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By W. R. Ingalls

WHAT proportion of the national wealth is represented by' the producing mines of the country?' Or by the- mining and metallurgical industry-as a whole, for it is impossible to make-an economic distinction between the mines that produce the ore and the plant that is used to get the metals from it. The total national wealth in fixed property is about $270,000,000,000. How much for the mines? I do not know that any one 'else has ever tried to furnish answers to these questions. In making such an attempt I am conscious that the result can be nothing more than a rough approximation. Yet even that will give an idea of relative values. No separate valuation for the mines of the country has appeared in any inventory of the national wealth previous to that which I compiled and published for 1916. -In earlier census estimates mines were supposed to be included under the head of real estate. However, an examination of the laws and practices of the several states with respect to mine taxation will make it evident that no good idea of the value of the mines of the coun¬try is obtainable from the assessment rolls. In my previous estimate for 1916, I computed the value of the mines at $8,000,000,000, which was approxi¬mately 10 times their net income as reported to the Bureau of Internal Revenue. In making that estimate I fell grossly into error, for several reasons that it is unnecessary to explain, but chiefly because the net income of the mines of the country in that year was exceptionally large. The whole subject of valuing the mines of the country en bloc is extraordinarily difficult At the best, no one can hope to arrive at, anything more than a rough idea about it. However, elements of reason may be introduced and may be made to serve as chief bases.

Jan 1, 1921

By W. R. Ingalls

THE paramount subject of interest and concern at the present time is the readjustment in economic conditions following the cataclysmic disturbance produced by the war and the misconceptions leading to an orgy of extravagance that prevailed during two years following the armistice he, time is too short for me to undertake to review the nature and extent of the upheavals occurring between August, 1914, and October, 1920. Bulky volumes will be written about them. . But I shall have to refer to some of the results in order to outline a prognosis. It is the future, not the past;' that is of most interest to us. Let me be so bold as to say, without further preface, that I am not optimistic as to the near future. .We shall, indeed, have revivals in trade, but they will be delusive if their nature be not 'understood. We shall build hopes and expectations upon political maneuvers and events, only to find in the end that they were folly. In the meanwhile fundamental economic influences will continue to exert their steady and irresistible pressure. The new administratiow at Washington has no magic wand with which to kindle the fires in our idle steel furnaces, or create a million new houses for the people; nor can the premiers of Europe put into motion the spindles of the cotton and woolen mills, or by any incantations compel the people of the Orient to buy goods. The people of the Orient, and of, Europe, and of the two Americas are in the grip of the same economic forces. The readjustment has proceeded further in some parts of the world than in others. In the United States I do not think we, have gone more than over the threshold. I shall tell you why 1 think thus, but in telling you I shall be limited, in view of the immensity of the subject, to a series of bald statements, without much elucidation.

Jan 1, 1921

By W. J. Joslin

The frontal-advance equation can determine how the fluid withdrawal rate and subsurface operating pressure influence oil recovery from pressure-maintained reservoirs having characteristics favorable for efficient vertical segregation. For effective vertical segregation in formations having low dip angles, the requirements are: thick, massive sands, low viscosity oil and high vertical permeability with few discontinuous shale members. This approach has been successfully applied to the LL-370, which is a massive Eocene sandstone reservoir containing crude with an average gravity of 26" APT, a dip of only 3" and vertical permeability of ½ darcy. The average gas cap saturation was calculated for various rates of vertical gas-oil contact movement corresponding to a wide range of reservoir producing rates. This method also evaluated the effect of different pressure maintenance levels on oil recovery. Applicability of this procedure for calculating the present oil saturation in the LL-370 gas cap has been substantiated from field performance, where the oil saturation was computed by comparing oil recovery with the gas cap volume vacated. INTRODUCTION During the natural depletion history of the LL-370 reservoir, located in Lake Maracaibo, Venezuela, excellent vertical segregation resulted in the formation of a thin gas zone over a substantial portion of the oil-productive area. Subsequently, gas injection forced this thin gas-saturated zone slowly downward, reducing the oil saturation in the gas cap to a low value. The oil recovery has been raised considerably above earlier predictions where vertical segregation effects were under-estimated. In order to determine the maximum efficient producing rate and optimum operating pressure for this reservoir, a vertical gas frontal-advance analysis has been made through application of the fractional flow equation. LL-370 RESERVOIR CHARACTERISTICS The reservoir consists of a truncated monocline of massive. highly-permeable Eocene sandstone, called the B-b formation, covering an area of more than 13,500 acres. The original oil in place was 2.17 billion STB. Internal non-sealing faults subdivide the structure into four blocks called the B-6-x.6, 10, 11 and 13, which are effectively bounded by major faulting on the flanks, an unconformity updip to the west, and an immobile aquifer to the southeast. The producing formation occurs at an average depth of 5,250 ft subsea and has a closure of more than 1,500 ft. A typical producing section has a net oil sand thickness of 170 ft. Scattered throughout the section are a few randomly-positioned shale lenses which increase in thickness and areal extent downdip. The reservoir rock and fluid properties vary with depth. The permeability and produced oil gravity are 1600 md and 28" API at the top, compared to 300 md and 18° API at the water-oil contact. The productivity of updip wells is, therefore, much higher than the reservoir average. The reservoir oil was originally saturated at the crest, grading to a slight degree of undersaturation at the water-oil contact. There was no original gas cap; and material balance and the field performance indicate no water influx. Except for the northern B-6-x.6 block, the fluid and rock properties have already been published.' Average LL-370 reservoir properties are shown in Table 1. RESERVOIR PERFORMANCE UNDER NATURAL DEPLETION Fig. 1 shows production performance from 1939 to date. Early development was gradual, with 30 wells pro-

Jan 1, 1965

By Stanley C. Suboleski, J. Richard Lucas

Simulator I, a program to simulate production in room and pillar mining systems containing up to six face operations, was developed at Virginia Polytechnic Institute under sponsorship of the Office of Coal Research. Since its inception, several hundred analyses have been run, with over thirty companies using the program. This paper describes the simulation technique used in this program, the output achieved from an analysis, and reviews the experience gained in working with Simulator I.

Jan 1, 1969

By AIME AIME

EVEN though most of the program of the joint meeting at Easton, Pa., on Oct. 30 to Nov. 1. was devoted to the interests of combustion engineers rather than to coal-mining engineers, nevertheless the A.I.M.E. Coal Division was well represented, with 83, or close to one third of those in attendance giving this as their affiliation. The fuels division of the American Society of Mechanical Engineers had 108 representatives, and an equal number reported no society affiliation. Added to the men's total registration was that of some twenty ladies so the total attendance was in the neighborhood of 325, exceeding that of the last two joint meetings, at Birmingham and Columbus, and equaling the 1938 crowd at Chicago.

Jan 1, 1941

By T. Sterry Hunt

IN my address on the " Geognostical Relations of the Metals," delivered before the Institute on the 20th of February last (Vol. I Transactions, p. 331), I spoke of the rocks in the vicinity of Thunder Bay, Lake Superior, where I indicated two series of uncrystalline rocks resting upon the Huronian schists, the lower one consisting of dark-colored argillites and sandstones overlaid, apparently in slight discordance, by nearly horizontal red and white sandstone and marls, which were compared with those of Sault Ste. Marie, and those of the Portage Lake district, on the south shore. These latter sand-stones, according to Brooks and Pumpelly, overlie unconformably the Keweenaw series of copper-bearing amygdaloids, sandstones, and conglomerates, and are in turn overlaid by the Trenton limestone. I then proposed to call this lower series of Thunder Bay, that is to say, the dark-colored argillites and sandstones which are traversed by the silver-bearing lodes of that region, the Animikie group. Shortly after the publication of that address I received an abstract of a paper on the geology of that region by Professor Robert Bell, read before the Montreal Natural History Society, February 24th. He there confirms the statement made in my address that the gold of Lake Shebandowan occurs in the Huronian, which is also seen to be cut by the silver-bearing lodes just mentioned. Professor Bell, in this paper, proposes to designate both what I have called the Animikie group, and the overlying red and white sandstones, by the name of the Nepigon group, for the reason that the upper series is best displayed about Lake Nepigon. This latter series is by Logan supposed to be overlaid by the copper-bearing amygdaloids with conglomerates and sandstones of the north shore (apparently identical with those of Keweenaw) ; and the whole together, including the Animikie group, constitute his Upper Copper-bearing group. These copper-bearing strata are by him supposed to be overlaid by the red and white sandstones of St. Mary, which are apparently the same with those sandstones which, according to Brooks and Pumpelly, overlie unconformably the similar cupriferous rocks of Portage Lake, and are, in their turn, overlaid by the Trenton limestone. Thus the sandstones which at Thunder Cape overlie the Animikie group are by Logan placed in the midst of the Upper Copper-bear-

Jan 1, 1874

By N. Cabrera

IN a recent paper Kuczynski' studied the rate at which the crack between a metallic plane and a spherical particle of the same material is filled up gradually when heated at temperatures near the melting point. If x is the radius of contact between plane and sphere (fig. I), Kuczynski shows experimentally that x5 = At [1] where t is the time. Assuming that the mechanism of transport of matter is the volume diffusion of vacant lattice sites, he is also able to prove Eq 1 theoretically. The constant A contains as a factor the self-diffusion coefficient of the metal and he shows that the values for this coefficient deduced from his experiments yield the same activation energy as that calculated by other methods, which is a confirmation of this point of view. Kuczynski has also considered theoretically the law of growth of x which would be expected if surface diffusion were the important mechanism. He suggests that x should then obey a law of the form x7 = At, and claims to be able to decide the mechanism involved from the observed law of growth., The purpose of this note is to prove this incorrect. On the contrary, when the mechanism is surface diffusion Eq 1 is also obeyed, but with a different constant A. Following Kuczynski, we suppose the bottom of the crack (surface A A) to have an average radius of curvature p. As a result of this curvature the concentration of adsorbed atoms in this surface, n(p) per cm2, will be smaller, and the concentration of vacant lattice sites in the neighborhood, N(p) per cm3, will be larger than the corresponding concentrations, n(w) and N(w), for a flat surface. For all practical cases we can write Thomson's formula in the form n(co)— n(P) N(P)—N(cc) _ 2a-a" n(oo) JV(co) kTp [2] where u is the surface energy of the metal and a the interatomic distance. 1. Let us now consider the mechanism of surface diffusion. We suppose the concentration of ad-

Jan 1, 1951

By M. F. Goudge

Production of many industrial minerals reached all-time records in 1965. In keeping with the high level of industrial activity throughout the nation, producers of many industrial minerals operated at capacity or near capacity, notably the producers of phosphate, potash and sulfur. In the case of sulfur, the demand exceeded production and orders were filled, in part, from stocks accumulated in previous years. Industrial minerals as a group continued to increase both in value and quantity at a faster percentage rate than metallic minerals and fuels, The U.S. Bureau of Mines estimated that the value of industrial minerals produced in 1963 was $4318 million vs. $2006 million for metals. Preliminary estimates for 1965 indicate that current value of production was again more than 2% times that of metals, thus making apparent their importance to the industrial life of the nation.

Jan 2, 1966

By Kenneth B. Powell

EIGHT years ago the Eagle Mountain iron ore deposit located in the hills of the Colorado Desert in the extreme southeast part of California was known only to a few geologists, mining men and the oldest of the desert prospectors. Today, the deposit is the Kaiser Steel Corp.'s Eagle Mountain Mine, and the once lonely hills now shelter a model community of 225 people enjoying all modern conveniences. Nearest town to the mine is Indio, 60 miles distant by an excellent highway. Elevations at the deposit vary from 1400 to 3000 ft. The mine enjoys winter resort weather between October and May with occasional drops to 25" at night. From June to September temperatures rise to 120" at times. Rainfall is scant, approximately 2 in. per year, the majority of which comes during the summer months as cloudbursts.

Jan 5, 1953

By Oliver Bowles

A HEAVY gel of bentonite clay has been proposed as an effective lubricant to speed down the ways to sea, river, or lake, the mighty cargo ships now hitting the water at the rate of about three a day. Another unusual application of a nonmetallic mineral is in food conservation, for the claim has been made that the next new item on the menu for poultry and rabbits will be vitamin tablets prepared from mont-morillonite clay. These uses have minor importance but illustrate not only the diversity in utilization, but the notable trend in 1942 toward mobilizing nonmetallic minerals for the war program. Although occupying less headline space than iron, steel, copper, aluminum, magnesium, and other metals, the nonmetallics are filling important emergency needs. Mica and quartz crystal are essential to communication; asbestos is urgently needed in fireproof heat and electrical insulation; and strontium minerals are utilized in the manufacture of signal flares and tracer bullets.

Jan 1, 1943

By G. E. Mellor, R. E. Lippoth, T. B. Faddies

The Trixie mine is located in the East Tintic Mining District. Since production began in 1970 over 450 000 tonnes of ore grading 239 grams of silver, 6.9 grams of gold, and 1.2% Cu have been mined from veins in Cambrian Tintic Quartzite. Detailed geologic mapping and extensive sampling are essential for compiling the data base required for efficiently developing and mining known reserves as well as planning exploration and development work. Although the basic techniques used by the geology group at the Trixie were developed many years ago, the reduced activity in underground precious metal mining in the U.S. have made these techniques less familiar to many presently active geologists. The increased activity in precious metals search and exploration again offer cause for the application of these techniques as a prerequisite to efficient exploration, development and production.

Jan 1, 1984

LEAD and tin mixed together make an alloy through an attachment of natural affinity which they have with each other, so that when they are mixed it is difficult to recognize by the sight which one it is, if the essences of their qualities are not surpassed by more than half. If, indeed, one can be recognized, it is the tin which gives off a certain sharp odor to the sense of smell, besides having a greater hardness and whiteness. The best of these is the one that is the purest in its kind. In the alloy of tin it is the one that is the whitest and hardest, or, when it is bent or some thin end of it is held tightly by the teeth, is heard to crackle as frozen water does. Because this happens more with this than with other metals, I do not wish now to inquire into it. It is enough that it be a sign for recognizing when tin is pure or mixed. Pewterers say that it should be joined in alloy with lead and that it is better for working when it contains four or six pounds to the hundred because it makes it softer to the hammer and more fluid in casting. But I do not like to hear this, even if all they say is true, for I see that the tin that comes from England, when worked as well as in cakes that show it to be pure, is much more beautiful and better in all works than is that made in Venice. And I believe that it is not better for any work when mixed than when pure, except for the advantage of the master who, if he does nothing else, sells lead that is worth little for tin that is worth much. I find that when mixed it serves in only two things. One is when it is wished to make a solder for copper, for use when it is not worth while to solder the bottoms and large pieces of vessels with low-grade silver as should be done. The other is when master potters calcine it in order to make glazes and to apply white to their vases. I consider lead to be useless in all other works of any kind of metal, since it unites with none of the other metals of good company except tin.

Jan 1, 1942

Discussion of the paper of F. C. NEWTON, presented at the New York meeting, Feb-ruary, 1915, and printed in Bulletin No. 9S, February, 1915, pp. 473 to 477. H. 0. HOFMAN, Boston, Mass.-The results of these large-scale experiments, which were carried on at Perth Amboy, show that there are many differences between theoretical conceptions and their applications to work on a large scale. The author has given reasons why the results of bringing a desilverizing kettle to the high melting point of the zinc-silver alloy, Zn3Ag2, melting at 665° C., are not satisfactory. In all probability the alloy is dissolved in the lead; it may also be decomposed by the lead; the practical result is that this high temperature does not work. It remains now for the laboratory man to carry on systematic experiments

Jan 5, 1915

By Wayne A. McCurdy

For the third consecutive year, predicted increases in coal production and consumption failed to materialize. Production of bituminous, sub-bituminous and lignite coal for 1961 was estimated by the U.S. Bureau of Mines at 400 million tons, a drop of 15,- 512,000 tons from the 1960 figure. Anthracite production for the year was 17.8 million tons compared to 18.8 million tons produced in 1960. Consumption figures are expected to show a proportionate decline. Of coal's major markets, only electric utilities showed an increase-and even here the increase of approximately 2% was smaller than had been expected. Major cause of relatively low consumption was a decrease of more than 20% in the use of metallurgical coal for making coke. Reductions of lesser importance were registered in general industrial, retail, and export markets.

Jan 2, 1962

By Blamey Stevens

(San Francisco Meeting, October, 1911.) My previous paper is entitled, The Laws of Igneous Emanation Pressure. The present paper lays no claim to the exactitude and completeness of a law, since it is of a provisional nature and may be disregarded when experiments have established a basis for more exact reasoning. The general physical states in which aqueous emanations may occur are first considered. The possible physical conditions under which the mineral elements may occur in emanations are then discussed, and a classification of deposits, dependent on emanation, is proposed. A system of scientific experimental investigation is outlined, and it is shown that the physical and chemical properties of emanation may be exactly determined thereby. The investigation is urged as feasible and simple, and not necessarily requiring large and costly apparatus. It is the only step necessary to make possible the formulation of a complete set of laws of igneous emanation. Process of Emanation. In a rising column, magma ranges in temperature from 900° to 1,200°C. Exhalation must begin at some fairly great depth. What this depth may be we can only surmise, since no experimental evidence is available. Exhalation, however, continues as the magma flows upward, until at another level the occluded gases have all escaped. This depth is probably upward of 5,000 ft. (See Fig. 1.) All exhalations must come from between these two levels. As the whole emanation is the sum of the exhalations and residues, the residues must come from below the uppermost level. They will be most abundant when coming, from those parts of the intrusion which have solidified below the lower level.

Apr 1, 1912

By R. C. Canby

JUDGE GRANT, in a delightful satire of his, says: "Boston is a state of mind." I think that this same statement might well be made of the metallurgy of lead. I was particularly impressed with this when about thirteen or fourteen years ago I prepared a paper on "Development of the American Water- jacket Lead Blast Furnace." Dividing the time, as I did into ten-year periods, from the commencement of lead smelting at Eureka, Nev. (1870), and showing the tendency for each of the five decades it was evident that the progress had been through a succession of states of mind from the rule of thumb through the ultra scientific, or from what I might call the slag type period up to the present highly developed art. Conservatism has been characteristic of the metallurgist. This may have been most natural, especially with the lead metallurgist, the development of whose art was so entirely in the custom smelting plant, where the metal contents of his ores were paid for in cash and therefore excessive metallurgical losses could mean nothing short of financial bankruptcy. The metallurgist himself was held to a personal account, in these smelting plants. It was the metallurgist who was accountable. In the concentrating plants, if undue losses occurred remodelling of the plant was discussed, but if there were excessive metallurgical losses in the custom smelting plant, a new metallurgist was considered as the remedy. For this reason the tendency was to adhere to recognized practice and to be wary of unusual methods, using the word unusual in the sense in which it is used in Article VIII of the Constitution of the United States, as to punishments and modes of death. This conservatism of the metallurgist was reflected as other branches of metallurgy were developed. We have heard of the wonderful development of flotation, but it had to be introduced over the dead metallurgical bodies of its opponents.

Jan 1, 1926

By D. A. Elgillani, S. Atak, D. A. Rice, M. C. Fuerstenau, R. B. Bhappu

Quartz and feldspar cannot be floated with sulfonate at any pH; spodumene floats over a narrow acid pH range, while beryl responds moderately over a broad pH range. After wet-grinding in a steel mill, beryl, quartz, and spodumene float well with sulfonate below about pH 7, whereas the improvement in the response of feldspar is not so marked. A mechanism by which iron can be adsorbed on these minerals is presented. Also, the responses of leached, natural, and wet-ground beryl to amine, sulfonate, and oleate flotation are shown and related to the measured zero-points-of-charge of these materials. Earlier work with leached beryl showed that good flotation could be obtained with alkyl aryl sulfonate over a rather wide pH range using a Fagergren flotation cell.' When a similar response was observed with leached quartz, it was decided that unintentional activation was being obtained from the metallic components of the Fagergren cell. To obviate this difficulty, a microflotation cell was designed, and an experimental technique was devised. These have been described elsewhere. Experiments conducted with the small cell showed that leached quartz could not be floated at any pH with any sulfonate addition,3 which is in agreement with the observations of Kraeber and Boppel.4 Similarly, it was also found that leached beryl responded to sulfonate flotation only over a narrow pH range rather than the broad range reported earlier.1 This early work,1 however, revealed the important effect that wet-grinding in a steel mill has on the flotation response of certain silicates. That is, it was found that quartz and especially beryl floated well over an unusually wide pH range after wet-grinding in a steel mill. Microcline, however, floated poorly below pH 4, even though wet-ground under the same conditions. The work of Eigeles6 on adsorption of oleic acid on leached quartz and iron-contaminated quartz at constant pH is in agreement with these flotation data. Other research has shown that ferric iron, added as a salt to the system, functions as an activator in the narrow pH range in which Fe +++ iron hydrolyzes to its hydroxy complexes.3,5 These phenomena indicate that iron functions differently in flotation systems depending on its method of introduction. The object of this paper is to determine the mechanism by which iron is adsorbed on certain minerals, the mechanism of collector adsorption after iron abstraction, and the role that Fe++ and Fe+++ assume in the selective separation of these minerals. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate, mol wt 450,7 pure potassium oleate, and pure dodecylamine were used as collectors. All other chemicals were reagent grade in quality, i.e., n-amyl alcohol as frother; HC1, H2SO4, and KOH for pH adjustment; and ferric chloride as activator. Conductivity water, made by passing distilled water through an ion exchange column, was used in the experimental work. All minerals used in the investigation were hand-picked specimens. Sample Preparation: Each of the minerals was crushed through 8 mesh, and the product was divided into two groups, one to be ground dry and the other wet. Dry grinding was accomplished with an alumina mortar and pestle. The product was dry-screened to 48 x 150 mesh, cleaned magnetically, deslimed in conductivity water, and dried. Preparation of the samples by wet-grinding involved grinding a 200-g charge of the mineral (-8 mesh) at 60% solids with natural water in a mild steel rod mill for four minutes. This charge was then wet-screened immediately with natural water to 48 x 150 mesh, dried, and cleaned magnetically. Some experiments were also conducted with leached beryl and quartz. These products were prepared by leaching the sized sample (48 x 150 mesh) with concentrated HC1 with a percolation technique until no iron could be detected in the leach liquor. Following this step, the sample was rinsed with conductivity

Jan 1, 1967

By C. E. Lundin, D. T. Klodt

The binary alloy systems, Y-Ti, Y-Zr, and Y-Hf, have been investigated throughout their entire composition regions. There is no compound formation in any of the systems, and each system is characterized by a single eutectic reaction. The eutectic compositions and temperatures are as follows: A eutectoid reaction pct Y and 870°C occurs in the Y-Ti system, whereas a peritectoid reaction,: pct Y and 880°C occurs in the Y-Zr system. Peri-tectic-type reactions at temperatures above the eutectic levels are postulated for the yttrium and hafnium transfovmations. The development of the technology of yttrium has been given considerable attention during the past few years, and studies of binary phase equilibria have, of course, taken a prominent position in this development. In many respects yttrium, in the third group of metals of the periodic table, is similar to the adjacent group of metals, titanium, zirconium, and hafnium, and the knowledge of the phase relationships of yttrium with these metals is basic to their technology. MATERIALS AND EXPERIMENTAL PROCEDURES Materials. The metals for this investigation were supplied by the General Electric Co., Aircraft Nuclear Propulsion Department. The yttrium was in the form of an arc-melted ingot, and the other metals were in the form of high-purity, iodide-Process crystal bar. Table I lists the purities of these materials. Alloy Preparation. Melting was done by conventional techniques in a nonconsumable electrode arc furnace in an atmosphere of purified argon. Melting conditions for each binary system were the same. Each alloy button was inverted and remelted several times to assure homogeneity. Accurate weights of the charges and resultant alloy buttons were obtained to indicate deviations from intended compositions. No chemical analyses were obtained since melting weight losses were consistently in the range of 0.1 to 0.2 pct of the total weight. 10- or 20-g buttons for each 5.0 wt pct composition increment were melted to survey the three individual alloy systems. Additional alloys differing in composition by 1.0 or 0.1 wt pct increments were also melted to study selected regions of the systems. Metallograpllic Techniques. Standard metallo-graphic techniques were followed for mounting and rough grinding. Preliminary polishing was accomplished using 6-u diamond paste as an abrasive on a Metcloth Lap. Final polishing was done on a Microcloth-covered wheel using 1-u diamond abrasive paste. Purified kerosene was used as a lubricant for both polishing stages. • sothermal- Annealing. Alloys were sectioned for as-cast structlure examinations and then homogenized in preparation for isothermal-annealing treatments. Homo{:enization was accomplished by cold pressing the alloy buttons followed by 72-hr anneals at 1100c. The alloys were encapsulated in Vycor or quartz for the homogenization treatments or for isothermal anneals. Resistance-wound or resistance-element tube furnaces were used for the annealing treatments. The homogenized alloy buttons were cold rolled until cracking occurred or until a -in. specimen thickness was obtained. Small -in. square) specimens for the isothermal anneals were then sawed from the alloys. Each specimen was wrapped in tantalum foil before being sealed in the capsule. Temperatures during the anneals were controlled The time at temperature necessary to equilibrate the structures during the anneals was determined for each alloy system by holding triplicate specimens of alloys at a constant temperature for three different periotls. The specimens were quenched and examined microscopically to determine the number and amounts of phases present in the micro-structure as a function of time. Melting Studies. Eutectic temperatures of the three alloy systems were established from the results of incipient-melting studies conducted on as-cast alloys. Specimens to be melted were suspended on a tungsten wire inside a graphite cylinder placed in a glass vacuum chamber. An optical pyrometer was used to follow the temperature of the specimen as it was inductively heated in a high vacuum. The temperatures were corrected for emissivity losses by standardizing the pyrometer with known-melting-point metals. Accuracy of the temperature measurements is estimated to be + 10°C. The melting point of the yttrium was determined to be 1550°C by this technique. The invariant-temperature levels were also checked by an anneal-quench technique. This technique consists of annealing a series of

Jan 1, 1962

By N. S. Stoloff, R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-Co and Fe- V alloys containing up to 25 pct solute have been studied in the temperature range 25° to - 196°C. The microyield stress is independent of temperature for all alloys studied, while the temperature dependence of the ordinary yield stress is large and comparable to that for unalloyed iron. An alloy-softening phenomenon is observed for many alloys relative to unalloyed iron, and appears to be a consequence of removal of inter-stitials from solution and their subsequent agglomeration. The ductile to brittle transition temperature is increased markedly by both cobalt and vanadium. Transmission electron microscopy observations reveal that cross slip and cell formation are restricted with increasing solute, which can account for many aspects of yielding and fracture behavior. IRON and other metals of bcc structure slip on many planes of the (111) zone at moderate and elevated temperatures, giving rise to wavy glide. At low temperatures, however, there is a tendency for slip to be restricted to planes of only one or two crystallographic types; in the case of Fe-Si alloys for example, (110) glide predominates, giving rise to planar slip bands."' Restriction of cross slip at low temperatures in iron has been linked by Brown and Ekvall3 to increased strain hardening in the preyield microstrain region, leading to an apparently large temperature dependence of the yield stress. Support for this view has been provided by Lawley and Gaigher4 from a transmission electron microscope study of molybdenum. They concluded that dislocations at lower temperatures, by virtue of their inability to change planes readily, are unable to interact and annihilate, leading to an increase in internal stress and work-hardening capacity. Restriction of cross slip at low temperatures has also been suggested to be an important factor in determining the ductile to brittle transition of single-phase solids, including metals of bcc structure.5 It is pertinent to note that most solute elements tend to raise the ductile to brittle transition temperature of poly crystalline ferrite,6,7 although in some cases, e.g., Fe-Cr7 and Fe-Al,8 the dilute alloys may actually yield at lower stresses than unalloyed iron. It appears, therefore, that solute elements may have an effect analogous to lowering the test temperature with regard to restricting cross glide. Such an effect has indeed been observed in the ionic alloy system KCl-KBr,9 in which bromine atoms, although causing little misfit and consequently little effect on the yield stress of KC1, have a pronounced effect in restricting wavy glide and inducing brittleness. The purpose of the present investigation was to determine the effects of selected solute atoms on the yield stress and fracture behavior of iron, and to elucidate in turn how the slip character was related to these properties. Since it is known that interstitial atoms exert a strong influence on the mechanical behavior of iron, the solute elements chosen for study were vanadium, which reacts strong with interstitials,10 and cobalt, which does not form highly stable interstitial compounds." EXPERIMENTAL PROCEDURE Four-pound ingots of each of the following alloys were vacuum-melted in zirconia crucibles: Fe-1, 5, 10, 25 at. pct Co, and Fe-1, 4, 10, 20 at. pct V. An ingot of unalloyed iron from the same original stock as that used for the alloy was remelted under similar conditions to eliminate variations in interstitial content arising from differing thermal histories. Chemical analyses of the iron, cobalt, and vanadium melt stock are listed in Table I. All ingots were rolled and swaged, commencing at 850°C, to 1/4-in.-diameter bar. The bars were then annealed at 850°C for 1 hr (except that the 10 and 20 pct V alloys were heated for 2 hr) to give a uniform equiaxed grain size of about 0.05 mm. Tensile samples of 0.125 in. diameter by 0.8 in. gage length were utilized for studies of the ductile to brittle transition. A second set of tensile samples were utilized for microstrain experiments in which strain sensitivity of 1 x 10"6 was achieved by a capacitance method.3 Cylindrical compression samples 0.250 in. diameter by 0.4 in. long also were prepared to study the influence of composition on the macroscopic yield stress, and for metallographic analyses of defor-

Jan 1, 1965

By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß'-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,' alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0' phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967