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By P. Chiotti, E. R. Stevens

The electromotive force between pure magnesium and Mg-Zn alloys in a fused KC1-LiCl-MgC12 cell was measured over the temperature range 360° to 730°C and for alloy compositions of 0.052 to 0.635 atom fraction magnesium. The calculated activity coefficients of magnesium in the liquid alloys may he represented by the relation These data and the phase diagram were employed in calculating the standard free energy of formation for the compounds MgZn, MgZn2, and MgZn2, In the temperature range from 25° to 590°C the relation ZINC-rich magnesium alloys have been shown to be very effective in reducing various solute chlorides or oxides from fused salts such as KC1-LiC1 eutectic. Such reactions are of interest in the developinent of pyrometallurgical methods for reprocessing nuclear reactor fuels.' As the conceniration of the magnesium is increased beyond 5 to 10 wt pct the extent to which solutes, such as yttrium, lanthanum, cerium, and other rare earths, can be reduced or removed from the salt decreases. This effect is due to the resulting change in the activity of the solutes in the Zn-Mg alloy as well as the change in the activity of both the zinc and mag- nesium. The purpose of the present investigation was to determine the thermodynamic properties of the Zn-Mg system which, in addition to yielding information on the alloying behavior of these two elements, would permit a more quantitative understanding of the above reactions. Since this investigation was initiated several publications have appeared in the literature giving results on the thermodynamic properties for the liquid alloys of this system. 2-4 Kozuka, Moriyama, and Kushima3 measured the vapor pressure of zinc over four different alloy compositions by a carrier-gas technique. Eremenko and Tukashenko2 and Terpilowski4 measured the electromotive force between pure magnesium and various alloys in a fused salt cell. Earlier work has been summarized by Hultgren, Orr, Anderson, and Kelley.5 In the present investigation electromotive-force measurements were made on a cell of the type The temperature range covered for the lower-melting alloys was roughly 375° to 730°C. These data were employed in calculating the thermodynamic properties for the liquid alloys and in conjunction with the phase diagram,' reproduced in Fig. 1, were used in calculating the standard free energy of formation of the compounds MgZn, MgZn2, and Mg2 Zn11. The results obtained are compared with available data from the literature. MATERIALS AND EXPERIMENTAL PROCEDURES Materials employed were: Bunker Hill slab zinc, 99.99 pct pure; Ames Laboratory magnesium containing 13 ppm N, 195 ppm C, and trace amounts of calcium, copper, nickel, and silicon; reagent grade KC1, LiC1; and high-purity MgC12 obtained from Dow Chemical Co. The electrolyte consisting of KC1-LiCl eutectic (44.4 wt pct LiC1) to which was added 15 wt pct MgCl2, was dried in a quartz tube by heating to 340° C under vacuum for a period of 4 to 5 hr, and then passing HC1 through the salt as the temperature was slowly raised to above the melting point of the salt. After about 3 hr the HC1 was shut off and the system flushed with argon and then vacuum applied for 1 hr. The salt was finally siphoned through a sintered glass filter and cast into a Pyrex container which was sealed and

Jan 1, 1965

By Michael Tenebaum

IN a previous investigation1 the authors studied the effect of pressure on the reduction of iron ores by hydrogen. With hydrogen as a reducing agent, the rate of reduction was increased substantially by increasing the pressure from 1 to 2 atmospheres. The results with hydrogen prompted the present study of the effect of pressure on reduction with carbon monox-ide and with mixtures of carbon monoxide and nitrogen. FEATURES OF REDUCTION PROCESS The gas stream in the lower part of the blast furnace always contains sufficient concentrations of reducing gases to complete reduction provided sufficient time is allowed for the reaction to proceed. Reducing gases react immediately with the iron oxide on the surface of lumps of ore. However, as the unreduced surface recedes from the easily accessible exterior of the lump, the reaction proceeds by virtue of the diffusion of the gases into and out of individual pieces. The rate of diffusion of gases, which undoubtedly plays an important role in the reduction of iron ores, depends on several factors, most impor-tant of which are: (1) molecular weight or density, (2) pressure, (3) tem-perature, (4) concentration gradient. Thus, the rate of reduction of a lump of iron ore at any temperature will depend not only on the specific reaction rate but also upon: (1) available surface of unreduced iron oxide, (2) rate of diffusion of the reducing gas to the reacting surface, (3) rate of effusion of the gaseous products of the reaction from the reacting surface, (4) adsorption of the gases on the reacting surface.

Jan 1, 1939

By D. L. Pentz

The use of "probability" methods in slope stability analysis has been practised by geotechnical engineers for some time. This paper questions whether the term probability has been properly used since in many cases the term is used in a classical statistical manner only to describe frequency distributions of data. This paper proposes a definition of the term probability which includes the engineers' subjective state of confidence for all critical parameters. Such parameters may include the slope stability model, undetected structural features, strength, groundwater pressure distribution, and geological framework. This process does not make a "better" analysis but it does force the geotechnical engineer to state his opinion in such a manner that others can understand and if necessary, criticize the assumptions. Further, this technique forces the question, "What impact would failure of a slope have on the production schedule or costs of a mine?" The level of risk taken in adopting a particular slope design strategy in a mine is not a question of what Factor of Safety should be selected but, rather, what trade-offs result from steeper slopes and the associated costs of failure. This paper also presents several simple probabilistic techniques which, though widely used in other fields have been all but ignored in geotechnical slope stability analyses. These include the use of stratified sampling to optimize Monte Carlo uncertainty approaches, and the use of simple functional approximations rather than complex stability models in probabilistic analysis. The author presents a case example of this technique and discusses the results in comparison with more traditional methods.

Jan 1, 1983

By S. Floreen, H. W. Hayden

The effects of additions of iridium, rhodium, ruthenium, and platinum on the mechanical properties of Fe-C alloys were determined. Each alloying element significantly improved the toughness. The results support the general correlation that substitutional alloying elements that stabilize austenite are beneficial to toughness, but the reason for this improvement is not obvious at this time. The effects of substitutional alloying elements on the toughness of steel has long been a subject of both practical and theoretical interest. Despite the obvious importance of this subject, there has been little progress toward understanding the mechanisms by which alloying elements influence the fracture behavior. In some cases the deleterious effects of alloying elements have been shown to be due to mechanisms such as embrit-tlement of prior austenite grain boundaries or inhibition of cross slip in the ferrite lattice. In other cases, however, the reasons for the change in properties are not clear. This is particularly true for elements, such as nickel, that improve the resistance to brittle fracture. Several investigators'-3 have pointed out that there is a correlation between an alloying element's phase diagram with iron and its effect on toughness. Those substitutional alloying elements that stabilize austenite generally are beneficial to toughness, while ferrite-stabilizing elements generally are detrimental to toughness. The word "generally" should be emphasized, because exceptions to this rule can be found. Nevertheless, this correlation does offer a starting point at which to try to understand the effects of alloying elements on toughness. Thus far only two austenite-stabilizing elements, manganese and nickel, have been considered. In order to test the validity of this correlation several other austenite-stabilizing elements were evaluated. The noble metals, iridium, rhodium, ruthenium, and platinum, have binary phase diagrams with iron similar to the Fe-Ni and Fe-Mn diagrams. That is, each element expands the austenite field, and also higher concentrations of each element produce martensitic transformations at low temperatures. Presumably then, each of these elements should improve the toughness of steel. The present study was conducted to determine if this were so. EXPERIMENTAL PROCEDURE The alloys were made as l-lb air-induction melts using electrolytic iron and commercially pure noble metals. Each heat was initially deoxidized by a carbon boil, and further carbon was added to attempt to produce a 0.05 wt pct C content in each alloy. Before pouring, a final refining addition of 0.2 wt pct A1 and 0.1 wt pct Ti was made to each heat. The alloys were cast in a copper mold to produce ingots approximately 1 in. in diam and 5 in. long. The chemical compositions of the alloys tested are given in Table I. The residual nitrogen, aluminum, and titanium contents were all relatively constant at 0.003, 0.03, and 0.02 pct, respectively. The carbon

Jan 1, 1968

THERE are two general types of scientific approach to a problem. One approach, which is the more widely known, involves an analysis of the situation at the beginning of the experiment; this is followed by an analysis of the situation at each instant of time during the experiment and leads to a-detailed description of the prevailing conditions at the end of the experiment. Suppose, for example, we wish to predict the final rest position on a billiard table of a ball moving initially in a certain known direction with a known speed. The obvious approach is to estimate or measure off its course by consideration of angles of rebound, taking account of the "English" or spin if necessary and finally estimating from experience (or calculating from coefficients of friction) the slowing down occasioned by friction, thus establishing the point of the course at which the ball may be expected to stop. Any interference with the calculated course occasioned by collision with an unanticipated object would obviously cause us to revise drastically our estimate of the rest position. This general method of approach characterized by detailed description of how one situation developed from another seems intuitively appealing and is the most widely known method. There is no doubt that it gives very satisfying results when it can be used. There is a second general method of approach. In this method, the final state of a system is predicted from knowledge of general broad principles and their application, considering only the restrictions imposed upon the system. It is unnecessary to follow the course in detail; intermediate steps are not even considered. For example, if the billiard table mentioned in the first paragraph were tilted to one corner, one could predict that the final resting place of the ball would be in that corner; this prediction can be made independent of any particular course the ball may follow. This second general method of attacking problems is the one used in thermodynamics. There its use is so outstand-

Jan 1, 1951

By C. R. Watts

The feasibility of producing composites containing nickel or molybdenum fibers in a beryllium matrix was inrestigated. The composties studied were jabricaled by powder mallurgical techniques. The 1-mil-diarr nickel fibers reacled completely below 900°C, converling the fibers .from nickel to Ni5Be2,. As the /LO/-pressing temperalure as raised above 1110oC, tlie nickel diffused outward from the beryllide fibers. The solid solubility of nickel in beryllium was clboul 20 wt pet at the 1100°C pressing temperature a1 the zone-fiber interface. The 1.5-mil-diam molybdenum fibers slzolred no evidence of reaction and little evidence of diffitsion after pressing at 900°C. Between 1000° and 1050°C pressing conditions, the fibers began lo react , producing 1ayers of MoBe2 and MoBe12, respectively surrounding the molybdenurn core. The struture remained the same at 1100°C with no evidenre of solid solubility of the molybdenum in the berylium or vice versa. In recent years a considerable amount of attention has been devoted to the determination of methods for improving the mechanical properties of materials through the use of fiber or whisker reinforcement. Previous work with metal matrix composites indicates that the study of the chemical compatibility of the fiber and matrix is an area requiring greater understanding. The metal-metal or ceramic-metal interface is frequently subject to chemical reactions that may result in the formation of hard brittle intermetal-lic compounds and/or low melting point eutectic compositions. The reaction products may reduce both the low-temperature and elevated-temperature strength of the composite by weakening the fiber-matrix bond, producing premature failure at the interface. It is well-known that most metal-metal systems and many metal-ceramic systems of interest for structural composites are thermodynamically unstable,'-" particularly at elevated temperatures. If, however, the rate of reaction under the conditions of fabrication is sufficiently low. composites can be fabricated that can be used efficiently for indefinite periods at low temperatures and for short periods at elevated temperatures. This paper presents the results of a series of tests to determine the compatibility of nickel and molybdenum fibers with beryllium at various hot-pressing temperatures. Nickel was selected as a candidate fiber material primarily because the relatively ductile fibers might be useful as crack arresters in applications such as ballistic impact where crack growth can result in catastrophic failure. The high density and the reactivity of nickel were primary factors detracting from its selection as a possible reinforcement. Molybdenum with a modulus of elasticity of 52 Xlo6 psi is one of the few metallic materials having a modulus higher than beryllium (42 X lo6). Its high modulus, coupled with its refractory characteristics, made molybdenum an attractive candidate for a relatively stable fiber reinforcement for beryllium. Its density, being higher than that of nickel and over five times that of beryllium: detracted from its other characteristics. EXPERIMENTAL PROCEDURE The specimens were prepared from beryllium powder with a dispersed phase of fibers by powder metallurgical techniques. P-20 grade powder, Table I, from Berylco was used as the matrix material. Short lengths of 0.001-in.-nominal-diam nickel fibers supplied by the Sigmund Cohn Corp. and 0.0015-in.-nominal-diam molvbdenum fibers obtained from the General Electric Co. were used as the dispersed phase. The composite constituents were combined under an argon atmosphere by mechanically mixing the powders and fibers. The compositions used were nominally 1 vol pct fibers. After mixing. the composites were hot-pressed into a-in.-diam pellets under an argon atmosphere at 900°, 1000". 1050". and 1100°C at a pressure of 6000 psi with no hold time at these temperatures so that a comparison could be made between the resultant microstructure and hot-pressing temperature. The billet was heated at a rate on the order of 30°C per min to the desired temperature and then cooled at a somewhat slower rate. The microstructure obtained should be considered as characteristic of the integrated time-temperature history of the sample, as well as the maximum temperature attained. Upon removal from the hot-pressing dies. the specimens were cut. mounted. and polished by standard procedures. No etchant was used in specimen preparation. Photomicrographs, electron microprobe scans, and electron back-scatter pictures were made. X-ray dif-fractometer patterns were made of several of the specimens. but only the lines for beryllium could be resolved. Specimens for optical and electron microprobe examination were selected partially for the roundness of the cross section. A round cross section was taken to indicate that the body of the fiber was approximately normal to the surface and that therefore effects due to fiber material immediately below the surface could be neglected. RESULTS AND DISCUSSION The microprobe scans indicated that nickel reacted as low as 900°C, converting the entire fiber cross section to NisBe21. Fig. l(a). There was no evidence of further reaction from the optical or the back-scatter pictures, Figs. 2(n) and 3(a).

Jan 1, 1970

Curlisle: We're sitting in Don McLaughlin's office overlooking Sun Francisco Bay, and he's going to be good enough to talk about early days in California, maybe about his college years in Berkeley, maybe about his first jobs in mining. Now, Don, would you be good enough to start it off by saying something about George Hearst. I know he died before you were born, but you know a lot about the family, and you no doubt know a lot about him. Certainly, nobody in those days matched his record in getting hold of good mines. McLaughlin: George Hearst died, actually, in the very year that I was born, but as I more or less grew up in the home of Mrs. Phoebe Hearst, who was his widow, I heard a great deal about the mines and the people that made the great fortune she inherited and used so wisely. But I don't think I really had an appreciation of George Hearst until 1 became active in the mining world and realized how many major mines he had picked in the early days and how much he had to do with their development into successful properties. He started in the California gold fields, but it was on the Comstock that he made his first big stake out of his substantial share in the Ophir mine. I believe at that time he was on his own. Then, later, he became associated with Ben Ali Haggin and Lloyd Tevis in San Francisco, and scoured the West for them. They made a little money in Eureka, Nevada, and other places, but the first important property that he obtained for them was the famous Ontario Mine in Park City, which became one of the great silver lead producers of the Continent. Then later he acquired the Homestake.

Jan 6, 1965

By W. M. McCardell, W. O. Winsauer

The abnormal conductivity found in shaly reservoir rocks containing an electrolyte is shown to be a consequence of the electrical double layer in the solution adjacent to charged clay surfaces. This increased conductivity results from a higher concentration of ions in the double layer than in the solution in equilibrium with the double layer. It is shown that the magnitude of the increased conductivity of a shaly reservoir material is influenced by the concentration and type of ions in the equilibrium solution as well as by the colloidal nature of the rock. INTRODUCTION An important factor in the quantitative interpretation of the electric log is the resistivity factor of reservoir rock. The resistivity factor is defined as the resistivity of the rock when completely saturated with an electrolyte divided by the resistivity of the electrolyte itself.' In the normal case, the resistivity factor for a particular rock sample is independent of the resistivity of the electrolyte and reflects the pore geometry of the rock.' In 1949. Patnode and Wyllie' showed that in some cases the resistivity factor is not constant, but instead varies with the resistivity of the electrolytic solution. It was shown that clean sands behave normally—i.e., that the resistivity factor does not vary with resistivity of the electrolyte — but that sands con- taining shale and clay may exhibit abnormally low resistivity factors when the solution used to saturate them is of fairly high resistivity. At low resistivities of the electrolyte, the resistivity factor for a shaly sand appeared to approach a normal behavior. It is evident that the resistivity factor of a shaly sand is dependent upon factors other than pore geometry when the solution used to saturate it is of high resistivity. Patnode and Wyllie, and later de Witte,' assumed that the conductivity of a shaly sand saturated with an electrolyte could be represented as the sum of two quantities. One of these was assumed, in effect, to be the conductivity which would be expected if the sample were a clean sand. and the other was assumed to be a conductivity inherent in the sample itself. The latter was supposed to be constant for a given rock sample regardless of the solution used to saturate it. The source of this added conductivity was ascribed to "conductive solids." In actual practice: the effect of the abnormal behavior of shaly sands is of minor importance except when the resistivity of a formation such as a sand is high. Thus the effect is more important when the sand is saturated with a dilute brine than when it contains a more concentrated electrolyte. The effect is also more important when the sample contains oil or gas than when it contains only saline water. Recently it has been suggested that the porosity of a stratum may be estimated from the electric log by use of the resistivity of the invaded zone." This is the zone flushed with the filtrate from mud used in drilling the well. which is ordinarily very dilute brine. When the method is applied to shaly sands, the effect of abnormal conductivity becomes of importance. This report describes an investigation of the mechanism responsible for the abnormal behavior of the resistivity of shaly rock saturated with conducting solutions. The investigation

Jan 1, 1953

By C. C. Martin, M. C. Fuerstenau, R. B. Bhappu

Experiments revealed that quartz could not be floated in conductivity water at any pH with a long-chained sulfonate as collector. Various cations, Fe+++, Al+++, Pb++, Mn++, Mg++, Ca++, are shown to function as activators when the pH is such that the cation hydrolyzes. As the solubility product of the various cation-sulfonates was exceeded at the concentrations involved, precipitated cation-hydroxy-sulfonates, e.g. Fe (RSO3)2OH must be functioning as the collector in these systems. A number of interesting and important phenomena were revealed during a study of the response of beryl to sulfonate flotation.' Perhaps the most important observation is the effect of various cations on flotation response. Experiments showed that in the vicinity of pH 3.0, about three ppm Fe+++ increased recovery of leached beryl from about 60 pct to 100 pct, whereas about four ppm Ca+ + reduced the recovery from 60 pct to 2 pct. With the exception of ferric iron, all of the other cations investigated reduced flotation recoveries drastically at this pH. As postulated in the paper Sulfonate Flotation of Beryl,' even with low concentrations of polyvalent cations and sulfonate (on the order of one ppm), cation-sulfonates are precipitated immediately in solution. That is, blueish-white clouds were noted to form after given additions of salts to known solutions of sulfonate. Furthermore, it was also shown that one-hundred-fold more ferric iron than necessary to form the precipitated cloud had to be added to effect complete flotation. In other words, some form of solid ferric sulfonate was found to function as the collector in these systems. The form of the compound was suggested to be Fe(RCO3)2OH and that bonding to the surface occurs through the hydrogen of the hy-droxyl. As the form of this compound was shown to be dependent on the extent of hydrolysis of ferric iron, it is to be expected that ferric iron will be unique in some pH region. Further, if the presence of hydroxyl in the neutral precipitated compound is of primary importance, then other cations should function similarly but at different values of pH, since they will hydrolyze at different concentrations of hydroxyl ion. To determine whether the premise of hydrolysis is correct, the study was extended to quartz systems in the presence of various cations at various values of pH. EXPERIMENTAL MATERIALS AND METHOD Sodium alkyl aryl sulfonate was chosen as the collector for the experimental work. The reagent, sup plied as a courtesy sample by the Shell Chemical Co., has the following physical properties: Physical form Solid — Finely ground Sulfonate content, pct wt 95 to 97 Molecular Weight 450 to 470 Number of carbon atoms in hydrocarbon chain 25 to 30 Melting Point, OF 250 to 260 Solubility Soluble in water with gel formation at concentrations higher than 25 pct by weight sulfonate This particular reagent was chosen because of its high active sulfonate content, long-chain length, and solid form. With the exception of the frother and sulfonate, all other chemicals were of reagent grade quality. Conductivity water was used in the experimental work. This water, made by passing distilled water through an ion exchange column, had an average measured conductivity of one micromho. Experiments were conducted at room temperature in a small glass flotation cell with the following procedure: 1) A redetermined amount of water and salt solution (e.g. CaC12 . 2H2O) were combined and the pH adjusted to a given value. 2) A given amount of sulfonate was added so that final solution volume was 130 cc. 3) One drop of Dow 250 frother was added. 4) Five g of quartz were added and the system conditioned for five minutes. 5) The pH of the system was measured (termed flotation pH).

Jan 1, 1963

By W. M. Corse

I bring this investigation to your attention to emphasize the needless waste attendent upon the use of tin plate with an unnecessarily heavy tin coating. With our present knowledge, we are unable commercially to produce coatings as light as the lower weights used in this test. If, however, future research should develop means to this end, the resultant product would meet all practical requirements, and a very considerable saving in pig tin would result. DISCUSSION G. H. Clamer.-—The National Canners' Association is studying the action of fruit juices, etc., on solders. Of course these tests will take quite a long time, and we hope by that time the war will be over and there will be no need for conserving tin for war purposes. Germany for a great many years has prohibited the use of more than 37 per cent. of lead in alloys used in contact with food products. The eutectic composition is 37 per cent. of lead and 63 per cent. of tin; alloys containing more than that percentage of lead have some free lead. J. W. Richards,' South Bethlehem, Pa.—A great deal of conservation can result from the packing of dry foods in cartons and in fiber packages instead of using sheet tin. Many of the boxes used for packing things other than food are frequently made of sheet tin because it prints and lithographs well; these could be made of sheet iron coated with copper or some other substitute metal which prints equally well. The Aluminum Bronze Industry W. M. CORSE,† Mansfield, Ohio.—The conservation of tin, in view of the shipping situation, is one of great importance. Several methods of conservation can be employed: 1. Reduction of the amount of tin in an alloy or compound. 2. Substitution of an entirely different metal or compound for tin. 3. A combination of the first and second methods. The second method is the one that I wish to discuss. Metallic aluminum, has been known for a long time, and its use in copper alloys was discovered about 1855 by Lord Percy. The high cost of production of metallic aluminum retarded its commercial development, and it was not until the discovery of the electrochemical processes for its production that it came to be known as a common metal. I have been particularly interested, for the past few years, in working with the alloy known as aluminum bronze, which is usually composed of approximately 90 parts of copper and 10 parts of aluminum, by weight.

Jan 1, 1919

By E. L. Anderson, J. R. Long, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By J. R. Long, E. L. Anderson, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By John S. Bell, J. M. Shepherd

pressure difference of 280 psi measured initially on opposite sides of the major fault in the Hawkins Field led to pressure determinations in the Woodbine sand throughout the East Texas basin. Considering the large area, there is unusually good correlation between pressure losses and points of major withdrawals, these losses indicating that the basin pressure has been materially reduced by withdrawals, primarily from the East Texas Field and secondarily from the old fault-line fields of Limestone and Navarro counties, with the pressure loss varying inversely with the log of the distance from these two main areas of basin withdrawals to the measurement points. Apparently faults located throughout the basin serve as local blocks to continuous pressure gradients. INTRODUCTION The pressure anomalies found in the Hawkins Field, Wood County, Texas,' shortly after discovery have led to an area-wide investigation of the pressure distribution within the Woodbine sand of the East Texas basin. These pressures were obtained by drill-stem tests made for that sole purpose while drilling wildcat wells to deeper horizons. The Woodbine sand of Gulf Cretaceous Age is or has been productive of oil and gas in 42 different fields, with the 28 oil fields currently active having produced 118,000,000 bbl of oil during 1949. With one exception, producing energy for all Woodbine reservoirs has been from water drive provided predominantly by expansion of the tremendous volume of water contained in the Woodbine sand. This producing mechanism was recognized at an early date and was described mathematically by

Jan 1, 1951

By John S. Bell, J. M. Shepherd

pressure difference of 280 psi measured initially on opposite sides of the major fault in the Hawkins Field led to pressure determinations in the Woodbine sand throughout the East Texas basin. Considering the large area, there is unusually good correlation between pressure losses and points of major withdrawals, these losses indicating that the basin pressure has been materially reduced by withdrawals, primarily from the East Texas Field and secondarily from the old fault-line fields of Limestone and Navarro counties, with the pressure loss varying inversely with the log of the distance from these two main areas of basin withdrawals to the measurement points. Apparently faults located throughout the basin serve as local blocks to continuous pressure gradients. INTRODUCTION The pressure anomalies found in the Hawkins Field, Wood County, Texas,' shortly after discovery have led to an area-wide investigation of the pressure distribution within the Woodbine sand of the East Texas basin. These pressures were obtained by drill-stem tests made for that sole purpose while drilling wildcat wells to deeper horizons. The Woodbine sand of Gulf Cretaceous Age is or has been productive of oil and gas in 42 different fields, with the 28 oil fields currently active having produced 118,000,000 bbl of oil during 1949. With one exception, producing energy for all Woodbine reservoirs has been from water drive provided predominantly by expansion of the tremendous volume of water contained in the Woodbine sand. This producing mechanism was recognized at an early date and was described mathematically by

Jan 1, 1951

By William D. Klopp, Joseph R. Stephens

A substantial reduction in the 300°F ductile-to-brittle transition temperature for unalloyed chromium was achieved in alloys from systems which resemble the Cr-Re system. These alloy systems include Cr-Ru, Cr-Co, and Cr-Fe. Transition temperatures ranged from -300° F for Cr-35 at. pct Re to -75°F for 0-50 at. pct Fe. The ductile alloys have high grain gvowth rates at elevated temperatures. Also, Cr-24 at. pct Ru exhibited enhanced tensile ductility at elevated temperatures, characteristic of superplas-ticity. It is concluded that phase relations play an importarlt role in the rhenium ductilizing effect. The ductile alloys have compositions near the solubility limit in systems with a high terminal solubility and which contain an intermediate o phase. The importance of enhanced high-temperature ductility to the rhenium ductilizing effect is not well understood although both may have common basic features. CHROMIUM alloys are currently being investigated for advanced air-breathing engine applications, primarily as turbine buckets and/or stator vanes. The inherent advantages of chromium as a high-temperature structural material are well-known1 and include its high melting point relative to superalloys, moderately high modulus of elasticity, low density, good thermal shock resistance, and superior oxidation resistance as compared to the other refractory metals. Additionally, it is capable of being strengthened by conventional alloying techniques. The major disadvantage of chromium is its poor ductility at ambient temperatures, a problem which it shares with the other two Group VI-A metals, molybdenum and tungsten. For chromium, the problem is further amplified by its susceptibility to nitrogen em-brittlement during high-temperature air exposure. In cases of severe nitrogen embrittlement, the ductile-to-brittle transition temperature might exceed the steady-state operating temperature of the component. The low ductility of chromium would make stator vanes and turbine buckets prone to foreign object damage. The present work was directed towards improvement of the ductility of chromium through alloying, with the anticipation that any improvements so obtained might be additive to strengthening improvements achieved through different types of alloying. The alloying additions for ductility were selected on the basis of the similarity of their phase relations with chromium to that of Cr-Re. The reduction in the ductile-to-brittle transition temperatures of the Group VI-A metals as a result of alloying with 25 to 35 pct Re is well established.a4 the temperature range -300" to 750° F. This phenomenon is commonly referred to as the &apos;<rhenium ductilizing effect"; this term is also used to describe systems in which the ductilizing element is not rhenium. Other alloy systems which have recently been shown to exhibit the rhenium ductilizing effect include Cr-Co and c-Ru.= In order to explore the generality of this effect, alloys were selected from systems having phase relations similar to that of Cr-Re, primarily a high solubility in chromium and an intermediate o phase. The following compositions were prepared: Cr-35 and -40Re; Cr-10, -15, -18, -21, -24, and -27 pct Ru; Cr-25 and -30 pct Co; Cr-30, -40, and -50 pct Fe; Cr-45, -55, and -65 pct Mn. Seven other systems were also studied which partially resemble Cr-Re. These systems have extensive chromium solid solutions or a complex intermediate phase, not necessarily o. The compositions evaluated include the following: Cr-20 pct Ti; Cr-15, -30, and -45 pct V; Cr-2.5 pct Cb; Cr-2.5 pct Ta; Cr-20 pct Ni; Cr-6, -9, -12, and -15 pct 0s; Cr-10 pct Ir. The compositions of alloys in these systems were chosen near the solubility limit for the chromium-base solid solutions, since in the Group VI-A Re systems, the saturated alloys are the most ductile. These alloys were evaluated on the basis of hardness, fabricability, and ductile-to-brittle transition temperatures. In addition to the studies of alloying effects on ductility, an exploratory investigation was conducted on mechanical properties at high temperatures in Cr-Ru alloys EXPERIMENTAL PROCEDURE High-purity chromium prepared by the iodide deposition process was employed for all studies. An analysis of this chromium is given in Table I. Alloying elements were obtained in the following forms: Commercially pure powder — iridium, osmium, rhenium, and ruthenium. Arc-melted ingot — titanium and vanadium. Electrolytic flake — iron, manganese, and nickel. Sheet rolled from electron-bearn-melted ingot — columbium and tantalum. Electron-beam-melted ingot — cobalt. Sheet rolled from arc-melted ingot — rhenium. All alloys were initially consolidated by triple arc melting into 60-g button ingots on a water-cooled hearth using a nonconsumable tungsten electrode. The melting atmosphere was Ti-gettered Ar at a pressure of 20 torr. The ingots were drop cast into rectangular slabs and fabricated by heating at 1470" to 2800° F in argon followed by rolling in air. Bend specimens measuring 0.3 by 0.9 in. were cut from the 0.035-in. sheet parallel to the rolling direction. The specimens were annealed for 1 hr in argon, furnace cooled or water quenched, and electropolished prior to testing. Three-point loading bend tests were conducted at a crosshead speed of l-in. per min over

Jan 1, 1969

By Augustus J. Bowie

THE discovery of the auriferous cement gravel deposits in and near Deadwood Gulch, Lawrence County, Dakota Territory, in 1876, created a mining excitement, and rush to the Black Hills. Numerous ten and twenty-stamp mills were built on Deadwood Gulch ; Central City and the town of Deadwood sprang into existence, and became the centres of the mining industry of the Hills. Gold quartz deposits were subsequently discovered and located on a so-called mineral belt, extending from Whitewood Creek on the south, to Deadwood Gulch on the north. A northerly group of these quartz locations was purchased in December, 1877, by parties in San Francisco,, who formed a company, incorporated under the name of the Father de Smet Consolidated Gold Mining Company. This company immediately commenced the work of exploration. The deposits were proved to be extensive, and easily mined, but it was found that the ore, on an average, would not. yield more than $10.00 per ton* of 2000 pounds. At this time the cost of supplies and materials in the Hills was high. Miners&apos; wages were $3.50 per diem, and custom mills charged $6:00. per ton. The successful working of mines on "the belt" necessitated cheap milling. The ores being of so low grade,† this could be accomplished only with large and economically running mills. To insure the greatest possible economy, the Father,& Smet mill * Up to December 31st, 1879; the de Smet mine had produced bullion of the value of $718,211.68 from 76,155 tons of ore, being an average value of $9.41 per ton. During the year ending December 31st, 1879, the mine produced 46,344 tons, which yielded $425,360.42, or $9.18 per ton. The total gross cost of working for the corresponding period, including deadwork, exchange, legal expenses, fete., wits $219,914.82. The yield of the mine for the year 1880 (Engineering and Mining Journal, February 5th, 1881), was $600,011, with total expenses of mining and milling, of $313,108. † The first 4083 tons extracted from the de Smet mine, were selected, yielding $62,783.97. The next 25,728 tons produced $230,067.24. The total 29,811 tons were weighed, and worked at custom mills. The yield of the first 409 tons from tine Golden Terra Mine was $11.44 per-ton.

Jan 1, 1882

The introduction and development of the flotation process have proved to be of such momentous importance to the mining industry of the United States that they deserve to be considered historically.* The origin of the use of oily matter in separating minerals in ores is obscure, because its beginnings were unregarded. The story told by Herodotus concerning the recovery of gold from the mud of a lake by means of feathers daubed with pitch in the hands of apocryphal virgins is as pertinent to our inquiry as the yarn, two thousand years later, of a young school-teacher in Colorado that was washing oil-stained ore-sacks in her brother&apos;s assay-office when she noted the floating of pyrite on the water contaminated by the oil. In any event, the method patented by Carrie Everaon in 1885 was a complete failure, except as factitious evidence for trying to disprove the originality of subsequent inventions. An early and inadvertent use of the affinity of oil for metallic surfaces is suggested by the story of Jason and the Argonauts, who extracted gold from the gravel of the river Colchis by means of sheepskins. The woolly hide sewed, like the blankets used in our early stamp-mills, to arrest the gold, which was further detained by the oil on the fleece. Strabo, referring to a later period, says that in the country of the Soanes, who inhabit the valley of the Colchis, “the winter torrents are said to bring down even gold, which the barbarians collect in troughs pierced with holes, and lined with fleeces; and hence the fable of the Golden Fleece”.† William Pryce

Jan 1, 1932

By John C. Branner

No precise geographic limits can be given for the zinc- and lead-region of North Arkansas. In general terms it lies N. of the Boston mountains and W. of the St. Louis, Iron Mountain and Southern railway; but the prospecting and the development of the ore-deposits have not gone far enough to outline more than vaguely the areas over which workable deposits are to be expected. The tardiness of the development of the region is due in part to its topography, as a hilly and partly mountainous country, through which there have been no railways until recently. There is no longer any doubt, however, about the existence in that region of large bodies of zinc-ores. I. General Geology. The general geology of the region is, in the main, quite simple, but that of the ore-deposits is less so. The zinc-regions of North Arkansas lie about the southern flanks of the Ozark dome. The rocks are approximately horizontal, but have a gentle southward dip away from the axis of this dome. Figs. 1, 2 and 3 show the broad features of the to-. pography and geologic structure. South of the zinc-region, the sandstones and shales of the lower Coal-Measures form the north-facing escarpment of the Boston mountains. Beneath the Coal-Measure rocks are the limestones and cherts of the Lower Carboniferous; and these rest upon Silurian and Ordovician beds. The uppermost beds (Coal-Measures) have been cut into by erosion along the mountain-slopes so that their edges or outcrops have a meandering or dendritic form. The same thing happens with the Lower Carboniferous beds; but these, haying been more or less protected by the overlying Coal-Measured, have broader bases, and cover a much larger area. In places,

Jan 1, 1902

By E. C. Babson

In order to explore the possibility of predicting reservoir performance from laboratory data, behavior of a hypothetical low-permeability reservoir has been estimated by applying data and methods currently available in the literature. A method of calculating decline in productivity index is discussed, and recoveries by internal gas drive, external gas drive and water drive are estimated. Introduction During the life of a producing oil property an operator is faced with many perplexing problems. Any attempt to determine proper well spacing, optimum rate of production, or the desirability of pressure maintenance requires the evaluation not only of a host of economic and practical operating factors but also of the future performance of the reservoir. Although in some cases economic or operating con-siderations may be of primary importance in planning a development or production program, the anticipated effect on ultimate recovery is more likely to be the decisive factor. The soundest basis for evaluating reservoir performance is past experience with oil fields, but pertinent data are difficult to obtain or apply under conditions normally encountered in California fields. Many of these fields are characterized by thick sections of alternating sands and shales complicated by faulting and rapidly changing lithologic conditions. Further compli- cations are introduced by haphazard development and production practices resulting from competitive conditions, changing demand for oil, and insufficient knowledge of structural conditions during early development. Even in the rare cases where development has been systematic and adequate, production policy has usually been controlled by economic and competitive factors rather than a desire to obtain information for use in future operations. In other words, comparable reservoirs in which development and production practices have been systematically varied are seldom found. In the light of these conditions, conclusions based on experiences usually lack the certainty required for decisions involving large sums of money. Some other method of attacking these problems is needed to supplement and orient field experience. Progress in laboratory investigations of the flow of oil, gas, and water through sands has been so rapid in recent years that these data may furnish such a supplementary approach in the near future. In order to explore this possibility the author has attempted to predict the behavior of one type of reservoir by applying published data and methods. Basic Data and Assumptions Calculations outlined in this paper are dependent upon a detailed knowledge of the properties of oil, gas, and water present in the reservoir and the portion of the total pore space originally filled by each. It is also necessary to know how the permeability of the sand to oil, gas, and water varies with the saturations of these fluids 20

Jan 1, 1944

By E. C. Babson

In order to explore the possibility of predicting reservoir performance from laboratory data, behavior of a hypothetical low-permeability reservoir has been estimated by applying data and methods currently available in the literature. A method of calculating decline in productivity index is discussed, and recoveries by internal gas drive, external gas drive and water drive are estimated. Introduction During the life of a producing oil property an operator is faced with many perplexing problems. Any attempt to determine proper well spacing, optimum rate of production, or the desirability of pressure maintenance requires the evaluation not only of a host of economic and practical operating factors but also of the future performance of the reservoir. Although in some cases economic or operating con-siderations may be of primary importance in planning a development or production program, the anticipated effect on ultimate recovery is more likely to be the decisive factor. The soundest basis for evaluating reservoir performance is past experience with oil fields, but pertinent data are difficult to obtain or apply under conditions normally encountered in California fields. Many of these fields are characterized by thick sections of alternating sands and shales complicated by faulting and rapidly changing lithologic conditions. Further compli- cations are introduced by haphazard development and production practices resulting from competitive conditions, changing demand for oil, and insufficient knowledge of structural conditions during early development. Even in the rare cases where development has been systematic and adequate, production policy has usually been controlled by economic and competitive factors rather than a desire to obtain information for use in future operations. In other words, comparable reservoirs in which development and production practices have been systematically varied are seldom found. In the light of these conditions, conclusions based on experiences usually lack the certainty required for decisions involving large sums of money. Some other method of attacking these problems is needed to supplement and orient field experience. Progress in laboratory investigations of the flow of oil, gas, and water through sands has been so rapid in recent years that these data may furnish such a supplementary approach in the near future. In order to explore this possibility the author has attempted to predict the behavior of one type of reservoir by applying published data and methods. Basic Data and Assumptions Calculations outlined in this paper are dependent upon a detailed knowledge of the properties of oil, gas, and water present in the reservoir and the portion of the total pore space originally filled by each. It is also necessary to know how the permeability of the sand to oil, gas, and water varies with the saturations of these fluids 20

Jan 1, 1944