitic transformations (particularly for iron alloys) and the phe-nomenological crystallographic theories15-l7 have been discussed many times and thus will require very little elaboration here. The end result of these theories, given in matrix form, is

Jan 1, 1968

By K. H. Coats

This paper describes an approximate technique for handling the problem of percolation of evolved gas upwards through the oil column in computer simulation of natural depletion. This technique has been incorporated into a general model for simulating three-phase flow in one, two or three dimensions. The mathematical model for perfonning these calculations is described in detail in a separate article. 1 While vertical gas percolation occurs during natural depletion in a reservoir of any configuration, it is especially pronounced in the pinnacle reel or bioherm. The reel may have an areal extent less than one section with a thickness of up to 800 It. The upward percolation of evolved gas often limits the time step in calculations as little as one day. Using this small time step, computer expense for a single 30- to 40-year simulation on even a one-dimensional basis has exceeded 92,000. The method described here for handling the percolation allows time steps of 60 days or more (depending on reservoir size and production rate), resulting in a considerable reduction in computing expense. The method also allows calculations in which secondary gas caps build up in tight zones of the oil column below the main gas cap. The validity of the method is indicated in connection with an example pinnacle reef field. Calculated results using a 2-day time step (where the method in question is not needed and not invoked) are compared with results using the method and a 60-day time step. The comparison shows good agreement. Results from one- and two-dimensional simulations of the reef are presented along with the corresponding computing times on the CDC 6600 computer. A three-dimensional simulation was also performed and the required computing time is given. INTRODUCTION A general analysis for simulating three-dimensional, three-phase flow in reservoirs has been developed. 1 In applying this model to reservoirs undergoing natural depletion, a time-step restriction was encountered due to the flow of evolved gas upwards through the oil column and toward the gas cap. A remedy for this problem has been incorporated in the analysis and is described here. The time-step restriction is encountered only in calculations which include flow in the vertical or near vertical direction. The restriction occurs to some extent in reservoirs of any geometrical configuration, but it is especially pronounced in the pinnacle reef or bioherm where the ratio of thickness to areal extent is unusually large. This paper describes the problem, a method of handling it, incorporation of the method in the three-dimensional, three-phase model, and, finally, a test of the method&apos;s validity in an application to an example pinnacle reef reservoir. THE PROBLEM During the early stages of reservoir depletion, pressure falls below bubble point in progressively lower regions of the oil column. Continuing production results in evolution of dissoived gas throughout the oil column. This gas then percolates upwards toward the top of the reservoir. If the gas encounters a sufficiently low permeability zone in its travel upward, then it can accumulate and form a secondary gas cap. If no zones are encountered which are tight enough to hold gas against the gravity forces, then the gas travels on until it reaches the top of the sand or the main gas cap. Numerical simulation of multiphase flow in reservoirs is generally performed with time steps such that the flow of a fluid into or out of a block in one time step is a fraction (considerably less than one) of the total amount of that fluid present in the block. Use of a time step where the time step&apos;s

Jan 1, 1969

By Robert R. Abbott

The practice of carbonizing steel for the purpose of case-hardening has assumed great commercial importance within the past 10 years. Formerly, case-hardened steel was held in more or less contempt, since it was considered a cheap substitute for tool-steel. This is no longer the case. The development of the motor-car industry, and coincidentally that of modern alloy-steels, has resulted in overcoming many difficulties formerly experienced in case-hardening. This result has been accomplished by increased knowledge regarding the analysis of the steel which would respond most readily to case-hardening, and by more careful methods of treatment of the carbonized steel. The ordinary method of carbonizing consists in packing the steel with the carbonizing-material in cast-iron boxes and placing them in a furnace at a temperature of from 1,500° to 1,900° F. for a time sufficient to give the required depth of " case." The steel is then either quenched directly from the box, or is allowed to cool without unpacking, and finally given a single hardening-heat, or, for special work, two or three heats. During the year 1911, more than 100,000 tons of carbonizing-material was sold in the United States, at an average price of probably $55 per ton. More than 85 per cent. of this material consisted of granulated bone. Within the past four years, many manufactured compounds have been placed on the market, consisting largely of some form of carbon or carbonaceous material, with or without the addition of chemicals. Steel will absorb carbon placed in contact with it at the temperature of the atmosphere. The reaction is exceedingly slow, but increases rapidly with increasing temperature. Below

Jan 1, 1913