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R. H. Sweetser, Sault Ste. Marie, Ont. (communication to the Secretary*):—The recent work of furnace No. 1 of The Algoma Steel .Co., at Sault Ste. Marie, Ontario, using for fuel, first all charcoal, then a mixture of charcoal and coke, and finally all coke, upsets the estimates given by Mr. Hall in the last two paragraphs of his interesting paper. Furnace No. 1 was built for a charcoal-furnace, and it was run on charcoal fuel from March 6 until July 9, 1905; then, for a week, a mixture of charcoal and coke was used, and, since then, coke alone has been the only fuel. It is to be regretted that at no time, during the run on charcoal, was there enough charcoal on hand and " in sight" to warrant blowing the furnace as hard as it should have been blown. During April and May the supply of charcoal limited the amount of blast to about 8,000 cu. ft. of air per min.; in June, to about 8,900 cubic feet. For a few days in July about 10,000 cu. ft. were blown, and then the maximum daily output, 173 tons (2,240 lb.), was reached. At all times the quality of the charcoal was poor, having been made from wood cut from three to four years before. Doubtless this furnace could have produced 200 tons of iron per day, even with this quality of charcoal, provided the supply had been sufficient; and with

Jan 1, 1906

By F. N. Pease, C. B. Dudley

Those who have worked a good deal on the chemistry of pig-irons of which the physical properties were known, cannot fail to have been struck by the remarkable want of relation between the physical properties of different samples, and the ultimate chemical composition. It is very well known among foundrymen that irons which will give say 4 inch of chill, and are, therefore, approximately the same in chemical composition, are very far apart, many times, in their physical properties. The foundryman's tests for strength are, of

Jan 1, 1886

ALL that I have been able to tell you concerning the ordinary practice of parting with aqua fords I have striven to demonstrate to you as briefly as possible. Now, before passing on to speak of other things, I wish to teach you the method that you must follow in order to recover whatever is good in those chalky precipitates of that acid and all the silver that you put in; it was for this reason that I told you to save them in a cucurbit by themselves. This is called "water of whites" by the master parters, and in reality is nothing other than the precipitates of thick phlegm of aqua fords, white as chalk. If these were not extracted from the acid, the spirits of the infused materials [69] would be almost without

Jan 1, 1942

By M. H. De Hora

(Butte Meeting, August, 1913.) IN giving my opinion of the importance of Colombia as a field for investment for those interested in mining for the precious metals, I must begin by quoting Sir Clement Markham, who, in one of his presidential addresses to the Royal Geographical Society of Great Britain, called the attention of its members to the fact that " although Colombia is the least known and least developed of the South American republics, it is far and away the richest mineral country of then all." This to American investors is extremely interesting, as the country is the most accessible of all the South American republics from the United States. Almost all of the gold shipped by the Spaniards from Madre de Dios, now Colon, came from Colombia, and statistics from the Mint at Medellin, the capital of the Department of Antioquia, go to show that the total production of the precious metals of Colombia, dating from the Spanish conquest in 'the fifteenth century to the present time, aggregates the enormous total of $700,000,000. Of this amount, nearly 70 per cent. represents gold obtained from the placers of the Republic, more than one-half of which came from the Department of Antioquia, the balance being divided between the placers of the Choco and the rest of the Republic. The remaining 30 per cent. of the $700,000,000 represents the silver and gold obtained from the quartz mines, the silver greatly predominating.

Jan 7, 1913

By Carl Altstetter, Roy Adams

Measurements of enthalpy changes and transformation temperatures me reported for the fcc -hcp marten-sitic transformation in pure cobalt single and multi-variant crystals andpolycrystalline specimens. From these measurements the free-energy difference between the two phases was calculated for both heating and cooling and for repeated cycles through the transformation. For heating of single crystals the average value of enthalpy change was 113 cal per mole but on cooling it was 84 cal per mole. This difference is interpreted in terms of lattice imperfections which are introduced during transformation. A calorimeter suitable for measurement of enthalpy changes of athertnal transformations is described. COBALT exhibits an allotropic phase transformation at around 417°C' where an hcp phase (a = 2.507, c = 4.0686, c/a = 1.6228)~ stable at low temperatures transforms to an fcc phase stable up to 1495°C. The transformation has a hysteresis of about 30°C— the exact magnitude of the hysteresis depending on the number of transformation cycles, grain size, impurity content, and prior treatment.'-6 The athermal character of the transformation and surface relief due to transformation shear indicate that the transformation is martensitic. Pole mechanisms for the transformation have been discussed by Sebilleau and Bibrin, Bilby, Seeger,' and Basinski and Christian. These authors have proposed that the cooling transformation is effected by rotation of a Shockley partial dislocation around a pole dislocation with a screw component of 2a/3(111). Such a rotation would change the stacking of close-packed planes from the abcabc fcc stacking to the ababab hcp stacking sequence. This mechanism would predict a lattice correspondence of {111}fcc~~(0002~cp, have been observed. One would expect the heating transformation to occur similarly, involving dislocation movements on the (0002)hcp. However, a high density of pole dislocations and high dislocation ve- locity are required to account for microscopic observations. Furthermore, the high back stress developed on the Shockley partial dislocation as it rotates toward the sessile dislocation associated with it makes it doubtful that this is in fact the transformation mechanism. A mechanism for spontaneous nucleation of partial dislocations1*l2 seems more reasonable. If a single crystal of cobalt is cycled through the transformation but never heated above 600°C, it will remain single."13 However, if the specimen is heated through the transformation and held for a short time at or above 1000°C before cooling, the cooling transformation usually involves all four {lll}fcc habits, resulting in neighboring orientations of hcp differing by 70.5 deg. This condition is termed multivariance and has been observed by Bibring and sebilleau5 and Nelson and ~ltstetter.' The latter authors used single crystals of cobalt grown in an electron beam zone refiner. They proposed that the strongly directional cooling caused the initial cooling transformation to occur on the {lll)fcc most nearly perpendicular to the temperature gradient. Transformation shear on one set of {lll}fcc planes immobilized dislocations on the other {lll}fcc planes involved in the initial transformation. Since there is only one (0002)hcp plane orientation, the product of subsequent heating transformations could have no more than two variants—the original fcc orientation or its twin. If, however, the specimen was annealed at a high temperature, such as 1000°C, there would be relaxation of dislocations into low-energy configurations, and in the absence of a sharp temperature gradient transformation on all four (111 Ifcc planes could occur. If a dislocation mechanism is responsible for the transformation, the perfection of the lattice should affect the reversibility of the transformation. Mutual constraints of neighboring grains in polycrystalline material would inhibit dislocation movement resulting in increasingly sluggish transformation. Indeed, Nelson and Altstetter found the M, to decrease and the A, to increase in going from single crystals to multi-variant specimens to polycrystals. The effect is enhanced by decreasing the grain size of a solid specimen or a powder.6'14 Data on the free-energy difference necessary to initiate the transformation gives information about the driving force of the transformation. This is an important consideration in the understanding of the transformation mechanism. The free-energy change associated with the transformation of the hcp phase to the fcc phase at some temperature T different from the equi-

Jan 1, 1969

By H. Sigurdson, T. V. Cherian, C. H. Moore

The phenomenon of recovery of cold-worked metals is interesting not only because of its practical importance but also because of its fundamental significance in solid state reactions. Although extensive investigations1,2 have already been made in an attempt to discover the mechanics of the recovery process, many of the observations have not yet been satisfactorily correlated to provide a completely consistent model for the process. The wide differences in the recovery rates of various properties can be cited as a typical example of one of the difficulties that are encountered. Frequently, for example, the electrical resistance will have almost completely recovered before any recovery in tensile strength can be detected. Of course, such differences in the recovery rates of different properties might be explained by assuming that each property is a unique function of the work-hardened state, and consequently each property exhibits its own unique recovery rate. The assumption that different properties are uniquely related to the work-hardened state cannot be denied. On the other hand, the properties that recover at different rates often exhibit more or less parallel changes upon work-hardening. This suggests that the microstructural changes attending recovery are not exactly the reverse of the changes attending work-hardening. Several types of imperfections must be postulated in order to account for this apparent anomaly. The different recovery rates for various properties, then, are due to the different recovery rales of the type of imperfection to which each property is most sensitive as well as the unique dependence of each property on the cold- worked state. This concept assumes that a simple model of the work-hardened state consisting only of one type of imperfection, such as Taylor's type of dislocation patterns, is inadequate to cope with the diversified phenomena attending work-hardening and recovery. Although current models for the work-hardened state are not useful for describing all aspects of the recovery process, the general trends of the recovery of each postulated type of imperfection as a function of time and temperature should be at least qualitatively deducible from the rather well developed laws of kinetics of reactions in the solid state. Consequently, recovery data might prove useful for elucidating some aspects of the complexities of the work-hardened state of metals. A preliminary attempt to study work-hardening by investigating recovery rates of cold-worked metals is outlined in the following pages of this report. Experimental Procedure Many properties recover when cold-worked metals are annealed below their recrystallization temperature. Therefore, electrical resistivity, thermal electromotive force, X ray diffraction line widths, X ray diffraction line intensities, elastic spring back, density and other physical and chemical properties have been used to study the recovery process. Major interest, however, has generally been directed toward the recovery of the mechanical properties such as hardness, yield strength, and tensile strength. But a search of the literature suggests that the effect of recovery on the true stress-true strain curve has been neglected, in spite of the current recognition of the fundamental importance of such an investigation. An investigation on the effect of recovery treatment on the true stress-true strain curves in tension, therefore, was undertaken in the present study. Commercially pure aluminum (99. + pet Al) in the form of 0.100 in. thick rolled sheet of 2S-O aluminum alloy was selected as the material for this investigation because rather extensive correlatable data are already available on the recovery of some of its properties. Tensile specimens having a 6 in. long gauge section and a uniform reduced section width of 0.500 in. were machined from the sheet in accordance with a design that has previously been reported.3 All specimens were selected with their axes aligned in the rolling direction. In order to eliminate the effects of previous work-hardening and the effects of machining, the specimens were annealed for 15 min. at 750°F before testing. During tensile testing the loads were measured by means of a proving ring (sensitive to 1/2 lb) in series with the specimen.4 Strains were determined from the extension of a rack and pinion strain gauge sensitive to a strain of + 0.0001. The stress was recorded as the true stress, namely

Jan 1, 1950

By R. C. Thompson

The lead-zinc mill of Phelps Dodge Corporation, Copper Queen Branch, Mines Division, Bisbee, Arizona, is about 3 miles from the main hoisting shafts of the Junction and Campbell mines at Lowell. All the ore treated in the mill is obtained from these two mines. The mill was designed for an all-flotation treatment of 450 tons of lead-zinc ore per day, and has been operated at that capacity since the start of milling operations on Nov. 17, 1945. An expansion program is underway whereby the mill capacity will be doubled, but this article describes only the original program and presents results of the 450-ton operation. General Description The milling plant consists of an ore-receiving bin and three steel-constructed buildings housing, respectively, the primary crushing equipment, the secondary crushing equipment, and the ore-storage bins, grinding, flotation, and filtering equipment. The mill site is the one that was used for a previous copper-concentrating plant, which was operated over a period of years and then dismantled. There remained from this operation some milling equipment, a reservoir for mill-water supply, railroad tracks, tailings-disposal ponds, and a steel-constructed building, all of which were incorporated in the design of the present lead-zinc mill. The location plan of the plant layout is shown in Fig I. The flowsheet of the mill is based on the conventional scheme for lead-zinc treatment, however, several innovations were made necessary in order to utilize the existing building. Placing of equipment also was governed by the design of the building; thus making the mill unique in many respects. The following brief description of the mill building as adapted to the flowsheet points out the compactness of the installation and some of its unusual features. The first floor (Fig 2) houses the grinding equipment, with connecting conveyors for ore feeding, also an air compressor, two vacuum pumps, bins for lead and zinc concentrate storage with individual conveying systems for loading the two kinds of concentrates. Filtering of concentrates is done on the second floor, the concentrates discharging directly into the concentrate-storage bins. On this floor are the lead and zinc filters, two diaphragm pumps, sample-filtering equipment, sample-preparation room and a change room for the mill employees. The flotation machines are on the third floor, at elevations allowing a gravity flow of the lead and zinc concentrates to the thickeners. The annex to the building contains a freight elevator and provides space for all reagent mixing and feeding, also storage of reagents and grinding balls. All the water used for milling purposes is pumped from the Junction mine and

Jan 1, 1949

By George Smith

IN discussing present-day business and industrial troubles we easily drop into the habit of clinical diagnosis. Talk of this kind, with its emphasis on suspicious symptoms and abnormal tendencies, makes us all morbid. As an English essayist has put it, we may thus induce a melancholy, temper that simply in-vites the ministrations of social and political quacks. It is far better-because nearer the truth-for us to recognize that our condition is in no sense diseased, that our body politic, social and economic, is suffering merely from growing pains; that America is not de-cadent-indeed, that any lapses from staid normality are traceable to the, excesses of youth. Our chief .trouble, then, is only that our industrial state is still young; it may be that we have been growing too fast. The growth in the industrial development of our country from pioneer days to the present time has been marvelous. Too many of us, however, take all this as a matter of course-we credit this record of American progress to our American genius alone. Too often we overlook the fundamental relationship between resources and progress-that man is aided and even guided by Nature. The fact is, social advance, indus-trial progress, national prosperity all have their ma-terial basis in natural resources. In furnishing the needed mineral raw materials to the great manufac-turing industries of the United States there has been no halt, but rather a general acceleration. No other phase of American activity can show-equal advance. As the decades have passed, the winning of mineral wealth has progressed from the role of a stimulus for western exploration to that of the foundation for nation-wide business. In 1890 the Sherman law was passed; since then the population of the United States has about doubled. Since then, too, thevalue of the annual product of the mines of this country has increased better than eight-fold-from 650 millions to 51/ billions of dollars. Since then the four largest branches of the mineral industry, which supply the iron and copper, the bituminous coal and petroleum-the bone and sinew and the energy of all other American industries-have increased their annual output nearly ten-fold as to value and six-fold as to quantity. Such a growth in the volume of mineral output must be taken as a true measure of the ex-ceptional service rendered by the mines of the United States. Not only is this a much larger country than it was 38 years ago, but its growing mineral industry has met demands that have been out of all proportion to the growth of the population.

Jan 8, 1928

The fall meeting of the. Institute of Metals Division will be held in Philadelphia on Sept. 30 to Oct. 2. All meetings will be held in the Ritz-Carlton Hotel, Broad and Walnut Streets, which is also the hotel headquarters. As this meeting is being held in conjunction with the meeting of the American Foundrymen's Association, the members of the Institute will have the privileges of the exhibit of the Foundrymen's Association. This, it is expected, will be one of the largest exhibits made in this country. On Monday evening, Sept. 29, there will be a meeting, in the Ritz-Carlton Hotel, of former officers and members of the Executive Committee of the Institute. It is requested that all officers and Committee members, the present as well as the past, will arrange to be present.

Jan 8, 1919

By J. A. Bowers

THIS investigation of the effect of bottom shape and life on slag volume was carried out in two Lectromelt top-charge furnaces whose rated capacity is 1000 lb per hour. Unfortunately, just as the work [ ] was started, our steel tonnage was reduced approximately one half, therefore we did not accumulate enough data from which to draw any definite conclusions. Furthermore, the life of the linings in these furnaces was greatly decreased by intermittent operation, which was a further handicap in making a study of this kind. The weight of the heats from which the data were taken varied 1200 lb but all the information was corrected to the standard weight charge for these furnaces of 4500 lb. Almost all the heats were plain carbon; a few contained a small percentage of added copper.

Jan 1, 1947

JOHN W. BELL (communication to the Secretary*).-I have to thank Mr. Merrill not only for his very kind remarks, but for the weight of his implied opinion that the work accomplished probably has an important practical aspect. I think there is a distinct although unuttered impression among engineers, that it will be time enough for them to begin to take an interest in the law of crushing when it emerges from the cloud of violent and even vituperative controversy that has hovered over it during the last 6 or 7 years. I have a very confident feeling that as the result of the work done by Mr. Gates, by me and by Messrs. Mitchell, Baily and Cockfield, who so loyally helped me to obtain the necessary data, at least the practical law of crushing has emerged; that it is ready and available for use by our fellow engineers, and that it will help them to unravel a number of the many practical problems they are con¬stantly confronted with. In regard to Mr. Gates' discussion, I would indeed like to believe that McGill could claim, as a minor achievement, the credit which Mr. Gates so generously bestows of having established the "law" of crushing. I think that more work would be required to establish this claim in the, strict sense of the word, as there is a fairly large gap between the coarse and fine crushing results. I am not worried about that gap, because the reason for it is quite clear to me; at the same time I-think it will be well to bridge it by a series of tests, and I am bound to admit that the testing machine is the most promising machine right at hand to work with, although whether the minute amounts of power required to crush small quantities of rock can be so accurately integrated as to insure high accuracy in the final result is still a question in my mind. If we had an Amsler-Laffon machine I would certainly try it. Mr. Gates' remarks about choke crushing are extremely interesting. He compels me to wonder, too. It is a new and probably a very important factor to be considered in this connection. I am in perfect accord with Mr. Gates about the desirability of the determination of crushing constants, because when this is accomplished the efficiencies (not relative mechanical, but real efficiencies) of different types of rock-crushing plants in any part of the world will then be comparable. For this reason it would, seem desirable that the American Institute Committee should not only consider ways and means for accom-

Jan 6, 1917

The fate of generations yet unborn lies in man's hands. Shall it be prosperity, a high standard of living, and the development of spiritual values; or ruin, misery, and a reversion to jungle law? World affairs move in high gear, at high tension, in many directions. Each nation fears the other fellow- races, crosses the white line on curves, skids, takes its half in the center; and the devil take the hindmost. For one, the United States is on the horns of dilemma; it must insure a flow of raw materials of industry and world-wide markets in order that the American people may maintain high standards of living, but the commitments of the United States cannot be fulfilled without trimming present standards of comfort and convenience back to the level of perhaps a quarter of a century ago. A way must be found to retreat without anarchy at home as well as abroad. Everything is relative and all things change, and change is the essence of civilization. It is now clear that man has not kept pace with changes of all kinds, some of them overnight, during the past 50 years. Conventionality has led to stagnation; man now seeks learning of all kinds at an accelerated pace, but men should not be educated beyond their native intelligence for they must be able to apply their education. There must be a resolute action now on 10 great challenges in regard to conservation of human and ma-

Jan 1, 1950

By Torgrim Eftestoel, Leif Olsen, Ove Sandberg

IN the vertical contact Soederberg electrode for aluminum furnaces more or less serious cracks are sometimes formed in the electrode, with harmful effect on furnace operation. The problem of crack formation has been studied on a laboratory scale to obtain a better understanding of this phenomenon. The primary cause of crack formation is the shrinkage of the electrode carbon, which is opposed by the normal thermal expansion of the steel contact studs. The forces thus set up are active in the temperature interval from which the electrode obtains a rigid structure (450" to 500°C) to furnace operational temperature (950°C). A visualization of our reasoning is given in Fig. 1, which shows the different behavior of mild steel and electrode carbon during baking. Research work performed to determine relationships between crack formation and shrinkage will be described. A brief description of the method developed for measurement of shrinkage will be given, as well as a critical analysis of this method. Also, raw material quality and paste composition variables will be related to shrinkage phenomena. Laboratory Test of Crack. Formation To test the tendency toward crack formations of Soederberg electrodes from different pastes, experiments were performed to simulate conditions of actual commercial electrodes, and are described as follows. A cylindrical test electrode is prepared by tamping the electrode paste to be examined in a sheet iron casing, 350 mm diam by 700 mm height. The casing is perforated, with the holes (2 mm diam) 50 mm apart, to facilitate the escape of volatile matter during baking. A cylindrical steel stud of actual service size, 100 mm diam, is welded eccentrically to the bottom steel plate, and protrudes up through the paste. During baking, a crack may thus occur in the weaker part of the test electrode. The electrode is baked by lowering the assembly slowly into an electric furnace, the temperature of which is kept constant at 900°C. After baking of the electrode, the sheet iron casing is removed and the electrode inspected for cracks. The pictures in Fig. 2 are of three different pastes baked according to the present method. Electrode 1 has a large crack; electrode 2, a somewhat smaller one; and electrode 3, only a minor crack. As will be seen from the simplified sieve analysis diagram of Fig. 2, the compositions of the pastes in question are very different. This subject will be discussed later in greater detail. Crack Formation and Shrinkage Relationships It is well known that shrinkage occurs in coke in the higher temperature ranges of coal

Jan 1, 1958

By W. G. Pfann

The problem of forming points on wires that were from 0.002 in. to 0.010 in. in diam arose in the recent appearance of silicon and germanium point contact rectifiers as elements in microwave radar.' In these devices a pointed tungsten wire makes a delicate contact with the surface of a semiconductor. Because the quality of such rectifiers is largely determined by the nature of this contact, considerable attention has been given to the formation of the metal point. Reproducibility of contour and freedom from burrs and even microscopic irregularities are considered essential. The operations involved must be simple and rapid enough for mass production. Previously tungsten wircs had been provided with conical points by a grinding method which involved rotating a wire about its axis and causing it to bear at an oblique angle against a spinning abrasive disc. This was later complemented with an electrolytic polishing treatment which removed irregularities from the ground point and also rounded it off at the tip—a desirable feature. Finally, these operations were supplanted by the electrolytic pointing method described here. Mechanism of Point Formation The wires to be pointed are partially immersed in an electrolyte in a vertical position whereupon they are provided with smooth rounded points entirely by electrochemical action. The process is independent of the depths to which the wires penetrate the electrolyte because the points are formed at the surface level. It may be used to point a single wire or many of them simultaneously and is applicable to wires of different diameters within a limited range. Solution of the immersed portion of a tungsten wire is accomplished by making it the positive electrode in an electrolytic cell, as shown in Fig I. While the wire is maintained at constant voltage the current through the cell falls continuously, principally because of the decrease in wetted area which results from solution of the tungsten. This increase in resistance occurs in a reproducible manner and is used as a control in the process. As thc immersed portion of the wire dissolves, it remains cylindrical in shape except for the short section which is wetted by the meniscus. Here the rate of solution is lower and decreases as the top of the meniscus is approached. The result is the formation of a tapered section inside the meniscus. As solution continues, the cylindrical section either dissolves entirely or drops off just before complete solution, leaving only the taper which is now sharply pointed. Further action causes this point to become rounded and then quite blunt, until finally the end of the wire is almost plane. Fig 2 shows the stages in this development. Contour PF is most representative of those used in point contact rectifiers. Thus a variety of point

Jan 1, 1949

By W. D. Von Gonten, R. L. Whiting

Regression analysis was used to correlate the physical properties of 478 sandstone and 90 carbonate core samples. Porosity, permeability, electrical formation resistivity factor, capillary pressure and the sonic velocity of the shear and compressional waves were measured. Prediction equations for porosity, permeability and electrical formation resistivity factor were found which should be useful in understanding the relationships between the physical properties of porous media in formation evaluation. INTRODUCTION The physical properties of porous media are important to the petroleum engineer and geologist. To evaluate fully the potential and behavior of a subsurface formation such as a petroleum reservoir, certain physical properties of the porous medium must be known. The problem of accurately determining physical properties of subsurface formations has not been solved because many determinations must be made by indirect measurements and because of the difficulties caused by complex pore structure and presence of clays in most naturally occurring porous media. Due to the difficulty in measuring some of the physical properties of porous media, it would be advantageous to be able to predict a certain physical property of a rock from other physical properties of the rock which could be measured more easily and more accurately. Since most potential reservoir rocks are heterogeneous, relationships between the physical properties are very complex and thus far no satisfactory correlations based on theory or laboratory models have been developed. It appears that empirical relationships obtained by measuring the physical properties of a large number of samples of naturally occurring porous media and applying regression analysis to develop equations for one physical property in terms of other rock properties is the best approach. REVIEW LITERATURE The three physical properties used as dependent variables for correlating purposes were porosity, permeability and formation factor. Since formation factor is more difficult to determine, a brief review of the literature is provided on this property. The first work on determining formation factors was published by Archie1 in 1942. He defined this property of a porous medium as F - Ro/Rw......(1) where Ro is the resistivity of the porous medium when completely saturated with a brine of resistivity Rw. Archie found the best correlation between formation factor and porosity was the following equation, where is the porosity fraction and m is the constant characteristic of the rock. The value of m was 1.3 for unconsolidated sand packs, and ranged from 1.8 to 2.0 for consolidated sandstones. In 1950 Patnode and Wyllie2 and De Witte3 observed that the formation factor as determined by Eq. 1 was valid only when the porous medium contained no conductive solids such as clay or shale. When conductive solids are present the formation factor is also dependent on the resistivity of the saturating fluid. Therefore, in samples containing conductive solids the formation factor decreased as the resistivity of the saturating fluid increased. Because of this. the measured formation factor was called the apparent formation factor and was designated Fa. Patnode and Wyllie proposed the following equation,

By F. A. Crossley

The titanium-rich end of the Ti-A1 system has been investigated up to 35 at. pct A1 (23 wt pet). One conzpound Ti3Al was found to occur between primary a and TiAl. It is ordered hcp with DO19 structure, it has virtually no solid-solubility range, and it has a closed maximum at about 875°C. OIL either side of the compound are a +Ti3Al two-phase fields. The limiting a1uminum solubility in primary a at the titanium-rich end is indicated to be 7.5 at. pct A1 (4.4 wt pet) at 550°C and about 6.8 at. pct Al fl wt pct) at 500°C. Quenching alloys from above the a + Ti3Al two-phase field produces the following structures with respect to alloy composition: Up to 13 at. pct A1 (7.8 wt pet), a solid solution; from 15 to 18 at. pct A1 (9 to 11 wt pct), shear transformation product or martensite; from 19 to approximately 30 at. pct (11 to 19 wt pet), submicro-scopic coherent Ti3Al in an a malvix. The twin hcp phase fields reported in the literature are the result of nonequilibrium corzdztions. Ti-A1 alloys, once partitioned by dwelling- in the a + ß phase field during either hot working or heat treatment, are extremely difjicult to homogenize at temperatures below 1000°C. Such partitioned alloys exhibit the characteristics or symptoms of two-phase materials, and may be said to suffer the "twin-phase syndrome". THE earliest investigations of the Ti-A1 system by Ogden et al.1 and Bumps et al.2 reported wide solubility of the primary solid solutions. Aluminum was reported soluble in the low-temperature allomorph to the extent of 37 at. pct (25 wt pct), and the first intermediate phase was reportedly TiA1. Somewhat later Kornilov et al.3 reported a similar diagram with phase boundaries displaced towards lower aluminum contents and higher temperatures. Beginning about this time (1956) reports in the literature made it very clear that one or more intermediate phases occurred at lower aluminum contents than TiAl.4-17 These reports included five major investigations of the titanium-rich end of the Ti-A1 diagram.4,12,14,16,17 Three of these diagrams show two two-phase fields below 37 at. pct Al, while two of them show a single two-phase field. The existence of the phase Ti3A1 is firmly established and is included in each of the diagrams, except one—that of Sato and Huang.12 The new phases are reportedly hcp and differ from primary a only slightly when disordered, and when ordered the "a" parameter is approximately one,4,12,15 two, 6-10,13,14 or four14 times that for primary a. Beyond this, however, the diagrams are remarkable for their lack of agreement. Two tacit assumptions are usually made in phase-diagram determinations of metal systems. These are: 1) equilibrium anneals bring the alloy to equilibrium or to indistinguishable closeness to it, and 2) equilibrium conditions established at elevated temperatures are either "frozen" by rapid quenching for evaluation at room temperature, or quench-transformation products are recognized as such. In the current investigation evidence was obtained that over substantial composition ranges neither of these two conditions was met in any of the more recent major investigations. I) MATERIALS, METHODS, AND TECHNIQUES The alloys of this investigation were prepared by nonc on sum able electrode arc melting. Materials used in the preparation of the alloys are summarized in Table I. The investigative tools employed were: optical and electron microscopy, differential thermal analysis (DTA), disatometry, X-ray diffraction, electron diffraction, and resistometry. Alloys for microscopic and X-ray investigations were prepared as 15-g melts. Alloys containing from 7 through 11 at. pct A1 were hot-rolled out of a furnace at 900°C, from 12 through 15 at. pct out of a furnace at 1000°C, and from 16 through 18 at. pct out of a furnace at 1125°C. Alloys containing more than 18 at. pct A1 could not be hot-rolled. The ingots were covered with Markal coating prior to hot rolling to minimize atmospheric contamination. After hot rolling, alloys containing up to 15 at. pct A1 were ground and pickled to remove 7 mils from each surface; alloys containing 16 and 18 at. pct A1 were skinned to a

Jan 1, 1967

By T. G. Digges, C. L. Vold, M. R. Achter

A study was made of the effect of the growth conditions on the perfection of single crystals of niobium (columbium). Dislocation densities, determined by means of double-crystal diffractometer measurements , were not greatly affected by the method of crystal preparation but could be reduced by annealing treatments. However, the size, sharpness, and tilt angles of the substructures, observed with X-ray reflection macrograph, were sensitive to variations in growth procedures as well as to subsequent thermal treatments. Although the dislocation density was the same in both types, there were more low-angle bound-aries in crystals grown by zone melting than in those prepared by strain anneal. Mechanisms to account for these observations are discussed in terms of dislocation movements. A planned study of the structure-sensitive properties of refractory metals required the use of single crystals of a high degree of structural perfection and, for ease of handling, of large cross section. It appeared that the strain-anneal technique could satisfy both of these requirements. First, crystals grown in the solid state have been reported to be more perfect than those obtained from the melt.' Second, the diameters of rods which may be produced by zone melting should have a theoretical limit determined by specific gravity, thermal conductivity, and surface tension, while the diameter of strain-annealed rods is limited only by practical considerations. Previously it was shown that niobium (columbium) single crystals of 1 in. diam2 may be grown by strain anneal, compared to the 0.5 in. maximum diameter achieved by zone melting, as reported for molybdenum by Belk.3 The current research was undertaken to investigate and optimize the effect of various process variables on the perfection of 1/4 and 1/2-in.-diam niobium single crystals grown by strain annealing and to compare their perfection to those grown by zone melting. Characterization of these crystals was more conveniently accomplished by means of X-ray than by metallo-graphic techniques. EXPERIMENTAL PROCEDURE Specimen Preparation. Zone-melted crystals of 1/4 in. diam were produced by the standard electron-beam zone-melting technique. The swaged and cleaned rods were outgassed, in the solid state at a temperature near its melting point, at a rate of 12 in. per hr, and single crystals were grown by making two molten passes at 2 in. per hr. By maintaining a zone length of 4 to % in., very uniform single crystals several inches long were obtained. For the strain-annealed crystals, an induction heater was used, in preference to other types of heating, to take advantage of the good penetration of large sections. A five-turn coil, 1 in. long, operating at 10 kc and powered by a motor generator, was contained in a vacuum chamber. The rod, suspended from the upper end, was raised through the coil for both recrystallization and crystal growth. In preliminary work single crystals of the same material were also grown with single and multiturn coils powered by a 450-kc generator. A vacuum of 2 X 10-6 Torr was maintained at temperatures up to 2400°C. Starting with electron-beam-melted ingots of 21/2 in. diam, the analysis for which is given in Table I, the material was cold-swaged to the desired cross section of 1/4 and 1/2 in. diam and then recrystallized. The rods were then strained in a tensile machine and converted to single crystals by passing through the induction coil. As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and smallman,4 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point in the poly crystalline portion. Finally, it is returned to the chamber and growth is continued "around the corner". This procedure has certain limitations. If the bending operation exceeds the critical strain, recrystallization may take place. Also, the amount of bending which can be imparted to the rod is limited by coil geometry, and up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. In preparation for X-ray examination, single crystals were sectioned and planed by means of the spark-erosion technique. To obtain the maximum reflected intensity, the (110) plane was exposed for examination. They were then etched 3 to 5 min in a mixture of con-

Jan 1, 1967

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

E. A. H. Tays, San Blas, Sinaloa, Mex. (communication to the Secretary*):—The results obtained by Messrs. Hofman and Hayward in their experiments, proving that a low percentage of copper sulphate with a variable percentage of salt, depending on the ore, gives the best results, confirm practical mill-work which I did in 1895. I have none of my notes, taken at the time, to refer to, so have to rely solely on memory, which precludes the conciseness that is alway desirable. In 1894 I took charge of the plant of the San Rafael Company, near Chinipas, Chihuahua, Mex., which at that time was treating a very refractory ore carrying about $15 in gold and from 20 to 25 oz. of silver per ton, the bullion being about 300 fine in gold. The silver in the ore was in the form of a sulphide. Although carrying an average of 0.75 oz. of gold per ton, free gold could rarely be seen by panning, but upon roasting a sample of the ore the gold became visible at once—a result which was discovered by chance and used to advantage later. In order to utilize the old mill to the best advantage, it was decided to use pan-amalgamation after roasting. The roasting, done in a lime-kiln, was similar to the ordinary " burning " operation. The roasted ore was trammed to the mill-bins and crushed by 10 stamps to pass a 30-mesh screen. The pulp was de-watered and fed to four 1-ton pans. My recollection is that upon starting the mill-work, the charge contained 1.5 lb. of copper sulphate and 5 per cent. of salt per ton. From the start the extraction was unsatisfactory and the loss of quicksilver was very large. Experiments were then carried out on a working scale. First, the quantity of copper sulphate was increased 4 oz. at a time; then it was reduced

Jan 1, 1910

By D. C. Hilty, W. Crafts

L. S. Darken—Laboratory investigation of deoxidizing and other steelmaking reactions is usually centered, at least first, on the determination of the equilibrium or equilibria involved. This seems a reasonable procedure since equilibrium, if attained, depends only on composition, temperature, and pressure; hence conclusions derived from data on small experimental quantities are applicable to a heat of steel providing eauilibrium is attained in both cases. A knowledge of equilibrium serves as a useful framework even though we may know that practical conditions do not correspond to complete equilibrium. On the other hand, nonequilibrium or rate phenomena depend on a wider variety of conditions and are more difficult to interpret; conclusions applicable to laboratory conditions may or may not apply to larger scale phenomena. Hence the attainment or nonattainment of true equilibrium in the experiments here reported is of critical importance in evaluating their significance. Since some of the statements in this paper and in the closely related preceding one (on aluminum deoxidation) imply some doubt on this matter, I should first like to ask the authors whether their conditions are intended and believed to represent equilibrium. I should like to point out three considerations which seem to cast considerable doubt on the achievement of equilibrium, at least of the particular equilibrium under consideration. 1. In the experiments on manganese deoxidation the authors point out that they could not maintain the manganese-oxide slag on top of the metal in their rotating crucible, and hence they substantially dispensed with this slag. This leads to serious trouble in the interpretation of the results, for any equilibrium is, of course, a particular specific equilibrium—in this case Mn + O = MnO The experimental deletion of the upper layer of manganese oxide means that if equilibrium is attained at all it is attained between the metal and the MnO which has soaked into or adhered to the crucible (under the metal) and has dissolved substantial amounts of the crucible material including impurities. These impurities may constitute a significant portion of the slag by virtue of the small total amount of slag, even though the crucible is relatively pure. Hence there would seem to be a strong presumption that the equilibrium (if attained) involves not a pure MnO (or MnO — FeO) slag but one saturated with alumina and containing perhaps considerable impurities which substantially lower the concentration and activity of MnO, causing the above reaction to proceed to the right further than it would in the absence of alumina and impurities. Hence it is not surprising that manganese here appears as a better deoxidizer than found by other investigators. The present results may represent equilibrium with a slag of unknown composition which seems unlikely to be particularly related to plant experience. 2. The curves representing the observed silicon deoxidation (figs. 3, 4, and 5) are all drawn with a discontinuity in slope at about 0.02 pct oxygen. This point is interpreted as corresponding to the three-phase equilibrium, metal, slag, solid silica. The type of construction shown in these figures (though apparently fitting the data) is contrary to a fundamental principle of heterogeneous equilibrium as pertains to the construction of phase diagrams. According to this principle, the two solubility curves (each of the two portions of the curves in figs. 3, 4, and 5) must intersect in such manner that their (metastable) extensions must lie outside the homogeneous field rather than inside as in these figures. In other words, the "point" in these curves should be aimed in the opposite direction, if it is to be interpreted as corresponding to the three-phase equilibrium. The construction adopted is in violation of the second law of thermodynamics. This matter is discussed in detail in several texts and also by Lipson and Wilson.&apos;" The same criticism applies to the later figures representing conditions for manganese additions. The occurrence of this discontinuity or break at 0.02 pct oxygen casts further doubt on its interpretation. The earlier investigation of this system by Korber and Oelsen is in substantial agreement with the several recent findings of Chipman and coworkers that the oxygen content of iron in equilibrium with silica and silica-saturated iron oxide slag is about one third to one half that (0.24 pct at 1600") of iron saturated with pure iron oxide; thus there seems reliable evidence that iron saturated with silica and iron silicate slag at 1600" contains about 0.1 pct oxygen, or certainly much more than the 0.02 pct proposed in this paper. 3. In the quarternary system iron-silicon-manganese-oxygen one of the equilibria involved may be written 2 Mn + SiO2 (solid) = 2 MnO <slag> + Si The activity of SiO, is constant (if equilibrium is attained) by virtue of its presence as a substantially pure solid. At not too low metallic manganese content, the activity of MnO in the slag is constant by virtue of the fact that the slag is substantially pure manganese silicate saturated with silica and hence of constant composition. Thus the equilibrium constant for the above reaction is asi/a2Mn. Barring unanticipated large changes in the activity coefficients, the equilibrium constant may be adequately approximated for the composition range covered as [% Si]/[% Mn]2. Thus a plot of log [% Mn] against log [% Si] would be expected to be linear with a slope of one half as found by Kijrber and Oelsen. In the present investigation the slope (shown in fig. 15) is found to be one. It is difficult to believe that this finding represents a correct equilibrium determination, since it is at odds both with prior experimental investigation and with. theory. In view of the above points it seems that, although this paper reports many interesting findings, there is room for considerable skepticism as to the attainment of equilibrium and as to the conclusions drawn. N. A. Gokcen—The authors consider that Si% x O2% product is constant. This product is a function of the asi X a0 activity of Si02. The true constant is -------------. If the asio2 slags of this investigation were always saturated with SiO2 then Si% X O2% product would be constant,

Jan 1, 1951