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By J. O. Nelson, C. J. Altstetter

Single crystals of hcp cobalt, 3 mm in diameter and up to 35 cm long, were grown using an electron-beam, zone-melting technique. The martensitic-phase transformation was studied in single-crystalline and polycrystalline specimens by making length-change measurements as a function of temperature under various elastic compressive stresses. Upon thermal cycling, single-crystalline or polycrystalline specimens repeatedly transformed almost entirely on the same variant of close-packed plane provided the maximum temperature did not exceed 600°C. Cycling to 1000°C resulted in transformation on more than one {111} variant. This behavior is termed multivariance. The multivariant transformation occurred very rapidly at an M, temperature 2° to 6°C lower than the M, of a transformation which would result in a single-crystal product. Elastic compressive stresses (up to 253 g per sq mm) tended to lower the A, and raise the M, temperatures, decreasing the width of the temperature vs dilatation hysteresis loop. The transformation habit plane and transformation shear direction of an as-grown single crystal were not grossly affected by elastic compressi?ie stress. This was evidenced by similar dilatations on the temperature us dilatation loops joy specimens with and without compressive stress. A dislocation mechanism is proposed to explain the observed results. IT has been shown that, on heating, cobalt transforms martensitically from the hcp to the fcc phase.' The transformation habit plane is (0001)hcp || (lll)fcc and the transformation shear direction is (1010)hcp || (112)fcc. The transformation involves a shear of 1g°28', which may be achieved by a shearing of a/6(112) of every two planes with respect to the plane beneath, thus changing the ABABAB stacking of hcp to the ABCABC stacking of fcc. Associated with the phase change is a 0.3 x 10"3 contraction in the habit plane and a 4.2 X 10"3 expansion perpendicular to the habit plane resulting in a 3.6 x X volume increase on heating.' On cooling, an identical volume decrease takes place. The temperature at which the fcc phase begins to form on heating (A,) is reported as 430°C, and the temperature at which the hcp phase begins to form on cooling from an elevated temperature (A&) is reported as 390oC1,3 Consequently, temperature vs dilatation plots have the form of a hysteresis loop. If heating or cooling is reversed during a transformation, a smaller hysteresis loop results. Upon heating, the transformation is always complete; whereas, fcc is often retained at room temperature as a metastable phase entrapped in the polycrystal-line hexagonal matrix.1,4,5 Two obstacles in the theory of the allotropic-phase transformation of cobalt have been: 1) a detailed knowledge of the product nucleus, and 2) a plausible method of propagation of the transformation. Bilby,8 christian, 7 and seeger 8,9 have suggested a "pole mechanism" as a means of propagation of partiai dislocations from plane to plane. A pole dislocation and a Shockley partial come together at a node. The a/6(112) Shockley partial rotates about the pole dislocation effecting the transformation shear. The pole dislocation must have a 2a/3(111) screw component which causes extension of the transformed region by two atomic planes with each full rotation of the Shockley partial. Bollmannl0 suggested, on the other hand, that transformation propagation occurs due to the stress fields of intersecting (111)-type stacking faults. As faults intersect, a stress distribution is set up about their intersection which is in turn reduced by the emergence of another fault on the second nearest plane. This process continues with the final result of a complete phase transformation. In view of the similarities between deformation and transformation in cobalt, the effect of stress on the transformation would, hopefully, yield valuable information concerning nucleation and propagation. In the present work single-crystalline and polycrystalline specimen length changes were measured as a function of temperature at various compressive loads. PROCEDURE Several orientations of single crystals of hcp cobalt in lengths up to 25 cm were grown by electron-beam floating zone melting from 99.95 and 99.999 pct, 3-mm-diam cobalt rod as supplied by Johnson

Jan 1, 1964

By Finney, W. R.

MUCH has been said and written of the "Big Inch," of the terrific obstacles encountered in its construction, of the colorful and tough men engaged in its building, but little has been publicized of the engineering and economic problems behind the scenes. Long before Pearl Harbor it was apparent to the petroleum industry that a critical oil shortage could be expected along the Atlantic seaboard, owing to delay in tanker deliveries as a result of convoy movements, and to allocation of vessels for foreign shipments. This area, with a normal consumption of approximately 1,800,000 barrels per day of oil and products, was almost entirely supplied by tanker. Pipe lines supplied an average of only 20,000 barrels per day in 1939, 40,300 barrels per day in 1940, and 55,000 barrels per day in 1941. A small amount of oil and products was also delivered via barge.

Jan 1, 1943

By R. H. Atkinson

With the object of improving the melting, casting, and working of palladium and 95.5 pct Pd-4.5 pct Ru, the effects of different melting atmospheres (reducing, oxidizing, and neutral), crucible linings, and annealing atmospheres have been studied. Some interesting observations are included about the solubility and diffusion of gases in palladium. THE object of the present work was to ascertain the effect of oxidizing, inert, and reducing ambient atmospheres on the melting and casting of palladium and a Pd-Ru alloy commonly used for jewelry. The need for such a study was indicated during World War I1 when jewelers experienced difficulty in their attempts to make small castings of the torch-melted Pd-Ru alloy by the lost-wax process. When the metal was melted under oxidizing conditions similar to those used for platinum, the castings were gassy; on the other hand, if the melting atmosphere was reducing, the castings were hot-torn and brittle. General Experimental Procedure Pure palladium sponge (99.9 pct Pd) and pure ruthenium powder (99.8 pct Ru) were used for making small ingots (50 g) of palladium and 95.5 pct Pd-4.5 pct Ru by induction melting. The coil, 3 in. high by 2 in. ID with 16 turns, was energized by a 20 kva Ajax high frequency converter. The melting crucibles, so-called sand crucibles, which were made of a highly refractory fireclay, were lined with different materials, including proprietary magnesia, alundum, zircon, and zirconia

Jan 1, 1957

By Donald E. Ackerman, Norman B. Pilling

The solubilities of a series of experimental alloys covering the range 0 to 100 per cent. Ni, 0 to 30 per cent. Cr have been studied under conditions of complete submersion in several fully aerated acid solutions, and in solutions containing sulfurous acid. In nonoxidizing, hydrogen-discharging acids, if the nickel content is below a certain critical amount, chromium increases the rate of solution and nickel decreases this rate; this critical content of nickel is about 13 per cent. Alloys containing more than this corrode at a constant minimum rate independent of iron, nickel or chromium contents. Austenitic chrome-nickel steels may thus have a resistance to these acids equal to that of nickel-chromium alloys. In nitric acid and in unaerated sulfurous acid rather sharp limits of attack occur which are principally dependent on chromium content. In the former the limit of attack is not related to a particular chromium content but varies continuously with acid concentration. The action of sulfurous acid on these alloys is highly dependent on the presence of small amounts of other substances in solution, and many sulfurous acid mixtures rapidly attack alloys to which the pure acid is wholly inert. The observed effects are not compatible with Tammann's theory relating corrosion resistance to lattice structure but are believed to be concordant with current views of the electrochemical nature of corrosion. Introduction The discovery, development and engineering application of iron alloys resistant to corrosion may well claim a place among the important developments in metallurgy of the past two decades. The varied demands of industry coupled with the skill of the metallurgist have resulted in the production of an extensive group of steels and alloys ranging from the now familiar "stainless " chromium steels of the kitchen to special alloys of great chemical complexity for particular, exacting needs. Any adequate description of the important properties of these-— physical, chemical and economic—would be a formidable undertaking.

Jan 1, 1929

By Miguel Bustamente

In 1890 I mas manager of a mining enterprise in the State of Michoacan. The ores were composed principally of iron pyrites (much decomposed), in a quartz matrix, with native gold in very irregular grains. Some portions, however, carried their metallic value in a matrix of calcite arid siderite. The mill in which the ores were treated consisted of two 800-lb. stamps, two amalgamating-plates, four pans, two automatic washers, two Frue vanners, and the necessary accessories for assaying, retorting and refining gold. The plant, originally erected with American capital, and directed by competent Americans, passed in 1890 into the hands of Mexican owners. On taking charge of the business I found on hand a large amount of ore assaying 35 grammes of gold per metric ton (about 1 oz. Troy per ton of 2000 lbs.); but the company was losing money, and was about to abandon the business. Obviously, the difficulty lay in the treatment of the ore. The extraction of gold scarcely reached one-tenth of the assayvalue ; the loss of mercury was considerable; and high freight; charges excluded the alternative of exporting the ores. This situation naturally suggested that amalgamation was not applicable to these ores, and that a more appropriate method must be adopted. The cyanide- and chlorination-methods had been tried already, without practically satisfactory results. For the first few months I employed a combined system, extracting a part of the gold by direct amalgamation, and cyaniding the concentrates. This saved 32 per cent. of the assay-value, but the cost of milling still exceeded the proceeds. Meanwhile I observed

Jan 1, 1902

R. L. Bullock (St. Joseph Lead Co., Bonne Terre, Mo.)— The progressive approach of The International Salt Co. as described by Mr. Ryon is certainly commendable as is his paper. St. Joseph Lead Co. has been shooting AN/FO in 13/8 to 1 1/4-in. holes for several months now (as of October 1960) on a trial basis. The results thus far obtained are excellent, but conclusive evidence at this date is premature. One point that he gave should interest even the most ardent skeptic. That is, they are getting a detonation of the 1 1/4-in. ANDO charges in 2 1/4-in. holes. In light of its low sensitivity and critical diameter, this would appear to be one of the worse conditions that one could expect in which to get proper detonation of AN/FO. It has been shown* that partial confinement sometimes decreases sensitivity of a column of explosive because the air space above the explosive becomes highly compressed and in turn compresses the explosive prior to passage of the detonation front. Apparently, this does not happen in their shooting and the poor explosive coupling caused by the 2 1/4-in. holes yields a minimum of overbreak and is an ideal condition for their back.

Jan 1, 1961

By A. E. Hall

The paper gives a general solution of ventilation net- works where densities play an important role and fans operating at different densities from branch densities are considered. Both the physics and computing techniques needed to deal with these networks are discussed.

Jan 1, 1977

By Oscar Glaeser

THE mine and plant of the United Verde Copper Co., located in Yavapi County, at Jerome, Arizona, have been described in various technical publications and, therefore, a brief outline of its essential features will suffice. The orebodies are of the schist replacement type, the main sulfide mass being a large lens-shaped body approximately 7 acres in cross-sectional area. In general, the mineralization is found along the iron-schist contact, with the orebodies extending-about 1000 ft. along this contact and varying from a few feet to 250 ft. in width. The mine is located on a mountain slope and has openings into it on three horizons, as follows: 1. Raises and ore passes open vertically into the shovel pit. These extend down to the 1000-ft. level, where they terminate as loading bins in the Hopewell adit. The main fan intake air shaft, which also extends vertically down to the 1000-ft. level, has its surface opening on the hillside at the extreme north end of the shovel pit, and the main mine air return exhausts through a raise at the extreme south end of the shovel pit. 2. The 500-ft. level adit. 3. The Hopewell adit on the 1000-ft. level. The mine has a vertical downward extent of 2000 ft. below the 1000-ft. level. Underground operations are carried on through two main shafts, both of which are wholly underground. Shaft 5 is the ore-hoisting shaft. It has three compartments and extends from the 800 to the 3150-ft. level. Shaft 6 is the service shaft, and is used for lowering and hoisting men and material. It has a large cage compartment and three smaller compartments for counterweights, ladderway, and pipe and power lines. This shaft extends from the 500 to the 2550-ft. level, and is now being extended to the 3000-ft. level. An air shaft for the downward movement of fresh air from the fan has been provided, and extends to the 2550-ft. level at this time. Work has been started to extend this air shaft to the 3000-ft. level. A return airway for vitiated mine air, in the form of raises and short connecting drifts, extends downward to the 2100-ft. level.

Jan 1, 1929

By Bruce T. Stanley

The concepts of ore reserve estimation at the Henderson mine are reviewed presenting a geostatistical approach and procedure as applied. Specific problems encountered are recapped and explained as to the nature and resolution thereof. The methodology and results are shown, along with an approximation of computer usage and capacities needed. The scope of the paper is to set forth an example of actual application, usage, and benefits realized from such a procedure. Local Conditions The Henderson molybdenite deposit is located in central Colorado about 69 kilometers west of Denver. The geology consists of a classic subvolcanic ryolite porphyry sequence with quartz-molybdenite mineralization occurring in an extensively fractured granite stock complex. Being assymetric and bilobate in section, the orebody measures approximately 300 meters thick and 600 meters by 1200 meters in plan. The orebody is sampled by means of underground drill holes which create an east-west fan pattern spaced roughly 60 meters apart in the north-south direction. Approximately 27,000 meters of drill hole assayed on 3.04-meter intervals were available for analysis. Recovery on the core is about 95 to 100 percent, thereby affording us with reliable data all prepared to the same standards.

Jan 1, 1977

Recent start-up of a new 3450 t/d (3800 stpd) copper-zinc concentrator complex in northern Manitoba, Canada, is expected to open new reserves and dramatically cut transportation costs for Hudson Bay Mining and Smelting Co.'s Snow Lake operations. The new $C33-million mill is located in Stall Lake, Manitoba, and includes a new crushing and grinding facility and two flotation circuits for the production of 23-25% copper and 55% zinc concentrates. A small amount of lead concentrate will also be recovered. The plant will produce some 145 000 t/y (160,000 stpy) of concentrates, to be shipped by rail to the firm's Flin Flon copper smelter and zinc refinery complex, located 177 km (110 miles) to the west on the Saskatchewan-Manitoba border.

Jan 9, 1979

By Michael B. Gross

A numerical study of the vulnerability of unlined tunnels in jointed rock has been performed with the STEALTH computer program, using the CAVS model for jointed rock. CAVS, for Cracking And Void Strain, is a constitutive model that can simulate the initiation/propagation of fractures and the slip along fracture planes in a jointed rock mass. The CAVS model is unique because it represents a spatially oriented approach to rock failure, rather than the traditional invariant formulation, and because the CAVS submodels for slip friction and slip-induced dilatancy are used to represent the weakening influence of joints, rather than applying ad hoc modifications to the elastic moduli of the host rock. The CAVS model, as embedded in the STEALTH computer program, has performed numerical simulations of tunnel collapse at high overstress levels. These calculations show that the ultimate strength of the tunnel depends strongly on the joint properties, and that the results of the calculations are in qualitative agreement with the observed data for collapse of a tunnel in tuff.

Jan 1, 1984

By A. J. Boyer, T. R. Meadowcroft

An experimental determination has been made of the efject of surface diffusion on the vapor pressure obtained in a Kwudsen cell. The results show that a knife-edge orifice in a molybdenum lid may give erroneous results for the vapor pressure of silver. when a correction suggested by winterbottom and Hirth is made, the results become meaningful. Experimental work with cylindrical orifices in molyhdenz~m lids and knife-edge orifices in ceramic lids shows that good vapor-pressure results may he obtained when the orifice is designed so that ejfusion is the only significant source of weight loss. THE Knudsen effusion cell technique has been used by many investigators to study relative and absolute vapor pressures over metals and alloys at elevated temperatures. As a result of this interest, some theoretical studies have been made of geometric factors affecting effusion from the orifice of a Knudsen cell. A review of these studies has been made by Margrave.1 Recently, Winterbottom and Hirth2 have suggested that a physical effect, that of condensation, surface diffusion, and re-evaporation, may seriously affect Knudsen cell measurements, especially when a knife-edge orifice is used. Inasmuch as many of the present vapor-pressure data have been obtained using knife-edge orifices. it was felt that an experimental evaluation of the effect of surface diffusion on Knudsen cell measurements would be of value both in the design of the cell orifice and in establishing realistic estimates of the limits of error for existing data. The experimental program was in two sections. Firstly, measurements of the vapor pressure of silver were made in cells with cylindrical and conical orifices in which the surface-diffusion contribution to the weight loss should be negligible. These results were correlated with existing data to give a reliable measure of the real vapor pressure of silver. Secondly, measurements made using knife-edge orifices were corrected using the surface-diffusion theory of Winterbottom and Hirth2 and were then compared to the real values. The experimental arrangement is shown in Fig. 1. The balance was an Ainsworth RV-AU-1 automatic recording microbalance capable of measuring weight changes of ±0.02 mg on a total load of up to 100 g. The temperature was measured by an optical pyrometer signted on the bottom of the suspended crucible. The temperature readings were calibrated in a separate experiment in which pyrometer measurements were made while at the same time thermocouple readings were taken of the temperature at the inside top and bottom of the crucible. The range of reproducibility with this technique was ±4°C. A constant voltage source maintained a temperature of ±2°C at 1200°C over 10 hr. Silver of 99.99 pct purity was used in nonporous alumina crucibles. Lids of molybdenum, tantalum, or magnesia were cemented to the crucible using a sodium silicate cement. Table I shows the characteristics of the lids used. The vapor pressure is obtained using the basic Knudsen formula:

Jan 1, 1965

By F. S. Knoll

The expanding role of electrostatics as applied to minerals and related fields is covered in this paper. New and existing forms of electrostatic separation are classified into two broad groups: separation of charged particles and separation of neutral particles. The basis for each form of separation is discussed along with particle examples and results obtained.

Jan 1, 1986

By Paul Tyler

THE extensive employment of nonmetallic minerals antedates the use of metals, but only within the last two decades has the production of nonmetals begun actually to keep pace with the complicated activities which characterize the so-called Machine Age. The economic changes ushered in by the Industrial Revolution were reflected first in an increased demand for metals and for fuels. In the modern sense, therefore, the nonmetallic mineral industries are new and afford new opportunities for engineer and economist alike. A certain amount of caution is indicated, therefore, before attempting to apply ready-made formulas to the problems of these industries. Economics is not an exact science. In the field of production technology where the number of variables is fairly well known, the principles of economics are readily applicable, but as the student proceeds through the province of marketing into the unexplored regions of psychology and sociology he must distinguish carefully between scientific reasoning and purely metaphysical speculation, even when the latter masquerades as economics. The present paper attempts to prove no preconceived theorems and is designed primarily to stimulate careful thinking on sundry neglected phases of these industries. An attempt is made to differentiate the general problems into single aspects which afford promise of being comprehended separately; also, some fundamental statistical data are presented, but merely to indicate a method of scientific approach applicable to more intensive studies.

Jan 1, 1933

By D. Gupta

Rates of autothermic reactions are sensitive to temperature variations to the extent of potential extinction of the reaction. Such reactions, when carried out in the countercurrent mode with feed-back of energy between reacting phases, may result in the possibility of multiple steady-states. In regions of great sensitivity, minor variations, especially feed-temperatures, are an important criterion for such instabilities. Mathematical models have been used to delineate the parameter-fields in which instabilities might occur. The metallurgical system chosen to experimentally verify the above theoretical findings was the exothermic oxidation reaction of magnetite to hemitite.

Jan 1, 1977

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By M. D. Hassialis, C. G. Myer

THE nature of a collector-coated mineral surface has been the subject of some experimentation and much speculation. Various aspects of the problem have been isolated and studied; it is probable, however, that there exist aspects as yet unrecognized, which are needed for a complete description of the system. The recognized elements of the problem are: 1—The nature of the chemical units comprising the film and the nature of the forces holding these chemical units to the mineral surface; 2—The orientation of the chemical units at the surface; and 3—The disposition of the collector units at the mineral surface. This report touches upon all three aspects of the broad problem; it deals, however, with a new and heretofore unrecognized element—the mobility of the collector units in the two dimensions of the solid-liquid interface. Regardless of the viewpoint adopted as to whether the chemical units comprising the collector film are collector ions or molecules, held either by chemical or physical forces, the writers on flotation theory are in apparent agreement as to the orientation of the chemical units at the mineral surface. Wark and Cox' showed that the contact angle at a stable collector-coated surface in a constant chemical environment is independent of the nature of the mineral and of any resurfacing agent; it depends solely upon the collector used. They showed further that the value of the contact angle increases with the number of carbon atoms in a homologous series of compounds. Taggart, Taylor, and Knoll2 postulated that the collector ion is oriented with the chemically reactive, polar end toward the mineral surface and the non-polar, hydrocarbon-like end toward the liquid phase. In support thereof they cited the abstraction of p-p1 dihydroxydiphenylthiourea and of glycol xanthate8 by galena without a concomitant increase in the contact angle above that of clean galena. It was argued that in these cases the water-repellent layer which normally would be presented to the liquid phase owing to the orientation of the collector ions is overlain by a layer of water-avid groups, the hydroxyl groups. Implicit is the analogous orientation exhibited by a monomolecular layer of an insoluble substance at an air-water interface. It should be pointed out that these facts also are consistent with the concept that the collector units be flat on the surface of the mineral and that the response of the surface to an air bubble is determined by the ratio of the area covered by water-avid groups to the area covered by water-repellent groups; the areas being weighted according to the relative watef-avidity or water-repellency of the groups involved. The disposition of the chemical units of the collector film at the mineral surface has not received the attention it merits. Taggart4 concluded from the observed stoichiometry of the ions entering and leaving a surface that the stoichiometry is obeyed in detail at the surface of the mineral. Thus, in the case of xanthate-coated galena, pairs of xanthate ions are attached to surface lead ions. In the case of chemisorption, Gaudin and Preller postulated an agreement between the atoms or ions of the substratum (the mineral surface) with those of the superstratum (collector film); in the case of the physical adsorption their position is not clear. In one place they state "the first type (physical adsorption) does not require any agreement between the atoms or ions of the substratum with that of the superstratum" and in another place that "It seems, in fact, as though some slight influence of the substratum is formed even in physical adsorption." The present work shows that in some cases of chemisorption the chemical units of the collector film are in constant surface-bound motion and may not be assigned to any site of the surface, hence there is no permanent association between the chemical units of the film and the atoms or ions of the solid. The physical property of the collector film that is of paramount importance is its surface energy. Although this property is not susceptible to direct experimental determination, the related contact angle is. Much of the knowledge of the properties of a collector film derives (by deductive and inductive reasoning) from the behavior of an air bubble thereat

Jan 1, 1952

By A. Cochardt, D. H. Feisel

HE success of the sintered aluminum powder material (SAP)' in raising the maximum useful temperature of aluminum alloys has stimulated effort in investigating similar systems in which the metallic matrixes have higher melting points. Examples of such systems which have been studied are nickel-alumina,2, 3copper-silica,4 copper-alumina,4 titanium-cerium oxide,5 and 80/20 nickel-chromium,8 cobalt,= and molybdenum7 matrixes with various hardeners. Conventional precipitation-hardened high-temperature alloys are often thermally unstable in service. The original fine particles that are responsible for good strength properties grow in size at elevated operating temperatures, a process termed "over-aging." This growth of precipitated particles causes a gradual loss in strength properties. A previous paperb describes the factors that govern the process of overaging, and estimates the time required for overaging of a nickel-alloy matrix dispersion-hardened by various precipitates such as are found in current high-temperature alloys, and by alumina. These calculations indicate that nickel-base alloys hardened with Ni3Al, Tic, or TiN are quite unstable at 1340" F (727°F). Such alloys should overage within a few hours at that temperature. A nickel-base alloy hardened with alumina, on the other hand, should behave differently. It should not overage appreciably within a thousand years. It was further shown8 that the thermal stability of the oxide-hardened alloy is mainly due to the low solubility of oxygen in equilibrium with alumina in the nickel-base matrix. Since the oxygen solubility is small, little oxygen can diffuse, and structural changes require very long times. This paper illustrates the effects of time and temperature on the structural stability of nickel alloy matrixes hardened by dispersions of Ni3A1, Ni3Ti, Tic, and alumina, and of nickel-chromium matrixes hardened by alumina. Hardness measurements and metallography have been used as a measure of structural stability. EXPERIMENTAL PROCEDURE Using the best information from published phase diagrams,'-l4 compositions of the Ni-Al, Ni-Ti, and Ni-Ti-C alloys were determined so as to have 5 vol pct of precipitate at 1350° F(732°C), the temperature selected to illustrate the effect of time on structural stability. Table I lists the chemical compositions of these alloys. Standard laboratory melting and alloying techniques were used in preparing ingots of the F-Series of alloys. The cast ingots, 1 3/4 in. in diam, were forged to 3/8-in. diam rods.

Jan 1, 1960

By R. F. Hehemann, S. T. Zegler

The w phase in zirconium alloys containing more than G pct Nb can form in a difjUsionless manner during quenching or with composition change during aging at temperatures below 550°C. The latter treatment establishes a metastable equilibrium between an w phase containing 5 pct Nb and a ß phase containing 45 pct Nb. The superconducting transition temperat~ire of quenched Z?-10 pct Nb and Zr-15 pct Nb alloys is increased by aging at 375°C and both alloys exhibit the same Tc after prolonged aging. The superconducting transition both in the quenched and in the aged alloys is relatively sharp (occurring ovev a temperature range of <0.5°K), and is interpreted in terms of the microstructure that characterizes the ß-w) mixture and proximity effects postulated for thin-film superconductors. At elevated temperatures alloys of the transition elements from groups 4 to 6 in the periodic table exhibit wide ranges of mutual solubility in the bcc structure. Except for compositions that are high in a group 4 element? the bcc structure can be retained at room temperature by quenching and several systematic studies of the influence of composition on superconductivity in bcc alloys have been reported.&apos;&apos;2 The high-temperature bcc form (ß) of the group 4 elements—titanium, zirconium, hafnium—is not retained upon quenching but instead transforms marten-sitically to the hcp structure (a). The Ms temperature can be lowered by alloying the group 4 metals with a solute from a higher group and with a critical amount of solute the martensitic transformation can be suppressed. The 3 phase, however, is not retained without modification. Rather, a metastable phase, w (in particular in titanium- and zirconium-base alloys), occurs over a fairly wide range of compositions above that required for suppression of the martensitic transformation.3,4 As in the formation of a, the transformation of ß to w occurs in a diffusionless manner during quenching and the temperature for its initiation (ws) is lowered by increasing solute content. The ws temperature can be well below room temperature and reversibility of the transformation allows w that forms on cooling to low temperatures to disappear again when the sample is returned to room temperature.5 In Zr-Nb alloys the w phase can also be formed during aging at temperatures below 550°c.5 In this treatment, a metastable equilibrium is established between a niobium-rich ß phase and a zirconium-rich w phase. The present study of Zr-Nb alloys was undertaken to examine the influence of microstructure: as controlled by composition and heat treatment, on the superconducting transition temperature, Tc. MATERIALS AND PROCEDURE The alloys were prepared from zirconium crystal bar that was spectrochemically pure except for 30 ppm of Al, 40 ppm of Cu, 100 ppm of Fe, and 1 ppm of each B and Pb. The niobium used was 99.5+ pct pure containing according to the suppliers&apos; (Stauffer Chemical Co.) analysis a maximum of 50 ppmO, 60 ppm of N, 30 ppm of C, 5 ppm of H, 200 ppm of Ta, 50 ppm of Mo, and 15 ppm each of Fe, Co, and Ni. The alloys were prepared in the form of buttons weighing approximately 4 g by arc melting on a water-cooled copper hearth in an inert-gas atmosphere. All alloys were heat-treated in the ß-phase region for 3 days at 1000°C and water-quenched. For heat treatment, the specimens, 0.5 cm in diam by 1.0 cm long, were wrapped in zirconium foil and sealed in an inert-gas atmosphere inside quartz capsules. Quenching was done by breaking the capsules under water. Subsequent aging treatments of Zr-10 pct Nb and Zr-15 pct Nb alloys were done by placing the specimens in a lead bath at 375°C and quenching in chilled brine. The phases present in the quenched and aged alloys were identified by optical and X-ray metallography. X-ray powder patterns were taken at room temperature with a 114.6-mm-diam Debye-Scherrer camera and CuK-a radiation. Superconducting transition temperatures were determined from magnetic-permeability measurements6 in a 10 oe field. The superconducting transition temperature was determined from a plot of galvanometric deflection as a function of temperature by extrapolation of the linear portion of the curve to zero deflection. In Figs. 1 and 3 the arrows indicate the temperature range of the transitions. RESULTS AND DISCUSSION Superconductivity in Quenched Alloys. In Fig. 1 Tc for alloys quenched from 1000°C is plotted against nominal composition. Indicated also in Fig. 1 are results of metallographic studies. Alloys containing less than 5 pct Nb transform martensitically to a during quenching from 1000°C and Fig. 1 demonstrates that Tc increases significantly as the niobium concentration in a is increased. On the basis of the Bardeen-Cooper-Schreiffer theory of superconductivity7 it seems most likely that this increase in Tc results from an increase in the density of electronic states as zirconium is alloyed with niobium. This increased density of states has been revealed clearly in low-temperature specific-heat measurements.8 The martensitic transformation to a is suppressed when the alloy content exceeds 5 pct Nb. In the range from approximately 6 to 30 pct Nb, quenched alloys consist of a mixture of B and w phases and the amount

Jan 1, 1967

By J. J. Gilman

IT is well established that dislocations exist in crystals and account for crystal plasticity.&apos; However, the origins of the dislocations are not clear. Among the means by which dislocations might originate are: a) through crystal growth accidents, b) by the collapse of condensed sheets of vacancies, or c) by stress-induced nucleation. Theoretical calculations&apos; have indicated that the last means should require very high stresses in order to operate. The purpose of this paper is to show that the stresses around the tips of cracks are large enough to nucleate large numbers of dislocation loops. Specifically, it will be shown that (100) cleavage cracks in LiF crystals nucleate dislocations in regions of the crystals where dislocations did not exist previously. It is believed that the use of LiF for this investigation does not restrict the significance of the 1 results. In fact, it is believed that this complements and extends previous papers by the same author which dealt with metal crystals.10,14 The dislocations were detected by means of the etching techniques that were described in a previous paper by Gilman and Johnston.3 In that paper it

Jan 1, 1958