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By F. H. Wilson, E. W. Palmer

The solid solubility of iron in 2 to 10 pct cupro-nickels increases with temperature and nickel content. Property changes accompanying various heat treatments indicate typical precipitation hardening behavior. Iron content also affects softening temperature and sub-scale formation. These factors, as well as impingement corrosion resistance, influence the optimum iron content of commercial alloys. FOR many years Cu-Ni alloys have been used extensively in the form of tubes, pipes, and plates for the construction of salt-water lines and surface condensers on shipboard and in tidewater power stations. The 30 pct Ni alloy has been considered more resistant to rapidly flowing sea water than alloys of lower nickel content, and has been standard on ships of the U. S. Navy. Some ten years ago, the still better corrosion resistance obtained by modifying the 30 pct Ni alloy with approximately 0.5 pct Fe was recognized, and the iron-bearing alloy rapidly superseded the plain alloy as the standard material for severe service. In 1945, Tracy and Hungerford1 published a study of the effect of iron on the corrosion of various cupro-nickels in sea-salt solutions, and their data indicated that the 10 pct Ni alloy containing about 0.75 pct Fe was equivalent to the 30 pct Ni alloy containing 0.5 pct Fe. This was confirmed by LaQue in discussion of the above paper, and by results in an experimental condenser set up at the Kure Beach marine test station of The International Nickel Co., reported by Freeman and Tracy.' The 10 pct Ni iron-bearing alloy is now being very widely used in applications where the 30 pct Ni iron-bearing alloy was formerly considered standard. While this "substitution" has undoubtedly been stimulated by the present extreme shortage of nickel, it must be emphasized that it involves no loss of service performance, and would have occurred anyway in the course of time, for economic reasons. In view of the increasing use of the 10 pct alloy, it seems desirable to make generally available the results of several investigations of Cu-Ni-Fe alloys carried out in the Metallurgical Research Laboratory of The American Brass Co. in recent years. The present paper, deals with the constitution of these alloys in the copper-rich corner of the system, and with the variations in hardness and tensile properties resulting from the heat treatment of alloys containing various amounts of iron. Most of this work is concerned with alloys containing 10 pct Ni. With over about 0.75 pct fe, the 10 pct Ni alloy is suscep- Alloys Several series of cupro-nickel alloys containing iron were used in these investigations. Most of them were prepared in the laboratory, but two samples of commercially fabricated alloys were included. Series A—Nominally 2 and 5 pct Ni, each with 0 to 1.5 pct Fe. Series B—Nominally 10 pct Ni with 0.1 to 0.4 pct Fe. Series C—Nominally 1.0 pct Ni with 0 to 2 pct Fe. Series D—Nominally 10 pct Ni with 3 to 5 pct Fe. Series E—Nominally 10 pct Ni with 1 and 1.5 pct Fe.

Jan 1, 1953

By Thomas Henderson

Strategically, intermaterials competition is important to companies involved in raw materials extraction, smelting, refining or other processing, semi-finished and finished goods fabrication, and end-use consumers. In other words, just about every company involved in manufacturing. The array of materials covered by other papers in this session is testimony to the subject's breadth. In trying to provide an over- view of such a broad topic, the purpose has been to relate some of the common characteristics of the markets, economics and technology of raw materials, and to describe some of the ways in which Intermaterials competition impacts the markets, economics and technology of raw materials.

Jan 1, 1982

By George C. Heikes

ALTHOUGH the application of light metals in war materiel increased during the year, based on the number of uses, the trend in aluminum and magnesium production in 1944 was characterized by a sharp decline in the production of both metals accompanied by a further accumulation of large Government reserve stocks. Several primary reduction plants were curtailed to prevent building excessive inventories. By the end of the year, however, a lively revival of war production took place when resistance stiffened on the western front in Europe. Production of primary aluminum ingot was reduced from over 90,000 tons per month at the start of the year to 45.000 tons per month by the end of the year.

Jan 1, 1945

By R. S. Shoemaker, F. W. McQuiston

CARLIN GOLD MINING COMPANY 1974 Operating Data to October MINE LOCATION: 40 miles from Elko, Nevada ORE DESCRIPTION: Gold with minor amounts of mercury occurring in siltstone and carboniferous limey shales. TYPE OF MINE: Open pit ORE HAULAGE TO MILL: By trucks up to a distance of 12 mi1es MILLING CAPACITY: 2500 tons per day ORE GRADE: 0.20 oz per ton oxide ore 0.25 oz per ton carbon type ore PRODUCTS: Gold bullion 993 fineness, by product quicksilver RECOVERIES: Oxide ore 887'0 Carbon ore 83% POWER FOR GRINDING: 7 Kwh/T POWER, other than grinding: 14 Kwh/T WATER SUPPLY: Pumped from wells 2- 112 miles through 13,000 ft of 8" buried pipe 6 ft underground. Consumption 0.60 tons of new water per ton of mill feed. TAILINGS: By 10" woodstave pipe a distance of 2500 ft to mine waste filled dam. RUNNING TIME: 10 ft x 10 ft mill on oxide ore, 98% 7 ft x 8 ft mill on carbon ore, 937'0 Principal causes of lost time, power outages and problems of feeding gaseous chlorine to carbon ore agitators. LABOR, TONSIMAN SHIFT: See detailed data sheet ILL BUILDING DESCRIPTION: Framed structural steel with sandwich type walls of marine plywood, then packaged pre - fabricated insulation and outer sheeting of galvanized corrugated steel.

Jan 1, 1975

By J. H. Brophy, S. J. Michalik

A constitution diagram for the system Mo-Ir has been determined. The maximum solubility of iridium in molybdenum is 16 at. pct at 2110ºC and decreases to less than 5 at. pct at 1500°C. The solubility of molybdenum in iridium is 22 at. pct. Three intermediate phases appear in the system: 8 MoJr, having the p-tungsten structure; a phase, a cornplex tetragonal structure; and the hcp ? phase. Metallography, melting point determinations, X-ray diffraction and fluorescence, and electron micro-probe unalyses were employed in establishing the diagram. PREVIOUS to the present investigation, the intermediate phases in the Mo-Ir system were identified, but no detailed account of the phase diagram has been reported in the literature. Raub1 investigated alloys of Mo-Ir over an extensive range of composition between the temperatures of 800º and 1600°C. The in-termetallic compound MosIr was found to exist with nearly pure molybdenum, as the solubility of iridium in molybdenum was not detectable parametrically in this temperature range. MO3Ir was found to be iso-morphic with a ß-tungsten type structure, having a parameter of 4.959Å. An intermediate hcp phase, designated as the ? phase, ranged in composition from 52 to 78.5 at. pct at 800ºC, and from 41 to 78.5 at. pct Ir at 1200°C. Parameters noted for the ? phase were as follows: at 42.7 at. pct Ir, a = 2.771i0, c = 4.4366, c/a = 1.601; at 78.5 at. pct Ir, a = 2.736A, c = 4.378A, c/a = 1.600. Molybdenum was found to be soluble in iridium up to 16.5 at. pct Mo (83.5 at. pct Irj, with the parameter of iridium increasing to 3.845A at the solubility limit. Knapton,2 who investigated alloys between 15 and 85 at. pct Ir, essentially agreed with Raub's data, but, in addition, found a a phase in as-melted alloys near 25 at. pcto Ir. The oaphase lattice parameters were a = 9.64Å, c = 4.96Å, c/a = 0.515. The a phase was replaced by the 8 -tungsten phase on annealing at 1600°C. Knapton concluded that the a was stable only at elevated temperatures, and placed the composition of the a phase at approximately 30 at. pct Ir. The intermetallic compound Mo3Ir, with a lattice parameter of 4.965A, was included among the 8-tungsten structures reported by ~eller.' Matthias and Corenzwit,4 and Bucke15 studied the superconducting nature of MosIr, and reported a superconducting transition temperature of 8.$K. The present investigation describes the phase relationships in the Mo-Ir alloy system determined by melting point measurements, X-ray diffraction and fluorescence, and metallography. EXPERIMENTAL PROCEDURES Alloys for the determination of the phase diagram were prepared from powders. Commercial 99.9 pct Mo from Fansteel Metallurgical Corp. and 99.9 pct Ir powder from J. Bishop and Co. Platinum Works were used. The powders were weighed to nominal compositions, mixed, and then pressed, without binder, into compacts weighing 4 to 6 g. These were presintered in uacuo between 1200' and 1400°C for 1 hr, to reduce the degree of spattering during subsequent arc-melting. The compacts were arc-melted in a nonconsumable tungsten electrode furnace six times on alternate sides on a water-cooled copper hearth in an atmosphere of zirconium-getter ed argon at 500 mm of mercury pressure. In almost all cases, this procedure yielded buttons of satisfactory homogeneity. The composition of all melted buttons were confirmed by X-ray fluorescent analysis using the experimentally determined ratio of the iridium La1 line intensity to that of the molybdenum Ka1 line as a function of composition. In this determination four alloys analyzed by wet chemical methods were used as standards. An uncertainty range of ±1 at. pct has been attributed to all indicated compositions. All heat treatments and solidus measurements were carried out in tantalum resistance heating elements in vacuum conditions of 10-4 to 10-5 mm of mercury. A detailed account of this procedure has been reported by Schwarzkopf and Brophy.8 In the heat treatment and solidus measurements of iridium-rich alloys (50 at. pct Ir or greater), a tungsten lining was inserted into the tantalum resistance heating element because of a eutectic reaction which occurs between iridium and tantalum at 1948ºc.7 Heat treatments and solidus measurements carried out at compositions less than 40 at. pct Ir both with and without tungsten linings within the resistance

Jan 1, 1963

By Robert Ammon

The milling practice at Mascot, at present, consists of dry crushing to % in., jigging, fine grinding, and flotation. The ore arrives at the mill from two mines, No. 1 mine shaft being located in the mill proper, and No. 2 mine shaft being situated about 2000 ft. east of the mill. No. 2 mine is served by a coarse-crushing plant and aerial tramway to the mill bins. In jigging the No. 2 mine ore, 50 per cent. of the mill feed is rejected by the jigs as a jig tailing ranging from 5/8 in. to 10 mesh; the balance of this ore, after removing a jig concentrate, is ground to flotation feed. In jigging No. 1 mine ore, approximately 80 per cent. of the mill feed is rejected as a coarse jig tailing, and the balance is ground to flotation feed without the removal of a jig concentrate. The difference in the treatment is due to the fact that No. 2 mine ore carries a higher content of zinc than that from No. 1 mine. Of the total concentrates produced, 30 per cent. is made on jigs and 70 per cent. by flotation. At present, 1350 tons of No. 2 ore and 800 tons of No. 1 ore are treated each 24 hours. The recoveries for a typical week are as follows: Heads.......................... 3.55 Jig concentrates................ 61.30 Jig tails......................... 0.80 Flotation concentrates........... 60.60 Flotation tails................... 0.09 Extraction..................... 86.50 The associated minerals are a straw-colored sphalerite, dolomite, calcite, pyrite, quartz, and a small amount of greenockite, which occurs as a stain and sometimes small crystals along with sphalerite, but is comparatively rare. Pyrite is present in small quantities, usually less than 0.5 per cent.; quartz occurs in bands a few inches thick. A complete analysis of the ore is as follows: PEr Cent. Per Cent. Calcium carbonate.............. 48.11 Zinc sulfide.................... 5.43 Magnesium carbonate........... 35.36 Cadmium sulfide............... Nil Silica.......................... 8.73 Lead sulfide................... Nil Alumina....................... 1.04 Iron oxide...................... 1.33 Total....................... 100.00

Jan 1, 1925

By Louis W. Huber

The Liberty tunnels extend through a very steep hill in Pittsburgh (locally called Mount Washington) for a distance of slightly over a mile. The two tunnels parallel each other and are 59 ft. apart, center to center (Fig. 1) They are for vehicular traffic, and in each there is ample space for two lines of vehicles. Northbound traffic, toward downtown Pitts- burgh, is confined to the east tunnel and southbound traffic to the west tunnel. The South Hills residential district is separated from downtown Pittsburgh by Mount Washington, a steeply rising escarpment south of and adjacent to the Monongahela River. The Mount Washington district immediately south of the Monongahela River has been reached, for many

Jan 1, 1927

By Hans Von Höfer

Apart from the hypothesis of a cosmic origin (which failed of acceptance because it was not adequately supported by facts), the only important controversy concerning the origin of petroleum has been, for a long time, between the advocates of inorganic and of organic origin respectively. Each of these theories has had a long history of development, and is still being perfected, under the influence of two causes: (1) the increasingly extensive and thorough study of the oil-fields (of which new examples are periodically discovered and opened); and (2) the progress of synthetic experiments devoted to this question. Moreover, the advance in our physical and chemical knowledge of the properties of this peculiar natural product has necessarily modified all criticism of conflicting views. I. The Hypothesis of Inorganic Origin That the nation of an inorganic origin of petroleum, first set forth by Berthelot in 1866, and afterward ingeniously developed and formulated by Mendelejeff, should thus have proceeded chiefly from chemists, is quite natural; for the question was one of possible chemical processes in the earth's interior, and of imagined chemical reactions to be verified by ex-periment. Hypotheses of this kind were suggested by many chemists, of whom two, P. Sabatier and J. H. Senderens, may be specially named by reason of their highly interesting chemical experiments. Among geologists, Mendelejeff's hypothesis was received at first with much interest and favor; for it rested on the assumption of a central terrestrial mass of iron carbide, and the geologists had good reasons for adopting that assumption. Yet comparatively few of them attempted to furnish geological proofs of the hypothesis: the majority either silently believed in it, or for one or another reason rejected it altogether. An apparently weighty support of Mendelejeff's view was furnished by the American, G. F. Becker, who found in the oil-regions of the United States important and abnormal disturbances of the isogons of terrestrial magnetism, and inferred that in these regions the central iron mass must

Jan 1, 1915

By Richard H. Jahns

Gem materials, comprising those minerals and closely allied natural substances used for personal adornment, for the fashioning of ornamental objects, or for other decorative purposes, have been valued in human commerce for thousands of years. Amber, jet, natural glasses, and at least 15 mineral species were sought and used by primitive man, and most of the materials in common use today were known well before the time of Christ. Their variety is remarkably great, and the traceable relationships among their respective sources, modes of occurrence, properties, and histories of production, preparation, and valuation are extremely complex. Their uses have been affected by numerous shifts in fashion, and from time to time by superstition, by decrees of church and state, by personal interpretations of religious significance, and by various presumptions concerning medicinal value and influence on human behavior (Ball, 1935, 1950; Kunz, 1913; Pogue, 1915; Whitlock, 1946). Thanks to their durability, portability, and relative scarcity, some gem stones have been employed as media of exchange, and the investment value of the more precious stones has long been recognized and exploited, especially in Asiatic and European countries. Demands for gem materials have stimulated trade among various peoples for centuries, and they also were responsible for much early geographic exploration. During more recent times they have prompted numerous geological studies and a considerable amount of research on the growth and properties of crystals. Apart from decorative uses, some naturally occurring gem materials also are employed directly in numerous fields of industry. Substances that are manufactured for gem or industrial uses are termed synthetic gem materials; most of these correspond in composition and crystal structure to certain minerals found in nature. Imitation materials are those whose use is based upon their resemblance to substances of different composition and greater intrinsic value. Gem stone is a designation commonly restricted to those materials suitable for personal adornment, and the complementary term ornamental stone is applied to the remaining materials not used industrially. This distinction is arbitrary and somewhat inconsistent, owing to numerous geographic differences and historical shifts in end uses. Further, there is a complete gradation between the category of ornamental stones and that of dimension stone. Substances that lose their identity in use are excluded from the gem category; thus a transparent crystal of beryl would not be classified as a gem stone if it were processed as a source of beryllium metal. The adjectives precious and semiprecious have been employed as a means for distinguishing different gem materials on the basis of recognized value. Diamond, emerald, ruby, and sapphire consistently have been regarded as precious stones, and in cut form they commonly are referred to as the noble gems. Opal, pearl, turquoise, and chrysoberyl also have been classed as precious at various times. In recent years, however, it has been increasingly recognized that no satisfactory distinction can be based upon assessed value or any group of specific properties, and now all gem stones normally are referred to as precious. Indeed, the tendency is to extend this term to include many of the so-called ornamental stones, and the designation semiprecious has been essentially discontinued. Unlike most mineral commodities of economic value, gem materials are little altered in processing for end uses. Some stones are used in essentially their natural form, and most are reshaped and polished without significant changes in their fundamental properties. Thus the preparation of gem and ornamental stones is intended chiefly to emphasize or enhance

Jan 1, 1983

By Rudolf Gahl

SOME time ago the Detroit Copper Mining Co. had to decide the question whether it would pay to re-treat slime-tailings, and several machines were tested in order to ascertain the type of construction which would give the greatest saving. In previous tests on the ore of this company, several tables proved far inferior to the Frue vanner, and for this reason they did not receive any serious consideration. In the late tests, however, one table was found to surpass the vanner in the percentage of saving made. The Frue vanner used in these tests had been adjusted approximately to the slope which the slime-vanuers in the concentrator of the Detroit Copper Co. had at that time, about 2 in. between the inside of the wooden posts, or 0.272 in. per ft. It had not been determined, however, if this slope was the most economical one for treating the slime-feed in the mill, or for re-treating the tailings from the slime-vanners, and I was instructed to ascertain by test-runs, under different conditions, the best adjustments for the work to. be done. In order to determine if a change in the adjustments of the machines would improve the results, it seemed sufficient to continue running the tests between the vanner and the table before mentioned, keeping the feed and all other conditions the same, but. varying the adjustments of the vanner .from run to run. I employed a vanner-man of long experience to operate these machines, who expressed the opinion that a slope between 2 3/8 and 2.5 in. between the posts (0.323 and 0.340 in. per ft.) would give the best results. Some runs made this way gave a considerable improvement. While for a slope of 2 in. (0.272 in. per ft.) the saving had been only 40.5 per cent. of that of the table, it .was 49.2 per cent. for 2.5 in. (0.340 in. per ft.) slope. A decrease of

Sep 1, 1909

By John Riegle

To date. utility company underground storage of gas has generally been restricted to depleted dry gas fields. The Playa del Rey project is probably the first to successfully store gas in a partially depleted oil reservoir with the recovery of large volumes of pas at high rates as the main objective. Oil recovery has been a secondary consideration. Problems encountered unusual to those of storage in a dry gas zone were: (1) the removal and retardation of formation of emulsion. (2) the upstructure movement of fluid during withdrawal periods which formed fluid blocks, and (3) reservoir shrinkage resulting from encroachment of edgewater. The solution of these problems as outlined in the paper has resulted in increasing the withdrawal rate from the original design capacity of 4,000 Mcf per hour to the current 10.000 Mcf per hour. Additional increase is anticipated as the operations continue. Migration. reservoir performance. operational procedure and a historical record are included to make this a resume of the project from its war-time inception in 1942 to the first of 1952. INTRODUCTION The Playa del Rey underground gas storage project is probably the first project in which gas has been stored in a partially depleted oil reservoir, with the recovery of large volumes of gas at high rates as the main objective and the recovery of oil a secondary consideration. Problems unusual to those of storage in dry gas zones have made this a pioneer endeavor. The total storage capacity of approximately 1,500,000 Mcf of this reservoir is small in comparison with other underground gas storage projects. However. by study and experiment the deliverability into transmission lines. operating at pressures in excess of 150 lbs., has been nearly tripled in the past three years. to the current 10.000 Mcf per hour late, without the use of compression. It is anticipated this rate will gradually increase as additional fluid is removed from the formation. LOCATION AND HISTORY Playa del Key is located on Santa Monica Bay about two miles south of the beach commuity of Venice and 15 miles southwest of the renter of the City city Los Angeles. Fig. 1. The discovery well was completed at 6,194 ft in 1929. An upper zone at 3,905 ft was found on June 18. 1930. Townlot development was very rapid and by the end of 1930 there were 141 producing wells in the field. The Union Oil Co. completed a lower zone well south of the Townlot Field in May, 1931, which was believed to be an extension, until additional drilling of about 50 wells during 1934 and 1935 indicated this area to be a separate accumulation as shown on Fig. 2. The lower oil horizon, which is now the storage zone, had no original gas cap and is believed to be a continental detrital deposit of conglomerate that accumulated in valleys and depressions of a weathered schist high. which later subsided and was overlain by an impervious nodular shale. This type of formation has rapid variation of porosity. permeability and thickness due to lack of sorting action common to marine deposition. and the uneven surface of the original schist high. Production was limited on the upstructure sides by the pinching out of the conglomerate, and downstructure by edgewater. Unrestricted production, together with high permeabilities, led to large wastage of gas from this new area as facilities were not available for transport of gas to market. The decline was very rapid and by 1942 the portion of the new area south of Ballona Creek was nearly depleted. ACQUISITION OF PROPERTY The rapid increase in industrialization of Southern California during World war 11 forced upon the local gas com-

Jan 1, 1953

By G. R. Wilms

A study has been made of the structural changes in polycrystalline high purity aluminum during the tertiary stage of creep under conditions of constant tensile load. It appears that there is no basic modification in the particular mechanism of deformation that characterized the preceding secondary stage of creep, but that the changes in crystalline structure produced during the tertiary stage are only a consequence and not a cause of the accelerated strain. Intercrystalline fissures were observed on entry into the tertiary stage, and these might supplement the accelerated rate of strain owing to local stress concentrations. There is evidence that the formation of these fissures may be associated with the presence of surface imperfections, and it is suggested that a more generalized treatment of the results may explain certain creep characteristics of commercial alloys. IN previous work'-4 a study was made of the changes produced when specimens of annealed aluminum were deformed at various temperatures and rates of strain, especially under conditions leading to creep under constant tensile load. It was shown that, as the temperature was increased or as the rate of strain was decreased, elements of the substructure produced within the grains became coarser, and with the strain rate constant at a given temperature, their size tended to an equilibrium value. The preliminary process of the breaking down of the grains into a substructure was identified with primary creep.' The subsequent equilibrium, condition was associated with secondary creep. The question then arose whether the tertiary stage corresponded to any further significant change in the substructure. The question is also of interest in view of the opinion, expressed for instance by Andrade,5 that the tertiary stage is merely an accelerated rate of strain due to the reduced area of section of a specimen under continuous tensile load, and the other opinion, as suggested by the observation by Sully, Cale, and Willoughby6 of a tertiary stage in com-pressive loading, that this third stage is a real effect in its own right. The object of this paper is to record some observations on the tertiary stage of high purity aluminum. Experimental Procedure The material was aluminum of 99.98 pct purity as previously used. The specimens had a rectangular section of l/8 x l/2 in., and extensions were measured over a 1 in. gage length. After machining to shape, the specimens were annealed to give a standard grain size of 0.2 mm and then electropolished. The general procedure involved metallographic and X-ray diffraction examination at progressive stages of elongation (marked by arrows on the curves shown in Figs. 1 and 2), the specimen being extended to fracture under constant load at a given temperature. The X-ray tests were made by the back-reflection method from a stationary specimen, using CoK radiation. The longer edge of the micrographs in the paper corresponds to the direction of applied stress. Results The previous work showed that, in the secondary stage of creep in aluminum, three basic types of structure could be developed according to the temperature and rate of strain. These were: 1—slip, which predominated at the lower temperatures and higher rates of strain and produced the finest and least perfect substructure; 2—cell structure, which superseded slip as the temperature was raised and the rate of strain decreased and which was characterized by a coarser and more perfect structure and an absence of slip lines; and 3—a stage termed "boundary microflow," which predominated at still higher temperatures and lower rates of strain when the cell size had increased and become comparable

Jan 1, 1955

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968

[Queensland :-(Continued.) petrography of the Mount Morgan mine, LV, 263. Queensland tin mine and mill, Santa Barbara, Guanajuato, Mex., XXXVI, 227. Quenner disintegrator, XLI, 801; XLII, 15011. Quenstedt, F.: petroleum deposits, Suabia, XLVIII, 14881. Queretaro, Mex., silver mines, XXXIX, 360. Quicksilver: mining and reduction, LI, 110. Oceanic mine, Cambria, Cal., LI, 110. Quicksilver and iron decompose silver sulphide, XL, 872. Quicksilver deposits: China, -XL111, 49. Pacific slope, XXXVI, 1311.. Siberia, Vhdivostok district, XLIV, 16001.]

Jan 1, 1918

By Richard P. Gerwels

Minas de Matahambre, a copper mine located 100 miles southwest of Havana, Cuba, has produced 10 million tons of copper ore since it was first opened up in 1913. During the mid-1950's the mine was producing approximately 1000 tpd and had attained a depth of 3600 ft. As shown in Fig. 1, the property contains three shafts: the No. 1 shaft, 2100 ft deep and located 2000 ft south of the No. 2 shaft, provided service to the 2100 level; the vertical 3600-ft No. 2 shaft handled all production to the 3400 level; the No. 3 shaft on the northeasterly fringe of the mining area was in a semi-active status.

Jan 12, 1960

By N. J. Grant, Per Knudsen, J. T. Blucher

The fatigue behavior of three SAP alloys was studied in ternzs of strain rate and temperature, at high strains. The k values in the modified Manson-Coffin equation, Nk4 = C, were less than 0.5 under all test conditions, and change with strain amplitude for the lower-oxide alloys at about 2 pct strain. Lowest k values were near 0.25. Strain rate had no effect on life at 80 F, but had an increasingly greater effect with increasing temperature above 500". Life decreased with decreasing strain rate, above 500"F, and with increasing temperature. Ductility at fracture in a tension test was indicated to be an important factor in determining 1ife in these big+-strain tests with the SAP alloys. INEVITABLY, in the course of mechanical tests at elevated temperatures, particularly if significant time at temperature is involved, there are large changes in structure; these changes make it difficult to relate behavior patterns over ranges of temperature or strain rates at high temperatures. Such changes are to be expetted in low cycle fatigue at low strain rates and high temperatures. Accordingly, it was of great interest to examine the low cycle fatigue behavior of SAP / an aluminum oxide dispersion-strengthened aluminum, a type of alloy which had shown unusual structure stability to temperatures as high as 1000" to 1150°F and resisted recrys-tallization essentially to the melting temperature.'j3 Since the matrix is pure aluminum, there are no complications of averaging, agglomeration, or phase solution. It was also desirable to check the Manson-Coffin equation4?' for the SAP alloys, namely N~E~ = , where ep is the total plastic strain amplitude, k and C are constants, and N is the number of cycles to failure. Here, too, was an opportunity to check the roles of temperature and strain rate with a very stable material. Tavernelli and coffin6 had concluded that k had a value of about 0.5 for many alloys and C was equal to ~/2, where E is the fracture ductility determined from a static tension test. The results were obtained from low-temperature tests where creep and diffusion processes are unimportant. Manson7 found k = 0.6 fitted his data reasonably well; however, in later analyses of a large amount of low cycle fatigue data generated at room temperat~re@"~ he found k to vary from 0.6 for short lives to 0.21 for long-life fatigue tests. In the latter studies,89g Manson separated the total strain range into elastic and plastic components when he found that k was influenced by the nature of the strain. The use of EL (total strain) instead of EP (total plastic strain)4'5 makes a difference in the resultant k value. The ratio of changes with temperature, strain rate, and strain; further, there are the problems in the determination of the elastic strain. Based on these considerations, and the improved fit of points in a plot of by Wells and Sullivan,' is also utilized in these studies. Anderson and wahl,14 using commercial 1100 aluminum, and Blucher and Grant,15 using 99.99 pct pure aluminum, found an increase in life with increasing test temperature. Anderson and Wahl were the first to report low cycle fatigue results from SAP materials. With increasing temperature, the role of strain rate becomes more important. In this regard, care must be exercised to differentiate between frequency (wherein strain rate may vary from zero to a maximum in each cycle, sinusoidally, for example), and constant strain rate, as used in the present study, in a saw-tooth type cycle; in the latter case, the frequency is not specified but can easily be calculated from the strain and strain rate data. It has generally been found that life in low cycle fatigue tests decreases with decreasing frequency16 or with decreasing strain rate at elevated temperatures.15 Coffin,17 reviewing Eckel's work,16 also reported that k increased with decreasing frequency for acid lead, yielding values from 4.0 at a frequency fo 6.6 cycles Per day to 1-46 at a frequency of 7440 cycles per day; the value of k decreased to 0.58 at a frequency of 2.38 x lo6 cycles per day. EXPERIMENTAL PROCEDURE Three SAP alloys, of two nominal compositions, were tested. Alcoa supplied XAP 005 as 2-in.-diam extruded bar, of nominal composition A1-7 wt pct A1203. The Danish Atomic Energy Commission supplied SAP 930 (A1-7 wt ~ct Ala3) and SAP 865 (A1-13 wt pct Al&) manufactured by Swiss Aluminium Ltd., in the form Of $-in.-diam extruded rod. Metallographic comparison of the structures of XAP 005 and SAP 930 showed the former to have a more uniform oxide distribution. Button-head specimens were machined in the longitudinal direction of the bar with 0.4 in. gage length by 0.2 in. diameter, with a fillet radius of j-B in. After machining, the specimens were electropolished in a 1 to 4 mixture of perchloric acid to methanol to remove all machining marks. All test bars were in the as-extruded condition. The fatigue tests were performed on a hydraulically activated, axial strain machine, with complete reversal of strain.15 Test conditions were:

Jan 1, 1969

By G. P. Conard, E. H. Rennhack

The creep behavior of hot-rolled, hypoeutectic Zn-Ti alloys was investigated in the temperature range from 0.43 to 0.53 TM. Secondary flow was found to originate primarily from strain-induced gvain growth where grain boundary )nigvation served to relieve the strain energy of distortion introduced by slip, grain boundary sliding, and subgvain formation. The extent to which this recovery mechanism operated was determined by the ratio of grain width to the spacing between planar fibers of TiZn,, compound particles generated in these alloys during rolling. When this ratio was unity, creep resistance demonstrated a marked improvement. In this condition, which was fulfilled by annealing following rolling, structural stability was enhanced with decreasing grain size below the equicohesive temperature (-0.5Tm), while the reverse was true above this temperature. TITANIUM concentrations approaching the eutectic composition of 0.23 wt pctl have been shown to promote a significant increase in the creep resistance of rolled zinc,2 The alloying effect created with titanium is somewhat unique; a structure closely resembling that of a fiber-reinforced metal composite can be developed which selectively modifies creep strength in preference to other mechanical properties. In an earlier investigation,~ the present authors found that, while the fiber network, composed of individual TiZn,, compound particles, had a distinct influence on rolled texture, the crystallographic variations produced were of minor importance with respect to creep. Rather, creep resistance seemingly increased when the grain size appeared to coincide with the in-terfiber spacing. The work described here was undertaken to explore this effect in greater detail. EXPERIMENTAL PROCEDURE Three zinc-base alloys containing 0.05, 0.12, and 0.16 wt pct Ti were prepared from CP zinc and iodide titanium in the form of 4 by 2 by f in. chill-cast ingots. The melting and casting procedures for these alloys have been detailed el~ewhere.~ Individual ingots of each alloy were hot-rolled at 200°C (392°F) to total reductions of 10, 25, 50, 75, and 90 pct in from one to five passes, respectively, employing a 10-min reheat prior to each rolling pass. With grain, tensile-type creep specimens with a 1-in.-long, -in.-wide gage section were machined from the rolled strips for test purposes. Annealing studies to explore the influence of grain size on secondary creep flow were carried out at 400°C (752°F) in argon for times extending up to 60 min. The grain-size effect was evaluated in terms of average grain width and length values statistically derived from lineal intersection measurements.4 A similar method was applied in establishing the average interfiber spacing, i.e., average perpendicular distance between adjacent planar fibers. The creep characteristics of the alloys were investigated by means of constant-load and constant-stress creep tests. The former tests were conducted at 25°C (77°F) under an initial stress of 10,000 psi, while the latter were performed in the range from 25°C (77°F) to 90°C (194°F) at stress levels varying from 8000 to 22,000 psi. Total specimen strain, as determined with Budd HE-1161-B strain gages, was in excess of 0.10. Maintenance of constant stress was achieved through periodic load reductions made at 0.01 strain intervals to compensate for the attendant incremental reduction in specimen cross-sectional area. The maximum indicated error in the applied stress at these strain intervals was less than 3.0 pct. RESULTS AND DISCUSSION Constant-Load Creep. In an effort to clarify the in-terrelation between interfiber spacing and grain size with respect to the creep resistance of the Zn-Ti alloys, their separate effects on secondary creep rate were determined as a function of titanium content and rolling reduction. These results are set forth in Figs. 1 and 2, respectively. The average grain diameter plotted in Fig. 2 was resolved from average grain width and length values. No data are presented for reductions of less than 50 pct because of the inability to obtain consistent measurements on these strips. The curves of Fig. 1 indicated that, for a given titanium content, a decrease in interfiber spacing, as produced with increasing reduction, promoted a decrease in creep rate. Depending on titanium content, however, wide variations in creep rate occurred at the same interfiber spacing suggesting that interfiber spacing, by itself, has little or no influence on creep resistance. Grain size, on the other hand, decreased progressively with both increasing rolling reduction and titanium content, the effect of which led to a pronounced decrease in creep rate, particularly when the average grain diameter became smaller than 3.0 x 10"4 in., Fig. 2. The continuity of this relationship tended to support the view that grain size rather than interfiber spacing was predominant in controlling secondary creep. Annealing Effect. The observed dependence of creep flow on grain size suggested that a further contribution to creep resistance would result when the alloys were annealed to effect a coincidence between grain width and interfiber spacing, see Fig. 3(b). ~eiides creating an immediate barrier to grain boundary movement, annealing offered the possibility of providing increased structural stability by eliminating many high-energy, mobile grain boundaries.= To test this hypothesis, specimens from the Zn-0.16 Ti strips reduced 75 and

Jan 1, 1967

Jan 1, 1902

By B. J. Nelson, F. N. Rhines

STUDIES upon the rates of oxidation of copper alloys containing small quantities of the alloying elements1,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidizable alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal subscale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants. Similarly, large volumes of precipitated oxides tend to deposit in various patterns that may be expected to hinder the diffusion of the reactants in the

Jan 1, 1943