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By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Jan 1, 1963

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By Ralph W. Bailey, William B. Price

ARSENIC, antimony and phosphorus are now used in the brass industry as standard inhibitors in preventing dezincification in [ ] condenser tubes. This subject has been thoroughly covered by Barry,1 who described the testing procedure by total immersion of suitable specimens in a I per cent cupric chloride solution at definite temperatures. Effects of dezincification were then determined by loss in tensile strength and elongation of the test specimens after definite periods of immersion. In the crystallography of the chemical elements as tabulated by William Hume-Rothery,2 phosphorus (metallic), arsenic, antimony and bismuth are placed in group V-B and the type of crystal lattice for arsenic, antimony and bismuth is given as rhombohedral. The Metals Handbook3 [ ] lists them as "rhombohedral hexagonal," with the additional notation that for arsenic this is the ordinary form at 20°C.; other modifications known or probable at other temperatures. In view of these statements and of the fact that phosphorus, arsenic and antimony are effective in increasing the resistance to dezincification, it was natural to assume that bismuth would act in the same manner. A series of tests was therefore carried out employing the methods described by Barry. Much to our surprise, bismuth did not inhibit dezincification, but rather seemed to accelerate it. Tensile-test speci-

Jan 1, 1942

By Robert A. Laurence

Ore deposits in the Southern Appalachians are ( 1) sedimentary or syngenetic, ( 2) epigenetic, and ( 3) residual. In general, deposits characteristic of high temperature and pressure are found in the Blue Ridge and Piedmont provinces and those of low and intermediate temperature and pressure, including the sedimentary ores, are found in the Valley and Ridge and Appalachian Plateaus provinces. Residual deposits are present throughout the area. Recognition of several periods of intrusion and metamorphism in the Appalachians has changed former concepts which held that most mineralization was of late Paleozoic age in a zonal pattern including all four provinces. Many deposits probably are of early or midPaleozoic age. Similarly, recent studies in geomorphology indicate that the formation of residual deposits is a continuous process and not related to specific cycles of peneplanation.

Jan 1, 1968

By F. L. Ransome

THAT geology and mining should stand in close and mutually helpful relationship was recognized in the United States at an early period, but it is not possible to set a precise date at which the study of ore deposits became a thoroughly reputable and important branch of geological science. As early as 1850, appeared the first ,part of Foster and Whitney's report1 on the Lake Superior region, devoted mainly to the copper-bearing areas, followed, in the succeeding year, by the second part,2 on the iron lands. This appears to have been the first comprehensive report on what might, at that time at least, be called "western" ore deposits to be prepared and published under the auspices of the Federal government. An outgrowth from this work was Whitney's Metallic Wealth of the United States,3 which appeared in 1854. It was the earliest general work on the ore deposits of the country, and remained a standard reference book for marly forty years. From 1853 on, various parties were sent out by the War Department to explore routes for proposed railways and wagon roads from the Mississippi Valley to the Pacific Coast. Geologists were attached to most of these parties, but their work was mainly of broad reconnaissance character, little attention being paid to ore deposits. Although the

Jan 1, 1933

By K. W. John, L. Mueller

The rock mechanics approach to stability problems of steep rock slopes dealt with in this article has particular reference to the concept and methods of analysis developed by the Salzburg, Austria, school of rock mechanics. These theories are based on the principal postulate of the anistropy of the technological properties of in-situ rock masses. The present approach, which is more in line with geological engineering concepts, differs distinctively from the soil mechanics and engineering geological concepts commonly practiced in the United States. PRINCIPAL ENGINEERING APPROACH TO GEOTECHNICAL PROBLEMS AVAILABLE ENGINEERING CONCEPTS At the present time two different concepts are available for engineering analysis of underground structures and foundations in different earth material: soil mechanics and rock mechanics. Of these two branches, soil mechanics is, after 40 years of initially revolutionary and more recently evolutionary development, well established. Its principal concept of replacing in-situ soils or rock masses by perfectly homogeneous substitues has resulted in many practicable methods of analysis which, if applied with judgement, have resulted in successful applications throughout the world. Conversely, rock mechanics is still in the early stages of revolutionary development. Few, if any, standard concepts or methods of analysis have been established. Opinions vary widely. At present the professional background of an investigator very often determines the engineering concept to be applied to a particular problem, rather than its actual requirements if considered objectively. This paper stresses the rock mechanics or geological engineering point of view advocated by the Salzburg group. A review of the soil mechanics concepts is considered beyond the scope of this paper. THE "SALZBURG APPROACH" TO ROCK MECHANICS The rock mechanics concept as outlined here was initiated by Stini, based upon work by sander.1 Since

Jan 1, 1963

By R. A. Generes, H. C. H. Darley

Laboratory tests showed that at elevated temperatures a reaction takes place between all metal hydroxides and clay muds, which results in a thickening or solidifying of the mud, the extent of which depends on the nature of the ingredients. Calcium hydroxide gave the strongest solidification whereas barium hydroxide only caused a mild thickening, indicating that the use of barium hydroxide muds instead of lime muds would be a good way of preventing high-temperature solidification. It was found possible to prepare barium mud in the laboratory with caustic soda and a thinner in the same manner as lime muds, and these barium muds had the same or better toleration of high solids content, resistance to salt contamination, and low gel strengths as the corresponding lime muds. Three field trials have been made with barium mud. The principal difficulty encountered was in determining the correct proportions of the tourly treatments required to maintain low gel strengths. A satisfactory systern was finally developed, and low gels were maintained throughout the third test. The wells on which the trials were made were not carried deep enough to test the resistance to solidification adequately, but oven tests at 350°F were made periodically and no tendency to solidification was noted except immediately after severe cernent contamination had introduced excessive amounts of calcium into the system. Although barium hydroxide costs considerably more than lime, the total mud costs were as low, and on the last well significantly lower, than the average cost of lime mud wells drilled in the vicinity. INTRODUCTION The advantages of repressing dispersion and hydra-tion of clay cuttings carried in the mud, particularly when drilling through thick clay formations, are well recognized. This repression is generally achieved by the use of lime, and lime muds have in consequence the desirable characteristics of high toleration of solids, low thixotropy, and good resistance to contamination. They have, however, the disadvantage of high-temperature solidification. This phenomenon has been described in detail by Gray et al, who have shown that it is the result of a chemical reaction between the hydroxides and the clay minerals. The work described in this paper was undertaken to find a substitute for lime which would not cause this solidification. LABORATORY EXPERlMENTS The principal positive requirement for a substitute for lime is that it should repress the hydration and dispersion of clay. It is well known that monovalent cations promote hydration while polyvalent cations repress it. Therefore, a few representative polyvalent salts and hydroxides were tested to determine whether they could be used as substitutes for lime. Their efficiency at repressing hydration and dispersion was measured by means of the clay-volume test. It has been shown elsewhere' that this test is a good measure of degree of dispersion of clay in suspension and that hydration accompanies and correlates with dispersion, so that measuring one measures the other. The test is made by centrifuging a 1:100 mixture of mud and 1-N NaCl and observing the volume of sediment—the greater the volume, the greater the dispersion. The tendency to caux solidification was measured by heating the muds in pressure vessels for 16 hours at 150°F and 370°F. An approximate quantitative

Jan 1, 1957

By Alexander Bowie

IN many places throughout the Western mountain plateau regions of the United States coal beds in place have been burned over very extensive, areas, the fire evidently originating on the nakedly exposed outcrop of the coal bed and gradually burning its way into the bed for considerable distances under very heavy cover. . The surface evidences of the burned-out coal beds are seen in the calcined and discolored rocks overlying the places of the outcrop. The greater the mass of the burned coal the higher the results of its combustion can be seen in the overlying strata. I have noted many instances of this condition in the States of South Dakota, Wyoming, Colorado, New Mexico, and Arizona. In the lignite fields of Dakota and Wyoming I noted stretches of level country many square miles in extent where the surface rocks were roasted and vitrified by the burning of a great bed of lignite lying nearly level and with a light cover; this is probably the most favorable natural condition for the burning out of a coal bed. The less the depth of the rock covering overlying the coal bed, the better the .chance for a continuous supply of air to the fire; but when the coal bed clips heavily into the ground, or even if level, if it, passes under a hill or mountain which gives the bed a heavy covering of strata, the fire has more chances of being extinguished from natural causes than in the first condition described. The distance which, a crop fire may extend into a coal field is very much influenced by the dip, the thickness of the coal bed, and the nature of the rock covering immediately overlying it.

Jan 2, 1914

SUGGESTIONS that existing schools give instruction bearing on the mineral industry, or that schools for that purpose should be established in the United States, began to be made early, and it would require too much space to catalogue them all. Some of the more important may be mentioned to indicate their general character. In the "advertisement to such parents as have now (or expect to have) children prepared to be educated in the College of New York," which appeared in the New York Mercury of June 3, 1754, Samuel Johnson, the first president of King's College, the predecessor of Columbia, said that it was the "design of this college to instruct and perfect the youth," among other things, "in the arts of Numbering and Measuring of Surveying, and Navigation and Geography. . . . and in the Air, Water and Earth around us, and the various kinds of Meteors, Stones, Mines and Minerals, Plants and Animals; and in the knowledge of all Nature in the Heavens above us, and of everything useful for the Comfort, Convenience and the Elegance of Life . . . " Though the concept that natural science should be used to enlarge the bounds of human life was thus implicit at Columbia from the , very beginning (John Stevens graduated from it in 1768, James Renwick in 1807, Horatio Allen in 1833, and A. W. Craven in 1899), it was only during the period of Renwick's professorship of Natural and Experimental Philosophy and Chemistry (1830- 1853) that much attention was given to applied science.* Among the Austin papers, published by the American Historical Association,~ there is a draft in Stephen F. Austin's handwriting of a proposed memorial from the legislature of , Missouri to Congress, not only urging "the propriety and utility * See chapter 4 for early interest in this subject in Philadelphia.

Jan 1, 1941

By Carl E. Swartz

In the course of a recent investigation1 to develop a more satisfactory white-metal bearing alloy, a number of alloy systems were studied. The cadmium-nickel system showed characteristics desirable in a bearing alloy, and the system was therefore studied in some detail. Experimental Method Alloying cadmium with nickel offered no serious difficulty. After melting the cadmium, clean sheet nickel was added while the temperature was maintained at 500" to 600" C. A few crystals of ammonium chloride2 served to clean the nickel when the latter did not "wet" readily. In preparing the individual alloys for thermal and microscopic investigation, a "hardener" containing about 10 per cent nickel was used. Thermal Experiments and Apparatus Time-temperature cooling curves were made by standard methods. Globe electrolytic cadmium was added to the hardener to make a melt of the desired composition weighing between 100 and 200 grams. This charge was placed in a Pyrex test tube, 1 by 10 in., closed with a rubber stopper carrying a thermocouple sheath and quartz stirring rod. The assembly was lowered to a depth of about 4½ in. into an electric resistance pot furnace containing a No. 0000 clay-graphite crucible (to catch the melt in case of a break in the test tube). After the tube was clamped in this position, an asbestos-magnesia mixture was loosely packed in the furnace around the tube and a "halved" cover of transite placed on top. This left at least 5 in. of the test tube protruding from the furnace. When the alloy had melted, the thermocouple was adjusted so that the hot junction was l! in. from the bottom of the test tube. The melt was stirred thoroughly for several minutes to insure composition homogeneity and absence of thermal gradients.

Jan 1, 1934

By Eric Jette

IN order to control a chemical process by other than empirical, rule of thumb methods, two types of knowledge concerning the reactions involved must be available: (1) the thermodynamics of the reactions, and (2), by no means less important for efficient operation, the mechanisms and kinetics of the reactions. Information on the thermodynamic side enables the operator to decide upon initial and final conditions, whether heat must be .added or removed from the system, whether the reactions proceed farthest in the desired direction at high pressure or low, etc. Knowledge of the mechanisms involves the determination of the individual steps by which an initial set of reactants, under given conditions, proceed to give the desired final products and kinetic studies upon which the mechanisms are based give the speed at which each of these reactions or steps take place. Thus thermodynamic studies of a 'reaction enable the operator to control the direction and extent to which the reaction can proceed, while kinetic studies enable him to control rates and thus the time' efficiency of the operations. The thermodynamics set the limit to which the reacting system approaches; the kinetics tell how fast the system actually approaches this limit. The two types of information are complementary and not antagonistic even though in discussing the mechanism the introduction of thermodynamics is entirely needless and generally of no assistance, while in thermodynamic studies mechanism need not even be mentioned.

Jan 1, 1931

By A. Mitchell, T. Bagshaw

A recent paper by Thomas1 has presented new data on the solubility of hydrogen in solid silver at 1 atm pressure in the temperature range 600° to 963°C. However, no data is reported in the literature on hydrogen solubility in liquid silver. The Sieverts technique which has been described previously2,3 was used in the present work. Charges of approximately 160 g were melted in Morgan "purox" recrystallized alumina crucibles and purified helium was used for the determination of the "hot volume" during each experiment. A chemical analysis of the silver indicates that the impurity content (Cu + Al) is less than 0.02 wt pct. Hydrogen solubility in the temperature range 963° to 1200°C was investigated. The results of three experiments are shown in Table I. Fig. 1 shows an Arrhenius plot of the present work together with the solid-state data of Thomas, Steacie, and johnson,4 Eichenauer et al.,5 and Siegelin et al.6 The following expression has been derived from the Arrhenius plot of the present data: log (solubility of hydrogen, cm3 per 100 g) = 2.154-3512.0/ToK The heat of solution derived from Fig. 1 is 31,150 cal per g mole H2 compared with the value of 33,020 cal per g mole H2 obtained by Thomas and 12,000 cal per g mole H2 obtained from the data of Steacie. It was observed that hydrogen evolution took place when the silver melts were solidified under 1 atm of hydrogen, which would not be expected from an extrapolation of the results of Steacie. Schenck and Lange7 have observed that, for several transition metals at their melting points, the ratio of the hydrogen solubility in the liquid to that in the solid lies in the range 2.1 to 3.1. The present results and those of Thomas are in accord in this respect having a ratio of 2.8. 'C. L. Thomas: Trans. TMS-AIME, 1967 vol. 239, pp. 485-96. 2T. Bagshaw and A. Mitchell: I. Iron Steel Inst., 1966, vol. 204, p. 87. 'M. Weinstein and J. F. Elliott: Trans. TWS-AIME, 1963, vol. 227, p. 382. 'E. W. R. Steacie and F. M. G. Johnson: Proc. Roy. Soc. (London), Ser. A, 1928, vol. 117, pp. 662-79. 'W. Eichenauer et al.: Z. Metallk., 1958, vol. 49, pp. 220-25. 6W. Siegelin et al.: Z. Elektrochem., 1957, vol. 61, pp. 359-66. 'H. Schenck and K. W. Lange: Arch Eisenhuettenw., 1966, vol. 37, no. 9, pp. 739-48.

Jan 1, 1969

By C. M. Shigley

Tan record of the largest magnesium plant in the country utilizing sea water as a primary raw material stands as another victory in the struggle for large-scale production of pure chemical elements from the oceans. Bromine was the first element to be economically and commercially recovered when, in 1933, a six million pound per year unit was built on the Atlantic Coast near Wilmington, North Carolina, by the Ethyl-Dow Chemical Co.1 The bromine was reacted with ethylene to produce ethylene dibromide, a necessary associate of tetraethyl lead in ethyl antiknock fluid. Within eight years that plant was doubled and redoubled, and another large unit was put into operation at Freeport, Texas, taking bromine from the Gulf of Mexico. In 1940, in fortunate anticipation of the impending demand for magnesium and the limitations of the production from natural brines, the Dow Chemical Co. turned again to the sea, and designed and erected a plant at Freeport to produce 18,000,000 lb. of magnesium per year from sea water.2 In March 1941, two months after the new plant had been put into successful operation, construction of an 18,000,000-lb. Government-financed addition was started. Late in 1941, as a part of the $400,000,000 defense program intended to produce 600,000,000 t0 700,000,000 lb. of magnesium per year, Dow was asked to build and operate for the Government a 72,000000-lb. plant near its original plant at Freeport. Within a few days after the Japanese made their attack at Pearl Harbor, preparation of a site was started at Velasco, Texas, for the construction of the Texas plant of the Dow Magnesium Corporation-the largest known magnesium plant utilizing sea water as its raw material. Less than six months after the first piling was driven, urgently needed magnesium was in steady production. Five months later, the plant had exceeded its rated capacity. It remained above rated production until the general magnesium curtailment was applied to Government-owned plants in September 1944. Credit for the construction and operation record of the Dow magnesium plant must be divided among the efforts of a very determined group of men, an extremely favorable location, and a simple process. It is with the two latter aspects of the plant that this article will deal. The site for the new enterprise was chosen near Velasco, Texas, on property bordering the Brazos River at a point approximately 6 miles inland from the original magnesium plant and y miles inland from the Freeport Harbor on the Gulf of Mexico. This location was far enough away from the operating units to reduce both interference from construction and the vulnerability of closely bunched manufacturing operations to the then feared air attack. Yet the distance inland was not too great for the economical construction of a barge canal from the harbor to serve both the transportation of raw

Jan 1, 1945

By D. J. McAdam

As shown in three recent papers by the author,6,7,8 in two papers by McAdam and Mebs,9,10 and in a paper by McAdam, Mebs, and Geil,11 the technical cohesive strength of a metal, in any particular state as regards mechanical treatment and heat-treatment, cannot be represented by a single stress value, but must be represented by a diagram with the principal stresses? as coordinates. Each point on the boundary of such a diagram represents a technical cohesion limit. The technical cohesive strength thus comprises an infinite number of technical cohesion limits, each representing fracture under a specific stress combination. Moreover, neither the yield strengths nor the ultimate strength can be represented completely by a single stress value, but must be represented by a diagram with the principal stresses as coordinates. All combinations of the principal stresses may be classified in three groups as illustrated by Fig. I. Fig. Ia shows three typical stress combinations with no two principal stresses equal. The magnitude of each principal stress is indicated qualitatively by the length of the arrow. Arrows pointing away from the cube indicate tensile stresses; arrows pointing toward the cube indicate compressive stresses. Typical stress combinations with two principal stresses equal are illustrated in Figs. Ib and Ic. Such stress combinations would be produced by subjecting a cylinder to combinations of uniform axial and radial stresses. The uniform radial stress may be resolved into two equal principal stresses, with the mutually perpendicular directions rotatable around the axis of the cylinder. Fig. Ib shows stress combinations with S2 equal to Sa. The greatest principal stress is in the axial direction, and the stress combination tends to cause either absolute or relative increase in length.* Fig. Ia shows stress combinations with Ss equal to Sl. The greatest principal stress is in the radial direction, and the combination tends to cause either absolute or relative decrease in length. The complete representation of either technical cohesive strength, yield strength, or ultimate strength generally requires a three-dimensional diagram. When two of the principal stresses are kept equal, however, the strength of a metal may be represented by a two-dimensional diagram with the coordinates representing the axial and radial stresses.6-11 In this paper, attention will be confined almost entirely to stress combinations with two of the prin-

Jan 1, 1944

By A. H. Bromly

The small agricultural village of Santa Barbara, in the State of Guanajuato, has been the center of spasmodic tin-mining operations during recent years. The deposits, so far as I know, are unique, and a few brief notes may be of interest. Santa Barbara, about 12 miles west of San Felipe station on the Mexican National Railway, and at an elevation of 2,400 m. above sea-level, is situated in a flat valley extending east and west, and bounded north and south by broken rugged hills rising about 330 m. above the general level of the valley. Tin-mining operations have been conducted at the Queensland mine, near this village. A small concentrating-mill was erected and attempts were made to smelt the ore in reverbera-tory furnaces. The country-rock of the district for many miles is rhyolite of great thickness. There are some local variations due to differences in cooling, or subsequent alteration or impregnation; but throughout the whole district the principal constituents of the rocks remain the same, viz., free silica, orthoclase-feldspar and sanidine. The latter is especially marked. The crevices and joints of the rock are frequently filled with calcedonic and opalescent quartz. The ore-formation at the Queensland mine is of an unusual nature, consisting of cracks in the rhyolite which have been filled with clay. This phenomenon is largely developed over a width of from 80 to 100 m., in which the principal fissuring follows an approximate direction of north and south. The average dip ranges between 70 and 80 degrees. Some of the fissures hold sufficiently true for a time to afford the impression that they are due to dynamic causes, or earth-movement. This may be true of some of the north by south fissures; but considering

Jan 1, 1906

By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965

By L. G. Huntley

A description f the geology and conditions affecting the occurrence and mining of oil; also the prospects of obtaining oil in different parts of the country. THE Colombian highlands consist of three parallel mountain ranges (Fig. 1) called respectively the eastern, central, and western cordillera of the Andes. A segment of the range that forms the backbone of the Isthmus of Panama also extends into Colombia, along the Pacific coast, as far southward as the mouth of the San Juan River. These four mountain ranges furnish the key to the varying climatic conditions and vegetation of the country. The river valleys are hot and covered with dense tropical growth. This is also generally true of the coastal plain, although in the northern portion there are some fairly open stretches where cattle are raised and even small districts where semi-arid conditions prevail. The population of this heavily wooded wet lowland depends almost entirely on river transportation for all intercourse. The elevated mountainous plateaus of the three ranges are more open and more generally cultivated; all traffic is by means of horses, mules, and the burro. The canoe and river-steamer transportation systems of the valleys are connected with the highland system of trails and roads by short cross trails and the few short railroads of the country. As these cross trails must pass through the intermediate foot-hill region, where the heavy rainfall reaches its maximum, they are exceedingly bad and the life of pack animals is short. The oil development of the Magdalena River valley is in this intermediate region, between the river and the sierras, north of Bogotá.

Jan 9, 1922

By J. E. Elliott

ALTHOUGH the firm in which the writer is a partner is not exactly the pioneer in the coring of rotary-drilled wells in Southern California, it has taken the lead in bringing coring to its present status. To the Shell Company of California belongs the, honor of having first used the core drill in its endeavors to locate subsurface structures west of Santa Fe Springs. Following those operations, similar work was done near Wasco in the San, Joaquin Valley. Results of the latter core drilling were successful, in that they made it possible to determine the under-ground structure. At, about the same time that the Shell Company was doing the work at Wasco, it was experimenting in the use of the core drill in connection with rotary-drilled holes. The oil sands in its dis¬covery well at Signal Hill were located by means of the rotary core drill. In 1921, in view of the trouble that the operators were having in the fields of Southern California, and particularly at Huntington Beach, R. E. Collom, of the State Mining Bureau, called their attention to the possibilities of the core drill for eliminating many of the serious problems that were facing them. It was this same difficulty encountered by the operator in locating the oil sands that caused the writer to enter into con-tract core drilling; late in 1921 the California operators became converted to the advantages of that method, and in the short space of one year core drilling in rotary-drilled holes has risen from a theory to an established practice.

Jan 10, 1923

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By H. C. Rogers

A phenomenological study of the failure of polycry stalline ductile metals at room temperature was carried out using light and electron microscopy. Tensile fractures as well as sections of partially fractured bars of OFHC copper in particular were examined. The initiation and growth of the central crack in the neck of a tensile specimen occurs by void formation. After the formation of the central crack the f'racture may be completed in either of two ways: by further void formation or by an "allernating slip" mechanism. The first leads to a "cup-cone" failure; the second, to a "double-cup" failure. In the past decade or decade and a half there has been a great deal of emphasis on the solution of the problem of the brittle fracture of metals, particularly those which normally exhibit considerable ductility such as steel. Since the problem of the fracture of metals after large plastic strains has less immediate commercial or defense significance, there has been considerably less effort expended in describing the details of the phenomenology and determining the mechanism of this type of fracture. The present research was undertaken to increase our knowledge in this area. The problem of ductile fracture has not been neglected completely, however. Ludwik1 first found by sectioning a necked but unbroken tensile specimen of aluminum that fracture began with a large internal crack which appeared to have started in the center of the neck. Examination of the fracture indicated that the crack had propagated radially with increasing deformation until a point was reached at which the path of the fracture suddenly left this transverse plane and proceeded at approximately 45 deg to the stress axis until the surface was reached. This gives rise to the commonly observed cup-cone tensile fracture. When MacGregor2 was attempting to demonstrate the linearity of the true stress-true strain curve from necking until fracture, he found that copper was anomalous in that the stress dropped off markedly from the straight line value before fracture occurred. Radiography indicated that in the copper an internal crack was formed long before the final fracture, the stress decreasing during the growth of this crack. One of the most significant advances in the understanding of ductile fracture was the result of work by Parker, Flanigan, and Davis.3 By the use of etch-pit orientations they were able to demonstrate conclusively that the fracture surface at the bottom of the cup, although on a gross scale normal to the tensile axis, did not consist of cleavage facets as had been previously supposed by many investigators. Recently, Forscher4 has shown evidence of porosity near the tensile fracture of hydrogenated zirconium which he attributes to hydride decomposition. The workers at the Titanium Metallurgical Laboratory5 have also shown evidence of porosity in a number of the commonly used metals after heavy deformation. Many metals have relatively low ductility during creep tests at high temperature. The fractures are intercrystalline, resulting from the nucleation and growth of grain boundary voids. The work in this area has been recently reviewed by Davies and Dennison.6 It is possible that some of the observations and conclusions may have a bearing on the present study? especially since at least two studies7,' have been extended down to room temperature and below using magnesium alloys. However, since magnesium does exhibit low-temperature cleavage, these results may not be pertinent to the present one. The use of the electron microscope as an aid to the study of fractures has been extensively exploited by Crussard and coworkers.9 The examination of direct carbon replicas of the fractures of a large number of metals and alloys showed that the bulk of the fracture surface was covered with cup-like indentations of the order of 1 to 2 µ in size. These frequently had a directionality by which Crussard claims to be able to tell the direction of the crack propagation. With this rather disconnected background of information, this investigation was undertaken in the hope of presenting a unified picture of the initiation and propagation of a fracture in a ductile metal. To this end all of the techniques previously used were employed simultaneously so that there might be a good correlation of the data obtained by different techniques. EXPERIMENTAL PROCEDURE The metal which was chosen as the starting material for this investigation was OFHC copper. Of the dozen or so materials considered, it best fulfilled the requirements of commercial availability in large sizes, good ductility, relatively high melting point compared with room temperature and

Jan 1, 1961