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By Gustav Egloff

AN unexpected and unprecedented demand for its products now challenges the petroleum industry. Between 1939 wand 1946, domestic oil demand increased nearly 45 per cent and in the first half of 1947 it was 10 per cent higher than in 1946. In 1939 the United States produced 1,264,962. 000 bbl of crude oil and indications are that about 1,860,000,000 bbl will be produced in 1947, a 47 per cent increase. Runs to stills are more than keeping pace with production. The crude capacity of 365 operating refineries is rated as 5,400.000 bbl daily and almost 100 per cent of this capacity was running crude oil in August 1947. The oil industry is cognizant of our need for a greater volume of petroleum products and is expending the huge stun of four billion dollars on exploration. production. transportation, refining. and marketing of petroleum. Of this amount about half will be spent on exploration and production. a billion on refining. and another billion on transportation and marketing facilities.

Jan 1, 1947

University of New Mexico, Albuquerque, N M Requests for publications should be addressed to the Librarian of the University Papers of the Geological Series of the University are bound in volumes: Vol 1, vol 2, pt 1, and vol 2, pt. 2, and vol. 3 are out of print, but separates of the following papers may be had at a uniform cost of 25 cents each. Vol. 1? No. 1, Geology of the environs of Albuquerque (1898); 2, Occurrence of copper and lead in the San Andreas and Caballo Mountains (1898), 3, Geological reconnaissance in western Socorro and Valencia counties (1898); Geology of the San Pedro and Albuquerque districts (1898). , Vol 2: No. 1, Geology of the Albuquerque Sheet (1900); 2, Miscellaneous economic papers by Herrick (1900); 3, Geological reconnaissance in western Socorro and Valencia counties (1900); 4, Geology of the White Sands of New Mexico (1900); 5, Identifi¬cation of an Ohio coal measure's horizon in New Mexico (1900); 6, Cyanide process in New Mexico (1900). Vol. 3. No 3, The oil situation in New Mexico (1920), 4, Geology of Sandia Mountains (1922); 5, Oil and gas m New Mexico in 1923.

Jan 1, 1933

By the courtesy of Sir Robert Hadfield, we have received the fol¬lowing communication relating to the development and encouragement of science and research in Germany at present. These statements have been translated by Sir Robert from various German sources, and are presented here as an indication of what Germany is doing not only to further her military power, but also to prepare for the period of trade rehabilitation to which she is looking forward after the close of, the war. KAISER WILHELM TRUST FOR PROMOTION OF WAR SCIENCE The Kaiser has approved the foundation of a Trust with the name given above. The aim of the Trust is to further the development of scientific and technical aids to warfare, by uniting the scientific and the military forces of the country for work together. The scientific Work is to be carried on by the following technical committees (or commissions) (1) Committee for the chemical raw materials, for the production of munitions-manufacturing materials. (2) Committee for chemical war materials (powder, explosives, gas, and the like). (3) Committee for physics, including ballistics, telephony, telegraphy, determination of targets and distances, measurements, and the like. (4) Committee for engineering and communication. (5) Committee for aeronautics. (6) Committee for obtaining and preparation of metals.

Jan 8, 1918

By Harry C. Wiess

PETROLEUM has come to be one of the most important and essential of the mineral re- sources of the nation. It is the most advantageous source of mineral fuels and of lubricants, and as such it has provided in large measure for the phenomenal development in our modern means of travel and in the facilities for transportation by land, sea, and air. Without it the remark- ably rapid industrial and social progress in our country during the past thirty years could not have occurred. In view of its important place and the fact that petroleum is irreplaceable and existent in limited quantities in nature, its conservation is essential.

Jan 1, 1939

By Amitava Gangulee, Michael B. Bever

The effects of changes in short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions have been investigated. The heats of formation at 273°K of several alloys after two different thermal treatments were measured by liquid metal solution calorimetry. Their electrical resistivities were measured at temperatures ranging from 4° to 773°k. Tensile tests and microhard-ness measurements were carried out at room temperature. An effective short-range order parameter and an effective interaction energy are defined. The measured changes in the properties are interpreted in terms of these quantities. The short-range order parameter is evaluated separately from calorimetric and X-ray data; the results are in fair agreement. Increasing short-range order lowers the resistivity of- the silver-rich Ag-Mg alloys but does not measurably affect the temperature dependence of the resistivity. Short-range order increases the yield stress of these alloys but does not affect the ultimate tensile stress. Changes in the effective short-range order parameter independently obtained from measured changes in the heat of formation, resistivity, and yield stress are in fair agreement. THE thermodynamic, electrical, and mechanical properties of solid solutions have been investigated as functions of composition in many alloy systems, but the effects of configurational variables, such as short-range or long-range order, on these properties have received much less attention. The silver-rich terminal solid solutions in the system Ag-Mg are well-suited for the investigation of the effects of order. The composition of these solid solutions may be varied over a range extending to about 27 at. pct Mg.1 Appreciable short-range ordering is likely to take place in these solid solutions; the degree of short-range order can be varied by suitable thermal treatments. In the alloy Ag3Mg long-range ordering is possible.2 This paper is primarily concerned with the effects of short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions.-The long-range ordering transition is the subject of a concurrent paper.3 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Ag-Mg alloys containing up to 26.4 at. pct Mg were prepared by melting 99.99 pct pure Ag (obtained from Baker Chemical Co.) and 99.99 pct pure Mg (obtained from Eastman Chemi- cal Co. or Johnson Mathey & Co.) in graphite crucibles under molten potassium chloride. The solidified ingots were homogenized at 823°K for 10 days in evacuated Vycor capsules. A surface layer 6 in. thick was then removed by machining. The ingots were swaged into rods (2.5 mm diam) which were drawn into wires (1.0 mm diam). The wire specimens were annealed at 773°K for 24 hr in vacuum and either quenched into iced brine or cooled to room temperature over a period of 15 days. The average grain diameter (obtained from the linear intercepts) was about 0.1 mm. 1.2) Calorimetry. The heats of formation of the alloys were measured in a tin solution calorimeter as the difference in the heat effects of alternate additions of samples of an alloy and the mechanical mixture of its component elements. The additions were made from 273°K to the bath at about 623°K. The heat effect on addition of the alloys was approximately 5.5 kcal per g-atom. The procedure and the method of calculation have been described.4 1.3) X-Ray Diffraction. Short-range order parameters of two alloys were calculated from diffuse scattering intensities,' obtained with briquettes made from powdered specimens. A GE-XRD 5 diffractometer with filtered copper radiation was used. The absolute intensities were based on calibrations with paraffin. 1.4) Resistivity Measurements. The electrical resistivities were measured by a potentiometric method in which the potential drop across the specimen was compared with that across a standard resistance. For measurements below room temperature, the specimens were immersed in liquid helium (4°K), liquid nitrogen (78°K), dry ice and trichloroethylene (195°K), or ice and water (273°K). Measurements above room temperature were made on specimens held in a furnace under helium or in vacuum. The resistivity measurements were reproducible to ±0.5 pct or less. 1.5) Mechanical Tests. Tensile tests were carried out at room temperature with a Tinius-Olsen XY elec-tromatic Universal testing machine. Wire specimens (nominal gage length 1 in.) were used. The strain was measured with an extensometer, which had a sensitivity of 4 x 10-5; the strain rate was 10-3 min-1. Microhard-ness measurements were made with a square-pyramid indenter and a 100-g load.11 2) RESULTS AND DISCUSSION All measurements were made on two parallel sets of specimens, one quenched and the other slowly cooled from 773°K. The reported values are the averages of at least three measurements. In the range of magnesium concentration substantially below that of the composition Ag3Mg, quenched alloys have less short-range order than slowly cooled alloys. As the magnesium concentration approaches that of Ag3Mg, slow cooling develops long-range order. Quenching sup-

Jan 1, 1969

By J. C. Fisher, J. H. Hollomon, David Turnbull

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By David Turnbull, J. H. Hollomon, J. C. Fisher

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By Nicholas J. Grant, W. Michael Yim

The creep-rupture properties of nickel, in as-prestrained or prestrain-polygonized condition, were studied at 1300°F and 4000 psi, and also at 700°F and 26,000 psi. An improvement of strength was noted in both the as -prestrained and the prestrain-polygonized tests at each temperature. The as-prestrained tests, however, showed superior creep resistance to the prestrain-polygonized ones. From the results of X-ray and etch-pit studies, the strengthc gain was interpreted in terms of dislocation density and the stability of preformed substructures. COLD work is known to improve the strength properties of metals at low temperatures. At high temperatures, however, the strength improvement is often lost if gross structural changes, such as re-crystallization, take place prior to or during the test. Even in the absence of recrystallization, a prestrained metal may undergo structural changes— polygonization and the formation of well-defined subgrains—which importantly effect the resultant properties. The relationship between substructure and creep properties has received considerable attention in recent years. The work of wood1 indicated that the creep strength of aluminum and its alloys was closely related to the subgrain size. Hazlett and Hansen,2 and Ancker, Hazlett, and parker,3 working with nickel and nickel alloys, had shown that small amounts of prestrain at room temperature followed by a recovery anneal at 800°C (1470°F) improved the strength at both low and high temperatures. The strength gain was attributed to an increase in the number of subgrain boundaries as a result of the prestrain-polygonization treatment. More recently Coldren and Freeman4 studied the effect of substructures on the creep rate of nickel at 1550°F. Their conclusions indicated that the substructure size as measured by the number of boundaries was the factor that controlled the creep rate. In addition, the perfection of the subgrain boundary has been indicated to have an important role on the strength.' On the other hand, there are data which disagree with the above observations. Grant, Chaudhuri, Silver, and Ganow6 found no creep strength improvement by a prestraining treatment. In reviewing the role of subgrains on high-temperature creep, Shepard and Dorn7 concluded that the contribution of the subgrains to high-temperature creep strength was a minor one. Guard,8 in a recent study on poly-gonized nickel, has cast doubt on the validity of the postulate that subgrain size controls the creep rate. In the majority of the previous studies, the subgrain boundaries have been singled out as the most important factor in determining creep strength; however, there is no firm theoretical ground for the postulate that the subgrain boundaries act as effective barriers to dislocation motion.B910 Little effort has been directed toward the study of the relationship between creep strength and other structural variables, such as dislocation density, lattice strain,

Jan 1, 1963

By Paul Sterling

1. INTRODUCTION. THE general impression regarding the preparation of merchantable anthracite is that it is confined to a colossal, grimy structure, called a "coal-breaker." This name is misnomer; for the desired result is not to break the coal, but to prevent its being broken. Preparation may be said to begin at the face of the chamber, with the mining and loading of the coal. Local conditions vary, not only in the same field or basin, but also in the same mine, so that there is no fixed empirical rule governing the method of blasting or cutting coal. Tests should be made, when possible, to determine the explosive, or the mechanical coal-cutter, which will produce the largest percentage of what are locally known as " lump " and " prepared sizes " of anthracite. The prepared sizes are those mostly consumed for domestic purposes. All other sizes might be called by-products of the anthracite industry; for they are not especially desirable, being the degradation resulting from the mining and handling of a brittle or laminated material. Being low in volatile combustible matter, anthracite burns most successfully when nearly of a uniform size, permitting the easy passage of air through the voids. This accounts for the large number of sizes into which the coal is separated. Table I. gives the various sizes, the diameter of ring over and through which each size is made, and the usual purpose for which it is employed.

Oct 1, 1911

By Charles W. Bloomquist

The profitability of miscible flooding in a hypothetical target oilfield is examined. The major costs, including Windfall Prof it Tax, are identified and their re1ative importance are discussed. The sensitivity of profit to important physical and economic variables is evaluated and discussed, including variance in oil recovery, oil price, injectant requirements, injectant cost, and capital requirements. Economic sensitivities to important development and operating decisions such as timing, Spacing, Slug size, and gas recycling are also analyzed. The Windfall Profit Tax (WPT) as it applies to gas miscible EOR projects is reviewed. The effect of WPT on each of the various project cases is analyzed and the effect of reduced WPT on remaining production from existing operations is evaluated. Tax implications are compared for integrated vs. "independent" controlled projects and the alternative of expensing vs. capitalizing tertiary injectants is also evaluated. The impact of the Net Income Limitation in reducing WPT. during early and late project life is determined and discussed.

Jan 1, 1982

By G. R. Love, M. L. Picklesirner

THE use of color adds a new beauty, power, and versatility to metallography. This has been amply demonstrated in a number of public exhibits and on the walls of corporate, government, and university metallographic laboratories around the world. Indeed, in a number of cases, the color not only is of esthetic value but is scientifically essential to the competent examination of particular samples and systems. Optical strain analysis,' determination of true grain size in U-A1 alloys: phase identification in Nb-base alloys,3 analysis of transformation rates in heat-treated Nb-Zr alloys,4 measurement of solidification segregation in cast Nb-Zr alloys,' study of the intermediate phases in Nb/Sn diffusion couples,6 investigation of the oxidation kinetics at various surface orientations in single crystals,7'8 and a number of other research efforts9'10 would have been vastly more difficult without the extra clarity and distinction introduced by color—either the colors resulting from particular polarized light techniques or the interference colors obtained by oxidation. It is unfortunate that the beauty of colored micro-structures cannot be shared more widely, but the economics of publishing a technical magazine apparently prohibits color plates except under extraordinary circumstances. It is doubly unfortunate that no convenient, general method exists for communicating the information available in colored microstructures to the scientific community. True, in some instances the color changes observed are dramatic enough that direct black and white photography is adequate. In photoelastic stress analysis, several orders of interference fringes may be produced and it is frequently desirable to suppress the color effects (use monochromatic light) to simplify interpretation. On the other hand, relatively minute color variations may be readily detectable by eye, be of considerable assistance in interpreting a structure, and yet be enormously difficult to reduce to an unambiguous black and white print. In order to illustrate a possible compromise or solution to the above problems, we wish to show three black and white photographs of the same region of an Nb/Sn diffusion couple whose interpretation depends heavily upon use of color techniques. These micro-structures were obtained from a section through a rod consisting of commercial-purity niobium tubing filled with 99.995 pct Sn (melt-filled in 10"6 Torr vacuum). The composite rod, measuring 500 mm long, was bent into a hairpin shape and inserted into water-cooled copper grips in a vacuum high-temperature furnace. The rod was outgassed for 2 hr at a furnace temperature of 800°C and was further heated by self-resistance using a 2.2-kva ac power supply. The rod was raised to 1910°C over a 4+-hr period, held for 15 min, slow-cooled to 1500°C over a -hr period, and free-cooled to room temperature (all temperatures were measured with W5Re/W26Re thermocouple). Throughout the heat treatment the ambient pressure was kept below 8 x lo-' Torr. Metallographic preparation of the sample was completely conventional except that it was necessary to extend the grinding steps to remove damage in the brittle NbsSn phase introduced by sectioning. No satisfactory chemical or electrochemical etch has been found for these diffusion couples; of those which have been tried, any that attack the niobium-rich phases at all attack the tin-rich phases disastrously. However, the final polishing steps did produce a slight relief effect and this, coupled with anodizing, yielded excellent clarity in the microstructures for direct observation. The anodizing voltage was chosen to give maximum change in color per unit change in composition. In this case, indeed normally, this maximum sensitivity occurred in the blue-to-red color range. The pure niobium tube wall anodized to a relatively bright blue

Jan 1, 1967

By D. Harrington

ONE of the main functions of the United States Bureau of Mines is to obtain and disseminate information that will promote safety in and around mines, and the health and safety of employees engaged in mining. Serious health and safety conditions arising out' of contamination of air in metal mines by dust, fumes from explosives and fires, and absorption of oxygen by timber and other causes, led the Bureau of Mines to cooperate with the United States Public Health Service in the study of dust occurrence and ventilation in metal mines in various parts of the country. Dr. A. J. Lanza, of the U. S. Public Health Service, and Edwin Higgins, mining engineer of the U. S. Bureau of Mines, in 1915, made a detailed study in the mines around Joplin, Mo., their reports1 are now available. In 1916, 1917, and 1918, a similar study was made in the Butte, Mont., region by Doctor Lanza and D. Harrington, mining engineer of the Bureau of Mines; the reports of this investigation will be available soon. In 1919, the study was continued in some of the Arizona mines by D. Harrington, of the Bureau of Mines, and G. E. McElroy and Dr. R. A. Koronski, of the U. S. Public Health Service, the underground work being completed in June, 1920; these reports are now being prepared for publication. In the spring of 1920, the scope of the work was extended, with D. Harrington in charge as supervising mining engineer, and short studies made in the mines of the Coeur d' Alenes in Idaho and around Oatman, Ariz. It is hoped soon to extend the work into mines of California, Nevada, Colorado, Michigan, and Minnesota, and ultimately to other states should the mining companies be willing to cooperate.

Jan 2, 1921

H. H. Kellogg (Columbia University)—The accurate measurements of the equilibrium gas ratios for the reaction: Pb(1) + H2S = PbS(c) + H2 [I] reported in this paper are a distinct contribution to the literature, and the authors are to be congratulated. I wish to comment, however, on the correlation of the data which is presented. The authors show a straight line correlation of log H2S/H2 vs 1/T, Fig. 1, and are satisfied with this for calculation of ?Fo even when extrapolated to low temperature (427 °C). Heat capacity data for the constituents of this reaction are available (at least to 900°K), however, and ACP for reaction [I] is finite and positive in the temperature range studied. Simplification of the heat capacity equations yields: ?CP= 2.71 + 1.65 x 10-3T (298°-900°K) This positive value of ?CP should result in a small but noticeable curvature of a plot of log K vs 1/T. That the experimental data fail to show such a curvature may be traced to another oversimplification of the author's treatment of their data. They assume that the activity of liquid lead is unity for all temperatures, so that

Jan 1, 1961

By G. W. Josephson

VIRTUALLY every year inventors find one or more startling new uses for one of the varied products of the nonmetallic mineral industries. For example, in November a major step toward positive control of rainfall was made when an experimenter converted a cloud to snow by dropping a few pounds of solid carbon dioxide into it. Other examples of ingenuity in the development of markets and production methods are noted in the following pages. For most of the industrial mineral products one of the outstanding features of 1946 has been the high level of production. There are exceptions, such as quartz crystal and lithium, whose production capacity during the war outgrew current peacetime needs, but they are few. Some technical men point out that this prosperity is not an unmixed blessing to technologic progress, because so much effort must go into day-to-day production problems that relatively little opportunity is left for the pursuit of new developments.

Jan 1, 1947

By H. N. Treaftis, J. W. Cahn

THE previous determinations of the solvus of tin in solid lead disagree with one another by as much as 40°C or almost 10 at. pct. Even determinations that appear to be careful differ considerably in both the solubility and its temperature coefficient. Recent kinetic workl -3 on the rate of precipitation of tin from lead-tin alloys and thermodynamic work4 on the heat of solution of tin in lead have given some insight into the time necessary to reach equilibrium in this system. As this time is longer than that used in almost all previous determinations of the solvus, these determinations are questionable. Since the interpretation of recent kinetic results requires accurate values of the equilibrium solubility the present work was undertaken. DISCUSSION OF PREVIOUS RESULTS The methods used in previous studies may be placed into three classes: 1) Several alloys covering a range of compositions are allowed to reach "equilibrium" at a certain temperature.5-7 Some property, such as the X-ray lattice parameter of the lead-rich phase or the re- sistivity of the alloy, is then measured as a function of composition. The solubility limit for that temperature is taken to be that composition at which a discontinuity in the property occurs. However, the recent kinetic work has shown that tin precipitates in two stages. The first stage is rapid but leaves the lead still supersaturated. The second stage is very slow, and it seems from the equilibration times quoted by the investigators of the solvus that the end of the first stage of precipitation was usually mistaken for equilibrium. This is especially true at temperatures below 100°C where the first reaction is still quite rapid (from minutes to months), but where the second stage is so slow that very long holding times are required to reach equilibrium. Alternatively micrographic work8 on several alloys of different compositions seems to have given good results if done carefully. 2) The beginning of precipitation in a homogenized alloy is measured as it cools slowly8-10. Since reactions in solids undercool easily, such determinations will always give too low a temperature for the solvus. 3) Some property of an alloy is measured as a function of temperature while the alloy is above the solvus.5,9,11 The range of temperature can usually be extended slightly into the two phase region. Then the alloy is precipitated at a much lower temperature and slowly reheated. The solvus is taken to be the lowest temperature where the property of the reheated alloy is equal to that previously determined for the homogeneous alloy. Usually one also expects a discontinuity at the solvus in the temperature variation of the property for the reheated alloy. The difficulty in this method is the sluggishness of the dissolution process, and this method may give too high a solvus temperature. EXPERIMENTAL The phase boundary or solvus temperature was determined by a modification of method 3 for a series of chemically analyzed high-purity alloys, ranging from 5.1 to 26.4 at. pct Sn. The resistance, as a function of temperature, of a sample of homogenized alloy (which could easily be undercooled) was compared with the equilibrium resistance which that alloy sample attained after precipitation at room temperature followed by long isothermal anneals at various temperatures. Before each anneal the sample was rehomogenized and reprecipitated. The solvus temperature could be located to within 1°C as the intersection of the resistance vs temperature curves for the homogenized and equilibrium alloys. No attempt was made to locate the phase boundary more accurately since the limiting factor was the precision with which the alloys could be analyzed. This precision was ±0.1 wt pct Sn and corresponds to an error of 1 deg in temperature. This use of isothermal anneals differs from some of the previous investigations in which method 3 was used with baths of slowly rising temperatures. It was found early in the investigation that solvus temperatures tended to be high if the latter method was used even at extremely slow heating rates. For example a

Jan 1, 1961

By H. C. Fiedler

Heats of high purity iron containing 3.1 pct Si and be -tween 0.0003 and 0.0295 pct N were prepared by vacuum melting ad then pouring while in a nitrogen atmosphere with the pressure between 0 and 90 psi. Strip from a heat with 0.0184 pct N underwent complete secondary recrystallization during the final anneal. Heats with less nitrogen had too few Si3N4 particles to restrain normal grain growth, and the heat with higher nitrogen had too many particles to allow complete secondary recrystallization. In the hot-rolled structure, Si3N4 precipitates only at the grain boundaries, with the consequence that annealing after hot-rolling diminishes the ability to subsequently undergo secondary recrystallization. In contrast to this behavior, ALNprecipitates uniformly in the hot-rolled structure. Under 1 atm of nitrogen, Si3N, in 3.1 pct Si-Fe dissociates between 900" and 950°C; the solubility of nitrogen increases from 0.0010 pct at 900" to 0.0030 pct at 1200°C. The solubility of nitrogen in Si-Fe has been the subject of many investigations. Corney and Turkdogan1 heated a 2.83 pct Si alloy in nitrogen and found the solubility, under 1 atrn of nitrogen, to be 0.0019 pct at 900°C. They claimed that Si3N4 did not form in the alloy above 705°C in 1 atrn of nitrogen. Fryxell et al.2 heated samples of 3.25 pct Si-Fe containing 0.0025 pct N over a range of temperatures and then analyzed for total nitrogen by vacuum fusion and for nitrogen in solution by a modified Kjeldahl technique. At 900°C, they reported the solubility of nitrogen in equilibrium with Si3N4 to be 0.0011 pct. pearce9 found the solubility of nitrogen at 900°C under 0.95 atrn of nitrogen to be 0.0017 pct in a 3.06 pct Si alloy. He reported that Si3N4 does not form above 770°C in 1 atrn of nitrogen. Although internal friction measurements have given somewhat higher values for the solubility,4-6 if the solubility of nitrogen is as low as has been reported by most investigators, and if Si3N4 is stable up to at least 945°C at 1 atrn pressure of nitrogen as reported by Seybolt,7 a small amount of nitrogen in properly processed Si-Fe should be effective in promoting secondary recrystallization. The requirement is that in the final heat treatment there be enough small, well-dispersed particles of Si3N4 to restrain normal grain growth. Fast8 has obtained secondary recrystallization by nitriding high-purity 3 pct Si-Fe after hot-rolling to a thickness of 0.118 in., followed by processing to 0.012 in., and annealing. A large amount of nitrogen, 0.076 pct. was introduced during the nitriding heat treatment, but he has since reported9 that "a few hundredths of a percent" is sufficient. Small amounts of aluminum10 or vanadium" nitride are capable of promoting secondary recrystallization. Heats containing as little as 0.010 pct A1 or 0.042 pct V and from 0.006 to 0.009 pct N underwent complete secondary recrystallization at final gage, whereas heats with lesser amounts of aluminum or vanadium did not.l2 To be reported is the behavior of nitrogen in high-purity 3.1 pct Si-Fe, and the relation of this behavior to the ability to undergo secondary recrystallization. PROCEDURE Ingots weighing 1 lb were made by vacuum melting high-purity electrolytic iron (A104, Glidden Co.) and high-purity silicon (Monsanto Co.). The latter was used in preference to ferrosilicon to insure a low aluminum content. The design of the melting furnace permitted pouring with the furnace atmosphere either below or above atmospheric pressure. Accordingly, at the completion of melting, nitrogen was admitted to the desired pressure and the heat then immediately poured. The ingots were sound, with no indication of porosity. In Table I are listed the heats investigated, the nitrogen pressure at pour, and the nitrogen and oxygen contents as determined by vacuum fusion with a platinum bath at 1850°C, a procedure which insures measurement of the total nitrogen.13 In addition, all heats contained 3.1 pct Si and not more than 0.002 pct C, 0.003 pct S or 0.005 pct Al. It was subsequently found that the quantity of nitrogen contained in the heats in Table I does not necessarily represent that obtained under equilibrium conditions. For example, the ingot poured immediately after 1 atrn of nitrogen was admitted to the chamber contained 0.0093 pct N, whereas an ingot poured 3 min after the nitrogen was admitted contained 0.021 pct N and another poured after a 6-min delay contained 0.029 pct N. While some bleeding of the hot top occurred in the latter instance, the ingot when examined in cross section appeared sound. The ingots were heated to 1325°C in hydrogen and rapidly rolled to 0.080 in. in 3 passes. The roll speed of the final pass was reduced so as to increase the quenching effect of the rolls. The hot-rolled pieces were processed both as-hot-rolled and after heating for 3 min at 900°C in hydrogen. After cold-rolling to 0.026 in., the strips were heated for 2 min at 900°C in hydrogen, then cold-rolled to the final gage of 0.012 in. The loss of nitrogen in going from the ingot to cold-rolled strip was no more than 10 pct. The final heat treatment, which was for the purpose of develop-

Jan 1, 1970

By H. E. Cline, T. H. Alden

A study zvas made of rate-sensitive plastic deformation and superplasticity in alloys of lead and tin. These alloys (lead, PO-19 pct Sn, Sn-38 pct Pb, Sn-2 pct Pb, tin) were extruded, aged at room temperature, or melted and resolidified to produce a variety of ~nicrostrnctures. Flow stress us strain rate data were obtained frorn tension tests for strain rates between 10-6 and 1 min-1. The curve log o .us log £ was S-shaped jor fine-grained materials and approxinzately linear for coarse-grained nzaterials. At constant grain size, the behavior was relatively insensitive to conposition. High rate sensitivity (d log o/d log k) and superplasticity occurred at intermediate strain rates in fine-grained materials and are believed to be associated with a transition with strain rate in the mode of plastic flow. This transition was shifted to higher strain rates with increasing temperataire or decrensing grain size. The high rate rneclzanisrn is presunzed to be slip, while rnetallographic evidence sug-gests that the low rate lnechanism is pain boundary sliding. PEARSON' discovered that extruded eutectic alloys of Pb-Sn and Bi-Sn could be elongated as much as 2000 pct in tension. The ability for stretching decreased with aging time or annealing to increase the grain size. At high strain rates, or if the material was in the cast condition, normal ductility was observed. Following deformation of the extruded Pb-Sn eutectic at low rates, Pearson observed an equiaxed granular structure on an initially flat surface, while rapid straining produced elongated grains. He attributed the large deformation in the extruded alloys to the persistence of extremely small grains to a temperature sufficiently high for inter granular flow. Avery and backofen2 measured the strain rate sensitivity of the flow stress, m = d In old In 6, in the Pb-Sn eutectic and established a correlation between m and the tensile elongation. In the extruded eutectic alloy the strain rate sensitivity was 0.1 to 0.2 at rapid rates and the elongation was small, while at low rates m increased to 0.4 to 0.6 and superplastic elongation was observed. They also noted a grain size effect. In the case of the cast Pb-Sn eutectic the strain rate sensitivity remained at 0.1 over the range of strain rates of their experiment (3 x 10"3 to 2 min-I). These authors suggested that diffusional (Nabarro-Herring) creep was the mechanism by which deformation occurred at low strain rates, while climb-controlled creep occurred at high rates. Two predictions of this model are that, at low strain rates, the strain rate sensitivity approaches 1, i.e., Newtonian viscosity, and that the strain rate at constant stress varies as D/L2, where D is the coefficient of self-diffusion and L the grain size. More recently, a mechanical and microstructural investigation of the dilute superplastic alloy, Sn-5 pct Bi, has been done.3 The results show that the high strain rate sensitivity is associated with a transition with strain rate of the mechanism of plastic flow. At low strain rates, grain boundary sliding and its associated accommodation processes were evident, while at high strain rates quasi-uniform slip was concluded to be the dominant deformation process. The following experiments were performed to extend our knowledge of the phenomena of superplasticity to a larger range of strain rates, compositions, temperatures, and microstructures in the Pb-Sn alloy system. The question of why a cast structure does not exhibit viscous behavior although it appears to have a fine microstructure2 was investigated.

Jan 1, 1968

By AIME AIME

WINFIELD SCOTT MORRIS, known from Coast to Coast within the petroleum industry as "Buck" Morris, is and has been for several years an outstanding man in the Petroleum Division of the A.IM.E., so it is most natural to have him as the Chairman of the Division. "Buck" has been such a vociferous promoter of everything TEXAS that most of his friends believe him to be a "Longhorn" by birth-but the records show he was born at Wilmington, N. C., on July 29, 1901. He worked his way through college and graduated from the University of North Carolina in 1924 with a B.S., followed by a C.E. in 1927. His graduation thesis was entitled "De¬sign of a Modern Oil Refinery."

Jan 1, 1944

By David B. Dill, Edgar R. Lea

The zinc deposits of the Balmat-Edwards Division of the St. Joseph Lead Company in northern New York State provide some 10 per cent of the domestic zinc produced annually within the United States. These complex ore deposits are contained within marbles of the Precambrian Grenville series, in a repetitive sequence of dolomites and silicated units. The Balmat ore bodies are localized at various intervals throughout some 1800 feet of the stratigraphic column on the northwest side of a band of gneiss that has continuity to the Edwards area, some 10 miles to the northeast. The Edwards ore bodies are located to the southeast of this gneiss. The marble formations are thought to have included repetitive intervals of marine sedimentation that provided mineralized source "beds" and were subsequently folded, flooded, and injected with melts at great depth and were sheared, recrystallized, and reconstituted. Detailed structural and stratigraphic studies throughout the northwestern Adirondacks, in the Balmat-Edwards district, and at each mine in particular indicate the close dependence of the ore deposits on the enveloping structure whether it be local, district-wide, or regional in scope. Primary folding has developed a northeast regional trend with northwest dips. Secondary folding has been developed by an almost horizontal northeast-southwest-oriented shear couple in the plane of the regional trend. The secondary folding has produced crossfolds that intersect the regional northeast trend and plunge north to northwest at various angles. The ore bodies are found within certain stratigraphic horizons where repeated alternation of competent and incompetent beds encouraged unusually complex folding. Analysis of individual mine structures indicates that the location of each deposit is controlled by structural crossing of primary and secondary folding. The ore bodies, which are tabular, lenticular, or pod-like in form, have features that suggest parallelism to true bedding or modified flow banding, developed by northeast-southwest shearing stresses related to the development of the crossfolds. The ore deposits in general follow both structural and recrystallization trends within the wall rocks. Mobilization of the pre-metamorphic ore minerals is believed to have involved a combination of plastic flow under stress and solution of the sphalerite, minor galena, and pyrite. The ore fluids are thought to have been guided by secondary shearing and microbrecciation into structurally prepared areas where reprecipitation took place. The presumed premetamorphic mineralization now exhibits epigenetic high-temperature features related to late-stage metamorphism.

Jan 1, 1968

By D. Turnbull, J. H. Hollomon, J. C. Fisher

UNDERSTANDING of the diffusion problem has recently been furthered by the analysis of Birchenall and Mehl.1 They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,2 Jost,3 Dehlinger,4 and Darken,' who assumed the net flux of dif¬fusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's' activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Hargreaves.7 The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinski10 in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitutional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitutional alloys were analyzed on the basis of the concepts of the chemical rate theory. CHEMICAL RATE THEORY According to the theory of absolute reaction rates8 the reaction [A,+A2+ ... +.A;->X,+X2 +...+X; EqI] is viewed as taking place in two steps. First the reactants A1, A2, . . . A[i] combine to form an activated complex M with which they are in equilibrium; [A, + A2 + .. . + Ai = M. Eq 2] Second the activated complex decomposes to give the products X1, X2. . .. X[j]; [M->X1+X2+ ... +.X;. Eq3] It has been shown8 that the number of activated complexes decomposing per unit volume per unit time is given by the expression† [kT]

Jan 1, 1948