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By H. B. Pulsifer

.ABOut 1.5 varieties, or tnodifications, of the best rnagnesiurn available were prepared and subjected to etching tests, then examined for micro-structure. Of the 30-udd etching reagents that were tried, nearly half, mostly ammonium salts, etched the metal satisfactorily. The surfacing and etching of magnesium is shown to be a very simple and quick operation. The density and hardness of magnesium were determined. The most interesting new observations relate to the finding of the hexagonal etch figures, the crystal laminations, and the fact that the metal is plastic, cold, when restrained or quickly deformed. Under slowly applied pressule cold metal deforms slightly, then shears to fracture without plastic flow. The chief structural features of magnesium arc presented in two reduced photographs and 30 photomicrographs. Materials Tested There are only two sources in the United States from which new metal can be procured: the American Magnesium Corpn. and the Dow Chemical Co. No pronounced structural or property differences in the metals from these two companies were disclosed by the work of this investigation. The following materials were obtained from the manufacturers: 1. Massive crystals of distilled metal (American Magnesium Corpn.). 2. Rods of hot-extruded metal, ½-in. squares and 5/8-in. rounds (American Magnesium Corpn.). 3. Sheet magnesium, 0.005-in. thick (American Magnesium Corpn.). 4. Cast stick metal, 13/8-in. dia. (Dow Chemical Co.). 5. Magnesium-aluminum alloy, hot-rolled plate, ½-in. thick (American Magnesium Corpn.). From these materials, were prepared: 6. Sections from a furnace-cooled ingot made from clistilled crystal. 7. Cold-strained pieces from (6), (4) and (2). 8. Pieces cold-squeezed to fracture from (6), (4) and (2). 9. Hammer-struck pieces from (6), (4) and (2). 10. Steam-hammer struck pieces from (6), (4) and (2). 11. Sections from furnace-cooled ingot of the magnesium-aluminum alloy.

By F. R. Morral, E. P. Miller

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals' Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

OPEN-HEARTH refractories are not merely an accessory to the furnace. They themselves ore the furnace, to all intents and purposes. The steel work of the main structure is merely a frame which helps to support the refractories; and the regenerators, a necessary part of the furnace system, consist almost entirely of refractories with very little supporting structure. Not only do refractories constitute the essential part of the furnace, but they also carry the liquid steel all the way to the point where it begins to solidify. On leaving the furnace the liquid passes through a refractory runner into a refractory-lined ladle, then through a refractory nozzle closed by a refractory stopper on the end of a refractory- protected rod. The liquid is sometimes sent through an additional refractory-lined tun-dish, a supplementary ladle, or a refractory runner for bottom pouring, until it finally enters the iron mold in which it solidifies. Even in the mold, refractory materials are sometimes used to provide a non-conducting "hot top." These materials, from ladle to hot top inclusive, are often referred to as the "pouring-pit refractories." CAUSES OF FAILURE Compared with the equipment used in most industrial processes the open-hearth furnace has a relatively short life. The most important quality of an open-hearth refractory, therefore, is its rate of failure. The discussion here of the individual refractory materials will therefore keep uppermost the question "Why, how, and where does it fail?" The principal causes of failure of open-hearth refractories are, in their order of importance: 1. Reaction with iron oxides. 2. Reaction with slag. 3. Flow and failure under load. 4. Melting. 5. Spallimg. 6. Mechanical breakage. Reaction with Iron Oxides and Slag. This is by far the most important cause of failure. Liquid iron oxide comes very near to being the

Jan 1, 1944

By E. P. Miller, F. R. Morral

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals' Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

By Yves Dardel

The literature concerning the remelting of alunlinum and its alloys is very rich. Unfortunately the majority of the papers on this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges, and the atmosphere of the furnaces bring into the bath during the successive remelt-ings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, or others, if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H², O2, H²O, co², CO, CH,, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of sieverts3 as a function of its partial pressure PH2 in the atmosphere m = K vPH² [I] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Rijntgen and Braun4, RÖntgen and M611er5, Bircum-shaw6 and Winterhagerl have rendered it possible to determine the value of K, when the temperature is less than 1.000°C. One obtains: log K = - 4,702.5T + o 238 [2] Besides its usual significance, the term Ph~ represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is1 when no gas exchange Occurs between the two phases, the Pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary Occurs, the quantity of H² should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature decreases, the internal pressure of H² increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a a depending On the hydro- static pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However1 even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1949

By R. J. Linney

Reserve Mining Co. produces 5 million tons of iron ore pellets per year. The finished product runs about 65.50 pct Fe, with 7.75 to 8.00 pct SiO2. Less than 12 pct arrives at the blast furnaces smaller than % in. This plant was originally designed to produce 3.75 tons annually—not 5 million. To handle the increased tonnage a fifth fine crushing line was added, and some very minor changes were made. When production can be stepped up 33 1/3 pct without extensive additions or changes—within the short period of a year—basic engineering has been sound. Operators of the plant consider it the best design job they have seen or heard of, and competent authorities have said that start-up was quicker and easier than for any previous large-scale minerals beneficiation plant. One big advantage is the elbow room allowed. Generally speaking, there is an eternal conflict between operator and designer over space. The designer has his costs per cubic foot, and he is keenly aware that if he permits the number of cubic feet to rise unnecessarily, total costs will be too high. But this was a new operation, and on a large scale. There were no proven standards to go by. Realizing this, Reserve's engineers provided ample and efficient access to machinery, allowing extra space for unanticipated situations. In three years of production this planning has paid off handsomely. Gravity Flow Saves Time and Money: This plant is on a rocky hillside, the car dumper about 270 ft above Lake Superior. In locating buildings and placing machinery the designers mad= good use of gravity flow, at considerable financial savings. In the concentrator building from rod mills to filters, gravity carries the material between all stages of the operation except one—the closed circuit pumping of concentrate between cone classifiers and ball mills. Since no machine is located directly above any other, an observer can stand on the truck ramp adjacent to the offices and laboratory and see practically every phase of activity in the huge building. The first mill section started in August 1955. After a day's run several modifications were made on auxiliary chutes and launders where spillage had occurred. This procedure was followed for the first

Jan 1, 1960

By W. E. Keck

THERE is a considerable tonnage of iron ore in the Menominee Range Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a rela-tively large quantity of finished concentrate would be obtained (deleteri-ous sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beneficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal min-erals in a nearly puree state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,000'. Of this quantity and value, Michigan produced approxi-mately 19 per cent4. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1937

By D. J. Jr. McAdam

Fort the past five years, an investigation of the endurance properties of metals has been in progress at the U. S. Naval Engineering Experiment Station, Annapolis, Md. As a result of the investigations at this Station1-5 and other laboratories6-11 "endurance limits" of practically all kinds of carbon and alloy steels have been determined and have been correlated with other physical properties, especially with tensile strength. About a year and a half ago, the investigation at the Naval Experiment Station was shifted to non-ferrous metals. As a result, several papers discussing the endurance properties of numerous non-ferrous metals and alloys, especially the alloys of nickel and of copper12-16 have been published. In these papers, stress-cycle graphs illustrate. the endurance properties of each individual metal and alloy, and other graphs illustrate the effect of cold working, heat treatment, and chemical composition on endurance and other physical properties. Endurance tests of non-ferrous metals were made by the machines used in the endurance tests of ferrous metals. 1-4 The specimen for the rotating-cantilever tests, which has been described, 1,2,13 has a conical surface, with taper so adjusted that the stress is nearly uniform over a length of about 1 ½ in. Alternating torsion tests were made with the machine of the inertia types17 and usually by an accelerated-fatigue method.12 As the rotating-cantilever endurance limits of metals are about twice the alternating-torsion endurance limits, the former values are more generally useful in correlating the endurance properties of nonferrous metals. In several recent papers by the writer13-16 correlation of the endurance properties of a number of non-ferrous metals has been discussed.

Jan 10, 1925

By Charles E. W. Bateson

The Mojave mining district is situated in a group of small hills centering around Soledad peak, in the Mojave desert, Kern county, Cal. These hills are about 4.5 miles SSW. of Mojave, a railroad town at the junction of the Santa Fé and Southern Pacific railroads. The town of Mojave is about 50 miles north of Los Angeles, to which it is connected both by telegraph and by rail. The distance on the Southern Pacific railroad is 102 miles, covered in 3 hr. and 45 min. by express train. A sketch-map of this region is shown in Fig. 1. The Mojave district is relatively isolated. The only other mining towns in this section of California are Randsburg and Johannesburg, in a district (containing the well-known Yellow Aster mine) at the northern end of a low range of hills, which begins about 20 miles NE. of Mojave, runs nearly N. for 35 miles, and varies in width between 3 and 6 miles. As will be seen later, the origin and formation of these hills are not the same as those of Soledad peak. II. Climate and VEgetation. The climate and vegetation of the Mojave district are typical of the arid regions of the southwestern United States. During the winter and spring there is some rainfall, and the tempera ture is generally from 60" to 70" F. in the day-time. The rainfall in the spring is often very considerable for short spaces of time, and cloud-bursts are not infrequent. In summer there is continual sunshine, with temperatures, as a rule, exceeding 100" F. in the day-time, while 115" F. in the shade of a house is not at all unusual; but at night the temperature falls considerably. No rain falls during the summer. The vegetation

Jan 1, 1907

By C. Schlumberger

SINCE the beginning of .the year 1928 the senior authors and their associates have applied a series of procedures which makes possible the detailed study in situ of the formations traversed by a drill hole before the casing has been landed. They have given the name "electrical coring" to the ensemble of these processes, which now replace in a large measure the mechanical coring performed by the drillers, and permit the gathering of bottom-hole data hitherto unobtainable. Three years have elapsed since the technique and interpretation of these measurements emerged from the experimental stage and entered the field of industrial application on a large scale. The total length of drill holes so far surveyed by the authors and their associates, all over the world, amounts to several millions of feet. Practical and strongly built equipment has been evolved, which permits the examination in a short time of an open hole several thousand feet long. No comprehensive paper has yet been published discussing the essential principles of the processes applied and bringing into evidence their economic interest. This is the object of the present paper.1 Numerous examples of field work performed under varied geological conditions are given, constituting a concrete illustration of the services rendered by the new methods. The study in situ of the formations penetrated by a drill hole is based on the measurement of a given physical factor or parameter associated with these formations. Generally. the measurements are made syste-matically along the whole length of the open hole. The physical factors or parameters which are now utilized by us to this end are: (1) the resistivities of the rocks; (2) their porosity; (3) their electrical anisotropy; (4) their temperature; (5) the resistivity of the muds. In order to

Jan 1, 1932

By Jack White, Ralph B. Adair

The Mufulira mine in Northern Rhodesia is 13° south of the Equator and at an altitude of 4100 ft above sea level. The concentrator was planned in 1930 to treat about 10,000 tons of ore per day, but before construction work had gone very far the size of the plant was reduced to 1500 tons daily capacity. Then just as the construction was finished in December 1931, the price of copper did not warrant the commencement of operations and it was not until October 1933 that the mine re-opened. Extensions have been made to the plant in 1934, 1935, 1936, 1937, 1940 and finally in 1945. The capacity of the plant when the 1945 extension is completed will be 9500 short tons per day. The various extensions have been carried out with the minimum confusion and with great skill on the part of the designers and the erection engineers. In dealing with the plant in this paper it is proposed to give an outline of the present practice and only to refer to past practice when it is considered of particular interest. Ore Treated The ore consists of fine grained highly siliceous, felspathic and argillaceous quartz- ites, the latter containing graphitic carbon and locally termed graywacke. These rocks are considerably altered near the surface and on the fringes of the ore body. Despite extensive efforts at mixing, both underground and in the crushing plant, many sudden changes of ore take place in the mill feed. The minerals are chalcocite, bornite and chalcopyrite with relatively unimportant amounts of malachite, native copper, azurite, covellite and chrysocolla. Gold is present at about I oz to a thousand tons, and silver at about 2 dwt. per ton. With increasing depth the nonsulphide content or,, as commonly termed locally, the oxide content of the ore is decreasing and is now less than 0.25 pct against a high of 0.77 pct- Crushing Operations The first stage of crushing is done under. ground where the oversize from I2-in. grizzlies is fed to a 56 X 72-in. jaw crusher. At the Selkirk shaft two 10-ton skips deliver the run of mine ore at a rate of 450 tons per hour to the 400-ton capacity shaft bins. One 6 ft wide Ross chain feeder and one locally made air-operated finger feeder feed the two 30-in. McCully crushers. Ahead of each crusher is a 6 X 9-ft spring grizzley spaced at 5 in. on a 35O slope. Neither the Ross chain feeder nor the finger feeder is entirely satisfactory and for the wet, muddy and sticky ore that has to be handled it is planned to replace these with two 6-ft wide apron pan feeders. The McCully crushers deliver a minus 5-in. product, at a.rate of over 500 tons per

Jan 1, 1949

By Albert F. J. Bordeaux

Alluvial gold was first discovered in Guiana in 1852, in the sands of the Arataye river, by Paulino, a Braziliaii convict. During the following years, gold was found also in the rivers Orapu, CirubQ, etc. In 1873 the famous placers of the Sinnamary system were opened: Saint-Elie, Dieu-Merci, Adieu-Vat, and Couriege. This group of mines has produced nearly $10,000,000, according to official records, not including the gold that escaped the taxes. The discoverer was a mulatto named Vitalo. Except in a few rich spots, the gold was rather evenly distributed along the creeks. In one instance, gold was found in the red dirt from the slope of a hill, which, after transport to the creek, gave an amount of 150 kilograms. The placers of the Mana system, Enfin, Elysee, Pas-Trop-Tot, date from 1878, and their production has been about %g5,000,000. In 1888, the Awa placers, along the boundary bet.ween the French and Dutch Guianas, on the Maroni and its tributaries, were discovered. They have yielded $12,000,000. The only industrial company, the Dutch Guiana Freiich Minillg Co., produced in 15 years about 2,500 kg. of gold, worth $1,500,000. From 1893 dates the famous Carsewene discovery, in territory then in dispute between France and Brazil. A settlement was made recently in favor of Brazil, by arbitration of the Switzerland State Council. Carsewene is said to have produced about $18,000,000 in six years (1894-1900), but not even one-fourth of tho production went through French Quiana and

Jan 1, 1911

By R. E. Grace

WHEN an Fe-C alloy, partially reacted to pearl-ite, is quenched rapidly enough to suddenly stop the growth process, it may be expected that any carbon concentration gradients will freeze in situ in the newly formed martensite. A short tempering treatment should precipitate finely dispersed iron carbide particles in approximately the same distribution in which carbon existed during the growth process. Examination with the electron microscope of areas of tempered martensite adjacent to the pearlite-martensite interface should reveal the existence of preferred areas of precipitation. Fig. 1 is an example of an electron micrograph used in this study. Small sections of a commercial steel (0.9 pct C, 1.6 pct Mn, 0.25 pct Si) were austenitized at 945°C in air for 45 min, furnace-cooled to 697°C, iso-thermally reacted to pearlite for 30 min, and quenched into iced brine. Two samples were tempered 5 and 20 min, respectively, in air at 498°C and were subsequently quenched in water. The samples were mechanically polished and etched in 1 pct picral. Collodion replicas were made by the conventional technique; these were shadowed with chromium at about 650' from the horizontal, and electron micrographs were taken at a linear magnification of 14,200X. Prints were made at a magnification of 44,100X. Lineal analysis of the prints was made as a function of the interlamellar spacing and volume percent of iron carbide. Straight lines were drawn into tempered martensite between adjacent lamellae at a distance S/4 or S/6 apart, where S is defined as the interlamellar spacing measured at the pearlite-martensite interface. The volume percent of iron carbide was measured along each of these traces with a "gage length" of S/10. The results of analyses of two samples are shown in Table I. The area included between the S/2 and S distance from the interface could be considered homogeneous within the sensitivity of the measuring technique. This value was used as a proportionality factor to evaluate an arbitrary carbon content of homogeneous austenite, and also as a parameter by which error in measurements could be evaluated. Results of the lineal analysis are shown in Figs. 2 and 3. Fig. 4 shows the statistical nature of the interlamellar spacing for all lamellae measured in this

Jan 1, 1954

By R. G. Gifkins

Mean boundary migration depended linearly upon creep extension under various conditions. Prolonged annealing or air-casting increased the proportion of immobile boundaries at a given stage of tests. Grain growth during annealing followed a power law. The linking of migration and sliding in creep and models for migration are examined; activation energies are calculated from these models. Segregation of oxygen to boundaries appears to be a controlling factor. THE idea that boundary migration and boundary sliding during creep are linked has often been suggested,'-5 especially when evidence has been obtained for an alternation between the two processes. In simple bicrystals sliding can occur without any migration6 but in more complex bicrystals7 it is observed. McLean' and Couling and Roberts 5 made measurements of both sliding and migration; McLean concluded that there was no linking of the two processes whereas Couling and Roberts supported the idea. McLean' also developed a model for migration during creep and annealing. The present work was initiated as part of a study of the recrystallization of lead during creep9 but has been extended to examine some aspects of the mechanism of migration. MATERIALS AND METHODS Specially refined high-purity lead* was used; the total of impurities, excluding oxygen, was 0.0008 wt pct. Oxygen was removed as far as possible by melting in vacuo, treating at 550" to 600°C with hydrogen and then casting at 450°C under a vacuum of 10-2 mm Hg; the oxygen was then believed to be 0.00005 wt pct. Specimens were made from extruded strip and then annealed at the required temperature in an air oven, controlled to 5 lac. They were then polished in a mixture of acetic acid and hydrogen peroxide. At this stage some specimens were etched to give grain contrast and their grain sizes determined by the intercept method. Migration of boundaries during creep was measured on the surface of polished (not etched) specimens, directly loaded at room temperature (22°C) or 50°C (52"C) to initial stresses of 300 to 700 1b per sq in. Twenty six vacuum-cast hydrogen-reduced specimens were used and, in addition, two specimens were from material air cast after hydrogen reduction ("partial" air cast) and two from air-cast material not treated with hydrogen ("full" air cast). Duplicates were made in the majority of tests. At intervals through the creep tests, specimens were unloaded and the migration measured, normal to the direction of migration at the point of measurement, for each boundary along standard traverses. Usually between 110 to 180 boundaries were measured at each of some twelve stages of the tests. Migration was measured on the projected image (X100) using prism illumination. Fig. 1 illustrates the method of measurement and shows the kind of variation of migration found from boundary to boundary and along particular boundaries. Fig. 2 gives an example of more extensive migration. The mean value of distance migrated was generally reproducible to *10 pct but occasional points gave a scatter of *20 pct. The correctibn applied by McLean8 to allow for the contribution sliding makes to the apparent distance of migration could not be used, for the sliding at most boundaries was too small to measure with the equipment available. There were two reasons for supposing the correction unnecessary in the present work;

Jan 1, 1960

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na' and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°'K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°'K and

Jan 1, 1968

By Wheeler P. Davey, Robert T. Phelps

A study of solid solutions has long been a source of interest because of the conditions controlling their formation. X-ray investigations so far have been conducted with the idea that there were two types of solid solutions. In the first type, an atom of the solute was supposed to replace an atom of the solvent in the crystal lattice. In the second type, an atom of the solute was supposed to lie in one of the interstices between the atoms of the solvent. These pictures both require that the sizes of the atoms must play an important part in the process of solution. It is the purpose of the present investigation to study the mechanism of solid solution, using pure silver as the solvent, and pure aluminum as the solute. X-ray measurements show that these elements have the same "shape" of atomic domains1 (they both crystallize as face-centered cubes) and that their atomic diameters differ by less than one per cent.' The results of the present investigation point toward a chemical rather than a physical picture of the nature of solid solution, and make the older pictures merely special cases of a more general picture. The new theory has the advantage, too, that it offers a rational explanation of certain phenomena which hitherto have been only interesting detached facts. The aluminum-silver system which was chosen for this study has been studied by various methods by several workers. By means of thermal analysis Gautier2 and Petrenko3 have determined the phase diagram. Hansen studied the aluminum-rich alloys by means of thermal and microscopic analyses. He showed that at high temperatures silver dissolved in aluminum to the extent of 47 per cent by weight at 560" C. But this solubility decreased to 1 per cent at 200" C. Westgren and Bradley5 made an extensive X-ray study of these alloys. They used the change in the lattice parameter of silver as a criterion of the solution State College, Pa.

Jan 1, 1932

By J. H. Frye, S. G. Holder, E. E. Stansbury

Internal friction studies on annealed and cold-worked pure silver and alloys of silver with 4.5 atomic pct each of Cd, Sn, and Sb are reported. Small amounts of cold work, introduced by stretching pure silver, decrease the internal friction; large amounts of cold work, by wire drawing, cause this decreased internal friction to rise. Results of severol anneoling histories on the room-temperature in-ternal friction indicate a rather complex recovery and recrystallization behavior. A rather system-atic alloy effect is observed for the elements of Period V-B in silver in both the annealed and cold-worked states. DURING recent years internal friction measurements at very small stress levels have been interpreted in terms of structural models and mechanisms occurring within the metal or alloy.These measurements have been made over wide ranges of frequency of vibration and of temperature. While the effects of impurities, alloying, and plastic deformation have been studied by numerous investigators, no investigations of the effect of a series of solutes related by their position in the Periodic Table on a given solvent seem to have been reported. The present paper reports internal friction measurements on silver and on certain silver-base solid solutions to determine the values of room-temperature internal friction associated with varying amounts of plastic deformation and after different annealing

Jan 1, 1957

By W. S. McCain, B. A. Wilcox, A. H. Clauer

The creep and creep-fracture behavior of a Ni-200-2Th0, alloy has been studied over the temperature range 816° to 1038°C and stress range 4000 to 19,000 psi Specimens having their axes either parallel or transverse to the final sheet-rolling direction were tested in air, and the apparent activation energy for creep was found to be 92 kcal per mole, regardless of specinien orientation. The stress dependence 01- the steady-state creep rate, was satisfied by where n depended on orientation; n = 9.7 for rrzaterial transverse to the rolling direction and n = 24.3 for material parallel to the rolling direction. In the latter case, the relation was also valid. The rupture strength of material parallel to the rolling direction was -1.5 times gveater than the transverse rupture strength. Several tests in vacuum revealed that here the creep rate was higher and rupture life lower than for comparable tests in air. THERE is an increased interest today in producing improved dispersion-hardened alloys for high-temperature structural applications. This had led various materials designers to modify existing alloys, such as thoriated nickel. One system that has received considerable attention is based on chromium additions to Ni-ThO2, with the obvious motive of improving the oxidation resistance. Another effect of chromium is that of lowering the stacking-fault energy, y, of nickel. For example, the addition of 30 wt pct Cr decreases y from -225 erg per sq cm for pure nickel1 to -70 erg per sq cm.' This decrease in y could have several effects on the deformation behavior. There is some evidence that cross slip of dislocations around Tho2 particles is a mechanism of tensile3 and creep4 deformation in TD Nickel (Ni + 2 vol pct ThO2) at temperatures below 0.5 the absolute melting point of nickel, T,. A decrease in ? by chromium additions should increase the difficulty of cross slip. Also it has been suggested that the high-temperature (T > 0.5Tm) rate-controlling creep process in "recrystallized" Ni-Tho2 alloys is the climb of edge dislocations over Tho2 particles.5 According to weertman6 a decrease in the stacking-fault energy should decrease the dislocation climb velocity resulting in a decreased steady-state creep rate. Thus, chromium additions to recrystallized Ni-Tho2 alloys would be expected to decrease the creep rate, all other conditions being constant. However, a difficulty arises when the stacking-fault concept is applied to high-temperature creep of dispersion-strengthened metals which are produced on a commercial or semicommercial scale. This occurs because the materials are processed so that they have a high-stored energy of cold work, and the other substructural effects could obscure any influence of stacking-fault energy per se. An example of an alloy with a high stored energy of cold work is TD Nickel bar. This material has a fibrous grain structure (1 I diam by 10 to 15 p long), and the structure is stabilized by the ThO2 particles. Annealing at high temperatures, e.g., 3 hr at 1300°C, causes no recrystallization or grain growth.4 Previous work by the authors4 showed that the high -temperature creep behavior of TD Nickel could not be related to any simple dislocation theory of creep, and this probably was associated with the complex initial structure of the material.

Jan 1, 1968

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By Mark E. Emerson

INTRODUCTION A long time has passed since geologists encountered encouraging mineralization in their regional exploration program for base metals deposits. Detailed drilling during the following two field seasons served to delineate the configuration of the deposit. Various statistical techniques were employed to provide confidence levels regarding the extent of the reserves and to categorize them according to whether proved, indicated or inferred. At this juncture, it appears that the company has an orebody. Time elapsed? - three years; money spent? - $2.5 million. Much remains to be done before the orebody becomes a mine. The company urgently needs to develop new orebodies to replace its existing mines which are being depleted. It therefore has expended sizable amounts in exploration, the life blood of the company. A staff of specialists is maintained to evaluate new projects and to conduct feasibility studies. The scale of new mining projects today is beyond the resources of most mining companies. Bank financing, therefore, is often vital if the company is to survive. The following scenario describes how a company goes about evaluating mine projects and what is needed to meet lender's criteria in securing the needed financing. MINE PLANNING Now that the company engineers have taken over the project, their concern is no longer with finding ore but in developing it. An exploration shaft has been put down and a tunnel driven into the orebody to verify, on a large scale, what has been seen so far only in pencil- like drill cores. A large tonnage bulk sample is mined and shipped off to an independent metallurgical process laboratory for beneficiation testing. The budget is expended to cover engineering studies. Preliminary capical and operating costs are developed in- house and profitability studies are made based or1 assumptions concerning the markets for the main product and the indicated gold, silver, and other by-products. Time elapsed? - four years; cost to date? - $3.5-$4.5 million. The staff prepares its own pre-feasibility study. After review, the Executive Committee authorizes management to proceed with full-scale studies. The task is to make preliminary designs and to develop definitive capital and operating cost estimates. Specialized consultants will be engaged to study slope stability for the open pit and rock strength if underground recovery proves more feasible. If it is near the sea, an oceanographic report might be commissioned to see if the tailings can be disposed of off shore. Environmental impact studies are commissioned from a firm familiar with government requirements and regulations in this important area. The company subscribes for an expensive multi-client study of the supply- demand-price outlook for the product to support its own long-range price forecast. Now all the numbers are available to make a definitive appraisal of the value of the project. Cash flow analyses and sensitivity studies follow. Reams of computer printouts are generated. Time elapsed: five years. Amount spent? - up to $9 million, depending on the size, complexity and attractiveness of the project. Marginal projects always take longer. Finally, an engineering and construction (E&C) company is given the task of integrating and compiling all the data into a feasibility study. The results of dozens of reports, memoranda, computer printouts, and charts are boiled down to one final summary report of a few hundred pages together with conclusions and recommendations. After thoughtful review at a board meeting, the directors authorize management to proceed with detailed engineering work - provided that

Jan 1, 1985