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By E. W. McAllister

The decision of the California Oil Umpire's' office to accept well potentials established from subsurface-pressure data has brought to the attention of many operators for the first time the application of such data to production problems. This paper reviews the development and application of subsurface-pressure data in kettleman Hills, where these data have been used in production work since 1932. The Kettleman Hills field was discovered in October 1928. The first subsurface-pressure surveys were made early in 1932 and by the middle of 1933 the two major operators in the field were making routine pressure runs in thcir respective wells. Shortly therefter, these companies agreed to exchange pressure data, and later a third company entered into the agreement. This made it possible to analyze the effects upon the reservoir pressure of past production practices, which are discussed in the latter part of the report. It is interesting that many of the applications of subsurface-pressure data discussed herein were anticipated by C. L. Clark and C. B. Kimberlint in a report2 dated March 1933. PRODUCTIVITY Index In the majority of individual well problems involving the use of subsurface- pressure data, it is necessary to use a factor known as the "productivity index," which indicates the ability of a well to produce and represents the number of barrels of oil or oil and water per day that will enter the well bore for each pound per square inch pressure drop made opposite the producing interval of the well. The productivity index may be determined from pressure and production data for one or more rates of flow and a static or shut-in pressure survey or from production and pressure data for two or more rates of flow. Productivity indices may be based upon either net oil or total fluid production. All indices referred to in this report are based upon net oil. The value of the productivity index for Kettlcman Hills wells decreases generally with time and it is not uncommon for the index to vary in value at any specific time fur various rates of flow. The decline of the productivity index may be attributed partly to the loss of reservoir pressure. As the reservoir pressure decreases, gas originally in solution is released from the oil, congesting the flow of fluids through the formation and increasing the viscosity and surface tension of the oil; thus the flow resistance of the fluids through the formation is increased, resulting in a decrease of the productivity index. For convenient reference, the productivity indices for each well are plotted against time and a curve is drawn through the points showing the trend of the average index value. Plotted on Fig. I are index values for five

Jan 1, 1941

By E. W. McAllister

The decision of the California Oil Umpire's' office to accept well potentials established from subsurface-pressure data has brought to the attention of many operators for the first time the application of such data to production problems. This paper reviews the development and application of subsurface-pressure data in kettleman Hills, where these data have been used in production work since 1932. The Kettleman Hills field was discovered in October 1928. The first subsurface-pressure surveys were made early in 1932 and by the middle of 1933 the two major operators in the field were making routine pressure runs in thcir respective wells. Shortly therefter, these companies agreed to exchange pressure data, and later a third company entered into the agreement. This made it possible to analyze the effects upon the reservoir pressure of past production practices, which are discussed in the latter part of the report. It is interesting that many of the applications of subsurface-pressure data discussed herein were anticipated by C. L. Clark and C. B. Kimberlint in a report2 dated March 1933. PRODUCTIVITY Index In the majority of individual well problems involving the use of subsurface- pressure data, it is necessary to use a factor known as the "productivity index," which indicates the ability of a well to produce and represents the number of barrels of oil or oil and water per day that will enter the well bore for each pound per square inch pressure drop made opposite the producing interval of the well. The productivity index may be determined from pressure and production data for one or more rates of flow and a static or shut-in pressure survey or from production and pressure data for two or more rates of flow. Productivity indices may be based upon either net oil or total fluid production. All indices referred to in this report are based upon net oil. The value of the productivity index for Kettlcman Hills wells decreases generally with time and it is not uncommon for the index to vary in value at any specific time fur various rates of flow. The decline of the productivity index may be attributed partly to the loss of reservoir pressure. As the reservoir pressure decreases, gas originally in solution is released from the oil, congesting the flow of fluids through the formation and increasing the viscosity and surface tension of the oil; thus the flow resistance of the fluids through the formation is increased, resulting in a decrease of the productivity index. For convenient reference, the productivity indices for each well are plotted against time and a curve is drawn through the points showing the trend of the average index value. Plotted on Fig. I are index values for five

Jan 1, 1941

By P. S. Rudman

Laves phases, AB2, are considered as Izerrzisub-stitutional solutions m1hich are defined by a one-for-truo replacement scheme. Atomic-size tnisfit is considered in terms of deviations of the ratio 2V°b/V°A from unity, where v° = atomic volume. A simple elastic model has been used to calculated deviations from "Vegard&apos;s law of atomic vol-umes". Comparison has been made between calculated and observed atomic-volume deviations fov 222 Laves phases. Agreement is generally very good although there ave some few exceptions which appear to be excusable in terms of electronic changes that ore beyond the scope of the present model. We can consider the formation of a binary sub-stitutional solution A-B from an A solvent as one-for-one replacements of A atoms by B atoms. As the atomic-size ratio deviates from unity, the solution becomes thermodynamically less stable and hence more restricted because of atomic-misfit strain energy. In accordance with our previously presented conclusion1 that the atomic volume, v, is in general the most appropriate measure of atomic size, the ideal size ratio for a binary sub-stitutional solution is vg/vA = 1. The Laves phases have been described by Berry and Raynor2 in terms of various stacking sequences of hexagonal layers of B atoms for the three structures MgZn2(C14), MgCu2(C15), and MgNi2(C36). To form the Laves phase of ideal composition AB, we start with complete hexagonal layers of B atoms in the appropriate stacking sequence and we remove, according to an appropriate scheme for each structure, two out of every four B atoms and replace the two removed atoms by one A atom. We thus might expect to find that the ideal size ratio for the Laves phases is 2v/B/ VA= 1. From this point of view, then, we call Laves phases hemi-substitutional solutions since we employ one-for-two replacements. By analogy with substitutional solutions we can expect for Laves phases that as the ratio 2VB/Va deviates from unity the phase occurrence will be more restricted. Laves3 has plotted the distribution of Laves phases as a function of the radius ratio, ?A/rB, and found that, while the distribution extended from 1.05 < rA/B < 1.50, the

Jan 1, 1965

By Corliss R. Kinney

Since the first atomic bomb exploded over Japan, a great deal of speculation has been published about the use of atomic energy instead of coal for the production of power. Atomic energy, in time, may displace coal for this purpose, but atomic energy will not displace coal in supplying chemical raw materials to the rapidly expanding carbon-chemicals market. Modern civilization demands large quantities of carbon compounds and the logical source of many of these is coal. Consequently, many progressive operators are considering the possibilities of the utilization of coal as a chemical raw material as never before. Furthermore, the demand for clean, smokeless, and ashless fuels will continue to increase and the only way to handle coal under those conditions is to take it apart, just as crude petroleum is taken apart. One can readily imagine where the petroleum industry would be now if it had insisted on selling customers only crude oil, perhaps emulsified with a little salt water to correspond to the moisture and mineral matter in raw coal. The time seems to be coming at an accelerated Dace when mine operators will find that competing for a highly selective fuel market by producing a larger tonnage at smaller cost will be less profitable than to increase the value of a smaller tonnage many fold by producing something more valuable to industry and civilization than raw coal. For example, about 750,000 tons of carbon black selling for $50 to $60 per ton was produced in the United States in 1945. This tonnage is insignificant compared with the total production of coal in the United States, but a very tidy tonnage, together with the coal necessary to operate the process, for any mine operator fortunate enough to obtain a method of producing a better carbon black from coal. From the point of view of tonnage, the manufacture of coke of various kinds and its by-products is at present the most important source of carbon chemicals from coal. Nearly 20 per cent of the coal mined in this country is used for this purpose. A large proportion of the coke is used for the production of iron and steel, but even in this operation a considerable part of the coke is used for a chemical purpose; that is, the reduction of the ore to metallic iron. In addition, large quantities of coke are used in manufacturing many important products that find their way into the market. Possibilities of Acetylene One of the important chemicals manufactured from coke is calcium carbide, from which many products are made. One of these is acetylene. This hydrocarbon can also be manufactured from natural gas or from waste oil-refinery gas and these industries will probably offer competition for the manufacture of acetylene. Coke-oven gas can be used for making acetylene and should receive consideration

Jan 1, 1947

By Corliss R. Kinney

Since the first atomic bomb exploded over Japan, a great deal of speculation has been published about the use of atomic energy instead of coal for the production of power. Atomic energy, in time, may displace coal for this purpose, but atomic energy will not displace coal in supplying chemical raw materials to the rapidly expanding carbon-chemicals market. Modern civilization demands large quantities of carbon compounds and the logical source of many of these is coal. Consequently, many progressive operators are considering the possibilities of the utilization of coal as a chemical raw material as never before. Furthermore, the demand for clean, smokeless, and ashless fuels will continue to increase and the only way to handle coal under those conditions is to take it apart, just as crude petroleum is taken apart. One can readily imagine where the petroleum industry would be now if it had insisted on selling customers only crude oil, perhaps emulsified with a little salt water to correspond to the moisture and mineral matter in raw coal. The time seems to be coming at an accelerated Dace when mine operators will find that competing for a highly selective fuel market by producing a larger tonnage at smaller cost will be less profitable than to increase the value of a smaller tonnage many fold by producing something more valuable to industry and civilization than raw coal. For example, about 750,000 tons of carbon black selling for $50 to $60 per ton was produced in the United States in 1945. This tonnage is insignificant compared with the total production of coal in the United States, but a very tidy tonnage, together with the coal necessary to operate the process, for any mine operator fortunate enough to obtain a method of producing a better carbon black from coal. From the point of view of tonnage, the manufacture of coke of various kinds and its by-products is at present the most important source of carbon chemicals from coal. Nearly 20 per cent of the coal mined in this country is used for this purpose. A large proportion of the coke is used for the production of iron and steel, but even in this operation a considerable part of the coke is used for a chemical purpose; that is, the reduction of the ore to metallic iron. In addition, large quantities of coke are used in manufacturing many important products that find their way into the market. Possibilities of Acetylene One of the important chemicals manufactured from coke is calcium carbide, from which many products are made. One of these is acetylene. This hydrocarbon can also be manufactured from natural gas or from waste oil-refinery gas and these industries will probably offer competition for the manufacture of acetylene. Coke-oven gas can be used for making acetylene and should receive consideration

Jan 1, 1947

By T. M. Daulton, Chester F. Lee

The Atlin Mining District is in the northwest corner of the Province of British Columbia. Ruby Creek, where the operation to be described is situated, is 17 miles east of the town of Atlin and about 18 miles south of the south line of Yukon Territory (Fig. 1). Gold was discovered in the district in January, 1898, and the production to date from placer mines has been $4,518,000, according to the reports of the Minister of Mines for the province. Geology The essential points in the regional geology are given in the following paragraphs. Long erosion produced a plane-like surface slightly above sea level with a few peaks and ridges.&apos; A gradual uplift followed and erosion increased, the streams cut deeper, the cuts so made being afterward increased by glaciation. The ice straightened and planed the slopes of the main valleys and widened and lowered their floors, in some cases flooring the valleys with silt, sand, gravel, and clay. As the glaciers rapidly retreated, lakes were formed. As to the origin of the gold, J. C. Gwillim says? "The Surprise granite has been carried northward toward Gladys Lake and Teslin, and the granite of the great plateau on the Taku trail was found in blocks on the opposite range across Hurricane River 10 miles north of its original position. Otherwise there is little evidence of far removed material, the boulders of the lake shore and creek beds being of local appearance. This appears to strengthen the opinion that the placer gold had its origin within the drainage basins where it is now found." In the gold-bearing creeks of the Atlin district there are two "runs"

Jan 1, 1917

By Woolsey Johnson

THE object of this paper is to, describe the several necessary characteristics of the zinc-retorting charge and to show how by certain improved methods; the large excess of coal, over that theoretically required, can be reduced, thereby effecting an increase in the smelting capacity of a retort plant as well as other economies. In the Southwestern zinc works a charge of roasted zinc ore with a side mixture of carbonates and silicates, analyzing on the average 50 per cent. Zn, is mixed with 55 or more per cent. of its weight of a mixture of coal and coke analyzing 60 to 70 per cent. fixed carbon. . The ore is of varying fineness and the coal and coke are usually crushed in a semi-moist condition through a 3/8 -in. screen. With ores of a slaggy nature, this coal proportion is increased, sometimes to as much as 100 per cent. of, the weight of the ore. With carbonate ores, or where anthracite screenings with higher carbon content are cheap enough, the percentage of reducing agent is cut to 45 per cent. or even somewhat lower. The average charge per retort for a monthly run of a plant on ore, as distinguished from retorts on blue-powder, ladle-skimmings and other between-products, runs from 60 to 66 lb., with a mean of 63 lb. for the Southwest with standard retorts of 8 ½ -in. inside diameter and 50 in. long inside, using roasted sulphide ores. Conditions will change these figures, but 40 lb. of ore per cubic foot of retort space is, I believe, an average in the better-operated plants. Since the rise in. the price of spelter, the tendency has been to overcharge. To remove the slag that is formed when retorts are overcharged, extra men are put on to "gum-chisel" the retorts to prevent "set" furnaces and "butchered, retorts." Taking the above conditions as premises, we find that from four to six times the amount of coal necessary for the reduction is used, as is evidenced by the fact that the residues analyze as high as 35 per cent, fixed carbon. There are good reasons why this excess of fixed carbon must be used and perhaps these can be best explained by a description of the metallurgical requisites of a zinc charge. We may enumerate these as follows: 1. High reducing power, especially at the end f the shift, to reduce any carbon dioxide to monoxide and bring about a good condensation

Jan 2, 1918

By R. W. Jenkins

TRACKLESS equipment is being used by the Coplay Cement Manufacturing Co. to develop a folded limestone deposit economically and safely with inexperienced men. Cost and quality of development stone results in a saving when it is used in- stead of outside sources of limestone. This favorable cost has been attained by following a methods development and training program described in this paper. It is expected that further savings in favor of the mined stone will be made when stopes now being prepared are in production. The present equipment will be used for loading from stope draw points. The limestone is blended with quarried cement rock to serve as raw material for Portland cement, first produced in this country by Coplay Cement Manufacturing Co. from a process developed by its president, David 0. Saylor, in 1873. For many years the cement rock alone or with a small amount of added limestone was used for raw materials. Later as specifications were raised and the richer portions of quarries were depleted, limestone from outside sources was required in increasing amounts. In 1925 D. J. Uhle, the general manager, began to prospect company property for limestone.

Jan 1, 1954

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By P. A. Boeck

(San Francisco Meeting, September, 1915) THE thermal insulation of high-temperature equipment for industrial purposes is a subject that has not received from engineers and designers the attention its importance deserves. This may be attributed to a number of causes: In the first place, heat flow is a rather difficult factor to measure under the working conditions of an industrial furnace, and until the comparatively recent introduction into certain operations of the heat balance sheet, with a systematic attempt to account for the discrepancies in the totals, the various causes of heat losses and the reasons for their existence were not brought to light. Moreover, such rapid advancement and radical changes in the design of equipment, especially in metallurgical lines, have occurred that practice has apparently outdistanced the theory of design. In the modern tendency toward greatly increased size of units, effort has seemingly been made to utilize the heat of fuel gases without proper. attention having been paid to conserving heat energy and confining it strictly to the points of maximum activity. The systematic study of the thermal properties of structural materials, which is being carried out by various government bureaus and also by a number of technical societies, is forming the basis for more intelligent and consistent work in the economically important subject of prevention of fuel waste.

Jan 8, 1915

By Ernest A. Hersam

The advantages of the tri-axial diagram in representing the composition of slags and silicates are well appreciated by many metallurgists. Prof. H. M. Howe* has pointed out the application of a fourth variable, in connection with the diagram, and has called attention to the usefulness of the general systern of tri-axial representation. In the discussion of Prof. Howe&apos;s paper, Mr. Firmstone† indicated how certain distances could be measured directly by projection. Prof. R. H. Thurston,‡ as early as 1877, had made use of a typtic model and of triangular diagrams, with contour-lines, rekrresenting varying physical properties corresponding to varying chemical composition. Still earlier, Prof. J. Willard Gibbs§ had used the diagram in similar work; and other scientists were thought by him to have preceded him in its use. During the period of nearly a quarter-century, following these early publications, there has been an ever-increasing use of graphic methods in numerous branches of scientific work, stimulated, in part, by the possibility of representation by three co-ordinates upon plane-surfaces. Yet the number of possible co-ordinates for graphic representation has always been, and always must be, insufficient to express many facts which are shown mathematically; while, without graphic representation, the involved nature of mathematical expression often fails to facilitate and promote research. The coming into use, therefore, of the fourth co-ordinate, permitting representation by four variables, marks but the beginning of some lines of research which could not well advance without this aid.

Jan 1, 1902

By Gerhard Derge

A SERIES of studies of the corrosion of tin is under way in the Metals Research Laboratory at the Carnegie Institute of Technology. The complete program includes examination of the corrosion properties of high-purity tin and the changes produced in these properties by the addition of varying amounts of alloying elements. Other studies of this subject have been made recently under the sponsorship of the Inter-national Tin Research and Development Council, but these researches have been confined largely to the weakly acid environments commonly encountered in the canning industry.1 There is little information avail-able regarding the corrosion of tin under alkaline conditions, but such data would be of value, for a large amount of the metal is used under such conditions. The potential measurements to be described were made because they seemed to offer the most rapid method for obtaining a general view of the conditions to be encountered in such service. These experiments will also serve to establish a technique that will be of value in further studies. It must be emphasized that the results reported are those of controlled laboratory experiments and that the conclusions drawn cannot yet be applied to service conditions; rather, they point to the directions in which, more exhaustive experimental work may be clone to best advantage.

Jan 1, 1938

By Jaakko Kajamaa

Neutron diffraction was applied to determine sheet textures by the transmission method. Cold-rolled and recrystallized copper sheets were investigated. The amount of cube texture was determined for three compositions, in which the phosphorus content was, respectively, 0, 0.005, and 0.03 wt pct. The heat treatment was in every case 8 sec at 650°C. In the two latter cases the cube texture was prevented. In addition a comparison with the X-ray diffraction transmission method was made with the 96 pct cold-rolled copper sheet. Outer parts of both (111) pole figures can be considered to be rather identical. This is seen from the fact that the intensity ratio ITD/120" was 0.45 for neutron diffraction and 0.40 for X-ray diffraction. Differences between the methods were discussed in detail. Features peculiar to neutron and X-ray diffraction in texture studies were listed and compared. In this work neutron diffraction was applied to determine sheet textures. Specifically, it was desired to ascertain whether this method can be used to reveal differences when compared to other methods. In addition, the amount of the cube texture in copper sheets was determined as a function of phosphorus content. Previous applications of neutron diffraction to texture problems include the following: nickel wires,&apos; wire of some bcc metals,&apos; and uranium bars.3 In the neutron diffraction technique the greatest difference is in the sample—its method of production and its volume. A sample needs no treatment and its volume is roughly 105 times larger than the volume of an X-ray diffraction sample. The cold-rolled sheet was investigated both by neutron diffraction and by X-ray diffraction, because it is expected that, due to large number of defects, possible differences in the results of the two methods would be revealed. It is a well-known fact that X-ray lines show broadening when cold-worked. Analysis has shown that this is based chiefly on small crystalline size, micro-stresses, and/or faults.4&apos;5 Neutrons are sensitive to the above-mentioned disturbing factors as well, but circumstances in diffraction are different from the X-ray case. Because the sample represents a larger volume, the result is an average over that volume. In addition, it can be assumed that the sample has preserved its original structure, because it needs no special preparation. The particular limitation of neutrons is the relatively low neutron intensity available from nuclear reactors. This decreases the resolution as compared to the X-ray diffraction methods. Furthermore, absorption mainly reduces diffracted X-ray intensity, while multiple scattering effects, i.e., secondary extinction, disturb neutron diffraction. SO neutrons and X-rays behave in a different way when interacting with matter. As in other structural investigations, one can utilize this difference in texture studies as well. One cold-rolled and three recrystallization textures in copper sheets were investigated by neutron diffraction. The samples were produced at the Outokumpu copper factory to the specifications shown in Table I. The paper is divided into five parts. The first deals with the theory of the measurement. In the second, experimental procedures are described. Results are presented in the third part. Both cold-rolled and re-crystallized samples are studied. Discussion is in the fourth part, and finally in the fifth part some conclusions are drawn. 1) THEORETICAL CONSIDERATIONS Properties peculiar to neutron diffraction are the following: a) the scattering length varies greatly between one element and another; b) many of the elements do not absorb neutrons appreciably. In this connection it is of primary interest to know the interaction of neutrons with lattice imperfections. As with X-rays this problem leads to diffraction analysis of deformed and recrystallized metals. From the physical point of view the main difference is that neutrons are scattered by nuclei (magnetic scattering is not considered here), whereas X-rays are scattered by electrons. The features peculiar to neutron and X-ray diffraction methods in texture studies are listed in Table 11. Pole figures are an important tool in performing structural analysis of deformed or recrystallized metal. Present texture research technology requires pole figures which are as precise as possible. The choice between these two methods depends on the technical information which is required. The X-ray diffraction transmission technique may give results which are not necessarily representative of the average physical state of the sample. Although foil samples normally contain enough crystallites for diffraction, they may not necessarily represent the whole structure. An example of this problem is the frequently observed difference between the "surface" and the "inside" texture of a sample. The production of foil samples may disturb the original structure of the parent material. The selection and orientation of the foil from the sample is quite arbitrary. Normally, a highly deformed piece of metal has several texture components. Different components are deformed in a slightly different manner. This is a re-

Jan 1, 1969

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&apos;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

C. M. Bishop (Aircraft Div., A. V. Roe Cnnada Ltd., Toronto)—Reference is made to the coherency hardening of ß due to ß&apos; and also to the hardening of ß due to a coherent precipitation of the a phase. What is meant by the term "ß&apos;?" Would not the coherency hardening of ß during cooling be due to precipitation of a sub-microscopic dispersion of a, as is the case during reheating a ß-quenched alloy? I feel that these two phenomena are essentially the same mechanism, i.e., precipitation of a from unstable or supersaturated ß. From the text, it would appear that Tables III and IV are intended to show the effect of the martensite transformation on the properties of Ti-Mn alloys. Referring to Table 111, the ß-quenched alloys would contain a greater proportion of retained ß than would the equilibrated alloy. Could not the increase in properties be attributed to this, along with possible coherency hardening of the ß? In the same way, the structures referred to in Table IV contain ß from which they could derive their hardness. It would appear to be difficult, if not impossible, to assess the role of the martensite transformation from the data contained in these tables. F. C. Holden, H. R. Ogden, and R. I. Jaffee (authors&apos; reply)—In reply to the first question raised by Mr. Bishop, the term "ß"&apos; designates an apparent retained-p structure which is harder than it is after the most rapid cooling from the ß field. It is thought to be the result of a coherent precipitation of a. The mechanism by which hardening takes place is undoubtedly the same as that involved in the early stages of aging of a re-tained-p structure, and we are in agreement with Mr. Bishop on this point. The term "ß&apos;" to designate the anomalously hard retained-ß structure was agreed upon at a symposium in 1953." The authors do not agree that the quantity of retained ß and/or ß&apos; in the ß-quenched specimens of Table III is necessarily greater than that of the 600°C equilibrated specimens. The ß-quenched specimen has a structure which appears to be completely a&apos; formed by the martensite reaction. It is recognized that there could be some retained ß (or ß&apos;) between the a plates if the M, temperature is below room temperature. This is unlikely for the 3.4 pct Mn alloy where the M, is known to be at about 640°C. Therefore, the increase in strength cannot be attributed to the presence of a greater quantity of coherency-hardened ß, but, rather, the increase in strength must be attributed to the transformation products formed, e.g., a&apos; (martensiti-cally formed a). Concerning the data in Table IV, we agree that it is difficult to estimate the role of the martensite reaction, since the 6.4 pct Mn alloy was retained ß in the quenched condition.

Jan 1, 1955

By Donald B. Hunter

The Ti-Be system up lo 10 wt pct Be with cortlmercialll&apos; pure titanium has been determined using metal-lographic techniques. Beryllium forms the p eutec-toid type of dinqarz with titanium; the eutectoid occurs at 0.5 xt pct Be azd 1500 F, while an eutectic is foritled at 1887°F containing between 5 and 7.5 rt pct Be. The solubility of beryllium in a titanium does not exceed 0.05 zvt pct and the maximum solubility of Beryllim in 0 titanium is 1 wt pet. PREVIOUS work on the Ti-Be phase diagram indicated that additions of beryllium to titanium resulted in a marked lowering of the melting point,&apos;&apos;&apos; and it was also observed that the solubility of beryllium in both a and p titanium was retricted.- With the limited data available, McQuillan and McQuillan constructed a partial hypothetical diagram of the Ti-Be system,= assuming that beryllium formed the 0 eutectoid type of system with titanium. Subsequently Bedford published a tentative diagram of the entire Ti-Be system: although he did not investigate alloys containing less than 10 wt pct Be. This diagram included several compounds described by other authorities.&apos;-l3 The following account describes work directed toward determining the form of the titanium-rich portion of the phase diagram up to 10 wt pct Be. MATERIALS AND METHODS Titanium sponge and a master alloy containing 25 wt pct Be were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 250-g compacts which were melted into buttons by arc melting under purified argon on a water-cooled copper hearth. Results of analyses for beryllium are shown in Table I but no determination of other elements was made at this stage. The alloys were hot-rolled at 1650°F to produce 0.1-in.-thick sheet. Alloys containing up to 1.5 pct Be were fabricated without trouble; samples containing 2 pct cracked initially upon hot rolling, but thereafter rolled satisfactorily to sheet. The 5, 7.5, and 10 pct were hot short and could not be rolled. Surface contamination was removed from samples by sandblasting and pickling in a 5 pct HF-35 pct HNOs solution. For metal log raphic examination, heat-treated specimens were mounted transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and electropolished at 20 v using a solution containing 600 ml of methanol, 60 ml of perchloric acid, 360 ml of butyl cellosolve, and 2 ml of Solvent "X". Difficulty was experienced in obtaining good electropolished surfaces with samples containing more than 1 pct Be, the degree of difficulty in-

Jan 1, 1967

By A. H. Daane, B. J. Beaudry

The Sc-Ti system was studied by thermal, metal-lographic, and X-ray methods. Scandium was found to transform at 1334 °C from a (hexagonal) to ß which was concluded to be bee since a continuous series of solid solutions is formed between ß scandium and ß titanium at elevated temperatures. There is a minimum in the solidus at 51 wt pet Ti and 1300°C, a monotectoid at 1050°C and 49 wt pet Ti, and a eutectoid at 875°C and 91.5 wt pet Ti. The maximum solubility of titanium in a scandium is 13.5 wt pet at the monotectoid temperature, while the maximum solubility of scandium in a titanium is 6.5 wt pet at 875°C. SCANDIUM, a member of Group 111 A of the periodic table, and now called a rare-earth metal,&apos; has become of interest recently due to its low density (2.99 g per cc) and relatively high melting point (1539°C).Spedding,&apos; et al. have described a method of preparation of pure scandium metal and have made a study of its basic properties. Since scandium is approximately 10 to 12 pet smaller in at. diam than the other rare earths while its electronegativity and valence are the same, a knowledge of its alloying behavior in contrast to these elements should be very helpful to fundamental alloy theory. Since scandium is quite scarce and difficult to prepare in pure form, its use as a structural material by itself seems quite unlikely. However, its use in special cases as an alloying addi- tive to other low-density materials is a possible application; the Sc-Ti system was chosen for this reason and for others of fundamental interest. Scandium was suspected of having a high temperature bee form as do some of the other rare-earth metals.3&apos;4 Since titanium has a high-temperature bee form, a continuous series of solid solutions at elevated temperatures between ß scandium and ß titanium would prove the existence and structure of the high-temperature form of scandium. The existence of a continuous series of hexagonal solid solutions at room temperature was predicted by Burkhanov and Savitskiy,5 but Hias shown to be incorrect in early X-ray studies. EXPERIMENTAL METHODS Materials. The metals employed in this investigation were crystal bar titanium and distilled scandium prepared by the method described by Spedding,2 et al. The major impurities are listed in Table I in PPm. Alloy Preparation. All the alloys examined were initially formed in a nonconsumable electrode are-melting furnace under an atmosphere of purified helium or argon. A curve based on the observed weight loss of 0.6 pet* when titanium was melted

Jan 1, 1962

By W. F. Domis, F. von Gemmingen, R. W. Whitmore, F. Garofalo

Constant-load creep-rupture tests at 1100°, 1300° and 1500°F were made on a Type-316, 18 Cr-8 Ni-ZMo, austenitic stainless steel to determine the relationship between ruptzire life and other aspects of creep behavior, The test program was designed on a statistical basis to check the variability of various creep properties and to determine emprically the dependence of minimutn creep rate and ruptzire life on initial stress, The dependence of the rupture life, tn, on the initial stress, a,, is found to be related to the stress dependence of the wrinimum creep rate, i,, and secondary creep strain, The instabilities or breaks found in the conventionual log - logt, plots can be traced to either a change in the linear dependence of log i, on log a, or to a change in secondary creep strain. In the alloy tested, rupture is found to be predowmanantly of the inter crystalline type, For this material, the secondary creep strain is -found to depend on the nature of the grain boundary precipitate, which affects grain boundary migration. It has been shown for a variety of metals and al tested at elevated temperatures under creep conditions that the empirical relationship exists between rupture life, tr, and minimum creep rate, i,. This relationship, in which C and a are in some cases independent of stress or temperature, shows in a general way that creep rupture depends on creep behavior prior to tertiary creep stage. To determine more fully the factors which control creep rupture requires, therefore, more knowledge of the relationship between rupture and creep behavior. To obtain such information, constant-load creep-rupture tests have been made on a Type-316, 18 Cr-8 Ni-2 Mo, austenitic stainless steel at 11000, 1300°, and 1500°F. These tests were designed on a statistical basis to determine the variability of the various creep properties measured and to determine empirically the stress dependence of minimum creep rate and rupture life. As a result of this work, various empirical relations have been established defining more closely the factor, C, in the relation between rupture life and minimum creep rate. This factor is found to be proportional to the amount of strain during secondary creep. The variation of secondary creep strain with rupture life and temperature is determined and its effect on rupture behavior discussed. The variability in minimum creep rate and rupture life is also dis- cussed and the dependence of these quantities on initial stress is interpreted. TEST MATERIAL AND TEST PROCEDURES The material tested is an austenitic stainless steel, AISI Type 316, of the following composition: C, 0.07 pct; Mn, 1.94 pct; P, 0.01 pct; S, 0.021 pct; Si, 0.38 pct; Cr, 18 pct; Ni, 11.4 pct; Mo, 2.15 pct; All 0.003 pct and N, 0.043 pct. The material was received as a hot-rolled 0.5-in. diam bar which was sectioned into 3.25 in. long blanks. Each blank was heat treated by holding 1/2 hr at 2000° F followed by water quenching. A 3/8-in. coupon was removed from each heat-treated blank and the microstructure was examined, the grain size determined, and the hardness measured. The microstructure was found to be uniform from blank to blank and the grain size was found to range from 4 to 6 ASTM numbers. Hardness, measured using a 20-kg load, varied between 127 and 148 Vpn. Tensile creep-rupture specimens having a 0.25 in. diam within a 1.5-in. reduced section were machined from the heat-treated blanks. Constant-load tests were made on these specimens at 1100°, 1300°, and 1500 F. Six specimens were tested at each stress level. Three creep-rupture machines were employed for tests at each temperature, two specimens being tested in each machine for each stress level. To minimize any effect due to local inhomogeneities along the length of the as-received bar the specimens were randomized before test. Each specimen was tested to rupture and in most cases an autographic extension-time curve was obtained. For very low stress levels at 1500°F no auto-

Jan 1, 1962

By Carl H. Samans

In their recent complete review of the subject of age-hardening,&apos; R. F. Mehl and L. K. Jetter classify the main types of precipitation-hardening alloys under two headings, depending upon the nature of the precipitate and the character of the precipitation. In the alloys falling under the first heading, which display "continuous precipitation" and are typified by the aluminum-copper alloys, "precipitation seems to occur without much regard to grain boundaries and apparently at much the same rate at every point," although an acceleration in regions plastically deformed has definitely been established.2 In the second type of alloys the precipitation is "discontinuous," as in the copper-silver system for example, and "seems to start in restricted regions, primarily those contiguous with the grain boundaries, and to spread inward in an advancing wave." The reasons for the occurrence of these two greatly different types of precipitation are unknown, as are those for many other reactions that take place in the solid state. In the present paper only the first or "continuous" type of precipitation will be dealt with, for which a complete crystallographic mechanism has been worked out for the process of precipitation from a supersaturated solid solution of copper in aluminum. Based upon this mechanism, an explanation of the various property changes found experimentally will be developed in the second paper of this series. In later papers (&apos;discontinuous precipitation" in copper-silver alloys will be explained, and an effort will be made to rationalize the two processes and types of precipitation. Crystallography of the Precipitation Process Through the extensive investigation by R. F. Mehl, C. S. Barrett and F. N. Rhines3 on the Widmanstätten structure in aluminum-rich copper

Jan 1, 1940

By Carl H. Samans

In their recent complete review of the subject of age-hardening,&apos; R. F. Mehl and L. K. Jetter classify the main types of precipitation-hardening alloys under two headings, depending upon the nature of the precipitate and the character of the precipitation. In the alloys falling under the first heading, which display "continuous precipitation" and are typified by the aluminum-copper alloys, "precipitation seems to occur without much regard to grain boundaries and apparently at much the same rate at every point," although an acceleration in regions plastically deformed has definitely been established.2 In the second type of alloys the precipitation is "discontinuous," as in the copper-silver system for example, and "seems to start in restricted regions, primarily those contiguous with the grain boundaries, and to spread inward in an advancing wave." The reasons for the occurrence of these two greatly different types of precipitation are unknown, as are those for many other reactions that take place in the solid state. In the present paper only the first or "continuous" type of precipitation will be dealt with, for which a complete crystallographic mechanism has been worked out for the process of precipitation from a supersaturated solid solution of copper in aluminum. Based upon this mechanism, an explanation of the various property changes found experimentally will be developed in the second paper of this series. In later papers (&apos;discontinuous precipitation" in copper-silver alloys will be explained, and an effort will be made to rationalize the two processes and types of precipitation. Crystallography of the Precipitation Process Through the extensive investigation by R. F. Mehl, C. S. Barrett and F. N. Rhines3 on the Widmanstätten structure in aluminum-rich copper

Jan 1, 1940