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By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-' of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963

By A. N. Holden

A DISLOCATION mechanism has been described by Cottrell' by which metals can yield locally, I. form Liiders bands, giving rise to a characteristic stress-strain curve with a sharp yield point and appreciable strain at constant or decreasing stress. It is undoubtedly the best mechanism that has been suggested to date." In its present development, however, the dislocation mechanism provides a more satisfying explanation for the sharp yield point than for the extensive localized flow occurring at the lower yield stress. The primary objective in this paper is to extend the dislocation mechanism to account for localized cataclysmic flow by a dislocation collision process and to give experimental evidence to support such a process. Only the yielding of iron containing carbon -will be discussed, although other metal-solute systems are known to behave similarly. Cottrell Mechanism In brief, Cottrell explains the yield point in the following way: The dislocations in iron which must propagate to produce slip usually lie at the center of local concentrations of carbon atoms, since segregation about these dislocatlons relieves some of the local stress resulting from them. A dislocation surrounded by a "cloud" of carbon atoms is thus anchored, and a higher stress is required to set it in motion than to move a free dislocation. Considering all available dislocatlons to be anchored in this fashion, the iron exhibits a yield point when the first dialocations break free and move through the lattice causing slip. This first breaking away of a dislocation enables other dislocations to break loose by "interaction" and the process becomes a cataclysm producing local deformation or Luders bands. The yield point in the stress-strain diagram for iron is absent in freshly deformed material, but returns gradually with time; the phenomenon is one aspect of what is called strain aging. The rate at which the yield point returns following straining depends on the temperature of aging. According to Cottrell the rate of return of the yield point in strained iron is limited by the rate of diffusion of carbon at the aging temperature, the mechanism is onr: of reforming the solute atmospheres around carbon-free dislocations that had stopped moving coincident with the removal of stress. If the specimen is retested immediately after straining and unloading, carbon will not have had time to diffuse to, and re-anchor, dislocations and the yield point will not occur. The carbon diffusion limitation for the rate of strain aging apparently applies if the criterion for strain aging is either the change in hardness" or the change in electrical resistance" of the strained speci- men with aging time. The possibility exists, however, that the yield point actually returns to strained iron at some rate other than that deduced from hardness or electrical resistance data. Therefore, as a preliminary experiment, the rate of yield point return in a rimmed sheet steel strained 6 pct in tension was measured at 27°, 77°, and 100°C. A plot of yield-point elongation for each of these temperatures against aging time appears in Fig. 1. The aging process is described by curves which rise to a plateau value of elongation that seems independent of temperature, but at a rate that depends on temperature. Very long times lead to a further rise in the yield-point elongation above the plateau value. However, if the later increase in yield-point elongation is ignored and the log of the time to reach half the plateau value of elongation is plotted against 1/T, a straight line results for which an activation energy of about 25 kcal pel- mol may be assigned. Within the accuracy of this sort of experiment this is approximately the activation energy for the diffusion of carbon in iron (20 kcal per mol), and the carbon diffusion limitation suggested for the yield-point return on strain aging is valid. The Cottrell mechanism thus explains in a qualitative manner the occurrence of a yield point in iron and its return with strain aging. It fails, however, to explain some of the other experimental observations that have been made of the yielding behavior of iron. For example, it is known that the yield point in iron becomes less pronounced with increasing grain size. Annealed single crystals of iron have very small yield-point elongations .if indeed they have any,' compared to a polycrystalline steel. If the only requirement for a yield point is that the dislocations in the lattice of the annealed. material be anchored by carbon atoms, the difference in the behavior of single crystals and polycrystals is not explained. That a dislocation mechanism may be entirely consistent with little or no yield point in an annealed single crystal will become apparent later when dislocation interaction is discussed. Strain aging produces a definite yield point even in single crystals. This accentuation of the yield-point phenomenon in single crystals after strain

Jan 1, 1953

By R. G. Davies, P. Beardmore, T. L. Johnston

The flow stress of a series of Ni-Cr-A1 alloys consisting of a dispersion of y' (based on Ni3Al) in a rnatrix of nickel-base solid solution y has been measured at temperatures up to 950°C as a fwzction of the volume fraction of y'. At high temperatures the flow stress is controlled by the amount of Y' in the alloy, i.e., the higher the volume fraction of y', the greater is the flow stress. This simple relationship is not obeyed at low temperatures in so far as a peak in the flow stress-volume fraction relation occurs at about 25 pct y'. The variation in the mechanical properlies of these alloys as a function of both temperature and volume fraction of y' has been correlated with changes in distribution of both the dislocations and y'. The results are interpreted on the basis that at low temperatures the y matrix is strengthened significantly bv the presence of a hyperfine y' precipitate due to decomposition on cooling; at high temperatures the y matrix is a single phase of low strength. It is clearly recognized that the high temperature strength of most nickel-base superalloys depends upon a dispersion of the ordered fcc phase y', based on Ni3A1, in a fcc solid solution matrix y based on nickel. Although the volume fraction of y' varies widely from about 0.2 in Nimonic 80A to about 0.6 in Mar-M200, all such nickel-base alloys manifest an unusual insensi-tivity of the flow stress with respect to temperature. In Mar-M200 for example, the 0.2 pct flow stress remains essentially constant from room temperature to 750°C. The conclusion has been drawn1 that the characteristically low temperature dependence of the flow stress of y-y' nickel-base alloys is obtained when the state of dispersion of y' is such that dislocations are forced to cut through the y' particles at the onset of yielding. When the spacing between the y' particles is so large that the flow stress is controlled by dislocation bowing between particles, then the initial flow stress decreases progressively with an increase in temperature at a rate determined by changes in elastic properties. The same conclusion is inherent in the detailed, mechanistic model of the deformation process in commercial superalloys which has been developed by Copley and ear' in which the temperature independent flow stress is attributed primarily to the contribution of the antiphase boundary energy created in the y' particles during deformation. In this theory the temperature insensitivity of the flow stress is a reflection of the constant antiphase boundary energy as a function of temperature. An important microstructural parameter that is relevant to the explanations that have been suggested' to account for the temperature insensitivity of the flow stress is the volume fraction of y'. To vary the latter to any significant extent in a given commercial alloy is clearly difficult. However, it is possible in a relatively simple Ni-Al-Cr ternary system which manifests analogous microstructures in terms of the distribution of y' in y and contains specific alloys which have flow properties that depend on temperature in a manner quite similar to their more complex commercial counterparts. Hornbogen et . have studied precipitation phenomena and deformation mechanisms in such alloys but only where the y' volume fraction was small (less than 0.2) and the y' particle size varied from less than 100A up to a maximum of -1000A. In the present study, a series of alloys was prepared in which the volume percent of y' at 900°C was varied from 0 to 100 pct with the y' particle size (of the order 0.5 p) comparable to the sizes obtained in commercial superalloys. Particular attention has been given to the relationship between variations in the volume fraction and distribution of y' and the temperature dependence of the flow stress EXPERIMENTAL TECHNIQUES The Ni-Cr-Al system was selected because it is well characterized, bears a close relationship to commercial alloys, and offers the advantage of an extra degree of freedom over a binary system. In the present investigation, a series of alloys across the tie line between NisA1 and Ni3Cr (Ni3Cr is not an in-termetallic compound, the nomenclature is only used to designate the composition) were vacuum cast. The pseudobinary6 and the composition of the alloys used are shown in Fig. 1. It is important to note that the compositions of the y phase and the y' phase in the two-phase alloys was always the same. Alloy compositions were selected from the binary diagram, Fig. 1, in order that aging at 900°C would produce from 0 (100 pct y) to 100 pct y' by volume percent. (The size of the y' particles produced during the equilibrium aging treatment increased as the volume fraction of y' increased, ranging from about 0.2 p at low volume fractions up to about 0.8 p at the highest volume fraction.) The y' phase is based on the inter-metallic compound Ni,A1 which has the fcc LIZ type superlattice structure, and chromium substitutes for aluminum in the structure. The y phase is a disordered fcc solid solution. The alloys were heat treated at 1150°C for 2 hr, air cooled to room temperature, and finally annealed for 16 hr at 900°C. The rods were then centerless ground to 0.25 in. diam and cut into compression samples 0.5 in. long. The compression tests were made on an In-stron machine at a strain rate of 7 x 10"4 sec-'. A rapid heating radiant heat furnace was used which minimized the heating and temperature stabilization time to 10 min for the highest testing temperature. All the tests were stopped after 5 pct plastic strain.

Jan 1, 1970

By A. C. Fieldner

ASH in coal has always been regarded as an undesirable substance, as the heat content of a coal decreases in direct proportion to its ash content. It represents so much inert material that has to be transported, handled when the coal is burned, and finally disposed of. W. R. Roberts, in an address before the Engineers' Society of Western Pennsylvania, Pittsburgh, on Sept. 29, 1925, said that on an annual output of five hundred million tons of coal, a reduction of 3 per cent. of ash means fifteen million tons of refuse and a decrease of $30,000,000 in freight charges. Ash also often prevents efficient utilization of the coal through the formation of clinker caused by the melting of the ash constituents when subjected to heat. The mineral constituents of coal may be of such nature as to make the coal unsuited for specific uses, as for instance, high-sulfur coal for making metallurgical coke. While the usual proximate analysis of coal gives the amount of ash, it gives no information as to the nature and composition of the ash nor of the mineral constituents from which the ash is produced. For the efficient washing of coal to remove ash-forming constituents it is desirable to know the composition and distribution of the ash-forming constituents. Obviously such information is also desirable for the most efficient utilization of coal.

Jan 1, 1926

By Gregory Dybalski

The purpose of this paper is to illustrate the forecast capability of the econometric model of the cobalt industry1/ as utilized by the Federal Preparedness Agency. Forecasts from this model are illustrated from the premise that the leading producer continues production of cobalt. An alternate forecast is presented where the model structure is altered to reflect the condition where the leading producer leaves the market. All estimations and forecasts presented here are shown for illustrative purposes. The cobalt industry is highly concentrated; one company, owned by the Zaire government, accounts for approximately three-fifths of world production. The cobalt supply outside of Zaire is determined by the level of activity of copper or nickel markets, as cobalt is mined as a by-product of copper or nickel. The demand for cobalt reflects a diversified usage pattern; cobalt is used mainly in heat and corrosion-resistant materials, high- strength materials and permanent magnets. According to 1974 U.S. consumption data superalloys accounted for 22%, magnetic alloys 18%, cutting and wear-resistant materials 13%, and catalyst 7%. Foreign consumption is probably similar in terms of usage categories, but the relative order of the categories is in variance.2/ The Cobalt Model The cobalt model's object is to explain consumption, supply and price movements by utilizing statistically estimated equations. Central to the econometric model is the role of Zaire as the profit-maximizing "dominant firm". Zaire sets the price that is most profitable for itself. The price of cobalt depends on industrial demand, production of other firms, and net exogenous purchases, such as government

Jan 1, 1977

By James H. Courtright, Kenyon Richard

TOQUEPALA is a porphyry copper deposit in which mineralization is localized by a large breccia pipe formed in close genetic relation to intrusive rocks. The deposit is in southern Peru, 55 airline miles north of the small city of Tacna and the same distance inland from the port of 110. Quellaveco and Cuajone, geologically similar deposits, lie 12 and 19 miles north of Toquepala. Chuquicamata is 400 miles to the south. The deposit is high on the southwestern slope about 20 miles from the crest of the Cordillera Occidental of the Andes Chain. It lies in a mountainous desert where the steep southwesterly slope of the Andes is dissected by a succession of rapidly downcutting, deep canyons. Local topography is moderately rugged with a dendritic drainage pattern and an elevation of 8000 to 14,000 ft. Volcanic peaks along the crest of the Cordillera rise over 19,000 ft. Local precipitation, including a little snow, amounts to about 10 in. during January and February, but general runoff in the region is slight. Throughout southern Peru the springs and streams are widely separated. Crude canals irrigate small farms on terraced slopes along the streams and provide sparse subsistence to the semi-nomadic inhabitants. During the past decade, engineering and geological explorations of the region, as well as the mineral deposits themselves, have required construction of a network of several hundred miles of roads. Before this, roads extended only a few miles inland. Many areas still can be reached only by trail. Toquepala was briefly described in 19th century geographical literature as a copper deposit, and it received desultory attention from Chilean prospectors early in the present century. It was first recognized as a mineralized zone of possible real importance by geologist O.C. Schmedeman during an exploration trip for Cerro de Paso Copper Corp. in 1937. The discovery was late as compared to earlier recognition of Chuquicamata, Potrerillos, and Braden of Chile and Cerro Verde of southern Peru. This was due partly to the region's difficult accessibility but principally to the obscure character of the outcrop evidence of copper. From 1938 until 1942 Cerro de Pasco Copper Corp. partially explored the deposit by adits and diamond drillholes. This campaign was supplied by a 60-mule pack train continuously shuttling over a 30-mile trail. Northern Peru Mining & Smelting Co., a wholly owned subsidiary of American Smelting & Refining Co., undertook regional engineering stud- ies in 1945 and drill exploration in 1949. According to published data1 the deposit contains 400 million tons of open pit ore averaging a little over 1 pct Cu. It is currently undergoing large-scale development by Southern Peru Copper Corp., which is owned by American Smelting & Refining, Phelps Dodge, Cerro de Pasco, and Newmont Mining. Summary of Geology: The deposit is situated in a terrane composed of Mesozoic(?) and Tertiary volcanic rocks intruded by dioritic apophyses of the Andean Batholith. These formations are exposed in a northwesterly trending belt about 15 miles wide. Along the northeast they are unconformably overlain by Plio-Pleistocene pyroclastic rocks, which occupy much of the crest of the Andes, and along the southwest they are covered by the Moquegua formation of Pliocene(?) age. The mineralized area, oblong in shape and about 2 miles long, has been a locus of intense igneous activity. Several small intrusive bodies having irregular forms occur within and adjacent to a centrally located, large breccia pipe. The mushroom-shaped orebody consists of a flat-lying enriched zone of predominant chalcocite with a stem-like extension of hypogene chalcopyrite ore in depth within and around the pipe. This breccia pipe is relatively large and has been formed by repeated episodes of brecciation. Small satellitic pipes occur at random within a 2-mile radius of this central pipe. These too were individual sourceways of mineralization, although not always of ore grade. Within and around the zone of breccia pipes and mineralization there are a few faults and veins, but these are discontinuous random structures of minor significance. There are no regional or local systems of faults or other planar structures recognized which could account either for the mechanical development of the breccia pipes or for their localization as a group or as individuals. Hydrothermal alteration is pervasive in the zone of mineralization. Clay minerals appear to be abundant in places, but their percentages are undetermined. Quartz and sericite are the principal alteration products, and in many instances original rock textures are obliterated. The principal sulfides, hypogene pyrite and chalcopyrite and supergene chalcocite, occur mainly as vug fillings in the breccia and as small discrete grains scattered through all the altered rocks. Sulfide veinlets are relatively scarce. Sulfides are more abundant and alteration is more intense in certain rock units, such as the diorite and most of the breccias. Although the Toquepala mineral deposit is similar in most respects to the porphyry copper deposits of southwestern U. S., it most closely resembles the Braden deposit of Chile, as described by Lindgren

Jan 1, 1959

By J. L. Gillson

Historically, rock deposits and sand deposits of titanium minerals came into production about the same time, although there may be some argument as to what is meant by production. Beach de- posits of heavy minerals in India (Figs. 1-4) and Brazil (Figs. 5) were worked for monazite about the turn of century, but as there was then no market for titanium minerals, these were thrown away. The rock rutile deposits at Roseland, Va., Fig. 6, were worked to supply rutile for titanium chemicals and for coloring ceramics long before there was a titanium pigment business. The pigment industry started about the middle twenties, both in Europe and the U. S., and almost simultaneously the rock deposits at Ponte Vedra Beach near Jacksonville, Fla., were worked for titanium content. Since those days, production from both types of deposits has continued to grow at a rapid rate; many deposits of both types have been found, and reserves have grown to very large figures. In total tonnage of reserves, there is no doubt that the rock deposits are far ahead of the sand deposits; nevertheless there is a very large tonnage of commercial sands available. It is the quality of titanium mineral in the sand and the relatively lower costs of operating sand deposits that have kept them abreast, at least in annual tonnage produced, with the rock deposits.

Jan 4, 1959

By R. J. Borg, C. E. Birchenall

The self-diffusion coefficients for a iron have been deternzined between 980° and 1167° K using Fe55 as the tracer. With decreasing temperature the diffusivity was found to decrease more rapidly than predicted by the Arrhenius equation in the region of the Curie temperature. The diffusion coefficients obtained well above the temperature of the magnetic transformation are more precise ard differ substantially from all the previously reported values. In the temperature region beginning at least 50" above T,, the diffusion coefficient is given by D = 118 (±2) exp 1 HE self-diffusion coefficients for a iron have been reported previously as the result of four independent investigations The general lack of agreement and the poor precision of most of the previous work prompted the redetermination by the present authors. The possible effect of the onset of ferromagnetism upon the diffusivity5 provided an additional impetus for this investigation. The earlier measurements of Birchenall and Mehl1 gave low values for the diffusion coefficient at temperatures below the Curie temperature, Tc. However, the precision of these measurements is not sufficient to establish an indisputable correlation between the low values and the magnetic transformation. The results of this investigation along with all the previous ones are shown in Fig. 1. EXPERIMENTAL Small rectangular samples, approximately 1 by 0.5 by 0.3 cm, of high-purity iron (Vacuum Metals Corp., "Ferrovac") are first heated in hydrogen at 900°C for24hr in order to remove possible trace amounts of dissolved carbon and oxygen. The small

Jan 1, 1961

By Douglas Bunting

In the anthracite fields of Pennsylvania, mine fires occur with more or less regularity and their existence is an ever-present hazard in coal mining. In all probability 90 per cent. of the mine fires can be ascribed directly or indirectly to the ordinary miner's open lamp. Other causes may be smoking, electrical installations, gas explosions, gas feeders, and the communication of fire to the outcrops from ash dumps, culm banks, timber and brush fires. Fires in pump rooms, engine rooms, and barns have been largely eliminated as a result of the Act of Assembly, approved June 15, 1911, which provides that all inside buildings, including engine rooms, pump rooms, barns, etc., shall be constructed of incombustible materials. Smoking of pipes, cigars, and cigarettes should be prohibited in the mines and too much care cannot be exercised in preventing fires by enforcing all rules designed for that purpose. Mine fires that involve underground fighting are invariably dangerous, and all fires, irrespective of the method pursued in extinguishing them, involve property loss and expense. Each fire generally presents a more or less original problem, dependent on the particular conditions. Generally mine fires may be divided into two classes: Those occurring in inaccessible workings and those occurring in accessible workings. The methods pursued in extinguishing or controlling mine fires are as follows: (I) direct attack, (2) smothering by sealing, (3) flushing with silt or other solids, (4) flooding with water, (5) cutting off, (6) surrounding with incombustible materials, (7) digging out by stripping from the surface. Most fires arc extinguished in their incipiency by direct attack and failure to extinguish by this method is due to late discovery, lack of water, and facilities for fighting, or improper procedure in the initial attack. Should the method first pursued be unsuccessful, careful consideration should be given in determining next the method to be adopted; then the work should be carried on as rapidly as possible and under the supervision of the most competent persons. Materials and supplies should be furnished without delay and in sufficient quantities for the work to be accomplished.

Jan 1, 1922

By J. W. Freeman, D. N. Frey

Fundamental reasons for the improvement in creep resistance of an austenitic alloy by cold working were investigated mainly by X-ray diffraction. The creep resistance was found to be improved by the internal stresses in the lattice of the alloy induced by the cold work. THIS investigation was concerned with the fundamental reasons for improvement in creep resistance of an austenitic alloy as a result of cold working. Also, the investigation was carried out to elucidate the conditions under which cold working could be expected to improve the creep resistance. To achieve these ends, creep resistance and internal structure were correlated for a variety of cold-worked conditions. Since the aim of the investigation was not to obtain specific and extensive information on any one alloy, creep testing was done with a single stress at 1200°F. Structural studies were carried out primarily with X-ray diffraction characteristics. The alloy used, low carbon N-155, was selected on the basis of being representative of at least some of the alloys used in gas turbines. Low carbon N-155 alloy in the form of %-in. sq bar stock was used in this investigation. The chemical composition, in percent, was: C, 0.13; Mn, 1.43; Si, 0.34; Cr, 20.73; Ni, 18.92; Co, 19.65; Mo, 3.05; W, 1.98; Cb, 0.98; N, 0.14; and Fe, balance. The bar stock was produced from a 13-in. sq billet, finished to 7/s in. round cornered square between 2060" and 1910°F. Prior to use in this particular investigation, the bar stock was solution-treated 1 hr at 2200°F and water quenched. This procedure was used in order to put the stock in a condition where effects of prior processing were minimized. Experimental Procedure The specific approach to the problem was twofold. First, the influence of cold working, under various conditions, on the creep rate under a single stress at 1200°F and on the internal structure was in part determined. Second, the effect of annealing at various times and temperatures on the creep rate and internal structure of the cold-worked samples was in part evaluated. The first step was basic to the investigation—creep resistance and structure were to be correlated. The second step was taken to see if the annealed samples showed some internal changes which could also be correlated with changes in creep resistance. This it was felt would facilitate solution of the basic problem. The creep and structural studies were carried out on samples reduced approximately 5, 15, and 40 pct at room temperature and 15 pct at temperatures up to 2200 °F. Annealing of various of the samples was done at 1200°, 1400°, 1600°, and 1800°F for time periods up to 1000 hr. Studies of the annealed samples were concentrated on materials rolled approximately 5, 15, and 40 pct at room temperature and 15 pct at 1400°F. The creep tests were carried out at 1200°F under 40,000 psi, the latter being approximately the 1000 hr rupture stress of the material

Jan 1, 1952

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By V. J. Sikora, T. S. Hutchinson

This paper presents a method for making a water-rlrive ana1gsis without prior knowledge of aquifer geometry and uniformity using a standard desk calculator. Although it is necessary to know the initial oil in place to use this method, this is a minor limitation to the scope of (he method since in most reservoirs it is possible to obtain reasonably accurate volumetric oil-in-place estimates. An equation is developed which relates pressure at the water-oil contact to the water influx rate as a function of time by a factor called the resistance function. The resistance function introduces the composite effect of the aquifer geometry and flow resistance disrribution. It is pointed out that the characteristic shape of this function makes it possible to start with on approximation of the function and successively improve the approximation until the correct resistance function curve is obtained. In this fashion water-drive estimates can be made without the limitation of assuming simplifed aquifer shapes and flow distributions. This is the novel feature of this development. Methods are given for extrapolating the final curve to calculate future aquifer behavior. Equations are developed for adjusting the pressures and water influx rates where it appears that possible errors in these quantities make it difficult or impossible to obtain a useuble resistance function curve without this adjustment. Application of the pressure build-up analysis techiiique to estimate. some of the aquifer properties is also presented INTRODUCTION A great many oil pools are the result of oil accumulation in some type of trap in an otherwise large and continuous porous stratum. The void space of this stratum outside of the oil pool itself is filled with water or brine. In analyzing performance of the oil pool surrounded by this water aquifer, it is quite necessary. in most cases, to include behavior of the water. When the pressure at any point in a fluid system is lowered, such as by opening a well in an oil sand, fluids in the immediate neighborhood of this point will begin flowing towards this lower pressure sink. As pressure in this area drops due to flow towards the sink, fluids from farther out will start to flow towards the lower pressure. As more and more fluid is removed from the system, the distance from the sink or well within which flow is occurring will continually increase; that is, thc region of disturbance will grow. If some rigid boundary such as a fault is reached by the disturbance, this area will cease to grow; but if some movable boundary is reached, such as a water-oil contact, the area will grow on out into the water, although rate of growth may and almost always does change. The relation between amount of pressure drop and amount of fluid flowing at any point and at any time in an aquifer depends on such factors as compressibility and viscosity of the fluids, the porosity and permeability of the rock, geometry of the whole system and withdrawal rate or pressure drop. With these factors known, it is theoretically possible to calculate the pressure-flow behavior of the system, However, in practice true solutions to the problem are next to impossible due to complexity of reservoir systems. A number of approximate methods of solution have been developed based on various simplifying assumptions. One frequent assumption is that the water-oil contact can be located and equations defining oil reservoir and aquifer solved separately by assigning values to various parameters so as to match past pressure and production history. Usually the properties of the aquifer are not known, since few, if any, wells are drilled through the aquifer; but the water influx and the pressure at the reservoir boundary are known over some time. If it can now be assumed that the aquifer is circular, pie-shaped, or linear, and that it has uniform properties, it is possible to fit a theoretical dimensionless curve to the past aquifer performance history and therefore calculate future water drive. These theoretical curves are available in the literature,1,2,3 Of course, the assumption of uniform aquifer properties is almost always somewhat in error. Fortunately, however, moderate variations from the average have little effect on behavior of the system; and, hence, the best fit of a theoretical curve is frequently satisfactory. In other cases variations in aquifer properties and geometry are large enough that none of the available theoretical curves will give an acceptable fit of the data. In these cases, methods of fitting the data with various electrical analyzers have been developed.1,2' It is the purpose of this paper to present an approach

By E. S. Fisher, L. C. R. Alfred

The elastic anisotropy factors, c4,/c6,, c3,/cll, and c12/cl,, for hcp metal crystals vary significantly among the dgferent unalloyed metals. Significant variations with temperature are also found. The effects of elastic anisotropy on the dislocation in an elastic continuum with hexagonal symmetry have been investigated by computing the elasticity factors for the self-energies of dislocations in fourteen different metals at various temperatures where the elastic moduli have been reported. For most of the metals the effects of the orientation of the Burgers vector, dislocation line, and glide plane are small and isotropic conditions can be assumed without significant error. Significant effects of anisotropy are, however, found in Cd, Zn, Co, Tl, Ti, and Zr. The elasticity factors have been applied in the calculations of dislocation line tensions, the repulsive forces between partial dislocations, and the Peierls-Nabarro dislocation widths. It is predicted that the increase in elastic anisotropy with temperature in titanium and zirconium makes edge dislocations with (a), (a + c), and (c) Burgers vectors unstable in basal, pyramidal, and prism planes, respectively. The probability of stacking faults forming by dissociation of Shockley partials in basal planes also decreases with increasing c4,/c6, ratio, when the stacking fault energy is greater than 50 ergs per sq cm. The widths of screw dislocations with b = (a) in titanium and zirconium increase very significantly in prism planes and decrease in basal planes as c4,/c6, increases. The effects of elastic anisotropy on various dislocation properties in cubic crystals have received considerable attention during the past few years. In the case of cubic symmetry the departure from isotropic elasticity depends entirely on the shear modulus ratio, A = 2c4,/(cl, —c12); i.e., the medium is elastically isotropic when A = 1. Foreman1 showed that an increase in the ratio A produces a systematic lowering of the dislocation self-energy for a given orientation and Poisson's ratio. ~eutonico~, has shown that large anisotropy can have a marked effect on the formation of stacking faults by the splitting of glissile dislocations in (111) planes of fcc and (112) planes of bcc crystals. ~iteK' made similar calculations for (110) planes of bcc metals. Both studies of bcc metals showed that the large A values encountered in the alkali metals tend to reduce the repulsive forces between Shockley partial dislocations. In fcc metals, however, A does not vary over the large range encountered in bcc metals; consequently, the effect of A on the forces between Shockley partials is masked somewhat by the differences in Poisson's ratio between metals. The effect of A on the line tension of a bowed out pinned dislocation has also been investigated for cubic crystals, first by dewit and Koehler5 and more recent- ly by Head.6 In both cases the line energy model is applied and the core energy is not taken into account, thus making the conclusions somewhat tenuous with regard to the physical interpretation. Nevertheless, the fact that a large A decreases the effective line tension is clearly evident and the tendency for large A to produce conditions that make a straight dislocation unstable (negative line tensions) also seem evident. Head, in fact, shows visual microscopic evidence that stable V-shaped dislocations occur in 0 brasse6 For hcp metals the definition of elastic anisotropy is more complex and, furthermore, significant deviations from an isotropic continuum are found among a number of real hcp metals, especially at higher temperatures. The present work was carried out to survey the effects of elastic anisotropy on the elasticity factors, K, that enter into the calculations of the stress fields around a dislocation core. Some isolated analytical calculations have previously been carried out for several hcp metals but they are restricted in the dislocation orientations and temperature.8'9 The present computations are based on single-crystal elastic moduli that have appeared in the literature and consider various orientations requiring numerical computations. The results are then applied to survey the effects of temperature on the dislocation line tension and dislocation splitting in hcp metals. PROCEDURE Anisotropy Factors. The degree of elastic anisotropy in hcp crystals cannot be described by a single parameter, such as the A ratio in cubic crystals. The following three ratios must be simultaneously equal to unity in order to have an elastically isotropic hexagonal crystal: The magnitudes of these ratios at several temperatures, as computed from the existing data for the elastic moduli of unalloyed hcp metals, are given in Table I. There are no cases of complete elastic isotropy, but the large anisotropy ratios encountered in the cubic alkali metals are also missing. There are, however, several significant differences among the hcp metals, the most notable being the relatively small A and B ratios in zinc and cadmium and the differences in the magnitudes and temperature dependences of A. It has been noted that the temperature dependence of A has a consistent relationship to the occurrence of the hcp — bcc tran~formation. For cadmium, zinc, magnesium, rhenium, and ruthenium, A is less than unity at 4'~ and, with exception for rhenium, decreases with increasing temperature. In the case of rhenium, A has essentially no temperature dependence between 923' and 1123"~, so that it is clear that A does not approach unity at higher temperatures. Cobalt is similar to the above-mentioned group of metals in that it also does

Jan 1, 1969

By Philip R. Strand

Vermiculite is the name used for those micaceous minerals with a ferromagnesian aluminum silicate composition and the unique property of exfoliating to a low density material when heated. Commercially, the exfoliated products are also called vermiculite, or more exactly, expanded vermiculite. In its exfoliated state, vermiculite serves many markets, chief among them construction, agriculture, horticulture, and general industry. Composition and Properties Vermiculite, in a natural state, has the characteristic mica habit, splits readily into thin laminae, flexible but inelastic. In a mineralogical sense, vermiculite is a hydrated silicate with no exact chemical composition. The structural formula for a macroscopic, trioctahedral vermiculite may be written: [ ] The structure of vermiculite is basically that of a talc, and it could be regarded as a trioctahedral member of the smectite group. Macroscopically, vermiculite displays the prominent monoclinic crystal faces that are commonly marked by lines at 60° and 120°. Hardness varies from 1.5 to 2.8 or more; specific gravities are between 2.1 and 2.8; color is amber, bronze, brown, dark green, or black. When heated quickly to an elevated tempera¬ture, vermiculite expands by exfoliating at right angles to the cleavage, into wormlike pieces (the name vermiculite is derived from the Latin `vermiculare,' to breed worms). This characteristic of expansion, the basis for commercial use of the mineral, is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The increase in bulk volume of commercial grades is 8 to 12 times, but individual flakes may expand as much as 30 times. All expansion occurs at right angles to the basal cleavage. Vermiculite may also be expanded by a number of chemical processes such as soaking in hydrogen peroxide, weak acids, and other electrolytes. There is a color change during expansion that is dependent upon the composition of the vermiculite and furnace atmospheres. Heating in an oxidizing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. The exfoliation of the vermiculite crystal results in large pores being formed between groups of platelets. Thus exfoliation can make available a large increase in void volume without significantly changing the surface area of the platelets. This characteristic is important in the chemical carrier applications of vermiculite. Although there has been much research on the chemical and structural composition of vermiculite, an exact formula and composition cannot be described. This is to be expected since vermiculite derives from a number of different mineral sources. As has been proposed, vermiculite is not a single mineral species, but families of related minerals. Additionally, commercial interest in the end product has resulted in the name vermiculite being applied to the very voluminous, bloated products from calcination of baueritized (bleached) phlogopite. This has also resulted in many names for the specific vermiculite found in a particular deposit. All of this difficulty arises from the nature of its crystal chemistry. Consequently, vermiculite is now thought of as several related variable mineral series rather than a group of related species. The vermiculites have a common silica tetrahedral sheet structure with separating ions. It is now generally agreed that vermiculites must also be regarded as true clay minerals. The properties of the mineral, such as cation exchange capacity, organic complexing ability, and vari-

Jan 1, 1975

By Joseph Taylor

THE Ducktown district is in the extreme southeastern corner of Tennessee, its principal railroad point being Copperhill, on the Blue Ridge division of the Louisville &Nashville Railroad, midway between Knoxville, Tenn., and Atlanta, Ga. The ore deposits were discovered about 1849 and development work was begun in the early fifties. Only the "black copper? ores, products of secondary enrichment, from beneath the gossan outcrops and overlying the massive sulphide deposits, were then mined and smelted for their copper content. Upon their exhaustion, attention was directed to the treatment of the pyritic ore remaining, resulting in the devising of a, process consisting of open-heap roasting, followed by blast-furnace smelting, which was practised until 1903, when semi-pyritic smelting was-adopted. In 1908, the companies operating in the district; on account of litigation brought about by alleged smoke damage to forests and vegetation in the adjoining counties of Georgia, were compelled to erect enormous acid plants to prevent the escape of the sulphur dioxide produced in the smelting operations. The utilization of this sulphur dioxide in the, manufacture of sulphuric acid as a byproduct has added to the revenues of the companies, and at the same time has furnished a valuable source of supply of sulphuric acid to the fertilizer trade of the South, and more recently to the manufacturers of explosives for use in the production of war munitions. The steadily increasing demand for sulphuric acid for the manufacture of fertilizers and explosives, together with the decreasing imports of pyrites, from which the acid is generally produced, now makes it imperative that greatly extended resources of pyrite be developed. While the Ducktown deposits do not predominate in pyrite, they do contain an inexhaustible supply of pyrrhotite, admixed with pyrite, which can be satisfactorily employed to supplement or substitute for pyrite in acid making.

Jan 2, 1918

By Chester A. Fulton

In Polk County, Florida, the mining of raw phosphates began some 50 years ago with dredging operations on the Peace River, and in other near-by places by removal of shallow overburden with negroes and wheelbarrows, or with mules and scrapers, and the excavation and screening of deposits found close to the surface. There were many individual operations of comparatively short life. Later steam shovels removed the overburden, and still later hydraulic methods were substituted for the steam shovel. Within the last 10 years large electrically operated draglines have almost entirely replaced hydraulic mining for overburden removal. The matrix is still mined by hydraulic giants and pumped to the washer or recovery plant. The many small operations have long since disappeared and the most desirable phosphate lands have gradually been acquired through purchase or merger by the seven companies that are operating in the field today. These companies are producing and selling about 2,000,000 long tons of phosphate per annum, or about two-thirds of what the industry likes to think is the normal output, with 1929 and 1930 in mind. To produce these 2,000,000 long tons of raw phosphate, they mine and treat about 1,000,000 tons of tailings from older and less efficient operations, about 11,000,000 tons of matrix, and remove from above this matrix some 22,000,000 tons of overburden. The mining practice that has made possible the excavation and handling of 34 million tons of material to win but 2 million tons of merchantable product, selling for probably an average of only $4 per long ton when dried, should be of interest to the mining profession, though little has been written of it. The Florida Pebble Field, as it has come to be known, comprises an area (Fig. 1) within a radius of about 18 to 20 miles centering around Mulberry in Polk County, a small town 30 miles east of Tampa, Florida's largest port on the Gulf coast. The geology1 of these phosphate pebble deposits may be described briefly. A fairly pure limestone was altered to a secondary apatite.

Jan 1, 1938

By Chester A. Fulton

In Polk County, Florida, the mining of raw phosphates began some 50 years ago with dredging operations on the Peace River, and in other near-by places by removal of shallow overburden with negroes and wheelbarrows, or with mules and scrapers, and the excavation and screening of deposits found close to the surface. There were many individual operations of comparatively short life. Later steam shovels removed the overburden, and still later hydraulic methods were substituted for the steam shovel. Within the last 10 years large electrically operated draglines have almost entirely replaced hydraulic mining for overburden removal. The matrix is still mined by hydraulic giants and pumped to the washer or recovery plant. The many small operations have long since disappeared and the most desirable phosphate lands have gradually been acquired through purchase or merger by the seven companies that are operating in the field today. These companies are producing and selling about 2,000,000 long tons of phosphate per annum, or about two-thirds of what the industry likes to think is the normal output, with 1929 and 1930 in mind. To produce these 2,000,000 long tons of raw phosphate, they mine and treat about 1,000,000 tons of tailings from older and less efficient operations, about 11,000,000 tons of matrix, and remove from above this matrix some 22,000,000 tons of overburden. The mining practice that has made possible the excavation and handling of 34 million tons of material to win but 2 million tons of merchantable product, selling for probably an average of only $4 per long ton when dried, should be of interest to the mining profession, though little has been written of it. The Florida Pebble Field, as it has come to be known, comprises an area (Fig. 1) within a radius of about 18 to 20 miles centering around Mulberry in Polk County, a small town 30 miles east of Tampa, Florida's largest port on the Gulf coast. The geology1 of these phosphate pebble deposits may be described briefly. A fairly pure limestone was altered to a secondary apatite.

Jan 1, 1938

By Stanley F. French

ELECTRICAL power and distribution for the sulphide ore plant is an addition and extension of the existing power system which has served the oxide reduction plant since its inception in 1914. The power plant is located at Tocopilla on the west coast of Chile, some 90 miles from Chuquicamata. A brief description of this plant and the existing transmission system is necessary to an understanding of the problems involved in the provision for the sulphide plant load. Originally the Tocopilla power plant consisted of four Escher Wyss turbines driving Siemens Schuckert generators, each rated 10,000 kw. At various times, units of 10,000 and 20,000 kw were added, all of which operated at 215 psi and 600°F at throttle. In order to improve the economy of the station, a Topping unit was installed in 1938 together with a high-pressure steam generator of 360,000 lb per hr capacity. This unit is rated at 11,000 kw and was designed for 750 psi, 880°F. The exhaust from this turbine passes to the low pressure station header for operation of part of the low pressure turbines. Total kw generated by the high pressure boiler, topping turbine and associated low pressure turbines totals 33,000 kw and the total station capacity is 113,000 kw. This installation proved one of the most successful of its kind, operating almost continuously. The original plant was of German design and consequently European characteristics were incorporated into the system, the frequency being 50 cycles and voltages of 500, 5000 and 100,000 were used for low, generator, and transmission voltages,

Jan 1, 1952

Mining examinations are of several kinds and the scope of the investigation depends in each case upon the purpose for which the examination is made. A formal examination of a developed mine is an expensive undertaking; from one to several months are allowed for the work according to the size of the property; many samples are taken; investigation is made of the geological features, including, perhaps, a topographical and geological survey of the surface; the metallurgical treatment of the ore is studied; finally, a determination of costs is demanded. Formal examinations are made for prospective purchasers or as a basis for the consolidation of several properties, and occasionally, in the owner's behalf, to verify the work of resident engineers, or to determine the readiness of a mine for equipment and the kind and capacity of equipment it shall receive. A formal examination of a mine should not be undertaken until a preliminary examination has shown that it is justified. It is regrettable that some engineers are in the habit of prosecuting long and exhaustive examinations of properties whose lack of merit should be, and perhaps is, apparent from the start, or of continuing their investigation long after an unfavorable result is seen to be inevitable. This wasting of a client's money is a species of trickery difficult to prove, and therefore the more contemptible. Preliminary examinations are precisely what the term implies, and are undertaken to determine the advisability of making

Jan 1, 1932