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By J. K. Stanley

Knowledge of the diffusivity of carbon in the low temperature form of iron (alpha iron existing below 910°C) is at the moment of considerable interest in the study of the decomposition of austenite and martensite, the elastic after-effect,123 the magnetic after-effect4 and the decarburization of steel below 910°C. Information on the solubility of carbon in iron, and to a lesser extent its diffusion, is also important in consideration of such phenomena as blue-brittleness, temper-brittleness, "magnetic" aging, quench-aging, strain-aging, and possibly the yield point. In order to obtain more information on these subjects more fundamental knowledge is necessary. It is the purpose of this work to present data on the diffusion and solubility of carbon in the alpha iron. The high temperature form of iron (gamma; face-centered cubic) existing above 910°C is capable of dissolving relatively large amounts of carbon, up to 1.7 pet at 1130°C, while the low temperature form (alpha, body-centered cubic) existing below 910° dissolves only a limited maximum amount of less than 0.02 pet carbon at 725°C, according to data obtained here. Since the solubility of carbon in the face-centered or gamma iron is large, relatively speaking, no great analytical difficulties have been encountered in the determination of the solubility lines5 or of the diffusion of carbon.0 The limited solubility of carbon in alpha iron offers difficulties because experimental procedures and analytical methods for low carbon contents below say 0.01 pet have to be more refined than techniques used for work with gamma iron. Because of the difficulties of applying conventional methods to the determination of the diffusion of carbon in alpha iron, virtually no work has been done on this subject. However, by proper refinement of the analytical method for small amounts of carbon, the determination of the diffusion coefficient can be made readily using modified procedures. The solubility of carbon in alpha iron has been determined over a temperature range by various investigators, but the agreement among them is poor. The present investigation establishes the limits quite accurately. Information of this kind is useful in establishing the correctness of equilibrium diagrams but, more significantly, such information on maximum solubilities, especially when extended to alloyed ferrites, should be extremely important in the study of aging and related phenomena. Literature The literature existing on the diffusion, in particular, and on the solubility of carbon in alpha iron is not extensive. The data which exist are not of a high order of accuracy, much of them being in the realm of conjecture. THE DIFFUSION OF CARBON IN ALPHA IRON Whiteley7 made the qualitative ob- servation, using metallographic techniques, that the rate of diffusion of carbon at the A1 (725°C) point was very rapid and that its diffusion was still rapid at 550°C. Snoek,4 studying the magnetic aftereffect in high purity iron, arrived at the conclusion that the after-effect could be explained by the presence of small amounts of carbon diffusing under the influence of magnetostrictive strain (lattice distortion due to magnetic interaction). In later work, Snoek8 made an estimate of the ratio of carbon diffusion in alpha to its diffusion in gamma iron, and concluded that for a temperature of 910°C the ratio of Da/D? was 2600. Polder,9 basing his calculations of D on relaxation phenomena in the elastic after-effect, estimated that Da is about 1/3 of D? at 910°C (1183°K) and is about 1/12 of Dy at 727°C (1000°K). Polder's equation for the diffusion of carbon in alpha iron was calculated to be 18000 D = 5.2 X 10-4 e-RT cm2 per sec Ham10 obtained data for the diffusion and solid solubility of carbon in alpha iron at two temperatures by using one technique similar to that employed in this study. He found a D of 8.0 X 10-7 cm2 per sec at 702°C and of 2.7 X 10-7 at 648°C. THE SOLUBILITY OF CARBON IN ALPHA IRON Although pearlite is absent in steels containing 0.06 pet,11 0.05 pet,12 or 0.045 pet C,13 it appears that the carbon in these steels cannot be in solution in ferrite. The solubility of carbon at the A1 (725°C) point was first determined by Scott14 on the basis of cooling curves, and was found to be between 0.03 and 0.04 pet C. Tamura15 by interpolating between the solubility of carbon in delta iron at 1400°C and in alpha at room temperature (assuming zero solubility) ar-

Jan 1, 1950

By R. Scot Clark

The reactively sputtered silicon dioxide capacitor -was developed for use in the monolithic integrated circuit, thereby requiring the capacitor to be fabricated on an oxidized silicon slice. The silicon dioxide film is formed by reactively sputtering silicon in a 50 pct Ar-50 pct 0, atmosphere and the physical properties are indistinguishable from silica. A practical upper limit of capacitance per unit area of 0.25 pf per sq mil is reached with the capacitors fabricated from the Si0, film. Methods shown to enhance this value are double stacking the thin-film capacitors and addition of aluminum to the silicon cathode during sputtering to form an aluminosilicate dielectric. A major contribution to the field of diffused integrated circuits would be the addition of auxiliary passive devices for replacement of diffused passive devices which are currently being fabricated for many integrated circuits. This accomplishment would increase the flexibility of the diffusion process in order to concentrate more on transistor parameters rather than on fabricating diffused resistors and capacitors. To pursue this technique, a thin-film SiOz capacitor was developed which has _ proven applicable to many integrated circuits. Although the SiOl capacitor has an application, the major deterrent from extending the integrated circuit into many useful areas such as low-frequency linear application is the low dielectric constant of SiO, and the low usable capacitance in an integrated circuit. This paper will cover the sputtering techniques used for forming the SiO, film, the physical and electrical properties of sputtered SiO,, and yield information concerning the application of these capacitors to integrated circuits. REACTIVE SPUTTERING Reactive sputtering is simply the sputtering of a metal or semiconductor in glow discharge in the presence of a reactive gas. The material to be sputtered is seen in Fig. 1 as the cathode of the system and is bombarded with positively charged ions of the ambient gas. In this investigation, the ambient gas is composed of 50 pct Ar and 50 pct O2 at a pressure of approximately 2.5 X l0-' Torr. The ions are accelerated toward the cathode in the cathode dark space by the electric field and upon striking the cathode effect a momentum energy transfer to the surface atoms. The transferred energy is sufficient to dislodge a surface atom or atoms and these particles diffuse through the glow discharge to the collector or anode. Several mechanisms of oxidation in the reaction chamber can be considered during reactive sputtering. 1) The surface of the cathode is oxidized and the oxide is subsequently sputtered. 2) Oxidation and sputtering occur simultaneously. 3) Sputtering of the cathode material is followed

Jan 1, 1965

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

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

Jan 1, 1970

By B. S. Butler

A. D. Mutch (Falconbridge Nickel Mines Ltd., Ona-ping, Ontario)—This contribution is prompted by the fact that the writer has recently published an article'!' which has in part the same general conclusions as B. S. Butler's, namely, the form of the standard mineral paragenesis in hypogene deposits and the parallel transition from early high temperature acid to late low temperature alkaline or neutral solutions. Since the writer also recognizes that he is not fully qualified to discuss the formation of ore deposits as a chemical problem, this discussion will be limited to summarizing other observations and will suggest how Butler's Table II might be made more effective. The form of Butler's table is not unlike that widely used by European geologists'" in which the various minerals are related to the types of ore fluids—peg-matitic, pneumatolic and hydrothermal. Thus the decrease in temperature and change in pH of the ore-bearing fluids as recognized by Butler may also be paralleled by perhaps even greater changes in composition, density, and character. W. H. Newhouse's article:" on the sequence of hypo-gene ore mineral deposition is still one of the most complete analyses of the problem. In it he makes four major observations: 1) The order of O, S, As, Sb is the same as their increasing atomic weights and the same as their melting points. 2) The order of the metallic elements is the same as the Schuermann series. 3) The general mineralogical order is paralleled by decreasing heats of formation. 4) The order is generally in decreasing hardness, higher metal content, and higher specific gravity. The order of 0, S, As, and Bi is also the same as their relative abundance. Another point worth mentioning about this series is that As, Sb, Bi, when abundant, often substitute for sulfur in the early pyrite-like minerals, whereas later in the sequence these elements appear to act more like metals. This behavior may be a further indication of the acid character of the early fluids. C. J. Sullivan"' has attempted to show that the sequence of the metallic elements is related to the order of their melting points and has discussed the interrelationship of the different types of bonding of sulfo-phile and oxiphile elements in minerals. Items 3 and 4 might best be summarized by saying that bonding of the minerals in the series appears to be from ionic to covalent to metallic, the early minerals being light in weight, hard, and near-transparent; the intermediate minerals of intermediate weight, semi-transparent, and semi-conducting; and the end minerals heavy, soft, and malleable, opaque and good conductors. A rapid fall in temperature has been assumed to be the cause of ore deposition in many deposits. Perhaps this in turn is the effect of a rapid release of energy in the form of pressure release and change of volume, the first minerals to form being those with the highest heats of formation which absorb the released energy the most rapidly. Butler's Table II could probably be streamlined and made more effective if the listed compounds were assembled as mineralogical groups as in Dana. Thus the sulfides, arsenides, antimonides, bismuthides, and sulfa salts could be arranged in AX,, AX, A2X2, etc. groups. Since these are continuous substitution series, in which the fields of stability and the heats of formation of the various individual minerals can be fairly regarded as similar, this should be accomplished with no loss of clarity. The occurrence of the individual minerals and the precise sequence of the mineral deposition in any one deposit is probably more dependent on the concentration and relative abundance of the component elements. The assembling of geological data in tabular form such as Butler's Table II will continue to be a very effective method of studying geological phenomena. The importance of this particular problem has been pointed out by C. F. Park,% who concludes that understanding of mechanisms of the standard paragenesis and interrelated problems of mineral zoning in space and time is one of the major keys to classification of ore deposits.

Jan 1, 1959

By S. Shapiro, G. Krauss

RECENT investigations1 3 of the products of marten-sitic transformation in Fe-Ni and Fe-Ni-C alloys have made use of light microscopy to describe mar-tensitic fine structure. The application of conventional metallographic techniques to this problem was possible because of the similarity of distributions of parallel striations developed by etching polished surfaces to distributions of transformation twins which are positively identified in thin films by transmission electron microscopy. The surface striations frequently are not well-defined, and could also be due to, for example, rows of etch pits which are not resolved by the light microscope. This note describes the etching effects revealed by examination of surface replicas of mar-tensite in the electron microscope. The application of a replica technique both extends the observations of fine structure made with the light microscope and allows the results of conventional metallography to be used with more confidence. Samples of an Fe-33 wt pct Ni alloy were used for this study because of the detailed knowledge of the fine structure of martensite which has been developed'-4 for alloys of about this composition. Samples transformed to martensite at -120°C, and transformed samples heated to 340°C to effect a small amount of reversal of martensite to austenite, were examined. Surfaces were first prepared for replication by elec-tropolishing in a chromium oxide-acetic acid electrolyte at a current density of 0.1 amp per sq cm and a temperature of 15°C or a perchloric acid-acetic acid electrolyte at a current density of approximately 2 amps per sq cm and a temperature of 15°C. The polished surfaces were then etched for 4 to 7 sec by immersion in a solution of equal parts HC1, HNO,, and H20. Application of the etchant for this period of time produced discrete attack of certain features without loss of resolution due to overlapping of areas most susceptible to etching. The etched surfaces were replicated by 1) preshadowing with Pt-Pd alloy at an angle of 20 to 30 deg, 2) depositing a thin carbon film, and 3) stripping the film and shadowing material by immersion in a 5 pct nital solution. Two types of etching effects were observed by examination of the surface replicas in the electron microscope: l) continuous striations centered at the bottom of long grooves or the tops of pyramidal elevations on the sample surface, and 2) high densities of fine etch pits. Examples of both types of features are shown in Figs. 1 to 4. The striations are in each case continuous and have the same characteristic configurations as do transformation twins in martensite. Fig. 1 shows that the density of grooves decreases toward the edge of a martensite plate and Fig. 2 shows a region where the striations are of varying length. Similar examples of transformation twin arrangements determined by transmission electron microscopy of thinned foils of martensite have been shown in the literature,'~ and, based on these similarities, the striations and their associated grooves or mounds are considered to be evidence for the presence of transformation twins. The transf~rmation twins in martensite are on the order of l00 A thick, much too fine for resolution by the light microscope. It appears that orientation-dependent etching of the matrix martensite about the twins results in grooves or surface elevations which

Jan 1, 1967

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

West Virginia University, Engineering Experiment Station, Morgantown, W Va C E Lawall, Director. For copies of Bulletins or other information address the Director Two classes of the Bulletins published by the Engineering Experiment Station are of particular interest in this directory- Research Bulletins, and Extension Bulletins, or bulletins published for use in extension work They are. Research Bulletin 1, The conservation of natural gas in West Virginia (1918), 2, Acceleration stresses in hoisting ropes (1927), 3, Classification of gas wells for operation (1927), 4, Mining methods in West Virginia (1929), 5, The whiteware industry of West Virginia, Extension Bulletin 1, Electricity in mines, series

Jan 1, 1933

By R. Schuhmann

PROBLEMS in expressing, interpreting, and using size-distribution data recur in many phases of mineral dressing; therefore it is desirable that size analyses be expressed in such a form, either numerically or graphically, that comparisons can be made readily. The size distribution of comminuted material is a result of a specific physical operation on the material and therefore should be governed by some definite physical principle, or cause-effect relation. Although this principle has not been discovered, it has been found that the size distribution of comminuted, homogeneous solids may be expressed by relatively simple mathematical equations. Two equations in particular, proposed by Gaudin1 and by Rosin and Rammler,2 respectively, have stood out, both having wide demonstrated ranges of application. The form and the method of application of the two appear almost irreconcilably different on the surface, but, as will be shown, they are asymptotic in the fine sizes when expressed in the same units. This paper gives the results of a further study of the Gaudin and Rosin-Rammler relations, made with the object of developing a form of size-distribution equation that will be more usable and more significant-particularly in comminution studies, both for interpreting the nature of size distribution and for evaluating surface. The work is summarized in the following: I. An equation relating cumulative per cent finer to particle size in the fine sizes is derived from Gaudin&apos;s original equation. That equation relates weight per cent retained on one size and through the next larger size in a geometric series of sizes to size (of the retaining screen, for example). 2. Comparisons with Gaudin&apos;s equation and with the Rosin-Rammler equation show that the cumulative equation applies to the fine sizes of all size distributions that fit either of these earlier relations, and, furthermore, has some advantages over each. 3. A simple graphical method of surface calculation based on the cumulative-equation plot is evolved and illustrated. 4. Additional confirmation of the cumulative equation was obtained in the more severe test of sizing down to the limit of a sedimentation balance a sample of jaw-crushed quartz. The equation was closely followed over a 20o-fold range in size, from approximately 0.4 mm. (35 mesh) down to 0.0023 mm. (2.3 microns), the lower limit of the size analysis made. There is no indication that the equation will not hold further to well below 2.3 microns. 5. Calculations of the surface produced in the jaw-crushing test mentioned above showed that at least 8o per cent of the total new surface was on particles finer than 35 mesh (about ½ 5 of the crusher setting). The minus 35-mesh portion was only

Jan 1, 1940

By Leonard R. Weisberg

HE procedure of directional freezing by the Bridgman technique1 is frequently used in crystal preparation. On those occasions where the crystal is regrown, it can be advantageous to Crop part of the ingot before regrowth to achieve purification. This note describes some simple, yet interesting, observations concerning the effects of cropping an ingot between successive freezes. First, it is not effective to Crop the front end of an ingot, whether or not the distribution coefficient, k , of the impurities is greater or less than unity. This can be shown as follows. The concentration C, of an impurity in a directionally frozen ingot of length d with a uniform cross section is given by where x is the distance along the ingot, and C0 is the initial concentration per unit length. It is assumed in deriving this equation that diffusion is negligible in the solid, is complete in the melt, and that k is constant. Consider that a section of the ingot Ad is removed from the front end. Then the average impurity concentration in the remaining (d- Ad) section of the ingot can be shown by integration to be given by When the ingot is remelted and refrozen, the new impurity distribution is given by where xl is the distance along the refrozen ingot. Substituting the value of c into Eq. [3], one finds This is identical to Eq. [11 when x = (x, Ad), which represents the original impurity distribution in the (d - Ad) section of the ingot after the first directional freeze. Therefore, the cropping and re-freezing accomplished nothing. This can also be seen physically by realizing that the average impurity content in the melt after the first Ad section is frozen, is identical to that after the resulting ingot has been cropped and remelted. Hence, it is assumed in the following sections that only the tail end of the ingot is cropped. However, it must be realized that for impurities with k greater than one, the pieces cropped from the tail end are purer, and are therefore saved. After cropping an amount Ad from the tail end of an ingot, the average impurity concentration of impurities in the remaining portion of the ingot is given by wheref= d/d. For the case of k < 1, the purification is defined as c,/c. It is obvious from Eq. [5] that the purification increases asf increases, but the increase in purification is not large. For example, iff is doubled from 0.1 to 0.2, the purification increases by only 10 pct for k = 0.5, by only 24 pct for k = 0.1, and by 32 pct for k =0.01. Much smaller values off than 0.1 are not desirable since insufficient purification is achieved. These figures indicate that much larger values off do not lead to substantial improvement, especially considering that much of the original ingot is lost. Therefore, it is generally useful to Crop about 1/10 of the ingot to achieve purification. As compared to doubling the value off, it is much more helpful to remelt, refreeze, and crop the ingot twice. Using Eq. [51 reiteratively, and assuming f= 0.1, it is found that the purification after this process is found to be increased over the purification after a single freeze and cropping by 33 pct for k= 0.5, 450 pct for k = 0.1, and 4100 pct for k = 0.01. This indicates that considerable purification can be obtained by this procedure. However, if purification is the main goal, one should resort to zone refining,3

Jan 1, 1962

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony&apos; states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By Edward H. Robie

OF the current Adirondack iron mine development, the Benson Mines operation of the Tones and Laughlin Ore Co. (Jones & Laughlin Steel Corp. wholly owned subsidiary) is the last to go into operation. Following an active construction program in 1943, the mine. concentrator and sintering plant were scheduled to enter production in the fall. This description therefore cannot include any operating data, and details of equipment and flowsheet have not as yet been released.

Jan 1, 1943

By L. Ekstrom, J. P. Dismukes

The homogeneity and microstrcture of zone-leveled Ge-Si alloys haw been investigated by sellera1 physical techniques and by metallography as a function of growth rate in the range 3 x 10 1x10 cm-sec&apos;, and as a system of alloy composition throughout the system. The temperature gradient at the solid-liquid interface was about 50 deg-cm-&apos; Cellular or dendritic structures char-acteristic of constitutional supercooling were ob-served except at very slow growth rates, which ranged from about 2 x 10 cm -sec for Ge 1 sio alloy to about 2 X 10&apos;5 cm-sec&apos;1 for Ge .sSio.s alloy. Using a simple model similiar to that employed for dilute solid the dependence upon compo-sition over the entire system of the critical growth rate for the onset of constiutional supercooling was calculated, and was .found to he in good agreement with the experimental results. THE recent discovery of the low thermal conductivity of Ge-Si alloys&apos; at high temperatures has revealed that these alloys have high efficiencies for thermoelectric-power generation.&apos;, Therefore, a reliable method was needed for the preparation of homogeneous samples required for definitive measurements throughout this alloy system. Due to the low diffusion rates in the solid alloys, the segregated samples obtained by quenching a melt are not readily homogenized by annealing.475 However. isothermal solidification from a melt of constant composition can produce uniform material. Of the available semiconductor crystal-growth procedures, the zone-leveling technique6 applied to a complete solid-solution alloy system by Wang and Alexander&apos; and by others provides a simple method of doing this. In the present work, the homogeneity and microstructure of zone-leveled alloys have been correlated with growth conditions, and the conditions for preparing homogeneous Ge-Si alloys have been established. This has provided insight into the solidification process of alloy semiconductors. EXPERIMENTAL PROCEDURE Sample Preparation. The Ge-Si alloy phase diagram4 shown in Fig. l(a) consists of a complete series of solid solutions. The zone-leveling technique used to prepare most of the samples consists of moving a zone of liquidus composition (C1) through charge material of the corresponding solidus composition (C,), as is illustrated in Figs. l(b) and l(c). To prepare the charge materials, high-purity germanium and silicon were pulverized in a steel hammer mill, cleaned magnetically, and melted together to make uniform chill castings. The zone leveling was carried out in a resistance-heated furnace similar to that of Mitrenin et al.&apos; shown in Fig. 2. However, a few specimens of high silicon content were prepared by the Czochralski technique. The growth rate ranged from 3.5 x X6 to 1.2 X 10~3 cm-sec-&apos;. Temperature gradients in the solid and in the melt were determined by recording the temperature as the molten zone passed over a Pt-Pt 13 pct Rh thermocouple contained in a small

Jan 1, 1965

By H. I. Aaronson

Isothermally formed plates of proeutectoid a, lengthen at approximately the rates predicted by the Zener-Hillert equation, indicating that their lengthening kinetics are controlled by the volume diffusion of chromium in the ß matrix. Solution annealing treatments in the vicinity of the transus introduce a second mode of transformation, in which the lengthening rate is at least 1.8 x 104 faster than predicted by this equation. Little or no volume diffusion appears to accompany the latter transformation. The Presence of oxygen is evidently a Prerequisite for the occurrence of this reaction. X HE effects of thermal history prior to the initiation of transformations which proceed by nucleation and diffusional growth are currently evoking considerable interest. The rate of nucleation (but not the rates of growth) of pearlitel and of bainite,2 and the over-all rates of aging reactions in Al-cu3 and Al-si4 alloys have been shown to be appreciably dependent upon thermal history in the solid-solution region"&apos; or in the two-phase region prior to the onset of pre~ipitation.3,4 In none of these reactions, however, was the transformation mechanism changed by variations in the temperature-time path used to reach the reaction temperature. Preliminary experiments reported by M. K. McQuillan5,8 and a systematic investigation by Farrar and Margolin7 have disclosed that the transformation behavior of hypoeutectoid Ti-Cr alloys is considerably more sensitive to thermal history. Qualitative evidence strongly suggests that not only the rate of nucleation but also the rate of growth and even the mechanism of the ß — a reaction can undergo remarkable changes when a solution annealing treatment in the vicinity of the ß/a +ß, or transus temperature, is interposed between a high-temperature solution anneal (conventionallq at 1000°C) and the isothermal reaction treatment. The present investigation was undertaken in an attempt to ascertain the nature and origin of these effects. Study of the changes in the kinetics and morphology of the ß - a, reaction produced by varialtions in thermal history was the primary means employed for this purpose. EXPERIMENTAL PROCEDURE The compositions of the alloys used in this in~esti~ation are given in Table I. These alloys were homogenized for 5 days at 1050° C in evacuated (2 x 10 -5 mm of Hg), zirconium-gettered fused quartz capsules. The capsules themselves were enclosed in a porcelain chamber evacuated with a mechanical pump during the homogenization anneals. Upon completion of homogenization, the alloys were cooled to room temperature and then reheated to 550°C for 3 1/2 days in order to transform the alloys to a finely divided mixture of a and TiCr2, and thus provide an approximately constant initial mi-crostructure. Individual specimens were sealed in evacuated and internally gettered Vycor capsules and heat treated as previously described.8,9 EXPERIMENTAL RESULTS Ti-10.64 Pet Cr. This investigation was largely performed on the 0.64 pet Cr alloy. The "base"

Jan 1, 1962

By B. L. Averbach, M. Cohen, G. P. Conard

IT has been frequently observed that, when metal crystals are bent and annealed or when they are bent at elevated temperatures, the asterism of the Laue spots is split discontinuously into tiny intensity maxima. This finding indicates that segmented crystallites or subgrains are produced, which are relatively undistorted within themselves but which differ slightly in orientation from their neighbors. The following viewpoints have been put forward concerning the nature of this segmentation process: 1—Crussard&apos; has described the phenomenon as "re-crystallization in situ." According to this mechanism, the deformed lattice recrystallizes on heating into an aggregate of comparatively strain-free subgrains separated from one another by low-angle boundaries and having nearly the same orientation as the original crystal. This process differs from the classical type of recrystallization in that the latter involves the formation of grains having quite different orientations from that of the mother crystal. 2—A similar but more detailed picture has been advanced by Cahn&apos; who adopted the term "polygonization." In this interpretation, the plastic bending of lattice planes results in an excess of dislocations of one sign, but at suitable temperatures these dislocations migrate along slip planes and collect in localized regions to form an array of low-angle boundaries. Concurrently, the lattice segments between the boundaries lose their curvature and elastic strain. 3—The "cell formation" concept of Wood and co-workers: unlike the two hypotheses cited, postulates that the segmentation of the lattice is basically a mode of deformation and is not an annealing phenomenon. Cell formation appears to compete more effectively with respect to the normal slip process as the deformation temperature is increased and as the strain rate is decreased. The present work was performed on 3.2 mm diameter 99.99&apos; pct Zn single crystals, grown from the melt in a gradient furnace. The major impurity was 0.003 pct Fe. The crystal orientations ranged from those with basal plane parallel to the rod axis to those with the basal plane almost perpendicular to the rod axis. The specimens were bent on templates to effective radii varying from 14.2 to 1.3 cm at the temperatures from —196" to 100°C. In each case, the axis of bending was parallel to the basal plane. Subsequent annealing was carried out at temperatures from —196" to 400°C. Back-reflection Laue pictures were taken on the convex surface of the bent specimens, before and after annealing. This procedure was found to yield better resolution of the detail in the diffraction spots than did the previously used Laue transmission technique. Some X-ray pictures of rods bent at —196" and —78°C were taken at these respective temperatures without intermediate warming to room temperature. In addition, bent crystals were acid cut" parallel to the basal plane, and double-crystal spectrometer rocking-curves were obtained from the etched (0001) face before and after increment an-

Jan 1, 1954

By T. M. Morris, W. E. Horst

W. E. Horst—In regard to the flotation rate being described as "first orcler" for flotation of quartz particles below 65 p in size (or any size studied in this work) in this paper, it appears that the authors&apos; conception of rate equations is not in agreement with cited references. A first order rate equation has as one of its forms the following: a In.=a/a-x=kt where a = initial concentration, a—x = concentration at time t, t = time, and k = constant. The constant, k, has the dimension of reciprocal time which is similar to the specific flotation rate, Q. described by Eq. 2 in the authors&apos; article, as has been previously discussed by Schumann (Ref. 1 of original article). The plotted data presented in Fig. 4 of the article utilizes the specific flotation rate, Q (min.&apos;); however, there is not adequate data given to indicate the order of the rate equation which describes the flotation behavior of the quartz system studied. Results from the experimental work indicate that the relationship between rate of flotation (grams per minute) and cell concentration (provided the percent solids in the flotation cell is less than 5.2 pct and the particle size is less than 65 p) is described by an equation of the first order (R, = k c+", n being equal to 1 in this size range) and the use of the first order rate equation does not apply. Similarly the relationship for other particle size ranges studied is expressed by equations of the second or third order depending on the magnitude of n. T. M. Morris—The authors are to be commended for the experiments which they performed. As they state in their discussion the concentration of collector ion In solution did change with change in concentration of solids in the flotation cell. Since for a given slze of particle, flotation rate increases with concentration of collector until a maximum is reached, the effect of concentration of particles in their experiments was to vary the concentration of collector ions. A collector concentration which insures maximum supporting angle for all particles eliminates the unequal effect of collector concentration on various sized particles and the effect of size of particles and concentration of particles upon flotation rate could be more clearly assessed. I believe that if the authors had increased the concentration of collector to an amount sufficient to attain a maximum supporting angle for all particles they would find that the specific flotation rate of particles coarser than 65 p would be constant with change in the concentration of solids in the flotation cell, and that a first order rate would apply to the + 65 as well as to the —65 p sizes. It might also be discovered when this change in collector concentration was made that the maximum specific rate constant would be shifted toward a coarser fraction than when starvation quantities of collector are used since this practice favors the fine particles and penalizes the coarse particles. P. L. de Bruyn and H. J. Modi (authors&apos; reply)—The authors wish to thank Professor Morris for his kind remarks and for mentioning the influence of equilibrium collector concentration on flotation rate. With a collector concentration sufficient to insure maximum supporting angle for all particles, a first order rate equation may indeed be found to be generally applicable irrespective of size. Such a concentration would, however, lead to 100 pct recovery of the fine particles and consequently defeat the essential objective of the investigation to derive the maximum information on flotation kinetics. To establish absolutely the validity of any single rate equation for a given size range, the ideal method would be to work with a feed consisting solely of particles of that size range. Use of such a closely sized feed would also eliminate the possibility of the interfering effect of different sizes upon one another. The authors do not believe that increasing the collector concentration would shift the maximum specific flotation rate (Q) towards a coarser fraction. Experimentation showed Q to be independent of solids concentration for all particles up to 65 µ in size, whereas the maximum value of Q was obtained in the range 37 to 10 p. Professor Morris contends that the addition of starvation quantities of collector favors fine particles at the expense of coarse particles, but the reason for this is not entirely clear to the authors. The comments by Mr. W. E. Horst are concerned only with the concept of the term "first order rate equation." According to the usage of this term in chemical kinetics, time is an important variable, as is shown in the equation quoted by Mr. Horst. All the experimental results reported by the authors were obtained under steady state continuous operations when the rate of flotation is independent of time. To be consistent with the common usage of the "first order rate equation," it would be more satisfactory to state that under certain conditions the experimental results show that the relation between flotation rate and pulp density is an equation of the first order.

Jan 1, 1957

By C. A. Siebert, S. H. Bush

Isothermal temper-embrittlement studies were conducted on a 5140 steel at various temperatures for times as long as 3000 hr. Specimens from the embrittled steel were subjected to impact tests, metallographic examination, microhardness, and lattice-parameter measurements. SEVERAL of the steels in the low alloy group are subject to a pronounced decrease in impact energy if held within, or cooled slowly through, a range of temperatures below the lower critical. This phenomenon, known as temper embrittlement, is quite pronounced in the chromium steels of which AISI 5140 is typical. This study considered the response of one heat of 5140 steel when embrittled isothermally at various temperatures for times as long as 3000 hr. Excellent reviews of the work done in the field of temper embrittlement have been written by Hollomonl and Woodfine.&apos; Both authors list the various theories which have been advanced to explain temper embrittlement. Some of the mechanisms considered were: 1—a transformation below 700°C; 2—an allotropic modification of iron; 3—precipitation from the ferrite of such compounds as carbides, nitrides, phosphides, or chromium oxides; 4—decomposition of retained austenite; 5—modification of special carbides; 6—grain-boundary segregation; and 7—selective distribution of carbides. The present study investigated the changes in hardness, Meyer&apos;s number, impact properties, micro-structure, and lattice parameter which occurred on embrittlement. Previous studies considered the influence of microstructure and of prior austenitic grain size3 on the response of 5140 steel to temper embrittlement. Equipment and Procedure All samples were taken from one heat of 5140 steel; the chemical composition of this steel was: 0.43 pct C, 0.86 pct Mn, 0.020 pct P, 0.019 pct S, 0.27 pct Si, 0.84 pct Cr, 0.10 pct Ni, 0.06 pct Mo, 0.10 pct Cu, and the remainder Fe. The material was received as % in. rounds. This stock was cut down to blanks measuring approximately 0.425~0.425~2.196 in. Heat Treatment: The rough blanks were normalized at 1600°F (870°C) for 1 hr, then austenitized at 1600°F (870°C) for 1 1/2 hr, and quenched into an agitated oil bath. The specimens were tempered at 1275°F (690°C) for 5 hr and water quenched. These tempered specimens were designated as the toughened state. Embrittling Treatments: The tempered bars were divided into sets and subjected to the various embrittling treatments listed in Table I. Temperatures from 750" to 1050°F were investigated for times of 1 to 3000 hr. Special tests to determine the effect of heating a short time at a higher temperature after long-time embrittlement at some lower temperature were also conducted. All specimens were water quenched at the end of the embrittling cycle, then ground and notched to obtain standard Charpy V-notch specimens. Impact Tests: The bars were fractured in a 260 ft-lb Charpy impact unit; specimens were fractured at temperatures ranging from —315°F to room temperature. Fixed temperatures used consisted of —315°F with liquid nitrogen, —115°F with dry ice and acetone, and 32°F with ice and water. Intermediate temperatures were obtained by suspending the bars in a jig over the liquid nitrogen, dry ice and acetone, or ice and water.

Jan 1, 1955

By D. W. Fuerstenau

Recently R. J. Charles1 showed that comminution of brittle or semi-brittle materials in batch operations is described more appropriately by a variable energy relationship than by the specific relationships proposed by Rittinger,2 Kick,3 and Bond.&apos; That is, the value of n in the empirical differential operation which applies to crushing and grinding (Eq. 1) is variable. Independently, Holmes&apos; developed an identical generalized equaton for size reduction. The experimental data of Charles and Holmes show that the value of n is determined by the material and the comminuting machine and is constant for a given combination of these two conditions. The general objective of the present article is to extend the Charles-Holmes concepts to continuous ball milling. The specific objective is to analyze the operation of a vibratory ball mill dry-grinding chromite in a continuous open circuit and to develop an equation for the comminution of chromite in this mill. Basic Principles: In a batch mill the length of time during which the material is ground is a direct measure of the energy expended on the material, except possibly for exceedingly fine grinding. However, in a continuous operation, the fraction of the total expended energy which is useful for grinding will vary according to feed rate and amount of material in the mill. If the amount of material within a continuously operating vibratory mill is low enough so that only part of the expended energy is used for grinding, the extent of size reduction at constant power input must depend upon the length of time the material is retained within the mill, namely, upon retention time. The following analysis pertains to a continuous mill operating under these conditions. The empirical differential equation that applies to the comminution of brittle materials is:" dE = -Cdx/x" [1] where dE is an infinitesimal energy expenditure, C a constant, dx an infinitesimal size change, x the particle size, and n a constant. For continuous grinding in an open circuit at constant power input, P, Eq. 1 must be written as (dtr)P = -C dx/x" [la] where dt, is an infinitesimal time during which a particle of size x is in the mill, and C&apos; is a constant. A ground product never consists of particles of single size but always comprises a distribution of sizes. In comminution, the expenditure of energy causes a lateral shift in the size distribution.&apos;, &apos; " The general objective of any engineering study of comminution is to correlate the magnitude of this size distribution shift with the energy expended, the ultimate aim being to cause the greatest shift with the least amount of expended energy. Although a number of criteria can be used to measure this shift, Schuhmann&apos;s size modulus has been found convenient.&apos; Mathematically, the Schuhmann size distribution can be expressed as follows:" y = l00(x/k) [2] or in differential form: dy = [F- xa-&apos; dx ] K, where y is percentage of material finer than size x, a is a constant that determines weight distribution among particles of various sizes, and k the size modulus that denotes the theoretically maximum-sized particle in any size distribution. By considering the energy required to reduce an element of weight of material, dy, from size x, to size x, the element of time during which the material must remain in the mill at at power will be (dt..).= J&apos;-Cax!(dy) [3] Summing up all the elements of weight from zero to 100 for a product that conforms to the Schuhmann size distribution yields C C f Cdx,\( 100«x°-&apos;dx\

Jan 1, 1960

By John Tabor, R. B. Spivey

INTRODUCTION Shafts have been sunk in a number of ways. By and large, however, most have been sunk by drill, blast, muck, and slip form methods. Most methods have provided satisfactory means of completion. The major drawbacks to the conventional methods have been: (1) un- reliable cost estimates for completion; (2) unreliable rates of progress; and (3) unreliable integrity of the shaft lining. Recently , engineering design studies have been done that strongly indicate, that, by the use of existing proven technology, shafts can be completed faster, more cheaply, safer, and with a better lining that has been possible using conventional methods. THE METHOD The alternate method utilizes the techniques of big hole drilling, shield excavator tunnelling, and pre-cast concrete lining. Big Hole Drilling - Drilled shafts have been completed for several years and I don&apos;t intend to address the technology, only to point out the use of drilled shafts is an alternate method of shaft sinking. Ideally, in a multi-shaft mine, the first shaft would be blind bored and cased to a size, whereby it can handle the muck from the excavation of subsequent shafts. It should be an 8&apos; to 10&apos; completed diameter. The cost of such a shaft in sedimentary formations compares favorably with a conventional shaft. However, it is much faster. For additional shafts, the role of the drill is to complete small holes (3&apos; to 4&apos;) to the desired horizon. This is merely a hole to allow slashing to a larger size with easier muck removal from an underground drift connected to the previously drilled shaft. The smaller holes, just as the larger one, should be cased and grouted into place so as to assure a smooth open hole. SHIELD EXCAVATOR Theory and History - Tunnelling Shields have been in common use for several decades, and steam powered shields were used in England over 100 years ago. The purpose of the shield is to provide temporary ground support, protect personnel during operation, and to house the excavating equipment. The excavating equipment approach has varied from attempts at a continuous or semi-continuous boring machine, the tunnel mole, to a mechanical or hydraulic digging arm. The shield may or may not be an active digging element. If not active, the boring tool or cutter is advanced ahead of the shield to full diameter and then the shield is moved up to the cutter, or the shield advances along with the cutter. If active, the cutter opens a conical free face, and the shield is either jacked forward so that the leading edge spalls rock to the free face or poling plates are thrust forward to spall to the free face. In either approach, various methods of muck removal are incorporated into the shield. These may be gathering arms, conveyors, or with moles, hydraulic transport, where the cuttings are sufficiently fine. The efficiency of the muck removal system is critical as excavation is rapid and the system could easily become muck-bound. Application to Shaft Sinking- Technically, the use of a shield to sink vertical shafts is no different than a tunnelling operation. It is, in fact, less complex in most respects. Muck and water removal are difficult in a blind-driven shaft. However, where an underground opening is available for handling muck and water, rapid shield sinking is possible, using a pilot hole for muck and water to fall through and be removed from below. The Tabor Mining Shield is basically a caisson approach, whereby, the ground is only seen at the face or bottom. It does have hydraulic jacks to force it downward and has segmented cutting edges which allows forepoling ahead of the shield. The hydraulic excavator allows mining in the center of the face around the previously drilled hole with the forepoling segments slabbing to this free face. First, the drilled hole is cased and grouted. The machine is a tube with an excavator. The work cycle is as follows: (1) The casing and grout are cut at predetermined intervals by shaped charges. (2) The casing is crushed by the excavator, removed from the hole and hoisted to the surface. (3) The excavator then rips out a face around the hole by digging the formation in tension and breaking the pieces

Jan 1, 1982

By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy&apos;s law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,&apos; Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962

By Leah L. Naugle, H. G. Landau, H. H. Lowry

EVIDENCE has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its "Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,1-12 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends-including coals numbered I to 55b, inclusive -which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or I8-in. cylindrical retorts." In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash; from 2.1 to 15.9 per cent, in moisture from o.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the go coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1941