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By Hugo L. Johnson, Robert Wallace

THE Midvale plant of the United States Smelting Refining and Mining Company consists of a flotation mill for concentrating sulphide ores of lead and zinc by differential flotation to produce three separate concentrates, one of lead, one of zinc, and one of iron pyrite; and a lead smelter for smelting ores and concentrates to produce base lead bullion, The plant, including its shops, laboratories, office, railroad yards which serve both mill and smelter, and areas reserved for tailing ponds and slag dumps, covers 646 acres on the right bank of the Jordan River at Midvale, Utah. It is twelve miles south of Salt Lake City and sixteen miles east of the West Mountain mining district at Bingham Canyon from which is drawn a large part of its ore supply. Custom ores are treated as well as the product of Company mines.

Jan 1, 1948

By W. P. Barba

IN THE early summer of 1917, it became evident that the then existing sources of supply of guns and gun forgings were totally inadequate for the enormous and rapidly growing requirements of the Ordnance Department of the Army, so arrangements were made with sixteen makers of other products to take up the manufacture of guns and gun forgings. Nine of these makers were required to produce their own steel from the raw materials and convert it into rough machined gun forgings; the others finished and assembled these forgings into completed guns. In December, 1914, four of these makers of steel and rough gun forgings were instructed to manufacture the same amount of the 6-in. and 9.5-in. guns and howitzers. It, therefore, seemed practical .and profitable to assemble these makers into a small group, together with the officers of the Ordnance Department, and provide standard 'equipment in each of the four works for the production of these two types of guns. The advantages of this cooperation were immediately manifested, and there commenced an interchange of shop practice and a free discussion of facilities and methods that covered not only the equipment but the manufacturing processes.

Jan 1, 1920

By E. J. McCaustland

The behavior of steel after overstrain and at moderate temperatures is fairly well known. It has been made the subject of much investigation, and our knowledge is clear and definite on many points. The ultimate raising of the elastic limit, after moderate overstrain, and the consequent lowering of the ductility, seem to be well established. It is also well understood that the immediate effect of overstrain is to lower the elastic limit, possibly to zero, but that if not interfered with, this limit will subsequently rise higher than before. The " tests after moderate temperature," reported in this paper, were undertaken to verify the above statements for the particular steel under investigation, and also to determine, if possible, the total time required for complete recovery from this state of overstrain. The behavior of overstrained steel at temperatures at or below 32" F. is not so well known. Tests made by Prof. E. G. Coker, at McGill University,' show that steel, overstrained and subjected to cold, will remain in a state of overstrain for an indefinite period. I am not aware of any other published results of tests along this particular line. The effect of time and temperature on the recovery of steel from overstrain was made in 1902-3 the subject of some investigation in the laboratories of the College of Civil Engineering of Cornell University. A general plan was outlined in connection with the regular courses of instruction in testing of materials; but the press of routine work and the demands of the schedules on the time of the students were so great as to presage long delay in the completion of the work. Not much had been accomplished up to 1904-05, when Messrs. E. C.

Jan 1, 1907

By E. Buehler, R. H. Willens

A Hew melting technique has hem adapted to the rapid quenching of- alloys from the liquid state. The inelting method has no limitations on the alloys investigated for there is no reaction with crucible materials and the most refractory materials are easily melted. The vate of heating is so rapid that alloys which have a high vapor pressure constituent can be melted with a minimal loss in material. Several new superconductovs have been discoveved by vapid quenching of lolten alloys. THE rapid quenching of alloys from the liquid state has led to the discovery of many new metastable phases. The methods initially used were limited to alloys which did not react with crucible materials.1,2 There was also the unmentioned limitation in tem- perature. Alloys with melting points much greater than 2000°C could not be melted in the rapid-quench apparatus. Recently, there have been successful attempts to rapidly quench reactive alloys by Moss et at. and Matthias Moss et al. injected powdered material (325 mesh) into a high-temperature plasma and the high-velocity molten droplets impinged on a cooled copper plate. The technique innovated by Matthias was to melt the alloy in an arc furnace and splatter it against a copper plate by means of a high-velocity gas jet aimed at the melt. I) FAST COOLING APPARATUS The creation of a metastable phase in a given alloy system by rapid cooling from the melt is contingent on the quenching rate. Some alloys require very slow rates while other alloys require the ultimate in quenching rate. At the present time, the vertical-gun technique of Duwez and willens' has demonstrated, in practice, the highest quenching rates and thus the best

Jan 1, 1967

By Frank Alfred Fahrenwald

A complete list of the elements as given for 1915 includes 18 that melt above 1,700" C. There does not exist one complete thermal equilibrium diagram for any pair of these 18 elements. Several of these elements have been combined, in relatively small proportions, with metals of lower melting point: e.g., tungsten, molybdenum, and vanadium, in steels, or with nickel and cobalt; but of this refractory group, platinum is the only one that has been extensively studied in this connection. When one considers that, with few exceptions, the industries have made use of alloys to the exclusion of pure metals, it is reasonable to expect that alloys of this refractory group will invade fields in which the pure metals have found little application. The past neglect of this class of metals has, no doubt, been partly due to the rarity of some of them, for even though alloys of very valuable properties should be developed, their cost, unless in exceptional applications, would be prohibitive. There is also a well-founded reluctance to undertake research involving very high temperatures which, in the case of most of these elements, must be accompanied by an inert atmosphere as well. This combination of high temperatures*and control of atmosphere within the heating chamber of any furnace of present design is a difficult problem. It is the purpose of this paper to give results,' of an investigation of one binary series of this group, in which methods were employed that avoided the usual difficulties accompanying high-temperature alloy investigation. , Historical.—The alloys of tungsten and molybdenum have received very little consideration during the past. A review of available literature reveals very little regarding this system, and that which has been recorded seems to be at fault. Mennicke2 writes, "Die bekannteste Verbindung

Jan 1, 1917

By I. L. Dillamore

I. L. Dillamore (University of Birmingham)—The different textures developed in various fcc metals have long awaited satisfactory explanation and it has now become clear that these differences are related to parallel differences in the deformation characteristics of the metals. Liu is correct, therefore, in seeking to account for the observed textures in terms of the flow mechanisms but I believe, for the reasons outlined below, that the particular interpretation of flow mechanisms proposed by Liu is open to substantial objections. By considering the forty-eight possible designations of the twelve octahedral slip systems found in fcc metals as distinct and separate deformation modes, Liu has fallen into the error of assuming that only positive glide dislocations associated with each system are present. In fact both positive and negative dislocations will be present and the only difference between for instance the systems B4 and B4' (in Liu's notation) is that under a stress of given sign the direction of motion of a dislocation is reversed on changing from B4 to B4'. For both orientations positive and negative dislocations will be present. In considering possible dislocation interactions it is, therefore, inadmissible to differentiate between R4 and R4' as Liu does. Liu considers those dislocation interactions which give the biggest reduction in energy to be the most favorable and neglects, on the grounds that they will form strong barriers to slip, interactions between dislocations with perpendicular Burgers vectors. Setting aside interactions between positive and negative dislocations of the same slip system, which must occur regardless of the combination of slip systems chosen, the biggest reduction in energy occurs for the Lomer-Cottrell interaction and it is Lomer-Cottrell barriers which are thought to provide the stronger dislocation obstacles. On the other hand the intersection of dislocations with perpendicular Burgers vectors is thought to be a low-energy process which contributes only a fairly small temperature-dependent part of the total work hardening. On this basis it seems doubtful whether the reduction in energy through possible dislocation interactions provides a reasonable criterion for choosing the operative slip systems. From the point of view of texture development it is unsatisfactory to ignore the slip rotations leading to an end position and to neglect to consider the stability of the chosen end point. It is also unsatisfactory to treat the two stress axes as interchangeable since, if the stress system is idealized as biaxial, one stress is compressive and the other is tensile. For the same reason the rotations of the two stress axes are not made compatible simply by assuming that the same slip directions are responsible for the rotations of the two stress axes. It is, in short, essential to treat the two stress axes as acting together on the same slip systems. Turning to the question of the difference between the copper-type and the brass-type texture, there now remains little doubt that the difference is attributable to differences in stacking-fault energy (y), as noted by Liu, but it is doubtful whether the temperature dependence of the texture in copper and in silver is due to increasing stacking-fault energy with increasing temperature. The results of Swann and Nutting42 cited by Liu were obtained in Cu-A1 alloys and the apparent increase in stacking-fault energy on raising the temperature may be influenced by short-range ordering. In pure metals such effects are absent and the only data available on the variation of y with temperature are those of Buhler et a1.43 for silver. They report a minimum at 200°C which does not fit the hypothesis put forward by Liu. It is much more likely that thermal activation of cross slip is important in determining which texture develops, as proposed by Dillamore and tors. These workers have proposed an explanation for the differences in observed texture among the fcc metals and the pole figures predicted consist of an orientation spread which is in better agreement with observation than the limited number of discrete orientations suggested by Liu. The theory of Dillamore and Roberts is also able to account for the differences between aluminum and copper which Liu still leaves unexplained. Y. C. Liu (author's veply)—The writer appreciates the interest of Dr. Dillamore, but must discuss some of his comments in order to avoid cross purposes. The phrase, "forty-eight slip systems," which appeared twice in the text—in the caption of Fig. 1 and the first paragraph in the Discussion—might unfortunately have led Dr. Dillamore to disagree

Jan 1, 1965

By Ernst F. Eurich

(Cleveland Meeting, October, 1912.) ALEXANDER PARKES patented in England in 1851-52-53 a process for desilvering lead by means of zinc, making use of the greater affinity of silver for zinc than for lead, discovered by Karsten in 1842. The efforts in England to develop it commercially were not particularly successful, nor was the attempted introduction into the United States. This last was not surprising, as it was about the beginning of our Civil War, and at that period there was very little lead-bullion produced in the united States and there was no field for the process here. There was at that time on Staten Island an establishment that pattisonized lead, probably from Rossie, N. Y., and Chester, Pa., and possibly some Spanish lead, but the production of lead-bullion in the Far West had not yet begun. In 1864, Edward Balbach, of Newark, N. J., patented in this country a process for desilvering lead by means of zinc, and in 1867 Edward Balbach, Jr., patented a " movable black-lead retort with a neck, placed in a furnace," for the purpose of distilling the alloy of zinc, lead, and the precious metals. A brief comparison of the Parkes and the Balbach processes is interesting. The Parkes process as practiced in England consisted in stirring into silver-bearing lead, melted in a kettle, from 1 to 2 per cent. of zinc, cooling, skimming the alloy of lead, zinc, and silver that rose to the surface, liquating it in an iron retort, distilling the residual rich alloy in fire-clay retorts, thus regaining the zinc, and refining the desilvered lead at a low heat in a shallow cast-iron pan that formed the hearth of a reverberatory furnace. If the lead was too impure, it was first softened * Presented also at the Joint Meeting of the Institute and Section IIIa, Metal¬lurgy and Mining, of the Eighth International Congress of Applied Chemistry, New York, September, 1919, and here published by mutual agreement.

Dec 1, 1912

By E. I. Larsen, F. R. Hensel

According to statements by Guertler1 Smith and Hamilton were the first to study the copper-titanium alloys, but owing to the presence of large amounts of impurities their data are inconclusive. M. A. Hunter and I. W. Bacon later investigated the electrical conductivity and the temperature coefficients at room temperature. The present writers reported their results2 in November, 1930. Recently Kroll published data on copper-titanium alloys3 which agree closely with those obtained by the authors. Material Tested The titanium used was in the form of square sintered rods, the analysis of which runs as follows: titanium, 95.4 per cent; silicon, 0.7; iron,l.8; aluminum, 1.4; copper, 0.1; manganese, 0.05. The ingots were prepared in a high-frequency induction furnace in air atmosphere. Their analyses are given in Table 1. Up to 5 per cent titanium the alloys could be forged. Above that amount they were red short and broke up easily. Owing to their rapid absorption of nitrogen and oxygen from the air, the alloys with the higher amounts of titanium tend to form surface films which greatly increase the casting difficulties, especially when small masses of metal are handled. It was, however, possible to prepare sound ingots up to 25 per cent titanium. Thermal and X-ray Investigation The cooling curves of some of the alloys are plotted in Fig. 1, and R tentative diagram constructed from these data is given in Fig. 2. From this it is evident that the solid solubility of copper for titanium is approxi-mately 4 to 5 weight per cent titanium at 878" C., which is the eutectic temperature. The melting point of copper is lowered gradually by adding

Jan 1, 1932

By S. A., Taylor

IT is very difficult to arrive at exact figures for the cost of maintaining excess capacity of coal mines, but we can approximate the various items. To do this, I will take the Pittsburgh district of Pennsylvania and the other districts can be compared to this one. I believe we can take the depreciation item of plant ac- count as a whole and discount it over a period of 20 years; while this is high for some items it is low for others and I believe it is not far from a safe basis. This equals 5 per cent per year, and this depreciation will take place about as rapidly when not in use as when in operation. A fair value in the Pittsburgh district to- day for plant and houses is close to $4 per ton per annum. At 5 per cent this will equal 20 cents per ton per year. The item of keeping the mine in condition, free from water, etc., will be close to an average of 2y2 cents per ton per annum.

Jan 1, 1928

By Tilden Cummings

The extractive mineral industries share a number of common characteristics and basic problems which are completely different from those associated with manufacturing and mercantile operations. These industries now supply about 95% of the inanimate energy consumed in this country, and share with agriculture in providing virtually all of our basic raw materials. Mineral producers, like farmers, are subject to the economic hazards of fluctuating markets and prices. Unlike farmers, however, they cannot renew the productivity of the earth, but must seek continually for new sources of supply. The necessity for exploration and development of new reserves, to replace those used up by production, introduces additional factors of economic risk. These operations require the expenditure of large amounts of capital, often well in advance of any assurance of profitability. Commercial banks that understand these special problems can provide a variety of constructive financial services to the mineral industries. The history of cooperation between banks and mining enterprises has yet to be written, but there is every indication that it would encompass a period of hundreds of years. Records refer to depository and lending services by the early European private bankers involving precious metals and jewels. Many of the exploratory voyages to the Far East and the New World were organized with the financial backing of wealthy syndicates, some of which also provided banking services, in the hope of finding new sources of gold and other precious minerals. In the United States many large banks are closely identified with the development of some of the larger mineral deposits such as the Mesabi Range and the gold fields of California.

Jan 5, 1965

By J. W. Ristori, V. R. Garfias

ONE of the most serious problems now confronting Gel- many-and one that will affect Italy even more seriously if she goes to war against England and France -is that of supplying her navy, mechanized army, and air force as well as her industrial and other needs with the necessary and related products. This problem, serious even now, will become vital should hostilities on a large scale develop.

Jan 1, 1939

DESPITE the very small number of engineers who can get away from their tasks to New York, a point so far from the Mid-Continent and Cali-fornia oil fields, where the real important, engineering progress in the industry is being made, the attendance was remarkably good, and it was generally remarked that all the sessions were "snappy," and there was no drag. This was largely because, under instructions from the chairman, very few papers were permitted to be read, and the "high lights" of each paper were pre-sented orally as an introduction to the large and varied discussions, many of which were prepared in advance. The round table discussion on petroleum engineering research problems, conducted by W. E. Wrather, proved a greater success than was anticipated, considering the difficulty in getting many of the men to discuss such problems. There has been no crystallization of opinion heretofore of what are important engineering research problems, as distinguished from pure science problems, and a digest of the discussion will be made available so as to present the results obtained. It is hoped that further round table discussions, as well as committee work, in the meantime summarizing problems appear-ing in papers published the last two to three years, will enable the oil industry to determine intelligently which of the problems are most important for immediate attack. The roundtable discussion on petroleum engineering educational problems, conducted by H. C. George of the University of Oklahoma, was equally fruitful, and since managers of companies, consulting engineers, and pro-fessors cooperated in these sessions, a cross-section of their opinions on improving the curricula for training the large number of petroleum engineers, which the industry can absorb in-the next few years, was obtained.

Jan 3, 1927

THE research and policy committee of the Committee for Economic Development, a non-profit research organization composed of leaders in industry and the professions, including such prominent figures as Dwight D. Eisenhower, Paul G. Hoffman, and Charles E. Wilson, recently published a report entitled "How to Raise Real Wages." Since its founding in 1942 the CED has initiated many objective studies on matters of national economic policy, and has gained a fair measure of prestige from its activities. The CED's latest report cites the more than three- fold rise in real wages in the United States in the past 50 years and attributes the accompanying improvement in the standard of living to the great in- crease in production per man hour. The report states that in order for production to continue rising in the future with the attendant increase in real wages four basic conditions must be manifest: (1) better methods, (2) more capital, (3) better training of workers, and (4) better management. The report cautions that although prospects for increases in output per man hour are good "it is desirable that steps be taken to encourage such a rise."

Jan 8, 1950

By M. Deighton, R. N. Parkins

The metals Cd, ,Wg-, Sn, TI, Zn, and Zr reach a peak hardness after a criticfir1 deformation by rolling- and then soften with fwther rolling-, thereby exhibiting wovk softening. Optical metallography on Cd, Mg, and Zn shows that work softening is accompanied by a change in grain size occurring during deformation. The creep of zinc from -1l° to +60°C at stresses in the range of 7.9 to 17.3 kg per sq mm is given by € = e0 -t- Bt + Kt +at6. The third and second rate constcints are related by the equation a = K~ K6 and their stress and temperature dependence can be represented by the equations K = A, . exp - (u, - Bu)/kT. A model based upon the stress activated glide of sub-boundaries is proposed which qualitatively accounts for the metallog-raphic observations. Expressions, which are in reasonable quantitative agreement with the ex-pe~inzental observations, are derived for the creep of zinc. THE term "work softening" has been used previously by Polakowski1 and by Cottrell and stokes2 to describe phenomena where further strain of a deformed material leads to a decrease in flow stress. In both cases, however, the conditions were changed for the second straining. Here, the term "work softening" is intended to refer to a decrease in flow stress after continued straining in the same direction at the same temperature: work softening is the antithesis of "work hardening". Work softening of zinc was reported by chadwick3 and in discussion of that paper Jenkins4 indicated that cadmium also work softens. More recently work softening has been reported5 in two magnesium alloys, -99.5 pct Mg. Chadwick found that the hardness, 0.2 pct Proof Stress and the UTS of electrolytic zinc all increased with progressive cold reductions up to 30 pct and then progressively decreased with further rolling. Gay and Kelly6 used a back-reflection X-ray technique to study the effect of cold rolling zinc and found that although deformations greater than 2 to 5 pct reduction in thickness produced some recrystallized grains, deformations greater than 40 pct caused com-plete spontaneous recrystallization. At deformations greater than 60 pct the material was found to consist solely of recrystallized grains, -20 pm diam, the size of which decreased with increasing reduction and was much less than the initial grain size of the annealed material (-300 pm diam). Similar results were also reported for cadmium, tin, and lead.6 Gay, Hirsch, and Kelly' suggest that these experiments indicate recrys-tallization takes place when the dislocation density exceeds a certain value. However, no measurements of MATERIALS AND EXPERIMENTAL PROCEDURE The purity of the metals used in this work is indicated by the following figures: Zn (99.99); Cd (99.94); Mg (99.95); T1 (99.99). The zirconium was iodide crys tal bar with a probable purity of about 98 pct. The metals were obtained in the form of 0.25 in. thick strip or 0.425 in. diam rod by various fabrication methods and then annealed to ensure complete re-crystallization. Hardness-deformation curves were obtained at room temperature by rolling 4 in. thick strip under conditions which left a surface adequate for diamond pyramid hardness tests immediately after rolling. The hardness was taken as the niean of five impressions made using a 5 kg load and the time elapsing between rolling and making the last impression never exceeded 5 min. The zinc specimens for creep testing were from 3 by 3 by 4 in. cast slabs which were rolled to 0.10 in. thickness starting at 350°C and finishing cold. The resulting strip was cut into pieces 1 in. wide and annealed in batches. With suitable choices of annealing temperature between 100" arid 400°C five different grain sizes varying from 4.54 x 10' to 3.03 x l05 grains per sq cm (530 to 20 um diam) were obtained. Creep tests were done in compression using a sub-press, based on a design after Ford,8 in which the strip is compressed between dies 0.100 in. wide under conditions of plane strain. Since there is no lateral spread of the material, the area of contact between the dies and strip remains constant throughout the test and the application of a constant load, using the load maintaining device of a hydraulic testing machine, resulted in a constant stress. Covering the dies with strips of P.T.F.E. reduced frictional effects to a minimum. The creep strain was obtained by measuring the travel of the crosshead of the testing machine to a sensitivity of 0.1 pct reduction in thickness. The complete subpress assembly was contained in a steel box and for tests above the ambient this was filled with liquid paraffin and heated electrically. Temperatures below the ambient were obtained with a cooling mixture of acetone and solid carbon dioxide in the box. The liquids were stirred and the temperature of the specimen, which was controlled to ±0.5"C dur-ing a test, was measured by a thermocouple placed near the dies. Compression testing of cylindrical specimens was also carried out in the subpress using hardened flat discs separated from the test material by P.T.F.E. sheets which obviated barrelling of the specimens. Various initial strain rates were supplied by the hydraulic testing machine, and the deformation was measured by a clock dial gage resting on the cross-

Jan 1, 1970

[Appalachian Petroleum Section: Chairman: Robert H. Edele, 1st V.C.: Robert Vutech, 2nd V.C.: Robert Tullis, Sec.-Treas.: Frederick T. Solomon. Meets last Tuesday of each month in Charleston, W. Va. Balcones Section: Chairman: Dr. Frank W. Jessen, 1st V.C.: Gilbert M. Andreen, 2nd V.C.: Lloyd N. Johnson, Seo.-Treas.: W. C. Vercellino. Big Horn Basin Subsection: Chairman: B. E. Yester, 1st V.C.: Robert J. Woodhall, 2nd V.C.: Herbert A. Koch, Secretary: Dean Costello, Treasurer: Thomas W. DeLong. Meets 2nd Wednesday; alternating between Cody and Worland. Billings Petroleum Section: Chairman: George O. Ellis, 1st V. C.: Robert L. Spottswood, 2nd V. C.: Robert M. Watkins, Sec-Treas.: Joseph H. Bato. Meets 5:30 p.m., 3rd Tuesday at Billings Press Club.]

Jan 1, 1961

By J. F. Abel, F. T. Lee

Subsidence is controlled by a complex com¬bination of mining and geologic factors. For example, a compilation of worldwide data shows that, as the percentage of shale in the overlying rock mass decreases and the amount of sandstone increases, the angle of draw (and the area affected by subsidence) decreases. Limestone in the over¬burden appears to cause a more than twofold decrease in the angle of draw compared to a like amount of sandstone. Increased amounts of sandstone were accompanied by a greater surface subsidence relative to the mining height. The total thickness of overburden did not appear to influence the subsidence magnitude above super-critical panels. The greater the thickness extracted, the smaller percentage of that thickness shows up at the surface as subsidence. The greater the percent of the seam extracted, the greater the subsidence reaching the surface. The maximum subsidence above room-and-pillar panels de¬pends on the pillar height and minimum width as well as the other factors listed.

Jan 1, 1984

By R. F. Domagala, D. J. McPherson

Iodide zirconium was combined with calculated amounts of ZrO2 or master alloys and arc-melted. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat treated specimens permitted construction of the binary phase diagram from zirconium to ZrO2. Oxygen additions to zirconium raise the transformation temperature as well as the melting point. Features of the diagram include the peritectic formation of beta, the formation of alpha directly from the melt, an intermediate phase ZrOB with a' range of homogeneity, and a eutectic between alpha and Zr02. PHASE relationships in the Zr-0 system were determined in the range 0 to 66. 7 atomic pct 0 (ZrO,). Arc-melted alloys were annealed at temperature levels between 600" and 2000°C. Determination of the phase boundaries was accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to determine solidus curves, and X-ray diffraction work was employed to study the lattice parameters of the a solid solution and the phase ZrO,. Experimental Procedures Westinghouse "Grade 1" iodide zirconium crystal bar (approximately 99.8 pct pure) was employed for the investigation. This material is substantially free of the impurity inclusions characteristic of most zirconium metal. Previous work has shown it to be the most satisfactory grade for phase diagram studies. The zirconium crystal bar, as-received, was coated with corrosion product from autoclave tests by which its grade designation is determined. The bars were sand blasted lightly, pickled for 1 min in a 20 pct HN0,-5 pct HF aqueous solution, rinsed in water and acetone, and dried. The bars were rolled to about 1/32 in. strip, cut into 10 in. lengths, and pickled again. The material was sheared to approximately Y4 in. squares, cleaned with acetone, and stored for use. Two pounds of specially prepared "chemically pure," and 100 grams of spectrographic grade ZrO, were obtained for the preparation of alloys. The "Specpure" ZrO, was obtained from Johnson, Mat-they Co.. Ltd.. and Titanium Alloy Manufacturing Div. of National Lead Co. supplied the other grade of oxide. The "chemically pure" material (henceforth referred to as C.P. ZrO,) was used for the preparation of all alloys employed in the determination of phase relationships. A limited number of alloys were prepared with the "Specpure" oxide to recheck certain phase boundaries. Analyses of the two grades of oxide are given in Table I. The C.P. ZrOI was received in powder form, not suitable for arc melting. Therefore, this material was compressed to wafers 1 in. in diameter and about Vn in. thick. These were segmented and stored for use. The "Specpure" material, in the form of small granules, was suitable for use in the as-received condition. A nonconsumable electrode arc-melting furnace was used to prepare alloys. A water-cooled copper crucible and tungsten-tipped electrode were employed. The material was placed in the crucible and rapidly melted under a protective atmosphere of helium gas by striking the arc on a tungsten stud and directing it upon the charge material. Details of operation, including drawings of this type furnace, have been published.'

Jan 1, 1955

By Rollin E. Hook, Attwell M. Adair

The yield and fracture behavior of recrystallized chromiztm have been studied in order to gain an understanding of the recrystallization embrittlement-rheotropic recovery phenomenon. The duc tile-brittle tensile transition temperature of recrystallized chromium was found to vary from 225 ° to -80°C as the ratio of specimen diameter/mean planar grain size decreased. The applicability of this observation to other bcc metals is briefly discussed. Brittle fracture in recrystallized chromium was found to be initiated predominately from intercrystalline rupture nuclei. Single crystals exhibit a high degree of ductility at 23 "C. The experimental data indicate that grain boundaries play a significant part in the yield and fracture behavim. Pres training significantly reduces the transition temperature, and high temperature aging does not result in re-embrittle-ment until complete recovery or re crystallization occurs. SEVERAL theories have been used to explain the recrystallization embrittlement-rheotropic recovery phenomenon in chromium. Wain, Henderson, and ohnstone' propose a Cottrell dislocation locking mechanism due to nitrogen, and Weaver and Gross and weaver 3 propose a strain-induced precipitation mechanism involving a chromium nitride precipitate. The researches of many investigators seem to leave little doubt that brittleness in chromium is promoted by interstitial impurities. Smith and seybolt4 have shown that the ductile-brittle transition temperature is lowered as the interstitial content is reduced. weaver3 provides evidence for a 150°C reduction in the tensile transition temperature as the nitrogen content is reduced from 20 to 5 ppm. Maykuth and affee' have suggested that the amount and orientation of grain boundary impurities may be responsible for the brittle nature of recrystallized chromium. This suggestion was based on their findings that wrought iodide chromium possessing a fiberous grain structure is ductile in tension at room temperature while a recrystallized grain structure is completely brittle. Previous investigations have not studied this phenomenon sufficiently to determine its cause. Perhaps this has been largely due to previous experimental findings that brittle fracture observed in chromium has been almost entirely transgranular.' In addition McNeil and imb,' who investigated coarse-grained as-cast chromium, describe the point of initiation of fracture as cleavage, close to the (100) plane, near or at grain bound-daries, or at included particles or voids. However, Hook, Adair, and ipsitt found that fracture in coarse-grained recrystallized chromium is initiated by intergranular rupture and then propagates nearly entirely by cleavage. This result, together with their finding that room temperature ductility in bending is observed for single crystals and coarse-grained polycrystalline specimens for which the number of grains through the specimen diameter is small, suggests that grain boundaries may play an important role in the brittle behavior of chromium. The recrystallization embrittlement problem can be resolved into two questions. These are, whether the controlling mechanism is predominately one of crack initiation or crack propagation, and whether brittle fracture is initiated predominately by slip or twin induced intergranular rupture or by cleavage. The following research was designed to study the role of grain boundaries on the brittle fracture of chromium in an effort to resolve these questions. EXPERIMENTAL PROCEDURES, RESULTS, AND DISCUSSION General Procedure. All tensile specimens (except 0.04 in. diam wires) were prepared from 1/4 in. diam swaged rod fabricated from one ingot. Details of fabrication are given elewhere. The results of impurity analysis for the swaged rod and for the

Jan 1, 1963

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By NEWTON B. KNOX

CHILEAN mining in the public mind is rightly associated with copper. Chuquicamata with its great hill of copper-bearing granodiorite as well as Sewell and Potrerillos with mineralized volcanic necks together can supply a good proportion of the world's normal necessities of that metal. Chile is an extremely long and narrow country, averaging only 109 miles wide. Its eastern frontier is the Andes and it is on the western slopes of these mountains that the great copper deposits have been discovered. West of the Andes a great longitudinal depres sion has permitted accumulation of nitrates and other soluble salts in the arid north; in the north center it is hidden by a series of cross ranges, but in the center a moderate rainfall makes it the country's most important agricultural region. In the south this depression is drowned and gives rise to a series of straits and fiords. This enormous cleft in the earth's crust is separated from the sea by a coast range of moderate elevation which in the south is represented by a series of islands and mushroom-shaped peninsulas

Jan 1, 1945