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By A. Martens

When I was honored with an invitation from the American Institute of Mining Engineers to present a paper at the Chicago meeting on the microstructure of iron, I hesitated about accepting, as the short interval that would remain at my disposal, after other pressing matters had received attention, could not but seriously affect the work of preparing such a paper. Unfortunately my fears have been realized and my work is neither completed, nor yet as comprehensive as I should desire. Mindful of my promise, however, and recognizing that 1 have reached a point where the results of my researches may prove suggestive, I am led to present them now, trusting that this brief explanation map secure indulgence for whatever deficiencies the paper may disclose. So far as my knowledge of published memoirs and treatises extends, microscopy cannot yet be said to possess a really firm foundation. In few cases only has any systematic development of the methods of investigation been undertaken, and broad gaps remain to be filled. It is not yet possible, therefore, to give a complete survey of the field, or, indeed, to supply a text-book on microscopic metallography. As Mr. F. Osmond, of Paris, a distinguished member of our profession, has undertaken to prepare for the Chicago meeting a historic review of the work actually accomplished I need not touch on that branch of the subject; but before entering upon my special theme, it may not be out of place for me to introduce certain explanations, as furnishing reasons for the course 1 have hitherto pursued, and to offer some suggestions for the further development of the methods of microscopic investigation. In microscopic metallography, the examination has to be conducted principally with incident light. Objectives of low power, in which the distance between the front lens and the abject is considerable, are adapted for directly incident light, and in such cases the relatively great depth of the image renders it possible to examine

Jan 1, 1894

By C. W. Volek, G. Mandl

Steam-injection tests in the field have shoum that heat transport into the oil/water region, ahead of the steam zone, may have a significant effect on the production process. Earlier theoretical work on reservoir heating by hot-fluid injection can be used to describe the growth of the steam zone, but only if heat transport from steam zone into oil/water region is neglected. It therefore became necessary to re-examine and extend the earlier theory. It was found that this theory ceases to be consistent with the physical model of the process at a certain critical time, tc, which depends on reservoir thickness, temperature, and quality of the steam. The critical time marks an important change in the heat flow across the condensation frovt: the heat flow, which is purely conductive during 0 < t < tc&apos; becomes predominantly convective at t = tc. Accordingly, at t = tc, the equation which governs expansion of the steam zone changes. On the basis of the new equation, an approximate description for the steam-zone growth during t > tc is developed by making use of upper and lower bounds for the exact solution of the problem. The boundary conditions for heat and mass flow inside the oil/water region are established, and a simple method of detennining the saturation at the downstream side of the condensation front is presented. Experimental results show that the theory gives an accurate description of steam-zone expansion before the critical time. At times near critical time, and also after critical time, experimental data show theoretical steam-zone volumes to be high. Even so, the accuracy of the calculated steam-zone volumes is sufficient for practical purposes. THEORY OF STEAM-ZONE GROWTH INTRODUCTION The engineering evaluation of steam-drive processes is based mainly on a mathematical description of reservoir heating by hot fluid injection presented several years ago by Marx and Langenheim.l This theory can be used to determine the growth of the steam zone,2 provided the flow of heat from the steam zone into the liquid zone ahead of the condensation front (Fig. 1) is neglected. Since we must expect, however, that heat transport into and inside the liquid region (the region between condensation front and production wells) will affect both the water/oil flow and the growth of the steam zone, it is necessary to re-examine and to generalize the Marx and Langenheim theory as applied to steam drive, which will hereafter be termed the "old" theory. Observations made in several field tests emphasize the need to study the heat flow across the condensation front (CF). On several occasions it was discovered that heat was transported in the liquid zone far ahead of the advancing CF, resulting in an early breakthrough of warm water. This seems to occur most often when high injection pressures are applied, when "wet" kONINKLIJKE/SHELL EXPLORATIE EN PRODUKTIE LABORATORIUM RIJSWIJK, THE NETHERLANDS SHELL DEVELOPMENT CO. HOUSTON, TEX.

Jan 1, 1970

If problems are opportunities in disguise, the mining industry certainly had plenty of "opportunities" in 1975. Considering the industry&apos;s generally lackluster 1975 profit record, and in view of the slowdown in inflation, there&apos;s some hope that 1976 might be a better year in spite of the increasing risks and uncertainties that plague the mining industry.

Jan 2, 1976

By John Eash

DURING recent years nickel has had an increasingly important role as an alloying element in the copper-tin bronzes. Nickel additions not only produce better casting alloys but also make alloys whose properties can be varied by precipitation hardening; thus leading to increased commercial application of copper-nickel-tin alloys. Recent investigations have indicated a decrease in the solubility of tin in the alpha phase as the annealing temperature is lowered and as the nickel content is increased within certain limits. A further change caused by the nickel additions is produced in the excess phase of the copper-tin bronzes. The alpha plus delta eutectoid is replaced by a clear precipitated constituent in the alloys containing up to 15 per cent tin and not less than 1 per cent nickel. This paper has a dual purpose. The first is to present a new determination of the alpha-phase boundary in alloys containing from 0 to 20 per cent nickel, together with the liquidus and solidus temperatures above that field. The second purpose is to give the equilibrium conditions existing in alloys exceeding the alpha phase containing up to 31 per cent tin and 5 per cent nickel, so that the disappearance of the alpha plus delta eutectoid constituent may be explained. After considering the earlier investigations of the related alloy systems and the experimental procedure used in this investigation, the alloys will be discussed in groups as separate quasibinary systems containing constant amounts of nickel. The systems considered contain 0, 1, 2, 3, 5, 10 and 20 per cent nickel. The straight copper-tin system was reinvestigated in order to establish a foundation on which to build the remaining material. The 1 per cent nickel alloys studied give the relations existing in the region of the eutectoid transformation between the copper-tin system and the 2 per cent nickel copper-tin system which has been investigated in detail. The thorough examination of the latter system was made since 2 per cent of nickel is representative of the commercial additions to the cast bronzes and also because it is sufficient to produce

Jan 1, 1932

By H. W. Meyer, H. N. Lander, F. D. Delve

A method of calculating the changes in blast-furnace performance brought about by burden and/or blast modifications is presented. Essentially the method consists of three simultaneous equutions derived from materials and heat balances. These equations can be used not only to evaluate quantitatively the effect of changes in process operating variables on furnace performance, but also to provide a useful means of evaluating changes in process variables which cannot be measured directly. It has been customary for a number of years to use simple heat and materials balances as a basis for assessing blast-furnace practice. A good example of the method used to set up these balances is that proposed by Joseph and Neustatter.1 This approach to process assessment has limited utility, however, in that it cannot be used to predict the furnace coke rate or production under new operating conditions. Using an approach based on multiple correlation of blast-furnace variables, R V. Flint2 has developed an equation which may be used to predict the change in coke rate that will result from some changes in operating conditions with a reasonable degree of accuracy. Although this equation has useful applications in production planning, it cannot be used to study the relationships between the operating variables and the fundamental thermochemi-cal characteristics of the process. In attempting to analyze the blast-furnace process quantitatively, the idea of dividing the furnace into zones3 may at first appear attractive. In our present state of knowledge, however, it is not possible to define with any accuracy the physical limits of such zones in relationship to their temperatures or to the reactions which may occur in them. Although its application is restricted, the zonal approach to blast-furnace analysis is useful in some instances. For example, the change in the calculated flame temperature in the "combustion zone" caused by injecting steam constitutes information which is helpful in understanding why the addition of steam to the blast is best accompanied by an increase in blast temperature. The zonal approach cannot, at the present time, be used to establish the relationships between process variables and process performance if the whole process rather than part of it is to be considered. One of the earliest approaches to the problem of relating blast-furnace operating variables to pro- duction and coke rate was that developed by Marshall.4 Essentially Marshall&apos;s work showed that it was possible to estimate the performance of a furnace by solving three simultaneous equations which consisted of rudimentary carbon and heat balances plus a further equation relating the production, wind rate, and the carbon burned at the tuyeres. Although these equations did not include all of the chemical and thermal variables of the process, their derivation and application seems to be the earliest attempt which achieved any success in relating prior furnace operating data to the calculation of furnace performance under different blast conditions. Work carried out in Germany has been directed mainly towards prediction of coke rates using material and thermal balances rather than statistical methods. wesemann5 used prior furnace operating data as part of the basis for predicting the change in coke rate accompanying a change in burden composition. This author employed a method of successive approximations to estimate the secondary changes in slag volume and stone rate brought about by the change in coke rate. The most recent analysis, which seems to have been developed concurrently with the thermochemical model presented in this paper, has been described by Georgen.6 This author has succeeded in improving on Wesemann&apos;s approach by expressing the total changes in the slag volume and stone rate in terms of the change in coke rate itself. This is accomplished in a manner similar to that used in the thermochemical model described in this paper. Although Georgen makes use of a calculated furnace heat loss, he does not relate the heat loss per unit of hot metal to the production rate as is done in the present work. Georgen&apos;s approach may be used to calculate the changes in materials requirements accompanying changes in furnace operation; it cannot be used to assess the resulting changes in production. The fact that blast-furnace behavior can be interpreted by consideration of the heat requirements of the process was demonstrated by Dancy, Sadler, and Lander.7 In the analysis of blast-furnace operation with oxygen and steam injection these authors showed that it was possible to account for the changes in production and coke rate

Jan 1, 1962

By A. H. Geisler, R. F. Mehl, S. Barrett

The studies of the mechanism of pre= cipitation and of the resulting property changes in aluminum-silver alloysl-3 have presented some new concepts of the aging reactioxl—concepts that may be fundamental in establishing a complete quantitative theory of age-hardening. With both aluminum-copper and aluminum-silver alloys, thin platelike aggregates form parallel to the Widmanstätten planes of precipitation.l,4 These platelets grow in lateral dimensions and in thickness with aging time until they arc thick enough to produce an X-ray diffraction line pattern. Their structure is that of a transition lattice which is coherent with the matrix, since the atomic spacings in the matrix and the precipitate are the same on each side of their common interface.2,4 The equilibrium precipitate forms later from and at the expense of the transition lattice. Since age-hardening occurs during the formation and growth of the transition lattice, the major contributor to the hardening no doubt is the stress condition in the matrix resulting from the matrix holding the precipitate in the coherent condition. The development of these stresses also appears to be responsible for an increase in the electrical resistance superimposed on the normal decrease resulting from a change in the concentration of the matrix during aging.3 The two consecutive reactions constituting the aging process are accompanied by characteristic microstructural alterations. The initial precipitation process results in the formation of a Widmanstatten figure, while the later transformation of the transition lattice to the equilibrium lattice is accompanied by a coalescence, in the case of aluminum-copper alloys,5 and by the appearance of light areas at the grain boundaries with aluminum-silver alloys showing a structural rearrangement of matrix and precipitate.3 This latter reaction is similar microscopically to the so-called "discontinuoils precipitation." Possibly discontinuous precipitation is a process that often if not always follows true precipitation of a coherent lattice and during which the transformation of the coherent transition lattice to the equilibrium lattice takes place accompanied by matrix recrystallization.3 Expermental Procedure The alloys were made using 99.97 per cent A1 or distilled magnesium, with

Jan 1, 1943

By R. F. Mehl, A. H. Geisler, S. Barrett

The studies of the mechanism of pre= cipitation and of the resulting property changes in aluminum-silver alloysl-3 have presented some new concepts of the aging reactioxl—concepts that may be fundamental in establishing a complete quantitative theory of age-hardening. With both aluminum-copper and aluminum-silver alloys, thin platelike aggregates form parallel to the Widmanstätten planes of precipitation.l,4 These platelets grow in lateral dimensions and in thickness with aging time until they arc thick enough to produce an X-ray diffraction line pattern. Their structure is that of a transition lattice which is coherent with the matrix, since the atomic spacings in the matrix and the precipitate are the same on each side of their common interface.2,4 The equilibrium precipitate forms later from and at the expense of the transition lattice. Since age-hardening occurs during the formation and growth of the transition lattice, the major contributor to the hardening no doubt is the stress condition in the matrix resulting from the matrix holding the precipitate in the coherent condition. The development of these stresses also appears to be responsible for an increase in the electrical resistance superimposed on the normal decrease resulting from a change in the concentration of the matrix during aging.3 The two consecutive reactions constituting the aging process are accompanied by characteristic microstructural alterations. The initial precipitation process results in the formation of a Widmanstatten figure, while the later transformation of the transition lattice to the equilibrium lattice is accompanied by a coalescence, in the case of aluminum-copper alloys,5 and by the appearance of light areas at the grain boundaries with aluminum-silver alloys showing a structural rearrangement of matrix and precipitate.3 This latter reaction is similar microscopically to the so-called "discontinuoils precipitation." Possibly discontinuous precipitation is a process that often if not always follows true precipitation of a coherent lattice and during which the transformation of the coherent transition lattice to the equilibrium lattice takes place accompanied by matrix recrystallization.3 Expermental Procedure The alloys were made using 99.97 per cent A1 or distilled magnesium, with

Jan 1, 1943

DAVID WHITE,* Washington, D. C.-This paper is very timely since the Philippine Islands are presumably open to the enterprise of the American driller, whereas much of the territory in that part of the world is closed to us. The United States has ambitious plans for the operation of a great merchant marine, which is to be oil burning in the main, and it takes but a glance at the world map to see the strategic advantage of oil supplies in the Philippines for such marine operations. It is a little difficult to understand why more attention has not been given to the Philippines, in spite of the difficulties attending development in these islands. A number of American oil companies are, I believe, at the present moment taking an interest in the possibilities of the Philippines. Important factors in the formulation of opinion regarding the importance of the oil deposits of the Philippines, as brought out by Mr. Pratt,1 are the point of view and the breadth of experience of the examining geologist. The average oil geologist, whose experience has been mainly in the Appalachian region, the Mid-continent, or Louisiana, or possibly even in California, on seeing the narrowness of the basins, the closeness of the folding, and the presence of igneous rocks here and there, would be likely to draw unfavorable conclusions as to the possibilities of the Philippine Islands. Geologists visiting that region should be familiar with the geological conditions of oil occurrence in Japan, Formosa, the East Indies, or in the Baku district, and their conclusions should be formulated with the knowledge and understanding of the occurrence of oil in those regions rather than in the United States.

Jan 8, 1920

By Hjalmar Sjögren

Introduction.............767 Group I. The Ores of the Archean Crystalline Schists.... 770 Distribution............. 770 The Rocks.............770 Structures............772 The Rocks of Norrbotten..774 The Ores.............775 Type A. Apatite.Ores..........776 Type B. Mixed Hematite and Magnetite..777 Type C. Quartz-Banded Ores....777 Type D. The "Skarn" .Ores l..778 Type E. Limestone-Ores,..779 The Origin. of the Ore-Deposits......... 779 Arguments against the Sedimentation Theory,... 780 Concentration and Transformation within the Deep-Seated (Ana-morphic) Zone........783 The Chemical Changes.......784 Transformations in the Surface.Zone....789 The Graingesberg and Norrbotten Deposits,.....791 Analogous Deposits........794 Group II. The Ores of the Porphyries (Keratophyres) ... 796 Kiirunavaara. Luossavaara and TuoIlavaara....797 The Syenite.........799 The Porphyry of the, Foot. Wal1 .....799 The Porphyry of the Hanging-Wal1 ....799 The Ores.........800 The Forms and Dimensions of the Ore-Bodies ..802 Contact-Zones........803 The Genesis of the Deposits .......804 Mertainen and Painirova.......806 Ekatrömsberg..........808 Analogous Deposits,........808 Group 111. Magmatic Seregations in Basic Eruptives,... 809 Taberg in Smaland,.........811 Segregations in Diabase Younger than the Dala Sandstone, . 814 Iron-Ore in Nepheline. Syenite.......815 Ekersund and Soggendal in Norway......816

Jan 1, 1908

By Richard H. Olson, Lawrence A. Roe

Talc, when it can be isolated as a pure mineral, has a composition of 63.36% Si02, 31.89% MgO, and 4.75% H20. However, as an industrial commodity, talc rarely approaches theoretical purity. Nevertheless, the impure talc products of commerce find a multitude of uses and few substitutes in many industrial applications. Minerals commonly associated with and sold together in talcose mixtures are tremolite, chlorite, dolomite, mica, and magnesite. Steatite was originally a mineralogical name applied to pure talc. In today&apos;s commerce steatite generally refers to the massive variety of talc suitable for electrical insulator manufacture. Block steatite ore can be machined into various shapes. Impure varieties of massive or block talc are still commonly referred to as soapstone. Soft massive talc, suitable for crayon manufacture, has been referred to as French chalk. It has been common practice to discuss talc, soapstone, and pyrophyllite under the same general heading. In the case of soapstone and talc, this is a natural thing since many different types of platy, soft minerals exhibiting a high degree of lubricity (commonly referred to as "slip") have been grouped together and called soapstone or talc. Further, there is a mineralogical relationship of pyrophyllite to montmorillonite and talc to hectorite. Thus, talc and pyrophyllite are sometimes referred to as clay minerals. When finely divided talc or pyrophyllite are combined with water in proportions to make a slurry, the end product does have the appearance of a clay-water mixture. Soapstone for utensils and ornaments was mined by prehistoric Indians on Santa Catalina Island, CA. In the mid-1800s, soapstone from deposits along the western foothills of the Sierra Nevada mountains was used by white settlers for building and ornamental stone and in the linings and foundations of furnaces (Anon. 1956). Previous to 1916, the annual recorded production in California did not exceed 2000 tons. In the period 1912 to 1918, output rose sharply when the Talc City, Western, and Silver Lake mines were put into operation. From 1916 to 1935, the state&apos;s annual output of talc was in the range of 9,000 to 20,000 tons. In the mid-1930s, the use of talc in wall tile grew rapidly. In California, the production of talc grew to 63,000 stpy in 1943. The post-war building boom helped California production to grow to 120,000 tons in 1951. In 1968, production was 165,000 tons, 1969 was 145,000 tons, 1970 was 185,000 tons, and 1972 was 155,000 tons. Talc mining in New York state dates to about 1878 when a Colonel Palmer and associates opened the first commercial talc mine on the Nelson Freeman farm near Talcville, New York. In 1893, this operation was sold to the International Pulp Co. which changed its name to the International Talc Co. in 1944. The company was acquired by R.T. Vanderbilt Co., Inc. in 1974. A new talc operation, the Gouverneur Talc Co. owned by the R.T. Vanderbilt Co., began operations near Balmat, NY, in 1948. The initial capacity of the processing plant was 200 stpd (Gillingham, 1950). Subsequent expansions have increased capacity to over 600 stpd. The Vermont talc industry began just after the start of the 20th century. Talc was discovered in the area of the present Johnson, VT, talc mine in 1902. The American Minerals Co. initiated plant operations at Johnson in 1904. The Magnesia Talc Co. opened a plant at Waterbury, VT, in 1913 (Burmeister, 1963; Trauffer, 1964) and acquired American Minerals Co. in 1923. The Waterbury mine has a long history as a producer of talc crayons. The Eastern Magnesia Talc Co. was formed in 1924 by a merger of the Eastern Talc, Co.

Jan 1, 1983

By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.&apos; It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

By E. C. Truesdale

A FEW years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.2 During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. TABLE 1.-Typical Analyses Percentage by Weight Sum of Zinc Pb, Fe, Pb Fe Cd Al Cd Special High Grades 0.007b 0.005b 0.0056 none 0.0106 C.P. (chemically pure) <0.0002 0.0005° 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 6-37). b Maximum. c Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By H. W. Mead, C. E. Birchenall

The rates of growth of graphite nodules in cast irons are calculated for a model of a growing graphite sphere surrounded by a shell of austenite through which carbon and iron are diffusing. The carbon is supplied by a cementite-austenite mixture at the outer edge of the shell. The calculated rates from carbon diffusion agree fairly well with the measured values, but the rates based on iron self-diffusion are much too low. Because the iron must be removed for the process to continue, o plastic deformation mechanism is suggested. THERE has been an unfortunate tendency in the literature of growth and dissolution reactions to identify the slope of a plot of the logarithm of the growth or dissolution rate vs reciprocal of temperature with the activation energies determined by diffusion measurements in chemically similar systems. If the solubility limits at the growing or dissolving phase interfaces change appreciably with temperature, such procedures may lead to serious errors in specifying the mechanisms controlling the rates of these processes. A reaction involving the simultaneous growth of graphite from and dissolution of cementite in austenite will be discussed here to show that substantial oversimplifications have been made in earlier studies of this process. From a dilatometric study of the overall y-range graphitization process, Bunin and Danil&apos;chenko&apos; found an apparent activation energy of 90 kcal per g-atom. They concluded that, since this value was much nearer the approximately 68 kcal per g-atom observed for self-diffusion in pure iron than it was to 32 kcal per g-atom for diffusion of carbon in iron, the rate-controlling process must be the diffusion of iron away from the growth interface to provide space for graphite to grow. Bunin and Salli&apos; bolstered this agreement with the observation that graphite forms preferentially at surfaces, cracks, and pores where free volume is present initially. Ziegler, Meinhart, and DeaconQ ad found an apparent activation energy for graphitization of 98 kcal per g-atom. This value, like that of Bunin and Danil&apos;chenko, applies to nucleation and growth occurring simultaneously. It is not generally assumed that nucleation is entirely diffusion-controlled. Treatments such as prior cold-working and prequenching, which strongly affect the rate of graphitization, would be expected to have little effect on diffusion processes occurring at the graphitization temperature. In any case 90 kcal per g-atom is not particularly close to the 54 kcal or lower to be expected for diffusion of iron which is carbon-saturated.&apos; The presence of silicon in iron is said to reduce the activation energy for diffusion,&apos; so its presence in cast irons would be expected to have a similar effect. The growth rates of nearly spherical graphite nodules have been studied by Brown and Hawkes." The initial rate of growth before impingement of adjacent carbon-depleted areas was found to be parabolic, and rate constants were measured at several temperatures. Their apparent activation energy for the growth process only was roughly 45 kcal per mol. Burke and Owen&apos; made growth-rate measurements on several alloys, recording appreciable induction periods, initial nucleation rates, and average radial growth rates based on an assumed linear rate of radial growth. They found that increased silicon content increases the ovel-all reaction rate and the initial rate of nucleation, and decreases the induction period. Assuming 1) spherical nodules. 2) constant volume rate of nucleation, 3) austenite in equilibrium with cementite at positions where the cementite is not depleted, and 4) a constant diffusion distance during the growth of a nodule, they calculated an apparent overall activation energy of 68 kcal per mol, which was related to an activation energy for nucleation of 79 kcal per mol and activation energy

Jan 1, 1957

By R. D. Pehlke, J. V. Gluck

The limiting activity coefficient of zinc in a "binary " solvent has been described for several dilute ternary solutions by combining literature data from recent interaction studies in the terminal regions with thermodynamic data for the central regions. Results are discussed in terms of the Alcock and Richardson random solution model. The observed behavior agrees semiquantitatively with predictions using the model. RECENT efforts in the thermodynamics of dilute ternary liquid metallic solutions have been mainly concerned with the interactions between two dilute solutes, that is, the terminal region at an apex of the composition diagram.&apos;-&apos; A more general case is that of the behavior of a dilute solute over the full range of a ternary system, or, more specifically, the limiting activity of solute i as projected to the k-j binary side of the i-j-k composition triangle. An implication of this is that the interaction between i and j at the k apex should connect in some way to the interaction between i and k at the j apex. A model to characterize various types of expected behavior has been discussed by Alcock and Richardson.9,10 Such behavior can range from a simple linear relation for In yi over the 1-k binary to more complex curved relations which depend on various assumptions regarding the heat of solution in the j-k binary system and the presence or absence of clustering with solute i. Quantitative data to assess these concepts have been limited primarily to the cases of nonmetallic interstitial solutes in ferrous solutions. Alcock, Richardson, and various coworkers9-13 have discussed the behavior of oxygen, sulfur, silicon, or hydrogen in dilute solution over the range of iron + metal systems; however, the only data considered by them for substitutional nonferrous metallic solutions were the results of Elliott and Chipman concerning the activity of cadmium in the Pb + Sn, Pb + Bi, and Pb + Sb systems.9 These data were limited and did not cover the terminal regions in detail. An opportunity to extend the Alcock and Richardson considerations to the dilute solution of zinc in various "binary" solvents has been afforded by combining results of several of the recent investigations of ter-minal-region interactions with previous data from the literature for the same more concentrated solutions. RESULTS AND DISCUSSION The results of the analysis are shown in Figs. 1 to 5 where the log activity coefficient, (In yZn)xzn--o, is plotted vs the composition of the "binary" solvent. In these plots the end points are the values for In yzn in the appropriate binary solution with Bi, Pb, Sn, Cd, or In at the indicated temperature—usually 550°C (823°K). For the terminal regions the slopes were drawn using the first-order interaction parameters taken from various studies reported in the literature. The data points shown in the central regions were obtained by the short extrapolation to infinite dilution of the logarithm of the activity coefficient calculated from thermodynamic studies reported in the literature for the same systems. The sources of the data are indicated on each figure. Second-order effects were not considered. Reasonably smooth curves can be drawn to connect the central region with the terminal regions for the Zn-Pb + Bi system, Fig. 1, the Zn-Pb + Zn system, Fig. 1, and the Zn-Bi + Cd and Zn-Bi + Sn systems, Fig. 2. As shown in Fig. 2, where central region data are available from two independent investigations, the agreement is quite good. The Zn-Pb + Cd system does not appear to be as well behaved as the previous four, Fig. 3; however, this type of behavior has also been

Jan 1, 1970

By S. Pearson, L. Rotherham

Measurements have been made of the variation of internal friction with temperature for spectroscopically pure silver, and for o series of solid solutions of silver with cadmium, indium, and tin, using a Ke-type torsion pendulum apparatus. Some experiments have also been made to investigate the effect of nonmetallic impurity on grain boundary relaxation in silver. The effect of the alloying elements is to increase the grain boundary viscosity, and to raise the activation energy for grain boundary relaxation from 22,000 cal per mol for pure silver to 43,000 cal per mol for the solid solutions; the same value being obtained, within the limits of experimental error, for all the alloying elements and solute concentrations investigated. Results of the experiments show exactly the same trend as those obtained previously for a similar series of copper solid solutions. They are in agreement with the general theory of grain boundary relaxation developed by Zener and Ke, but do not seem to be in agreement with either of the mechanisms so far put forward to explain grain boundary slip. EXPERIMENTS described in this paper were made as part of an investigation into the effect of alloying elements in substitutional solid solution on grain boundary viscosity, measured by the internal friction method developed by Ke.&apos; The apparatus and experimental procedure have already been described.&apos; Preliminary work was done with spectro-scopically pure silver. Experimental Work Materials Used—All the materials were supplied in the form of % mm diam wire by Messrs. Johnson Matthey and Co. Ltd. The silver and all the alloying elements used were spectroscopically pure. Composition of the alloys is given in Table I. They were all melted and chill cast under the same conditions as the copper alloys. The ingots were rolled to 1/4 in. sq rod with intermediate annealing at 600°C in an atmosphere of cracked ammonia when necessary. These rods were then drawn to wire by standard procedure with intermediate bright anneals at suitable steps in the drawing operations. Specimens from the annealed wires were sectioned longitudinally. mechanically polished, and examined under the microscope. They were then etched and reexamined. Grain sizes were reasonably uniform for all wires, and no traces of a second constituent were observed. The wires were weighed before and after testing so as to measure any loss of the alloying element due to evaporation. The loss was less than the accuracy of measurement—< 0.1 pct of the total weight— for the Ag-In and Ag-Sn alloys, but appreciable loss of weight occurred in the case of the Ag-Cd alloys. The percentage loss is given in Table 11. X-ray diffraction photographs were taken of all thc wires after test to determine whether there was any marked preferred orientation. Results of the examination are given in Table 111. Experiments on Spectroscopically Pure Silver-— Experiments were made on specimens in which the grain diameter was small relative to that of the wire, and on one specimen in which the grains were grown by the usual strain-anneal method to extend across the full diameter of the wire. These large grained specimens will be referred to as single crystal specimens. The wires were annealed for 11/2 hr at 700°C, and experiments were made at two frequencies of vibration, 1.5 and 0.4 vibrations per sec. The variation of internal friction with temperature is shown in Fig. 1. Experiments on a second small grain specimen gave approximately the same results as for the first wire. It will be seen from Fig. 1 that the peak in the curve for the small grained wire, which is presum-

Jan 1, 1957

By H. J. McQueen, G. C. Kuczynski

ThE useful properties of k6-Alfenol and the thermenol alloys (summarized by J. E. Nachman and W. J. Buehler&apos;) have encouraged research into those alloys which, having compositions near 25 at. pct Al, 75 at. pct Fe, undergo an ordering transformation between 500° and 550°C. The equilibrium diagram of the iron-rich iron-aluminum alloys was first determined by Bradley and Jay.2,3 They distinguished three structures: the disordered, which is bcc; FeAl, which is simple cubic with one Fe atom and one Al atom per lattice site; and Fe3Al, which is fcc with three Fe atoms and one Al atom per lattice site. This last structure may be conceived as eight body-centered cubes with Al atoms at the centers of alternate ones, so that Al atoms have only Fe as first and second nearest neighbors. Later, Osawa and Murata4 determined the boundaries of the different superlattice regions in the iron-rich Fe-Al solid solution by dilatometric and X-ray methods. Two of the six phases, which they found between 0 and 50 at. pct Al, were never identified by other workers. A. Taylor and R. M. ones,&apos; concurrently with and independently of this research, redetermined this diagram by measuring lattice parameters at temperature. Further reference will be made to their results. EQUILIBRIUM DIAGRAM A) Experimental Procedure—The alloys were prepared from NRC gas-free iron (99.9 pct Fe) and 99.99 pct Al. They were melted in alumina&apos; crucubles under vacuum in an induction furnace. If the ingots were unsound or showed more than a 3 pct weight loss, they were rejected. The ingots were homogenized at 1100°C for 24 hr before hot-rolling at 700" to 900°C from 1 in. to 0.25 in. thick. It is interesting to note that alloys containing more than 28 at. pct Al were able to take an 80 pct reduction of area in the ordered FeAl region. The dilatometer specimens and specimens for chemical analysis were cut from these plates. A Leitz dilatometer was used to measure the coefficient of linear expansion as a function of temperature. The specimens were slowly cooled from 900" to 300°C where they were annealed for 10 hr before slowly cooling to room temperature. The expansion was recorded photographically as the alloys were heated and cooled at 1.5oC per min between 100" and 1000°C. The magnetic measurements determining the Curie points were performed on the dilatometer specimens in the dilatometer, by using direct current in the furnace windings both to heat the specimen at 1.5°C per min and to serve as the primary coil. The regular specimen holder was replaced by a thin alundum tube on which was wound, as a secondary, a closely spaced coil of fine copper wire. A reversal of current in the furnace windings produced, in the secondary, an emf which was proportional to the induction in the specimen, and which could be detected on a galvanometer. In this way, it was possible to determine the Curie points of alloys to within * 5°C. B) Results and Discussion—The coefficients of linear expansion, as obtained from the dilatometer curves, are plotted as a function of temperature and composition in Fig. 1. Since in many cases the heating and cooling curves were superimposed, it was decided to measure slopes of heating curves only. Definite high peaks, due to the transformations, were observed on each curve between 400" and 520°C, and, for alloys containing more than 23 at. pct Al, a second set of smaller peaks at temperatures above 660°C. The sharpness of the peaks indicates that ordering to Fe3Al is a first-order reaction. The compositions and the temperatures of these peaks are listed in Table I. When these temperatures are plotted as a function of the composition, the result is the constitution diagram presented in

Jan 1, 1960

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-&apos; have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.&apos; Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By R. Lagneborg, R. Gullberg

An X-ray method for determinig volume fractions of phases in textured materials has been developed. The method involves measurements of the integrated intensities of reflections of each phase for one single orientation of the sample. The method was checked by evaluating the phase contents in samples from two stainless Cr-Ni steels containing austenite and ferrite in known amounts. In the present case measurements of about five reflections from each phase were required. The agreement between calculated and known volume fractions was found to be very close. AN X-ray diffraction method is often employed for determining the amounts of two or more phases in a material. The details of the method have been described at several instances.&apos;" In short, the method is based upon the fact that the integrated intensity of a reflection is directly proportional to the volume fraction of the phase considered. In principle, the method only requires the measurement of the intensity of one reflection for each phase. The most severe shortcoming with this method is that it disregards influences from preferred orientation in the material. In a diffractometer, where this type of analysis is most conveniently carried out, the geometry is such that the diffracting planes for a specific Bragg peak are all parallel to the surface of the specimen. This implies that it must be required that the occurrence of the diffracting planes parallel to the specimen surface must be as frequent as for any arbitrarily oriented physical plane of the sample. This requirement will generally only be fulfilled for a material free of texture. Since all materials in reality always exhibit a preferred orientation to some extent. the deficiency of the method is quite serious. In cold-deformed material the texture is appreciable, but also annealed material will in many cases display a considerable texture. The problem of quantitative phase analysis in textured material is one of obtaining the integrated intensity averaged over all orientations of the specimen with respect to the X-ray beam. Lopata and ~ula~ have shown that this can be accomplished by integration of intensities over the whole pole figure, or by random rotation of the specimen in the X-ray beam, or by a combination of both. Hence, in this method the average integrated intensity for a specific reflection is obtained by directly determining the intensity for a sufficient number of physical orientations of the sample. However, since an excess of diffracting planes in a certain surface plane necessarily must be accompanied by a deficiency of another type of diffracting plane, it appears to be possible to obtain the correct average intensity for a specific diffracting plane by performing an appropriate averaging of intensities belonging to a large number of diffraction planes of different hkl when all intensities have been produced from one single orientation of the specimen surface. In the present work such a method has been attempted and tested experimentally for two stainless Cr-Ni steels containing austenite and ferrite. 1) THEORY The expression for the integrated intensity of a Bragg reflection diffracted from a phase in a polycrys-talline sample in a diffractometer is: where C is a constant only dependent on the incident X-ray power and the diffractometer geometry, v the volume of the unit cell, F the structure factor, m multiplicity of the diffracting plane, L Lorentz factor, P polarization factor, e-2 temperature factor, p average linear absorption coefficient of the irradiated vO1umej and V volume fraction of the phase &apos;Onsidered. Hence, the factor R in the abbreviated form of Eq. [I] can be calculated and depends only on 0 and the diffracting plane {hkl}. For an alloy containing two phases, a and y, we can write

Jan 1, 1967

By C. C. Martin, M. C. Fuerstenau, R. B. Bhappu

Experiments revealed that quartz could not be floated in conductivity water at any pH with a long-chained sulfonate as collector. Various cations, Fe+++, Al+++, Pb++, Mn++, Mg++, Ca++, are shown to function as activators when the pH is such that the cation hydrolyzes. As the solubility product of the various cation-sulfonates was exceeded at the concentrations involved, precipitated cation-hydroxy-sulfonates, e.g. Fe (RSO3)2OH must be functioning as the collector in these systems. A number of interesting and important phenomena were revealed during a study of the response of beryl to sulfonate flotation.&apos; Perhaps the most important observation is the effect of various cations on flotation response. Experiments showed that in the vicinity of pH 3.0, about three ppm Fe+++ increased recovery of leached beryl from about 60 pct to 100 pct, whereas about four ppm Ca+ + reduced the recovery from 60 pct to 2 pct. With the exception of ferric iron, all of the other cations investigated reduced flotation recoveries drastically at this pH. As postulated in the paper Sulfonate Flotation of Beryl,&apos; even with low concentrations of polyvalent cations and sulfonate (on the order of one ppm), cation-sulfonates are precipitated immediately in solution. That is, blueish-white clouds were noted to form after given additions of salts to known solutions of sulfonate. Furthermore, it was also shown that one-hundred-fold more ferric iron than necessary to form the precipitated cloud had to be added to effect complete flotation. In other words, some form of solid ferric sulfonate was found to function as the collector in these systems. The form of the compound was suggested to be Fe(RCO3)2OH and that bonding to the surface occurs through the hydrogen of the hy-droxyl. As the form of this compound was shown to be dependent on the extent of hydrolysis of ferric iron, it is to be expected that ferric iron will be unique in some pH region. Further, if the presence of hydroxyl in the neutral precipitated compound is of primary importance, then other cations should function similarly but at different values of pH, since they will hydrolyze at different concentrations of hydroxyl ion. To determine whether the premise of hydrolysis is correct, the study was extended to quartz systems in the presence of various cations at various values of pH. EXPERIMENTAL MATERIALS AND METHOD Sodium alkyl aryl sulfonate was chosen as the collector for the experimental work. The reagent, sup plied as a courtesy sample by the Shell Chemical Co., has the following physical properties: Physical form Solid — Finely ground Sulfonate content, pct wt 95 to 97 Molecular Weight 450 to 470 Number of carbon atoms in hydrocarbon chain 25 to 30 Melting Point, OF 250 to 260 Solubility Soluble in water with gel formation at concentrations higher than 25 pct by weight sulfonate This particular reagent was chosen because of its high active sulfonate content, long-chain length, and solid form. With the exception of the frother and sulfonate, all other chemicals were of reagent grade quality. Conductivity water was used in the experimental work. This water, made by passing distilled water through an ion exchange column, had an average measured conductivity of one micromho. Experiments were conducted at room temperature in a small glass flotation cell with the following procedure: 1) A redetermined amount of water and salt solution (e.g. CaC12 . 2H2O) were combined and the pH adjusted to a given value. 2) A given amount of sulfonate was added so that final solution volume was 130 cc. 3) One drop of Dow 250 frother was added. 4) Five g of quartz were added and the system conditioned for five minutes. 5) The pH of the system was measured (termed flotation pH).

Jan 1, 1963